JPS63193947A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent heat-resistance, paintability, impact resistance and chemical resistance, by compounding a polyamide resin with an aromatic vinyl resin copolymerized with an imide compound of an unsaturated dicarboxylic acid. CONSTITUTION:The objective composition can be produced by compounding 5-50wt.%, especially 20-40% polyamide resin with 50-95%, especially 60$80% imide compound of an alpha,beta-unsaturated dicarboxylic acid. The aromatic vinyl resin is selected from (A) a copolymer of (A1) 70-99.9.% monomers consisting of (a1) 20-80% aromatic vinyl compound, (a2) 20-80% imide compound of an unsaturated dicarboxylic acid and (a3) 0-60% copolymerizable vinyl compound and (A2) 0.1-30% monomer containing functional group copolymerizable with the above monomers, (B) a copolymer produced by the graft copolymerization of the monomers (a1)-(a3) in the presence of a non-conjugated diene rubber polymer, (C) a mixture of a copolymer of (a1)-(a3) and the polymer B (at lest one of the polymers is copolymerized with the monomer A2), (D) a mixture of the polymer A and a non-conjugated diene rubber polymer modified with the monomer A2 and (E) a mixture of the polymers B and D.

Description

Detailed Description of the Invention: a. Industrial Application Field The present invention relates to a thermoplastic resin composition having excellent heat resistance, paintability, impact resistance, chemical resistance and solvent resistance, and particularly relates to a thermoplastic resin composition having excellent heat resistance, paintability, impact resistance, chemical resistance and solvent resistance. , an aromatic vinyl compound resin containing an imide compound of β-unsaturated dicarboxylic acid;
The present invention relates to a thermoplastic resin composition that has excellent paintability, impact resistance, and chemical resistance, particularly excellent paintability and chemical resistance.

b. Prior Art Aromatic vinyl compound thermoplastic resins modified with non-conjugated diene rubbery polymers such as acrylonitrile-ethylene propylene rubber-styrene resin (hereinafter simply referred to as AES resin) have excellent properties. It has excellent moldability and mechanical strength, as well as weather resistance and impact resistance, so it is widely used in industrial fields. In addition, by introducing α-substituted styrene or an imide compound of α, β-unsaturated dicarboxylic acid as a constituent component into these aromatic vinyl compound thermoplastic resins, we have created aromatic vinyl compound thermoplastic resins with improved heat resistance. Development is being attempted.

However, when these aromatic vinyl compound-based thermoplastic resins modified with non-conjugated diene-based rubbery polymers are painted for decorative effects and to prevent deterioration due to ultraviolet rays, problems arise due to surface adhesion and residual distortion during molding. This may have caused paint defects.

Therefore, in order to solve this problem,
In the invention described in the specification of No. 54, it is proposed to add polyamide, but in the aromatic vinyl compound resin with improved heat resistance like the present invention, when polyamide is blended, the dispersion state is poor. As a result, it has disadvantages such as a decrease in impact resistance and a phenomenon of delamination.

Also, JP-A-59-93747 and JP-A-61-
The invention described in the specification of No. 157552 suggests a blend of a rubber-modified styrene-α,β-unsaturated dicarboxylic acid imide compound resin and a polyamide, but such a blend has a high dispersibility of the polyamide. This resulted in poor impact resistance.

Problems to be Solved by the C0 Invention The present inventors have successfully dispersed polyamide in a resin containing an aromatic vinyl compound modified with a non-conjugated diene rubber and an α,β-unsaturated carboxylic acid as constituent components. To obtain a thermoplastic resin with excellent heat resistance, paintability, and impact resistance.
As a result of extensive studies, we found that by copolymerizing a monomer containing a specific functional group with an aromatic vinyl compound in a specific ratio, polyamide can be well dispersed in a thermoplastic resin, improving heat resistance, paintability, and resistance. It has been discovered that a thermoplastic resin with excellent impact resistance and chemical resistance can be obtained, and the present invention has been achieved based on this knowledge.

d9 A means for solving the problem, that is, the present invention, consists of (11(A) polyamide component 5% by weight or more to 50% by weight)
(B) A thermoplastic resin composition consisting of 95 to 50% by weight or more of an aromatic vinyl resin component copolymerized with an imide compound of an α,β-unsaturated dicarboxylic acid shown in (a) to (e) below. thing.

