JP3228448B2 - Rubber-modified thermoplastic resin and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a monomer or a (meth) acrylic acid mainly containing an aromatic vinyl compound in the presence of a hydrogenated product of a block copolymer comprising a conjugated diene and a vinyl aromatic compound. It is obtained by graft copolymerization of a monomer mainly composed of an ester compound. It has excellent coloring properties and remarkably improves poor phenomena such as flow marks. It also has weather resistance, impact resistance, chemical resistance and moldability. The present invention relates to a rubber-modified thermoplastic resin having excellent heat resistance and a composition thereof.

[0002]

2. Description of the Related Art An E which does not substantially contain an unsaturated bond in its main chain.
Graft copolymer with styrene, acrylonitrile, etc. using PM and EPDM as rubber components (AES resin)
It is known that, compared to an ABS resin using a conjugated diene rubber, has higher resistance to ultraviolet rays, oxygen and ozone and has much better weather resistance.

However, AES resin has the following disadvantages. Poor colorability. Generally, rubber-modified resins typified by ABS resin are considered to be inferior in coloring property to homogeneous resins. According to the studies by the inventors, AES resin lacks sharpness and depth, particularly in vivid and dark colors, as compared with ABS resin. Large amounts were needed.

[0004] Poor chemical resistance. AES resin is used for automobile exterior parts because of its excellent weather resistance. However, because of its poor chemical resistance, it is necessary to take measures such as reducing the amount of rubber, and as a result, the strength decreases. In some cases, there are restrictions on the site of use and the method of use.

In general, polymethyl methacrylate resin or a resin containing methyl methacrylate as a main component is widely used in a wide range of fields such as automobile parts, electric parts and displays because of its excellent properties such as transparency, gloss and weather resistance. However, there is a disadvantage that the impact strength is low. As a method for improving the impact strength, a vinyl monomer mixture composed of methyl methacrylate, styrene, acrylonitrile, and the like is used in the presence of a diene rubber such as polybutadiene, and the refractive index of the diene rubber and the vinyl monomer. There is known a method of performing polymerization by selecting the composition of a vinyl-based monomer mixture so that the refractive index of a polymer obtained by polymerizing the mixture alone substantially matches. For example, methyl methacrylate-butadiene-styrene copolymer resin and methyl methacrylate-butadiene-styrene-acrylonitrile copolymer resin obtained by the method are used in various fields. However, since these resins contain unsaturated double bonds in the molecular main chain, they are deteriorated by ultraviolet rays or oxygen in the air, resulting in discoloration and reduced impact resistance. There are drawbacks.

As a method for improving the weather resistance, a method in which a rubbery polymer having a substantially saturated molecular main chain is used in place of the diene rubber and various vinyl monomers are graft-copolymerized thereto. Has been proposed. However, this rubbery polymer does not have a double bond like a diene rubber,
Since the radical activity is low, the vinyl monomer often becomes simply a blend of the rubbery polymer and the vinyl polymer resin without graft polymerization. For this reason, when the obtained resin is injection-molded, the flow pattern of the resin, called a flow mark, is seen to be uneven on the surface, the gloss and the transparency are extremely low, and the impact resistance and the tensile strength are inferior.

[0007]

The inventors of the present invention have conducted intensive studies on these points, and as a result, using a hydrogenated product of at least one block copolymer of a conjugated diene and a vinyl aromatic compound as a rubber component, Graft polymerization of aromatic vinyl compound or graft copolymerization of aromatic vinyl compound and monomer compound copolymerizable with aromatic vinyl compound, resulting in excellent weatherability with excellent colorability, moldability, impact strength and chemical resistance The resin was successfully obtained. Further, in the presence of the rubber component, a vinyl monomer containing (meth) acrylic acid ester as a main component and satisfying specific conditions is graft-polymerized, so that excellent transparency is obtained.
The present invention succeeded in obtaining a weather-resistant resin having excellent impact resistance, particularly excellent moldability and appearance without flow marks and the like, and has led to the present invention.

