JPH0759670B2 - Impact resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent impact resistance and heat resistance.

[Conventional technology]

Polycarbonate resin has high impact strength and tensile strength,
Furthermore, it is excellent in transparency and electric characteristics, but on the other hand, it has drawbacks such as large impact strength thickness dependence, small impact strength at low temperature, poor solvent resistance, etc. There is.

Thermoplastic polyester resins, especially polybutylene terephthalate (hereinafter abbreviated as PBT), have well-balanced good physical properties and excellent moldability and are widely used in machine parts, electronic / electrical parts, automobile parts and other fields. However, it also has a big drawback that the notch impact strength is low. That is, PBT shows good impact strength without notches, but impact strength is significantly reduced with notches, which is an obstacle to expanding applications.

Polyacetal resins are expected to be in great demand as engineering plastics because of their excellent heat resistance and mechanical properties, but on the other hand, notched impact strength is particularly small and residual stress and minute scratches during molding exist. Then, there is a drawback that breakage easily occurs, and there is a problem in molding mechanical parts such as gears, bolts and nuts, and molded products with complicated shapes.Therefore, in order to expand the demand for polyacetal resin, its impact resistance should be improved. There is a strong demand for improvement.

Polyamide resins are generally excellent in wear resistance, electrical characteristics, heat resistance, mechanical strength and the like, and are widely used as engineering plastics in various mechanical component materials, but they have the drawback of insufficient impact resistance.

Therefore, various studies have been conducted in the past to improve the drawbacks of these thermoplastic resins, particularly, with respect to impact resistance, and many results have been announced.

For example, polycarbonate is obtained by graft-polymerizing styrene and acrylonitrile or methyl methacrylate on a butadiene-acrylonitrile copolymer (JP-A-49-48752), polybutadiene or butadiene-styrene copolymer as an additive for improving impact resistance. Known polymers (JP-B-38-15225, JP-B-39-71) are known, and for PBT, blends with ethylene copolymer (JP-B-60-7662), polybutadiene, butadiene-acrylonitrile copolymerization are known. Compounds and blends with isoprene-isobutylene copolymer (JP-A-58-45256) and blends with acrylic rubber (JP-A-57-9040) are known,
Regarding the polyacetal resin, a blend with a rubbery copolymer having a nitrile or carboxylic acid ester group (Japanese Patent Publication No. 45-12674), a blend with an α-olefin and an α, β-unsaturated carboxylic acid copolymer (Japanese Patent Publication No. 45-18023) and the like, and regarding polyamide resins, blends of butadiene-acrylonitrile copolymer, butadiene-styrene copolymer (JP-A-54-54166), unsaturated carboxylic acid Blend with a graft-polymerized α-olefin-vinyl acetate copolymer (JP-A-53-146754), blend with an epoxy group-introduced olefin copolymer (JP-A-54-54754)
65748), and a blend with an ethylene-α-olefin copolymer graft-polymerized with an unsaturated carboxylic acid (JP-A-60-14).
4362) and the like are known, but in any case, the drawbacks regarding impact resistance have not been overcome.

[Problems to be solved by the invention]

Therefore, as a result of intensive studies to overcome the drawbacks relating to impact resistance, the present inventors have found that a thermoplastic resin (α), an acrylic polymer rubber (I), and a conjugated diene-nitrile compound copolymer rubber (II). And a resin composition comprising a mixture of one or more kinds of hydrides (III) thereof with a copolymer rubber (β) and a vinylidene fluoride resin (γ) have significantly improved impact resistance and further improved heat resistance. The present invention has been found to be excellent in properties and has led to the present invention.

[Means for Solving Problems] The present invention relates to a thermoplastic resin (α), an acrylic copolymer rubber (I), a conjugated diene-nitrile compound copolymer rubber (II) and hydrogen of the above (II). Compound (III) and one or more kinds of copolymer rubber (β) and vinylidene fluoride resin (γ) having a composition content of (α)
The present invention provides a resin composition comprising 56 to 85% by weight, (β) 10 to 40% by weight, and (γ) 5 to 35% by weight.

The present invention will be described in detail below.

Examples of the thermoplastic resin (α) used in the present invention include thermoplastic resins such as polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, acrylic resin, polyamide resin, polyester resin, polycarbonate resin, polyether resin, and polyacetal resin. Examples of the resin include a resin and a mixture of two or more of these resins. Among them, a polycarbonate resin and a polyamide resin are preferable, and a polycarbonate resin is particularly preferable.

Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally, 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl)
It is a polymer or copolymer obtained by polymerizing bisphenols such as sulfone sulfides or sulfoxides, and is a polymer using bisphenols substituted with halogen according to the purpose. Regarding the types and manufacturing methods of polycarbonate resin, "Polycarbonate resin" published by Nikkan Kogyo Shimbun (issued September 30, 1969)
Can be used.

Polyamide resin, usually following formula _{H 2 N- (CH 2) x} -NH 2 ( wherein, x is an integer between 3-12.) With a linear diamine and formula HO ₂ represented C- ( CH ₂ ) _y —CO ₂ H (wherein y is an integer between 2 and 12) produced by condensation with a linear carboxylic acid, or by ring-opening polymerization of a lactam. Can be used. Preferred examples of these polyamides include nylon 6,6, nylon 6,10, nylon 6,12,
Nylon 4,6, nylon 3,4, nylon 6,9, nylon 6, nylon 12, nylon 11, nylon 4, etc.
Nylon 6 / 6,10, nylon 6 / 6,12, nylon 6/4,
6, Nairo 6/12, Nylon 6 / 6,6, Nylon 6 / 6,6 / 6,10,
Nylon 6 / 4,6 / 6,6, Nylon 6 / 6,6 / 6,12, Nylon 6 /
Copolyamides such as 4,6 / 6,10 and nylon 6 / 4,6 / 12 are also used.

Furthermore, semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as nylon 6/6, T (T: terephthalic acid component), terephthalic acid, isophthalic acid and metaxylenediamine or alicyclic diamine, and metaxylenediamine and the above Mention may be made of polyamides, polyester amides, polyether amides and polyester ether amides obtained from linear carboxylic acids.

Next, the acrylic copolymer rubber (I) used in the present invention
Is (A) alkyl acrylate and / or alkoxy substituted alkyl acrylate compound,
(B) a crosslinkable monomer, and (C) the above (A),
The (A) component acrylic acid alkyl ester has the following general formula (i), provided that it comprises (B) and another ethylenically unsaturated compound that is copolymerizable. Is represented by, for example, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, n-
Butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, etc. Are preferred, and methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-butyl acrylate are preferred, and methyl acrylate and ethyl acrylate are particularly preferred.

Further, as the acrylic acid alkoxy-substituted alkyl ester of the component (A), the following general formula (ii) And is represented by, for example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-
(N-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2-
(N-propoxy) propyl acrylate, 2- (n-
Butoxy) propyl acrylate and the like can be mentioned, and 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are preferable, and 2-methoxyethyl acrylate is particularly preferable.

The crosslinkable monomer which is the component (B) of the copolymer (I) is a monomer capable of introducing a crosslinked structure into the resulting copolymer by copolymerization, and for example, a diene compound. At least one selected from the group consisting of a dimethydicyclopentadienyl group-containing (meth) acrylic acid ester, an epoxy group-containing ethylenically unsaturated compound, an active halogen-containing ethylenically unsaturated compound and a carboxyl group-containing ethylenically unsaturated compound. A class of compounds may be mentioned.

Among the crosslinkable monomers of the component (B), examples of the diene compound include non-conjugated dienes such as alkylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadiene and dimers thereof, and conjugated dienes such as butadiene and isoprene. It is desirable to use a non-conjugated diene selected from the group consisting of alkylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadiene and dimers thereof.

In addition, among the crosslinkable monomers of the component (B), examples of the dihydrodicyclopentadienyl group-containing (meth) acrylic acid ester include dihydrodicyclopentadienyl (meth) acrylate and dihydrodicyclopentadienyloxyethyl. (Meth) acrylate is preferred.

Further, among the compounds of the component (B), the epoxy group-containing ethylenically unsaturated compound is preferably allyl glycidyl ether, glycidyl methacrylate, or glycidyl acrylate.

Furthermore, among the compounds of the component (B), specific examples of the active halogen-containing ethylenically unsaturated compound include vinylbenzyl chloride, zynylbenzyl bromide, 2-
Chlorethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone, 2-chloroacetoxymethyl-
5-norbornene and the like can be mentioned, and among these, vinyl chloroacetate, 2-chloroethyl vinyl ether, vinylbenzyl chloride, 2-chloroethyl methacrylate and 2-chloroethyl acrylate are preferable.

