JPH1081807A - Styrene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrene resin compsn. which is adaptable to all the resin production processes, has a low odor, is suitable for a long-time operation, and retains a good balance among physical properties. SOLUTION: This low-odor styrene resin compsn. comprises 99.995-95.0wt.% styrene resin and 0.005-5.0wt.% sesquiterpene. The resin comprises 95-0wt.% styrene copolymer and 5-100wt.% rubberlike graft copolymer produced by the graft copolym. of a monomer mixture comprising 50-90wt.% styrene monomer, 10-50wt.% acrylonitrile monomer, and 0-40wt.% copolymerizable monomer in the presence of a rubberlike polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a styrene resin composition. More specifically, the present invention has a low odor and an excellent balance of physical properties. In particular, it requires a long time (many labors) for processing and molding, so that it is necessary to stay in a work place for a long time. It is a styrenic resin composition suitable for making.

[0002]

2. Description of the Related Art Conventionally, a styrenic resin composition is a resin composition in which a rubbery graft copolymer is dispersed in a styrenic copolymer to impart impact resistance. Heretofore, such styrene-based resin compositions have always been made into various products through various processing and molding processes (for example, injection molding and extrusion molding for primary processing and vacuum molding for secondary processing). As is well known, in the processing and molding process of such a resin, it is unavoidable that odor peculiar to the resin is generated in any molding method and processing method.

However, in recent years, awareness of environmental protection has been increased, and there has been a demand for improvement of the work environment, and the odor of the work environment is regarded as one of the important matters to be improved.

[0004] When improving the odor at the resin processing / molding site (improving the working environment), the worker cannot be completely isolated from the odor at the processing / molding site.
In order to improve the working environment, there is a demand for the development of a resin with less odor generated during processing and molding. Moreover, it is desired that such a resin does not impair the balance of physical properties.

That is, the development of a styrenic resin composition that produces little odor at the time of processing and molding, does not give a worker unpleasant sensation due to odor generated even after working for a long time, and further does not impair the balance of physical properties has been required. It is desirable that the solution be made promptly in the technical field.

Therefore, conventionally, in order to suppress the odor generated in the processing or molding step of the styrene resin, an antioxidant is added in the production process to promote devolatilization and reduce residual monomers. (Japanese Patent Application Laid-Open Nos. 7-149817 and 7-149818). However, with any of these methods, the degree of odor that can be suppressed is small, and since only one odor source can be suppressed from among many odor sources, the deodorizing effect is extremely limited. is there. Therefore, the styrenic resin provided by such a method is sufficient styrenic resin even in the case where the work must be continuously performed at the resin processing / molding site currently generally performed. Not. That is, the styrene-based resin composition provided by the above-described conventional method only slightly extends the time during which an operator can endure the off-flavor when performing operations such as injection and extrusion.

[0007]

SUMMARY OF THE INVENTION The present invention is suitable for all manufacturing processes using a resin, has a low odor, and is suitable for long-time work in order to solve the above-mentioned drawbacks of the prior art. Nevertheless, the present invention proposes a styrene-based resin composition that does not impair the balance of physical properties.

[0008]

The styrenic resin composition of the present invention is obtained by adding a sesquiterpene compound obtained from a natural plant or the like during the kneading process.
A styrene-based resin that can effectively remove the odor generated during the kneading process and the subsequent processing and molding processes, and also produces a subtle refreshing wood scent, and does not suffer from the unique odor of the resin even when working for a long time. A composition.

The styrenic resin composition of the present invention, which has a low odor and is suitable for a long-time operation, yet has a better balance of physical properties, can be obtained by (1) in the presence of a rubbery polymer. A rubbery graft copolymer obtained by graft copolymerizing a mixture of 50 to 90% by weight of a styrene monomer, 10 to 50% by weight of an acrylonitrile monomer, and 0 to 40% by weight of a monomer copolymerizable therewith. 5 to 100% by weight of polymer (A),
And styrene-based copolymer (B) in an amount of from 95 to 0% by weight, and 9.95 to 95.0% by weight of (2) sesquiterpene compound (C) in an amount of from 0.005 to 5.0% by weight.

[0010]

By mixing and kneading the components so as to obtain a styrene resin composition having the composition described above, it can be used in any molding and processing. Thus, a styrene-based resin composition suitable for an operator to continuously perform resin processing and molding operations can be obtained.

