JPH09124864A - Aromatic vinyl-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic vinyl-based resin composition improved in melt flowability and mold processability without reducing heat resistance, strength and rigidity by adding a hydrogenated aromatic vinyl-based resin to an aromatic vinyl-based resin. SOLUTION: In this aromatic vinyl-based resin composition, preferably (B) 0.5-25 pts.wt. hydrogenated aromatic vinyl-resin is added to (A) 100 pts.wt. aromatic vinyl-based resin. As the component A, styrene homopolymer or a rubber reinforced aromatic vinyl-based resin obtained by graft copolymerizing styrene on polybutadiene is preferable. The number average molecular weight of the component A is preferably 150000-500000. The component B can be obtained by reacting styrene homopolymer with hydrogen in the presence of a nickel-diatomaceous earth catalyst at 30-200kg/cm<2> hydrogen pressure and 200-310 deg.C for 2-7 hours. It is preferable to hydrogenate 10-98% aromatic rings in the styrene homopolymer. The number average molecular weight of the component B is generally 500-10000 and the softening point is preferably 100-160 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to household articles, toys,
Aromatic vinyl resin composition that can be used for packaging materials, sheets and films, electrical appliances, automobile parts, electronic and electrical equipment parts, and various molded products that require rigidity, heat resistance, etc. It is intended to provide an aromatic vinyl resin composition which is excellent in fluidity and molding processability, and is also excellent in heat resistance, strength and rigidity.

[0002]

2. Description of the Related Art Aromatic vinyl resins have been widely used in various fields such as packaging materials, household products and toys because they have good melt flowability and excellent moldability, and they are widely used in electrical appliances and Since the strength required as a material is high in the use in the electronics field, the strength has been increased by increasing the average molecular weight of an aromatic vinyl resin and the like. However, there is a problem that the melt fluidity is lowered by increasing the molecular weight and the moldability is lowered, and various means have conventionally been considered to improve the lowered melt fluidity.

For example, addition of a plasticizer is one of them.
Addition of a plasticizer improves the melt fluidity but reduces the heat resistance, strength and rigidity. On the other hand, by adding a terpene-based resin or a hydride thereof as in JP-A-4-370131, or a petroleum resin, a coumarone-indene resin or a hydride thereof as in JP-A-6-263394, the strength and the like can be improved. A method for improving melt flowability without lowering the temperature has been proposed, but since these resins have a relatively low molecular weight, aromatic vinyl resins containing these resins are Wasn't enough yet.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an aromatic vinyl resin having improved melt flowability and moldability without lowering heat resistance, strength and rigidity.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a composition obtained by further adding a hydrogenated aromatic vinyl-based resin to an aromatic vinyl-based resin. It was found that the product meets the above-mentioned object, and the present invention has been completed.

That is, the present invention relates to an aromatic vinyl resin composition containing an aromatic vinyl resin (A) and a hydrogenated aromatic vinyl resin (B). In the following description, the aromatic vinyl-based resin that is hydrogenated to be used as the hydrogenated aromatic vinyl-based resin (B) is referred to as an aromatic vinyl resin (C).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic vinyl resin (A) used in the present invention is a homopolymer consisting of only one kind of aromatic vinyl compound or a copolymer combining two or more kinds of aromatic vinyl compounds. A copolymer of an aromatic vinyl compound monomer and another polymerizable monomer containing 50% by weight or more of the aromatic vinyl compound monomer, and the aromatic vinyl compound polymer such as butadiene, isoprene or chloroprene. Modified with a homopolymer of a conjugated diene compound, modified with a copolymer of an aromatic vinyl compound with a copolymer of a conjugated diene compound and an unsaturated nitrile compound or an aromatic vinyl compound, and further an aromatic vinyl Examples thereof include those obtained by modifying the polymer of the compound with various rubber components such as natural rubber. In the present invention, from the viewpoint of excellent fluidity and heat resistance among these examples, a resin containing a polymer composed only of an aromatic vinyl compound as a main component, and a monomer of an aromatic vinyl compound in the presence of a rubber component. A rubber-reinforced aromatic vinyl-based resin obtained by graft copolymerizing a rubber component by emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization is preferable.

Aromatic vinyl compounds used in the above various polymerizations include styrene, vinyltoluene, α-methylstyrene, α-methyl-p-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene,
Examples thereof include bromostyrene, chlorostyrene, and indene. Among them, styrene is preferable because it has extremely excellent melt fluidity.