[0008]

According to the present invention, there are provided polymer blocks A, B and C in the molecule (where A is a polymer block mainly composed of a vinyl aromatic compound containing at least 90% by weight of a vinyl aromatic compound). , B has a 1,2-vinyl bond content of 2
5-70% of a copolymer block of butadiene and a vinyl aromatic compound, and C is a polybutadiene polymer block having a 1,2-vinyl bond content of less than 25%. ), Wherein the content of the polymer block A in the block copolymer is 1 to 40% by weight, the content of the polymer block B is 30 to 80% by weight, A block copolymer in which the content of the block C is 10 to 50% by weight, or at least one of the polymer blocks A, B, and C in which the block copolymer unit has a coupling agent residue. And a hydrogenated block copolymer having a number average molecular weight of 40,000 to 700,000, obtained by hydrogenating at least 80% or more of the olefinically unsaturated bonds in the block copolymer. In the presence of (A), 30 to 100% by weight of an aromatic vinyl compound monomer and / or a (meth) acrylate monomer,
A rubber-deformed thermoplastic resin obtained by graft copolymerization of 0% by weight with 0 to 70% by weight of another copolymerizable monomer, and the rubber-modified thermoplastic resin 10 to 9
A composition comprising 9% by weight and a polymer comprising 90 to 1% by weight of the following (B) and / or (C), and the content of the hydrogenated block copolymer (A) in the composition: Is 3
It is intended to provide a rubber-modified thermoplastic resin composition characterized in that the content is from 45 to 45% by weight. (B) A polymer obtained by polymerizing 30 to 100% by weight of a monomer comprising a vinyl aromatic compound and / or (meth) acrylate and 70 to 0% by weight of a vinyl cyanide compound. (C) 50-97% by weight of a monomer comprising a vinyl aromatic compound and / or (meth) acrylate, 3-50% by weight of a maleimide monomer, and 0-47% by weight of a vinyl cyanide compound. Polymer obtained by

Hereinafter, the present invention will be described in more detail.
The hydrogenated block copolymer (A) of the present invention has at least one of the following polymer blocks A, B and C, respectively.

As the vinyl aromatic compound, for example, styrene, paramethylstyrene, α-methylstyrene, vinyltoluene, P-tert-butylstyrene and the like are preferable, and styrene is preferable.

The polymer block A comprises 90% by weight of one or more vinyl aromatic compounds selected from vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-tert-butylstyrene. A polymer containing the above or a copolymer with butadiene containing at least 90% by weight of a vinyl aromatic compound, wherein 80% or more of the olefinically unsaturated bonds are hydrogenated.

The content of the polymer block A in the block copolymer before hydrogenation is 1 to 40% by weight, preferably 3 to 35%.
% By weight, and the content of the polymer block A in the polymer is 1%.
When the amount is less than the weight%, the coloring property is reduced, the orientation of the resin is increased, and the strength anisotropy is increased. If it exceeds 40% by weight, the impact resistance decreases. Further, the number average molecular weight of the polymer block A is preferably from 5,000 to 70,
000. When the content of the vinyl aromatic compound in the polymer block A is less than 90% by weight, the coloring property is reduced.

The polymer block B is a random copolymer of butadiene and a vinyl aromatic compound. The content of the polymer block B is 30 to 80% by weight, preferably 35 to 70%.
When the content of the polymer block B in the block copolymer before hydrogenation is less than 30% by weight, the impact resistance decreases, and when it exceeds 80% by weight, the coloring property decreases. The ratio of butadiene / vinyl aromatic compound in the polymer block B is 99/1 to 60/40, preferably 98/2.
~ 65/35, particularly preferably 96/4 ~ 70/30.
It is. When the amount of the aromatic vinyl is 1% by weight or less, the processability of the base rubber is reduced, and a flow mark is generated. On the other hand, when the content is 40% by weight or more, the hardness of the base rubber increases, and the impact resistance when resin is used decreases.

The 1,2-vinyl bond content of the polymer block B is from 25 to 70%, preferably from 30 to 60%. The polybutadiene before hydrogenation has a 1,2-vinyl bond content of 2
Below 5%, when hydrogenated, polyethylene chains form and lose rubbery properties. If it exceeds 70%, the glass transition temperature increases when hydrogenated, and the rubbery properties are lost. The polymer block B is preferably a polymer having a number average molecular weight of 30,000 to 300,000 and a hydrogenated polybutadiene portion of at least 80%.

