JPH1036599A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having excellent impact resistance and molding appearance. SOLUTION: This thermoplastic resin composition comprises (A) 0.1-99.9wt.% graft copolymer obtained by subjecting one or more kinds of rubber components (a-1) having <=10 deg.C glass transition composition to graft polymerization with one or more kinds of vinylic monomers (a-2) containing a functional group such as an epoxy group and (B) 0.1-99.9wt.% modified polyolefin resin containing a functional group such as epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent molded appearance.

[0002]

2. Description of the Related Art It is well known that a thermoplastic resin containing a copolymer obtained by graft-polymerizing a vinyl monomer onto a rubber component such as polybutadiene, acrylate rubber or polyorganosiloxane exhibits high impact resistance. Acrylonitrile butadiene styrene (ABS) resin,
Acrylonitrile, acrylate rubber, styrene resin, etc. have been industrialized.

For example, Japanese Patent Application Laid-Open No. 63-69859 proposes a graft copolymer using a composite rubber comprising a polyorganosiloxane and a polyalkyl (meth) acrylate rubber as a rubber component. -1
No. 90746 discloses that a thermoplastic resin containing a graft copolymer using a composite rubber composed of a polyorganosiloxane and a polyalkyl (meth) acrylate rubber has excellent impact resistance and also excellent weather resistance. Is described.

However, the resin compositions containing these graft copolymers have a drawback that the appearance of the molded product is extremely poor depending on the type of thermoplastic resin used. For example, inexpensive polyolefin resins have high utility value in terms of cost, but polyolefin resin compositions containing the graft copolymers can be used in automobile interior and exterior materials, which require high designability, home appliances, and OA equipment housing materials. In order to use it, it was necessary to have an excellent molded appearance.

[0005]

SUMMARY OF THE INVENTION For example, Japanese Patent Application Laid-Open No. 2-17 / 1990
No. 63 and JP-A-7-33836 disclose the impact resistance of thermoplastic resin of polyolefin resin by adding a graft copolymer containing a composite rubber of polyorganosiloxane and polyalkyl (meth) acrylate rubber. Is described as being improved.

Further, Japanese Patent Application Laid-Open Nos.
No. 9385, the impact resistance of a thermoplastic polyolefin resin is improved by the addition of a graft copolymer containing a composite rubber of a polyorganosiloxane containing an epoxy group and a polyalkyl (meth) acrylate. Is described.

However, it has been difficult to obtain a molded article having an excellent molded appearance from the thermoplastic resin composition described in the above publication.

An object of the present invention is to obtain a thermoplastic resin composition having excellent impact resistance and excellent molded appearance.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to obtain a thermoplastic resin composition having good molded appearance, and as a result, have found that a vinyl monomer constituting a graft copolymer,
By specifying the functional groups contained in the polyolefin resin, it has been found that a thermoplastic resin composition having excellent molded appearance can be obtained, and the present invention has been achieved.

The gist of the present invention is that one or more rubber components (a-1) having a glass transition temperature of 10 ° C. or lower.
At least one selected from the group consisting of an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxylic acid group, a carboxylic anhydride group, a halogen group, a carbonyl halide group, an ammonium base, a carboxylic acid metal base and an amide group 0.1 to 99.9% by weight of a graft copolymer (A) obtained by graft polymerization of one or more vinyl monomers (a-2) having a functional group of (a), an epoxy group, an amino group, and a hydroxyl group , Mercapto group, carboxylic acid group,
Modified polyolefin resin (B) containing at least one functional group selected from the group consisting of carboxylic anhydride groups, halogen groups, halogenated carbonyl groups, ammonium bases, carboxylic acid metal bases and amide groups (B) 0.1 to 9
9.9% by weight of the thermoplastic resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Rubber component (a-1) according to the present invention
The glass transition temperature is not particularly limited as long as it is 10 ° C. or lower, and examples thereof include polybutadiene, ethylene-propylene copolymer, polyalkyl (meth) acrylate, and polyorganosiloxane. Although used as two or more kinds of composite rubbers, a composite rubber composed of a polyorganosiloxane component and a polyalkyl (meth) acrylate component is preferable in consideration of the impact resistance and weather resistance of the obtained resin composition.