In the case of forming a copolymer with another polymerizable monomer, the other polymerizable monomer to be copolymerized with the above-mentioned aromatic vinyl compound monomer is (meth) acrylic acid; (meth) acrylic. Methyl acid, (meth)
(Meth) acrylic acid alkyl esters such as ethyl acrylate, butyl (meth) acrylate and isobutyl (meth) acrylate; vinyl cyan compounds such as (meth) acrylonitrile; itaconic acid, maleic acid, fumaric acid, croton Acid, polymerizable unsaturated fatty acid such as cinnamic acid; N-
Methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-octylmaleimide, N-isopropylmaleimide, N-phenylmaleimide, Np-bromophenylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide, etc. Maleimides; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; epoxy group-containing unsaturated compounds such as allyl glycidyl ether; amino group-containing unsaturated compounds such as allylamine; acrylamide compounds; 2 Examples thereof include hydroxyl group-containing unsaturated compounds such as -hydroxyethyl-acrylate. Among them, (meth) acrylic acid alkyl esters are preferable from the viewpoint of improving heat resistance.

Examples of the rubbery polymer used in the rubber-reinforced aromatic vinyl resin include natural rubber (NR),
Acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), ethylene-propylene-non-conjugated diene rubber (EPDM), Acrylic rubber (A
CM, ANM), chlorinated polyethylene rubber, (CS
R), fluororubber (FKM), silicone rubber (Q) urethane rubber (AU, EU), polysulfide rubber (T), epichlorohydrin rubber (CO, ECO), chlorosulfonated polyethylene (CMS), norbornene rubber and / or These include vulcanized polymeric materials.

Among these, polybutadiene rubber (B
R), acrylonitrile-butadiene rubber (NBR),
Styrene-butadiene rubber (SBR) and ethylene-propylene-non-conjugated diene rubber (EPDM) are preferable, and polybutadiene rubber (BR) is particularly preferable because it significantly improves impact resistance.

Although the number average molecular weight of the aromatic vinyl resin (A) is not particularly limited, it is usually from 100,000 to 100,000.
600,000, preferably 150,000-500000
It is. When the molecular weight is smaller than this range, the effect of improving melt fluidity is small even if the hydrogenated aromatic vinyl resin (B) is blended, and when the molecular weight is larger than this range, the aromatic vinyl resin (A) is molded and processed. And the productivity of the aromatic vinyl resin (A) itself decreases, which is not preferable. The aromatic vinyl resin (A) of the present invention can be obtained by a generally known method, that is, emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization.

In the present invention, a hydrogenated aromatic vinyl resin (B) used as an additive for improving the melt fluidity.
Is a hydride of an aromatic vinyl resin (C). As the aromatic vinyl-based resin (C) to be hydrogenated, a homopolymer composed of only one kind of aromatic vinyl compound, a copolymer obtained by combining two or more kinds of aromatic vinyl compounds, a monomer of an aromatic vinyl compound and Copolymers with other polymerizable monomers, containing 50% by weight or more of monomers of aromatic vinyl compounds, homopolymers of polymers of aromatic vinyl compounds of conjugated diene compounds such as butadiene, isoprene and chloroprene And a polymer of an aromatic vinyl compound modified with a copolymer of a conjugated diene compound and an unsaturated nitrile compound or an aromatic vinyl compound. In the present invention, among these examples, a resin containing a polymer composed only of an aromatic vinyl compound as a main component is preferable because it has excellent fluidity and heat resistance.

The aromatic vinyl compound used in the aromatic vinyl resin (C) has 8 to 10 carbon atoms such as styrene, vinyltoluene, α-methylstyrene, dimethylstyrene, isopropenyltoluene, indene and the like.
And the aromatic vinyl compound. By polymerizing only one kind or two or more kinds of compounds selected from such aromatic vinyl compounds by cation polymerization, radical polymerization or the like, a polymer consisting only of aromatic vinyl compounds can be obtained. Among these polymers composed of only aromatic vinyl compounds, a homopolymer composed of styrene alone is preferable in terms of price and availability.

