CA2006868A1 - Two-solution acrylic adhesive compound - Google Patents
Two-solution acrylic adhesive compoundInfo
- Publication number
- CA2006868A1 CA2006868A1 CA002006868A CA2006868A CA2006868A1 CA 2006868 A1 CA2006868 A1 CA 2006868A1 CA 002006868 A CA002006868 A CA 002006868A CA 2006868 A CA2006868 A CA 2006868A CA 2006868 A1 CA2006868 A1 CA 2006868A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- solution
- styrene
- acrylate
- acrylic adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/906—Multipackage compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/939—Multipackage system
Abstract
ABSTRACT
A two-solution acrylic adhesive composition, consisting of a solution A, in which the following ingredients [1][3] are dissolved and mixed as nec-essary ingredients, in the proportions mentioned below, and a solution B, in which the following ingredients [4]-[6] are dissolved and mixed as necessary ingredients, in the proportions mentioned below:
Solution A
(1) Chlorosulfonated polyethylene 12.5-35wt%
(2) At least one (meth) acrylate selected from a group consisting of (meth)acrylic acid, (meth)arylate, di(met)acrylate, and (meth)acrylates with hydroxyl, glycidyl, or amino groups 50-85wt%
(3) Organic peroxide 0.2-10 wt%
Solution B
(4) Butadiene-acrylonitrile copolymer elastormer 10-25 wt %
(5) At least one (meth) acrylate selected from a group consisting of (meth) acrylic acid, (meth) acrylate, di(meth) acrylate, and (meth) acrylates with hydroxyl, glycidyl, or amino groups 40-90 wt %
(6) Curing accelerator consisting of an amine-aldehyde conden-sate 1-20 wt %
A two-solution acrylic adhesive composition, consisting of a solution A, in which the following ingredients [1][3] are dissolved and mixed as nec-essary ingredients, in the proportions mentioned below, and a solution B, in which the following ingredients [4]-[6] are dissolved and mixed as necessary ingredients, in the proportions mentioned below:
Solution A
(1) Chlorosulfonated polyethylene 12.5-35wt%
(2) At least one (meth) acrylate selected from a group consisting of (meth)acrylic acid, (meth)arylate, di(met)acrylate, and (meth)acrylates with hydroxyl, glycidyl, or amino groups 50-85wt%
(3) Organic peroxide 0.2-10 wt%
Solution B
(4) Butadiene-acrylonitrile copolymer elastormer 10-25 wt %
(5) At least one (meth) acrylate selected from a group consisting of (meth) acrylic acid, (meth) acrylate, di(meth) acrylate, and (meth) acrylates with hydroxyl, glycidyl, or amino groups 40-90 wt %
(6) Curing accelerator consisting of an amine-aldehyde conden-sate 1-20 wt %
Description
ZOOfi868 TWO-SOLUTION ACRYLIC ADHESIVE COMPOUND
Two-~olu~ion acrjilc adhe~iYe~, charæterized by the fa~:t~ th~t they con-ario~ clfistomer ingredients d~solYed in rcactive acryiic monomer~ and ~re curct with redox catalys~, ha~e been wldely ~ed fior some tLme. Exam-ple~ of such two-~olution acrylic adhe~i~es are those shown in P~iblic Patent Di~closure ~3ulleti~ Nos. 49-132119, 51-7040, and 55-129470. A~ can be seen in these e.~ample~, the general method of stic~ing two ob~ect~ together is that a (meth) acryla~e ~3olution contai~lng a chloro~fon~l:ed polyethyiene and a polymerlzation initiator ~main adhe~lve~ i~ applled to one of the ob~ects ~Ofi~i8 and a curing accelerator sllch as an amlne-aldehyde condensate ls applled to the other one; the two suriace~ to which these soll~Hons have been applled are then put into cont ct wlth each other. In thls type of adhesive, 3ince the acryllc monomer ls gra~-polymerized onto the chlorosulfonated polyethylene ln the curing process, the advantages are obtained that the shrinkage rate is comparatively small. and there ls eYcelle~t hea~ reslstance. 0~ the other hand, however, since a large quantity of chlorine ls present ln the chlorosul-fonated polyethylene structure. there is the problem that when the adhesive ls used on metal surfaces, and the parts to whlch the adhesiYe was applied are left under a high temperature for a long perlod, the aforementioned chlorLne ls e3iminated and corrodes the metal suriaces. Moreover, there is the prob-lem th~, slnce the viscositles of curing æcelerators containlng amlne-aldehyde condensates, etc., are low, the curing accelerator penetrates lnto the surface to whlch the adhesive is applied when the o~ects to whlch the adhe-slYe is to be applied haYe porous ~urfaces, such as wood or foams, and after they are adhered together the adhesiYe strength is uneYen; moreover, since the quantity of curing æcelerator used is very sm~ll, it is difflcult to controlthe correct quantity that must be applled.
Therefore, lt has been proposed that the c~ing æcelerator solu~on be thic~ened wlth an acrylic r~ber or acrylic resln (Public Patent ~isclosure Bulle~n ~o. 61-51072~, or an eplchlorohydrin rlibber (Public Patent Dls-closure Bulletin No. 56-74165).
However, the aforemen~oned acrylic rui~bers haYe poor solutJlli~e~ ln (meth) ærylate monomers, and if the quantity compounded is increæd, a gel ~.~)n~i~ti8 3 ls ~ormed and u~i~arm m~d~ ls prevented. Moreover. the stre~gth of the adhered layers after the two solu~lons are mixed and cured ls stlll in~ufflcient.
Acryllc resins h~e good soiu~llities ln (meth)a~ryla~e monomers, but it is nece~y to compou~ld a large quan~ty of such restns ln order to obt~n the target vlsco~ d the rubber ela~clty of the adhered layers whtch ls obtatned whe~ a large quantity [of the reslnj ls compounded i~ lost, whtch is not deslrable. Moreover, the splnn~ity lof these resln~ tro~g, whlch presents a problem of workabil~
In ~dition, eplchlorohydrtn ru~ber, in ~rldition to having the ~ne problem~ a~ the aforementtoned acrylic rubber, h~ a large q~nttty of chlor~ne in lt~ molecl~le, like the chloro~ulfonated polyethylene, and ~hen it i~ expo~edto high tempera~e~ for long period~, the free chlorine corrode~ the ~dhe-~ion lnterfa~:e.
This inventlon was m~e with thl~ ~itua~on in view, and has the pur-pose of providing a t~o-solution acrylic adhesil~e composition with e2ccellent resl~tance to thermal deterioration and excellent worka~llity.
In order to accomplish this purpose, the t~o-solulion acrylic adhesiYe composition of thls invention con~s of a solution A, ln whlch the follow~ng ingredle~s ~ 3) are dissolYed and mixed as nece~ary ingredien~, in the proportion~ mentloned below, and a solution B, ln which the following lngre-dients (4)~6) are dissol~ed and mi2~ed as necessary lngredlens, ln the pro-portion~ mentioned below:
Solution A
( 1) Chlorosl~lfonated polyethylene 12.5-35 wt %
;~)0~8~i8 (2) At least one (meth)a~ryiale selected from a group cons~ng of (meth~ ærylic æld, (meth~ æryla~e, di(meth) acryi~e, and (me~ cryla~es wlth hydro~yl, glycldyl, or ~m1no groups 50~S wt Yo (3) Organ~c peroxlde 0.2-10 wt %
Sol~on B
Two-~olu~ion acrjilc adhe~iYe~, charæterized by the fa~:t~ th~t they con-ario~ clfistomer ingredients d~solYed in rcactive acryiic monomer~ and ~re curct with redox catalys~, ha~e been wldely ~ed fior some tLme. Exam-ple~ of such two-~olution acrylic adhe~i~es are those shown in P~iblic Patent Di~closure ~3ulleti~ Nos. 49-132119, 51-7040, and 55-129470. A~ can be seen in these e.~ample~, the general method of stic~ing two ob~ect~ together is that a (meth) acryla~e ~3olution contai~lng a chloro~fon~l:ed polyethyiene and a polymerlzation initiator ~main adhe~lve~ i~ applled to one of the ob~ects ~Ofi~i8 and a curing accelerator sllch as an amlne-aldehyde condensate ls applled to the other one; the two suriace~ to which these soll~Hons have been applled are then put into cont ct wlth each other. In thls type of adhesive, 3ince the acryllc monomer ls gra~-polymerized onto the chlorosulfonated polyethylene ln the curing process, the advantages are obtained that the shrinkage rate is comparatively small. and there ls eYcelle~t hea~ reslstance. 0~ the other hand, however, since a large quantity of chlorine ls present ln the chlorosul-fonated polyethylene structure. there is the problem that when the adhesive ls used on metal surfaces, and the parts to whlch the adhesiYe was applied are left under a high temperature for a long perlod, the aforementioned chlorLne ls e3iminated and corrodes the metal suriaces. Moreover, there is the prob-lem th~, slnce the viscositles of curing æcelerators containlng amlne-aldehyde condensates, etc., are low, the curing accelerator penetrates lnto the surface to whlch the adhesive is applied when the o~ects to whlch the adhe-slYe is to be applied haYe porous ~urfaces, such as wood or foams, and after they are adhered together the adhesiYe strength is uneYen; moreover, since the quantity of curing æcelerator used is very sm~ll, it is difflcult to controlthe correct quantity that must be applled.
Therefore, lt has been proposed that the c~ing æcelerator solu~on be thic~ened wlth an acrylic r~ber or acrylic resln (Public Patent ~isclosure Bulle~n ~o. 61-51072~, or an eplchlorohydrin rlibber (Public Patent Dls-closure Bulletin No. 56-74165).
However, the aforemen~oned acrylic rui~bers haYe poor solutJlli~e~ ln (meth) ærylate monomers, and if the quantity compounded is increæd, a gel ~.~)n~i~ti8 3 ls ~ormed and u~i~arm m~d~ ls prevented. Moreover. the stre~gth of the adhered layers after the two solu~lons are mixed and cured ls stlll in~ufflcient.