As the polyorganosiloxane, for example, an organosiloxane mixture comprising a diorganosiloxane and, if desired, a grafting agent for a polyorganosiloxane or, further, a crosslinking agent for a polyorganosiloxane is mixed with an aqueous emulsifier solution and subjected to shearing by high-speed rotation. After atomizing with a homomixer or a high-pressure generator that atomizes with force, polymerize by dropping into a high-temperature aqueous solution of dodecylbenzenesulfonic acid, and then neutralize dodecylbenzenesulfonic acid with an alkaline substance Is obtained by

Examples of the diorganosiloxane include organosiloxanes having 3 or more members, and those having 3 to 6 members are preferred. Preferred examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. Siloxane and the like can be exemplified, and these can be used alone or in combination of two or more.

As the cross-linking agent for polyorganosiloxane, a trifunctional or tetrafunctional silane-based cross-linking agent, that is, a silane compound having three or four alkoxy groups is used, and trimethoxymethylsilane, triethoxyphenyl Examples include silane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane.

The amount of the crosslinking agent for polyorganosiloxane used is preferably from 0 to 30% by weight, more preferably from 0 to 10% by weight, based on the weight of the organosiloxane. Even if the amount of the crosslinking agent for polyorganosiloxane exceeds 30% by weight, it tends not to contribute to the formation of a further crosslinking structure.

The graft-crosslinking agent for polyorganosiloxane means that the alkoxysilane moiety is involved in the polymerization and is incorporated into the polyorganosiloxane, but is not reacted at this time but in the presence of the polyorganosiloxane for the preparation of a composite rubber. Is a silane compound having a functional group that reacts during the polymerization of the poly (meth) acrylate rubber in Example 1. As a specific example, a unit represented by the following formulas (1-1) to (1-4) can be formed. And the like.

CH ₂ ＣＲCR ² —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} 1-1 CH ₂ ＣＨCH—SiR ¹ _n O _{(3-n) / 2} 1-2 ^{_{CH 2 = CR 2 -C 6 H}} 4 SiR 1 n O (3-n) / 2 1-3 HS- (CH 2) p -SiR 1 n O (3-n) / 2 1-4 ( in each formula R ¹ represents a methyl group, an ethyl group, a propyl group or a phenyl group; R ² represents a hydrogen atom or a methyl group; n represents an integer of 0 to 2; and p represents an integer of 0 to 6). (Meth) acryloyloxysilane capable of forming the unit of 1-1) has a high grafting efficiency and can form an effective graft chain, and is advantageous in impact resistance of the obtained resin composition. Note that methacryloyloxysilane is particularly preferable as a unit capable of forming the unit of the formula (1-1).

Examples of the unit capable of forming the unit of the formula (1-2) include vinylmethyldimethoxysilane. Examples of the unit capable of forming the unit of the formula (1-3) include 4-vinylphenyldimethoxymethylsilane. , 4-vinylphenyltrimethoxysilane and the like, and those which can form the unit of the formula (1-4) include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldisilane. Ethoxyethylsilane and the like can be exemplified.

Examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Diethoxymethylsilane, γ-methacryloyloxypropylethoxydiethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like can be exemplified,
Among them, γ-methacryloyloxypropyldimethoxymethylsilane and γ-methacryloyloxypropyltrimethoxysilane are more preferable.

The amount of the grafting agent for polyorganosiloxane used is 0 to 10% by weight in the polyorganosiloxane, and 0 to 5% by weight in consideration of the impact resistance of the obtained resin composition containing the graft copolymer. % Is preferred.