(b) (a) 20 to 80% by weight of aromatic vinyl compound (b)
) Imide compounds of α,β-unsaturated carboxylic acids 20~
(dl
A monomer component containing at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group that can be copolymerized with these.
A copolymer made by copolymerizing monomer components with a weight composition of 30%.

(b) In the presence of a non-conjugated diene rubbery polymer, the above (
A graft copolymer obtained by graft copolymerizing the monomer components of (a).

(c) A composition comprising the above-mentioned component (a) and component (b).

(d) a non-conjugated diene rubber-like polymer component modified with a monomer containing at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group; b) A composition consisting of an ingredient.

(E) A composition comprising the above-mentioned (B) component and (D) component.

e0 Detailed Description of the Invention (A) Polyamide Resin 8 The polyamide resin as the component (A) used in the present invention is usually represented by the following formula % formula % (wherein, X is an integer between 4 and 12). ) and a linear carboxylic acid represented by the following formula % (where y is an integer between 2 and 12), and lactams. Those produced by ring-opening polymerization can be used. Preferred examples of these polyamides include nylon 6.6, nylon 6.9, and nylon 6.10.
, nylon 6.12, nylon 6, nylon 12, nylon 1 and nylon 4.6.

Also nylon 6/6.6, nylon 6/6.10, nylon 6/12, nylon 6/6.12, nylon 6/6
．． Copolyamides such as 6/6.10 and nylon 6/6.6/12 can also be used.

Furthermore, nylon 6/6.7 (T: terephthalic acid component)
, semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine, or alicyclic diamines, polyamides obtained from meta-xylene diamine and the above-mentioned linear carboxylic acids,
Mention may be made of polyesteramides, polyetheramides and polyesteretheramides. Note that these polyamides may be used alone, or two or more types of polyamides may be used in combination. Among these, preferred polyamides include nylon 6, nylon 6.6,
It is nylon 4.6.

The amount of polyamide in the thermoplastic resin composition of the present invention is 5% to less than 50% by weight, preferably 10 to 45% by weight, more preferably 20 to 4% by weight in the final composition.
It is 0% by weight.

If the amount of polyamide resin is less than 5% by weight, a resin with excellent paintability and chemical resistance cannot be obtained. Further, if the amount exceeds 50% by weight, the heat deformation temperature and impact resistance of the resulting resin will decrease, which is not preferable.

(B) Aromatic vinyl resin The aromatic vinyl resin containing the imide compound of α,β-unsaturated dicarboxylic acid used in the present invention has high heat resistance and impact resistance, and is a polyamide resin component. In order to improve the compatibility with aromatic vinyl compounds and α, β-
It is a resin containing an imide compound of unsaturated dicarboxylic acid and a monomer having a specific functional group as the main constituents, and in the resin, (a) a copolymer of the main constituents, and (b) a non-conjugated diene system. Graft copolymer obtained by graft copolymerizing the main constituent components onto a rubber base (c) A composition obtained by mixing the above (a) and (b) (d) Modified with a monomer containing a specific functional group A composition formed by mixing the above-mentioned ethylene-propylene rubber with (a) and a composition formed by mixing (b) and (d).

Specific examples of the main components include the following.

Vinylation A The aromatic vinyl compounds used here include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, p-tert-butylstyrene, Examples include ethyl styrene and vinylnaphthalene, and these may be used alone or in combination of two or more. A preferred aromatic vinyl compound is styrene.