The polymer block C is polybutadiene, and the content of the polymer block C is 10 to 50% by weight, preferably 15 to 45% by weight. The 1,2-vinyl bond content of the polymer block C is less than 25%, preferably 3 to
20%. When the 1,2-bond content of the polybutadiene before hydrogenation in the polymer block C exceeds 25%, the chemical resistance is reduced.

The polymer block C is preferably a polymer obtained by hydrogenating polybutadiene having a number average molecular weight of 10,000 to 300,000 by at least 80% or more. Also,
Polybutadiene with less than 3% of 1,2-vinyl bonds is difficult to produce. When the content of the polymer block C in the block copolymer before hydrogenation is less than 10% by weight, the chemical resistance decreases, and when the content exceeds 50% by weight, the low-temperature impact strength decreases.

The hydrogenated block copolymer (A) is a block copolymer composed of polymer blocks A, B and C, or the block copolymer unit is composed of a polymer block A, It is a block copolymer bonded to a polymer unit comprising at least one polymer block of B and C.

The polymer molecular chain of the hydrogenated block copolymer (A) may be linear or branched. The number average molecular weight of the hydrogenated block copolymer (A) is from 40,000 to 700,000. If it is 40,000 or less, the impact strength is reduced, and if it is 700,000 or more, the appearance of the molded product is poor. It is important that the hydrogenated block copolymer (A) has been hydrogenated with at least 80%, preferably at least 90%, of olefinically unsaturated bonds, and if it is less than 80%, the weather resistance is reduced.

The hydrogenated block copolymer (A) comprises α, β such as maleic anhydride, itaconic anhydride and fumaric anhydride.
-It may be modified with an acid anhydride of an unsaturated carboxylic acid or modified with an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, allyl glycidyl ether or vinyl glycidyl ether. In this case, the compatibility when blended with another resin such as engineering plastic can be improved, and the performance can be improved.

The molecular weight distribution ( _Mw / _Mn ) of the hydrogenated block copolymer (A) is preferably 10 or less from the viewpoint of molding appearance.

The hydrogenated block copolymer (A) can be obtained, for example, by conducting anionic living polymerization in a hydrocarbon solvent using an organic lithium initiator. Also,
The branched polymer is obtained by adding a required amount of a tri- or higher functional coupling agent at the end of the polymerization and performing a coupling reaction.

In order to control the content of vinyl bonds such as 1,2- and 3,4-bonds, ethers, tertiary amine compounds, alkoxides of alkali metals such as sodium and potassium, phenoxides and sulfonates are used. .

As the organic lithium initiator, n-butyllithium, sec-butyllithium, tert-butyllithium and the like are used. As the hydrocarbon solvent, hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, 2-methylbutene-1, 2-methylbutene-2 and the like are used.

The polymerization may be a batch system or a continuous system,
The polymerization temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C.
C. and the polymerization time is from 10 minutes to 3 hours. The coupling agent is a coupling agent having three or more functions, such as tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, divinylbenzene, and adipic acid. Diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate,
Examples include diphenylmethane diisocyanate and 1,2,4-benzenetriisocyanate.

By hydrogenating the block polymer thus polymerized, a hydrogenated block polymer (A) is obtained. The hydrogenation reaction is performed by dissolving the above block polymer in a hydrocarbon solvent, at 20 to 150 ° C., 1 kg / cm ² to 10
It is carried out in the presence of a hydrogenation solvent under 0 kg / cm ² of pressurized hydrogen.

Examples of the hydrogenation catalyst include a catalyst in which a noble metal such as palladium, ruthenium, rhodium and platinum is supported on silica, carbon and diatomaceous earth, a complex catalyst such as rhodium, ruthenium and platinum, and an organic carboxylic acid such as cobalt and nickel. And a catalyst consisting of organoaluminum or organolithium, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl titanium ditolyl, dicyclopentadienyl titanium dibenzyl and other titanium compounds and lithium,
A hydrogenation catalyst composed of an organometallic compound composed of aluminum and magnesium is used.

