CA2090566A1 - Thermoplastic resin composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
There is disclosed a thermoplastic resin composition comprising as principal components a [A] thermoplastic resin having a functional group reactive with an amino group, a [B] olefinic polymer and/or styrenic polymer, the subtotal of the above [A]+[B]
being 100 parts by weight, and 0.05 to 20 parts by weight of a [C]
copolymer having in a molecule thereof a formamide group and/or an amino group or a salt thereof, said copolymer having the repeating unit 1, II, III or IV represented by the general formula (1), (II), (III) or (IV), respectively, ... (I) ... (II) ... (III) ... (IV) wherein Y is a group selected from the groups of the general formula . (V) ... (VI)

Description

2 ~ 9 ~

rl'HERMOPLAS'rlC RESIN CO~IPOSIl'ION

BACKGROUND OF Tl~lE lNVEN'I'lON
1. 1 ;~1~1 0I ll~C lI1VCI1ljOI1 The present invention relates to a therllloplastic resin eomposi~ioll. More particulally, it pertains to a thelmopklstic resin composition which comprises at least two types of speeific thermoplastic resins compounded with a novel copolymer having a formamide group ancl/or an amino group to enhance the compatibility among the aforesaid resins, which composition is excellent in all respects including surface impact strength, Izod irnpact strength aLncl appearance.
2. Deseription of the Relatecl Arts 13eing gcnerally exeellent in both mechanical and thellllal characteristics, an engineering pklsties has reeently been exp~mcling to great proportions. Nevertheless, it is inferior to other general-purpose resins with respeet to moldability, proeessability and production eost.
In sueh eireumstanees, intensive researeh is eoneentrated on the settlement of the aforesaid problems ancl ttle developrnent of eoncomitant eharacteristies by blending or alloying an engineering plasties with an olefïnie resin or a styrenie resin eaeh exeellent in fluidity and advantageous in eost. A simple blencling, however, leads to failure to eompatibilize a plurality of clitferent resins with eaeh othel, theleby eausing sueh problems as remarkable (leterioration of impclet ehalaeteristies, liability to peeling or (lelall~hlatioll ~an~l ullt`avolableappealance.
AS ~hC C0UI1tCI nleaS~IIe a~a jnSt tl1C al)OVC-I11CI1liOnCCI PIOblCI11S~

thele has been carriecl out the development of compatilbilizers capable of irnplovillg the miscibility amon~ the resins parallel to the improvement in the method of mokling or processing. Examples of lolo~ <~ o~1 ol` illll~l'OVill~ y il~
s moclitïcation of resills, additiol1 ol` a copolymer theleto, reaction with a ~ca~tiv~ rcsin Or a rcaclive rcagel1t in all cxlruclel an(l thc combination of at least two of them Specifically, the modification of a constituen~ resin for polycarbonate is disclosed in Japanese Patent ~pplication Laid-Vpen lO Nos~ 157648/1980, 123251/1982, 201842/1983, 223742/1984and 223749/1984 There is also proposed an intricate method of improvement with the combinatioll of sever~l means as disclosecl in Japanese Patent Application Laid-Open Nos. 215714/1988, 215749 to 215753/1988 anci 75543 to 75550/1989. In aclclitioll, thclc ale lS disclosed the rnodi-t`ication of polyamicle or polyester with a modifiecl polyolcfin in J~lpallcsc Palcnt Applic~ltiol1 Publicalioll No. 3()~54/1970 and a method of improving a resin composition comprising a styrenic copolymer containing maleic anhydride and a polyamicle by Ineans of glass fiber in Jap~mese Patent Application Laicl-Open No.
20 62844/ 1981. Furthermore, an attempt is made to improve the delamination ancl lzod impact strength ot the blencl Or polycarl~ol1ate, polyamide, polyester or polyether with a polyolefin by incolporating therein a polymer having an amino group ancl wllen necessary, a polyulelllarlc in aclclitior1 thelelo in Japanese Patent Applic~ltioll L,~lid-25 C)pell No. 36248/1990.
The above mentionecl moclificatiorl is intenclecl to provicle a newcharact~listic rll~lteri~ll by ingeniously combirlillg the ~Iclvantage ot`

3 2 ~ 9 ~

each of the components. However, ;n any of the aforesaid methocls, the Iniscibility with each other is still insutiïcient, the above-describecl problems with regard to blending still remain unsolved and in~plovclneill ca~ ol l~e s.~ O be sllll`icielll On .Ippe.ll-lllCC .111~1 s peeling on the SUI face o~ a resin procluct, especially on impact cl~ ctcl is~ics. For cxalnple, ~vcn it` a resill as moclificd in tlle aforestated manner has a high Izod impact strength in impact characteristics evaluation which is usually made by means of Izod impact test, it is sometimes deteriorated in surface impact o characteristics that is valuabie in practice. In view of the above, the resin is required to be excellent in both Izod impact strength and surface impact characteristics in order that the resin may render itself really excellent in irnpact characteristics.
In the light of tlle above-described backgrouncl, intellsive 5 research and investigation were made by the pl~sent inven~ors on the improvement of engineering plastics. As a result, it has been found by them that a thermoplastic resin composition excellent in impact characteristics, especially surface impact characteristics as well as appearance, minimizecl in coloration and free ~from delamination or 20 peeling is obtained by melt kneading a thermoplastic resin such as engineering plastics and an olehnic polymer and/or a styrenic polymer with a novel copolymer having a formamide group ancUor an amino group. The present invention has been accomplishecl on the basis of the above-mentioned finding and in~ormation.
25 SlJMMARYOI~ LE NVFNrrlON
Lt is an object of the presellt invention to provide a tl~erlllopklstic resill composition e~cellellt in impact cllalactelistics, ~ 2 ~

especially s-lrface inlpaet characteristics as well as appearance, mirlitllizecl in colorcltion an~l flee l`rom delamination or peeling Specifically, the present invention provides a thermoplastic l~sill ~o~ o~si~ioll wl~ oll~ e~ oll~pollc~ s 5 lo ~5%
S by weigllt ol a [A~ thermoplastic resin having a funetiollal group Ie~ iv~ Will~ illO ~lo~lp, 95 ~o 5% l)y wci~ ot` LB~ c~ OI-IC
polymer selectecl from an olefinic polymer an(l a styrenic polylnel, the subtotal of the above [~]+[B] being 100 parts by weight and 0.05 to 20 parts by weight of a [C] cvpolymer or a salt thereof, said 10 copolymer having in a molecule thereof at least one group selected -from a formamide group and an amino group, saicl copolymer having 20 to 99.8 mol% of the repeating unit I represented by the genercal formula (I); 50 to 0 mol% of the repeating unit II represented by the gcnct ~ll rOI tll~lla (~ l 60 to 0 ~ ol% o~` ~lle I cl~c~ll itl~ ~tllit 15 represented by the general formula (lII) or the repeating Ullit lV
rer~lesel1te~1 by tlle ~enel~l forrnllla (lV) R ' - C ~I 2 - C--- ~ = C -I I (Il) R~ R I

1~. n 1~ l o - C C

C C
,~\/~ (111) O l O
R "- Y

2 ~

R.5 R7 R ~ R 10 6 1'~ 8 ~-- C -- C --3 n R ' C C
(IV) O N O
R "- Y

lo wherein Rl, R2, RS, R6 and R7, independently of one another, are each a hycirogen atom, an alkyl group having 1 to 10 carbvn atoms, a cycloallcyl group having 3 to 8 carbon atoms, an aryl group h;lving 6 to lO carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having I to 4 carbon atollls~ an .alkoxycarbonyl gro-lp having 1 to 18 carbon atoms, an alkylcarboxyl group having 1 to 17 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms, an arylcarbonyl group having 6 to 8 carbon atoms, a halogen atom or a nitrile group; R3 and R4, independently of one anothet, are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl 20 group having 2 to 4 carbon atoms or a halogen atom; R8 is absent or denotes a methylene group or an ethylene group; R9 and lRIO, inclependerltly o:f one another, are each a hydrogen atom, an alkyl group having I to 6 carbon atoms or all aryl group llaving 6 to 8 Cal'bOIl ntOIl)S; Rl I iS all allCylCrle gl-OUp haVillg I lo 12 Cal'bOIl atOIllS, 25 a CyCIOalkylerle gl'OUp ha'l/ill~; S to 17 calbon atoIns, an arylcne grollp havirlg 6 to 12 carbon atoms, an arylalkylene group havillg 7 to 12 carbon atolns or a polyoxyalkylene group llaving 4 to 30 carbon 6 ~ r~ ~ !O

atoms; Rl2 is a hydrogen group or an alkyl group having I to l0 carbon atoms; Y is at lcast one kincl of amino group selectecl l~rom tbe group consisling of tlle general form~llae (V) to (VIII).

~ N ~ ( V ) --N y C H O (VI) --NI-I-R 13 ' (Vll) .
- I -CHO (Vlll) R l3 where Rl3 in the general formula (VII) and (VIII) is an alkyl group 15 having 1 to 6 carbon atoms; Rl to R:13 may be the same or di-fferent in each of the repeating unit; ancl n is ~n integel ~îO~n I to 1û.
DESCRIP'rION OF THE PREFERRED EMBODIMENTS
As ~lescribc~l helcinbeiole, the composition accolding to the present invention comprises the components [A], ~B] and [C]. The 20 component [A] may only have a functional group which is reactive witll an amino group. It is thought that the f~rmamide group incorporatecl in the component [Cl causes carbon monoxide removing reaction to take pklce clue to the heat at tlle time Or melt kneading, and thereby a copolymel havillg the formamide group turns into a 2$ copolymer havillg an amino group having lligh reactivity.
Accolclingly, since the functional group of the component LC]
t`ullcliolls sul stnntially as a secolldary alnine witll l-ligll re~lctivity, llle : i ':

7 ~ 5~

thelrnopklstie resin having a functiorlal group reaetive with an arnino group is usable as the eomponent (A) in the composition of the present invention.
Speeilïe examples of the fullelional group reaetive with an s amino group include the group Irom a calboxylie aei~i, othel orgallie aeid, an ~ster an~l a salt th~leo~`, all aei~l anlly~ le an~l a salt thereof, hydroxyl gro~lp, a thiol, oxazoline, an epoxy group, arl isoeyanate group, an amide bond, a earbonate bon~l, a uretllane bvncl, a urea bond and an ether boncl. The preferably ~Isable thermoplastie resin as the lo component [A] is that having at least one bond selected -from earbonate bond, ester bond, arnide bond ancl ether bond.
The thermoplastie resin having a carbonate bond to be usecl as the above-mentioned eomponent (A) is typified by polycarbonate resin, which may be aliphatic or aromatie. The moleeular weight of 15 the resin is not specifically limited bu~ is usually 10,000 to 100,000, pret`erably 10,000 to 40,000 in terms of viscosity-average moleeular weight taking into consideration the molclability an(l physical properties of the resin composition to be procluced. The polycarbonate resin is acceptable only if the terminal group thereof is 20 the orclin.lry monohydrie phenolie terminal [including pllenol, a halogen-substituted phenol (eumylphenol, oetylphenol) and other substitute(l phenol]. There is also permissible the polyearbonat~ resin intc~ whiell the l`unetional glOUp or boncl reaelive with the above-nlentionecl amino glOUp is introcllleecl at the terminal ot a moleellle Or 2s in tl~e t()rm ot gral`t, bloek or rallclom eopolylllel ization. Tlle resin may also be ineotl)olate(l with any of a variety ol a(l~litives, ~m elasloll~el Or a Iiller l'ot llle E)lllpOSC Ol` InO~IiliC.lli()ll 01 ICinl`OlCClllell 8 2~9~56~

at the time of or al`ter the polymerization.
The polycalbonate resin as clescribed above can be procluced by any o:f publicly known processes, which include phosgene process, C~lCI jI`jC(I~jOI~ PIO~C~;S, I~CIl POIYI11CI jZ~It jOI1 ~)IO~CSS, ct~.
5Various polycarbonate resins are available and exemplificd by ~l1e POIYII1Cr l1aV;I~g rcpe.l~ g uniis reprcsclllc~l by ll~c gcncl,ll lormul, ( A) a ( A) b 10 - - C-O-~- Z -~ O _ ~ lX) o wherein Z is merely a bond, an alkylene group having 1 to 8 carbon atoms, an alkyli~lene group having 2 to 8 carboil atoms, a cycloalkylcnc group havillg S to lS calboll atOlllS, a cycloalkyli(lcllc 15 group having 5 to 15 carbon atoms, SO2, SO, O, CO or the group represented by the -fvrmula;
C ~I3 ~ EI3 C H 3 C ~-I 3 A is a hydrogen atom, a chlorine atom, a bromine atom or a saturated alkyl group having 1 to 8 carbon atoms; and a and b, independe:ntly of one allotller, are eacll a number t`ronl 0 to 4 The aforementioned polycarbonate resin cnll be procluced by, 25 t`or example, a solvent process in whicll a clillydric pheIlol is reactecl with a carbonate prccursor sucll as phosgene or a ditlycllic pheIlol is trarlsestelit`ied with a carbonate precursor such as cliphellyl carbonate ,, .