The amount of these aromatic vinyl compounds to be used is preferably 20% to 80% by weight of the monomer component of 70 to 99.9% by weight, excluding the functional group-containing upper part of component (A). is contained in an amount of 30 to 70% by weight, more preferably 35 to 60% by weight. Also, the content is 20% by weight.
If the content is less than 80% by weight, the processability will be adversely affected when blended with the polyamide resin component, and if the content is more than 80% by weight, the ratio of α,β-unsaturated dicarboxylic acid to be copolymerized will decrease, so it is difficult to improve heat resistance. cannot have a significant effect.

Imide compound of α,β-unsaturated dicarboxylic acid The imide compound of α,β-unsaturated dicarboxylic acid used in the present invention can be represented by the following formula.

R+ Rz C=C Specific examples of the compound include maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-octylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- Phenylmaleimide, N-(p-methylphenyl)maleimide, N-
(p-hydroxyphenyl)maleimide, N-(3,5
-dimethylphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-benzylmaleimide, N-
Examples include (1-naphthyl)maleimide and N-hydroxyethylmaleimide. These may be used alone or in combination of two or more.

Among these compounds, N-phenylmaleimide is preferred. The amount of these α,β-unsaturated dicarboxylic acid imide compounds used is 20 to 80% by weight of the monomer composition of <70 to 99.9% by weight excluding the functional group-containing monomer in component (A). , preferably 30-70% by weight
, more preferably 40 to 60% by weight. If the amount used is less than 20% by weight, no significant effect on improving heat resistance will be observed, and if the amount is 80% by weight or more, processability will decrease.

Furthermore, aromatic vinyl compounds and other vinyl compounds that can be copolymerized with imide compounds of α,β-unsaturated dicarboxylic acids can be used as component (a) of the present invention. Other copolymerizable vinyl compounds include vinyl cyanide compounds such as acrylonitrile and methacrinitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, Cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate,
Acrylic acid alkyl esters such as phenyl acrylate and benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl acrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate ,
Examples include methacrylic acid alkyl esters such as benzyl methacrylate, and other copolymerizable vinyl compounds may be used alone or in combination of two or more. A preferred vinyl compound is acrylonitrile, and copolymerization of this compound improves impact resistance and chemical resistance.

These copolymerizable vinyl compounds are 60% by weight or less of the 70 to 99.9% by weight monomer components excluding the functional group-containing monomer in component (a) of the present invention, preferably 40 heavy cylinders or less. More preferably, it is used in an amount of 30% by weight or less.

In the present invention, a monomer having a functional group can be copolymerized with an aromatic vinyl compound and an imide compound of an α,β-unsaturated carboxylic acid in order to further improve the compatibility with the polyamide component. A monomer having at least one functional group selected from anhydride group, epoxy group, hydroxyl group and amino group is used.

(i) Carboxyl group-containing unsaturated compound Examples of the carboxyl group-containing unsaturated compound used here include acrylic acid, methacrylic acid, lylotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid being preferred. ,
It is methacrylic acid.

These may be used alone or in combination of two or more.

(ii) Unsaturated compounds containing acid anhydride groups Examples of unsaturated compounds containing acid anhydride groups include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, and tetrahydrofucuric anhydride. A particularly preferred unsaturated acid anhydride is maleic anhydride. Here, by partially post-imidizing a copolymer of an aromatic vinyl compound and maleic anhydride with an aromatic amine or an aliphatic-class amine, an aromatic vinyl compound-α,β-unsaturated dicarboxylic acid is produced. A resin having the same composition as the present invention in which maleic anhydride is copolymerized with an imide compound can be obtained, but in the case of post-imidization, it is difficult to control the amount of maleic anhydride, and the resin produced by post-imidization is mixed with polyamide. When used in blends, it is difficult to obtain reproducible physical properties. These may be used alone or in combination of two or more.

(iii) Epoxy group-containing unsaturated compound The epoxy group-containing unsaturated compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

For example, the following general formulas (II), (III) and (IV
) Unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, p-
Unsaturated epoxy compounds such as glycidylstyrenes.

"R-C-CH2 (IV) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, allyl glycidyl ether, 2-
Methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
Examples include 1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and p-glycidylstyrene. These can be used alone or in combination of two or more. Preferred epoxy group-containing unsaturated compounds are glycidyl methacrylate and glycidyl acrylate.

