CA1263979A

CA1263979A - Fire-retardant l-butene resin composition

Info

Publication number: CA1263979A
Application number: CA000454316A
Authority: CA
Inventors: Motoyasu Yusawa; Chikara Igarashi
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Petrochemical Industries Ltd
Priority date: 1983-05-17
Filing date: 1984-05-15
Publication date: 1989-12-19
Also published as: JPH0437097B2; DE3473465D1; ATE36547T1; US4983742A; JPS59210963A; EP0131358A1; EP0131358B1

Abstract

Abstract of the Disclosure:
A fire retardant 1-butene resin composition composed of (A) 100 parts by weight of a 1-butene polymer or copolymer containing 0 to 20 mole% of an olefin with 2 to 20 carbon atoms other than 1-butene as a comonomer, (B) 110 to 1,000 parts by weight of an inorganic hydroxide selected from the group consisting of magnesium hydroxide and aluminum hydroxide, and (C) 10 to 150 parts by weight of a graft-modi-fied olefin resin resulting from grafting of an unsatu-rated carboxylic acid or its functional derivative to a polymer or copolymer of an olefin having 2 to 8 carbon atoms.

Description

~3'3'~9 67566-~7s This .invention relates to a fire retardant 1-butene resin composition having excellent improved properties and comprising an inorganic hydroxide such as magnesium hydroxide as a fire retardant. The composition overcomes troubles, such as a deterioration in mechanical properties and moldability, which are due to the incorporation of the fire retardantr and has excellent fire retardancy and improv~d mechanical properties and moldability. Moreover, the composition of this invention can advantageously overcome the 1-butene resin's inherent disadvan-tage that the speed of its crystal transition to a stable crystalline state is low.
More speclfically, this invention relates to a fire-retardant l-butene resin compositlon composed of ~A) 100 parts by weight o:E a 1-butene polymer or copolymer conkaining 0 to 20 mole % of an olefin with 2 to 20 carbon atoms other than 1-butene as a comonomer, (B~ 110 to 1,000 parts by weight of an lnorganic hydroxide selected from the group consisting of magnesium hydroxlde and aluminum hydroxide, and ~C) 10 to 150 parts by weight of a graft-modified olefin resin resulting from grafting of an unsaturated carboxy~ic acid having 3 to 10 carbon atoms or its fun~tional derivative ~o a polymer or copolymer of an olefin having 2 to 8 carbon atoms.
~:~ Crystalline 1-butene resins have excellent creep characterist~cs, streng~h against deformation, and heat resistance, and by taking advantage of these properties, research and development work has been undertaken on their utiliæation in ~3~3~9 melt-shaped articl.es and other applications. As wlth the other olefin resins, l-butene resins have the defect of readily burning.
Attempts have been made to impart. flre retardancy to the l-butene resins by incorporating fire 1~