Further, among the compounds of the component (B), specific examples of the carboxyl group-containing ethylenically unsaturated compound include:
Examples thereof include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid and itaconic acid.

Examples of the other ethylenically unsaturated compound as the component (C) include:
Various compounds can be used if necessary, and examples thereof include carboxyl group-containing compounds such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, and methyl methacrylate. , Methacrylates such as octyl methacrylate,
Cyano-substituted alkyl (meth) acrylates such as 2-cyanoethyl acrylate, 3-cyanopropyl acrylate and 4-cyanobutyl acrylate, amino-substituted alkyl (meth) acrylates such as diethylaminoethyl acrylate, 1,1,1-trifluoroethyl acrylate Such as fluorine-containing acrylates, hydroxy-substituted alkyl (meth) acrylates such as hydroxyethyl acrylate, alkyl vinyl ketones such as methyl vinyl ketone, vinyl or allyl ethers such as vinyl ethyl ether, allyl methyl ether, styrene, α-
Vinyl aromatic compounds such as methylstyrene, chlorostyrene and vinyltoluene, vinylnitrile such as acrylonitrile and methacrylonitrile, vinylamide such as acrylamide, methacrylamide and N-methylacrylamide and ethylene, propylene and vinyl chloride,
Examples thereof include polyfunctional monomers such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl alkyl fumarate acetate, divinylbenzene, divinyl ether, and ethylene glycol di (meth) acrylate. Of these, acrylonitrile, 2-cyanoethyl acrylate, ethylene and vinyl acetate are preferable, and acrylonitrile is particularly preferable.

In addition, a preferable combination of the component (A) and the component (C) is an acrylic acid alkyl ester of the component (A) and /
Or a combination in which the acrylic acid alkoxy-substituted alkyl ester compound is at least one compound selected from the group of methyl acrylate, ethyl acrylate and methoxyethyl acrylate, and the other ethylenically unsaturated compound of component (C) is acrylonitrile Is.

The composition ratio of the components (A), (B) and (C) in the acrylic copolymer rubber (I) of the present invention is (A).
Components 30 to 99.9% by weight, component (B) 0.1 to 10% by weight and component (C) 0 to 70% by weight.

If the amount of the component (A) is less than about 30% by weight, the resulting compounded composition is inferior in impact resistance, which is not preferable. It is preferably 50% by weight or more, and particularly preferably 70% by weight or more.

On the other hand, if the content of the component (B) is less than about 0.1% by weight, the bondability at the interface between the rubber and the resin at the time of compounding will decrease, while if it exceeds 10% by weight, the dispersed state of the rubber and the resin will deteriorate, which is not preferable. . It is preferably 1 to 7% by weight, more preferably 2 to 5% by weight.

Further, if the amount of the component (C) exceeds about 70% by weight, the amount of the component (A) becomes too small, which is not preferable.

The multi-component copolymer rubber (I) can be produced by emulsion polymerization using an ordinary radical polymerization catalyst.

Next, the conjugated diene-nitrile compound copolymer rubber (II) used in the present invention is (D) α, β-unsaturated nitrile,
Specific examples of the α, β-unsaturated nitrile as the component (D), which comprises (E) a conjugated diene, and (F) the above (D) and (E) and another ethylenically unsaturated compound copolymerizable therewith Examples include acrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, methacrylonitrile, ethacrylonitrile, and among them, acrylonitrile is particularly preferable.

As the conjugated diene as the component (E), there are butadiene-1,3, 2-chlorobutadiene-1,3, 2-methylbutadiene-1,3-, and the like. Among them, butadiene-1,3 is particularly preferable. preferable.