In the rubber-deformed thermoplastic resin of the present invention, a method of radically polymerizing a vinyl monomer in the presence of the hydrogenated block copolymer (A), for example, an emulsion polymerization method, a bulk polymerization method, and a suspension polymerization method. Legal or the like can be adopted.

The monomer used in the present invention is an aromatic vinyl compound monomer and / or 30 to 100% by weight of a (meth) acrylate, 70 to 0% by weight of a vinyl cyanide compound, and a copolymerizable monomer. Other monomers 0-7
0% by weight.

Examples of the aromatic vinyl compound monomer include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, and p-tert-butylstyrene. , Ethyl styrene,
Vinyl naphthalene and the like are used alone or in combination of two or more. The preferred aromatic vinyl compound monomer (B) is styrene or an aromatic vinyl compound containing 50% by weight or more of styrene.

(Meth) acrylic acid esters include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate,
Alkyl acrylates such as ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, and benzyl acrylate; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-
Examples thereof include alkyl methacrylates such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Particularly, methyl methacrylate is preferred. Examples of the vinyl cyanide compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
Used in species or two or more. Acrylonitrile is particularly preferred. Examples of other copolymerizable monomers include acrylic acid, methacrylic acid, N-alkylmaleimides such as cyclohexylmaleimide, and N-aromatic maleimides such as N-phenylmaleimide.

Specific examples of preferred combinations of monomers used in the present invention are shown below. Styrene-acrylonitrile Styrene-methyl methacrylate Styrene-acrylonitrile-methyl methacrylate By replacing a part or all of the above styrene with α-methylstyrene, heat resistance can be imparted. Flame retardancy can be imparted by substituting part or all of styrene with halogenated styrene. Also,
When methyl methacrylate is used in combination with the above monomers, the transparency of the rubber-modified thermoplastic resin is improved, and the rubber-modified thermoplastic resin has excellent coloring properties.

The rubber-modified thermoplastic resin obtained by the above production method has an intrinsic viscosity [η] of a methyl ethyl ketone-soluble component.
(Measured at 30 ° C.) is preferably at least 0.2 dl / g, more preferably 0.22 to 1.5 dl / g, particularly preferably 0.24 to 1.2 dl / g.

The graft ratio of the rubber-modified thermoplastic resin of the present invention is preferably in the range of 20 to 90%, more preferably 25 to 85%, and particularly preferably 3 to 85%.
0-80%. When the graft ratio is 20% or less, the impact strength is sufficient even if the graft is not substantially formed, but the solvent resistance such as kerosene resistance and gasoline resistance is significantly reduced, and the coloring property and weld appearance Molded appearance also deteriorates.

The content of the hydrogenated block copolymer (A) in the above-mentioned rubber-modified thermoplastic resin (hereinafter referred to as rubber content) can be arbitrarily selected according to the purpose.
In order to satisfy the impact resistance, moldability and transparency of the resin, the range is 5 to 70% by weight, preferably 10 to 65% by weight.
It is. If the rubber content is less than 5% by weight, only a resin having insufficient impact resistance can be obtained, and if it exceeds 70% by weight, the surface hardness is undesirably reduced.

As the polymerization method for producing the rubber-modified thermoplastic resin, known methods such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method and an emulsion polymerization method can be employed.

The rubber-modified thermoplastic resin thus obtained has excellent molding appearance, weather resistance, impact resistance, molding processability and chemical resistance, and can be widely used for various applications utilizing these characteristics. it can.

The rubber-modified thermoplastic resin (A) of the present invention comprises:
It can be blended with other polymers described below according to the purpose. For example, polyvinyl chloride, polyphenylene ether, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polyvinylidene fluoride, polystyrene, high impact polystyrene, styrene-acrylonitrile copolymer, ABS resin, styrene-methyl methacrylate copolymer Styrene-maleic anhydride copolymer, chlorinated polyethylene, AES resin other than the present invention, EPR, EP
DM, 1,2-polybutadiene and the like. These can be used alone or in combination of two or more.