The rubbery graft copolymer (A) of the present invention
In the presence of a rubber-like polymer, styrene-based monomer 50-90% by weight, acrylonitrile-based monomer 10-50% by weight, and copolymerizable with these monomers 0-40% by weight Can be produced by any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method, or a polymerization method in which any of these polymerization methods is combined with each other.
In the polymerization method, an emulsion polymerization method, a bulk polymerization method, and a solution polymerization method are preferable from the viewpoint of improving the balance of physical properties, and the emulsion polymerization method is particularly preferable.

The rubber-like graft copolymer (A) obtained by the above emulsion polymerization method contains 50 to 90% by weight of a styrene-based monomer in the presence of a rubber-like polymer such as a diene-based rubber emulsion.
An acrylonitrile monomer is polymerized from 10 to 50% by weight and a monomer copolymerizable therewith with 0 to 40% by weight to obtain a rubbery graft copolymer (A) having an average particle size of 0.05 to 0.8 μm. It is preferably an emulsion. In this case, the proportion of the rubbery polymer in the rubbery graft copolymer is usually 15 to 85% by weight, preferably 45 to 80% by weight. A diene-based rubber emulsion, which is an example of the rubbery polymer, includes 100 to 60% by weight of a conjugated diene monomer and 0 to 40% by weight of an unsaturated monomer copolymerizable with the conjugated diene monomer. % Of a homopolymer or a copolymer thereof. The conjugated diene monomer is represented by the following formula.

[0013]

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Wherein R is hydrogen, methyl or chlorine.
Examples of the unsaturated monomer copolymerizable with the conjugated diene monomer include a styrene monomer, an acrylonitrile monomer, a methacrylate monomer, and an acrylate monomer.

Examples of the diene rubber emulsion (rubber-like polymer) having the above composition include polybutadiene and butadiene-
Styrene copolymer, butadiene-acrylonitrile copolymer and butadiene-methyl methacrylate copolymer,
And isoprene-butyl acrylate copolymer. In any case, the monomer is directly used, and the average particle size is 0.05 to 0.
Polymerized to 8 μm polymer or first 0.05-0.18
After polymerization into a rubber emulsion having a small particle diameter of μm, the rubber emulsion having a small particle diameter of 0.05 to 0.18 μm is further reduced to 0.
It can be made to enlarge until it becomes a rubber emulsion of 2 to 0.8 μm. Examples of such a rubber enlargement method include a chemical enlargement method in which an organic acid, a metal salt or a polymer coagulant having a carboxylic acid group is added, a mechanical enlargement method by mechanical stirring, and a frozen enlargement method. Examples of the polymer flocculant used in the chemical enlargement method include a butyl acrylate-methacrylic acid copolymer.

The rubbery graft copolymer (A) (hereinafter referred to as "emulsion graft copolymer") obtained by polymerization by the emulsion polymerization method is a monomodal particle having an average particle size of 0.05 to 0.8 μm. It has a size distribution or an average particle size of 0.05 to 0.
Typically, a bimodal particle size distribution of 18 μm and 0.2 to 0.8 μm is used.

As a method for obtaining the rubbery graft copolymer (A) by the bulk polymerization method or the solution polymerization method, first, 50 to 90% by weight of a styrene monomer and 10 to 50% by weight of an acrylonitrile monomer are used. % And a monomer mixture comprising 0 to 40% by weight of a monomer copolymerizable with the styrene-based monomer and the acrylonitrile-based monomer, and a mixture obtained by further adding a solvent as an optional component. A rubber-like polymer such as a system rubber is dissolved, and this solution is put into a reaction tank by a pump, and a graft polymerization reaction is performed while uniformly mixing. During the reaction, an appropriate amount of a polymerization initiator or a chain transfer agent (for example, bis-t-butylperoxycyclohexane,
By adding (t-dodecyl mercaptan), the polymerization rate / graft rate and the molecular weight of the polymer can be adjusted. The reaction tank may have a configuration in which a large number of tanks are combined, and a kettle type reaction tank equipped with a powerful stirrer is particularly preferable. Typical examples of the solvent added to the monomer mixture include toluene, xylene, ethylbenzene, methyl ethyl ketone, and ethyl acetate.