,.~

~ ~ ~3~3'~9 retardants, but have not proved to be entirely successful.
Or when such ~ire retardants are added ln amounts which serve for fire-retarding purposes, there is a substantial deleterious effect on the desirable properties of the l-butene resins.
For example, Japanese Patent Publication No.
5254/1973 (corresponding to British Patent No. 1,280,248) discloses that an olefin resin is rendered fire-retardant by incorporating antimony oxide, ammonium fluoroborate and a halogen-containing compound such as tris(2,3-dibromo-propyl~phosphate and chlorinated paraffin. The resin composition provided by this patent document exhibit improved fire retardancy. But when it burns, the amount of smoke is large and toxic gases are generated.
The use of an inorganic hydroxide fire retardant such as magnesium hydroxide free from such a trouble is also known. For example, Japanese Patent Publication No.
10890/1982 proposed a magnesium hydroxide powder having a bulk density of 0.35 to 0.70 g/cc, a specific surface area of 10 to 30 m2/g and a ratio of the thickness of crystal-lites in a direction perpendicular to the (1103 plane to that in the (001) plane in its crystal lattice of from 1.7 to 2.7 as a filler useful for rendering plastics fire-retar-dant. This patent document states that the magnesium hydroxide powder is used preferably after it is surface-treated with a higher fatty acid or its salt, or a silane coupling agent, and it is possible to provide plastics having fire retardancy and good mechanical properties and moldability.
This patent document states that the plastics include rubbers and thermosetting plastics, but thermo~
plastic resins are particularly suitable, and it exempli-fies polybutene along with many other resins. But it does not give any actual example of incorporating such a fire retardant in polybutene. ~aturally~ therefore, this patent document fails to suggest or disclose the 3~37 overcoming of the l-butene resin's inherent disadvantage that the speed of its crystal transition to a stable crystalline state is low.
As will be experimentally shown in Comparative Examples given hereinbelow, when the magnesium hydroxide fire retardant is incorporated in the 1-butene resin in an amount capable of rendering it fire-retardant, the mecha-nical properties of the resin are not entirely satisfac-tory~ Moreover, the crystal transition speed of the l-bu~ene resin remains low.
It is known that when solidified from its molten state, the l-butene resin initially assumes a pseudostable II type (tetragonal system transformation), and then slowly passes into a stable I type (hexagonal system transformation) over several days. In the state of the II
type, a shaped article o the l-butene resin is soft. If, thereore, the shaped article undergoes deEormation by handling, storage, transportation, or otherwise while it is of the II type and is transformed in this state to the I type, the deformation remains in the article to make it commercially valueless. Accordingly, the handling of the shaped article before complete transition to the I type is troublesome, and much expertise and labor are being - used in trying to prevent the remaining of such undesir-25~ able deformation.
~ he present inventors have made extensive in-vestigations in order to de~elop a fire-retardant 1-butene resin composition having excellent fire retardancy and improved mechanical properties and moldability whi}e solving the aforesaid technical problem inherent to the l~butene resin. These investigations have led to the discovery that a l-butene resin composition composed of (A? the l-butene polymer or copolymer, (B) the inorganic hydroxide and (C) the graft-modified olefin resin, which may further contain additives, is a new type of fire-retardant l-butene resin composition which has excellent 9t'~

fire retardancy, improved mechanical properties and mold-ability and an increased crystal transition speed witho~t such troubles as a deterioration in mechanisal properties and moldability which are ascribable to the incorporation of the fire retardant (B) selected from magnesium hydr-oxide and aluminum hydroxide.
It is an object of this invention therefore to provide a new type of fire-retardant l-butene resin com-position having improved properties.
The above and other objects and advantages of this invention will become more apparent from the follow-ing description.
The l-butene resin (A) utilized in this in-vention is a l-butene polymer or copolymer containing 0 to 20 mole% of an olefin with 2 to 20 carbon atoms other than l-butene as a comonomer. Examples of the olefin having 2 to 20 carbon atoms used as a comonomer include ethylene, propylene, 4-methyl-1-pentene, l-hexene, l-octene, 1-decene and l-octadecene. They may be used either singly or in combination.
Preferably, the l-butene polymer or copolymer (A) has a melt flow rate (MFR), determined by ASTM D
1238N, of from 0.1 to 50 g/10 min., and a degree of crystallinity of 20 to 65%. The degree of crystallinity is determined by the X-ray method. Specifically, the l-butene polymer or copolymer is melted at 200C for 10 minutes, and then pressed by a cold press at 30C under a pressure of 50 kg/cm2.G to prepare a 1 mm test speci-menO The test specimen is left to stand at room temper-ature for 10 days. The diffraction pattern of the speci-men is then measured by X-rays (Cu-Ra) at a diffraction angle 2~ in the range of 3 to 40~. The crystallinity is calculated in accordance with the following equation.
Crystallinity = Crystal peak aea x 10 Halo + crystal area peak area ~ ~i3''3~9 Among the l-butene polymer or copolymers, a random copolymer of l-butene is preferred. In particular, copolymers of l-butene with olefins having 2 to 8 carbon atoms, which have an MFR, determined by ASTM D1238N, of 0.1 to 50 g/10 min. and a degree of crystallinity of from 20 to 55%, are preferred.
The inorganic hydroxide (B) selected from the group consisting of magnesium hydroxide and aluminum hydroxide is preferably in the form of a fine powder ; 10 having an average particle size of about 50 millimicrons to about 5 microns, more preferably 200 millimicrons to 2 microns. The fine powder of the inorganic hydroxide may be in the shape of a petal, a plate or a needle. If the average particle size is too small below about 50 milli-microns, the particles tend to agglomerate into secondary particles. The agglomerated particles are likely to exist as such in the final ~esin composition and may adver~ely affect the mechanical strength of the resin composi~ion.
Accordingly, the average particle size should be at least about 50 millimicrons. On the other hand, if the average particle si~e is too large above about 5 microns, the fire~retarding effect and mechanical properties of the final resin composition are deteriorated, and its mol~-abili~y is also adversely affected. Moreover, there is a deleterious effect on the surface luster and smoothness of a molded article produced from the resulting composition.
Hence, the inorganic hydroxide used in this invention preferably has an average particle size within the abovP-specified range.
The amount of the inorganic hydroxide (B) in the composition of this invention is 110 to 1,000 parts by weight per 100 parts by weight of the l-butene polymer or copolymer (A). If it is too small below 110 parts by weight, it is difficult to impart a satisfactory fire-3~ retarding effect. If it is too large beyond 1,000 parts ~; ~ by weigh~, there is a reduction in mechanical strengths ~i3~3~7~
~ 6 such as tensile strength and impact strength, and adverse effects are exerted also on the moldability of the result-ing composition and the appearance of molded articles therefrom. Accordingly, the amount of the component (B~
is properly selected within the above-specified range.
The graft-modified olefin resin used in this invention is an essential component in combination with the component (A) and the component (C) described above.
The combination of these three components in the amounts specified contributes to the imparting of excellent fire retardancy, mechanical properties and moldability to the resin composition of this invention and to the increasing of the crystal transition speed of the l-butene polymer or copolymer.
The graft-modified olefin resin (C) results from grafting of an unsaturaked carboxylic acid or its func-tional derivative to a polymer or copolymer of an olefin with 2 to 8 cabon atoms. The graft-modified olefirl resin can be produced by methods known per se, or is commer-cially available. For example, it can be produced by grafting an unsaturated carboxylic acid or its functional derivative as a grafting monomer to a polymer or copolymer of an olefin with 2 to 8 carbon atoms as a trunk polymer in the presence or absence of a solvent and in the pre-sence or absence of a radical initiator. Another copoly-merizable monomer such as styrene may be present in the reaction system. The grafting reaction can be carried out at a temperature of, for example, about 100 to about 200C. Examples of the solvent that can be used in this reaction are hexane, heptane, octane, decalin, benzene, toluene and xylene.
Examples of the radical initiators that can be used include organic peroxides and peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl per-oxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(peroxybenzoate)hexyne-3, 1,4-bis~tert-butylperoxy-: :