As the component (F), various compounds can be used if necessary, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate. , Isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, and the like alkyl acrylate ester, 2-methoxyethyl Acrylate, 2-ethoxyethyl acrylate, 2-
(N-Propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-methoxypropyl acrylate, 2-
(N-propoxy) propyl acrylate, 2- (n-
Butoxy) propyl acrylate and other acrylic acid alkoxy-substituted alkyl esters, methyl methacrylate,
Alkyl methacrylate such as octyl methacrylate, alkyl vinyl ketone such as methyl vinyl ketone, vinyl or allyl ether such as vinyl ethyl ether and allyl methyl ether, vinyl aromatic such as styrene, α-methylstyrene, chlorostyrene and vinyltoluene. Compounds, acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid and other carboxyl group-containing compounds, 1,1-dihydroperfluoroethyl (meth) acrylate, 1,1-dihydroperfluoropull Pill (meth) acrylate, 1,1,
5-trihydroperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, 1,1,7-trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl ( Meth) acrylate, fluorine-containing acrylic acid ester such as 1,1-dihydroperfluorodecyl (meth) acrylate, allyl glycidyl ether,
Epoxy group-containing compounds such as glycidyl methacrylate and glycidyl acrylate, vinylpentyl chloride,
Vinylbenzyl bromide, 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone, 2
-Active halogen-containing compounds such as chloroacetoxymethyl-5-norbornene, hydroxyl-containing compounds such as 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate, dimethylamino (meth) Acrylate, diethylaminoethyl (meth) acrylate,
Tertiary amino group-containing monomers such as dibutylaminoethyl (meth) acrylate, vinylamides such as acrylamide, methacrylamide, and N-methylolacrylamide, and ethylene, propylene, vinyl chloride, vinylidene chloride, alkyl fumarate, divinylbenzene, divinyl ether. , And polyfunctional monomers such as ethylene glycol di (meth) acrylate. Among these, (meth) acrylic acid ester is particularly preferable.

The composition ratio of the components (D), (E) and (F) in the conjugated diene-nitrile compound copolymer rubber (II) of the present invention is such that the component (D) is 10 to 60% by weight and the component (E) is 15 to 90% by weight and 0 to 75% by weight of component (F).

When the amount of the component (D) is less than 10% by weight, the oil resistance of the composition is deteriorated, which is not preferable.

On the other hand, if the amount of the component (D) exceeds 60% by weight, the processability of the composition is deteriorated, which is not preferable. It is preferably 20 to 50% by weight.

If the amount of the component (E) is less than 15% by weight, the cold resistance of the composition deteriorates, which is not preferable. It is preferably 30% by weight or more, particularly preferably 50% by weight or more.

Further, if the component (F) exceeds about 75% by weight,
The amounts of components (D) and (E) are too small, which is not preferable. It is preferably 25% by weight or less.

The conjugated diene-nitrile compound copolymer rubber (II)
Can be produced by emulsion polymerization using an ordinary radical polymerization catalyst.

In the hydrogenated product (III) of the copolymer rubber (II), the degree of hydrogenation of the conjugated diene unit portion in the polymer chain is 10% or more, preferably 30% or more, and particularly preferably 50% or more.

As the hydride (III), for example, a copolymer rubber (II) can be prepared by a conventional method (for example, JP-B-45-39275, JP-A-50-716).
No. 81, GB2070023), and the conjugated diene unit portion in the rubber is hydrogenated.

Next, the vinylidene fluoride resin (γ) used in the present invention
Is polyvinylidene fluoride and vinylidene fluoride and hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), acetic acid. It is a copolymer of one or more of vinyl, ethylene, propylene, butadiene, styrene, acrylic acid ester and the like, and its vinylidene fluoride content is 90 mol% or more, preferably 95 mol% or more. A vinylidene fluoride resin having a vinylidene fluoride content of less than 90 mol% is not preferable because the workability is lowered and the effect of impact resistance cannot be obtained. The vinylidene fluoride resin is not particularly limited, but preferably has a polymerization degree of 100.
~ 100,000 is used.

The vinylidene fluoride resin used in the present invention can be produced by a usual suspension polymerization or emulsion polymerization, for example, the method introduced in JP-A-49-74291 and JP-A-50-104287. can do.

As described above, the resin composition of the present invention is selected from the thermoplastic resin (α) and the copolymer rubbers (I) and (II) or the hydride (III) of the copolymer rubber (II). One or two or more kinds of copolymer rubber (β) and vinylidene fluoride resin (γ) are used, and the weight fraction of each of these (α), (β) and (γ) is (α). )But
56-85% by weight, (β) 10-40% by weight, (γ) 5-35
% By weight.

If the thermoplastic resin (α) is less than 56% by weight, the molding processability is deteriorated, which is not preferable. It is preferably 60 to 80% by weight.

If the content of the copolymer rubber (β) is less than 10% by weight, the effect of improving impact resistance is not observed, and if it exceeds 40% by weight, moldability is deteriorated, which is not preferable. It is preferably 10 to 30% by weight.