Preferred examples of the diene rubber which is a rubbery polymer include butadiene rubber, isoprene rubber,
Chloroprene rubber and the like. Butadiene rubber includes a high cis type and a low cis type. High cis type rubber is cis /
A typical weight composition of vinyl groups is 94-98% / 1-5%, the remaining composition is trans type and Mooney viscosity is 20-98%.
120, the molecular weight is preferably 100,000-800,000.
On the other hand, the low cis type rubber has a typical weight composition of cis / vinyl group of 20 to 40% / 1 to 20%, the remaining composition being trans type, and a Mooney viscosity of 20 to 120. Other applicable rubber materials include acrylonitrile / butadiene rubber and styrene / butadiene rubber (usually abbreviated as "SBR"). The polymerization type of the styrene / butadiene rubber applied to the present invention is a di-block copolymer,
Examples include tri-block copolymerization, random copolymerization, or star copolymerization. In addition, styrene /
The butadiene rubber composition has a weight ratio in the range of styrene /
Butadiene ratio of 5/95 to 80/20, molecular weight range of 50,0
It is preferably from 00 to 600,000. The rubber applied to the present invention is preferably butadiene rubber and styrene / butadiene rubber. In the present invention, the diene rubber used for the bulk or solution graft copolymer is one of the above rubbers.
Species or a mixture of two or more can be used.

The rubbery graft copolymer (A) obtained by the bulk or solution polymerization method (hereinafter referred to as "bulk or solution graft copolymer") generally has an average rubber particle diameter of 0.2 to 10 μm.
m, and preferably 1.0 to 7.0 μm. Here, the proportion of the rubbery polymer in the bulk or solution graft copolymer is usually 3 to 25% by weight, preferably 4 to 15% by weight.

As the rubbery graft copolymer (A) used in the present invention, either the above-mentioned emulsion graft copolymer or bulk or solution graft copolymer is used alone, or these copolymers are used. May be mixed to form a bimodal or trimodal particle size distribution.

Examples of the range of the bimodal and trimodal particle size distributions when the emulsion graft copolymer and the bulk or solution graft copolymer are used in combination are shown below. Bimodal: (1) Average particle size: 0.2 to 0.8 μm (emulsified) Average particle size: 0.2 to 10 μm (bulk or solution) or (2) Average particle size: 0.05 to 0.18 μm (emulsified) Average particle size: 0.2 1010 μm (bulk or solution) Trimodal: Average particle size: 0.05-0.18 μm (emulsified) Average particle size: 0.2-0.8 μm (emulsified) Average particle size: 0.2-10 μm (bulk or solution) The above “average particle size” Was obtained by dyeing a sample with osmic acid, measuring the particle size of 1000 particles with a transmission electron microscope, and obtaining the value by the following equation.

Average particle size = ΣnD ⁴ / ΣnD ³ (where n is the number of particles) Specific examples of the styrene monomer used in the present invention include styrene, α-methylstyrene and p-chloromethylstyrene. , Pt-butylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,5-
Examples thereof include dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromostyrene, 2,5-dibromostyrene, and divinylbenzene, and among them, styrene or α-methylstyrene is preferable.

Specific examples of the acrylonitrile monomer used in the present invention include acrylonitrile and α-methacrylonitrile, among which acrylonitrile is preferred.

The monomer copolymerizable with the styrene monomer used in the rubbery graft copolymer (A) in the present invention includes, for example, (meth) acrylic acid ester,
There are maleimide monomers, acrylic acid, methacrylic acid, and maleic anhydride. Examples of (meth) acrylate monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxy methacrylate. Ethyl, glycidyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate,
Examples thereof include butyl acrylate, and among them, methyl methacrylate and butyl acrylate are preferable. The maleimide monomers include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenyl Maleimide, N-2,3-dimethylphenylmaleimide, N-2,4-dimethylphenylmaleimide, N-2,3-diethylphenylmaleimide, N-
2,4-diethylphenylmaleimide, N-2,3-dibutylphenylmaleimide, N-2,4-dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-
There are 2,3-dichlorophenylmaleimide, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide, N-2,4-dibromophenylmaleimide, and among them, N-phenylmaleimide is preferable.