Other polymerizable monomers to be copolymerized with the aromatic vinyl compound monomer used in the aromatic vinyl resin (C) include (meth) acrylic acid;
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and isobutyl (meth) acrylate;
Vinyl and cyan compounds such as (meth) acrylonitrile; itaconic acid, maleic acid, fumaric acid, crotonic acid,
Polymerizable unsaturated fatty acids such as cinnamic acid; N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N
-Octyl maleimide, N-isopropyl maleimide,
Maleimides such as N-phenylmaleimide, Np-bromophenylmaleimide, N-o-chlorophenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride;
Epoxy group-containing unsaturated compounds such as allyl glycidyl ether; amino group-containing unsaturated compounds such as allylamine; acrylamide compounds; 2-hydroxyethyl-
Examples thereof include a hydroxyl group-containing unsaturated compound such as acrylate. Among them, (meth) acrylic acid alkyl esters are preferable from the viewpoint of improving heat resistance.

The hydrogenated aromatic vinyl resin (B) used in the present invention is 5 to 100%, preferably 10 to 98% of the aromatic ring of the aromatic vinyl resin (C).
% Is hydrogenated. If the hydrogenation rate of the aromatic ring is less than 5%, the residual ratio of the aromatic ring in the resin increases, and the heat resistance of the aromatic vinyl resin composition cannot be sufficiently improved. On the other hand, if it is less than 5%, the color tone of the aromatic vinyl resin composition deteriorates when exposed to high temperatures, which is not preferable. If at least 5% of the aromatic ring is hydrogenated, the olefinic double bond of the hydrogenated aromatic resin (B) is generally completely hydrogenated.

The softening point of the hydrogenated aromatic vinyl resin (B) of the present invention is preferably about 80 to 180 ° C. More preferably, it is 100-160 degreeC. Softening point is 1
When it exceeds 80 ° C, the melt viscosity becomes high, and the melt fluidity of the obtained aromatic vinyl resin composition cannot be sufficiently improved. On the other hand, when the softening point is lower than 80 ° C, various performances such as heat resistance and rigidity of the aromatic vinyl resin composition are deteriorated. The hydrogenated aromatic resin (B) of the present invention
The molecular weight of is not particularly limited, but is preferably in the range satisfying the above softening point, and generally, the number average molecular weight is 500.
The thing of about 10,000 is used.

The hydrogenated aromatic vinyl-based resin (B) of the present invention is prepared by hydrogenating the aromatic vinyl-based resin (C) by a known method in the presence of a hydrogenation catalyst. It can be manufactured by

As the hydrogenation catalyst, various ones such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, molybdenum or metal compounds such as oxides or sulfides thereof can be used. Such a hydrogenation catalyst may be used by being supported on a porous carrier having a large surface area such as alumina, silica, diatomaceous earth, carbon, or titania.
In the present invention, among these catalysts, it is preferable to use a nickel-diatomaceous earth catalyst from the viewpoint of cost. The amount of the catalyst used is about 0.1 to 20% by weight, preferably 0.1 to 3% by weight with respect to the aromatic vinyl resin (C) as a raw material.
% By weight. If it is less than 0.1% by weight, hydrogenation is difficult to proceed, and if it exceeds 20% by weight, it is economically disadvantageous.

The conditions for the hydrogenation reaction may be appropriately adjusted so that the hydrogenation rate of the hydrogenated aromatic vinyl resin (B) falls within the above range. Usually, hydrogen pressure is 10-300kg
/ Cm ² , preferably in the range of 30 to 200 kg / cm ² , and the reaction temperature is in the range of 150 to 330 ° C, preferably 200 to 310 ° C. Hydrogen pressure is 10
If less than kg / cm ² or reaction temperature is 150 ° C
If it is less than the above, hydrogenation is difficult to proceed and the hydrogen pressure is 30
When it exceeds 0 kg / cm ² or the reaction temperature is 330 ° C
If it exceeds, the decomposition reaction of the resin is likely to occur,
This causes a decrease in softening point and a decrease in yield, which is not preferable in any case. The reaction time is usually about 0.5 to 10 hours, preferably 2 to 7 hours.

Regarding the amount of catalyst used and the reaction time, the case where the batch system is adopted as the reaction system has been described, but the reaction system is not limited to the batch system.
A flow type (fixed bed type, fluidized bed type, etc.) can be adopted as the reaction type. In addition, the hydrogenation reaction can be performed in a state where the aromatic vinyl resin (C) is melted or dissolved in a solvent. Examples of the solvent include cyclohexane, n-hexane, n-heptane, decalin and the like.