The graft copolymer (A) according to the present invention comprises:
For example, in the presence of a polyorganosiloxane having a number average particle size of 10 to 100 nm obtained by emulsion polymerization of an organosiloxane mixture, a monomer for polyalkyl (meth) acrylate rubber is polymerized, and the resulting polyorganosiloxane component is It can be obtained by graft-polymerizing the component (a-2) according to the present invention to the rubber component (a-1) in which the polyalkyl (meth) acrylate rubber component is composited.

The amount of the polyorganosiloxane used is 0.5% based on 100% by weight of the entire graft copolymer (A).
~ 90% by weight is preferred. If the amount of the polyorganosiloxane used is less than 0.5% by weight, the seed polymerizability of the subsequent composite rubber polymerization and graft polymerization tends to decrease, and the yield of the desired graft copolymer tends to decrease. If the amount is more than 90% by weight, the powder properties of the obtained graft copolymer tend to decrease.

The particle size of the polyorganosiloxane is 10 to
Preferably it is in the range of 100 nm. When a polyorganosiloxane having a number average particle diameter of less than 10 nm is used,
The performance of the obtained graft copolymer as an impact modifier is reduced, and when a polyorganosiloxane having a number average particle size of more than 100 nm is used, the powder properties of the obtained graft copolymer tend to be reduced.

Examples of the polyalkyl (meth) acrylate rubber monomer include, for example, a specific alkyl (meth) acrylate and, if desired, a crosslinking agent for the polyalkyl (meth) acrylate rubber, and further, if desired, a polyalkyl (meth) acrylate.
A monomer mixture consisting of a graft crosslinking agent for acrylate rubber is used.

Specific alkyl (meth) acrylates include linear or branched acrylates having 1 to 8 carbon atoms in the alkyl group and alkyl methacrylates having 6 to 12 carbon atoms in the alkyl group. Acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, 3-pentyl acrylate, hexyl acrylate, n-heptyl acrylate , 2-
Heptyl acrylate, n-octyl acrylate, 2
-Octyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, n-lauryl methacrylate, 2-ethylhexyl methacrylate, and the like,
Among these, n-butyl acrylate is preferred.

As the crosslinking agent for the polyalkyl (meth) acrylate rubber, a (meth) acrylate having two or more polymerizable unsaturated bonds is used, and ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol is used. Dimethacrylate,
Examples thereof include 1,4-butylene glycol dimethacrylate.

The graft-linking agent for the polyalkyl (meth) acrylate rubber is polymerized together with other components during polymerization for producing the polyalkyl (meth) acrylate rubber, and is incorporated into the rubber. A monomer having two or more polymerizable unsaturated bonds having different reactivities such that the unsaturated unsaturated group remains without reacting and the remaining unsaturated group can be polymerized together with the graft branch component during the subsequent graft polymerization. , Allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate is partly formed by the reaction of both unsaturated groups to form a crosslinked structure during polymerization of the polyalkyl (meth) acrylate rubber, and the remainder is caused by the reaction of only one of the unsaturated groups and the other unsaturated bond. Remains as a result of the polymerization of the polyalkyl (meth) acrylate rubber, and during the subsequent graft polymerization, the remaining unsaturated bond reacts to form a graft bond, so that it functions as both a crosslinking agent and a graft crossing agent.

Each of these crosslinking agents and grafting agents for polyalkyl (meth) acrylate rubbers may be used alone or in combination of two or more.
The amount of the crosslinking agent and the amount of the grafting agent to be used is 0 to 10
The amount is 10% by weight, and when only the allyl methacrylate is used as both a crosslinking agent and a graft crossing agent, it may be used in an amount of 0 to 20% by weight.

The amount of the polyalkyl (meth) acrylate rubber monomer used is 0.5 to 90% by weight based on 100% by weight of the whole graft copolymer. When the amount is less than 0.5% by weight, the pigment coloring property of the resin composition used as the impact modifier is reduced, and when the amount exceeds 90% by weight, the powder properties tend to be reduced.