The other polymers preferably include the following (b) and (c). (B) 30 to 100% by weight, preferably 30 to 90% by weight, of a monomer comprising a vinyl aromatic compound and / or a (meth) acrylic acid ester and a vinyl cyanide compound 70
A polymer obtained by polymerizing 〜0% by weight, preferably 5５〜70% by weight. (C) 50 to 97% by weight, preferably 55 to 95% by weight, of a monomer comprising a vinyl aromatic compound and / or a (meth) acrylic acid ester, 3 to 50% of a maleimide monomer
A polymer obtained by polymerizing 0 to 47% by weight, preferably 5 to 45% by weight, and 0 to 47% by weight, preferably 2 to 40% by weight of a vinyl cyanide compound.

The above-mentioned vinyl aromatic compounds, (meth) acrylic acid esters and vinyl cyanide compounds correspond to those mentioned above, and preferred vinyl aromatic compounds are styrene and
α-Methylstyrene, a preferred (meth) acrylate, is methyl methacrylate.

Examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. Is N-phenylmaleimide.
Alternatively, a method of copolymerizing maleic anhydride or the like and imidizing it may be used.

The composition ratio of the composition comprising the polymer of (b) and / or (c) to the rubber-modified thermoplastic resin (a) is preferably 10-99 / 90-1% by weight, more preferably 30 to 95/70 to 5% by weight, and the content of the hydrogenated block copolymer (A) used in (A) in the composition is 3 to 45% by weight, preferably 5 to 40% by weight. % By weight. The composition using the above (c) is more excellent in heat resistance.

The rubber-modified thermoplastic resin of the present invention and a composition using the same are added to a hindered phenol-based, phosphorus-based, sulfur-based antioxidant, a light stabilizer, an ultraviolet absorber, and a lubricant. Commonly used additives such as a colorant, a flame retardant, and an enhancer can be added.

[0043]

The present invention will be described in more detail with reference to the following examples. In the following text, “parts” and “%” are all by weight. Various physical property test methods were measured according to the following procedures. (1) Izod impact strength: ASTM D-256
(1/4 x 1/2 inch cross section, notched) (2) Drop weight impact strength: Drop weight impact of a 1.6 mm thick molded product with a hitting rod tip R = 1/2 "using a Dupont impact tester (3) Weather resistance: Sunshine weatherometer using carbon arc as a light source (Suga Test Instruments Co., Ltd. WEL-6)
XS-DC) for 1000 hours, the Izod impact strength was measured, and the retention was calculated. Test conditions Black panel temperature 63 ± 3 ° C Chamber temperature 60 ± 5% RH Rain cycle 18 minutes every 2 hours Carbon exchange cycle 60Hr Izod impact strength ASTM D-256 (1/8 × 1/2 inch cross section) (4) Warm kerosene resistance: Black pellets (100 parts by weight of compounded resin, 0.5 parts by weight of carbon black, stearic acid C
a 0.3 part by weight) was immersed in JIS No. 6 kerosene (kerosene temperature: 80 ° C.), left at 50 ° C. for 1 hour, wiped off the surface, and dried to determine whether there was any abnormality. Judgment criteria A: No discoloration is recognized. …: Discoloration is slightly observed. X: Changes such as whitening and gloss reduction are observed. (5) The graft ratio was measured by the following method. A certain amount (x) of the graft polymer is put into acetone, and shaken for 2 hours with a shaker to dissolve the free copolymer. The solution was centrifuged at 23000 rpm.
p. centrifugation at m for 30 minutes to obtain an insoluble matter. Next, it is dried at 120 ° C. for 1 hour by vacuum drying to obtain an insoluble matter (y). The graft ratio was calculated from the following equation. (6) Colorability The thermoplastic resin composition was blended in the following blending amount, and colored pellets were obtained through an extruder. It was further molded to obtain a color tone evaluation plate. Regarding the coloring property of the black compound, the lightness was measured using a color difference meter, and the value was represented by the Munsell color value (the larger the value, the worse the coloring property). For other coloring formulations, the saturation was visually determined. Black blended resin 100 Carbon black 0.5 Ca stearate 0.3 Red blended resin 100 Bengala 1.0 Ca stearate 0.5 Blue blended resin 100 Ultramarine blue 1.0 Ca stearate 0.5 Criteria ◎ ... very clear It is. …: Clear. Δ: between ○ and × ×: lack of sharpness ××: lack of sharpness. (7) Flow mark 1. Using an injection molding machine with a mold clamping pressure of 120 ton, and a wall thickness of 2.
A flat plate having a size of 5 mm and a length and width of 150 × 150 mm each was formed (forming temperature: 22 ° C.), and the occurrence of flow marks was visually determined.