The styrene copolymer (B) used in the present invention can be copolymerized with, for example, 90 to 50 parts by weight of a styrene monomer and 10 to 50 parts by weight of an acrylonitrile monomer, if necessary. Obtained by polymerizing 0 to 40 parts by weight of a suitable monomer. Examples of the styrene-based monomer, acrylonitrile-based monomer and copolymerizable monomer include monomers used in the rubbery graft copolymer (A). The styrenic copolymer (B) can be produced by any polymerization method such as bulk / solution / suspension or emulsion polymerization, and is preferably a bulk / solution polymerization method. The styrene copolymer (B) has a weight average molecular weight of 60,000 to 400,000 and a number average molecular weight of 30,000 to 200,000. If the weight average molecular weight of the styrenic copolymer (B) is too high, processing becomes difficult, while if it is too low, impact resistance deteriorates. In the present invention, the proportion of the rubbery polymer in the total of the rubbery graft copolymer (A) and the styrenic copolymer (B) is usually 3 to 30% by weight, preferably 5 to 25% by weight. is there.

The sesquiterpene compound (C) used in the present invention is a compound having a molecular formula of C ₁₅ H ₂₄ or a derivative thereof, for example, cadinene (cadinene).
s), caryophyllene, copaen
e), α-farnesene, β-farnesene, β-farnesene, humulene, longifolene, thujopsene, ylanggene and the like. The content of the sesquiterpene compound (C) in the styrene-based resin composition of the present invention is 0.005 to 5.0% by weight, preferably 0.01 to 2.0% by weight, based on 100% by weight of the styrene-based resin composition. is there. If the content of the sesquiterpene compound (C) is less than the above range, the deodorizing effect cannot be exhibited, and if it is too large, another odor is generated, which is suitable for the worker to continuously perform resin processing and molding work. And physical properties decrease.

By kneading the rubbery graft copolymer (A), styrene copolymer (B) and sesquiterpene compound (C) in a general kneading step, the low odor of the present invention is obtained. In addition, a styrene-based resin composition having an excellent balance of physical properties and suitable for an operator to continuously perform resin processing and molding operations can be obtained. Here, during the kneading step, part of the sesquiterpene compound (C) is removed by evaporation. Therefore, the amount of the sesquiterpene compound (C) used in the kneading step is larger than the content of the sesquiterpene compound (C) contained in the finally obtained styrene resin composition.

As a kneading apparatus that can be used in the present invention, For example, single or twin screw extruders, kneading rollers, internal kneaders and the like can be mentioned. In the present invention, the styrenic resin composition, if necessary, a light stabilizer, a lubricant,
Flow improvers, ultraviolet absorbers, heat stabilizers, antioxidants,
Antistatic agents, fillers, glass fibers, processing aids, pigments and the like can also be added.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, in order to facilitate understanding of the present invention, a description will be given based on more specific embodiments. In addition,
In the examples, unless otherwise specified, the components of the composition indicate parts by weight.

<Production Example 1> (Production of synthetic rubber emulsion) Ingredients Parts by weight 1,3-butadiene 150.00 Aqueous potassium persulfate solution (1%) 15.00 Potassium oleate 2.00 Distilled water 190.00 Ethylene glycol dimethacrylate 0.13 The product was reacted at a reaction temperature of 65 ° C. for 12 hours to obtain a conversion of 94%, a solid content of about 40%, and a weight average particle size of 0.4%.
A 1 μm synthetic rubber emulsion is obtained.

(Preparation of Enlarged Rubber Emulsion) A polymer flocculant having a carboxyl group is prepared from the following components. Ingredients Parts by weight Butyl acrylate 90.0 Methacrylic acid 10.0 Potassium persulfate aqueous solution (1%) 0.5 Sodium dodecyl sulfate 1.0 n-dodecyl mercaptan 1.0 Distilled water 200.0 The above components are reacted at a reaction temperature of 75 ° C. for 5 hours, and the conversion is 9
A polymer coagulant having a carboxyl group of 5% and pH 6.0 is obtained. Next, using 3.0 parts by weight of a polymer coagulant having a carboxyl group (solid content), 100 parts by weight of a synthetic rubber emulsion (solid content) is enlarged to have a pH of 8.5 and a weight average particle size of about 8.5.
A thickened rubber emulsion of 0.31 μm was prepared.