() CclCtl in a solvent suc h as melilylene chloride in the presence of a known acicl acceptor ancl a molecular-weigllt moclifier.
Examples of the l`avorably usable clihyclric phetlols include bi~sphe~nols, ot` whicll is pal ticulal ly clcsir~lblc s 2,2-bis(4-hyclroxyphenyl)propane [~Isually termed bisphenol Al; a bispllenol A replacecl in part or in wllole with tlle other dihyclric phenol; dihydric phenols exemplified by hyclroquinone;

4,4'-clihydroxycliphenyl; bis(4-hydroxyphenyl)alkane;
bis(4-hyclroxypllenyl)cycloalkane; bis(4-hy(lroxyphenyl)sulfide;
1 O bis(4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl)sulfoxide;
bis(4-hydroxyphenyl)etber; ancl halogenated bisphenol such as bis(3,5-dibromo-4-hydroxyphenyl~propane; and bis(3,5-dichloro-4-hydroxyphenyl)propane. The dihyclric phenol may he a holllor)olynlcl ol a clilly(lli~ pllcllol, a copolynlel ol ~lt lc~lsl lwo 15 thereof or a blend of at least two thereof. In addition the polycarbonate resin rnay be a thermoplastic randomly branclled polycarbonate obtainecl through the reaction among a multit`unctional aromatic compouncl and a dihydric phenol ancl/or a carbonate precursor. The therlnoplastic resin having a carbonate bond other 20 than the above-mentioned polycarbonate is exemplified by polyester polycarbonate resin, which is f`avorably usecl.
The resin lo be usecl as the aforesaicl componcllt lAl is exemplif`iecl by n thelmoplastic resin having all ester boncl, namely polyester resill in acklitioll t~) the resill l~aving a calbollate bon(l. A
~5 wi(le cliversity of polyestel resins may be employecl without specific linlitatioll to the types theleo~. They Inay be eithel alipllalic or arolllatic, but alOIllatic polyestcrs are preferable in view of the ~o ~ 66 physical properties. rr`he molecukll weight thereof may be suitably sclectecl in accolclallce with the purpose ot use ancl the like, and is ~Is~lally (1.2 to 2.0 dl/g, preferclbly ().5 lo 1.2 dl/g expressecl in terms Or intl iJ~sic viscosity. Thc tertninnl of the polyester resin nlay be 5 constituted of a carboxylic acicl terminal or an alcollolic hydroxy l't)ll~ uill.ll. 'I'lle ~o~ u~io~ iO l)elw~cl~ e abovc lCII~
is not specifically limitecl but is pref~lably 9/1 to 1/9 Thcre is also usable the polyester resin into whicll the hlnctional group or bond reactive with the alorementioned amino group is introclucecl at the 1() tcrmillal of a n-olcculc vr in thc lorrrl of gralt, block or random copolymerization. The resin may ~Iso be incorporated with an - elastomer, a filler or any of a variety of additives at the tinle of or after the polymelization lol the pulpose of Ino~lification or reinforcement or with two or more types vf dicnl boxylic acid 15 component ~o the extent that the physical properties of the composition is not impaired.
Such polyester resin can be produced by any of known processes ancl exemplitied by a wide diversity of kinds.
Specific examples of the polyester resin usable in the present 20 invention include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexaclimethylene terephthalate (PCT) ancl polyarylate, among which are particularly desirable polyethylene terephtllalate (PET) and polybutylene tereplltllalate (PBT), Tl~e PET
may be tl~e pOIyeStel- which comprises an aronlatic dicalboxylic ncicl 2:~ COl{lp()llC`llt (~Olllpl'iSillg tC'l'Cpl~tllaliC ~ICid as tlle plilllaly COIllpOllent allCI ;l glycol componcnt compl ising ethylene glycol component a~ the prhllary coll~ponent, or the polyester proclucecl by copolylnel izing " 2 ~

olllel dicalboxylic aci(l cornponcnt ancl a glycolic cornponent.
Fln thet- examplcs Or the resin to be employed as the aforestate~
component [A-l include the therrnoplastic resin having an amide bond, llalllCIy a pOIyalllidC lCSill. ValioUS pOIyalnidC ICSillS Illay be 5 employed without specific limitation to the types thereof. They may be eithel aliphatic or aromatic The molecuklr weigh~ theleof is not specilically limited b-lt is us-lally 4t0û0 to 50,0()0, prefelably 5,000 to 30,000 in terms of nulnbel-average molecular weight talcing into consideration tl~e mokLIbility and physical propelties vf the resin 10 composition to be produced There is also usable the polyamide resin into which the functional group or bond reactive with the aforestated amino group is introduced at the terminal of a molecule or il:l the form of gra~t, block or random copolymerization. The resin may also be incolpolatcd witl~ all clastolllcl, a l'illcl or ally o~' a valicty ol a(lditiVCS
15 at the time o:l~ or after the polymerization for the purpose o:F
modification or reinforcement.
Such polyamide resin can be produced by any of known processes, for example, by ring-opening (co)polymerization, (co)polymelization or (co)polycondensation of a lactam of three or 20 more-membered ring, a polymerizable (l)-amino acid Ol a dibasic acid with a piperazine derivative or a diamine, more specifically, by (co)polymerization of -caprolactam, amino caproic acid, 1 I-amino un(lecanoic aci~l or thc likc, or (co)polymeriza~ion or (co)polycondensation ot ~I piperazine derivativc SLICII as a 25 hexarlletllylerlepiperazine clel ivative, hexatlletllylclle(lia[nille~ a nonametl~ylcnepipelazille delivative, nollamet}lylene(liamine, a ndec~lmetllylenepiperazille clerivative, ull(lecametllylene(lialnine~ a 12 s~ ~ 9 ~

do~lecLlnletllylellepipelazine cleliva~ive, (loclecalmethylenediamine, a I~CtaXylylC`IlCpipeI~lZillC CICliVatiVe all(l IlletaXyIylelle(lialllillt:~ 01 a cliamine with a clicarboxylic acicl such as lerepilthalic acid, isophthalic aci~l, aclil)ic aci(l, sebacic aci(l, (libasic (lo(lecalloic acicl an~l gllltalic S ~Ici~.
A valiety ol polyami(le resins are aYailable ail(l specifically enumeratell by aliphatic polyal~icle sllcll as nylon 6 (polyarr-ide 6);
nylon 6,6; nylon 6,10; nylon 11; nylon 1~; nylon 6,12; ancl nyion 4,6;
aliphatic copolymerize(l polyamide such as nylon 6/6,6; nylon 6/6,10;
10 and nylon 6/6,12, an(l aromatic polyamicle s-lch as polyhexamethylenepiperazine derivative terephthalamide;
polyhexamethylenediamine terephthalamide;
polyhexamethylenepiperazine derivative isophtllalamide;
pOIyhCXaIllCthylc`nc(lia~ c iSOphtllalaIllidC .ItlCI XylyICIlc 15 group-containing polyamide [for example, nylon-MXD
(metaxylylenepiperazine derivative and metaxylylene~liamine)], and in a~lclitioll, polyester ~amicle, polyether amicle ancl polyesteretller amicle. Among those are particularly desirable nylon 6 ancl nylon 6,6.
Still further examples of the resin to be ~mployed as the above-20 mentioned component ~A] include the thermoplastic resin having anether bond, narnely a polyether resin. Various polyether resins may be employecl without specitic limitation to the types tllereof whether they nle aliphatic or aromcltic. 'l~here is also usLIble the polyetllel resi illtO WhiCIl the furlctional gro~lp or boncl reactive with the atolestatecl 25 alnino gro~lp is introclllcecl at terminal ot a molecule or in the ~rln ot graft, block or rallclolll copolymeriz.-ltioll.
I~anlples ol sucll polyether resins C.lll be rougllly cklssilie~l illto pOIyaCetal hOmOpOIymel SUCII as polyoxynle~llylelle (POM);
polyacetal copolymel having mixe(l polyetllel unit rnoieties such as trioxalle/etllylelle oxide copolym r; polyphenylene ether (PPE~);
ycl~ ll'ollc ll~lvi~ ixc~l clll~i gl'Olll~S ~ lll'ollc gl'O~lpS
s (PE~S); polyether ketorle having mixecl ether groups and carbvnyl ~,rOLIp~ (PEK); l~olypllcllylcne sulli~te llaVill~ a tlliOCtllCI grO~lp (PPS);
and polyslllfone (PSO), anlollg which are prefelable polyacekll (polyoxymethylene (POM)) and polyphenyielle ether (PPE).
The polyacetal hornopolymer is a polymer having 10 oxymethylene unit as the main chain in a molecule ancl can be producecl by homopolymel ization of formaklehyde or trioxane. On the other hancl, the polyacetal copolymer is a copolymer in whicll oxyalkylene unit such as oxyethylene unit, oxypropylene unit and oxytetramethylelle ~Init; oxyphcnyletllylclle Ullit; or the like is ls r~mdomly mixed in the chain consisting ol the al`orementioned oxymethylene unit. The polyacet~al copolymer can be produced by copolymerization of formaklehycle or trioxane with a cyclic ether such as ethylene oxide.
In the thermoplastic resin composition accor(:ling to the present 20 invention, one or two or more kin(ls of the above-desclibecl resills are employed alone or as the mixture as the component [AJ along with an olefinic polymer, a styrenic polymer or a mixture thereof as the component ~B]. Various olefinic polymers may be employed without specific limitation provicled that the polynner has a polyolefinic 25 c(~mp()nent. Spccifi(, ex~llnples ot the p()lyolelinic resill inclucle polycthylene (linc,lr low (lcnsity poly~thylerle (LLDPE), low clcllsity polyetllylcnc (LDPL), ~lltralow clcnsity polyetllylelle (UL,DPE), higll 1~ 2091)'j6~

lensity polyethylelle (HVPE)), polypropylene, polybutelle~
polyisob~ltene, ethylerle/(x-olefill copvlylnel such as elllylenclpropylctlc copolylllel, cthylenc/plvpylene copolymel rubbe (EPR), ethylelle/butelle copolyl~er (EBM), etllylenc/plopylelle/(lielle 5 copolymer (~EPDM), etllylene/propylelle/bu~ene copolymer ancl ethylene/butylene copolymer, propylene/other c~-olefin copolymer such as propylene/b~ltene copolymcr, ethylenic copolymer (ethylene/vinyl acetate copolyrner (EVA), ethylene/vinyl alcohol copolymer (EVOH), ethylene/mclleic anhydride copolymer, 10 ethylene/alkyl (meth)acrylate copolymer, etc.) poly(4-methyl-1-pentene) and a rnixture thereof. The terrll "copolymer" as used herein include ran(lom, block, random block ancl graft copolymer.
The molecular weight of the above-mentioned olelïnic polyme rnay be suitably selected in accolclance with various conditions an(l is 15 usually 5,0()0 to 1,000~0()0, prel`elably 10,00() lv 701),000 in tcrms of nllmber-average molecular weight.
On the other hancl~ various styrenic polymers may be employed without specific limitation also as the componellt [B] provicle~l that the polymer has a styrellic component such as styrcne, 20 a-methylstylelle and p-methylstyrene. Examples ot` the styrenic polymers include gencral-pulpose polystyrene (GPPS), higll-impact polystyrene (HIPS), syndiotactic polystyrene (SPS~, styrene/maleic acid copolymer (SMA), styrcne/maleic acicl/maleimicle copolymer, styrene/maleimi(le copolymer, GPSMA, r~lbbel reinfolce(l SMA, l~lS
2~ I'eSill, AS leSill, Al3S ICSill illC~ illg lligllly lle(lt r~sistant ABS l'eSill.
AAS resin ancl AES resin an~l turthel, so-callc(l styrenic thellnopklstic eklstolner incl~l(ling SEBS resill, SE~PS resin, SF~P leSill an~l (lerivative 1 S 2 ~ 6 ~

thereof.
The molecular weight of the aforestated styrenic polymer may be suitably selected in accorclal1ce witl1 various cvnditions and is llsually 2(),()()1) lo 60(),()~)~), plel`el~lbly 3(),()l)() ~o S0(),()0() in lell11s .,r s number-average mol~cuLlr weight.
~ rl1e ~ io ill % I)y weigllt Or ~l~c COlllpOllCtlt [AJ lo ll1e component [B l in the composition of the present invention is ~A]: [B]
= S to 95: 95 to 5, prel`erably 30 to 9S: 70 to S. In the case where the ~lbove raliv ~leviates t`rOIll tlle ran~e, ~ln excessiveîy higl1 amo-lnt of lO the component [A~ results in the cleterioration of moldability, whereas an excessively high amount of the component [B] lead to the clisadvantage of insufficient mechanical-strength such as rigidity.
The composition according to the present invention comprises a copolymer having formamide group and/or amino glOUp as tl1e - 15 componeIlt [C~ in ad~lition to the componerlts [A] and [B], whicl1 is a new random, block or graft copolymer of the repeating unit I
represented by the general formula (I), the repeating unit Il represented by the general -formula (II) ancl the repeating unit lII
represented by the general formula (III) or the repeating unit IV
20 represented by the general formula (IV). As to the proportion of each of the repeating units based on tl1e total amount of the repeating units 1, Il and llI or I, II and IV, the proportion of the repeating unit I is 20 0 to 99,8 mol%, pret`erably 45.0 to 99.51110i%, tlle proportion of tl1c~ repeating Ul1it 11 is 50.0 to 0.0 n1ol%, pret`erably 40.() to 0.0 mol%
25 and tlle propoltion of the repeatin~ llnit lll is 60 to 0.2 mol%t pret`erably 50 to 0.2 mol% or the proportion of the repeatil1g ~lnit IV is 6() lo 0.2 nlol%~ prelelably 20 to () 2 mol%~ rl'lle proportiol1 of tilC

repcatitlg unit 111 or IV lcss tlliln 0.2 mol% results in failure to mallilest tlle eff~ct of aclclition tllcleof, while that exceecling 60 rnol%
lcads to worscllc(l clispersion Or thc componellt ~CI, resultillg in (lclcriOI alion ol' Illc pllysical pl'OpCI ~iCS espccially Illc SUI face illlpact 5 strength of the composition to be pro(luced. The symbol Y in the general forlllllla (111) Ol (IV) of tlle repeating Utlit III or IV is the amino group as rcplescnted by the general l`orlllulae (V) to (VIIT) and may be the same or different in eacll rcpeating Ullit. Accorclingly, ~he repeatillg unit llaving C~-IO ~aklehyde gro~lp) coexists witll tlle lo repeating unit not having CHO as the case may be.
The copolymer having formamide group and/or amino group is constihlted basically of the aforesaid repeatirlg units 1, II and III or I, Il and IV, but mcly have othcr repeating unit in some quantity in 3itio~ clcto.
Is Specifically, the copolylllcl that is constitutecl basically of the repeating units I, II ancl III may have, to some extent, the repeating unit replesented by tlle general formula (X).