Acryllc resins h~e good soiu~llities ln (meth)a~ryla~e monomers, but it is nece~y to compou~ld a large quan~ty of such restns ln order to obt~n the target vlsco~ d the rubber ela~clty of the adhered layers whtch ls obtatned whe~ a large quantity [of the reslnj ls compounded i~ lost, whtch is not deslrable. Moreover, the splnn~ity lof these resln~ tro~g, whlch presents a problem of workabil~
In ~dition, eplchlorohydrtn ru~ber, in ~rldition to having the ~ne problem~ a~ the aforementtoned acrylic rubber, h~ a large q~nttty of chlor~ne in lt~ molecl~le, like the chloro~ulfonated polyethylene, and ~hen it i~ expo~edto high tempera~e~ for long period~, the free chlorine corrode~ the ~dhe-~ion lnterfa~:e.
This inventlon was m~e with thl~ ~itua~on in view, and has the pur-pose of providing a t~o-solution acrylic adhesil~e composition with e2ccellent resl~tance to thermal deterioration and excellent worka~llity.
In order to accomplish this purpose, the t~o-solulion acrylic adhesiYe composition of thls invention con~s of a solution A, ln whlch the follow~ng ingredle~s ~ 3) are dissolYed and mixed as nece~ary ingredien~, in the proportion~ mentloned below, and a solution B, ln which the following lngre-dients (4)~6) are dissol~ed and mi2~ed as necessary lngredlens, ln the pro-portion~ mentioned below:
Solution A
( 1) Chlorosl~lfonated polyethylene 12.5-35 wt %
;~)0~8~i8 (2) At least one (meth)a~ryiale selected from a group cons~ng of (meth~ ærylic æld, (meth~ æryla~e, di(meth) acryi~e, and (me~ cryla~es wlth hydro~yl, glycldyl, or ~m1no groups 50~S wt Yo (3) Organ~c peroxlde 0.2-10 wt %
Sol~on B
(4) Buladle~e-acrylonitrile copolyrner elastomer 10-25 wt Yo (5) At least one ~meth~acryla~e selected from a group cons~sting of ~me~h)acry~1c acld, ~meth)a~rylate, di(meth)acrylate, and (meth~acrylates wlth hydro~yl, glycldyl, or amino grou~s 40~0 wt ~
(6) Curlng a~celerator consl~tlng of ~ amine-aldehyde conden-~ate 1-20 ~t ~6 The in~entors performed a series of studies with the purpoæ of lmprovlng the worl~ y and thermal deteriora~on reslstance of two-sol~ion acrylic adhe 31ve compo~tions containing chloros~onated polyethylene~ ln the main adhesi~e; as a res~t, they discovered that if bul adiene asrylonitrlle 0', copolymer elastomers (NE~ are used to regulate the vlscosity of solu~ion B, and the proportions of the variols nece~ssary lngredients of solu~ons A and B
are ~imited as mentioned above, the desired purposes c~ be ~ccompll~hed, and th~s they achieved this invention. They also discovered that if spec~flc ~rrene bloc~ copolymer~ are included in at least one of the aforementioned , . . .
solutlons A and B, the spinnabllity durlng a,~plication, which was a problem prevtously, is improved, in addltion to the aforementioned effect~
Next, thls Inventlon ~rlll be explained In det~ll.
The t~ro-~olution acryllc adhesive compo~itlon of thi~ lnventton 13 com-posed of a solution A whlch has as Its neces~3ary ingredlents ~1) a chloro~-fonated polyethylene, (2) a (meth)acryla~e monomer, and (3) an orgsnic per-oxtde, and a ~3olu~on B which has a:3 Its necessa~ tngredients (4) an N13R, (5) a (meth)acrylate monomer, and (6~ an amine-aldehyde condensate.
As the chlorosuLfonated polyethylene ( 1), w~lch 13 a necessary Ingredl-ent of the aforementtoned 801utlon A, one can use any one, but those with chlorlne contents of 20~~5Yo and Mooney vlscostttes (ML 1~4, lOU(~ of about 20-100 are especlally s~table. As commerctal produs~ts of thls ktnd, ~dp~:ron (made ~y Dupont Co.), etc., are known. Moreover, the content of the chloro-sulfonated polyethylene ln solullon A must be 12.5~5 wt 9~) (abbrevlated below a~ ); a range of 20~(Y~ is e~peclally sult~ible. If the quantlty of chlorosulfonated polyethyiene is le~ than 12.5g~, lt 18 difflc~lt to obtaln a practlcal adhe~lve strength, and lf lt is greater than !~5%, the vlscoslty of 801 tio~ A become~ too hlgh, and lts misclblllty wlth solu~on B becomes poor.
A~ the (meth)acrylaie monomer (2) whlch 1~ also a nece~sary Ingredlent of ~olution A, one can u3e any o~ the following: (meth) acryllc acld, ethyl (meth)acryiate, propyl (meth)acrylate, bulyl (meth)acryla~e, i~obu~l (meth)-acrylate, 2-ethylhexyl (meth)acrylate l~n ort~ (meth)acryllc acid-2-ethylhexyl], isodecyl (meth)acrylate, la~l (meth)acrylate, stearyl (meth)acryl-ate, alkyl (meth)acrylate~ of C~ g, cyclohexyl (meth)acrylate, lsobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate l~n ort~ (meth)acrylic acid-2-hydroxyethyl~, 2-h~roxypropyl (meth)~rylate, dimethylamlnoethyl (rneth)-. * trade-mark A
~C)0~ i8 acrylate, dlmethylaminoethyl ~meth)acrylate, diethylaminoethyl (meth)acryl-ate, ethylene glycol dlmethacrylate, diethylene glycol dlmethacrylate. tetra-ethylene glycol dlmethacrylate, trimethylol propane trimethacrylate, 1,6-hexanedlol dimethacrylate, 2-methacryloyloxyethyl succlnate, 2-methacryloyl-oxyethyl phthalate, glycidyl methacrylate, dimethylamlnomethyl methacrylate, mono(2-methacryloyloxyethyl~acid phosphate, mono(2-acryloyloxyethyl)acid phosphate, tetrahydrofurfuryi metha~ryl~te, n-butoxyethyl methæryiate, methylf~bitol Im~sprfntfor ~sur~tol"'~] methærylate, methy~triglycol meth-acrylate, butanediol dimethacrylate, neopentylglycol dimethacrylate, epoxy (meth) acryiates which are adducts of epoxy compounds and (meth) acryllc æid, urethane poly(meth)acrylates, cyanoacrylates, etc. These compounds may be used indlvidually or ln combina~ons of two or more. The content of the (meth)acrylate monomer must be ln the range of 50~5%. If the (meth)-acrylate monomer content ls less than 5~Yo, the viscosity of the solution will become too hlgh, and the application workability wlll be poor; i~, on the con-trary, it is greater than 85%, the viscosity wlll become too low and the appli-cation workabllity will also be poor, as well as the proportion of the rubber ingredient becoming too low, so that a cured product with rubber elasticity is not obtalned.
Other monomers besides the aforementloned (meth)acrylate mono-mers, such as s~rene, æryionitrlle, vinyl acetate, vinyl versatate, or other vlnyi ester monomers can be added ln suitable quantities, depending on the kind of ob~ects to which the adhesive ~ to be applied. However, the quantity of such monomers added is llmited to 20~ or less of solu~ion A. That ~, lf lt is greater than 20Yo, the adhe~ive properties of the adhesive wlll be limited, ti8 and lt wtll not be able to be widely ~sed, or a separa~on phenomenon will be produced in solu~on A durlng storage ln the tube.
As the organic pero~cide (3) whlch ls also a necessary lngredient of sol~lon A, one can ~;e tertlary b~yl peroxlde, cumene hydroperoxlde, dilso-propylbenzene hydroperoxide, dl-tertlary-buiyl peroxlde, tertiary bu~l cumyl peroxide, dlcumyl peroxlde, methylethylketone peroxlde, benzoyl peroxlde, etc. These compounds can be used lndlvldually or ln comblna~ions of two or more. These organic pero~des must be contalned ln solu~on A ln a range of 0.2-10%; arange of 0.5-5% ls especlaUy s~table.
On the othcr hand, the N~R (4) which 1~ a nece~ary lngredient of solution 13 ls ~elected especi&lly for thls lnvention, ~o th&t lts misclbillty ~7rlth the (meth)acrylate solution of chloro~ulfonated polyethylene i~ good, and it does not markedly ch&nge the properties [of the adhesive], ~u~-h as adhesive strength, adhesive heat resistance, and curing rate, even when it ls used together with the chloro~ulfonated polye~ylene ln large quantltie~. The nitrile content of such NE~R ~hould be 18~5~6. Moreover, NE~R cont&lning cærboxyl, amino, &nd vlnyl group~ in thelr molec~eY m&y also be u~ed. F~r-thermore, lf a hydrogenated NE3R ls u3ed, &n adhe~ive ~th s1dll greater re:3~-tance to thermal deterloration will be obtatned. The content of the &fore-mentioned N13R in ~ol~ion B mu~t be 10-2596; a range of 12.5-2096 1~ ~ttll more de~sir~ble. If lt 19 les~ th~n 1096, the vbco~i~y of ~olutton B will be reduced, and lf lt 1~ greater than 259S, the vtxoslt3~ of ~olution B ~rlll be lncre~ed; ln either casc, the ~vork~blll~y will be poor.
The (meth)acrylate monomer (5) whlchl~aneces~aryingredientof solutlon B m2y be any of the (methlacrylate monomer~ (2) ln ~olu~on A men-tloned above. Its content must be ln the range of 4~90~6.
,lAs the c~ng a~celera~or (6) composed of an amlne-aldehyde conden-sate whlch ls a necessa~y lngredlent of solu~on B, one can ~E;e, for example, a condensate of abu~l aldehyde and an anlllne or bui~iamlne; ordlnarlly, one uses the commerclal products Accelerator ~08, Accelerator 833 (both made by E. I. Dupont de Nemours Co.), Nokusera 8 (Ou~l Shinko Ragaku Kogyo Co.l, etc. The content of the aforementlo~ed curing accelerator must be 1-80g6 of solu~on ~, a range of 2-1 5Yo ls especlally deslrable. If the aforemen-t~oned c~ing accelerator ls less than 1%, the curing when the two solu~ions are mixed wlll be slow, and s~clent adheslve strength cannot be obtalned.