(iv) Hydroxyl group-containing unsaturated compound The hydroxyl group-containing unsaturated compound is a compound that has at least one unsaturated bond (double bond, triple bond) and also contains a hydroxyl group.

Typical examples include alcohols with double bonds, alcohols with triple bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols,
Examples include esters of the unsaturated carboxylic acid with unsubstituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted five or more alcohols.

Among the hydroxyl compounds used in the present invention,
Representative examples of suitable ones include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene.
butene, 3-hydroxy-2-methyl-1-propene,
cis-5-hydroxy-2-pentene, trans-5-
Hydroxy-2-pentene, cis-1,4-dihydroxy-2-butene, trans-1,4-dihydroxy-2
-Butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3°4.
5.6-pentahydroxyhexyl acrylate, 2,
Examples include 3,4,5.6-pentahydroxyhexyl methacrylate, 2.3,4.5-tetrahydroxypentyl acrylate, and 2,3.4.5-tetrahydroxypentyl methacrylate.

These may be used alone or in combination of two or more. Preferred hydroxyl group-containing unsaturated monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 3-hydroxypropyl methacrylate.

(v) Unsaturated compound containing an amino group The unsaturated compound containing an amine group is a vinyl monomer having at least one type of amino group or substituted amino group represented by the following general formula, and a specific example is acrylic acid. Alkyl ester derivatives of acrylic acid or methacrylic acid, such as aminoethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate;
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine and N-methylarylamine, acrylamide derivatives such as acrylamide and N-methylacrylamide, and p-amino Aminostyrenes such as styrene are used. Among them, acrylamide, allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and the like are particularly preferably used because they can be obtained economically on an industrial scale. These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.

The amount of the above various functional group-containing monomers used in component (a) is 0.
．． It is within the range of 1 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably 0.5 to 15% by weight.

If it is less than 0.1% by weight, the dispersibility in polyamide will not be improved, resulting in a decrease in impact resistance. If it exceeds 30% by weight, heat resistance, heat deterioration resistance, and fluidity will deteriorate, which is not preferable.

Component (a) of the present invention is a known polymerization method, emulsion polymerization,
It can be obtained by bulk polymerization, suspension polymerization, solution polymerization, bulk-suspension polymerization, bulk-solution polymerization, etc.

As polymerization conditions, for example, in the case of solution polymerization, generally 6
By using a suitable radical polymerization initiator at a temperature of 0 to 150°C, preferably 80 to 120°C, using a suitable reactor such as an autoclave, a polymer can be obtained in about 10 minutes to 8 hours. .

In the present invention, as a means to further improve the impact resistance of the thermoplastic resin composition, component (a) is graft copolymerized in the presence of a rubbery polymer. (b) of the present invention
ingredients can be obtained.

In the case of a resin composition having high heat resistance like the resin composition of the present invention, the molding temperature is also high, so the rubber-like polymer that is inevitably used is also a non-conjugated diene rubber-like polymer with high heat resistance deterioration. Preference is given to using polymers. Examples of the non-conjugated diene-based rubbery polymer include acrylic rubber containing alkyl acrylate as a main component, ethylene propylene rubber, chlorinated polyethylene, ethylene-vinyl acetate copolymer, and fluororubber. As a combination, there is an ethylene-propylene rubber-like polymer. The amount of the non-conjugated diene rubbery polymer used in component (b) is within the range of 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight. If the amount used is less than 5% by weight, impact resistance cannot be obtained;
If it exceeds 0% by weight, it is not preferable because heat resistance decreases.

Additionally, other rubbery polymers and thermoplastic elastomers can be used in combination to improve impact resistance.

The rubbery polymers used here include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, ethylene-α-olefin-polyene copolymer,
Non-diene rubbers such as polyacrylic esters are available, and these may be used alone or in combination of two or more.