The aromatic vinyl resin composition of the present invention is obtained by adding a hydrogenated aromatic vinyl resin (B) to an aromatic vinyl resin (A). The addition amount of the vinyl resin (B) is usually 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, based on 100 parts by weight of the aromatic vinyl resin (A). If the amount of the hydrogenated aromatic vinyl resin (B) added is less than 0.1 part by weight, the melt fluidity of the aromatic vinyl resin composition cannot be improved, while if it exceeds 30 parts by weight, the aromatic vinyl resin is not added. Various properties such as heat resistance and rigidity of the resin composition are reduced,
Either case is not preferred.

The hydrogenated aromatic vinyl-based resin (B) may be added by dissolving it in the aromatic vinyl-based compound monomer used for the aromatic vinyl-based resin (A) and polymerizing it, or by adding the aromatic vinyl-based resin. Whether the hydrogenated aromatic resin (B) is melted or dissolved in a solvent during the polymerization of (A), or
A method of adding before or after removing unreacted monomers after the completion of polymerization can be used. Further, the aromatic vinyl resin (A) and the hydrogenated aromatic resin (B) are mixed,
It is also possible to knead with an extruder or a molding machine.

The aromatic vinyl resin composition of the present invention contains various known additives other than the above-mentioned components, such as stearic acid, behenic acid, and their metal salts (calcium,
Magnesium, zinc, etc.), ethylenebisstearic acid amide, etc. can also be added. Further, a colorant, an antioxidant, an antistatic agent, etc. can be added. Further, a thermoplastic elastomer such as a styrene-butadiene block copolymer may be added within a range that does not impair the object of the present invention. In addition to the above, there are conventionally used fluidity modifiers such as a petroleum resin (hereinafter referred to as a C9-based hydrocarbon resin) obtained by cationically polymerizing a C9 fraction obtained by cracking naphtha, and cracking of naphtha. The petroleum resin (hereinafter referred to as C5 / C9 hydrocarbon resin) obtained by copolymerizing the C5 fraction and the C9 fraction obtained by the above, coumarone-indene resin, terpene-styrene resin and the like, and hydrides thereof are also the object of the present invention. Can be added within a range that does not inhibit

[0025]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an aromatic vinyl resin composition which is excellent in melt fluidity and moldability, and is also excellent in heat resistance, strength and rigidity. The aromatic vinyl resin composition of the present invention can be used for household products, toys, packaging materials, sheets and films, electric appliances, automobile parts, electronic / electrical equipment parts, etc., as well as rigidity, heat resistance, etc. It can be used for various molded products that are required.

[0026]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production Example 1 (Production of Hydrogenated Styrene Homopolymer Resin (B)) 500 g of a styrene homopolymer resin having a softening point of 100 ° C. and a number average molecular weight of 1370 as an aromatic vinyl resin (C),
7.5 g of nickel-diatomaceous earth catalyst (trade name N-113, manufactured by JGC Chemical Co., Ltd.) was charged into a 1-liter rotary stirring type autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Then, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C., 15 m
Distilled under reduced pressure for 20 minutes under heating and depressurizing conditions of mHg,
A hydrogenated styrene homopolymer resin having the properties shown in Table 1 was obtained in a yield of 96% by weight. The resulting hydrogenated styrene homopolymer resin is referred to as compound (a).

Production Example 2 (Production of Hydrogenated Styrene Homopolymer Resin (B)) 500 g of a styrene homopolymer resin having a softening point of 100 ° C. and a number average molecular weight of 1370 as an aromatic vinyl resin (C),
10 g of nickel-diatomaceous earth catalyst (manufactured by JGC Chemical Co., Ltd., trade name N-113) was charged into a 1-liter rotary stirring autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Then, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C., 15 mm
A hydrogenated styrene homopolymer resin having the properties shown in Table 1 was subjected to a vacuum distillation treatment for 20 minutes under a heated and depressurized condition of Hg.
Obtained in a yield of 7% by weight. The resulting hydrogenated styrene homopolymer resin is referred to as compound (b).