Con~reræly, lf lt ls greater than 20%, the e~ccess portlon of the curlng accel-erator acts a~ a pla3ttclzer, and the adheslve strength ls reduced. Moreover, slnce the vlscoslty of the whole sol~ion B ls reduced, lts ~lform mlscl~lllty wlth solutton A become~ worse.
Furthermore, tn th~3 invention, when solulions A and B are prepared ~y ~sing the sforementloned nece~y ingredlcnts, it ~ de~rablc to make the monomer ingredients of solu~ons A and B as close to e~h other as pos:31ble.
For the degree of closeness of the aforementloned monomer lngredlent~, the dlfference tn the ~econdsry tran~tlon temperah~es Tg of the monomer copo-lymer~ of the two solutlons c~n be ~ed a~s a crlterion; lt has been fo~d that this difference ~ho~d be ~1rlthln 80C, e~peclally 65G The secondsry transl-tlon temperature of thc aforementloncd monomcr copolymer~ can be easily obt~ned from thc followlng form~a of Fox:
W 1 W2 wn lg lgl lg2 * trade-mark .~
;~)0~ i8 7 (where wl, w2, .. wn are the wel~ht frætlons of e~h monomer and T~l Tg2, T~ are the secondary transltlon temperatures of the varlous mono-mer slngle polymers).
Moreovcr, thc v~co~itie~ of the two solution~ ~hould be m~ie cloæ to eæh other by ha! ing solution A as well ~ ~olution B contain the ela~tomer NBR. That is, ~y havlng solution A contain NE~R in the range of 15% or le~, ~o that the ratio of the elastomer ingredlent content Wa of solution A and the elastomer lngredient content Wb of solutlon B ~Wa/W~ made 0.~.0 ~y welght, an adhesiYe layer with excellent s~lhesive ~trength is obtalned when a two-solution æparate type la~ihe9ive1 is applied. Furthermore, the aforemen-tioned elastomer ingredient is chloro~fonated polyethylene, N~R, or other ela~tlc sub~tances.
The two-sol1ltion acrylic adhesive composition obtained in this way may be applied ~y applylng solutions A and B separa!tely, and making the two sur-faces on which they are applied adhere, as with conventlonal two-solution acrylic adhesives. It is deslrable, however, for the two liquids to be mixed before they are used, lnsofar as is po~ble. If this is done, there is no need toconsider the balance of the two solutlons as care~ly, and not only will the applicatlon workabllity be good, but an adhesive layer can be formed which will have a high resistance to thermal deterioration, which could not be obtained prevlously. Thi~ appears to be becauEe the N~R used as a necessary ingredient does not have chlorlne in its molecular structure.
F~rthermore, the inventors discovered that if a sbrene block copoly-mer i8 added to either solution A or solution B of the two-solution acrylic aclhesive composition o~ th~ Invention, or both solutions, the splnnabillty when the a~hesive ls applled, which was a problem prevlo~31y, ls lmproved.
For the aforementioned styrene block copolymer, one can ~e, for ex~nple, styren~bu~adiene-styrene block copolymers, styrene-isoprene-styrene block copolymer~, styrene~thylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene block copolyrners, styrene-lsoprene block copolymers, styrene-ethyiene~utylene block copolymers, or styrene-ethylene-propylene block copolyrners. Especi-ally d~sirable ones are styrene-ethylene~utylene-styrene block copolymers and styrene-ethylene-~ropyiene-block copolyrners. These may be used indlvidually or in combina~ions of two or more. Furthermore, commercial * *
products of such styrene block copolymers are Kartfurek1cus and Kure~on (both made by Shell K~gaku Co.) . The qu~ntity of the aforementioned styrene bloc3~ copolyrner used should be 5-200Yo, preferably 10-140Yo, with respect to the elastomer ingredient. If the qu~ntity added ls less than 5%, the curing which improves the spinna~ility wlll be small, and lf lt ls greater than 2~0%, the viscasl~;y and thixotropy of the solution to which it ls added will become too high.
Besldes che aforementloned Ingredients of ~che two-solu~on acryllc adhe~;lve composltion of thls lnventlon, one can also add, lf de~red, suttable quantltle~ of colorlng agents, paraEin, ~llers, anti-o~idants, epo~y reslns or other chlorrine trappers, cobalt naphthenate, copper naphthenate, magne-~um naphthenate, or other metal soaps, or curlng accelerators such as dlmethyl-p-toluldlne, dlethyl-p-toluldlne, dlethanol-p-toluidlne, dllsopro-panol-~toluidlne thlourea, ethylene urea, acetylthlourea, tetramethyl thlourea, dlbu~yl thlourea~ mercaptobenz~nidazole, etc.
* trade-mark A
~00~;8 ~ I
A~ mentiolled aboYe, the two-solutlon acrylic atihesiYe compo~ition of this ln~entlon h~ good wor~abllity, ~ince it ma~ be u~sed in the two-~olL~lon ~epara~e form, a~ with conYentional adhe~iYe~, or applled after the t~o 901 tion~ are mised. FL~rthermore, the adhe~iYe layer obtalned has excellent thermal deterior~tlon re~istance; eYen when lt 1~ ~3ed in adhering metal~, corrosion of the adhered surfæes i~ ~uppre~sed, and it i~ pos~ible to pre~erre good adhesion oYer long perlods. Con equently, the two-~olution ærylic adhe-5ive compo~ltlon of th~ inYention can be used ln a ~ide range of applica~lon~, includlug not only the ~f3he~ion of construction panel~ hroom bs~ins, ~olar panels, alltomobile doar panel~, etc., but al~o the acihe~on of electrical machi-nery parts requirlng heat re~i~tance and thermal deterioration re~istance, such as ~peal~er and motor magnet~ etc.
Nextt ach~al e~amples of this lnvention wlll be explained.
First, be~ore the actual eYamples, 15 solutionsAwere prepared, as shown in Ta~le 1 below, and 15 solu~ions B were prepared, as shown in Table 2 below. The Ylscosities of the solut~ons were lnYesti~a~ed, and their states o~composition were ohserved by the naked eye. These results are shown in Tableq 1 and 2.
(rest of page blank) ~)Otj~;B
a. Composltion ~ . M~hacryllc acld b. ~pc~r~n k. ~y~oxyethyl me~hacrylah c Nlporu 1. l~t~ylene~ycol dlmethacrylate d. Zettoporu m. Cumecle hydroperD~dde e. Aayllc resln ~l~zraroldD A-30 n. 2,~dl-tcr~ary-b~yl-hydroq~none o. Vlsco~
f. Acryllc r~bcr H~lka4051 EP p. Compos~tlon sta~ll~y Eplchlorohydrln rubbcr q. Good h. Mcthyl methac~ylate r. adlcd 1. IsobuLyl mcthaaylate 8. S~aratcd ~= 5 zo--~-coo~o~) =
1~ ~ ~ 3 L~ ~ a o o ~
~0 o o ~ o, ~n l ~ l l l l l l l l o :D
1~ o o o ~ _o l o _ I l l l l l 61 ~
1~ o in ~n ~ O l l ~ _ I l l l l l l .~ :1-1~ 80 ~n _ ~ ~n ol ~n o l l l l l l l l 1~ :D
I_ _ _ _ _ _ _ _ _ _ _ ~o~ ~ ~ -~. l _ l _ l l l , __ ~ _ o :- ~
1~ in ~n __ O ~ o> ____ _ _ _ ~n o ~ o o _ o o _ ~ l ___ _ _ ~n _ _ 1~ ~o o o _ o _ ~ __ _ ~n _ _ o :~
L~ o o _ l o l o l l l l ~n l l l o 9 ~ ~o o o _ o _ _ 2 l _ _ ~n _ _ _ _ ., 9 ~ o c o _ _o _ ~1 _ _ _ ~ __ _ o :.
_ ~ o o _ _ ~ _ o l ___ _ _ _ _ o r 8 ~n o o _ _o _ a~ _--__ _ _ _ _ o 9 P~ - 13 _ = : -- =
; ZO~ 07~00 g ~ O O æ O ~ l l ~ ~ l l l , l l ~n w 8 o o _ b o __ _ _ c __ __ __ O w ~ O Io ~ æ O ~ l l l ~ l l l l l l ~ w n 20~ o b b o _ _ _ _ _ _ _ _ _ _ ~ _ w æ O _ _ _ _ æ _ _ _ _ _ _ O w 0 O . æ O _ l _ _ ~ _ l l l 1~ l co w _ O O æ O- _ __ _ _ ~ _--_ _ _ _ _ w ¦~
æ O ~ l l l æ l l l l l l ~
_ _ _ _ _ _ _ _ _ _ _ _ g O O O æ O ___ _ ~ ___ _ _ tn O w g O O ~ æ ~0 ~ O l O ~n l l l l l ~n l w 8 8 o _ ~ o ____ o ____ O __ m ~ ~ O ~ æ O _ O _ _ ~ ___~ _ _ _ w 1~ o o ~ 8 c _ ___ c _ _' _ __~
~ Ox O . æ O ~ l l l 8 l o l l l l l ~r 8 _ P ~, o o _ _ _ _, _ _ _ _ _ _ _ m ,~ . f (Actual Examples 1-10, Comparison ExampleY 1-5) The 15 kinds of solution A shown in Table 1 and the solution B shown as B3 in Table 2 were mixed rapidly in equal quantities by weight, and the workabilities of mixing with solution 8 and applying were observed, after which [these adhesives]
were used to adhere resins to each other and ~anded spec [BiC] copper plates to each other. Moreover, after leaving [these samples] at room temperature for 1 day, their tensile shear strength~ were measured (measurement temperature: 20C, pulling speed: 3mm/min).
Furthermore, the~e adhered bodies were left for 2 month~ at 120C, after which the temperature was returned to 20C and the tensile shear strengths were measured.
These results are shown in Table 3 below.
B
l~lol~l I
01~101~1 ~ l ~ ~ O ~ ~ I
~ ~ _ _ ~ I
' ~_ From these re~ults, it can be seen ~hat the actual examplea in which solution~
A with a chlorosulfonated polyethylene content of 12.5-35~ were used, or the actual examples in which ~ome of solution A was replaced with nitrile rubber, had excellent ~tates of composition, miscibility with solution R and applicability, adhesive strength, and resistance to thermal deterioration.