R ~ R ' 2~ C--C -O=C C=O
(X) 11 N N ~-1 Y - r ~

2~ wherein R9 lo Rl I ancl Y are cacll as previollsly definccl. Likewîse, the copolyincl that is constitlltecl basically ol` tllc rcpcatillg ~Inits ~
all~l IV nlay have, lo SOlllC exlelll, tllc rcpcalin~ Ullit l'Cpl'CSCllle(l l~y 17 ~ 6~

the genelal t`ormula (Xl) R ~ R 7 --C ~ C-- RD T~ ' r~ 6 R 8_( C--C ~-- R ~ 2 O-C C-O
' (Xl) I-I N N I I
Y ~ R l ' R " - Y

lo wherein R5 to Rl2, Y and n are each as previously defined.
The molecular weight of the copolymer having formamide group and/or amino group is not specifically limited but is usually 3,000 to 500,000 expressed in terms of viscosity-average molecular weight, which corresponds to the viscosity in the range of 10 to lS 50,000 cPs of the 10% by weight of solution of the aforementioned copolymer in a proper solvent such as toluene, xylene, cumene, tetralin, 1,3-dimethyl-2-imidazolidinone, climethyl sulfoxicle~ acetone, methyl ethyl ketone or the like.
The copolymer as the component [C] ;s characterizecl by its 20 having :formamide group and/or amino group in the side chain of the rcpealing unit 111 or IV via in1icle group. Examples of the copolymer also include the copolymer having a salt formecl by the combination of the aforesaicl amino gro-lp with an acid exetIlplifiecl by s~ ric acid; SUIt'OlliC ~ICid SUCIl as benzenes~lll`ollic acicl, tolllenes-llfonic acid ~5 and naplltllalcncsull`onic acicl; halo~eno-acid sucll as hyclrocl~loric ackl, hyclrofluoric aci(l, hydrobrolllic acid ancl hyclroioclic acid; nitlic acicl; boric acicl; alld phosptloric aci(l.

Irl the genelal torlllulll (I) which represellts the repeating Ulllt i~
R I allct R2, in(lepen~lelltly of one anotller, tllat is, tney may be the sallle Or (liftereIlt in eacll repeatinX, unit, are each a hyclrv$esl atom, an allcylglollpllaving I lo l(),plcl'cl.lbly 1 lO4Cal'bOil-llOlllS,-I
S cycloalkyl group having 3 to 8, prefelably 3 to 6 carbon atoms, an aryl glOUp having 6 to 10, prelerably 6 to 9 calbon atolllS, an alkoxy group having 1 to 4 carbon atoms, an alkoxycalbonyl group havlrlg I to 18, preferably 1 to 8 carboll atoms, an alkylcarboxyl grvup l~a~ing I to 17, preferably I to 3 carbon aton1s, an alkylcarbonyl grvup having 1 o to 6, preferably 1 to 4 carbon atoms, an arylcarbonyl group having 6 to 8 earbon atoms, a halogen atom, pre~ferably a chlorine or bromine atom, or a llitrile group. The general formula (I) includes the ease where one repeating unit I is an ethylene unit (Rl and R2 are ~simultaneously hy(llogen alolms) an~l tl~e anolllel is a plOpylCllC llllit 15 (Rl is a hydrogen atvnl a~ R2 is a methyl group).
In the general formula (II) whieh represellts the repeatillg unit Il, R3 ancl R4, in~îepen~lently of one another, th~t is, they may b~ the same or different in eaeh repeating unit as is ease with the aforestaled R1 and R2, are each a hydrogen atom, an alkyl group having 1 to 4 20 earbon atoms sueh as a methyl group or an ethyl group, an alkenyl group having 2 to 4 calbon atOlllS SUCIl as vinyl group vr allyl group or a halogen atom suell as a ehlorine atom or a bromine atom.
In the general folmulae (III) and ~IV) which represent the repeating units III and IV, respeetively, R5 to 1~7 are each the same as 25 any of the al`orestate(l ~l alld R2; R8 is absel1t, that is, mealls a bond only or den()tes n metllylene group or an etllylene group; R9 all(l Rl, in~lepen(lently of one allotller, are eacll a lly(lrogen atoln, all alkyl ,~, 2~9~

group having l to 6, prefcrably l to 2 ciarboll atoms or an aryl group hllvillg G to 8 carbon atoms; Rl l is all allcylclle gl~Ollp haviflg I to 12, prefelably I to 8 calbon atoms such as a group of methylene, etl1ylenc, tetrallletllylcne or hcxamctl~ylcllc, a cycloalkylene gloup :~ 5 having S to 17, prel:`erably 6 ~o 10 carbon atoms such as a cyclohexylcne group or a metllylcnccyclollexylmc~llylelle group, an arylene group having 6 to 12 carbon atoms~ preferably a phenylelle ; ~
group or an oxydiphenylene group, an arykll:lcylene gro-lp having 7 to ~; ;
12, preferably 8 to 10 carbon atoms such as a xylylene group or a o polyoxyalkylene gloup having 4 to 30, preferably`4 to 15 carbon atoms such as polyoxymethylene a polyoxypropylene; ~12 Is~a hydrogen atom or an alkyl group having 1 to 10, ~preferably l ;to 8 carbon atoms;;Y is~an amino group replesented by the general formula~ :
(V), (VI), (VII) or:(VI:lI).
~: 15 N N H~ ( V ) --N/~l C 11 0 ~ (Vl) --N ~I - R 1~ 3 ' ( V l -- IN _ C H~O ( Vl l [) 25 wherein Rl3 is an alkyl glOUp having 1 to 6 carbon atoms.
In thc above-mel1tiolled: formulae~ R5 to Rl 3 an(l Y may be e~ch thc ~nlc or dirt`elelll in euch rcpec~tin~ ~Init as is lllc casc wilh lhe '~
':~

.'.

;,.' ' :
. ~ ~ . ~ . . . .

2() 2~9~5~

at`orestated Rl an-l R2; n is all integel from I to 10, pref~rably 1 to 3;
when n is plulal, thclt is, 2 Ol mole, R9, R10, Rl 1, R~3 and Y each being present in the numbel same as that Or n may be each the same or ~lillcrcllt; wl~cn tlle amillo group Y is n sccon(laly amillo group as S representecl by the general t`ormukl (V) or (Vll), Y may be in the t`orm Ot'~l ~;al~ WlliC~ ; COIlll~inC~I with all a(,'i~l e~CC~llplil`ie~l by in~lude sultul ic acid, sulf`onic acid such as benzenesultonic acicl, toluenesull`ollic acicl ancl napllttlalenesult`onic aci(l, halogeno-acid s~lch as hycllochloric acicl, hycllofluoric acicl, hydloblornic acid and 10 hyclroioclic ncid, nitric acid, boric acicl and phosplloric acicl.
Various processes are avaiklble l`or the production of the copolymer as the component [C] to be used in tlle present invenlio without specific limitation7 alnong which ~my of the lollowing processs~s (a)~ (b) and (c) is capable Or mole~ efliciently pro~lucillg tl~e 1 5 copolyrner.
The process (~) is exemplifïed by the process in which the copolymer which comprises in a molecule thereor 20 to 99.8 rnol% of the repeating unit I, 50 to 0 rnol% of the repeating unit II and 60 to 0.2 mol% of the repeating unit represented by the general formula (XII) 20 (starting copolynler a) r~ r~o ( X i l ) C ~
O O O
wlleleirl R9 nncl R10 nre encll as previollsly delined or tl~e copolyme wl~ ol~ ;es i~ ole~llle tl~ ol 2() to9~.8 Illol% ol llle 2 0 ~ O

repeatillg ~lnit 1, 50 to 0 mol% of lhe repeating Ullit II and 60 to 0.2 mol% of the repeclting ~Init representecl by the genelal tormula (XIII) (starting copolymer b) R b R 7 - C -- C-- R ~ R ' R ~ R fl--~-- C -- C ~) n ~ 1 2 C C
( X l l l ) O O O

wherein R5 to R10, R12 and n are each as previously defined each is reac~e(l with a salt of a piperazine clerivative represented by the general formula (XIV) /~
15 ~I2 N- R "-N N H (XIV) wherein Rl I is as previously defined or a salt of the diamine represented by the general formLlla (~V) 1-1 2 N - R ' I - N ~I - R ' 3 ( XV) wherein Rt I ancl Rl3 are eacll as previously clefïlled in the presence of a forrnyl group-containing compolln(l an(l theleaflel the reacti()[l procluct is bro~lght into contact with a base for the rcllloval of tllc 25 resi(lual aci(l.
'I'he process (b) is exelllplifie(l by the process in wllicll the skllting copolymel a or b is reactecl with the reaction procluct that is 2?~ 2~056~

procluce~l in ~ vallce by reactillg lhe piperazine clelivative representecl by t]lC genclal t`vrmllla (XIV) Ol the diamine replesented by the gelleral IOrl~ a (XV) Witll cl l`Ollrlyl glO~lp-COllklillillg COIIlpOUllCI, 'rl~e p~O~ xelllplilie~l by ~ plo~ess ill wl~ lle s starting copolymer a or b is reacte(l with a salt of the piperclzine clelivative rcplesente~l by tllc~ gener~ll t`orlllukl (XIV) or a scllt of the cliamine replesente~l by the general forrrl-l1a (XV) in the absence of a formyl group-containing compoulld ancl thereafter the reaction product is brou~ght into contact with a base t`or the moval of the I o residual acid.
According to the process (a), prvcess (b) and process (c) there are obtainecl, respectively a copolymer having a formamide group mixed with a secondaly amillo group, a copvlymer having a formamide group without secondary amino group and a copolymer 15 having a secondary amino group witllout formamide group.
As the copo1ymer as the componellt [C] in aclclition to that procluced by the process (a), (b) or (c), there is usable the copolytner obtained through the known process as clescribecl, ~for example, in Japanese Patent Application Laid-Open No. 93817/1991, though the 20 effect of the present invention tends to be somewhat lowerecl by the use thetcof.
'I'he starting copolymer a having the repeatil~g units I, II ancl Xll t`Or the pro(l~letiorl ol` thc eopolymel as the copolymel ~Cl is prod~lce(l by sub jeclillg the monolllers giVillg th~ repeating UllitS
25 replesente(l by the general f~ nulae (1), (Il) al~Ct (Xll), respectively to ra~lical polymcrizati()ll or ionic polymel ization by a known methocl, Tlle Stclltillg copolylllel b llavillg tlle repealillg urlils 1, ll ancl XIII t`or the proclucti~ of the copolymel as lhe copolymer [CJ is proclucccl by subjccting llle IllOllOIllCI-S giving tlle repeatillg units rcpresellte(l by thc gcnclal t`ormulae (1) ancl (II), respectively to raclical polylllcl iz~ltion or iollic polylllcl i~ ioll by a knowll nlctho(l ~m~l S subsequently grafting tlle monolller gi\/illg the repeating ~Init rcp1c~;cn~c~1 by t11e gcnc1al l`orulul~l (X111) o1~lo ~ c rc~lltillg polyllle by a known method.
A variety of mono1ners giving the repeating unit I represented by the general formula (I) are available and specifically exemplified io by olcfin sucll as cthyîelle, propylcllc, I-butcnc, I-octene ~and isvbutylene; cyclic olefin such as cyclopentene, cyclohexene ancl cyclooctene; styrenic monomer (aromatic vinyl compound) such as styrene, oc-methylstyrene, vinyltoluene and p-tert-butylslyrene; vinyl ester such as vinyl acetate, vinyl butyr~te and vinyl stea1~lte; vinyl 15 etller sucll as methylvinyl ether ancl ethylvinyl ether; halogeno-oletïn ch ~s vinyl ch!olicle an(l vinylicle1le chlori~lc; (metll)~lcl-ylatc SllCh ~I~S
methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl ~meth)acrylate, decyl (rneth)acrylate, octadecyl (tneth)acrylate ancl methoxyethyl 20 (meth)acrylate; nitrile such as acrylonitrile and methacrylonitrile ancl vinyl ketone such as methylvinyl ketone and phenylvinyl ketone.
Each of them may be used alone or in combination with at least one of others.
~\mong therll are pret`erable ethylelle, propylene, stylene, 2s nle~llylvinyl cther, isob~ltylelle~ vinyl acetate at~ netll)acryklte.
Speciric cxalllple~ ol` mononlerg giving the repeatillg unit 11 rel)lcscntcd by thc gcnelal torlnula (Il) inclu(le conjugatecl dictlc sucll 2~ 2 ~