Examples of thermoplastic elastomers include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, styrene gelast ethylene-propylene elastomers, and ethylene ionomer resins. Styrene
Butadiene block copolymers include AB type, ABA type,
Includes ABA taper type, radial teleblock type, etc. These may be used alone or in combination of two or more.

The (oral) component in the present invention is a known polymerization method such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, bulk-suspension polymerization,
It can be obtained by bulk-solution polymerization.

As for the graft copolymerization conditions, the graft copolymer (b) is generally obtained under the same conditions as in (a) above.

The composition (c) used in the present invention is obtained by mixing the copolymer of the component (a) and the graft copolymer of the component (b) to obtain the composition of the component (c). be able to.

``Sanshimoritate-'' Also, the composition of component (2) used in the present invention is (
b) An ethylene-propylene rubber-like polymer modified with a monomer containing at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. The composition of component (2) can be obtained by adding a non-conjugated diene-based rubbery polymer, and thereby the impact resistance can be improved.

As a method for modifying a non-conjugated diene-based rubbery polymer with the above functional group, an unsaturated compound containing the carboxyl group, acid anhydride group, epoxy group, hydroxyl group, or amino group,
It can be obtained by adding at least one selected from a chain transfer agent and a polymerization initiator to a non-conjugated diene rubber-like polymer.

When the unsaturated compound, chain transfer agent, and polymerization initiator are added to the nonconjugated diene rubbery polymer, the amount of these used is preferably 0.000% relative to the nonconjugated diene rubbery polymer.
01 to 50% by weight, more preferably 0.1 to 1
0% by weight, particularly preferably 0.2-5% by weight. If the amount of modification is too large or too small, the impact resistance will be poor.

The modified non-conjugated diene-based rubbery polymer of the present invention contains an ethylene-propylene-based rubbery polymer, at least one selected from the group consisting of an unsaturated compound having a specific functional group, a chain transfer agent, and a polymerization initiator. Mix oxides, e.g. 100~
0.25-3 at 300°C, preferably 150-250°C
It can be obtained by heat treatment (kneading) for 0 minutes (preferably 1 to 10 minutes).

These reactions can be carried out using an extruder, kneader, Banbury mixer, or the like. Alternatively, it can be obtained by dissolving each of the above components in an organic solvent and heating the solution.

As the solvent used at this time, a hydrocarbon having 6 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, tetrahydrofuran, or the like is used.

The heating temperature varies depending on the type of organic peroxide used as a polymerization initiator, but is usually 40 to 300°C, preferably 50 to 200°C, and the heating time is 1 minute to 10 minutes.
The time is preferably 5 minutes to 5 hours.

After the reaction is completed, the product solution is solidified by pouring it into a polymer-insoluble solvent such as alcohol, or solidified by steam stripping, and then dried.

Furthermore, one or more types selected from other vinyl monomers copolymerizable with the unsaturated compound having a specific functional group of the present invention can also be used in combination.

Examples of the other copolymerizable vinyl monomers include the aromatic vinyl compound, the vinyl cyanide compound, the alkyl acrylate ester, and the alkyl methacrylate ester.

As the peroxide used in the production of the modified non-conjugated diene rubbery polymer, all known organic peroxides can be used.

For example, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexyne-3,2,5-dimethyl-
2,5-di(tert-butylperoxy)hexane,
2,2-bis(tert-butylperoxy)-p=nidiisopropylbenzenedicumyl peroxide
er t-butyl peroxide, tert-butyl peroxybenzoate, 1,1-bis(tert-butylperoxy)-3,3,5-)limethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide oxide, p-chlorobensyyl peroxide, p-chlorobensyyl peroxide, azobisisobutyl nitrile, etc., preferably 2,5-
Dimethyl-2,5-di(tert-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di(tert-
butylperoxy)hexyne-3.

The amount of peroxide used here is 0.05 to 2 parts by weight per 100 parts by weight of the non-conjugated diene rubbery polymer;
Preferably it is 0.1 to 1 part by weight.

Furthermore, in obtaining the modified non-conjugated diene rubber-like polymer of the present invention, a known antioxidant may be used in combination, if necessary.