(Actual Examples 11-19, Comparison Examples 6-11) The 16 kinds of solution B shown in Table 2 and the solution A shown as A3 in Table 1 were mLxed rapidly in equal quantities by weLght, and the workabilities of mixing with solution A and applying were observed, after which [these adhesives]
were used to adhere re~ins to each other and sanded spec copper plates to each other. Moreover, after leaving [these samples] at room temperature for 1 day, their ten~ile shear strengths were measured (mea~urement temperature: 20C, pulling speed: 3 mm/min).
Furthermore, these adhered bodies were left for 2 month~ at 120C, after which the temperature was returned to 20C and the tensile ~hear strengths were measured.
These results are shown Ln Table 4 below.
'' ~3 ~1~
R ~
From these re3ults, it can be seen that the actual examples in which solutions B with an NBR content of 10-25% and butylaldehyde-aniline condensate content~ of 1-20% were used had excellent states of compo3ition, miscibility with solution A and applicability, adhesive strength, and resi~tance to thermal deterioration.
(Actual Examples 20-25, Comparison Examples 12, 13) Using the combination~ of solutions A and B ~hown in Table 5 below, adhesion of resins to each other and sanded spec copper plates to each other was performed.
Moreover, the ca3e in which solutions A and B were used unmixed (solution A applied to one of the objects and solution A and an equal quantity of solution B applied to the other ob~ect, after which the surfaces to which they were applied were stuck together) and the case in which they were used after being mixed (equal weight~ of solutlon~ A and B mixed for 30 seconds, and the whole solution confirmed to have a uniform green color, after which the adhesion wa~ performed rapidly) were used in the mea~urement of the tensile shear adhe~ive force. The measurement~ were performed with a number n=5 for adhered objects under the ~ame condition~. The~e results are shown in Table 5 below.
~2 ~J1 ~, ~ 3 .~ r . =
r 3 ~ r L D L L_ ~ _ o ~ J~ ~ ~ o o _ ~ 2 ~3 8 _ ~ 8 1~ ~ o _ D O 1 1--~ ~ !~ ~ ~5t a~ _ ~ 1~ K a;
L _ _ _ _ _ _ _ _ _ _ ~ I ¦~
~ ~ ~ o~ o 3 _ ~n w a~ ~i; ~ 31 g ~ ~ ~n ~ ~ _ o ~ o ~ ~ I
, ~ ~ ~3 ~B ~ o K w _ i!~; K l !~ ~ ~o ~ ~ s~ ~ o ~ ~ ;~; ~
L_ _ _ _ _ _ _ _ _ _ _ ~' _ _ _ $ _ ~ r cn W _ ~i _ 3 l ~ = = = _ = _ = = = = = a~
` ?
'~:
From these results, it can be seen that when solutions A and B are used without mixing, those in which the ratio W8/Wb of the elastomer ingredient contents in solutions A and B i8 in the range 0.5-3.0 had comparatively small scattering of the adhesive strength, and whsn solution~ A and B were mixed before use, their adhesive strengths are high and the scattering ~mall whatever the ratios of the elastomer compositions of sOlutiOnB A and B are.
(Actual Examples 26-38) Fir~t, as shown in Table 6 below, ~olutions A and B were prepared ~uch that the copolymer compositions had (meth)acrylate monomer part~ with various glass transition temperature~. The secondary transition temperature of the various compositions (T8A, TgB) were obtained by calculating according to the method described above. In this calculation, since the quantity of the di-(meth)acrylate monomer u~ed is ordinarily small, it was ignored, and the secondary transition temperature~ were obtained by assuming that the other ingredients of BolUtionB A and B have no Qffects on the glass transition temperatures of the (meth)acrylate monomer copolymers.
'' T3 L~
~:
D m z ~ ¦
. L l ..................... ~ ~ 1~ ~ L~
_ _ o o ~n u _ o _ _ _ o _ _ ~D _ _ _ a~ ,-l l o o ~n o l o l u l l l l ~ l l l o >
_ _ o o a u _ o _ _ _ _ _ _ u _ _ _ a~ :~ zi l l o o ul u u tn l l l l l o ~ l l u ~n :D _ _ _ O O O O O O = ___ O ~ æ O _ _ O æ o~ ¦~
l l o o u u l o l l l l o ~ tn l l l o ~
_ _ o r u u _ o _ _ _ _ ;~; _ _ _ _ _ ~ 2 _ o u _ r o~ u _ _ _ u _ o _ _ ~ _ ~ _ _ ~
o u l o l o ~n l l l l l l l ~J l l u l W
o ~n _ r _ u u _ _ _ _ _ _ ~ ~ _ _ u _ x z;
o u _ r _ u _ _ _ _ _ _ _ o ~ o _ _ _ w o o u l o l o ~n l ul l l l U l ~ l ~n l l _ S
o u~ l J~ l ~ l l l l o l u l ~: l u o ~n I o l _ l l l l l l l ~:
o _ _ o _ _ _ _ _ _ _ _ u~ _ _ _ _ o _ E:~ _ ^. `i - 22 -Next, the various solutions A and B shown in Table 6 above were selected as shown in Table 7 below, and ~esins and sanded spec copper plates were each adhered to each other. In the adhe~ion, in the case in which the solution~ A and B were used without being mixed and the ca~e in which they were used after b0ing mixed, as in Actual Examples 20-25, the tensile shear strengths were compared. The measurements were performed under the same conditions as in Actual Examples 20-25.
These results are shown in Table 7 below.
~' ~ ~ ~ ~ `. ~ o 8 w 8 2- X _ ~ ~ ~ ~ ~ ~ ~ ~ w 3 ~ ~ l ti 8 ~ - ~ ~ o $ w 5~ 2- a~ l _~ _ _ _ æ--~ ~ tD----¦ ¦~
~ ~ O ~ ~ O~ 0 3 ~O ~ O l _ _ _ _ _ _ _ _ _ _ I
_ _ _ _ ~ _ ~3 o m _ :1~ o, I
~ _ _ _ _ _ _ __ _ _ ~ I
L~ ~ ~ ~ _ O~ ~ ~ ~ u~ :~ ~ ~ I
~o a ~ ~ ~ o W ~ 1 ~ ~ I
æ
æ ~ ~ _ ~ ~ ~3 ~3--:1. o x a 8 ~-- X ~ ___ l ~ ~ ~; L o ~ g ~ W ~ i~ ~ I
~ ~ æ _ _ 8 _ ~ ~ _=
.A 3 -- 24 From these result~, it can be seen that when solutions A and B are used without mixing, the scattering of the adhesive ~trength i8 smaller, the smaller the difference i~ between the aecondary transition temperature~ TgA and TgB of the monomer composition copolymers of solutions A and B, and that when solution~ A and B are mixed before use, the scatter of the adhesive strength is small regardless of the difference between TgA and T
(Actual Example~ 39-50, Comparison Esamples 14, 15~
Solutions A and B shown in Tables 1 and 2 were selected according to Table 8 below, and adhesive compositions with different rations of the total elastomer quantity to the quantity of chlorosulfonated polyethylene in the adhesive composition, when the solutions A and B were used in equal quantities, were prepared. [These adhesives] were used to adhere resins to each other and sanded spec copper plates to each other; after leaving [the~e ~amples] at room temperature for 1 day, their tensile shear strengths were measuredO Furthermore, these adhered bodie~ were left for 2 months at 120C, after which the temperature was returned to 20C and the tensile shear ~trengths were measured; their resistance~ to thermal deterioration were compared. Moreover, after letting the adhered bodies cure for 3 days at room temperature after adhesion, their impact strengths were measured.
The~e results are shown in Table 8 below.
B
~l ~ i ~
J~ _ ~ ~} ol O O~ O ~n ~y o o 2 _ a _ ~ _ ~ ~ o _ w o ~ ~> o o~ ~n O~ ~ 8 _ ~ o _ !~! o ~g 2 ~
_ _ _ _ r _ o o _ _ o ------~ I lo ~ _ 1~> _ r _ _ o o 1~ o o 3 ~;
~ ~ ~ ~n ~ ;~- _ o `J w ~n i~; :~ ~1 ~- ~- _ à~ a~ i~ ~3 O O w o ~ ~ ;!~; 3 1 ~ _ ~ ~ % ~ O æ w O ~ ~ ~
o) o ~ ~ ~ ~ ~ o o w n ~n ~ ~ I
__ ~n ~ ~ ~ ~ o o o w o æ ~ ~
_ __ ~ - _ O O- O W O ~ _ ~ I
.p I~ O Y~ ~ O~ _ u~ O æ _ 0 _ 11 _ _ _ L~ _ O O O _ O _ _ ~ ~
_ ~ _ _ u~ ~ _ _ _ ~ ~n ~' .1 ~17 - 2 6 From these reaults, it can be seen that the combinationa of ~olutions A and B in which the ratio of the total elastomer ingredient to the quantity of chlorosulfonated polyethylene was 28.5-160 wt % had excellent adhesive strengths, resistances to thermal deterioration, and impact strengthQ, and that these properties were better with the mixed adhesion than with the non-mixed adhesion.
(Actual Examples 51-64, Comparison Examples 16-19) First, solutions A and B were prepared a~ ~hown in Table~ 9 and 10 below. The thixottropy) coefficients and spinnabilities of the various aolution~ were mea~ured.
The thixo coefficients were obtained by mea3uring the empirical visco~ity with two revolutions ~2 and the empirical viscosity with 20 revolution~ ~20 at 20~C,using a type B viscometer, and taking their ratio ~2/~20 The spinnability was obtained by pulling a glass rod from a container containing a solution A or B and checking the ease with which the thread of the adhe~ive was cut and the spinning time, etc.;
those ~olutions which were easy to cut are ~hown as 0, those which were somewhat difficult to cut ac ~, and tho~e which could be pulled to a great degree as X.