When the vinylidene fluoride resin (γ) is less than 5% by weight, the effect of improving impact resistance and heat resistance is not observed, and it is preferably 10
It is more than weight%. As the amount of vinylidene fluoride resin (γ) in the mixture increases, processability deteriorates,
Further, since the cost increases, the upper limit of the amount used is naturally determined and is usually 35% by weight or less, preferably 30% by weight or less.

Thermoplastic resin (α) of each component in the resin composition of the present invention,
Copolymer rubber (β) and vinylidene fluoride resin (γ)
The use ratio of can be appropriately determined within the above range according to the purpose of use and required performance.

In addition to the above components, the resin composition of the present invention has a flame retardant, a release agent, an antioxidant, a weather resistance imparting agent, etc.
Auxiliary components such as antistatic agents, heat-resistant agents, colorants, plasticizers, reinforcing agents, cross-linking agents, surfactants, lubricants and nucleating agents can be added as appropriate. There are no particular restrictions on the method of adding these auxiliary components, the timing, etc., and any conventional method may be used.

The method for mixing the resin composition of the present invention is not particularly limited,
It is preferable to first prepare a mixture of the copolymer rubber (β) and the vinylidene fluoride resin (γ) in advance using the following method, and then mix the thermoplastic resin.

(A) A method in which the copolymer rubber (β) and the vinylidene fluoride resin (γ) are mixed using a mixer such as a roll, Banbury mixer or intermixer, (b) the copolymer rubber (β) and fluorine Examples thereof include a method in which vinylidene chloride resin (γ) is mixed in a latex form or a suspension form and then coagulated by coagulation treatment, or (c) a method in which (a) and (ii) are used in combination. .

Next, copolymer rubber (β) and vinylidene fluoride resin (γ)
There is no particular limitation on the mixing method of the mixture of and the thermoplastic resin (α), and a commonly known method is adopted. From an industrial point of view, the above mixture and the thermoplastic resin (α) are usually dry blended with a Henschel mixer and then melt-kneaded and extruded, or an extruder with an automatic metering feeder is used. Is taken. In any case, a condition device may be selected so that the mixture and the thermoplastic resin (α) are sufficiently dispersed and mixed. Specific examples of the kneading device include a Banbury mixer, a roll, an extruder and a kneader.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Example 1 60 parts by weight of a copolymer rubber (β) composed of ethyl acrylate, methoxyethyl acrylate, allyl glycidyl ether and acrylonitrile shown in the upper part of Table 1 and 40 parts by weight of polyvinylidene fluoride (hereinafter abbreviated as PVDF) were heated by heating. Kneading with a roll to prepare a copolymer rubber / PVDF masterbatch, 30 parts by weight of the masterbatch and 70 parts by weight of a polycarbonate resin are used in HAAKE BUCHLER HAAKERHEO-
Melt kneading was performed using CORD SYSTEM 40 RHEOMIX MIXER 600 to obtain the composition of the present invention.

The impact resistance was evaluated by subjecting the composition obtained above to compression molding with an electrothermal press to prepare Izod impact test pieces, and
This was done by measuring the impact value according to SK 7110.

The heat resistance was evaluated by measuring the Izod impact value according to JIS K 7110 for a sample that was left in air heated to 120 ° C for 120 hours and then returned to room temperature using a gear oven.

Example 2 n-butyl acrylate, methacrylic acid, acrylonitrile, shown in the upper part of Table 1 as a copolymer rubber (β),
Compounding and evaluation were carried out in the same procedure as in Example 1 except that the copolymer rubber (II) composed of 1,3-butadien was used.

Example 3 As the copolymer rubber (β), the hydride (III) of the copolymer rubber composed of acrylonitrile and 1,3-butadiene shown in the upper part of Table 1 was used, and PVDF was used at the ratio shown in Table 1. After producing the masterbatch, the kneading with the polycarbonate was carried out in the same manner as in Example 1 and evaluated.

Example 4 Compounding and evaluation were carried out in the same procedure as in Example 1 except that a polyamide resin was used as the thermoplastic resin (α).

Comparative Example 1 In the same manner as in Example 1 except that the copolymer rubber (β) composed of acrylonitrile and 1,3-butadiene shown in the upper part of Table-1 was used and compounded in the proportion shown in the upper part of Table-1. Blending and evaluation were performed.