`:

~ ~ ~i3 ~ h ~3 -- 7isopropyl)benzene, lauroyl peroxide, tert-butyl per-~ce~ate7 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,

2,5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate~ cumyl perpivalate and tert-butyl perdiethylacetate, and azo compounds such as azobisisobutyronitrile and dimethyl-asodiisobutyrate.
Examples of the polymer or copolymer of an olefin with 2 to 8 carbon atoms used as trunk polymer include low-density polyethylene, high-density poly-ethylene, polypropylene, poly-l-butene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/l-butene copolymer, propylene/l-butene copolymer and mixtures of these. Among them, polypropylene is preferred because it results in a resin composition having excell~nt mechanical properteis.
The unsaturat~d carboxylic acid or its func-tional derivative used as the grafting monomer may pre-ferably be an unsaturated carboxylic acid having 3 to 10carbon atoms, or its functional derivative such as its anhydride or lower alkyl ester. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic an-hydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, 3-cyclohexenecarboxylic acid, 4-cyclohexenedicarboxylic acid, 5-norbornene-2,3-di-carboxylic acid, and lower alkyl esters of these acids.
Alpha, beta-unsaturated dicarboxylic acids and their functional derivatives, particularly maleic anhydride, are more preferred.
The amount of the grafting monomer grafted to the trunk polymer may be properly selected. Preferably, about 0.01 to about 10 parts by weight of the unsaturated carboxylic acid or is functional derivative is grafted per 1~0 parts by weight of the polymer or copolymer of an olefin having 2 to 8 carbon atomsO