*
Q v~ r o ~ z o ~ o ~ ~ o c~
I b L ~ ~
O _ ~ ~ _ _ o ., _ ~ _ ~ _ __ a = 6~ 3~
O :g ~ O . O = ~ l l . l l ~ ~
O o~ ~} ~ 8 _ o ~ l ~n ~n æ l ~ ~ l l O ~
O u- g ~ O O- -O ~ = 1~
O ~ ~ _ O r O 1~ _ O _ i~; _ 1;1 __ _ ~ ~
D C !~ 1~ . = = l o l ~ l _ l l l a~ ii~
O = ~ g = 0-~ l O l ~ l Y l l l ~ ~-r O ~g O O O l l ~ ~
x _ ~ ~! _ ~ _ _ _ _ _ _ _ _ _ _ _ ~ ~
~ = = = = = = = = = ~ = ~
~ ~ -- 2 8 ~ r-- = ~
Q 1 ~ x ~ Z o--~--co O ~ 3: G ~ l I IL ~ F
O _ _ 8 o _ o o m .~ _ S _ _ _ _ _ _ ., S~
O _ 8 8 _ _ m o o ~ ~ m __ _ _ __ ~ m O b g g _ b h h r~ _ i~ _ __ _-- _ m ~
O J. 8 ~ o o o o ~) _ h _-- __ _ _ _ ~
O IV N ~ 2 O C O O _ O _ ~ __ _ C 8 x _ ~1 _ m o c o o .~ _ 8 __ _ c _, _ ;j O o _ _ 'ti o ~ h h ~ _ C _ " ____ m ~ t ~ tl Moreover, the spinnabilities of mixtures of the various solutions A shown in Table 9 and the solution B26 ~hown in Table 10, at a 1/1 weight ratio, mixed by hand for 30 second~, and mixtures of the various solutions B shown in Table 10 and the solution A25 shown in Table 9, mixed by hand in the ~ame way, wera measured, and these results are shown in Tables 11 and 12.
In addition, using these mixtures of solutions A and B, resins were adhered to each other and sandblasted spec copper plates wera adhered to each other; after curing for 1 day at room temperatura, their tensile shear strengths were measured.
These results are also shown in Tables 11 and 12 below.
~s~
8 O ~ 3 l B 1~
l f : --~o ~ ~ I
~ o æ I
are ~imited as mentioned above, the desired purposes c~ be ~ccompll~hed, and th~s they achieved this invention. They also discovered that if spec~flc ~rrene bloc~ copolymer~ are included in at least one of the aforementioned , . . .
solutlons A and B, the spinnabllity durlng a,~plication, which was a problem prevtously, is improved, in addltion to the aforementioned effect~
Next, thls Inventlon ~rlll be explained In det~ll.
The t~ro-~olution acryllc adhesive compo~itlon of thi~ lnventton 13 com-posed of a solution A whlch has as Its neces~3ary ingredlents ~1) a chloro~-fonated polyethylene, (2) a (meth)acryla~e monomer, and (3) an orgsnic per-oxtde, and a ~3olu~on B which has a:3 Its necessa~ tngredients (4) an N13R, (5) a (meth)acrylate monomer, and (6~ an amine-aldehyde condensate.
As the chlorosuLfonated polyethylene ( 1), w~lch 13 a necessary Ingredl-ent of the aforementtoned 801utlon A, one can use any one, but those with chlorlne contents of 20~~5Yo and Mooney vlscostttes (ML 1~4, lOU(~ of about 20-100 are especlally s~table. As commerctal produs~ts of thls ktnd, ~dp~:ron (made ~y Dupont Co.), etc., are known. Moreover, the content of the chloro-sulfonated polyethylene ln solullon A must be 12.5~5 wt 9~) (abbrevlated below a~ ); a range of 20~(Y~ is e~peclally sult~ible. If the quantlty of chlorosulfonated polyethyiene is le~ than 12.5g~, lt 18 difflc~lt to obtaln a practlcal adhe~lve strength, and lf lt is greater than !~5%, the vlscoslty of 801 tio~ A become~ too hlgh, and lts misclblllty wlth solu~on B becomes poor.
A~ the (meth)acrylaie monomer (2) whlch 1~ also a nece~sary Ingredlent of ~olution A, one can u3e any o~ the following: (meth) acryllc acld, ethyl (meth)acryiate, propyl (meth)acrylate, bulyl (meth)acryla~e, i~obu~l (meth)-acrylate, 2-ethylhexyl (meth)acrylate l~n ort~ (meth)acryllc acid-2-ethylhexyl], isodecyl (meth)acrylate, la~l (meth)acrylate, stearyl (meth)acryl-ate, alkyl (meth)acrylate~ of C~ g, cyclohexyl (meth)acrylate, lsobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate l~n ort~ (meth)acrylic acid-2-hydroxyethyl~, 2-h~roxypropyl (meth)~rylate, dimethylamlnoethyl (rneth)-. * trade-mark A
~C)0~ i8 acrylate, dlmethylaminoethyl ~meth)acrylate, diethylaminoethyl (meth)acryl-ate, ethylene glycol dlmethacrylate, diethylene glycol dlmethacrylate. tetra-ethylene glycol dlmethacrylate, trimethylol propane trimethacrylate, 1,6-hexanedlol dimethacrylate, 2-methacryloyloxyethyl succlnate, 2-methacryloyl-oxyethyl phthalate, glycidyl methacrylate, dimethylamlnomethyl methacrylate, mono(2-methacryloyloxyethyl~acid phosphate, mono(2-acryloyloxyethyl)acid phosphate, tetrahydrofurfuryi metha~ryl~te, n-butoxyethyl methæryiate, methylf~bitol Im~sprfntfor ~sur~tol"'~] methærylate, methy~triglycol meth-acrylate, butanediol dimethacrylate, neopentylglycol dimethacrylate, epoxy (meth) acryiates which are adducts of epoxy compounds and (meth) acryllc æid, urethane poly(meth)acrylates, cyanoacrylates, etc. These compounds may be used indlvidually or ln combina~ons of two or more. The content of the (meth)acrylate monomer must be ln the range of 50~5%. If the (meth)-acrylate monomer content ls less than 5~Yo, the viscosity of the solution will become too hlgh, and the application workability wlll be poor; i~, on the con-trary, it is greater than 85%, the viscosity wlll become too low and the appli-cation workabllity will also be poor, as well as the proportion of the rubber ingredient becoming too low, so that a cured product with rubber elasticity is not obtalned.
Other monomers besides the aforementloned (meth)acrylate mono-mers, such as s~rene, æryionitrlle, vinyl acetate, vinyl versatate, or other vlnyi ester monomers can be added ln suitable quantities, depending on the kind of ob~ects to which the adhesive ~ to be applied. However, the quantity of such monomers added is llmited to 20~ or less of solu~ion A. That ~, lf lt is greater than 20Yo, the adhe~ive properties of the adhesive wlll be limited, ti8 and lt wtll not be able to be widely ~sed, or a separa~on phenomenon will be produced in solu~on A durlng storage ln the tube.
As the organic pero~cide (3) whlch ls also a necessary lngredient of sol~lon A, one can ~;e tertlary b~yl peroxlde, cumene hydroperoxlde, dilso-propylbenzene hydroperoxide, dl-tertlary-buiyl peroxlde, tertiary bu~l cumyl peroxide, dlcumyl peroxlde, methylethylketone peroxlde, benzoyl peroxlde, etc. These compounds can be used lndlvldually or ln comblna~ions of two or more. These organic pero~des must be contalned ln solu~on A ln a range of 0.2-10%; arange of 0.5-5% ls especlaUy s~table.
On the othcr hand, the N~R (4) which 1~ a nece~ary lngredient of solution 13 ls ~elected especi&lly for thls lnvention, ~o th&t lts misclbillty ~7rlth the (meth)acrylate solution of chloro~ulfonated polyethylene i~ good, and it does not markedly ch&nge the properties [of the adhesive], ~u~-h as adhesive strength, adhesive heat resistance, and curing rate, even when it ls used together with the chloro~ulfonated polye~ylene ln large quantltie~. The nitrile content of such NE~R ~hould be 18~5~6. Moreover, NE~R cont&lning cærboxyl, amino, &nd vlnyl group~ in thelr molec~eY m&y also be u~ed. F~r-thermore, lf a hydrogenated NE3R ls u3ed, &n adhe~ive ~th s1dll greater re:3~-tance to thermal deterloration will be obtatned. The content of the &fore-mentioned N13R in ~ol~ion B mu~t be 10-2596; a range of 12.5-2096 1~ ~ttll more de~sir~ble. If lt 19 les~ th~n 1096, the vbco~i~y of ~olutton B will be reduced, and lf lt 1~ greater than 259S, the vtxoslt3~ of ~olution B ~rlll be lncre~ed; ln either casc, the ~vork~blll~y will be poor.
The (meth)acrylate monomer (5) whlchl~aneces~aryingredientof solutlon B m2y be any of the (methlacrylate monomer~ (2) ln ~olu~on A men-tloned above. Its content must be ln the range of 4~90~6.
,lAs the c~ng a~celera~or (6) composed of an amlne-aldehyde conden-sate whlch ls a necessa~y lngredlent of solu~on B, one can ~E;e, for example, a condensate of abu~l aldehyde and an anlllne or bui~iamlne; ordlnarlly, one uses the commerclal products Accelerator ~08, Accelerator 833 (both made by E. I. Dupont de Nemours Co.), Nokusera 8 (Ou~l Shinko Ragaku Kogyo Co.l, etc. The content of the aforementlo~ed curing accelerator must be 1-80g6 of solu~on ~, a range of 2-1 5Yo ls especlally deslrable. If the aforemen-t~oned c~ing accelerator ls less than 1%, the curing when the two solu~ions are mixed wlll be slow, and s~clent adheslve strength cannot be obtalned.
Con~reræly, lf lt ls greater than 20%, the e~ccess portlon of the curlng accel-erator acts a~ a pla3ttclzer, and the adheslve strength ls reduced. Moreover, slnce the vlscoslty of the whole sol~ion B ls reduced, lts ~lform mlscl~lllty wlth solutton A become~ worse.
Furthermore, tn th~3 invention, when solulions A and B are prepared ~y ~sing the sforementloned nece~y ingredlcnts, it ~ de~rablc to make the monomer ingredients of solu~ons A and B as close to e~h other as pos:31ble.
For the degree of closeness of the aforementloned monomer lngredlent~, the dlfference tn the ~econdsry tran~tlon temperah~es Tg of the monomer copo-lymer~ of the two solutlons c~n be ~ed a~s a crlterion; lt has been fo~d that this difference ~ho~d be ~1rlthln 80C, e~peclally 65G The secondsry transl-tlon temperature of thc aforementloncd monomcr copolymer~ can be easily obt~ned from thc followlng form~a of Fox:
W 1 W2 wn lg lgl lg2 * trade-mark .~
;~)0~ i8 7 (where wl, w2, .. wn are the wel~ht frætlons of e~h monomer and T~l Tg2, T~ are the secondary transltlon temperatures of the varlous mono-mer slngle polymers).