(Production of rubber-like graft copolymer (A-1)) Finally, the enlarged rubber emulsion is subjected to a graft polymerization reaction according to the following formulation to obtain a rubber-like graft copolymer (A-1). ) Manufactured. Ingredients parts by weight enlarged rubber emulsion (solid content) 100.0 styrene 25.0 acrylonitrile 8.3 potassium oleate
1.2 Tertiary dodecyl mercaptan 2.0 Isopropylbenzene hydroperoxide 3.0 Ferrous sulfate aqueous solution (0.2%) 3.0 Sodium formaldehyde sulfoxylate aqueous solution (10%) 0.9 Sodium ethylenediaminetetraacetate aqueous solution (0.25%) 3.0 Distilled water 200.0 Was coagulated with calcium chloride (CaCl ₂ ) to obtain a rubbery graft copolymer (A-1) (rubber content: 75% by weight).
Its average particle size is 0.31 μm.

<Production Example 2> (Production of Rubbery Graft Copolymer (A-2)) Production Example 1
Synthetic rubber emulsion (rubber weight average particle size is 0.1μ)
m) is directly subjected to a graft polymerization reaction with the following compound to obtain a rubbery graft copolymer (A-2). Ingredients Parts by weight Synthetic rubber emulsion (0.1 μm) (solid content) 100.0 Styrene 32.4 Acrylonitrile 12.6 Potassium oleate 1.5 Tertiary dodecylmercaptan 2.0 Isopropylbenzene hydroperoxide 3.0 Ferrous sulfate aqueous solution (0.2%) 3.0 Sodium formaldehyde sulfoxylate Aqueous solution (10%) 0.9 Sodium ethylenediaminetetraacetate aqueous solution (0.25%) 3.0 Distilled water 200.0 The rubber-like graft copolymer emulsion prepared by the above formulation is coagulated with calcium chloride (CaCl ₂ ), and the rubber-like graft copolymer ( A-2) (the rubber content was 69% by weight) was obtained. Its average particle size is 0.1 μm.

<Production Example 3> (Production of Rubbery Graft Copolymer (A-3)) Polybutadiene (trade name: Asadene 55AS, manufactured by Asahi Kasei Kogyo Co., Ltd.)
6.6 parts by weight, 0.1 part by weight of third dodecyl mercaptan,
Benzoyl peroxide (0.07 parts by weight) is used as an initiator, and styrene (74.4 parts by weight), acrylonitrile (25.6 parts by weight) and ethylbenzene (30 parts by weight) are completely dissolved to form a feed solution. This feed solution (feed solution) is continuously charged into a first reactor having a volume of 44 liters and a screw stirrer having a cooling circulation pipe,
The reaction is carried out with stirring at a reaction temperature of 100 ° C. and a stirring speed of 300 rpm. Then, the mixture after the reaction in the first reactor is continuously taken out and charged into the next second reactor. The second reactor had the same configuration as the first reactor, and was operated at a reaction temperature of 130 ° C. and a stirring speed of 120 rpm. When the conversion of the mixture reaches 60%, the mixture is taken out and put into a devolatilizer,
Unreacted monomers and volatiles were removed, and the mixture was extruded to obtain a rubber-like graft copolymer (A-3) formed into a pellet. Its average particle size is 1.1 μm and its rubber content is 11% by weight.

<Measurement Criteria> Physical properties and molded appearances of the compositions obtained in the following Examples and Comparative Examples are measured according to the following measurement criteria. * Tensile strength: Measured according to ASTM D-638. (unit:
kg / cm ² ) * Izod impact strength (IZOD): Measured in accordance with ASTM D-256. (Unit: kg · cm / cm) * Melt index (MI): Measured according to ASTM D-1238. (Unit: g / 10 min) When a sheet is formed from the styrene-based resin composition prepared as described below through a T-die by a twin screw extruder, an odor generated from a die lip (an outlet of a die of an extrusion molding machine). To evaluate. The evaluation is performed by an evaluation team composed of three or more persons (including three persons) over a continuous hour, from the viewpoint of endurance of the odor or continuous comfort of the operation site.
In Table 1, when all the members agree and the odor is not bothersome, it is indicated by “○”, and when someone feels unpleasant, it is indicated by “X”.