The amount of the modified non-conjugated diene rubbery polymer used in the thermoplastic resin composition of the present invention is 1 to 50% by weight, preferably 2 to 30% by weight, preferably 5 to 2% by weight.
It is 5% by weight. If it is less than 1% by weight, even better impact resistance cannot be obtained, and if it exceeds 50% by weight, processability will be poor, which is not preferable.

Among these (a) to (e) components, (b), (c)
Components (d) and (e) contain rubbery polymers and therefore have high impact resistance, and are particularly preferably used. In addition, in the case of a combination of component (A) and polyamide, from the viewpoint of processability, component (d) of component (A) is at least one selected from acid anhydride groups, epoxy groups, hydroxyl groups, and amino groups. Preference is given to using monomers having a @ functional group.

To further improve the impact resistance, other rubbery polymers and thermoplastic elastomers can be used in combination, as described above.

In the present invention, the graft copolymer of the component (b) and (
It is possible to obtain a composition of component (e) by mixing the composition of component (d).

(c) Production of thermoplastic resin composition When producing the thermoplastic resin composition of the present invention (A)
The amount of the aromatic vinyl resin component containing the imide compound of α,β-unsaturated carboxylic acid, which is the components (A) to (E) of the component (B), is as follows: 50-95% by weight, preferably 55-90% by weight
, more preferably 60 to 80% by weight.

When the amount of components (a) to (e) is less than 50% by weight, heat resistance decreases. Moreover, if it exceeds 95% by weight, the paintability and chemical resistance will not be improved.

In order to obtain the thermoplastic resin of the present invention, the method for kneading the polyamide resin component (A) and the components (A) to (E) of the component (B) includes various extruders, Banbury mixers, kneaders, etc. Used in rolls, etc.

A preferred kneading method is a method using an extruder.

The mixing temperature must be higher than the melting point of the polyamide to be mixed, and is generally 180 to 350°C, approximately 210 to 330°C.
The temperature is preferably .

When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as walrus night, calcium carbonate, talc, and barium sulfate can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

It is preferable that these fillers are contained in an amount of 5 to 15 parts by weight based on 1-00 parts by weight of the thermoplastic resin composition.

Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added.

Preferred flame retardants and antioxidants are phosphorus compounds.

Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, BRSNBR, and SBR.

5-B-S block copolymer, hydrogenated 5-B-S, polystyrene, AS resin, old PS, ABS resin, ES resin, polysulfone, polyether sulfone, NBS,
Methyl methacrylate-styrene copolymer, S-1-S block copolymer polyimide, pps, polyetheretherketone, vinylidene fluoride polymer, etc. can be blended as appropriate.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

The various molded products obtained by the above molding method take advantage of their excellent properties to be used in automobile exteriors, interior parts, electrical equipment, etc.
It can be used for various electronic-related parts, housings, etc.

f. Examples The present invention will be explained in more detail by the following examples and manufacturing examples, but these are merely illustrative and do not limit the content of the present invention.

Note that in each side below, parts and % indicate parts by weight and % by weight, respectively.

Production Example-1 After replacing the stainless steel reactor with a stirring device with nitrogen, the iodine value was 15, the Mooney viscosity was 65, and the propylene content was 43.
%, E containing ethylidene norbornene as diene component
30 PDM (BP-24 manufactured by Japan Synthetic Rubber Co., Ltd.)
35 parts of mistyrene, 7 parts of acrylonitrile, and 100 parts of tetrahydrofuran were charged and stirred at 50°C until the rubber was completely dissolved.

After further adding 0.1 part of t-dodecyl mercaptan and 0.2 part of dibenzoyl peroxide, the reactor was heated, and when the internal temperature reached 65°C, N-phenylmaleimide 2
A solution consisting of 4.5 parts of maleic anhydride, 3.5 parts of maleic anhydride and 50 parts of tetrahydrofuran was started to be added dropwise using a variable flow rate continuous device.