Moreovcr, thc v~co~itie~ of the two solution~ ~hould be m~ie cloæ to eæh other by ha! ing solution A as well ~ ~olution B contain the ela~tomer NBR. That is, ~y havlng solution A contain NE~R in the range of 15% or le~, ~o that the ratio of the elastomer ingredlent content Wa of solution A and the elastomer lngredient content Wb of solutlon B ~Wa/W~ made 0.~.0 ~y welght, an adhesiYe layer with excellent s~lhesive ~trength is obtalned when a two-solution æparate type la~ihe9ive1 is applied. Furthermore, the aforemen-tioned elastomer ingredient is chloro~fonated polyethylene, N~R, or other ela~tlc sub~tances.
The two-sol1ltion acrylic adhesive composition obtained in this way may be applied ~y applylng solutions A and B separa!tely, and making the two sur-faces on which they are applied adhere, as with conventlonal two-solution acrylic adhesives. It is deslrable, however, for the two liquids to be mixed before they are used, lnsofar as is po~ble. If this is done, there is no need toconsider the balance of the two solutlons as care~ly, and not only will the applicatlon workabllity be good, but an adhesive layer can be formed which will have a high resistance to thermal deterioration, which could not be obtained prevlously. Thi~ appears to be becauEe the N~R used as a necessary ingredient does not have chlorlne in its molecular structure.
F~rthermore, the inventors discovered that if a sbrene block copoly-mer i8 added to either solution A or solution B of the two-solution acrylic aclhesive composition o~ th~ Invention, or both solutions, the splnnabillty when the a~hesive ls applled, which was a problem prevlo~31y, ls lmproved.
For the aforementioned styrene block copolymer, one can ~e, for ex~nple, styren~bu~adiene-styrene block copolymers, styrene-isoprene-styrene block copolymer~, styrene~thylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene block copolyrners, styrene-lsoprene block copolymers, styrene-ethyiene~utylene block copolymers, or styrene-ethylene-propylene block copolyrners. Especi-ally d~sirable ones are styrene-ethylene~utylene-styrene block copolymers and styrene-ethylene-~ropyiene-block copolyrners. These may be used indlvidually or in combina~ions of two or more. Furthermore, commercial * *
products of such styrene block copolymers are Kartfurek1cus and Kure~on (both made by Shell K~gaku Co.) . The qu~ntity of the aforementioned styrene bloc3~ copolyrner used should be 5-200Yo, preferably 10-140Yo, with respect to the elastomer ingredient. If the qu~ntity added ls less than 5%, the curing which improves the spinna~ility wlll be small, and lf lt ls greater than 2~0%, the viscasl~;y and thixotropy of the solution to which it ls added will become too high.
Besldes che aforementloned Ingredients of ~che two-solu~on acryllc adhe~;lve composltion of thls lnventlon, one can also add, lf de~red, suttable quantltle~ of colorlng agents, paraEin, ~llers, anti-o~idants, epo~y reslns or other chlorrine trappers, cobalt naphthenate, copper naphthenate, magne-~um naphthenate, or other metal soaps, or curlng accelerators such as dlmethyl-p-toluldlne, dlethyl-p-toluldlne, dlethanol-p-toluidlne, dllsopro-panol-~toluidlne thlourea, ethylene urea, acetylthlourea, tetramethyl thlourea, dlbu~yl thlourea~ mercaptobenz~nidazole, etc.
* trade-mark A
~00~;8 ~ I
A~ mentiolled aboYe, the two-solutlon acrylic atihesiYe compo~ition of this ln~entlon h~ good wor~abllity, ~ince it ma~ be u~sed in the two-~olL~lon ~epara~e form, a~ with conYentional adhe~iYe~, or applled after the t~o 901 tion~ are mised. FL~rthermore, the adhe~iYe layer obtalned has excellent thermal deterior~tlon re~istance; eYen when lt 1~ ~3ed in adhering metal~, corrosion of the adhered surfæes i~ ~uppre~sed, and it i~ pos~ible to pre~erre good adhesion oYer long perlods. Con equently, the two-~olution ærylic adhe-5ive compo~ltlon of th~ inYention can be used ln a ~ide range of applica~lon~, includlug not only the ~f3he~ion of construction panel~ hroom bs~ins, ~olar panels, alltomobile doar panel~, etc., but al~o the acihe~on of electrical machi-nery parts requirlng heat re~i~tance and thermal deterioration re~istance, such as ~peal~er and motor magnet~ etc.
Nextt ach~al e~amples of this lnvention wlll be explained.
First, be~ore the actual eYamples, 15 solutionsAwere prepared, as shown in Ta~le 1 below, and 15 solu~ions B were prepared, as shown in Table 2 below. The Ylscosities of the solut~ons were lnYesti~a~ed, and their states o~composition were ohserved by the naked eye. These results are shown in Tableq 1 and 2.
(rest of page blank) ~)Otj~;B
a. Composltion ~ . M~hacryllc acld b. ~pc~r~n k. ~y~oxyethyl me~hacrylah c Nlporu 1. l~t~ylene~ycol dlmethacrylate d. Zettoporu m. Cumecle hydroperD~dde e. Aayllc resln ~l~zraroldD A-30 n. 2,~dl-tcr~ary-b~yl-hydroq~none o. Vlsco~
f. Acryllc r~bcr H~lka4051 EP p. Compos~tlon sta~ll~y Eplchlorohydrln rubbcr q. Good h. Mcthyl methac~ylate r. adlcd 1. IsobuLyl mcthaaylate 8. S~aratcd ~= 5 zo--~-coo~o~) =
1~ ~ ~ 3 L~ ~ a o o ~
~0 o o ~ o, ~n l ~ l l l l l l l l o :D
1~ o o o ~ _o l o _ I l l l l l 61 ~
1~ o in ~n ~ O l l ~ _ I l l l l l l .~ :1-1~ 80 ~n _ ~ ~n ol ~n o l l l l l l l l 1~ :D
I_ _ _ _ _ _ _ _ _ _ _ ~o~ ~ ~ -~. l _ l _ l l l , __ ~ _ o :- ~
1~ in ~n __ O ~ o> ____ _ _ _ ~n o ~ o o _ o o _ ~ l ___ _ _ ~n _ _ 1~ ~o o o _ o _ ~ __ _ ~n _ _ o :~
L~ o o _ l o l o l l l l ~n l l l o 9 ~ ~o o o _ o _ _ 2 l _ _ ~n _ _ _ _ ., 9 ~ o c o _ _o _ ~1 _ _ _ ~ __ _ o :.
_ ~ o o _ _ ~ _ o l ___ _ _ _ _ o r 8 ~n o o _ _o _ a~ _--__ _ _ _ _ o 9 P~ - 13 _ = : -- =
; ZO~ 07~00 g ~ O O æ O ~ l l ~ ~ l l l , l l ~n w 8 o o _ b o __ _ _ c __ __ __ O w ~ O Io ~ æ O ~ l l l ~ l l l l l l ~ w n 20~ o b b o _ _ _ _ _ _ _ _ _ _ ~ _ w æ O _ _ _ _ æ _ _ _ _ _ _ O w 0 O . æ O _ l _ _ ~ _ l l l 1~ l co w _ O O æ O- _ __ _ _ ~ _--_ _ _ _ _ w ¦~
æ O ~ l l l æ l l l l l l ~
_ _ _ _ _ _ _ _ _ _ _ _ g O O O æ O ___ _ ~ ___ _ _ tn O w g O O ~ æ ~0 ~ O l O ~n l l l l l ~n l w 8 8 o _ ~ o ____ o ____ O __ m ~ ~ O ~ æ O _ O _ _ ~ ___~ _ _ _ w 1~ o o ~ 8 c _ ___ c _ _' _ __~
~ Ox O . æ O ~ l l l 8 l o l l l l l ~r 8 _ P ~, o o _ _ _ _, _ _ _ _ _ _ _ m ,~ . f (Actual Examples 1-10, Comparison ExampleY 1-5) The 15 kinds of solution A shown in Table 1 and the solution B shown as B3 in Table 2 were mixed rapidly in equal quantities by weight, and the workabilities of mixing with solution 8 and applying were observed, after which [these adhesives]
were used to adhere resins to each other and ~anded spec [BiC] copper plates to each other. Moreover, after leaving [these samples] at room temperature for 1 day, their tensile shear strength~ were measured (measurement temperature: 20C, pulling speed: 3mm/min).
Furthermore, the~e adhered bodies were left for 2 month~ at 120C, after which the temperature was returned to 20C and the tensile shear strengths were measured.
These results are shown in Table 3 below.
B
l~lol~l I
01~101~1 ~ l ~ ~ O ~ ~ I
~ ~ _ _ ~ I
' ~_ From these re~ults, it can be seen ~hat the actual examplea in which solution~
A with a chlorosulfonated polyethylene content of 12.5-35~ were used, or the actual examples in which ~ome of solution A was replaced with nitrile rubber, had excellent ~tates of composition, miscibility with solution R and applicability, adhesive strength, and resistance to thermal deterioration.
(Actual Examples 11-19, Comparison Examples 6-11) The 16 kinds of solution B shown in Table 2 and the solution A shown as A3 in Table 1 were mLxed rapidly in equal quantities by weLght, and the workabilities of mixing with solution A and applying were observed, after which [these adhesives]
were used to adhere re~ins to each other and sanded spec copper plates to each other. Moreover, after leaving [these samples] at room temperature for 1 day, their ten~ile shear strengths were measured (mea~urement temperature: 20C, pulling speed: 3 mm/min).
Furthermore, these adhered bodies were left for 2 month~ at 120C, after which the temperature was returned to 20C and the tensile ~hear strengths were measured.
These results are shown Ln Table 4 below.
'' ~3 ~1~
R ~
From these re3ults, it can be seen that the actual examples in which solutions B with an NBR content of 10-25% and butylaldehyde-aniline condensate content~ of 1-20% were used had excellent states of compo3ition, miscibility with solution A and applicability, adhesive strength, and resi~tance to thermal deterioration.