~i39~3 The amount of the graft-modified olefin resin (C) in the composition of this invention is 10 to 150 parts by weight per 100 parts by weight of the l-butene polymer or copolymer (A). If it is too small below 10 5 parts by weight, it is difficult to impart excellent improved properties to the composition of this invention by the combination of the component (C) with the com-ponents (A) and (B~. If, on the other hand, the amount is too large beyond 150 parts, the mechanical properties of the composition of the invention are deteriorated.
Accordingly, the amount of component (C) is selected within the above-specified range.
The amount of the graft-modified olefin resin (C) can be properly varied depending upon the kind of the trunk polymer and the amount of the grafting monomer yrafted. Preferably, lt is about 3 to about 35~ by weight based on the total weight of the components (~), (B) and (C) .
As required, the composition of this invention may further contain additives in addition the three es-sential components (A), (B) and (C).
An example of the additives is an olefin resin other than the l-butene polymer or copolymer (A). For example, it is a polymer or copolymer of an olefin having 2 to 6 carbon atoms such as low density polyethylene, high density polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene-propylene copolymer and propylene-l-butene copolymer. One or more of these polymers or co-polymers may be used. The amount of the additional poly-mer or copolymer may be any suitable one which does notadversely affect the improved properties of the compo-sition of this invention. For example, it is up to about 200 parts by weight, preferably up to about 150 parts by weight, per 100 parts by weight of the l-butene polymer or copolymer ~A)~ If the additional resin is used in an excessive amount, ~he effect of adding the graft~modified ~:
:

:- ~

3q3t~t3 olefin resin ~C) is reduced.
Other examples of the additives include weather-ability stabilizers, heat stabilizers, slip agents, nucleatin~ agents, coloing agents (pigments, dyes), and lubricants. Specific examples of the other additives include heat-stabilizers of the phenol, sulfur, amine or phosphorus type, such as p-hydroxyanisole, 3-methyl-4-isopropyl phenol, ascorbic acid, 2-tert-butyl-4,6-dimethyl phenol,2,6-di-tert-butyl phenol, propyl gallate, styre-nated mixed cresol, 2-(1-methyl cyclohexyl)-4,6-dimethyl phenol, 2,4-di-tert-butyl-5-methyl phenol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butyl-4-hydroxy-phenol, 4-hydroxymethyl-2,6-di-tert-butyl phenol, 2,4,6-tri-tert-hutyl phenol, 2,6-di-tert-butyl-~-dimethylamino-p-cresol, 1,1-bis(4-hydroxyphenyl)cyclohexane, octyl gallate, nordihydroguaiaretic acid, dodecyl gallate, butylated bisphenol A, 4,4'-methylene-bis(2-tert-butyl-6-methyl phenol), 2,2'-methylene-bis(4-methyl-6-tert-butyl phenol), 4,4'-thio-bis(2-methyl-6-tert-butyl phenol), 4,4'-thio-bis(3-methyl-6-tert-butyl phenol), 2,2'-thio-bis(4-methyl-6-tert-butyl phenol~, 2,2~ methylene-bis(4-ethyl-6-tert-butyl phenol~, n-stearoyl-p-aminophenol, 4,4'-butylidene-bis(6-tert-butyl-m-cresol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, 2,2'-methylene-bis(4-methyl-6-cyclohexyl phenol), 4,4'-bis(2,6-di-tert-butyl phenol)l 2~2'-dihydroxy-3,3'-di(~-methylcyclohexyl)-5,5'-dimethyl dimethyl diphenyl methane, 4~4'-methylene-bis(2,6-di-tert-butyl phenol), D,L-~-tecopherol, 2,2'-methylene--bisl6-~-methylbenzyl-p-cresol), 2,6-bis(2'-hydroxy-3'-tert-butyl-5'-methylbenzyl)-4-rnethyl phenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butyl phenyl)-propionate, 1,1,3-tris(2-methyl-4~hydroxy-5-tert-butyl ;~ phenyl~butane, 4,4'-butylidene-bis(3-methyl-tert-butyl phenol), 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis(octylthio)-1,3,5-triazine, 2,4-bis(4-hydroxy-3,5-di-tert-butylanilino)-6-(n-octylthio~-1,3,5-triazine, .