IS blltaCIielle, iSOplC'lle clll(l cl~loroplene. Each of them may be used alol~e Or in combination wilh ~It least on~ of others. Among them are prclclablc~ butaclicl1e ancl isoprel1e.
Spccific cxamplcs ot` Ins)llolllers giVil1g the repeating unil Xll 5 represented by the genelal formukl (XIi) inclucle unsalurated (licalboxylic anhyclri(le; such as n1alcic anhycllicle, mc~hylmaleic anhyclricle, 1,2-climethylIllaleic anhyclride, ethylmaleic anhydride, pl1enylmaleic anhyclride and itaconic ~mhydride.
The repeating unit XlII represcnted by the general t`ormula lo (XIT~) can be formecl by copolymclizil1g the monomel giving the repeating unit I with tlle monomcr giVillg the repeating Ul1it ll through a known method and gralting onto the resultant copolymer, an unsaturated dicarboxylic anhydricle such as maleic anhydricle, methylmaleic anhyclrisle, 1,2-climethylmaleic acid, ethyl maleic lS anhydride, phenylmaleic anhydricle and itaconic anhydride by the use of a known peroxide or a polymeri:~ation initiator. The pre~erable grafting monomer is maleic anhydriclc. The gratt reaction proceecls by thc bonding of a graftiIlg monolner S-lC}I as maleic anhycll ide with the rcpcating unit I or Il. As the starting polymel having the rcpe~lting 20 unit Xlll to be used in the present invention, tl1ere may be employccl thc polymel available in tlle tnalkct as lhc pc)lyll1cl in whicl1 tl1c unsaturatecl dicarboxylic anhycllicle is gra-ftecl such as maleic acicl-I-nodifiecl EPR al1cl maleic acicl-lnodified SEBS. The starting copolytllers n ancl b tl1at are slarting nlatcl ials f`or proclucing tl~c 25 copolymcr as thc colnpol1cnt [Cl n~ay l1avc~, as neccssaly, the repcalillg unit llavillg catbon-cnrboll (louble bon(l oliginatillg t`rolll cOIl,jllgalccl cliclle sucll as buta(licne, isoplcnc ancl cllloroplcllc along 2 ~
2s witl~ the rcpe.lting Ul1itS 1~1l allcl Xll or Xlll.
The starting copolymer a for the cs)mponel1t [C] is exel11plifïed by but sl1all not be limited to styrcne/mclleic an}1y(liicle copolymer, ethylenc/rllalcic anllycllicle copolylllcr, propylclle/m.llcic all}~yclricle copolymer, etl1ylene/propylene/maleic anhycllicle copolymer, isobutylene/nlaleic anhydl icle copolymel, mctllyl vinylethellmaleic anhyclride copo"lymer, styrene/isoplerle/n1clleie anl1ydri(le copolymel, ethylene/maleic anhydride/~thyl acrylate copolymer, ethylene/maleic anhydride/methyl acrylate copolymer, ethylene/vinyl acetate/maleic anhycll ide copolymer and styrene/butadiene/mclleic anhydricle copolymer.
The starting copolymer b -for the component [C] is exemplii~ied by but shall not be limited to the copolyl11er obtained by gra~fting an unsaturated dicarboxylic anhydride such as maleic anl1yclride, lS methylmaleic anhydride, l,2-dimethyln1aleic acid, ethylmaleic anhydride, phenylmaleic anhydride and itaconic anhyclricle onto polyethylene, polypropylene, polyisoprene and hyclrogenated procluct thereof, polybutadiene and hydrogenated procluct thereof, chloroprene rubber and hydrogenatecl procluct thereof, nitrile rubber ancl hydrogenatecl prod~lct thereof, ethylene/propylene copolymer, ethylene/(meth)acrylate copolymer, styrene/isoprene copolymel ancl hydrogenatecl procluct thereof, styrene/butadiene copolyrner and hycllogencltecl procluct thereor, in w}-ich the copolymel may be any Or r al1(lonl~ block a~ lteln~lting copolyn1els~
Aceorclin~ lo the ~lt`oresklte(l process (n), the slartil1g col~olyl11e a or b as proclucecl in the above-nlel1lionecl mannel cal1 be reactecl Witll cl S~ ()I tllC ¦--ip(~l~lZillC (ICI iV~ltiVC ICpl(~;C,lltCCI l~y tllC gCllCI~II

26 ~O~a~;

I`urlnul a (XIV) or a salt of the ~liamine replcsenle~l by the general form~ll a (XV) in the presellce of at least one l`ormyl group-eontaining compoull(l selecled frotll formalnicle t`ormic acicl an(l ~lerivatives tlleleof whicll colnpoullcl is available trom the nlalket. Examples of S tlle fornlamicle clerivative inclll(le N-metllylrolmami~le~
N-etllylfol nlamide, N-butyll`ol Inalllicle, N-clilrlethyll'ollllamide, N-cliethylfolmamicle, N-methylf~rlllallilicle arlcl N-cthylfolmallilicle, each bein~ nitlogen-s~lbstitute~l lornla~nicle. Exalllples Or tlle lorlllic acicl ~lerivative inclu(le esters of l`ormic acicl such as methyl formate ethyl formate propyl formate and butyl l`ormate an(l salts of t`ormic acid such as soc!ium formate potassium formate arld ammonium formate. The above-mentioned -formamides it`unction not only as the solvent but also as a reaction reagent~
~ccording to the aforestatecl process (b) tlle starting copolymer s a or b is reacted with the reaction product obtained by reacting in advance the piperazine derivative represented by the general forn-lula (XIV) or the diamine represented by the general t`ornlula (XV) with at least one formyl group-containing compound selectecl flos formamide formic acid and clerivatives thereof.
The aforestatecl process (c) is put into practice in the same manner as in the process (a) except that the reaction is carlied out in tlle absence of a lolmyl group-cotltainillg co~npo~ln~l sucll ax folll-lamicle formic acid or n delivative thereof.
Speeific exanlples ol the pipelazille derivntive represelltecl by 2s the gellelal l`ormula (XIV) inclucle N-aminollletllylpiperazille;
N-aminoetllylpipel azinc;
N-alllinopropylpiperazine; N-aminobutylpiperazine;

27 2 ~

N-.lminohexylpipelazine; N-n~ ooctylpiperazi[le a~

N-(4-amino-2,2-climethylb~ltyl)pipclcl~ine; ot` which are pre~erable N-alnilloetllylpipel azille; N-alllinopl opylpipcl azille;

N-nl~ obutylpiperazineatlcl N-nn~ ollexylpipcl-clzine.

Specific exnmples of the clialllille repleselltecl by the gencral forlllula (XV) incl~lde N-lower alkyl-substitl~te(l clirec~-chain aliph~ltic (liamine sucll ns N-methyllnetl-ylelledinllline;
N-et}lylmettlyleneclinllline; N-prs)pyllrletllylelle(liLli~ e;
N-butylmethylellecliallline; N-methylethylenedinmine;
10 N-ethylethylenediamine; N-propylethylenediaminc;
N-butylethylenecliamine; N-methyl-1,3-propanediamine;
N-ethyl- 1 ,3-propanedinmine; N-propyl- 1 ,3-propanediamirle;
N-butyl- I ,3-propane~lialllirle; N-m~thyl- I ,4-butanediamine;
N ethyl- I ,4-butanediamine; N-propyl- 1 ,4-butanediamine;
15 N-butane- I ,4-butanediamine; N-methyl- 1 ,6-hexanediamine;
N-ethyl-l,6-hexanediamine; N-propyl-1,6-hexanediamine;
N-butyl- 1 ,6-hexanediamine; N-methyl- 1 ,8-octanediamine;
N-ethyl- I ,8-octanediamine; N-rnethyl- 1,1 2-dodecanediamine;
N-ethyl- 1,1 2-dodecanediamine; N-propyl- 1,1 2-clodec~mediamine;
20 N-butyl- 1,1 2-doclecnnediamine; N-methyl- 1, I 8-octadecanedinmine;
N-ethyl- 1,1 8-octadec~mecliamine; N-propyl- 1,1 8-octadecanedianline;
all(l N-butyl-1,18-octaclecnlle(liaminc~ N-lower alkyl-sllbstilutc(l brclllcllccl aliphntic cliarlline sllch as ,; N-rnethyl-2,2,5-trimelhyl- 1 ,6-hexancdial~lirle;

~5 N-elhyl-2,2,5-lrilllelllyl- 1,6-hexnneclinmirlc;

N-pt opy l -2,2,5 -trimethyl- :1 76-hexallecliallline; nncl N blltyl-2,2,5-trinlctllyl-1,6-hexallediamille, 28 2~

N-IOWel- alkyl-SUbStitllte-l alicyclic Clialnine SllCh as N-rnethyl-isopllotoneclialrlille; N-ethyl-isophorollecliamine;
N-propyl-isophoronecliamine; N-butyl-isophorone(liclmine;
I-N-mclhyla~ lolllc~hyl-3-alllitlollletllyl-cyclollexane; and S l-N-ethylaminomethyl-3-aminomethyl-cyclohexane~
N-lower alkyl-substitutecl alylalkykliamille SLlCh as N-metlly!-ln-xylylclleclia~ e; N-cthyl-rl~-xylyleneciiallline;
N-methyl-p-xylylenediamille; ancl N-ethyl-p-xylylenecliamine, N-lower alkyl-substituted arylcliamine such as I o N-methyl-p-phenylenecliamine; N-ethyl-p-phellylenecliamine;
N-met}lyl-m-phenylenediamine; and N-ethyl-p-phenylenediamine, and N lower alkyl-substihlted polyoxyalkylenediamine such as N-methylpolyoxypropylenediclmine; and N-ethylpolyoxyethylenediamine.
Among the above-mentioned examples are desirable N-lower alkyl-substituted aliphatic or alicyclic diamine, of which are particularly preferable N-methylethylenediamine, N-ethylethylenediamine; N-methyl-1,3-propanediamine;
N-ethyl- 1 ,3-propanediamine; N-methyl- 1 ,4-butanecliamine;
20 N-ethyl-1,4-b~ltanediamine; N-methyl-1,6-hexanecliarnine; ancl N-ethyl- I ,6-hexanecliamine.
In the process (a) and process (c), the salt of the above-mentioned piperazine derivative or diamine may be either a partially neutralizecl salt (monosalt) or a completely neutralized salt (disalt) b~lt 25 tllc ll,sc ol ll~c l`orlllcl i~ plcl`clablc bccallsc ol it.s lli~llcr Ic~lclioll ~. .
erllclency.

r['he atoresaict piperazille allcl cliamine are each pret`erably use(l ~9 2~9~

in the t`orlll of partially neutlalize(l salt with all acid, which is prerelably selectecl trom those e~lctl h~lVil1g an acicl strengtll higher thall thclt of a carboxylic acid, and specifically enumelatecl by sulfuric acid; sultonic acicl sucll as bc nzcllesult`o~-lic aci(l, tolllellesultollic aci(i, S toluenesult`ollic acid and naphtllalenesult`orlic acici; halogeno-aciclsucll as hydlochlolic acicl, hydlorluoric aci(l, hycllobrolllic acicl and hydloioclic acicl; nitric acid; boric acid an(l phosplloric acicl. Alllollg them are preferable hydrocllloric acicl and toluenesul~onic acicl.
In pro(lucin~ a s~llt ol ~he piperazille cl~l ivative or ~l salt of the 10 diamine each to be used in the process (a) and process (c) t`or the production of the copolymer as the component [C] according to the present invention, the molar ratio of the piperazine derivative or diarnine to the acid is selected so that the resultant salt has a degree of neutralization of 50 to 100% in terllls of acid equivalent basecl Oll the s total amino groups of the piperazine derivative or the diamine. A
degree of neutralization tllereof less than 50% results in inevitable crosslinkage or gelling at the time of imidization reaction, whereas that exceeding 100% leads to a long time require(l for imidization reaction~ thus causing disadvantage from economical viewpoint. The 20 preferable degree of nelltralization is in the range of 50 to 80%.
A salt of the piperazine derivative or a salt of tlle diamine can be easily prepared by the neutralization reaction between the piperazille derivative or the cliamine ancl the corlespollding acid.
There may be acloptecl a metllo(l in which the piperazille (lerivative or 25 (lia~ lc is a(kle(l (~ )wisc lo ~I solulioll ol a~ aci(l in all alcollol a the tesultarlt prodllct is eoncentrate(l wherl necessaly ancl 3() to be llSe(.l as the starting rnateri~ll. l'here may be also adoptecl a rnethocl hl whicl1 th~ piperclzine Ol the cliclmine and the corresponding acici are l`orlllecl into ~he partially neutralizecl salt to be usecl for the reilclioll ns sllcll in lhe presetlce ol à lormyl group-colltnit~ g S conlpouncl as an esseIltial colnponent in the case ol ihe plOCeSS (a), while in the case of the process (c~, in the presellce of an aplotic polar solvent such as 1,3-climetllyl-2-imidazoliclinone (DMI); N-lnetllyl-2-pyrroliclone; clilnetllyl sullo~icle (DMSO); climetllyl sull~ne; dioxal1e;
1,2-dimethoxyethane; hexamethylenephosphoric triamicle; ancl l0 tetramethyl urea. It is preferable in the operation of the process (a) that a salt be formed in a formyl group-containing cornpound ~md usecl as such -for the reaction because of its higher e~ficiency.
In both the process (a) anci process (c), the resultant reaction pro~luct is brought into contact with a bnse for lhc rel11oval of the 15 residual aci(l.
Another recommendable process for producing the copolysner as the component LC] is the process (b) in which the copolyrner h~ving the repeating units I, II and XII Ol XIIl is imidiz~cl wilh and by the use of the reaction procluct as the reaction reagent, which procluct 20 is obtainecl in advance by renctiIlg the piperazine clerivative representecl by the general formula (XIV) or the clia~ e represented by the general formula (XV) with the af~restatecl t`ormyl group-containing compouncl. The reaction reagent to be used in the process (b) is plepnle(l by subjecting the piperazille delivntive or the clial~ e 2~ in an amollnt of nt least one (l), prefclably 1.5 to 5 tilllCS of l-nols bnse~l on one ( I ) mol ot the tolmyl ~gro~lp-containit1g compollrlcl lo ioll Ol .IIlli(le i~llelcll~ e lC~lCliOl~ l lelllpel~ le o~ 60lo 3 1 2 ~