(Actual Examples 20-25, Comparison Examples 12, 13) Using the combination~ of solutions A and B ~hown in Table 5 below, adhesion of resins to each other and sanded spec copper plates to each other was performed.
Moreover, the ca3e in which solutions A and B were used unmixed (solution A applied to one of the objects and solution A and an equal quantity of solution B applied to the other ob~ect, after which the surfaces to which they were applied were stuck together) and the case in which they were used after being mixed (equal weight~ of solutlon~ A and B mixed for 30 seconds, and the whole solution confirmed to have a uniform green color, after which the adhesion wa~ performed rapidly) were used in the mea~urement of the tensile shear adhe~ive force. The measurement~ were performed with a number n=5 for adhered objects under the ~ame condition~. The~e results are shown in Table 5 below.
~2 ~J1 ~, ~ 3 .~ r . =
r 3 ~ r L D L L_ ~ _ o ~ J~ ~ ~ o o _ ~ 2 ~3 8 _ ~ 8 1~ ~ o _ D O 1 1--~ ~ !~ ~ ~5t a~ _ ~ 1~ K a;
L _ _ _ _ _ _ _ _ _ _ ~ I ¦~
~ ~ ~ o~ o 3 _ ~n w a~ ~i; ~ 31 g ~ ~ ~n ~ ~ _ o ~ o ~ ~ I
, ~ ~ ~3 ~B ~ o K w _ i!~; K l !~ ~ ~o ~ ~ s~ ~ o ~ ~ ;~; ~
L_ _ _ _ _ _ _ _ _ _ _ ~' _ _ _ $ _ ~ r cn W _ ~i _ 3 l ~ = = = _ = _ = = = = = a~
` ?
'~:
From these results, it can be seen that when solutions A and B are used without mixing, those in which the ratio W8/Wb of the elastomer ingredient contents in solutions A and B i8 in the range 0.5-3.0 had comparatively small scattering of the adhesive strength, and whsn solution~ A and B were mixed before use, their adhesive strengths are high and the scattering ~mall whatever the ratios of the elastomer compositions of sOlutiOnB A and B are.
(Actual Examples 26-38) Fir~t, as shown in Table 6 below, ~olutions A and B were prepared ~uch that the copolymer compositions had (meth)acrylate monomer part~ with various glass transition temperature~. The secondary transition temperature of the various compositions (T8A, TgB) were obtained by calculating according to the method described above. In this calculation, since the quantity of the di-(meth)acrylate monomer u~ed is ordinarily small, it was ignored, and the secondary transition temperature~ were obtained by assuming that the other ingredients of BolUtionB A and B have no Qffects on the glass transition temperatures of the (meth)acrylate monomer copolymers.
'' T3 L~
~:
D m z ~ ¦
. L l ..................... ~ ~ 1~ ~ L~
_ _ o o ~n u _ o _ _ _ o _ _ ~D _ _ _ a~ ,-l l o o ~n o l o l u l l l l ~ l l l o >
_ _ o o a u _ o _ _ _ _ _ _ u _ _ _ a~ :~ zi l l o o ul u u tn l l l l l o ~ l l u ~n :D _ _ _ O O O O O O = ___ O ~ æ O _ _ O æ o~ ¦~
l l o o u u l o l l l l o ~ tn l l l o ~
_ _ o r u u _ o _ _ _ _ ;~; _ _ _ _ _ ~ 2 _ o u _ r o~ u _ _ _ u _ o _ _ ~ _ ~ _ _ ~
o u l o l o ~n l l l l l l l ~J l l u l W
o ~n _ r _ u u _ _ _ _ _ _ ~ ~ _ _ u _ x z;
o u _ r _ u _ _ _ _ _ _ _ o ~ o _ _ _ w o o u l o l o ~n l ul l l l U l ~ l ~n l l _ S
o u~ l J~ l ~ l l l l o l u l ~: l u o ~n I o l _ l l l l l l l ~:
o _ _ o _ _ _ _ _ _ _ _ u~ _ _ _ _ o _ E:~ _ ^. `i - 22 -Next, the various solutions A and B shown in Table 6 above were selected as shown in Table 7 below, and ~esins and sanded spec copper plates were each adhered to each other. In the adhe~ion, in the case in which the solution~ A and B were used without being mixed and the ca~e in which they were used after b0ing mixed, as in Actual Examples 20-25, the tensile shear strengths were compared. The measurements were performed under the same conditions as in Actual Examples 20-25.
These results are shown in Table 7 below.
~' ~ ~ ~ ~ `. ~ o 8 w 8 2- X _ ~ ~ ~ ~ ~ ~ ~ ~ w 3 ~ ~ l ti 8 ~ - ~ ~ o $ w 5~ 2- a~ l _~ _ _ _ æ--~ ~ tD----¦ ¦~
~ ~ O ~ ~ O~ 0 3 ~O ~ O l _ _ _ _ _ _ _ _ _ _ I
_ _ _ _ ~ _ ~3 o m _ :1~ o, I
~ _ _ _ _ _ _ __ _ _ ~ I
L~ ~ ~ ~ _ O~ ~ ~ ~ u~ :~ ~ ~ I
~o a ~ ~ ~ o W ~ 1 ~ ~ I
æ
æ ~ ~ _ ~ ~ ~3 ~3--:1. o x a 8 ~-- X ~ ___ l ~ ~ ~; L o ~ g ~ W ~ i~ ~ I
~ ~ æ _ _ 8 _ ~ ~ _=
.A 3 -- 24 From these result~, it can be seen that when solutions A and B are used without mixing, the scattering of the adhesive ~trength i8 smaller, the smaller the difference i~ between the aecondary transition temperature~ TgA and TgB of the monomer composition copolymers of solutions A and B, and that when solution~ A and B are mixed before use, the scatter of the adhesive strength is small regardless of the difference between TgA and T
(Actual Example~ 39-50, Comparison Esamples 14, 15~
Solutions A and B shown in Tables 1 and 2 were selected according to Table 8 below, and adhesive compositions with different rations of the total elastomer quantity to the quantity of chlorosulfonated polyethylene in the adhesive composition, when the solutions A and B were used in equal quantities, were prepared. [These adhesives] were used to adhere resins to each other and sanded spec copper plates to each other; after leaving [the~e ~amples] at room temperature for 1 day, their tensile shear strengths were measuredO Furthermore, these adhered bodie~ were left for 2 months at 120C, after which the temperature was returned to 20C and the tensile shear ~trengths were measured; their resistance~ to thermal deterioration were compared. Moreover, after letting the adhered bodies cure for 3 days at room temperature after adhesion, their impact strengths were measured.
The~e results are shown in Table 8 below.
B
~l ~ i ~
J~ _ ~ ~} ol O O~ O ~n ~y o o 2 _ a _ ~ _ ~ ~ o _ w o ~ ~> o o~ ~n O~ ~ 8 _ ~ o _ !~! o ~g 2 ~
_ _ _ _ r _ o o _ _ o ------~ I lo ~ _ 1~> _ r _ _ o o 1~ o o 3 ~;
~ ~ ~ ~n ~ ;~- _ o `J w ~n i~; :~ ~1 ~- ~- _ à~ a~ i~ ~3 O O w o ~ ~ ;!~; 3 1 ~ _ ~ ~ % ~ O æ w O ~ ~ ~
o) o ~ ~ ~ ~ ~ o o w n ~n ~ ~ I
__ ~n ~ ~ ~ ~ o o o w o æ ~ ~
_ __ ~ - _ O O- O W O ~ _ ~ I
.p I~ O Y~ ~ O~ _ u~ O æ _ 0 _ 11 _ _ _ L~ _ O O O _ O _ _ ~ ~
_ ~ _ _ u~ ~ _ _ _ ~ ~n ~' .1 ~17 - 2 6 From these reaults, it can be seen that the combinationa of ~olutions A and B in which the ratio of the total elastomer ingredient to the quantity of chlorosulfonated polyethylene was 28.5-160 wt % had excellent adhesive strengths, resistances to thermal deterioration, and impact strengthQ, and that these properties were better with the mixed adhesion than with the non-mixed adhesion.
(Actual Examples 51-64, Comparison Examples 16-19) First, solutions A and B were prepared a~ ~hown in Table~ 9 and 10 below. The thixottropy) coefficients and spinnabilities of the various aolution~ were mea~ured.
The thixo coefficients were obtained by mea3uring the empirical visco~ity with two revolutions ~2 and the empirical viscosity with 20 revolution~ ~20 at 20~C,using a type B viscometer, and taking their ratio ~2/~20 The spinnability was obtained by pulling a glass rod from a container containing a solution A or B and checking the ease with which the thread of the adhe~ive was cut and the spinning time, etc.;
those ~olutions which were easy to cut are ~hown as 0, those which were somewhat difficult to cut ac ~, and tho~e which could be pulled to a great degree as X.
*
Q v~ r o ~ z o ~ o ~ ~ o c~
I b L ~ ~
O _ ~ ~ _ _ o ., _ ~ _ ~ _ __ a = 6~ 3~
O :g ~ O . O = ~ l l . l l ~ ~
O o~ ~} ~ 8 _ o ~ l ~n ~n æ l ~ ~ l l O ~
O u- g ~ O O- -O ~ = 1~
O ~ ~ _ O r O 1~ _ O _ i~; _ 1;1 __ _ ~ ~
D C !~ 1~ . = = l o l ~ l _ l l l a~ ii~
O = ~ g = 0-~ l O l ~ l Y l l l ~ ~-r O ~g O O O l l ~ ~
x _ ~ ~! _ ~ _ _ _ _ _ _ _ _ _ _ _ ~ ~
~ = = = = = = = = = ~ = ~
~ ~ -- 2 8 ~ r-- = ~
Q 1 ~ x ~ Z o--~--co O ~ 3: G ~ l I IL ~ F
O _ _ 8 o _ o o m .~ _ S _ _ _ _ _ _ ., S~
O _ 8 8 _ _ m o o ~ ~ m __ _ _ __ ~ m O b g g _ b h h r~ _ i~ _ __ _-- _ m ~
O J. 8 ~ o o o o ~) _ h _-- __ _ _ _ ~
O IV N ~ 2 O C O O _ O _ ~ __ _ C 8 x _ ~1 _ m o c o o .~ _ 8 __ _ c _, _ ;j O o _ _ 'ti o ~ h h ~ _ C _ " ____ m ~ t ~ tl Moreover, the spinnabilities of mixtures of the various solutions A shown in Table 9 and the solution B26 ~hown in Table 10, at a 1/1 weight ratio, mixed by hand for 30 second~, and mixtures of the various solutions B shown in Table 10 and the solution A25 shown in Table 9, mixed by hand in the ~ame way, wera measured, and these results are shown in Tables 11 and 12.