1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(lH,31~,5H)-trione, tris(3,5-di-tert-butyl-4-hydroxy)phosphate, 1,3,5-~rimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzyl benzene, 1,3,5-tris-(3'~5'-di-tert-butyl-4'-hydroxybenzyl)~s-triazine-2/4,6-(lH,3H,5H)-trione, di-stearyl(4-hydroxy-3-methyl-5-tert-butyl-benzyl~malonate, ethyleneglycol-bis[3,5-bis(3'-tert-butyl-4'-hydroxyphenyl)]butyrate, tris[2-ter~-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-b~tyl phenyl)-5-methylphenyl]phosphite, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, phenol condensation products, hindered phenol derivative, 3,5-di-tert-butyl-4-hydroxybenzyl phosphoric acid, di-stearyl ester, 2-mercaptobenzimidazole, phenothiazine, N,N'-diphenylthiourea, tetramethy} thiuram disulfide, N-oxy-diethylene 2-benzothiazolylsulfenamide, N-cyclohexyl-~-benzothiazolylsulfenamide, cyclohexylamine salt ~f ~-mercaptobenzothiazole, N,N-diisopropyl-2-benzothiazelyl-sulfenamide, 2-N,N-diethylthiocarbamoyl thiobenzothiazole, tetraethylthiuram disulfide, dibenzothiazyl disulfide, zinc diethyldithiocarbamate, zinc ethylphenyldithio-carbamate, zinc di-n-butyldithiocarbamate, dilaulyl thiodipropionate, dilauryl thiodi-l-l'-methylbutyrate, dimyristyl-3,3'-thiodipropionate, lauryl stearylthiodi-propionate, distearyl thiodipropionate, distearyl thio-dibutyrate, penta(erythrythyl-tetra-~-mercaptolauryl)-propionate, phenyl-~-naphthylamine, phenyl-~-naphthyl-amine, oxanilide, hydrazine derivatives, 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, triphenyl phoshite, 2-ethylhexyl acid phosphate, dilauryl phosphite, tri-iso-octyl phosphite, tris(2,4-di-tert-butylphenyl)phos-: phite, trilauryl phosphite, trilauryl di-thiophosphite, trilauryl trithiophosphite, trinonylphenyl phosphite, distearyl pentaerythritol diphosphite, tris(mixed mono : 35 and dinonyl phenyl)phosphite, trioctadecyl phosphite, :

3~

1,1,3-tris(2-methyl-4-di-tridecyl phosphite~5-tert-butyl-phenyl butane and diphenyl phosphite, 4,4'-butylidene-bis(3-methyl-6-butyl)tridecyl phosphite, and 4,4'-butyl-idene-bis(3-methyl-6-tert-butyl-phenyl-d.itridecyl)phos-phite; weatherability stabilizers such as 2,4-dihydroxy-benzophenone, 2-hydroxy-5-chlorobenzophenone~ 2-(2'-hydroxy-5'-methylphenyl~benzotriazole, 2--hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-

4'-chlorobenzophenone, p-tert-butyl-phenyl salicylate, 2,2'-dihydroxy-4,4'-dimethoxyben~ophenone, ethyl-2-cyono-3,3-diphenyl acrylate 2-hydroxy-4-benzyloxybenzophenone, 2~(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chloro-benzotriazole, 2-t2'-hydroxy-3',5'-di-tert-butyl-phenyl)-lS benzotriazole, 2-(2'-hydroxy-4'-tert-octoxyphenyl)benzo-traizole, p-octyl phenyl salicylate, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-~2'-hydroxy-3'-tert-butyl-5'-hexyl phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-hexyl phenyl)benzotriazole, 2-(2' hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzo-triazole, 2-ethyl-2'-ethoxy-5'-tert-butyl-N,N'-diphenyl oxamide, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxy benzoate, 3,5-di-tert-butyl-4-hydroxy myristyl benzoate, bis(2,2 7 ,6,6'-tetramethyl-4-piperidinejsebacate, 12,2'-thio-bis(4-tert-octyl phenolate)]-tert-butyl-amino nickel (II), nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoyl phospholic acid monoethyl ester, nickel salt of bis(3,5-di-tert-butyl-4-hydroxybenzoyl phosphoric acid monooctyl ester, nickel salt of 2,2'~thio-bist4,4'-alkylphenol), dimethyl succinate[2-(4-hydroxy-2,2,6~6-tetramethyl-1-piperizyl)ethanol]polycondensate, poIy~{6-(1,1,3,3-tetramethylbutyl)imino}-1,3,5 triazine-2,4-diyl-{4-12,2,6,6-tetramethyl piperizyl~imino}hexamethylene], : 35 and 2-hydroxy-4-dodecyloxybenzophenone; lubricants and slip agents, for example aliphatic hydrocarbons such as ~3~9 paraffin wax, polyethylene wax and polypropylene wax, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, maryaric acid, stearic acid, arachidic acid and behenic acid, metal salts of the higher