Then, while maintaining the internal temperature at 90°C, a mixed solution of N-phenylmaleimide and maleic anhydride was continuously added dropwise over 3 hours. After the dropwise addition was completed, the temperature was raised to 120°C and the polymerization reaction was carried out for an additional 3 hours, for a total of 6 hours.

After polymerization, 2,2-methylenebis-
5 g of (4-methyl-6-t-butylphenol) was added, and the residual monomer and solvent were removed by steam stripping, solidified, and then dried to obtain Polymer A-1.

(2) Production of polymers A-2 to A-7 and A-8 In the production method of polymer A-1, the type of maleimide compound,
Polymers A-2 to A-6 as shown in Table 1 were obtained by varying the amount and type of functional group-containing polymer.

Moreover, in the manufacturing method of A-1, resin matrix A-8 was obtained in the absence of rubber.

Production Example-2 Component (d) of the present invention used in Examples and Comparative Examples was obtained by the following method.

Ethylene-propylene rubber (Japanese Synthetic Rubber (! JS manufactured by Xun)
REP-02P, Mooney viscosity ML. ,,1°. 'C
24) For 100 parts, 1 part of maleic anhydride, 0.0 parts of organic peroxide (Kayahexa AD manufactured by Kayaku Nuri ■).
Three parts were premixed in advance and melt-kneaded using a 5511φ extruder (single-screw full-flight type screw) at 200° C. and a screw rotation speed of 3 Orpm (residence time of about 4 minutes) to cause a polymerization reaction.

A polymer purified from the obtained reaction product by acetone extrusion (boiling point x 2 hours) was formed into a film, and the amount of maleic anhydride grafted was determined by infrared spectroscopic analysis. The graft ratio was 0.5 parts by weight based on 100 parts by weight of ethylene-propylene.

Examples and comparative examples The various polymers described above were mixed in the composition ratios shown in Table 2.

The mixing conditions were as follows: Various polymers were mixed using a Henschel type mixer, and the resin composition was pelletized at an appropriate temperature of 240 to 320°C using a PCM-45 twin screw extruder manufactured by Ikegai Iron Works as an extruder. did. Screw rotation speed is 2Or
The speed was varied within the range of pm to 300 rpm.

After sufficiently drying the obtained pellet-shaped thermoplastic resin composition in a vacuum dryer, a test piece was prepared using an injection molding machine,
Impact resistance, heat resistance, and processability were evaluated using pellets after drying.

The evaluation results are shown in Table-2. The evaluation results in Table 2 were performed using the following measurement method.

■ The external molded product (plate shape) was coated with urethane paint Hi-Urethane + 15000 manufactured by Nihon Yushi Kogyo ■ with a film thickness of 2 μm. Cracks on the surface of the paint film after drying at 70°C for 20 minutes,
The appearance and occurrence of crazes and suction were visually evaluated according to the following evaluation criteria.

◎: Very good, ○: Good, △: Slightly poor, ×: Bad■
Adhesion The above-mentioned urethane paint was re-coated to a thickness of 40 μm to the undercoated product whose appearance was observed.

Adhesion was evaluated by observing the state of the paint film after repainting and according to the following evaluation criteria.

◎: Very good, ○: Good, △: Slightly swollen paint film, ×: Large swell of paint film Also, regarding the molded products obtained in Example 1.2 and Comparative Example 1.3.5 Chemical resistance was evaluated.

The measurement method is as follows.

The results are shown in Table 3.

1 Riyaku Easy Strain Solvent Crank: Test Piece (1/8' Xl15
'x5'') is subjected to constant strain with a strain rate of 0.5%, brake oil (hereinafter simply abbreviated as BO) is applied to the bent part, and the time until it breaks when it is left at 23°C A similar measurement was conducted using dioctyl phthalate (hereinafter abbreviated as DOP) under the condition of a strain rate of 1.0%.The longer the time, the better the chemical resistance.

Table-3 The following can be understood from Table 2.

As is clear from a comparison of Examples 1 to 7 and Comparative Example 1, the resin composition of the present invention is a resin with improved paintability and excellent heat resistance and impact resistance.