The polymerization of the monomer for polyalkyl (meth) acrylate rubber is carried out by using sodium hydroxide, potassium hydroxide,
The above-mentioned monomer for an alkyl (meth) acrylate rubber is added to a latex of a polyorganosiloxane neutralized by the addition of an aqueous solution of an alkali such as sodium carbonate, and impregnated into polyorganosiloxane rubber particles. What is necessary is just to carry out by making a radical polymerization initiator act. As the polymerization proceeds, a latex of a composite rubber from which the polyorganosiloxane component and the polyalkyl (meth) acrylate rubber component cannot be substantially separated is obtained.

Considering the impact resistance of the obtained resin composition, as the rubber component (a-1), the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the polyalkyl (meth) acrylate It is preferable that the main skeleton of the rubber component has a repeating unit derived from n-butyl acrylate, and the ratio of the polyorganosiloxane component to the polyalkyl (meth) acrylate rubber component in the rubber component (a-1) is Preferably, the former is 1 to 99% by weight and the latter is 1 to 99% by weight, the former is 5 to 95% by weight, and the latter is 5 to 95% by weight.
Is more preferable.

The component (a-2) according to the present invention includes an epoxy group, an amino group, a hydroxyl group, a mercapto group,
One or more vinyl monomers containing at least one functional group selected from the group consisting of carboxylic acid groups, carboxylic anhydride groups, halogen groups, halogenated carbonyl groups, ammonium bases, carboxylic acid metal bases and amide groups. However, in view of the molded appearance of the obtained resin composition, the functional groups contained in these vinyl monomers include a 1,2-epoxyethyl group, a 1,2-epoxypropyl group, and a 1,2-epoxypropyl group. Epoxy groups such as 2-epoxybutyl group, 2,3-epoxybutyl group, 1,2-epoxycyclohexyl group, glycidyl group; amino group, monomethylamino group, monoethylamino group, monopropylamino group, dimethylamino group Amino groups such as, diethylamino, ethylmethylamino group, aminomethyl group, aminoethyl group, diaminoethyl group; Hydroxy groups such as droxymethyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group and hydroxyphenyl group; mercapto groups such as mercapto group, mercaptomethyl group, mercaptoethyl group and mercaptopropyl group; hydroxycarbonylmethyl group and hydroxy Carboxylic acid groups such as carbonylethyl group, hydroxycarbonylpropyl group and the like or different carboxylic acid anhydride groups; α, β
Dicarboxylic acid groups such as -di (hydroxycarbonyl) ethyl group, α, β-di (hydroxycarbonyl) propyl group or anhydrides thereof; chloro group, bromo group, iodo group, chloromethyl group, bromomethyl group, chloroethyl Groups, dichloroethyl groups, chloropropyl groups, chlorophenyl groups and other halogen groups; chlorinated carbonyl groups, brominated carbonyl groups, iodinated carbonyl groups and other carbonyl halide groups are preferred, and 1,2-epoxy is more preferred. Ethyl group, 1,2-epoxypropyl group, 1,2
-Epoxybutyl group, 2,3-epoxybutyl group, 1,
Epoxy groups such as 2-epoxycyclohexyl group and glycidyl group; amino group, monomethylamino group, monoethylamino group, monopropylamino group, dimethylamino group,
Amino groups such as diethylamino group, ethylmethylamino group, aminomethyl group, aminoethyl group and diaminoethyl group; hydroxy groups such as hydroxymethyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group and hydroxyphenyl group; Mercapto groups, mercaptomethyl groups, mercaptoethyl groups, mercaptopropyl groups and other mercapto groups, more preferably 1,
2-epoxyethyl group, 1,2-epoxypropyl group,
An epoxy group such as a 1,2-epoxybutyl group, a 2,3-epoxybutyl group, a 1,2-epoxycyclohexyl group, and a glycidyl group.

Examples of the vinyl monomer containing an epoxy group include glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, and glycidyl ether of polyalkylene glycol (meth) acrylate. And glycidyl ether of polyalkylene glycol (meth) acrylate, diglycidyl itaconate, and the like. In view of the raw material cost, at least one selected from glycidyl (meth) acrylate and diglycidyl itaconate is preferable.