[0036]

【Example】

Example 1 In this example, a styrene resin 100 composed of 18.7% by weight of the rubbery graft copolymer (A-1) and 81.3% by weight of the styrene copolymer (B) obtained in Production Example 1 was used.
Use parts by weight. The styrene-based copolymer (B) has a weight average molecular weight (Mw) of 130,000, a number average molecular weight (Mn) of 67,000, an acrylonitrile content of 28% by weight, and a styrene content of 72%. % By weight. The rubber content in the styrene resin composition is
14% by weight.

Next, as a sesquiterpene compound (C) component, sesquiterpine (manufactured by Yashara Chemical Co., Ltd.)
(Trade name) 1.0 part by weight is added to 100 parts by weight of styrene resin,
The mixture was uniformly kneaded with an extruder, extruded into a rod shape, and then cut into pellets. About 66.6% by weight of the initially used sesquiterpene compound (C) was removed by evaporation in the extrusion process,
The content of the sesquiterpene compound (C) in the obtained styrene-based resin composition was 0.334% by weight as measured by gas chromatography. Tables 1 and 2 show the results of measuring the physical properties of the pellets and evaluating the odor.

Example 2 The ratio of (A-1) and (B) was changed and the styrene copolymer (B) used
Has a weight average molecular weight (Mw) of 140,000, a number average molecular weight (Mn) of 69,000, an acrylonitrile content of 24% by weight, a styrene content of 76% by weight, and a rubber content of 23.5% by weight. Except for this, the procedure was the same as in Example 1 above. Only the evaluation of the odor was performed on this, and the results are shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out except that the amount of the sesquiterpene was changed to 0.1 part by weight. The content of the sesquiterpene compound (C) contained in the obtained styrene-based resin composition was 0.033% by weight. Table 1 shows the results of measuring the physical properties and evaluating the odor.
And Table 2 below.

Example 4 The procedure was performed in the same manner as in Example 1 except that the amount of the sesquiterpene was changed to 5.0 parts by weight. The content of the sesquiterpene compound (C) contained in the obtained styrene-based resin composition was 1.65% by weight.
Tables 1 and 2 show the results of measuring the physical properties and evaluating the odor.

Example 5 The same operation as in Example 1 was performed. However, the proportion of the rubbery graft copolymer (A) was changed to 23.3% by weight. The rubber-like kraft copolymer (A) was composed of 9.3% by weight of the rubber-like graft copolymer (A-1) and 14% by weight of the rubber-like graft copolymer (A-2).
It is. Only the evaluation of the odor was performed on this, and the results are shown in Table 1.

Example 6 The styrenic resin composition of this example was prepared using a rubbery graft copolymer (A-3) 100
The sesquiterpene was prepared from 1.0 part by weight of the sesquiterpene. Then, the physical properties were measured and the odor was evaluated in the same manner as described above. Table 1 shows the results.

Example 7 The same operation as in Example 1 was performed. However, the proportion of the rubbery graft copolymer (A) was changed to 44.5% by weight. In the rubber-like kraft copolymer (A), the rubber-like graft copolymer (A-1) was 16.5% by weight, and the rubber-like graft copolymer (A-3) was 28% by weight.
It is. As the styrene copolymer (B), the one having a higher molecular weight (Mw = 230,000, Mn = 120,000) was used. Only the evaluation of the odor was performed on this, and the results are shown in Table 1.

Example 8 The same operation as in Example 7 was performed. However, the ratio of the rubbery graft copolymer (A) was changed to 42.2% by weight. The rubber-like kraft copolymer (A) is composed of 8.9% by weight of the rubber-like graft copolymer (A-1), 13.3% by weight of the rubber-like graft copolymer (A-2), and the rubber-like graft copolymer. (A-3) is 20% by weight. For this, only odor evaluation was performed. Table 1 shows the results.

[Comparative Example 1] After uniform mixing with the composition shown in Table 1, the odor was evaluated and physical properties were measured in comparison with the product of Example 1 above. The results are shown in Tables 1 and 2. From this result, it is clear that odor is generated when no sesquiterpene is added.

Comparative Example 2 The same operation as in Example 1 was performed. However, the added amount of the sesquiterpene is 0.005
Parts by weight were used. The content of the sesquiterpene compound (C) contained in the obtained composition was 0.002% by weight. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From this result, it is clear that the composition obtained with this composition produces an odor even when the content of the sesquiterpene compound (C) is insufficient.