Production Example 3 (Production of Hydrogenated Styrene Homopolymer Resin (B)) 500 g of a styrene homopolymer resin having a softening point of 100 ° C. and a number average molecular weight of 1370 as an aromatic vinyl resin (C),
10 g of nickel-diatomaceous earth catalyst (manufactured by JGC Chemical Co., Ltd., trade name N-113) was charged into a 1-liter rotary stirring autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Then, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C., 15 mm
A hydrogenated styrene homopolymer resin having the properties shown in Table 1 was subjected to a vacuum distillation treatment for 20 minutes under a heated and depressurized condition of Hg.
Obtained in a yield of 9% by weight. The resulting hydrogenated styrene homopolymer resin is referred to as compound (c).

Production Example 4 (Production of Hydrogenated Styrene Homopolymer Resin (B)) 500 g of a styrene homopolymer resin having a softening point of 100 ° C. and a number average molecular weight of 1370 as an aromatic vinyl resin (C).
And 15 g of nickel-diatomaceous earth catalyst (trade name N-113, manufactured by JGC Chemical Co., Ltd.) were charged into a 1-liter rotary stirring autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Next, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C., 15
A vacuum distillation treatment was carried out for 20 minutes under a heated reduced pressure condition of mmHg to obtain a hydrogenated styrene homopolymer resin having the properties shown in Table 1 in a yield of 100% by weight. The obtained hydrogenated styrene homopolymer resin is referred to as compound (d).

Production Example 5 (Production of Hydrogenated Styrene Homopolymer Resin (B)) 500 g of a styrene homopolymer resin having a softening point of 120 ° C. and a number average molecular weight of 1900 as an aromatic vinyl resin (C),
10 g of nickel-diatomaceous earth catalyst (manufactured by JGC Chemical Co., Ltd., trade name N-113) was charged into a 1-liter rotary stirring autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Then, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C., 15 mm
A hydrogenated styrene homopolymer resin having the properties shown in Table 1 was subjected to a vacuum distillation treatment for 20 minutes under a heated and depressurized condition of Hg.
Obtained in a yield of 8% by weight. The resulting hydrogenated styrene homopolymer resin is referred to as compound (e).

Production Example 6 (Production of Hydrogenated Aromatic Vinyl Compound Homopolymer Resin (B)) Aromatic vinyl compound homopolymer resin having a softening point of 125 ° C. and a number average molecular weight of 950 as the aromatic vinyl resin (C). (Mitsui Petrochemical Industry Co., Ltd., trade name FTR-812
0) 500 g and 15 g of nickel-diatomaceous earth catalyst (manufactured by JGC Chemical Co., Ltd., trade name N-113) were charged into a 1-liter rotary stirring autoclave, and hydrogenation reaction was carried out under the conditions shown in Table 1. went. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated aromatic vinyl compound homopolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Next, cyclohexane was distilled off from the obtained colorless varnish, and finally 220 ° C. and 15 mmHg under heating and reduced pressure conditions.
After vacuum distillation for 20 minutes, a hydrogenated aromatic vinyl compound homopolymer resin having the properties shown in Table 1 was obtained in a yield of 94% by weight. The obtained hydrogenated aromatic vinyl compound homopolymer resin is referred to as compound (f).

Production Example 7 (Production of Hydrogenated Styrene-Butyl Acrylate Copolymer Resin (B)) The aromatic vinyl resin (C) has a softening point of 95 ° C., a number average molecular weight of 1040, a styrene component of 95% by weight, and an acrylic resin. 500 g of styrene-butyl acrylate copolymer resin containing 5% by weight of butyl acid component and 10 g of nickel-diatomaceous earth catalyst (trade name N-113, manufactured by JGC Chemical Co., Ltd.) were placed in a 1-liter rotary stirring autoclave. After charging, the hydrogenation reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the reaction mixture was cooled to room temperature, the obtained hydrogenated styrene-butyl acrylate copolymer resin was taken out from the autoclave, dissolved in 3 liters of cyclohexane, and the catalyst was filtered off. Then
Cyclohexane was distilled off from the obtained colorless varnish, and finally, vacuum distillation treatment was performed for 20 minutes at 220 ° C. under heating and reduced pressure conditions of 15 mmHg to give hydrogenated styrene-acrylic acid having the properties shown in Table 1. Butyl copolymer resin was obtained in a yield of 96% by weight. The obtained hydrogenated styrene-butyl acrylate copolymer resin is referred to as compound (g).