1 80C, pref~r.lbly 80 to 1 5()C for 2 to S hours In the aforesai~l re.lction by the use of the tornlyl group-cont/lining compound, it is pretelable to ~listil aw~ly water, an ~llcollol all~l ammonia Or~lmin~ in the s respectively T}le reaction pl`U(~UCt thus obtainecl tmay be employed as sucll as the imidization reagent ~lowever since the reaction mixhlle ~Isu~lly contains unre~lcted piperazine clerivative or unleactecl ~ mline, tlle use of whicll as s-lch in the imi~lization reaction causes crosslinkage or o gelling, it is preiF~rable to clistil away the umeacted pipera~ine clerivative or the unreacted diamine by heating the reaction mixture under reduced pressure or in tlle case o~` a higll-boilillg piperazine derivative or a high-boiling diamine to once neutralize the reaction mixture with hy~llocllloric ~Icid Or lhe like and reîllove the 15 dihydrochloride of the piper~zine (lerivative or the cliamine by recrystallization The processes (a), (b) and (c) are put into practice by reacting the starting copolymer h~ving the repeating units I, II and XII or XIII
with a salt of the piperazine derivative represented by the general 20 forrllula (XIV) or a salt of the diamine represente(i by the general formula (XV) in the presence or absence of the formyl group-cont~ining compound or by reacting the starting copolymel ns mentiolle(l above with the reaetion pro~ ct between ~he al`ores~li(l pipelazine clelivative or the diarlline all(l the l`orlllyl group-contailling 25 colnpoull(l The inli(lizaii()ll reaetion can be eallie(l O~lt in Illolten ~tate in the absenee of ~ solvellt by means of a ~screw e,~trlldel Fo the p~lrpose of preventitlg IOCal le~lCtiOII ~Itl(l Ullil'Ol'llliZing the 32 ~9~

rcclction, howeve~ n inert solvent is prel`elably employecl in adclition to tlle forlrlyl group-cont<lining compoullcl tllat is indispensable in the casc of tlle process (a). Exanlples of t!le usable solvent fol the at`oresaicl plnpose inclucle alolllatic hycllc~carbons sucll as benzene, s toluel1e, xylene, cumene, cyrnene, ethyltoluene, propyltoluene ancl cli~tl1ylbenzenc; alicyclic l1yclrocarbons sucll as metllylcyclopentane, cyclohexane, ethylcyclopentane, metl1ylcyclohexane, l,l-din1ethylcyclohexane ancl ethylcyclohexane; aliphatic hyclrocalbol1s such as l1exane, l~eptane, octal1c, clecal1e, lO methylheptane, 3-ethylhexane an~l trirnethylpentane; clnCI aprotic polar solvent such as DMI, tetramethyl urea, dimethyl sulfone, dioxane, 1,2-dirnethoxyethane, hexamethylenephospl1olic tri~mide, DMSO ancl N-me~hyl-2-pyrrolidone. In the processes ~a), (b) and (c), the reactive substrates that are each consiclelably clift`erellt in polarity ale reacted 15 with each other, and therefore, it is pre~ferably to simultaneollsly use a nonpolar solvent and a polar solvent.
The amount of the aforestated solvent to be used is not specifically limitecl but may be suitably selectecl accorcling to the situation. It is cleterlninecl in the range Or 0.3 to 20 times, prefelably 20 one ( l~ to l O times in weight based on the weigllt of the stal ting copolymel h~lvillg tlle repeatillg ullils 1, ll all(l Xll or Xlll to be used as a starting material, that is, the multit`unctional copolymer havil1g substitutecl or nonsubstihlted succinic anhyclricle as the -functional group An alnount thcreof less than 0.3 times may result in 25 insllflicient clilution e!`t~ct ~lnd higllly viscous reactioll nlixtllle causing clifriclllty in hancllillg, wheleas that excceclillg 20 limcs will reslllt in lailllle lo clevelop tllc~ eflect corlesponcl;llg lo Illc higl~ usage 33 2 ~

causirlg disaclvclnt.lge fiolll the ecvnomicai viewpvint.
The r~ltio by weight of the inel-t solvent for the pUrpOSe of lilution to thc fonllyl group-colltaillillg conlp~ n(l as the reactio ,c~ c l)I'O~C~;CS ~ (1 ) 01 lo lllc ~II)I'O~i~ l)ol.ll ~olv~
s without formyl group in the process (c) (the l~tiV by weight of tlle r(~lCtiOIl SOI`/Cllt to th~ fOInlyl glO~Ip-COlltaiilillg COIllpOUIld (>I' to tlle aprotic polar solvent) is 40/60 to lOû/0, preferably 50/50 to 95/5 ~n the case of the proeess (b) in which is used, as ~he substrate fvr imiclization reaction, the reaction pro(Juct between the pipelazine lo derivative or the diamine ancl tl~e l`ormyl group-containing compound t`or lhe procluction of the copolymer as the component [C], it is not always necessary to use a formyl group-containing eompound as the solvent. In the case of the proeess (a), hvwever, the a~foresaid compouncl is inclispensably used not as the solvenl but as the reaetion ls reagent in the -fvrm of a mixed solvent with an inert solvent for clilution. The proportion of tlle atol-esaicl compound to be llsecl is preferably increase(l in aecorclance with the proportioll of tlle tunctional group of the starting material witll a view to improving tlle solubility of the substrate and enhancing the rate of reaetion.
In the imidization reaetion aeeording to the proeess (a), (b) or (e), a catalys~ is not palticularly re(luired but, if used, it is pref~rably selectecl from the tertiary amines sueh as trirllethylamille, triethyk~ inG, trib~ltylnllline, N,N-clhlletllylnl~ e, N,N-cliclllylnllilitle nncl 1-8-dinznbicyclol5,4,0,1ullclcc-7enc.
~5 In lhe ~Ibove-lnentioned prveesses, tlle proportions of lhe startin~ copolymel, pipClnZillC 01 salt theleol, clinlllillc or snlt tllereof allcl lorlllyl group-colltailling eompo~lllcl to be llse(l valy clepell(lillg On 3~ 90~

the kin(l ol stal ~ing materi/ll ancl Othel conclitiolls ancl can not be llne(]lliVOCally cletel lllillCCl. HOWeVel, th~ r ~ItiO ol` the pipe( azine clelivative or the cli~an~ e is llsually I.() to I() times, pref~lably 1.05 to 5.0 ~inles e,~plessecl in tertns vl noll-lleutlcllizecl alllillO gro~lp or 5 unleacte(l amino gro~lp, basecl on one (1) mol of ~he s~lbstitlitecl Ol n~ llbsti~ e~l slle~illi~ alllly(lli~le ~IO~p, ~llat ix, llle repealillg ~nil Xll Or XITI COllt.lillC~I ill tllC` Slclltitlg eOpOIylllCI. ~ latiO tllClCOI Icss thall 1.0 un~;dvorably lea(ls to tlle resiclual succinic allllycll icle gro~lp remainillg non-imi(lizecl even alter the encl of the reaction ancl, in the 10 processes (a) ancl (c), to the possibility of causing gelation by amicle - crosslinkage due to the reaction between the seconclary amino group reproduced in the acicl removal step and the aforesaicl succinic anhydricle grollp, wheleby tlle effect of the presell~ hlv~nlion is unfavolably (lemolished. On the othel hallcl, a ratio Ihereof excecclillg 15 10 times results in the inevitable economic hardship in the excessively large amount of tlle reaction reagent requile~l in spite of the advantage in high rate of imiclization re~ction.
The reaction temperature ~md reaction time in tl-le processes (a), (b) and ~c) vary depending on the type o~ solvent lo be used and 20 whether or not a catalyst is present. The reaction temperature is usually in the range of 100 to 250C, preferably 1 10 to 200C with the re~ctioll tirne of one ~1) to 20 l10LIIS. A reaction temperat~lle lower th.ltl 100C clisnclvantageo~lsly ca~lses a lon~ reaelioll time requile(l, whelecls thclt llighel thclll 25()C urltavol~lbly leclcls to the possibitity ol2s color~ltion of lhe re~lcti()tl plocl~lct alollg witll tlle tller ~lecolllpositiorl ot ~ e intro~lucecl lorlllcllllicle grollps.
Tllclc is incorpolate(l into the reclction procl~lct, sonle amo~lllt of 3~ 2 ~

~hc amicle colllpouncl represelltecl by the repcatirlg urlits X ancl XI
otllel tllan 111 ~lncl IV wl~en the reaction is ca~ l o~ll in the presence of a catalyst or at a relatively lligil tempel~at~lle or in a high molal ratio ol' Ihc rcacliOll rcagclll basc{l on lllc sl(lllillg copolyll~cl, With regalcl to tlle latiO of tlle ~ormamicle group to the ancl IV, in the process (a) there is obtaitle(l the copolymel having forlllarniclc group lningle(l with tl~e seconclaly alnillO gro~lp ancl the formatioll ratio of the forman1icle group increases with increase in the reaction temperature ancl also with increase in thc~ reaction time; in the process (b), there is obtained the copolymer having substantially 1û0% of the formamicle group; and in the process ~c), there is obtained the copolymer having substantially 100% of the s~condary arnino group.
Thus under the above-mentioned reaction conditions, there is obtained the copolymer having a ratio [(III) or (IV)]/L(X) Ol (XI)3 of 100/0 to 30/70 ancl a ratio (formamide group/seconclaly ami~o gro~lp) of l00/0 to 30/70.
The composition of the cop~lymcr as tlle component [Cl in the present invention is analyzecl, t'or example, by means of nuclear InagllC'tiC rCSOllallCe SpeCtl um allalySiS ~ISillg a carbon isotope (13C-NMR) and is specil'ically sllown thereirl by peak intellsity ratios of; carbonyl carbon of imicle r ing cmerging at tlle cllemical sllit't of 176 to 180 ppnl, applox. (W); calbollyl carboll of amicle grollp cll~crgil1~ at tlle cllell~ical sllirt ot' 1'72 to 174 ppln, approx. (Q); ancl carbonyl carboll of formamide gr~ p emelging at thc~ cllelllical shirt ol' 162 l~,t)lll, ~l,ol)lo~

36 2~9~6~

Tllc orclel of f~eding taw m(lterialS 101 re.lction, etc. in the prOccss (a) is not spccifically lilnitecl but may bc sclcctGd in a wicle val icty of nlanllcrs. In genel,ll, tlle salt in tllc ~rm of powclel or sol~ltion pro~ cd lrom thc piperazine clelivative or ~liamine ancl an 5 acid is adclccl to the f~rmyl group-containing compouncl or the iol~ ol'il~ o~ olvs~ lo 1`l)1'111 .1 ~olllli(3ll .1ll~ c~ l lo the resultant solution is graclually aclclecl the copolyll~cl h~ving the rcpcating units 1, 11 and X51 or Xlll, all~l thc rcvclsc ordcl ll~ay bc aclopted. The ~ecling cluring the step may be carriecl out uncler 10 hcatillg and rcflux of a solvcnt Or thc l`ormyl group-colltairlillg compound.
Likewise, the orcler of t`eeding raw materials for reaction, etc. in the process (b) is not specifically limited but may be selected in a wi(lc valicly of n~anncls. In gcncral, ~]1C startillg copolylnel l1aVing 15 the repeating units 1, II and XII or XIII is dissolved in a solvent, alld to the resultant homogeneous solutioll is gradually added the reaction product between the piperazine clerivative or the diamine and the formyl group-containillg compound, ancl the revelsc or(lel m.ly bc adopted. The-feeding during the step may be carried out unde 20 heating alld reflwc of a solvent.
The imidization reactions arnong tlle starting copolymer, a salt of the piperazine derivativc or n salt of the diamine and the fornlyl group-containing compollncl nnd bctwcen the stnrting copolymcr an(l thc rcacti()n pro(luct ol thc pipclazillc (lcrivativc Or lhc (linnlillc witl 2.S lllc lol~llyl ~ lp-~Olll~ ollll)ollll(l is ~ l by w~
t'ormaliorl (Illring tllc pl-ogless thelcot, tll~ls t'orming an azcotlopic nlixll.llc ol tllc solvcllt alld walcl. 'I'llc rcaclioll call bc cl`liciclllly 37 ~n~

effcclccl by cliscl~ ging the n%cotlopic water olltsicle the rcac~ion system by mcans of a Deatl-~talk watcl separatol or the like The conlplelion of the imicliza~ioll reaction carl be confirme(l by c ~Izco~lol~ic W~llCI t`ollT~ ioll iS 110 lollgcl obsclvc~l ol tll~lt ~llc 5 increase in the absorption capacity of ~he carbonyl group of the imide rill(~ at alourl(l 17()() lo l X()() cln- l is nO lOllgCI' obscrvcd ill inl`lclled (IR) spectrllm analysis in whicll n salllplc is collccted frolm tllc resultant reaction mixt~lrc, In the reaction mixture thus obtaine~l is containecl a salt of tlle 10 copolymer as the component ICI in the presellt invelltion having the formamicle group and/or the secondary amino group that are bonded theteto via imide bond, The resultant salt can be converted to tlle t`ree amine by a method wherein the reaction mixttlre as sucll or, when necessaly, al'tel bcing p~llvcrizccl by pO~rillg in a noll-solvcnt sllch ns 15 methanol, isopropanol, isobutanol, llexane or water, is brougllt into contact with an aqlleous solution of a base or, when necessary, a mixed solution of a base in methanol/water for tlle acicl removal, Specific examples of the above-mentioned base usable l`or the acicl removal include a watcr-soluble base such as sodi~lm hy(lroxicle, 20 potassium hyclroxide, lithium hydroxicie, sodium carbonate, potassium carbonate, so(:lium hydrogencarbonate, potassi~lm hydrogencarbonate, ammonia, methylamine, ethytamine, trimethylamine nnd lrietllylnmine. Anlong thosc nrc prcl~rablc sodi~llll hy(lloxicle, socliu calbonatc all(l sodiull~ hydlogellcnlbollatc 1;olll the CCOllOllliC
2~ vicwpoilll, 11l lllc ~locc~ (t)), ll~c ~lci~l Iclllov~ll slc~l) is ~lispclsc~l wi~ll, since a salt of tl~c copolymer is not prodllcecl~
'l~llc copolylncr llaving thc lorlllalllklc group ollly witl-out thc 3x '~ ) 5 6 ~;

~ImillO gl-OUp Cnll easily pUIifiC`CI by pOUIillg tlle reactioll Inixtule in Inetllnllol, isopropnllol, isobllklnol~ hexclne Ol water as mentioned nbovc clnd rccovcl-ing llle rcsultant precipitate as powclery prociuct.
1ll tlle reSill COIllpOSitiOIl ol' tlle prcsent inventioll comprising the s componcnts [AJ, [B] and [C] as the principal components, the ratio by wcigl~t of thc COIllpOIlCIlt [Al ~;llall be 5 ~o 95%, prcfclably 30 ~o ~5%
based on the total amount of [A~ and [B~ ancl the ratio by weight of the component LB~ shall be 95 to 5%~ preferably 70 to 5% based the same. A ratio Or [A] or [13~ outside the above range results in lo disa(lvantagcofdclcliorate(llllolclabilityolc~ecleascilllnccllnnical strength such as rigidity for the resin composition. The ratio by weight of the component [C~ is selected in the range of 0.05 to 20 parts, prel'erably 0.5 to 10 parts basccl on the ts)tal amount Or [A~ ancl LBl of lûO parts by weight. A compounding ratio of LC3 less tl-an ls 0.05 part by weight causes insufficient eff`ect on improving various physical properties, especially sur-face impact strengtll -for the resultant resin composition, whereas that exceeding 20 parts by weight results in l-`ailule lo develop thc improvclllcnt in thc el'l`cct corlcspon(lillg to the compounding ratio, thus causing economic hardship as well as 20 cleterioration of physical property baklncing.
The resin composition of the present invention comprising the components [A~, LB] and [C~ as the principal componcnts may be ~furthçr incorporatecd, when necessary, with other adclitive such as reinforcing material (e.g. glass fiber ancl cnrbon fiber), inorgnnic filler, 2~ tllcrln~ tnbilizcl, allli()xi(kll)t~ l sklbilizcl ~ l`lalllc rct~ll(klllt, weatllering ngent, pklsticizel, antistatic agellt, molcl-releasillg agent, foanling agent Or the like.