Comparative Example 2 Compounding and evaluation were carried out using the same sample as in Example 3 except that the copolymer rubber (β) was not used.

Comparative Example 3 The copolymer rubber (β) composed of ethyl acrylate and ethylidene norbornene shown in the upper part of Table 1 was used,
In addition, the evaluation was performed in the same manner as in Example 4 except that PVDF was not used.

Comparative Example 4 Example 1 except that only the polycarbonate resin was used.
Evaluation was performed in the same procedure as.

Comparative Example 5 Evaluation was performed in the same procedure as in Example 1 except that only the polyamide resin was used.

Example 5 The evaluation was performed using the same sample as in Example 1 except that the copolymer rubber and PVDF were not previously masterbatched in Example 1.

Example 6 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 60 parts by weight of the polycarbonate resin, 28 parts by weight of the copolymer rubber (β) and 12 parts by weight of PVDF were used in Example 1.

Example 7 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 85 parts by weight of the polycarbonate resin, 10 parts by weight of the copolymer rubber (β) and 5 parts by weight of PVDF were used in Example 1.

Example 8 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 60 parts by weight of the polycarbonate resin, 35 parts by weight of the copolymer rubber (β) and 5 parts by weight of PVDF were used in Example 1.

Example 9 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 60 parts by weight of the polycarbonate resin, 10 parts by weight of the copolymer rubber (β) and 30 parts by weight of PVDF were used in Example 1.

Example 10 Compounding and evaluation were carried out by the same procedure as in Example 1 except that the copolymer rubber (β) composed of ethyl acrylate and ethylidene norbornene shown in the upper part of Table 1 was used.

Comparative Example 6 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 35 parts by weight of the polycarbonate resin, 5 parts by weight of the copolymer rubber (β) and 60 parts by weight of PVDF were used in Example 1.

Comparative Example 7 Compounding and evaluation were carried out by the same procedure as in Example 1 except that 37 parts by weight of the polycarbonate resin, 60 parts by weight of the copolymer rubber (β) and 3 parts by weight of PVDF were used in Example 1.

[Effects of the Invention] The resin composition obtained by the present invention is significantly impact-resistant and heat-resistant by adding a vinylidene fluoride resin as an essential component as compared with conventionally known polycarbonate-based resin compositions. It turned out to be improved.

LE is a specific application of the resin composition obtained by the present invention.
D lamps, relay cases, switch connectors, coil bobbins, resistors, computer parts, telephone exchanges, condenser cases, tuners, terminal blocks, timer cases and other telecommunication parts, hair dryers, irons, shavers, egg boilers, coffee Manufacturer, VTR component, microwave oven component, TV component, audio component, compact disc, refrigerator component, air conditioner component, word processor,
For home appliances parts such as lighting covers, camera bodies, camera parts, clock parts, strobe parts, binoculars, microscope parts,
For precision machine parts such as projector parts, power tools, vending machine parts, handler bellows, elevator parts, escalator parts, motor cases, oil filter cases,
Pump parts, bolts, nuts, gears, cams, fiber bobbins, counter frames, office computer parts,
Machine parts such as register parts, calculator parts, typewriter parts, drafting machine parts, facsimile parts, copying machine parts, car heater fans, bumpers, instrument panels, instrument panels, motorcycle windshields, headlamps, tail lamps, air conditioning Plates, rail insulation parts, vehicle armrests, curtain covers, wiper covers, mold grips, meter hands, wheel covers and other parts for automobiles and vehicles, leisure parts such as surf riders and golf equipment, various covers, surface treatment It can be used for applications in which polycarbonate resins are used, such as agents and coatings.

Front Page Continuation (72) Inventor Yasuhiko Takemura 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. (56) References JP 61-225227 (JP, A) JP 61- 62538 (JP, A)

Claims (2)

[Claims] 1. A thermoplastic resin (α) and an acrylic copolymer rubber (I), a conjugated diene-nitrile compound copolymer rubber (II), and a hydride (III) of the above (II). And one or more copolymer rubbers (β) and vinylidene fluoride resin (γ), and the composition content is (α) 56 to 85% by weight, (β) 10 to 40% by weight, (γ ) 5-
35% by weight of a heat-resistant resin composition. 2. The heat resistant resin composition according to claim 1, wherein the thermoplastic resin is a polycarbonate resin or a polyamide resin.