An epoxy group, an amino group, a hydroxyl group, a mercapto group, which constitutes the component (a-2) according to the present invention,
At least one functional group selected from the group consisting of a carboxylic acid group, a carboxylic acid anhydride group, a halogen group, a halogenated alkyl group, a halogenated aryl group, a halogenated carbonyl group, an ammonium base, a carboxylic acid metal base and an amide group. The amount of the one or more vinyl monomers to be used is 1 to 30% by weight based on 100% by weight of the entire graft copolymer (A).

If necessary, at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, methacrylates, acrylates and vinyl cyanide compounds is used as a copolymer component.

For example, when a vinyl monomer which gives a polymer having a glass transition temperature of 50 ° C. or higher is used, the powder characteristics of the obtained graft copolymer are good. Examples of such vinyl monomers include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyltoluene;
Methacrylates such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.

The amount of one or more vinyl monomers selected from the group consisting of aromatic alkenyl compounds, methacrylic esters, acrylic esters and vinyl cyanide compounds is from 5 to 60 parts by weight based on 100% by weight of the entire graft copolymer. % By weight. If it is less than 5% by weight, the powder properties tend to decrease, and if it exceeds 60% by weight, the performance as an impact modifier tends to decrease.

The modified polyolefin resin (B) according to the present invention includes an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxylic acid group, a carboxylic anhydride group, a halogen group, a halogenated carbonyl group, an ammonium base, and a carboxylic acid. A polyolefin resin containing at least one functional group selected from the group consisting of an acid metal salt, an amide group and a carboxylic acid group is used.

For example, when the reactivity of the functional group contained in the modified polyolefin resin (B) and the functional group contained in the graft copolymer (A) is high, the appearance of the resin composition obtained is extremely good. For example, graft copolymer (A)
When a graft copolymer containing an epoxy group is used as the functional group, the functional group contained in the modified polyolefin resin (B) includes an epoxy group, an amino group, a hydroxy group,
A mercapto group, a carboxylic acid group, a carboxylic anhydride group, a halogen group, and a carbonyl halide group are preferred, and a functional group of a carboxylic acid group and / or a carboxylic anhydride group is more preferred.

The modified polyolefin resin (B) containing a functional group according to the present invention can be obtained, for example, as a copolymer of an α-olefin and a vinyl monomer or by graft-modifying the polyolefin resin by a known method. can get.

The α-olefin is an α-olefin having 2 to 10 carbon atoms.
-Consisting of one or more olefins. Examples of α-olefins include ethylene, propylene, butene-
1, pentene-1, hexene-1, 3-methylbutene-
1,4-methylpentene-1,3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5-methylhexene-1, allylcyclo Pentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1,
Vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1] heptane, heptene-1,
Octene-1 and the like, and one or more of these α-olefins are used as a polymerization component.

As the copolymerization component, 4-methyl-1,
Non-conjugated dienes such as 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and 1,9-decadiene, vinyl acetate, acrylic acid, methacrylic acid, alkyl (meth) acrylate, and fragrance One or more vinyl monomers such as aromatic vinyl and maleic anhydride are used so as to account for 50% by weight or less of the entire polymerization components.

As a method for graft-modifying the polyolefin resin, for example, the polyolefin resin is melt-kneaded with an α, β-unsaturated carboxylic acid and its anhydride and an organic peroxide by an extruder or heated in a solvent. And then stirring to obtain a polyolefin resin containing a carboxylic acid group and an anhydride group thereof (Japanese Unexamined Patent Publication (Kokai) No. 7-18018, Polymer Chemistry 2).
9, No. 324, PP259).

The α, β-unsaturated carboxylic acid and its anhydride are not particularly restricted but include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and the same or different anhydrides of these acids and these acids. However, maleic anhydride is preferred in consideration of the molded appearance of the obtained resin composition.