39 2 ~

In prepcll ing the conlposition of the present inventivn, each of tlle above-[llentione(i con-potlellts is kneaclecl in the neat-molten state by tlle usc of a single screw extl ~Icler, a tWill screw ext! ~ el ~ a 13al1bUly miXCI, .I klleaCIing 1011, a l~labellCtCI, cl knCa(lillg ma(~hille 5 S~lCh as a kneaclel, a nlixer sucll as a ~lenscllcl mixer Ol the like. The or~lel (~I' kllca~ nol spe~il'iccllly linli~ t Illay l~c ~suii~ ly selected The kneacling tempelature varies clepenltling on the type of the component, compounding amount, the aimed pllysical propert;es of the composition to be producecl9 etc and is not unequivocally 10 cleîerlnine~l. It is selectecl us~lally in the range ot IX0 to 340C.
The resin composition of the present invention can be preparecl by kneading the components LA]~ [B] and [C3 in suitable combination.
Taking into consideration the miscibility among the components, f`or example, an olefinic polymel as the component [B] is pref~l~bly 1S combined with an olefinic compound having forrnamide group ancVor amino group as the component LC] such as ethylene/ethyl acrylate/maleic anhydride copolymer havillg formamide group nncUor amino group, ancl a styrenic polymer as the compollellt ~B] is preferably combined Witll a styrenic compound having formarnide 20 group ancl/or amino group as the component [C] such as styrelle/maleic anhydride copolymer having formamide glO~lp and/or amino group, and so forth.
The present invention can provicle a resin connposition excellent in impact strength, especially SUI face impact strength as well as Izo(l ~.'; ill~paCt Stl-CIl~tll, WCalllCI- I'(:~Sislalle~ allCI SOIVellt l-CSiSt.lllCe .IIlCI l-l-ee froln tlle problems with clel.ll~ lalioll, peelillg or ulll;avolable appealallce by virtue of compollll(ling the mixe(l system betweell an 2~9~

el1gillcelill" plastics and a get1e~ pllrpose resin with a cvpolymer haViilg formamicle group ancUol amino gro~lp whicll copolymer is minirnized in gelling.
Accor~ gly, tlle le~;in colnposili()n o!' ll~c plcscnt invclltiOn is s expected to l;ncl a wide variety ot useful applications in the fiekls of ~l~ltonlobilc illtel iOI Ill.llCl i.li~ lO~ Ill.llCl i.llS t`~r ol ficc alltOIll.lti nl.lcllinely an(l apparatus, electrical home appliallces.
In the following, the present invention will be described in nlore detail with referencc to relercnce exannples, preparation lO examples, working examples (simplifiecl as "examples") and comparative examples, which however shall not be construed to limit thc present hlvcntion thereto.
Reference Exam~le 1 Prcpar,ltion of partially ncutlalizc~l salt of N-(2-aminoc~l1yl) 15 piperazine with p-toluenesult`onic acid ---A I litcr flask eqllippe~l witll a thcll1lomctcr~ a stirrer, adropping funnel and a reltlux conclenser was chargecl with 300 ml of methanol ancl 95 g (0 5 mol) o-f p-toluenesulfonic acicl monohydrate to prepare a solution. To the resultant solution was added clropwise a 20 solution of 323 g (2.5 mols) of N-2-aminoethyl) piperazine in 300 ml of methanol on an ice bath at such a rate that the temperatule of the mixed solution was maintaille(l at 10 to 20C After the colnpletion of the (Iropwise a(lclitioll~ the mixe(l solutiol1 was he/lte(l to 70C an(l tl1en clistille~l at 1'C`dUCeC1 pressure to distil away the Inethallol allcl 25 unleactecl N-(2-alllinQetllyl) piperazine allCI (k~poSit 170,2 g of n Wllite solicl, Tl~e white solicl thus obtained was klken OUt from tlle fl.lsk, slurl ied with 300 ml of toluene, t`iltelecl ancl furtller wasllecl twice witl 41 ~9~

10() ml eacll of tol~lenc to obtairl white powclers, wllich were dried unclcl reclucG~I press~lre. Tlle wllite pow~lers obtaine(l at a yiekl o:f 142.9 g wcre titrate~l with ().~ N hycllochloric aci~ ICI) by the use o:f brolllo~ cilol bluc as lllc in~licalol lo ~k~ nillc ll~c n~llll-(lliz~ oll s eqUiValellt an(l the ~leglee of neUtlclliZatiOll. Tlle leSUItS clre giVerl iil Tablc 1.
Reference Example 2 Preparation Or partially ne~ltralized salt of N-(2-aminoetilyl) piperazine with lly~lrochloric acicl ---The procedure in Rcferellce Exalnple I was repeatecl by the llse of Ihe same flask as that usecl therein as the reaction vessel except that 35% aqueous solution of hydrogen chloricle (35% hyclrochloric acid) was employecl in place of p-toluenesLIlfonic aci~l to prepare white pOW(~ClS of N-(2-aminoctl~yl) pipclazinc mollolly~llocllloli(le. Thc 15 neutralization equivalent an(l the degree Or nelltralization -for the monollycllochlolide were ~letelmined in the same mannel as in Ret`erence Example 1. The results ale given in Table 1.
Reference ExampLe 3 Preparation of partially neutralized salt of N-(3-aminopropyl) 20 piperazine with p-toluenesulfonic acid ---In thc sa~-nc manncl as in Rcl`elellce Examplc 1, 95 g (0.5 mol) of p-toluenesulfonic acid monol~ycllate was dissolved in 500 ml oi ~limctl~y:lt`o~ llni(le (DMF) at roolrl tempelatllle. 'I'o tllc le~llt~lnt sollltion was gr~ lnlly a(kled 6~.5 g (().45 Inol) of N-(3-~1mil-loplopyl) ~5 pipclazitle lo ~lissolve il all(l prepnlc ~I solutioll ot p~lrtially neutlalizc(l salt c,r N-(3-aminoplopyl) pipelaZillC with p-tOlllelleSlllt'OlliC aCi(l ill DMI~ so th~lt tl~e lesultant solution tempcratlllG might not ~xc~e~l ~2 ~9~;6 20C. Tlle ncutralization eclLlivalent an(l thc (legrce of neutr~ ation basecl on tllc soli~l contcllt for lhe res~llt~lllt salt arc given in 'I'able 1.Rel`el~llce Exalllple 4 Prcpal<ltion ol paltially nc~ltlalizc~l salt ol` N-(6-alllinollexyl) piperazille with p-toluellesull`onic aci(l ---ln lllc salllc nlallllcl as in Rcl`clcncc EXalllplC 1, 95 g (0.5 mol) of p-toluenesulfonic acid monohycllate was ~issolve(l in 500 ml of 1,3-dimethyl-2-inliclazoliciinone (DMI) at room telllperature. To the resultant solution was gr~dually aclclecl 83.3 g (().45 mol) of N-(6-aminohexyl) piperazine to clissolve it ancl prepare a solution of partially neutralized salt of N-(6-aminohexyl) piperazine with p-toluenesul-fonic aci~ in DMI so that the resultallt solution temperature might not exceed 20C. The neutralization equivalent and the clegïee of nc~ltlali7~atioll ba~sc~l on tllc ~oli(l contcnl ol`tllc rcs~llt~lllt p~lrlially ne~itrillize~l salt are given in Table 1.
Reference Exal_ple 5 The proced~lre in Reference Example 4 was repeated to prepare the salt of N-(4-aminobutyl) pipera~ine w;th the salt except that N-(4-~minobutyl) piperazine was used as the piperazille derivative The neutralization equivalerlt of the residue thus obtaine(l as determined by neutralization titration is given in Table 1.
Refe~ence Example 6 Preparation of a reaction pro(luct between N-(2-alninoetllyl) piperazille nn~ )rmamkle ---'rhe sallle reactioll vessel as tllat llse(l in Reterence Fxalllple I
was chargecl with 646 g (5.0 mol) of N~(2-a~ loetl-1yl) piperazille, to wllicll w.ls gra~lually n~l(lecl ~Iropwisc 45 g ( 1.() mol) of l`orl~ llli(lc at 2 ~ 6 6 roonl tempelahlle. Aftel the completioll ol the drl)pwise aclclition, the mix~ule was heatecl at 80 to 120C to react lhem for 9 hours, (luring whicll time the evolutioll of amlllonia gas was observecl. Aftel the completion of the re.lctioll, the unleaclccl N-(~-alllinoetllyl) pipelazine s was distilled away to obtain a resiclue. The reaction procluct th-ls obtaine(l was subjectecl to the cletermination by means of thc neutlalization titration, an~l the results are given in Table 1.
Reference Exatllple 7 Preparation of a reaction procluct between N-(3-aminopropyl) 10 piperazine ancl DMF ---Substantially the procedure in Reference E~xample 5 wasrepeated to gradually add DMF dropwise to N-(3-aminopropyl) piperazine and react them at room temperature without the use of p-toluenesull`onic aci(l~ The resultallt Ieactioll mixtule was clissoivccl in 15 a solvent (ethanol/water= 7/3 (ratio by volume)). The solution was neutralized with a 35% hyclrocllloric aci(l, concentrate(l, recrystallized ancl filtered to remove a crystal of N-(3-aminopropyl) piperazine hyclrochloride. The concentlated resi(lue thus obtainecl was subjectecl to the detelmination by rmeans of the potentiometric titratioll, an(l the 20 results are given in Table 1.
Referellce Example 8 Preparation of partially neutralizecl salt of N-ethylethylenediamine with p-toluenesul-fonic acid ---A I liter flask-equipped with a thelmonleter, a stirret, a 25 dlopping f`unnel ancl .1 rel`lllx conclellsel was cllar~e(l witll ~()0 ml of methartol al~ 5 g (0.5 nlol) ol p-toluellesulfonic aci(l motlolly(llate to prepale a sollltion. 'ro the resultallt solutiotl was a(lcle(l dlopwise a 2 ~ 9 ~

solution of 220 g (~.S mols) of N-ethyletllylenediamine in 300 ml of n~etllallol whilc cooling the sol~ltion on an ice bath at sucl- a rate that th~ temperatule of the mixecl solution was maintained at 10 to 20C.
Altcl lllc co~ )lclioll ol ll~c ~lloi~wisc ad~liliol~, tllc nlixccl sollltion was hcatecl to 70C ancl then distillccl at reducecl pressllle to distil away the l c~ c(l N-~lllyl~ ylc~ ;1ll(l (Icl~o~ () 3 ~
of a white solicl. The white solid thus obtainecl was taken out fiom the flask, slurriecl with 300 ml o~ toluene, filtered ancl fulthel washed twice with 1()0 ml each of toluene to obtain white powclers, which lo were dried uncler reduced pressure. The dlied whi~e powclels obtained at a yield of 124.8 g were titrated with O.S N hydrochloric acid (HCI) by the use of bromophenol blue as the indicator to determine the neutralization equivalent and the degree of neutralization. The results are given in Tablc 1.
15 Reference Example 9 Preparation of paltially neutralizecl salt of N-ethyletllylenediamine with hydrochloric acid ---The procedure in Reference Example 8 was repeated by the useof the same flask as that usecl thelein as the reactioll vessel except that 20 35% aqueous solution of hydrogen chloricle (35% llyclrochl()lic acicl) was elnployed in pklce of p-tolueneslllfollic acicl to prepare white powders of N-ethylethylenediatnine monohydroclllol ide. The neutralization eguivalent and the deglee of neutralization for the monohydlochloricle were determined in the same manner as in 25 Rcl`elellce E~xaml)le 8. Ttle results are given in Tablc 1 ~e~ nce Ex_m~ c I () I'rcpalalioll ol partially neutlalizcd sall ol N-n~ctllyl- 1,6-~S 2 ~

hexanecliarnine with p-tvluerlesultonic acicl---ln thc same rnanner ns in Reference 13xample 8, 95 g (0.5 mol) of ~-toluenesulfonic acid monolly(llate was dissolved in 500 mI of dilnethylfolmamide (DMF) at room temperatule. 1'o the resultant s solution was gradually added 58.5 g (0.45 mol) ot`N-methyl-1,6-l1ex~llediallline to clissolve i~ ancl pr~palc a sollltion of paltially neutralized salt of N-methyl-1,6-hexclrlediamine with p-toluenesulfonic acid in I)M~ so that the resultant solution tenlperatu1e might not exceed 20C. The neutralization equivalent and the ~degree lo of neutralization for the salt thus obtaine(l ale given in Table l.
Reference Exan Preparation of partially neutralized salt of N-methyl- 1,6-hexanediamine with p-toluenesul~onic acid ---In thc sarne manncr as in l~ef~1cllcc Exalllple 8, 95 g (0.5 nlol)~
lS of p-toluenesul-fonic acid Inonohydrate was dissolved in 500 ml ot` ~
1,3-dimethyl-2-hllidazolidinone~DM~) at room temperatul-~ To the resultant solution ~vas &radually added 58.5 g (0.45 mol) of N-methyl-1,6-hexanediamine to dissolve it and prepare a solution of partially neutralized salt of~N-methyl-1,6-hex?nediamine with p-?0. toluenesull~onic aclcl in DMI so tbat the res~lltant svlution temperature might not exceed 20C. The neutralization ecluivalent and the degree of neutrallzation bnsed on the solid content of the resultant partially neutralized salt are given in Table 1.
Reference Example 12 The procedll~e in Re~elence Example 11 was repeate(l ~o prepare tlle salt ot N-ethyl- l ,4-butanecliamine with the ac,icl except ~llal N-clllyl- l ,4-b~ o~lia~ lc was ~Isecl as tllc ~lialllillc . . .