Table 1 shows the reaction conditions of Production Examples 1 to 7 and the properties of the obtained compounds (a) to (g). The hydrogen pressure was 200 kg / cm ² in each of the production examples. The aromatic ring hydrogenation ratio was calculated by measuring the proton nuclear magnetic resonance spectra ⁽¹ H-NMR). That is, a deuterium-substituted chloroform (CDCl ₃ ) solution having the same concentration as the raw material resin, that is, the aromatic vinyl-based resin (C) and the hydrogenated aromatic vinyl-based resin (B), was prepared, and ¹ H
-H NMR of an aromatic ring appearing at around 7 ppm by measuring NMR
It was calculated from the spectrum area based on the following formula. Aromatic ring hydrogenation rate = {1- (spectrum area of hydrogenated aromatic vinyl-based resin (B) / spectrum area of aromatic vinyl-based resin (C))} × 100 (%). The softening point is JIS K
2531 ring and ball method.

[0035]

[Table 1]

Examples 1 to 7 Polystyrene (number average molecular weight 250,000) synthesized from styrene monomer as the aromatic vinyl resin (A) 9
10 parts of the compounds (a) to (g) obtained in the above Production Examples 1 to 7 were mixed as 0 parts by weight of the hydrogenated aromatic vinyl resin (B) and pelletized by a twin-screw extruder.

Comparative Example 1 The hydrogenated aromatic vinyl-based resin (B) in the example was used as a hydrogenated terpene resin (Yasuhara Chemical Co., Ltd., trade name CLEARON M115, softening point 115 ° C., hereinafter referred to as compound (h)). Pelletization was performed in the same manner as in the example except that it was replaced.

Comparative Example 2 The hydrogenated aromatic vinyl resin (B) in the example was used as a hydrogenated terpene resin (Yasuhara Chemical Co., Ltd., trade name CLEARON M105, softening point 105 ° C., hereinafter referred to as compound (i)). Pelletization was performed in the same manner as in the example except that it was replaced.

Comparative Example 3 The hydrogenated aromatic vinyl resin (B) in the example was used as a hydrogenated C9 hydrocarbon resin (Arakawa Chemical Industry Co., Ltd., trade name Alcon P115, softening point 115 ° C., compound ( Pelletization was carried out in the same manner as in the example except that (a) was used instead of j).

Comparative Example 4 The hydrogenated aromatic vinyl resin (B) in the example was replaced with C
Pelletization was carried out in the same manner as in Example except that 9-type hydrocarbon resin (Mitsui Petrochemical Industry Co., Ltd., trade name Petrosin PR120, softening point 120 ° C., hereinafter referred to as compound (k)) was used.

Comparative Example 5 The hydrogenated aromatic vinyl resin (B) used in the example was replaced with coumarone-indene resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name Esclon V120, softening point 120 ° C., compound (l) below.
Pelletization was carried out in the same manner as in Example except that

Using the pelletized aromatic vinyl resin composition obtained in the Examples or Comparative Examples as a raw material, test pieces for measuring physical properties were prepared with an injection molding machine, and various physical properties were tested by the following methods. (1) Melt flow rate (MFR) Based on JIS K-7210. Generally, when the MFR value is 7.5 or more, the melt fluidity is good, and when it is 7.5 or less, the melt fluidity is poor. (2) VICAT softening point Based on JIS K-7206. Generally VICA
When the T softening point is 97 ° C or higher, the heat resistance is good, and when it is 97 ° C or lower, the heat resistance is poor. (3) Tensile strength Based on JIS K-7113. Generally 520k
Tensile strength is strong when g / cm ² or more, 520 kg /
When it is less than cm ² , the tensile strength is weak. Table 2 shows the evaluation results
Shown in

[0043]

[Table 2]

From Table 2, the aromatic vinyl-based resin compositions shown in Examples 1 to 7 are superior in heat resistance to the aromatic vinyl-based resin compositions shown in Comparative Examples 1 to 5, and have melt flowability and It is possible to provide a well-balanced aromatic vinyl resin composition having excellent strength properties.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 16, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

Claims (3)

[Claims] 1. An aromatic vinyl resin composition comprising an aromatic vinyl resin (A) and a hydrogenated aromatic vinyl resin (B). 2. The number average molecular weight of component (A) is 10,000.
0-600000, the number average molecular weight of component (B) is 500
The composition according to claim 1 or 2, which is from 1 to 10,000. 3. The (B) based on 100 parts by weight of the (A) component.
The composition according to claim 1, wherein the added amount of the components is 0.1 to 30 parts by weight.