[Base rubber No. Production of 1] (1) After charging 25,000 g of degassed and dehydrated cyclohexane and 800 g of 1,3-butadiene to a 50 L autoclave, 1.0 g of n-butyllithium was added thereto.
Isothermal polymerization at a polymerization temperature of 50 ° C was performed. After the conversion reaches almost 100%, tetrahydrofuran 30.0%
g, 1,3-butadiene 2400 g, styrene 200 g
Was added, and the temperature was raised from 50 ° C. to 80 ° C. for polymerization.

After the conversion reached almost 100%, 600 g of styrene was added and polymerization was carried out for 15 minutes. Obtained ABC triblock copolymer (hydrogenated polymer)
The molecular characteristics of are shown in Table 1. (2) Next, titanocene dichloride is placed in another container.
0 g was dispersed in 240 ml of cyclohexane and reacted at room temperature with 20 g of triethylaluminum. The obtained dark blue apparently uniform solution was added to the polymer solution obtained in (1), and a hydrogenation reaction was carried out at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours. Thereafter, the solvent was removed with methanol / hydrochloric acid, and 2,6-di-tert-butylcatechol was added, followed by drying under reduced pressure. Table 1 shows the molecular characteristics of the obtained hydrogenated ABC triblock copolymer (hydrogenated polymer).

[Base rubber No. Production of base rubber No. 2 having the polymer structure shown in Tables 1, 2 and 3 by changing the monomer composition and polymerization conditions. 2-20 were produced.

[0047]

[Table 1]

[Table 2]

[Table 3]

Example 1 A hydrogenated base rubber N previously made into a uniform solution was placed in a stainless steel autoclave having an internal volume of 10 L equipped with a ribbon-type stirring blade.
o. 30 parts by weight, styrene 70 parts by weight, toluene 1
20 parts by weight and 0.1 part by weight of tertiary dodecyl mercaptan were charged, the temperature was increased while stirring, 0.5 parts by weight of benzoyl peroxide and 0.1 parts by weight of dicumyl peroxide were added at 50 ° C., and the mixture was further heated. Warm, 80
After the temperature reached 200 ° C., the polymerization reaction was carried out at a stirring rotation speed of 200 rpm while the temperature was constantly controlled at 80 ° C. 6 after the start of the reaction
It took 1 hour from the time to raise the temperature to 120 ° C., and further reacted for 2 hours to complete the reaction. The polymerization conversion was 97%.

After cooling to 100 ° C., 0.2 parts by weight of 2,2-methylenebis-4-methyl-6-t-butylphenol was added, the reaction mixture was extracted from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. After removing and pulverizing finely, an extruder with a 40 mmφ vent (220 ° C, 7
At a pressure of 00 mmHg), the volatile matter was substantially distilled off, and the polymer was pelletized.

Comparative Example 1 The base rubber was 25 parts by weight of JSR EP22 (iodine value 15, Mooney viscosity 42, propylene content 43% by weight, diene component 5-ethylidene-2-norbornene), 52.5 parts by weight of styrene, Acrylonitrile 22.
The polymer was obtained in the same manner as in Example 1 except that the amount was 5 parts by weight.

Example 2 The base rubber type was No. Example 1 except that the monomers were changed to 1 and the monomers were changed to 49 parts by weight of styrene and 21 parts by weight of acrylonitrile.
A polymer was obtained in the same manner as described above.

Example 3 35 parts by weight of methyl methacrylate and styrene 3
A polymer was obtained in the same manner as in Example 1, except that the amount was changed to 5 parts by weight.

Example 4 35 parts by weight of methyl methacrylate and styrene 1
A polymer was obtained in the same manner as in Example 1 except that 7.5 parts by weight and 17.5 parts by weight of acrylonitrile were used.