Comparative Example 3 The same operation as in Example 1 was performed. However, the added amount of the sesquiterpene was 20.0 parts by weight. The content of the sesquiterpene compound (C) contained in the obtained composition was 6.2% by weight. Only the evaluation of the odor was performed on this, and the results are shown in Table 1.
From this result, when the content of the sesquiterpene compound (C) is too large, the composition obtained with this composition generates an unpleasant odor that is too strong and takes a long time to mold and process the resin. Not suitable for

Comparative Example 4 The same operation as in Example 1 was performed. However, 2.0 parts by weight of terpinolene was added instead of 1.0 part by weight of the sesquiterpene. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From these results, it can be seen that the composition obtained with this formulation cannot completely remove the odor, and that the low boiling point and unstable properties of the added terpinolene greatly limit the range of application.

Comparative Example 5 The same operation as in Comparative Example 4 was performed. However, 2.0 parts by weight of terpinolene was changed to 2.0 parts by weight of dipentene. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From this result, it is clear that the composition obtained with this formulation cannot completely remove the odor.

Comparative Example 6 The same operation as in Comparative Example 4 was performed. However, 2.0 parts by weight of terpinolene is replaced by limonene (L
imonene) 2.0 parts by weight. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From this result, it is clear that the composition obtained with this formulation does not completely remove the odor.

Comparative Example 7 The same operation as in Comparative Example 4 was performed. However, 2.0 parts by weight of terpinolene is vanilla flavor.
(Vanilla Spice) Changed to 2.0 parts by weight. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From this result, it is clear that the composition obtained with this formulation not only does not completely remove the odor, but also produces an unpleasant odor.

Comparative Example 8 The same operation as in Comparative Example 4 was performed. However, 2.0 parts by weight of terpinolene was changed to 2.0 parts by weight of lavender spice. Only the evaluation of the odor was performed on this, and the results are shown in Table 1. From this result, it is clear that the composition obtained with this formulation produces a strong odor and causes discomfort to the respiratory organs, making it extremely difficult to work for a long time.

The above Comparative Examples 4 to 8 show the results when various fragrances other than sesquiterpene were added. In all cases, the results of the odor evaluation were not good.

[0054]

[Table 1]

[0055]

[Table 2]

Claims (7)

[Claims] (1) In the presence of a rubbery polymer, 50 to 90% by weight of a styrene monomer, 10 to 50% by weight of an acrylonitrile monomer, and 0% of a monomer copolymerizable therewith. ~
Styrene resin 9 comprising 5 to 100% by weight of a rubbery graft copolymer (A) obtained by graft copolymerizing a 40% by weight mixture and 95 to 0% by weight of a styrene copolymer (B)
A styrenic resin composition containing 9.995 to 95.0% by weight and (2) 0.005 to 5.0% by weight of the sesquiterpene compound (C). 2. The rubbery graft copolymer (A) is produced by an emulsion polymerization method and has an average particle size of 0.05 to 0.1.
The styrenic resin composition according to claim 1, which has a thickness of 8 µm. 3. The rubbery graft copolymer (A) is an emulsion graft copolymer and has an average particle size of 0.05 to
The styrenic resin composition according to claim 1, having a bimodal particle size distribution of 0.18 µm and 0.2 to 0.8 µm. 4. The rubber-like graft copolymer (A) is produced by a bulk or solution polymerization method, and has an average particle size.
The styrenic resin composition according to claim 1, which has a thickness of 0.2 to 10 µm. 5. The rubbery graft copolymer (A) comprises an emulsion graft copolymer and a bulk or solution graft copolymer, and the average particle size of the emulsion graft copolymer is 0.
2. The styrenic resin composition according to claim 1, having a bimodal particle size distribution of from 0.05 to 0.18 [mu] m and from 0.2 to 0.8 [mu] m, wherein the bulk or solution graft copolymer is from 0.2 to 10 [mu] m. 6. The weight average molecular weight of the styrenic copolymer (B) is from 60,000 to 400,000, and the number average molecular weight is 30,000.
The styrenic resin composition according to claim 1, wherein the amount is from 0 to 200,000. 7. The styrenic resin composition according to claim 1, wherein the amount of the sesquiterpene compound (C) is 0.01 to 2.0% by weight.