. ,.

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T}~e ne~ltlaliz~ltis)ll e~l~livalen~ ol the resid~le as ~letcrminecl by n~eal1s of neutlalizatioll titration is giverl in Table 1.
Reterencc Example 13 Prepalation of a reactiorl pro(luct bc~weell N-S ethylethylenediamitle ancl t`ormalllide ---TIlC S.llne lcaeliOn vcssel ~IS that usc~l in Reterellcc Exalnple 8 was charged with 440 g ~5.0 mol) of N-ethylethylenediamine, to which was gradually aclded dropwise 45 g (1.0 mol) of formamide at roorn temperature. After the completion thereof, the mixture was lo heated at 80 to 120'aC to react them for 9 hours, during which time the evolution of ammonia gas was observe-l. Al`ter the completion of the reaction, the unreacted N-ethylethylenediamille was distilled away at 61 C/88 mmHg to obtain a resiclus. The reaction procluct thus obtained was subjected to the determination by means of the neutralization titration, ancl the neutralization equivalent thus determined ;s given in Table l.
Re-ferenceExample 14 Preparation of a reaction product between N-mctllyl-1,3-propanediamine and l~)MF ---Substatltially thc proccdule in Relerencc Exarllplc 12 was repeated to gradually acld Dl\IF drop\,vise to N-n~etllyl- 1,3-propanecliamine ancl react them at room temperahlle without the use of p-toluenesulfonic acid. The resultant reaction mixture was dissolved in a solvent (ethanol/water= 7/3 (ratio by volume)) and the rcsultarlt ~olutiorl was nclltralize(l Wittl 35% llyclrocllloric aciclt t c(~ncc~ llc~la Ic~l~yst~lllizc~l llllcl filtc~lc~cl to l'CIllOVC ~I Cl'ySt~ll otN-metllyl-1,3-plopalleclialllitle hycllochloricle. Tlle concentlatecl ~7 2 ~

resic~ue thus obtained wns subjected to the determination by means of the potentiometric titration, ancl the results are given in Table 1.

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~_erellee Exa ~
Preplllalion ot`maleie anllydlicle-grat'tecl pl)lyplopylene: Rel'er to Japallese l'ateilt Applieation Publiea~ioll No. 9925/'i981 ---I()() palls by weiglll ol' powclely ~rystallirle polyplopylelle s havillg a weigllt-a~elage nloleeulal weighl (Mw) ol' 60,0()0 with a nulllbel-avelage nloleeulal wei~ /ln) ol'24,()()0, 12 palts by weigllt of Inaleie anhydricle ancl 4 palts of weight of clieumyl peloxi~le wele prelilmillal ily blenclecl witll eaell other ancl subjeetecl to exlrusioll reaetion with an extrudel haYing a serew cliameter of 3V mm ancl an aspeet ratio (rfltio of serew Iengtll to serew wicltll) of 2~3 at a barlel termperature set at 230C allcl a number of serew revolution o~' 60 rpln.
The resultant grafted procl~let th-ls cliseharge from the extrucler was ground, immersed in ~eetone to remove unreaetecl maleie anhydricle by extraetion ancl clrie(l to aff`olcl maleie allllycllicle-g,lafted polypropylene resin (1) wi~h a grafted amount by Inaleie anhydricle of 4.5% by weight. The resin thus obtainecl had an Mw of 15,000 with an Mn of 6,500 expressed in terms of polystyrene as determinecl by gel permeation ehromatoglaplly (GPC).
,Refelenee E~xample 16 ln tlle s~lme mllnnel as in 13el`erenee Example 15 mclleie llnhydricle-glafted eopolymers (2) to (6) wele obtaillecl as given in 'l'able 2, so 2~9~66 t~

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5l 2~9n~6 Rct`erellce Example 17 By the use of the publicly known methocl, maleic anhy(lride copolymers (7) to ( 10) were obtained as ~given in Table 3.

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A I litel flask e~luippe(l with cl thelmorlletel, ~ stirlel, ~I
~Iroppill" furlllcl an~l ~I De~ Sl~llk watel separ~l~ol was charged with 3()() 1~l1 ol ,~yl~ 1 1 2() t, ol ~ l llci~ y~ lc-gl~ltt~
s polypropylelle (I) as prepaled in Relelence Exalnple IS, which WcIS
~lissolve(l in the xylene with hc~ltillg un(lel the reflux thclcor at 1 40C, T}len, to the result~lnt solution was gla(lually a~!ded clropwise a solution ol` 12 0 g ol`tl~e IC~lCliOIl plOdUCt Or N (2-a~ oclllyl) piperaziIle with formami(le as prepale(l in Relerellce Example 6 in o 20() ml of DMF over a periocl of 3 hours, while tlle mixed reactioll solutioll was nIaintaille(l at the reflux ten~perahlre of xylene ancl the azeotropic water res~lting l`ronl imidization reaction was discharged outsicle the reaction system by means of the Dean-Stark water The reaction was furtller continued at I 40C for 10 hours until the completion theleof where the azeotropic watel formalion was no longer ol>served Subsequently the snixed reaction prnduct was poured into 5 liters of methanol to recover the pro~l~lct as precipitated, which was washed with methanol ancl driecl giving a yiekl Or 126 4 g The resultant copolymer was in the forn~ oi` white powder7 soluble in xylene and dissolve(l in xylene into 10% by weigllt of tt~e solution to measure the viscosity at 25C by means of <a Brooki'ield type viscometer The result was 140 cPs A solution of the copolymel in xylene was nlade into cast films, 2~ whicll were s~lbjectecl to IR spectlulll analysis As a res~llt, tlle absoll)lion base(l On l`or~ allli(le was observe(l al 1662 cnl-l (slloul(lel) all(l 1~31 cn~-l in ~lcklition lo tlle absoli)tioll based On in~i(le rillg at 3 i~

1775 cln-i all~3 17()4 Clll-I, hllt ~llele was not observe(l the absorptioll b~l~SC(I Oll alllillO glO~p.
Asi~lc frolll lhe above tl~e copolymcl w ls sllbjecIecl to nucleal s isotope (13C-NMR). As a res~llt thclc clner~cd a pc~lk assiglled lo tlle ~al bonyl cal bons ol inlide r ings al 176 lo I XO pplll al an ill~C~llSi~y l'aliO
of 2.00 ancl a peak inc!icating tlle existence of the c(ll bonyl c Irbons of forrnamide at 162 ppm at ~Itl intellsity ratio of 1.0() bul a pe lk inclicating the existcnce Or the cal bonyl cal bons c~r arnicte group at 17 I() to 174 ppm cli~l not cmelge.
As the result of the 13C-NMR analysis the f~inctional group ratio in molal ratio was cletermine~l to be (IV)/(XI) = 100/0 allC
formamicle group/seconclary amino group = 100/0 Prcpa7 alion Exanlplc 2 1~ A 1 liter t`lask ecluipped with a thermometer a stirrer a dropping funncl ancl a Dcan-Stark watel scpalator w as charge~l with 80 ml of DMF and 8 g ol the reaction procluct of N-(3-aminopropyl) piperazine with DMF as prepalecl in Reference Example 7 which was dissolved in the DMF with heating to 80C.
Then to the resultant solution was graclually adcled dropwise a solution of 71 g of the styrelle/lnaleic anllyclli~le (95:5 mokll ratio) copolymer [(7); Mw = 52 ()00 Mn = 2$ 000] as prepared in Reference EXan]PIe 17 in 350 ml of xylcne.
Aftel tllC` COlllplCtiOIl 0f lhC` drOI)WiSC a(klitiOIl, a Sallll)le wa~;
2s l~akcll lrOlll thc nlixe(l rc Iction plo(l-lct an(l sul jecle~l lo infraled (IR) spcclrulll all llysis. As a Icsult the absolption basc(l orl ttle alltly(ll i(ler ing It 17X0 cm-l h a~l colnplclely (lisappcale(l ~ 2Q9~

~ ICatillg fOI tCIllpC`I-alUIC laiSillg ol` the mixed reaetion produet was eOn~inlle(l to boil watel at alollllcl 140C as ~he azeollope witl~ the lef~ ;eCI XylCIle, allCi tilC` boilecl Watel- was cs)nclensed and sepalatecl wiil~ c Dc~ lalk walcl scpal~ . 'Illc Icacli()ll was fullllcl 5 eontinue(l at 1 40C I`or 9 ho~lrs until the eompletion thereof whele the aZC`Otl-OpiC WatCI- fOIIll.ltiOI~ W.IS no l0l1'JC~I- ObSelVeCI. SLIbSeCIUCtltly IllC`
mixed reaetion prod~let was pourecl into 5 liters of methanol to reeover the procluet as preeipitate, whieh was wasllecl wit]l rl1ethanol ancl dried giving a yield of 73 4 g lo The resultant eopolylner was in the form of white powcler, sol~lble in toluene ancl dissolvecl in toluene into 10% by weigllt Or the solutioll in toluene to measure the viseosity at 25C by means of a 13rookfield type viseometer, Tl-le result was 700 ePs A solution of the eopolymer in toluetle was made ;r.to east filtns, whiell were subjeetecl lo IR SpCCtl'UIll analysis As a result, the absorption basecl on formamid~ was obselved at 16~5 ern-l (shoulcler) in addition to the absorption based on imicle rings at 1775 em-l and 1695 em-l, but there was not observecl the absorption basecl on amino group Asicle from the above, the eopolymer was subjeeted to nuelear magnetie resonanee speetrull1 analysis in CDCI3 llsing a earbon isotope (I3C-NMR), As a rcs~llt, tl-el~ enlelge~l a peak assignecl to tl~e earbonyl earbons of imide ring at 176 to 180 ppnl at an intensity ratio of 2 00 and a peak inclieating the existenee of the eal bonyl earborls of 2~ lol~ l 16'~ ily l~llio ol i.()(), b~ k in(lieatin~ tlle existenee of the earl)ollyl eall)olls Of alllicle gr~)llp at 172 to 174 ppln clicl not enlerge s~

As tl~c res~ of tllc l-~C-NI\~IR analysis~ lllc Illnction.ll grv ratiO in Inol.ll ralio W~lS dc~cllllillccl to bc (III)/(X) = 1()()/() arlcl l`Ollll.llllide grOUI)/SCCOllCklly alllillO glOUp= 100/().
Prcpal ation E,~anlplçs 3 lo I () Tlle procedllle in Prep.llatioll Exalrlple I or 2 was repeatecl cx~cpt tllat Illclc wcre cn~ loyc(l lllc plo(lllcl~ s obklillccl irl Ret`erellce E~xamples I to 7 as tlle piperazille clel ivative salt or the reaction prodllct of a piperazine clel ivalive with a t`ormyl group-containing compound; and the copolymers as clesclibecl in E?ef~rence lo Examplcs 15 to 17 as thc staltillg copolylncl. ~lOWC`VCI, ill E~XalllplC`S3, 4 and 7 to 10, the mixecl inliclization reaction product was poured in methanol to recover the precipitate, which was imlnelsed in a watellmethanol solution ( l: l by volume) contailling 8.0 g of potassium carbonate overnigllt, filtered, thorougllly wasllccl with water and methanol, driecl ancl prepared. The results obtained are given in Table 4.
Measurements were rnade also of the visGosities of the copolyrners thus obtainecl, which results are given in Table 4.