The organic peroxide is not particularly limited as long as it is generally known, and ketone peroxides such as 1,1-bis-tert-butylperoxy-3,3-trimethylcyclohexane Dialkyl peroxides such as dicumyl peroxide; hydroperoxides such as 2,5-dihydroperoxide; diacyl peroxides such as benzoyl peroxide;
And peroxyesters such as dimethyl-2,5-dibenzoylperoxyhexane.

The polyolefin resin (C) according to the present invention
Is composed of one or more α-olefins having 2 to 10 carbon atoms. Examples of α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1,
3-methylbutene-1, 4-methylpentene-1,3
3-dimethylpentene-1,3-methylhexene-1,
4-methylhexene-1,4,4-dimethylhexene-
1,5-methylhexene-1, allylcyclopentane,
Allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1] heptane, heptene-1, octene-1 and the like. One type is used as a polymerization component.

As the copolymerization component, 4-methyl-1,
Non-conjugated dienes such as 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and 1,9-decadiene, vinyl acetate, alkyl (meth)
One or more vinyl monomers such as acrylate and aromatic vinyl are used so as to account for 50% by weight or less of the whole polymerization components.

Specific examples of the polyolefin resin (C) include polyethylene, polypropylene and ethylene-propylene copolymer, and polypropylene is particularly preferred.

The resin composition of the present invention can be obtained by blending and kneading the graft copolymer (A), the modified polyolefin resin (B) and the polyolefin resin (C).

The compounding ratio is (A) 0.1 to 99.9% by weight,
(B) 0.1 to 99.9% by weight, and (C) 0 to 99.8% by weight. In consideration of the impact resistance and elastic modulus of the obtained resin composition, (A) 5 to 9 40% by weight,
(B) 40 to 95% by weight, (C) 0 to 80% by weight, more preferably (A) 10 to 40% by weight, (B) 60 to 9%.
0% by weight and (C) 0 to 20% by weight.

If necessary, various known additives, stabilizers and reinforcing agents can be blended.

The compounding and kneading may be carried out by a commonly known method,
For example, a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-roll, or the like is used. The obtained resin composition is a commonly known molding method, for example, injection molding, hollow molding, extrusion molding,
Compression molding, calendar molding, etc. can be applied,
Various molded products can be manufactured.

Hereinafter, the present invention will be described with reference to examples.

[0054]

EXAMPLES In the description, "parts" indicates "parts by weight". In addition, the measurement of various physical properties in each Example and Comparative Example is based on the following methods.

Average particle diameter: A latex diluted with water was used as a sample liquid for dynamic light scattering (DLS, Otsuka Electronics Co., Ltd.)
800, temperature, 25 ° C., scattering angle, 90 °).

Molding appearance: Evaluated visually.

Gloss: Measured according to ASTM 523. Note that the incident angle is 45 °.

Izod impact strength: ASTM, D-25
6 was measured. The measurement conditions were as follows: specimen thickness 3.
2 mm, temperature 23 ° C., humidity 50% RH.

Flexural modulus: Measured according to ASTM, D-790. The measurement conditions were a temperature of 23 ° C and a humidity of 50.
% RH.

Reference Example 1 Silicone Latex L-1
Production of 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 99.5 parts of octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. To this, 300 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate was dissolved was added, and the mixture was stirred at 10,000 rpm for 2 minutes with a homomixer. Latex was obtained.

On the other hand, dodecylbenzenesulfonic acid 10 was placed in a separable flask equipped with a condenser and a stirring blade.
And 90 parts of distilled water, to prepare a 10% by weight aqueous solution of dodecylbenzenesulfonic acid.

While the aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 2 hours, and after the completion of the addition, the temperature was maintained for 3 hours, followed by cooling.
The reaction was then kept at room temperature for 12 hours and neutralized with aqueous sodium hydroxide.

The thus obtained latex L-1
Was dried at 170 ° C. for 30 minutes to obtain a solid content.
18.1% by weight. The number average particle size of the latex was 32 nm.