5 fatty acids such as the lithium, calcium, sodium, magnesium and potassium salts, aliphatic alcohols such as palmityl alcohol, cetyl alcohol and stearyl alcohol, aliphatic amides such as capramide, caprylamide, capric amide, lauric amide, myristic amide, palmitic amide, stearamide, esters between fatty acids and alcohols, and fluorine-containing compounds such as fluoroalkyl-carboxylic acids or the metal salts thereof, and fluoro-alkylsulfonic acids or the metal salts thereof; antiblock-ing agents such as silica, talc, clay and diatomaceous earth; antistatic agents such as lauryldiethanolamine, dioxyethylene laurylamine, N,N-bis(2-hydroxyethyl)-stearylamine, stearyl mono~lyceride, sodium ditridecyl sulfosuccinate, sorbitan fatty esters, a mixture of an N,N-bis(2-hydroxyethyl)alkylamine and an n-alkyl alcohol silica, polyoxyethylene laurylamine, and stearyl di-ethanolamine monostearate; antihaze agents such as gly-ceric acid esters, sorbitan acid esters, acylsarcosines, polyoxyethylene glycerine monostearate and diethanolamine;
coloring agents such as titanium dioxide, calcium carbo-nate, carbon blackr lead suboxide, cadmium red, vermil-lion, red iron oxide, brown iron oxide, barium yellow, titanium yellow, virdian, ultramarine, cobalt blue, cobalt violet, azo pigments, nitroso lake pigments, nitro lake pigments, basic dye lakes, phthalocyanine pigments, organic fluorescent pigments and pearl essence; inorganic or organic fillers such as calcium carbonate, clay, talc, silica, diatomaceous earth, siliceous sand, mica powder, slate flour, alumina white, wood flour, hard rubber dust and cellulose powder; HCl absorbers such as calcium oxide, lithium stearate, sodium stearate, an epoxidation product ~: of octyl stearate, hydrotalcite, calcium stearate, zinc ~i3~

stearate and calcium 12-hydroxystearate; and nucleating agents such as organic ca~boxylic acids or the metal salts thereof and benzylidene sorbitol or the derivatives there-of.
S The amounts of these additives may be properly chosen so long as they do not substantially affect the excellen~ properties of the 1-butene resin. For example, the amounts may be about 0.005 to about 5% by weight for the weatherability stabilizers, about 0~05 to about 5% by weight for ~he heat stabilizers, about 0.1 to about 5% by weight for the slip agents or lubricants, about 0.05 to about 1~ by weight for the nucleating agents, about 0.05 to about 5% by weight for the HCl absorbers, about 0.1 to about 5% by weight for the coloring agents, about 0.01 to about 5% by weight for the antiblocking agents, about 0.1 to about 5~ by weight for the antihaze a~ents, about 0.1 to about 5~ by weight for the antistatic agents, and about 0.1 to about 20% by welqht for the fillers, all based on the weight of the l-butene polymer.
The fire-retardant composition of this invention can be prepared by mixing the components lA), tB) and (Cl with or without the additives described above~ Any known means can be used for the mixing operation, and the choice depends upon whether a homogeneous composition can be formed. For example, there may be used (i) a method in which the components (A), (B) and (C) are simultaneously melt-kneaded, (ii) a method in which the components (B~
and (C) are melt-kneaded in advance to form pellets and then the pellets are melt-kneaded with the component (A), ; 30 and (iii) a method in which the components (A) and melt-kneaded in advance to form pellets, and the pellets are then melt-kneaded with the component ~C). The additives may be incorporated at any desired stage before the for-mation of a final blend, and for example, they may be 3S pre-mixed with the components (A), (B), and/or (C)O The melt-kneading temperature may be any suitable temperature ;: ~
-:

~i3~3~9 at which the components become molten, and is, for ex-ample, about 180C to about 290C. Mixing devices that can be used may be any known devices such as a single-screw extruder, a multiscrew extruder, a Banbury mixer, or a kneader.
The composition of this invention ~ay be in any form suitable for producing melt-shaped articles, such as a powder, particles and pellets, or may also be in the form of a melt-shaped article. Melt-shaping of the com-position may be performed at a temperature of, for ex-ample, about 180 to about 280C, and a pressure of, for example, about 0.5 to about 300 kg/cm2.G.
According to this invention, the drastic dete-rioration in the mechanical properties of a l-butene resin, which is ascribable to the incorporation of fire retardants, can be prevented, and the speed of crystal-lization oE the l-butene resin can be increased.
The following examplles illustrate the present invention more specifially. It should be understood that these examples should not be construed as limiting the scope of the invention.
Examples 1 to 9 and Comparative Examples 1 to 3 In each run, a l-butene resin, magnesium hydr-oxide, maleinized polypropylene (amount of maleic an-hydride grafted 1 wt~) and optionally another olefin resinwere mixed in the proportions indicated in Table 1, and 0.2~ by weight of tetrakis~methylene-3-(3,5-di-tert-butyl-hydroxyphenyl propionate]methane, 0.2% by weight of 3,5 di-tert-butyl-4-hydroxytoluene and 0.5~ by weight of calcium stearate were added. They were thoroughly mixed with stirring by a Henschel mixer, and then kneaded by a Banbury filler mixer at 220C for 5 minutes. The kneaded mixture was pulverized, and press-formed at 200C and 50 kg/cm2 for 10 minutes to form a sheet having a thickness of 3 mm. Five rectangular test specimens having a width of 1.52 cm and a length of 12~7 cm and f ive test specimens ~ ~ ~3~3~

for a tensile test were cut out from the sheet. Using these test specimens, a fire retarding test in accordance with UL 94V and a tensile test by an Xnstron tenstile tester were conductedO Furthermore, ~he crystal tran-sition speed of the specimens were measured by X raydiffraction.
The results are shown in Table 2.
It is seen that the 1-butene resin compositions of this invention are excellent particularly in fire retardancy, mechanical properties and crystal transition speed.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fire-retardant 1-butene resin composition composed of (A) 100 parts by weight of a 1-butene polymer or copolymer containing 0 to 20 mole % of an olefin with 2 to 20 carbon atoms other than 1-butene as a comonomer, (B) 110 to 1,003 parts by weight of an inorganic hydroxide selected from the group consisting of magnesium hydroxide and aluminum hydroxide, and (C) 10 to 150 parts by weight of a graft-modified olefin resin resulting from grafting of an unsaturated carboxylic acid having 3 to 10 carbon atoms or its functional derivative to a polymer or copolymer of an olefin having 2 to 8 carbon atoms.

2. A composition according to claim 1 wherein the 1-butene polymer or copolymer (A) has a melt flow rate, determined by ASTM
D 1238N, of from 0.1 to 50 g/10 min.

3. A composition according to claim 1 wherein the 1-butene polymer or copolymer (A) has a degree of crystallinity of from 20 to 65%.

4. A composition according to claim 1 wherein the inorganic hydroxide (B) has an average particle size of from about 50 millimicrons to about 5 microns.

5. A composition according to claim 1 wherein the graft-modified olefin resin (C) results from grafting of about 0.01 to about 10 parts by weight of the unsaturated carboxylic acid or its functional derivative to 100 parts by weight of the olefin polymer or copolymer.

6. A composition according to claim 1 wherein the amount of the graft-modified olefin resin (C) is about 3 to about 25% by weight based on the total weight of the components (A), (B) and (C).

7. A composition according to claim 1 which further comprises up to about 200 parts by weight of an olefin resin other than the 1-butene polymer or copolymer per 100 parts by weight of the 1-butene polymer or copolymer.

8. A composition according to claim 1 which further comprises at least one additive selected from the group consisting of weatherability stabilizers, heat stabilizers, slip agents, nucleating agents, coloring agents and lubricants.

9. A composition according to claim 7 which further comprises at least one additive selected from the group consisting of weatherability stabilizers, heat stabilizers, slip agents, nucleating agents, coloring agents and lubricants.

10. A composition according to claim 1, 7 or 8 which is in the form of a melt-shaped article.

11. A composition according to claim 9 which is in the form of a melt-shaped article.