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c plo~e~ tio~ lT)l~ I w~ ep~at~cl ~c~pt tlla~ X.~) g ol tlle lcactiOll plo~l~lct ol N-etl-ylctllylel-c(iial~ le allcl l`ori1n~ lc a~; plcl)alc(l ill l~cl`clcl~c E,~alllplc 1~ was clnployc(l i place of the rcaction procl~lct of N-(2-amilloetl1yl) pipelazille allcl ol l~ l to R~t`el c~ c Ex~ lc (~) Tlle copoiymer was obtaillecl in a yiekl of 125 3 g in tlle form of white powclel, soluble in xyleile arld ~lissolved in xylene illtO 10% by weight of the solution in xylene to measule the viscosity iat 25C by o means of a Brookfield type viscometer The res~llt was 145 ~Ps A solution of the copolynler in xylene was ma(;le inlo cast films, which were subjectecl to IR spectrum analysis~ As a result, the absorption basecl on -formamicle was observecl at 1662 cln-l (sho~llder) in acl(litioll to tllc absorptiot1 basc(l 0n imi(le rings at 1772 cm-l al~
1700 cln-l~ b~lt there was not obselvccl the absolption base(l 0n anlino gro~lp.
Aside -from the above, tlle copolymer was subjecte(l to nuclear magnetic resonance spectrum allalysis in CDC13 using a carbon isotope (13C-NMR) As a result, there emerged a peak assigne(l to the calbollyl calbol1s of imicle ril1g at 176 to 18() ppln at an intensity ratio o~ 2 00 allcl a pc~ak inclicatil1g lhc cxistel1cc ol Illc calbol1yl calbol1s ol formarnicle at 162 ppm at an intensity ratio of 1 00, but a peak indicating the existence of the carbonyl carbons of amide group at l72 to 174 ppm clicl not emerge ~s lllc rcslllt o~ c l3C-NMR al1~llysis, tlle r~lnctioll~ll gro~
ratio ill nlol~ll ratio wns clcterlllincci to be (IV)/(XI) = 1()()/0 all(l (`,~ 2~9~5~

PlCp<llaliOIl E'`~Y~a~ )IC 12 'rhC plOCC(I~llC ill l're~)al1ltioll Exalllplc 2 was repealccl except tlla~ ~.6 g of tllc reactioll plo(llle~ ol N-n~elhyl-l,~-plopallecli~ inc alld 13M~; as plep~sled il~ l~et`el-ell~e f xalllple 14 ~as ClllplOyC`(I ill S place of the rc~lctiOIl prod~lct of N-(3-alllirloplopyl) pipelazille (Relclell~e Ex~alllple 7).
In the IR spccllulll analysis CillliCCi olll allel lhe con~pletioll ol (lropwise acklitioll ol styrclle/lllalcie aeicl copolymcl (7), tlle absorption based on the anhyclri(le ring at 17X() Clll-l llad COlnpletely I O clisappeal ed.
The eopolymel was obklined in a yiekl c,r 73.8 g in the form o~
white powder, soluble in tol~lerl~ and clissolvecl in toluelle into 10% by weight of the solution in tolueTle to measure the viseosity ~It 25C by means of a Brook-field type viscomctel. The result was 690 cPs.
1~ A solution of tlle copolymel in tviucne was ma~le into cas~
films, whicl- were sub jectecl to IR spectrum analysis. As a result, the absorption basecl on forlllamicle was observe~l at 1665 cm-l (slloulder) in aclclition lo the absorption basecl Oll illliClC` I'illgS at 1775 cm l ancl 1665 em-l, but there was not observecl thc absolplion base(l on amillO
20 gl-O~lp.
Asicle flom the above, the eopolymer was subjeetecl to nuclear nlagllctie l'CSOllallCC SpeCtl'-llll allalySiS ill CDC13 using a ealbon isotope (13C-NMR). As a res~lt, there emerged a pcak assignecl to tllc carbollyl earbons ol` imiclc ring at 176 to 180 ppm at an intcllsity ratio ol` 2.~)() .~n(l ~I pc~lk in(licalill~ lllc cxislcllcc ol` Illc C.ll bonyl ~albolls ol l`orlll.lmi(le at 162 ppm at all intellsity r.llio ol 1.()(), b-ll a petlk in(lic~ ing tllc cxislenee ol li~c e.lll)ollyl ealbolls ol all~iclc ~ro1lp at 172 (,3 2 to 17~ }~ l ll(?t CIllCI ~'~C.
As thc reslllt ol`the I~C-NMR arlalysis, the furlctional grou ratiO in molal ratio was dclellllille~l to be (lll)/(X) = 10()/0 arld l'olll~ lct,l'Oll~ 011~1~11'y~llllillOgl'Olli~= I()()/().
s Preparatioll Exalnples 13 to 20 1h~ pro~lule il~ p.~ iol~ E,~ npl~ I I Ol 12 w.ls l~pC.llCd cxc~ept tl-at thelc were cmploye~l the pro(lucts .IS obtainecl in Relelence Exalnples 8 to 14 as the di~ le salt Or Ille reactioll product of a diamine with a lormyl group-containing compvuncl; ancl o the copolymers as clescribed in Refelellce Examples 15 to 17 as the stal-ting copolymer. Howevel, in Exanlples 13, 14, an~l 17 to 20, the potassiutn calbonate-tleatments were calrie~l out in the same manner as in Prepalation E,xalllple 3.
The results obtainecl are given in Table 5.
s Preparation Example 21 An attempt was made to proceed with reaction by the use of the starting raw material salne as in Preparatioll Example 11 except that there were used 5.3 g of N-ethyletllylene~liamine in place of the reaction procluct of N-etllylethylenediamiJle Witll lorrnalllide; atld 20 xylene in pklce of DMF. Ilowever, immediately aftel tllc cllopwise acldition of 1/3 of the solutioll Or N-ethylethylenediallline, the reactio mixture turned out to be higllly viscous, but the reactioll was continuecl to proceed with imiclization reaction. The resultant reaction mixtllle was pollrect into S liters of` nletl-allol, wa~slled wilh n~etllarlol l, 'I'llc ~ol)oly~ ol)l~ (l w.lx ~ xolvc~l il- l~ll.llill .ll 1()()C to l`ollll 1()% by weigllt Or tlle soluliol~, ~he Brookriekl viscosity ot wllicll was Ineasuled at I ()()C. Il-le Icslllt was 53()0 cP~s, whicll Iecl 6 i 2 ~ 6 lo thc jllclgelllc~nt th.lt a par~ lly clos.slillkccl pro(l~ict h~acl beell formed dUlillg tlle (COlliSC` Ol reas,[iOn.
Prepalatioll Exall-lple 22 An attelllpt was n-acle to ploceed with reaclioll by the use of the 5 stalting raw matelial same as in Preparatioll :Exainple :12 exccpt that v~ , ol N~ yl~ ol~ c of lllc reactioll procl~lct of N-me~hyl- 1 ,3-propaneclialninc with DMF; and xylelle in place Or DMF. However, inllnecliately aftel the start of distilling out of the azeotlope in the step of heating tor telnperature 0 raiSillg at`tC`I the completion ol thc dl-opwise acl(lition of thc solution of styrene/maleic anhydride~ ocliliecl product, the reactioll mixture turned out to be highly viscous, but the reaction was still continued to procccd with the clellyclla~ioll.
The resultant reaction mixture was poured illtO 5 liters of l s methanol, washed with meth~mol and clriecl. The copolymer tllus obtained was clissolved in xylene to t`orm 10% by weight ol` the solution, the Brookl`ie}cl viscosity of which was measured at 25C.
Tlle result was 7500 cPs, which lecl to the juclgelllent that a paltially Cl'OSSIillkeCl plOdUCt hacl bC`CIl fOllllC`CI CIUl'illg the COUI'SC` of reaction.

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Example.s I to 34 ancl Compnl ative Examples 1 to 35 The presc~ e(l comp()llellts [Al ancl ~Bl as givcn in T~ablcs 6 7 .~ olllpol~ olllpli!;illg ll~c l`o~ clmillo group-moclifiecl proclllct or maleic nci(l-rnodifiecl proclllct or s unmoclifieci product were clry blended, sufficiently clried and thoroughly kneacled with venting by the use of a NVC single screw extruder (produce(l by Nnkatani Machine Co, Ltd.). Subsequently, test pieces were mokled t`rom the kneaded product by using an IS ] 00 EN injection molcling machine (produced by Toshiba Machine Co., o Ltd.).

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By tllc use ol` tl~e test picccs thlls s3btaille~cl, va~iolls pllysical propertics o~ the resin composition were evalllntecl by the -following Illclllo(ls.
( I ) Izocl impacli test: ~accol(ling to J~S-K-7 1 10 s [Conditiollsl tempelatule = 23C ancl -3()C witll a notch, n=5.
(2) Sulface impact test: Automatic falling weight impact test was conducted to cletelmine the ~racture conl~igulation an(l fracture energy.
[Metllod] An injection molclc(l pklte (gO x 80 x 3 mm) was lo fixe~l to a test piece supporting plate having 2 inclles hole so that the center of the molcled plate is positionecl at the center of the supporting plate. A displacement curve vs. applied force was obtained under the ~ollo~,ving conclition ancl the area until the (lisplaccment point at which the applie(l force suddellly clecreasecl was obtained to determine 15 fiacture energy [J]. The t`ract~lre configuration was also observed atter the end of the test to evaluate with the symbols: ductile (D)-->
somewhat dLIctile ~D') -) somcwhat brittlc (B')--> brittlc (B).
[Conditions] temperature = -IO~C, load o-f weight = 3.75 kg, falling velocity - 7.0 sn/sec., n = 5. The testing machine was RDT
20 5000 (ploduced by Reometrics Corp.).
~3) Peeling evaluation: accorcling to cross cut test ~ Method] 10() nulrlbels ol checkers eacll having 1 mm squale werc macle by notching with a sharp bla(le inside the square of 10 x 10 mm in the nlkl(lle of an in.jection moklecl plate (80 x 8() x 3 mm) 2~ pr()~ cc(l lln(lel a clclinitc in jcction timc ancl a ~Icl`inite filling time.
Tllcll a ccllopl~allc scll:a(lllcsivc tapc was plcssc(l agaillst Ihc cllcckc to stick itscll!all(l wn,s su(ldcllly pcclc~l tllcrcl`roln at all anglc of 45 73 2~

cleglee. Thus the residual ratio of I mm sq~lare checkers was clefined as the l~llowing t`ormllla to evaluate the peeling. The test was pel lol lllecl five ~5) times l`or cacll sarnple ancl the average value wax take2l as the average residual ratio.
S (Resiclual ratio) = (number of resiclual 1 mm square checkers)/ I ()~) (4) Appearance: Visual evaluation W.IS madei~l untavorable appearance s~lch as flow mark, r ibbed pattern an(l tiuff to designate with the symbols: O ~good), ~ (rathel bad) ancl x (bad).
The results obtained are given in Tables 8 to 11, in which the symbols *a to *m shali have the following me~lnings:
*a percentage based on the total amount of [A] and [B]
kb ratio base(l on 1()() parls by wcigllt ol` ~Al an(l IBI in total *c MBS elastomer (C223/Mitsubishi Rayon Co., Ltcl.) was added in ~n amount of 10 parts by weight based on 100 parts by weight of [A3 and [B] in total ~d accor(ling to Example 5 *e notchecl Izod impact strength (kg cm/cm) I f visual observation 20 ~g cross Cllt (number of peeled checkels/100: the nurnber of originai checkers) *1- visllal observation i cr- I in(licates tllc col~olymcr of Prcpalatioll E xamplc I, CP-2 is thc copolynlel of Pleparation Example ~ all(l so l`orth.
25 '11j UM-S in~licates the unmo(lified proclllct priOI to malcic acid grat`tillg ill Prepalatioll Exalllple 5, an(,l so l`orlll.
k Gllass fibcl (()3 MA 4()~C/Asal-li Glass Pibel Co., l.,tcl.) was 7~

a(kle(l in .an alllollnl of 1() parts by weight t~asecl orl 10() parts by weigllt of lAI .Incl [Bl in to~
1 Twin SCICW cxtrllclel ( I EM-35/rl~osllib.l M.lellinc Co., I tcl.) was usecl to ~kl gklss fiber. The conlponents [A~, [B i ~ncl [C]
s were fed at the top theleof ~Incl tl~e glass fiber in the sicle :for kneacling togethel m 15 p~rts by weight of PE- I w~as ackle~l basecl on 100 p~rts by weight of [A~ ~an(l ~Bl in tot~ll 7 5 2 ~ 6 3 3 o O O
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Claims

WHAT IS CLAIMED IS:
(1) A thermoplastic resin composition which comprises as principal components 5 to 95% by weight of a [A] thermoplastic resin having a functional group reactive with an amino group, 95 to 5% by weight of [B] at least one polymer selected from an olefinic polymer and a styrenic polymer, the subtotal of the above [A]+[B] being 100 parts by weight, and 0.05 to 20 parts by weight of a [C] copolymer or a salt thereof, said copolymer having in a molecule thereof at least one group selected from a formanide group and an amino group, said copolymer having 20 to 99.8 mol% of the repeating unit I represented by the general formula (I); 50 to 0 mol% of the repeating unit II
represented by the general formula (II); and 60 to 0.2 mol% of the repeating unit III represented by the general formula (III) or the repeating unit IV represented by the general formula (IV) ... (I) ... (II) ... (III) ... (IV) wherein R1, R2, R5, R6 and R7, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 18 carbon atoms, an alkylcarboxyl group having 1 to 17 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms, an arylcarbonyl group having 6 to 8 carbon atoms, a halogen atom or a nitrile group; R3 and R4, independently of one another, are each a hydrogen atom, an alkyl group having I to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms or a halogen atom; R8 is absent or denotes a methylene group or an ethylene group; R9 and R 10, independently of one another, are each a hydrogen atom, an alkyl group having 1 to 6 control atoms or an aryl group having 6 to 8 carbon atoms; R11 is an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms or a polyoxyalkylene group having 4 to 30 carbon atoms; R12 is a hydrogen group or an alkyl group having 1 to 10 carbon atoms; Y is at least one kind of amino group selected from the group consisting of the general formula (V) to (VIII).
... (V) ... (VI) ... (VII) ... (VIII) where R13 in the general formula (VII) and (VIII) is an alkyl group having 1 to 6 carbon atoms; R1 to R13 may be the same or different among the repeating units; and n is an integer from 1 to 10.

(2) The composition according to Claim 1 wherein the [A]
thermoplastic resin having a functional group reactive with an amino group has at least one bond selected from carbonate bond, ester bond, amide bond and ether bond.