(Reference Example 2) Production of Graft Copolymer G-1 The silicone latex L-1 obtained in Reference Example 1 was converted to 55.2.
A portion was collected, placed in a separable flask equipped with a stirrer, 144.8 parts of distilled water was added, and after purging with nitrogen, 5 parts were added.
The temperature was raised to 0 ° C., and a mixed solution of 74.8 parts of n-butyl acrylate, 0.2 parts of allyl methacrylate and 0.3 parts of tert-butyl hydroperoxide was added. Next, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalit and 10 parts of distilled water was added to start radical polymerization. After holding for a time, a composite rubber latex was obtained.

A mixture of 10 parts of methyl methacrylate and 0.05 part of tert-butyl hydroperoxide was added dropwise to the composite rubber latex over 15 minutes, and the mixture was maintained at an internal temperature of 60 ° C. for 1 hour.
A mixture of 0.025 parts of tert-butyl hydroperoxide was added dropwise over 8 minutes, and the mixture was maintained at an internal temperature of 60 ° C. for 2 hours to complete the graft polymerization onto the composite rubber. The latex of 1) was obtained. The number average particle diameter of G-1 latex was 71 nm.

G-1 latex at 40 ° C. with a concentration of 5% by weight
Was added to the aqueous solution of calcium chloride so that the weight ratio of the latex and the aqueous solution was 1: 2. Thereafter, the temperature was raised to 90 ° C. to coagulate, and the solid content was separated by repeating washing with water. It dried at 24 degreeC for 24 hours, and obtained the dry powder of G-1.

(Reference Example 3) Production of Graft Copolymer G-2 The silicone latex L-1 obtained in Reference Example 1 was converted to 55.2.
A portion was collected, placed in a separable flask equipped with a stirrer, 144.8 parts of distilled water was added, and after purging with nitrogen, 5 parts were added.
The temperature was raised to 0 ° C., and a mixed solution of 74.8 parts of n-butyl acrylate, 0.2 parts of allyl methacrylate and 0.3 parts of tert-butyl hydroperoxide was added. Next, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate, 0.2 part of Rongalite and 10 parts of distilled water was added to start radical polymerization, and then 2 minutes at an internal temperature of 70 ° C. After holding for a time, a composite rubber latex was obtained.

A mixture of 15 parts of methyl methacrylate and 0.075 part of tert-butyl hydroperoxide was added dropwise to the composite rubber latex over a period of 23 minutes.
For 1.5 hours to complete the graft polymerization onto the composite rubber, thereby obtaining a latex of the graft copolymer (G-2).
The number average particle diameter of G-2 latex was 72 nm.

G-2 latex at a concentration of 5% by weight at 40 ° C.
Was added to the aqueous solution of calcium chloride so that the weight ratio of the latex and the aqueous solution was 1: 2. Thereafter, the temperature was raised to 90 ° C. to coagulate, and the solid content was separated by repeating washing with water. It dried at 24 degreeC for 24 hours, and obtained the dry powder of G-2.

Reference Example 4 Production of Maleic Anhydride Modified Polypropylene Resin Maleic anhydride 9 ground to 100 μm or less
The mixture was mixed with 8.2% by weight and 0.2% by weight of maleic acid. 100 parts of polypropylene (MA2 manufactured by Mitsubishi Chemical Corporation), 0.05 parts of organic peroxide (Perbutyl P manufactured by NOF),
6000 ppm of a mixture of maleic anhydride and maleic acid was blended. Twin screw extruder (WERNER & PFLEIDE)
RSK ZSK30), barrel temperature 200 ℃,
The mixture was melt-kneaded at a screw rotation speed of 200 rpm, and the resulting strand was pelletized to obtain a maleic anhydride-modified polypropylene resin as pellets.