In addition, using these mixtures of solutions A and B, resins were adhered to each other and sandblasted spec copper plates wera adhered to each other; after curing for 1 day at room temperatura, their tensile shear strengths were measured.
These results are also shown in Tables 11 and 12 below.
~s~
8 O ~ 3 l B 1~
l f : --~o ~ ~ I
~ o æ I
Claims (6)
1. A two-solution acrylic adhesive composition, consisting of a solution A, in which the following ingredients (1)-(3) are dissolved and mixed as nec-essary ingredients, in the proportions mentioned below. and a solution B, in which the following ingredients (4)-(6) are dissolved and mixed as necessary ingredients, in the proportions mentioned below:
Solution A
(1) Chlorosulfonated polyethylene 12.5-35 wt%
(2) At least one (meth) acrylate selected from a group consisting of (meth)acrylic acid,(meth)acrylate,di(meth)acrylate, and (meth)acrylates with hydroxyl, glycidyl, or amino groups 50-85 wt %
(3) Organic peroxide 0.2-10 wt %
Solution B
, (4) Butadiene-acrylonitrile copolymer elastomer 10-25 wt %
(5) At least one (meth)acrylate selected from a group consisting of (meth)acrylic acid, (meth)acrylate, di(meth)acrylate, and (meth) acrylates with hydroxyl, gycidyl, or amino groups 40-90 wt %
(6) Curing accelerator consisting of an amine-aldehyde conden-sate 1-20 wt %
Solution A
(1) Chlorosulfonated polyethylene 12.5-35 wt%
(2) At least one (meth) acrylate selected from a group consisting of (meth)acrylic acid,(meth)acrylate,di(meth)acrylate, and (meth)acrylates with hydroxyl, glycidyl, or amino groups 50-85 wt %
(3) Organic peroxide 0.2-10 wt %
Solution B
, (4) Butadiene-acrylonitrile copolymer elastomer 10-25 wt %
(5) At least one (meth)acrylate selected from a group consisting of (meth)acrylic acid, (meth)acrylate, di(meth)acrylate, and (meth) acrylates with hydroxyl, gycidyl, or amino groups 40-90 wt %
(6) Curing accelerator consisting of an amine-aldehyde conden-sate 1-20 wt %
2. A two-solution acrylic adhesive composition in accordance with Claim (1), in which a butadiene-acrylonitrile copolymer elastomer is contained in the aforementioned solution A, and the proportions of the elastomer content in solution A
(Wa) and the elastomer content in solution B (Wb) are such that Wa/Wb=0.5-3.0, by weight.
(Wa) and the elastomer content in solution B (Wb) are such that Wa/Wb=0.5-3.0, by weight.
3. A two-solution acrylic adhesive composition in accordance with Claim (1) or Claim (2), in which at least one of the aforementioned solutions A or B contains at least one styrene block copolymer, selected from a group including styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block co-polymers, styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-ethylene-butylene block copolymers, and styrene-ethylene-propylene block copolymers.
4. A two-solution acrylic adhesive composition in accordance with Claim (3), in which the aforementioned styrene block copolymer has the proportion of 5-200 wt% with respect to the elastomer ingredient contained in the solution A or B which contains the styrene block copolymer.
5. A two-solution acrylic adhesive composition in accordance with Claims 1, 2 or 4, in which the butadiene-acrylonitrile copolymer elastomer is a hydrogenated nitrile rubber.
6. A two-solution acrylic adhesive composition in accordance with Claim (3), in which the butadiene-acrylonitrile copolymer elastomer is a hydrogenated nitrile rubber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-331016 | 1988-12-29 | ||
| JP63331016A JPH0781115B2 (en) | 1988-12-29 | 1988-12-29 | Two-component acrylic adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2006868A1 true CA2006868A1 (en) | 1990-06-29 |
Family
ID=18238886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002006868A Abandoned CA2006868A1 (en) | 1988-12-29 | 1989-12-28 | Two-solution acrylic adhesive compound |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5059656A (en) |
| EP (1) | EP0376350A3 (en) |
| JP (1) | JPH0781115B2 (en) |
| CA (1) | CA2006868A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676540B2 (en) * | 1988-12-23 | 1997-11-17 | ノガワケミカル株式会社 | Two-component non-mixing type acrylic adhesive composition |
| IT1244842B (en) * | 1990-11-21 | 1994-09-06 | Mini Ricerca Scient Tecnolog | HIGH RESILIENCE ADHESIVE COMPOSITIONS. |
| US5286821A (en) * | 1992-03-17 | 1994-02-15 | National Starch And Chemical Investment Holding Corporation | Acrylic adhesive composition and organoboron initiator system |
| DE4328960A1 (en) * | 1993-08-27 | 1995-03-02 | Thera Ges Fuer Patente | Radical polymerization curable, low-odor (meth) acrylate preparations and their use |
| JPH07326635A (en) * | 1994-05-31 | 1995-12-12 | Hitachi Chem Co Ltd | Adhesive agent and semiconductor device |
| US6831116B2 (en) * | 1995-03-07 | 2004-12-14 | Landec Corporation | Polymeric modifying agents |
| US5650138A (en) * | 1995-03-15 | 1997-07-22 | Resler; Renee | Composition and method for applying protective coating on a nail surface |
| JP3934701B2 (en) * | 1996-03-07 | 2007-06-20 | 大倉工業株式会社 | Heat resistant acrylic adhesive composition |
| JP2000234061A (en) * | 1999-02-16 | 2000-08-29 | Okura Ind Co Ltd | Elastic curable resin composition of quick curing type |
| JP3765731B2 (en) * | 2000-04-10 | 2006-04-12 | 住友ベークライト株式会社 | Die attach paste and semiconductor device |
| US6376579B1 (en) | 2000-07-18 | 2002-04-23 | Illnois Tool Works | Low temperature curing, sag-resistant epoxy primer |
| US6602958B2 (en) * | 2001-07-10 | 2003-08-05 | Ips Corporation | Adhesives for bonding composites |
| US20050014901A1 (en) | 2001-07-10 | 2005-01-20 | Ips Corporation | Adhesive compositions for bonding and filling large assemblies |
| FR2827607B1 (en) * | 2001-07-17 | 2005-08-26 | Gti Process | PROCESS FOR POLYMERIZING VINYL MONOMERS AND / OR OLIGOMERS COMPRISING AT LEAST ONE VINYL RADICAL |
| US20070155899A1 (en) * | 2005-12-21 | 2007-07-05 | Ips Corporation | Elastic methacrylate compositions |
| US20070155879A1 (en) * | 2005-12-22 | 2007-07-05 | Ips Corporation | Adhesive compositions for bonding metals |
| JP2009046551A (en) * | 2007-08-17 | 2009-03-05 | Toray Fine Chemicals Co Ltd | Radical curable type adhesive composition |
| JP2009051944A (en) * | 2007-08-27 | 2009-03-12 | Toray Fine Chemicals Co Ltd | Radical-curable adhesive composition |
| JP2009067814A (en) * | 2007-09-10 | 2009-04-02 | Toray Fine Chemicals Co Ltd | Visible light-curable adhesive composition |
| US8323448B2 (en) * | 2007-09-26 | 2012-12-04 | Denki Kagaku Kogyo Kabushiki Kaisha | Adhesive composition and bonding method |
| JP5352094B2 (en) * | 2008-02-22 | 2013-11-27 | 電気化学工業株式会社 | Adhesive composition, bonding method, bonded body, and manufacturing method of bonded body |
| FR2973037B1 (en) * | 2011-03-25 | 2014-12-19 | Adhesifs Et Composites Polymers | STRUCTURAL ADHESIVES, PROCESS FOR THEIR PREPARATION, AND THEIR APPLICATION |
| US9757898B2 (en) | 2014-08-18 | 2017-09-12 | Lord Corporation | Method for low temperature bonding of elastomers |
| WO2019180791A1 (en) * | 2018-03-19 | 2019-09-26 | 日立化成株式会社 | Adhesive set and method for producing structure |
| JPWO2023054234A1 (en) * | 2021-09-29 | 2023-04-06 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3890407A (en) * | 1972-07-20 | 1975-06-17 | Du Pont | Novel adhesive compositions |
| US4112013A (en) * | 1975-02-21 | 1978-09-05 | E. I. Du Pont De Nemours And Company | Adhesive composition |
| US4182644A (en) * | 1975-03-27 | 1980-01-08 | E. I. Du Pont De Nemours And Company | Polymer in monomer adhesive composition and method employing same |
| US4200480A (en) * | 1976-07-14 | 1980-04-29 | Pratt & Lambert, Inc. | Adhesive joining of pipes |
| IE51059B1 (en) * | 1980-07-11 | 1986-09-17 | Loctite Corp | Butadiene toughened adhesive composition |
| JPS5896666A (en) * | 1981-12-05 | 1983-06-08 | Okura Ind Co Ltd | Two-pack type adhesive |
| US4942201A (en) * | 1988-08-29 | 1990-07-17 | Illinois Tool Works, Inc. | Adhesive for low temperature applications |
-
1988
- 1988-12-29 JP JP63331016A patent/JPH0781115B2/en not_active Expired - Lifetime
-
1989
- 1989-12-28 US US07/458,030 patent/US5059656A/en not_active Expired - Fee Related
- 1989-12-28 CA CA002006868A patent/CA2006868A1/en not_active Abandoned
- 1989-12-29 EP EP19890124145 patent/EP0376350A3/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0376350A2 (en) | 1990-07-04 |
| US5059656A (en) | 1991-10-22 |
| EP0376350A3 (en) | 1990-12-27 |
| JPH02178374A (en) | 1990-07-11 |
| JPH0781115B2 (en) | 1995-08-30 |
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