Example 5 Rubber No. 1, 50 parts by weight, styrene 35 parts by weight, acrylonitrile 15 parts by weight, toluene 150 parts by weight, t-
Dodecyl mercaptan 0.05 parts by weight, benzoyl peroxide 0.4 parts by weight, dihumyl peroxide 0.0
After polymerization by the same method as in Example 1, a matrix resin having the same monomer composition as in this example was blended to give a final rubber content of 25% by weight.

Example 6 As the monomer composition, 25 parts by weight of methyl methacrylate, 12.5 parts by weight of styrene, and acrylonitrile
A polymer was obtained in the same manner as in Example 5 except that the amount was 5 parts by weight,
A matrix resin having the same monomer composition as in this example was blended to give a final rubber content of 25% by weight.

Examples 7 to 12 Example 2 except that
A polymer was obtained in the same manner as described above. In addition, Example 7 used styrene-
1 shows an example of a blend of an N-phenylmaleimide-methyl methacrylate copolymer. Example 13 A polymer was obtained in the same manner as in Example 1, except that the monomer was changed to 70 parts by weight of methyl methacrylate.

Comparative Examples 2 to 14 A polymer was obtained in the same manner as in Example 2 except that the polymer was 8 to 20. Examples and comparative examples are shown in Tables 4 and 4, respectively.
5, 6, and 7.

[0058]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[0059]

As is apparent from Examples and Comparative Examples relating to the rubber-modified thermoplastic resin of the present invention listed in Tables 3 and 4, and compositions thereof, when a rubber other than the rubber structure of the present invention is used, No requirements have been found for the requirements for weather-resistant resins on the premise that they are not subjected to surface treatment such as painting, ie, impact resistance, molded appearance (coloring, flow mark etc.), chemical resistance, and weather resistance. Was. On the other hand, it was found that all of these characteristics can be satisfied by using the rubber-reinforced resin of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 55/02 C08L 55/02 (72) Inventor Yoichi Kamoshida 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Japan Synthetic Rubber Co., Ltd. (56) References JP-A-2-302415 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 287/00 C08L 25/04 C08L 33/06 C08L 35/00 C08L 35 / 04 C08L 55/02

Claims (2)

(57) [Claims] 1. The polymer blocks A, B and C in a molecule
(However, A is a polymer block in which a vinyl aromatic compound is 90% by weight or more, and B is a 1,2-vinyl bond content of 25 to
70% of a copolymer block of butadiene and a vinyl aromatic compound, and C is a polybutadiene polymer block having a 1,2-vinyl bond content of less than 25%. ), Wherein the content of the polymer block A in the block copolymer is 1 to 40% by weight, the content of the polymer B is 30 to 80% by weight, A block copolymer having a C content of 10 to 50% by weight, or a block copolymer unit having at least one of the above polymer blocks A, B and C via a coupling agent residue; A block copolymer having a number average molecular weight of 40,000 to 40%, which is obtained by hydrogenating at least 80% of olefinically unsaturated bonds in the block copolymer.
In the presence of 700,000 hydrogenated block copolymer (A), 30 to 100% by weight of a monomer composed of a vinyl aromatic compound and / or a (meth) acrylate, and 70 to 0% by weight of a vinyl cyanide compound %, And 0 to 70% by weight of another copolymerizable monomer are graft-copolymerized. 2. The rubber-modified thermoplastic resin of claim 1
99% by weight (a) and the following (b) and / or (c)
A rubber modified composition comprising 90 to 1% by weight of a polymer consisting of: and a hydrogenated block copolymer (A) in the composition having a content of 3 to 45% by weight. Thermoplastic resin composition. (B) A polymer obtained by polymerizing 30 to 100% by weight of a monomer comprising a vinyl aromatic compound and / or (meth) acrylate and 70 to 0% by weight of a vinyl cyanide compound. (C) 50-97% by weight of a monomer comprising a vinyl aromatic compound and / or (meth) acrylate, 3-50% by weight of a maleimide monomer, and 0-47% by weight of a vinyl cyanide compound. Polymer obtained by