In Comparative Example 2, the amount of polyamide resin in the thermoplastic resin composition was 55% by weight, which was outside the scope of the present invention, and therefore the impact resistance and heat resistance were poor.

In Comparative Example 3, the content of the functional group-containing monomer in component (A) is 0.1% by weight or less, so the compatibility with the polyamide resin is reduced and the impact resistance is significantly reduced. .

In Comparative Example 4, the component (a) contained as much as 35% by weight of the functional group-containing monomer, so the heat resistance was significantly lowered.

Comparative Example-5 is 20 in which the amount of the imide compound of α,β-unsaturated dicarboxylic acid in component (A) is outside the scope of the present invention.
% by weight or less, the heat resistance is significantly reduced.

In Comparative Example 6, the amount of the imide compound of α,β-unsaturated dicarboxylic acid in component (A) was 80% by weight or more, which is outside the scope of the present invention, so the processability was significantly reduced. .

Comparative Example-7 does not contain a non-conjugated diene rubber component (
Although the resin is composed of component (a), the impact resistance is lower than that of Example 7 because it does not contain polyamide resin.

Comparing Examples 1 to 2 and Comparative Examples 1.3.5 in Table 3, it is clear that the resin composition of the present invention is a resin with excellent chemical resistance. In particular, when comparing Examples 1 to 2 and Comparative Example 3.5, the chemical resistance of the thermoplastic resin composition containing the functional group-containing monomer component and the imide compound of α, β-unsaturated dicarboxylic acid is further improved. It is clear that it is superior.

g0 Effects of the invention A book obtained by mixing a polyamide resin with a non-conjugated diene-modified heat-resistant resin containing an imide compound of α, β-unsaturated dicarboxylic acid and a specific functional group-containing monomer as constituent components. The thermoplastic resin composition of the invention can significantly improve the paintability and chemical resistance of non-conjugated diene rubber-modified heat-resistant resins.

Furthermore, since the thermoplastic resin composition of the present invention has improved compatibility with the polyamide resin, it is a composition with excellent impact resistance.

Therefore, since the thermoplastic resin composition of the present invention has highly balanced physical properties, it can be used in automobile exterior and interior parts and electrical/electronic-related materials that require high quality. It can provide molded products such as various parts and housings, and has extremely high industrial value.

Patent applicant: Japan Synthetic Rubber Co., Ltd. (2 idiots)

Claims (2)

[Claims] (1) (A) Polyamide component 5% by weight or more - 50% by weight
and (B) 50 to 95% by weight of an aromatic vinyl resin component copolymerized with an imide compound of an α,β-unsaturated dicarboxylic acid shown in (a) to (e) below. thing. (b) (a) 20 to 80% by weight of aromatic vinyl compound (b)
) Imide compounds of α,β-unsaturated carboxylic acids 20 to 80
(c) 70 to 99.9 weight % of a monomer consisting of 0 to 60 weight % of a vinyl compound copolymerizable with (a) or (b); and (d) a carboxyl group copolymerizable with these; 0 monomer components containing at least one functional group selected from acid anhydride groups, epoxy groups, hydroxyl groups, and amino groups
．． A copolymer obtained by copolymerizing 1 to 30% by weight. (b) In the presence of a non-conjugated diene rubbery polymer, the above (
A graft copolymer obtained by graft copolymerizing the monomer components of (a). (c) In the presence of a copolymer component [1] obtained by copolymerizing components (a), (b), and (c) of (a) above, and a non-diene rubbery polymer, the above (b) A graft copolymer component [2] obtained by graft copolymerizing components (a), (b), and (c) of [1] and [2], and (a) of (a) in at least one of [1] and [2]. d) A composition in which the components are copolymerized. (d) a non-conjugated diene rubber-like polymer component modified with a monomer containing at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group; b) A composition consisting of an ingredient. (E) A composition comprising the above-mentioned (B) component and (D) component. (2) The thermoplastic resin composition according to claim (1), wherein the non-conjugated diene rubbery polymer is an ethylene-propylene rubbery polymer.