(Example 1) 15 parts of the epoxy group-containing graft copolymer (G-1) obtained in Reference Example 2 and 100 parts of the maleic anhydride-modified polypropylene obtained in Reference Example 3 were blended. Twin screw extruder (WERNER & PFLEIDE)
RSK ZSK30), barrel temperature 200 ℃,
Screw rotation speed 200rpm, discharge rate 10kg / hr
The mixture was melt-kneaded. When the appearance of the obtained strand was visually evaluated, the surface was very smooth. Cut the strands using a pelletizer,
From the obtained pellet-shaped resin composition, using an injection molding machine (IS-100 manufactured by Toshiba Machine Co., Ltd.), a flat plate for measuring glossiness (100 × 100 × 3 mm), an Izod impact test piece, a bending test piece Was molded.

Various measurements and tests were carried out using the obtained test pieces. The obtained resin compositions were excellent in surface gloss, impact strength and elastic modulus. Especially 85% gloss
It satisfies the standard of molded appearance (70% or more) in the field where high designability is required.

Comparative Example 1 15 parts of the epoxy group-containing graft copolymer (G-1) obtained in Reference Example 2 and 100 parts of polypropylene (MA2 manufactured by Mitsubishi Chemical Corporation) were blended.
Twin screw extruder (Z made by WERNER & PFLEIDERER)
Using SK30), the mixture was melt-kneaded at a barrel temperature of 200 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 10 kg / hr.

When the appearance of the obtained strand was visually evaluated, a large amount of bumps were generated on the surface, and the molded appearance was poor. Various measurements and evaluations were performed in the same manner as in Example 1. As a result, the obtained resin composition was inferior in surface gloss and impact strength.

(Comparative Example 2) 15 parts of the graft copolymer (G-2) obtained in Reference Example 3 and 100 parts of the maleic anhydride-modified polypropylene obtained in Reference Example 4 were blended. Twin screw extruder (ZSK manufactured by WERNER & PFLEIDERER)
Using 30), the mixture was melt-kneaded at a barrel temperature of 200 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 10 kg / hr.

When the appearance of the obtained strand was visually evaluated, a large amount of bumps were generated on the surface, and the molded appearance was poor. Various measurements and evaluations were performed in the same manner as in Example 1. As a result, the obtained resin composition was inferior in surface gloss and impact strength.

(Comparative Example 3) 15 parts of the graft copolymer (G-2) obtained in Reference Example 3 and 100 parts of polypropylene (MA2 manufactured by Mitsubishi Chemical Corporation) were blended. Twin screw extruder (W
Barrel temperature 200 ° C, screw rotation speed 200r using ERNER & PFLEIDERER ZSK30)
The mixture was melt-kneaded at pm and a discharge rate of 10 kg / hr. When the appearance of the obtained strand was visually evaluated, a large amount of bumps were generated on the surface, and the molded appearance was poor. Various measurements and evaluations were performed in the same manner as in Example 1. As a result, the obtained resin composition was inferior in surface gloss and impact strength.

[0078]

[Table 1]

[0079]

Since the thermoplastic resin composition of the present invention has an excellent molded appearance, it can be used for interior and exterior materials of automobiles and home electric appliances and OA equipment housing materials which require high designability. The effect is enormous.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichi Ito 20-1 Miyukicho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd. Otake Works

Claims (1)

[Claims] 1. An epoxy group, an amino group, and one or more rubber components (a-1) having a glass transition temperature of 10 ° C. or lower.
Hydroxyl group, mercapto group, carboxylic acid group, carboxylic anhydride group, halogen group, carbonyl halide group,
Graft copolymer (A) 0 obtained by graft polymerization of at least one vinyl monomer (a-2) containing at least one functional group selected from the group consisting of ammonium bases, metal carboxylate groups and amide groups. 0.1 to 99.9% by weight and an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxylic acid group, a carboxylic anhydride group, a halogen group, a halogenated carbonyl group, an ammonium base, a carboxylic acid metal base and an amide group A thermoplastic resin composition comprising 0.1 to 99.9% by weight of a modified polyolefin resin (B) containing at least one functional group selected from the group consisting of: