JP2002030191A - Rubber-modified aromatic vinyl-based copolymer resin mixture composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber-modified aromatic vinyl-based copolymer resin composition exhibiting transparency and excellent in practical characteristics, particularly in Charpy impact strength and falling weight impact strength. SOLUTION: The composition comprises a rubber-modified aromatic vinyl- based copolymer resin obtained by employing a styrene/butadiene block copolymer having a specific glass transition temperature and at least one resin selected among terpene resins, terpene-based hydrogenated resins and petroleum resins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is widely used for food packaging containers, blister packs, general container cases, sheets, films, etc., which are transparent and have improved practical properties such as impact strength, fluidity, low-temperature moldability and the like. The present invention relates to a high impact aromatic vinyl resin copolymer composition. Specifically, terpene resin (a), terpene hydrogenated resin (b),
It contains at least one or more resins selected from petroleum resins (c), and aromatic vinyl-(-) (meth) acrylic acid alkyl ester-based structural units having a specific ratio and at least one aromatic vinyl-based structural unit ( A rubber-modified aromatic vinyl with excellent transparency, impact strength, and low-temperature moldability containing a (meth) alkyl acrylate copolymer as a continuous phase and containing dispersed particles of a rubbery polymer having a specific glass transition point as a dispersed phase. The present invention relates to a system copolymer resin mixture composition.

[0002]

2. Description of the Related Art In general, various styrene-butadiene block copolymers such as those having a linear block structure and those having a radially branched block structure are known.
As its properties, it is remarkably excellent in transparency, and generally changes from a rubbery state to a resinous state as the styrene content increases. However, such a styrene-butadiene block copolymer has a drawback of being inferior in practical physical properties such as rigidity and strength. Conventionally, polystyrene is blended in order to solve such a drawback. However, blending polystyrene with the styrene-butadiene block copolymer improves rigidity, but has problems such as impairing transparency, which is an excellent property of the styrene-butadiene block copolymer.

[0003] In order to maintain and improve the transparency and enhance the impact resistance developed by rubber reinforcement, there have been proposed a number of methods for polymerizing a mixed solution comprising styrene, an alkyl (meth) acrylate and a butadiene rubber polymer. Have been. For example, JP-A-52-124095, JP-A-62-169812, and JP-A-62-1
No. 51415 describes a method for polymerizing a mixed solution comprising an aromatic vinyl, an alkyl (meth) acrylate and a diene rubber polymer.

[0004]

However, in the techniques disclosed therein, the obtained thermoplastic resin is transparent and shows a high elongation in tensile properties, but as shown in the Izod impact strength, The effect of rubber reinforcement is still inadequate. That is, although the transparency and elongation are improved, the impact strength including the Izod impact strength is not improved. As a remedy, there is a method of adding a petroleum resin (JP-A-8-109304). In such a method, although the appearance characteristics, printing characteristics, etc. are improved, the impact strength and transparency of the molded body, the balance of gloss is poor,
They have not yet fully satisfied the market requirements. Also, a method of adding a terpene-based hydrogenated resin (Japanese Unexamined Patent Publication No.
No. 1001) is disclosed, but even with such a method, the balance between the impact strength and the transparency and gloss of the molded article is improved, but simply adding a terpene-based hydrogenated resin has not been sufficient. . Similarly, a method of adding a terpene resin (JP-A-6-057085)
Although moldability, strength, rigidity, poor balance of transparency, low-temperature moldability, secondary workability tends to improve, but still transparency, impact strength, surface properties, heat resistance There is a bad problem.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the inventors of the present invention have transparency, a good balance of impact strength and fluidity, and appearance properties such as gloss and practical physical properties such as low-temperature moldability. As a result of diligent studies on a rubber-modified aromatic vinyl copolymer resin composition having excellent properties, the present invention was completed. That is, the present invention relates to a rubber-modified aromatic vinyl copolymer resin containing a rubbery polymer as dispersed particles in a continuous matrix resin, wherein (1) the continuous matrix has a refractive index substantially equivalent to that of the rubbery polymer. Wherein a mixed solution of 20 to 80% by weight of an aromatic vinyl compound having at least one structural unit and 20 to 80% by weight of an alkyl (meth) acrylate compound having at least one structural unit is copolymerized. , (2) the content of the rubbery polymer is 3 to 20% by weight based on the rubber-modified aromatic vinyl copolymer resin,
(3) The average particle diameter of the rubber-like polymer dispersed particles is 0.3 to
Terpene resin (a), terpene (4) and (4) and the glass transition point of the dispersed particles thereof is in the range of -75 to -30 ° C. 1 to 30% by weight of at least one compound selected from the group consisting of a hydrogenated resin (b) and a petroleum resin (c) (1% by weight ≦ a +
b + c ≦ 30% by weight), and a rubber-modified aromatic vinyl copolymer resin mixed composition.

Hereinafter, the present invention will be described in detail. The rubber-modified aromatic vinyl copolymer resin constituting the present invention, in the presence of a rubbery polymer, an aromatic vinyl compound and (meth)
The acrylic acid alkyl ester compound can be copolymerized or copolymerized with an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound if necessary.
It is obtained as an aromatic vinyl copolymer obtained by copolymerizing two or more kinds of compounds. Here, as the aromatic vinyl compound, for example, in addition to styrene, α-methylstyrene, α-methyl-p-methylstyrene, etc.
-Alkyl-substituted styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4 dimethylstyrene, ethylstyrene, nuclear alkyl-substituted styrene such as tert-butylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromo Styrene, 2-methyl-1,4-chlorostyrene,
One or two of styrene compounds conventionally known for rubber-modified styrene resins, such as nuclear halogenated styrenes such as 2,4 dibromostyrene and vinyl naphthalene.
A mixture of more than one kind is used, and a typical one is a compound in which styrene alone or a part thereof is replaced with the above-mentioned vinyl aromatic single substance other than styrene.

The alkyl (meth) acrylate compounds include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methoxyethyl acrylate,
Lauryl methacrylate, tridecyl methacrylate, palmitin methacrylate, pentadecyl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, tridecyl acrylate, palmitin acrylate, pentadecyl acrylate, acrylic acid Stearyl and the like.

The compound which can be copolymerized with the aromatic vinyl compound and the alkyl (meth) acrylate compound constituting the aromatic vinyl copolymer resin of the present invention includes, for example, acrylonitrile, methacrylonitrile, fumaronitrile, Vinyl cyanide such as maleonitrile and α-chloroacrylonitrile; maleimide such as methacrylic acid, acrylic acid, maleic anhydride and phenylmaleimide; vinyl acetate and divinylbenzene; and aromatic vinyl compounds and alkyl (meth) acrylates. Used as a mixture with an ester compound. The rubbery polymer dispersed in the rubber-modified aromatic vinyl copolymer resin component of the present invention in the form of particles has a rubbery property at room temperature, and is preferably a random or tapered copolymer of styrene and butadiene. Block part composed of united parts (A)
And a styrene homopolymer or a block copolymer composed of a styrene-butadiene random copolymer block part (B) mostly composed of styrene.

More preferably, (a) a random or tapered copolymer block part (A) of butadiene and styrene comprising 5% to 35% by weight of styrene and 65% to 95% by weight of butadiene, and 90% by weight of styrene.
(B) a styrene homopolymer or a random copolymer of butadiene and styrene (B) comprising 100% by weight and 0% by weight to 10% by weight of butadiene;
The glass transition point of the random or tapered copolymer part (A) of butadiene and styrene is in the range of -80 to -35 ° C, and (c) the ratio of 1,2-vinyl bonds among the unsaturated bonds based on butadiene is 8 0.020.0% by weight, and (d) a styrene-butadiene-based block copolymer in which the viscosity of a 5% by weight styrene solution at 25 ° C. is in the range of 20 to 50 centipoise. Still more preferably, (a) a random or tapered copolymer block part (A) of butadiene and styrene comprising 10% to 25% by weight of styrene and 75% to 90% by weight of butadiene, and 95% to 100% by weight of styrene. % Of butadiene and 0 to 5% by weight of a styrene homopolymer or a random copolymer of butadiene and styrene (B), and (b) a random or tapered copolymer of butadiene and styrene (A). Has a glass transition point of −80 to −40 ° C., and (c) a ratio of 1,2 vinyl bonds among unsaturated bonds based on butadiene is 10.0 to 17.0% by weight, and (d) A) a styrene butadiene block copolymer having a 5% by weight styrene solution viscosity at 25 ° C. in the range of 25 to 40 centipoise; Desirably. The bonding ratio of 1,2 vinyl is
If it exceeds 20% by weight, the morphology and particle size of the rubber particles become irregular, resulting in poor impact resistance. If it is less than 8% by weight, the rubber form becomes irregular and the impact resistance is poor. If the viscosity of the 5% by weight styrene solution at 25 ° C. is 20 centipoise or less, the impact resistance is poor. If it exceeds 50 centipoise, the particle size of the dispersed rubber particles will be irregular, and the resulting resin will have poor gloss.

[0010] In addition, as long as the effects of the present invention are not impaired,
Boundaries (A) and (A) of a block part (A) composed of a random or tapered copolymer of styrene and butadiene and a styrene butadiene random copolymer block part (B) composed mainly of styrene homopolymer or styrene And / or a butadiene block portion at both ends of (B), and a common styrene-butadiene-based block copolymer can also be used together. Here, the styrene / butadiene random copolymer block portion (A) refers to a copolymer block portion having a structure in which the bonding mode of styrene and butadiene is randomly and uniformly distributed along the polymer chain. The butadiene tapered copolymer block portion (A) refers to a copolymer block portion in which the bonding mode of styrene and butadiene has a gradient structure of styrene and butadiene composition along the polymer chain or a structure corresponding thereto.

The rubbery polymer used in the resin mixture composition of the present invention is produced by a usual living anionic polymerization method using an organolithium catalyst in a hydrocarbon solvent. For example, any method such as a method of mixing two or more different block copolymer rubbers is not particularly limited. When the rubbery polymer is produced in a hydrocarbon solvent using an organolithium catalyst, examples of the organolithium catalyst include n-propyllithium, isopropylpropyllithium, n-butyllithium, and sec-butyl. Lithium, t
Ert-butyllithium, methyllithium, ethyllithium, n-hexyllithium, cyclohexyllithium, benzyllithium, lithium naphthalene and the like are used, and preferably, n-butyllithium and sec-butyllithium are used. As the hydrocarbon solvent, pentane, n-hexane, n-heptane, isooctane, n-
Aliphatic hydrocarbons such as decane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, and aromatic hydrocarbons such as benzene, xylene and toluene are used. Further, a polar substance may be produced in the presence of a polymerization system. Examples of polar substances include triethylamine, tri-n-butylamine, pyridine, N, N, N ', N'-tetramethylethylenediamine, hexamethylphosphoramide,
Triphenylphosphine, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol methyl ether, diethylene glycol dimethyl ether, potassium butoxide, sodium butoxide and the like,
Preferably, N, N, N ', N'-tetramethylethylenediamine, tetrahydrofuran or the like is used.

The rubbery polymer used in the present invention is preferably a random or tapered copolymer block part (A) of butadiene and styrene and a styrene homopolymer or a styrene butadiene random composed mostly of styrene. A styrene-butadiene-based block copolymer composed of a copolymer block portion (B) is used,
As a method for producing such a styrene-butadiene-based block copolymer by a normal living anion polymerization method, for example, in a hydrocarbon solvent in which an organolithium-based catalyst is present, a mixture of butadiene and styrene was set. A method in which the polymerization is carried out by supplying at a polymerization rate lower than the polymerization rate of the monomer at the polymerization temperature (for example, Japanese Patent Publication No.
No. 94, etc.). That is, polymerization is performed while supplying a monomer mixture having a desired ratio of butadiene and styrene at a rate lower than the polymerization rate, and if necessary, then supplying a monomer mixture having a different composition ratio of butadiene and styrene at a rate lower than the polymerization rate. If necessary, this operation is repeated one or more times to obtain the block copolymer of the present invention. In addition, application of a method of adding a polar substance to a polymerization system containing an organolithium catalyst (for example, a method described in JP-B-36-15386) can also be mentioned as a production method by a living anion polymerization method. . That is, in a polymerization system containing an organolithium catalyst and a polar substance, a monomer mixture having a desired butadiene / styrene composition ratio is polymerized, and if necessary, a monomer mixture having a different butadiene / styrene composition ratio is added. The block copolymer of the present invention can also be obtained by repeating this operation once or more if necessary. A method based on a combination of these methods is also possible.

In the production of the rubber-modified aromatic vinyl copolymer resin mixture composition of the present invention, an organic solvent can be used if necessary. Examples of the organic solvent include benzene, toluene, xylene, ethylbenzene, acetone, isopropylbenzene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and the like. Particularly, aromatic hydrocarbons such as toluene and ethylbenzene alone or a mixture of two or more thereof are used. It is preferable that other solvents such as aliphatic hydrocarbons and dialkyl ketones be used in combination with aromatic hydrocarbons as long as the dissolution of the rubbery polymer is not impaired. The rubbery polymer is composed of an aromatic vinyl compound and an alkyl (meth) acrylate compound or an aromatic vinyl compound and an alkyl (meth) acrylate compound and a monomer copolymerizable therewith, or a solvent. Dissolved in the mixture. When an organic solvent is used, the concentration of the monomer in the polymerization solution and the concentration of the produced copolymer are reduced, so that the polymerization rate is reduced to an easily controllable level, thereby preventing runaway of the polymerization reaction. In addition, the viscosity of the polymerization liquid decreases, and the uniform mixing of the polymerization liquid and the movement of the polymerization liquid are facilitated, so that the operability as a production process is improved.

However, if the concentration of the organic solvent in the polymerization solution is too high, the polymerization rate is too low, and the productivity is reduced. It is not preferable because the polymer particles easily aggregate and the transparency of the resin decreases. In addition, the recovery energy of the solvent becomes large and the economic efficiency becomes poor. Therefore, the concentration of the organic solvent in the reaction vessel is usually in the range of 5 to 50 parts by weight based on 100 parts by weight of the total amount of the polymerization solution. The solvent may be added after the polymerization conversion rate at which the viscosity becomes relatively high, or may be added before the polymerization. It is preferable to add them before polymerization in view of uniformity of quality and control of polymerization temperature. When polymerizing the monomer, it may be polymerized in the temperature range of 110 to 190 ° C. in the absence of a polymerization initiator, or 50 to 180 ° C. using an organic peroxide that generates radicals as a polymerization initiator. The polymerization can be carried out in a temperature range of preferably 90 to 150 ° C, but it is preferable to carry out the polymerization in the presence of a peroxide.

In the present invention, a polymerization initiator can be used. The organic peroxide used is 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-
Peroxyketals such as butylperoxy) octane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate; -Butyl peroxide, t-butylcumyl peroxide, sicumyl peroxide, α, α'-bis (t-
Dialkyl peroxides such as butyl peroxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne-3,
Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4 dichlorobenzoyl peroxide, m- Diacyl peroxides such as toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di2
Peroxycarbonates such as ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t- Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypiparate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexano Ethate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxybenzoate, di-t-butyl diperoxy isophthalate, 2,5-dimethyl-2,5 (Benzoi) Peroxy esters such as peroxy) hexane and t-butylperoxyisopropyl carbonate; ketone peroxides such as acetylacetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide , T-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane 2,5 dihydroperoxide, 1,1,3,3
-Hydroperoxides such as tetramethylbutyl hydroperoxide, polyacyl peroxides of dibasic acid, polyperoxyesters of dibasic acid and polyol, and one or more initiators are used. it can. However, the use of an organic peroxide is preferred because a high grafting efficiency is easily obtained. The amount of use is not particularly limited, but is preferably 0.001 to 5.0 parts by weight based on 100 parts by weight of the monomer mixture.

In the polymerization, a chain transfer agent such as mercaptans, α-methylstyrene linear dimer,
Monoterpenoid-based molecular weight regulator (turbinolene),
Examples of antioxidants include hindered phenols, hindered bisphenols, hindered trisphenols, and the like, for example, 2,6-di-tert-butyl-4-methylphenol, stearyl-β- (3,5-di-tert-butyl-4-hydroxy). (Phenyl) propionate may be used.

The resins obtained by the above polymerization methods include:
Known antioxidants, for example 2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) 4,6-dimethylphenol, 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol), 4 Inorganic stabilizers such as 4,4'-thiobis (6-tert-butyl-3-methylphenol), dilaurylthiodipropionate, tris (dinonylphenyl) phosphite, calcium and tin; known ultraviolet absorbers;
For example, p-tert-butylphenyl salicylate,
2,2'-dihydroxy-4-methoxybenzophenohen, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzothiazole; known lubricants, for example, paraffin wax, stearic acid, hydrogenated oil, stearoamide, methylenebisstearo Amide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride;
Known flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, chlorinated paraffins, tetrabromobutane, hexabromobutane,
Known antistatic agents such as stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate; known colorants such as titanium oxide, carbon black and other inorganic or organic pigments; known fillers; For example, calcium carbonate, clay, silica, glass fiber, glass sphere, carbon fiber, MBS, SBR, SBS, SI as a reinforcing elastomer
S or a hydrogenated product thereof can be added as required, but is not limited thereto. Further, when these additives are blended with the resin, the additives may be blended alone or a plurality of kinds of additives may be blended. Furthermore, it can be blended with another resin and provided for molding. Further, these additives may be added at an intermediate stage of the polymerization process. Further, in order to modify the properties of the surface of a product such as a sheet or a film, a modifier used in a styrene resin or an acrylic resin can be applied.

In the present invention, the molecular weight of the matrix resin can be controlled by changing the type, amount and timing of addition of the chain transfer agent. Also,
The particle size of the rubber-dispersed particles can be controlled by changing the stirring conditions as well as the type, amount and timing of addition of the chain transfer agent. In order to maintain transparency, a method is used that does not change the composition of the polymer formed during the polymerization process. For example, a method of adding a monomer as needed during the polymerization or a method of continuously adding the monomer after the addition is used.

In the rubber-modified aromatic vinyl copolymer resin containing the rubbery polymer as dispersed particles in the continuous matrix resin according to the present invention, the continuous matrix has a refractive index substantially equal to that of the rubbery polymer. And a mixed solution of 20 to 80% by weight of an aromatic vinyl compound having at least one structural unit and 20 to 80% by weight of an alkyl (meth) acrylate compound having at least one structural unit. Preferably, the continuous matrix has a refractive index substantially equivalent to that of the rubber-like polymer, and has a structural unit of 40 to 65% by weight of an aromatic vinyl compound having at least one kind of (meth) acrylic acid. It is desirable that a mixed solution comprising 35 to 60% by weight of the alkyl ester compound is copolymerized.

In the resin composition of the present invention, the content of the rubbery polymer is 3 to 20% by weight based on the rubber-modified aromatic vinyl copolymer resin. Preferably, the content of the rubbery polymer is 5 to 20% by weight based on the rubber-modified aromatic vinyl copolymer resin. Further, the average diameter of the dispersed particles of the rubbery polymer derived from the rubber-modified aromatic vinyl copolymer resin composition is in the range of 0.3 to 2.1 μm, and the glass transition point of the dispersed particles is −75. It needs to be in the range of -30 ° C. More preferably, the average particle size of the dispersed particles of the rubbery polymer derived from the rubber-modified aromatic vinyl copolymer resin composition is in the range of 0.5 to 1.0 μm, and the glass transition point of the dispersed particles. Is -70 to -35
It is desirably in the range of ° C. Average particle size is 2.1μ
If it exceeds m, the appearance will be poor, and if it is less than 0.3 μm, the impact resistance will decrease, which is not preferable. As used herein, the average particle size is determined by measuring dimethylformamide as a dispersant with LS-230 (trademark of a particle size analyzer manufactured by Coulter, USA) to obtain a volume average value. The particle size distribution state is not particularly limited, and may be a distribution state having a single peak distribution or a distribution state having a double mountain distribution.

The terpene resin (a) of the present invention comprises a Friedel-Crafts catalyst comprising dipentene and aromatic hydrocarbon obtained by isomerization of d-limonene obtained from citrus cortex or α-pinene obtained from raw pine resin. (For example, aluminum chloride, boron trifluoride, or the like) and is obtained by performing cationic polymerization.

The degree of polymerization of the terpene resin (a) is not particularly limited, but is 500 or less, preferably 200 or less, more preferably 100 or less. If the degree of polymerization exceeds 500, the compatibility with the rubber-modified styrenic resin decreases, and as a result, the transparency decreases, which is not preferable. Examples of the terpene-based resin (a) include YS Resin TO-1 manufactured by Yashara Chemical Co., Ltd.
25, TO-115, TO-105, TO-85 (Yashara Chemical
(Trade name of Co., Ltd.) can be used.

In the present invention, the terpene-based hydrogenated resin
(b) is a copolymer of an aromatic vinyl hydrocarbon and a terpene,
It is a resin obtained by hydrogenating this copolymer. Styrene, α-methylstyrene and vinyltoluene are preferably used as the aromatic vinyl hydrocarbon. As the terpene, α-pinene, β-pinene, limonene alone or a mixture can be suitably used. The hydrogenation rate is not particularly limited, but is preferably hydrogenated at 10% or more. Ten%
If it is less than 1, the color tone of the rubber-modified aromatic vinyl-based copolymer resin becomes unfavorable when exposed to high temperatures.

The degree of polymerization of the terpene-based hydrogenated resin (b) is not particularly limited, but the degree of polymerization is 500 or less, preferably 200 or less.
More preferably, it is 100 or less. If the degree of polymerization exceeds 500, the compatibility with the rubber-modified styrenic resin decreases, and as a result, the transparency decreases, which is not preferable. As the terpene-based hydrogenated resin, for example, Clearon M-115, M-105, P-85 (all trade names of Yashara Chemical Co., Ltd.) of Yashara Chemical Co., Ltd. and the like can be used.

The petroleum resin (c) used in the present invention is cationically polymerized with a Friedel-Craft type catalyst using a C5 fraction and a C9 fraction among cracked fractions produced as a result of steam cracking of petroleum as raw materials. There is a resin obtained by:
In this case, the proportion of the C9 fraction in the petroleum resin needs to be 30% or more. It is preferably at least 40% by weight. When the proportion of the C9 fraction is less than 30%, the transparency of the styrene-based resin composition is reduced, and the compatibility with the rubber-modified aromatic vinyl-based copolymer resin is reduced. This leads to a phase separation phenomenon of the film, which is not preferable.

The degree of polymerization of the petroleum resin (c) is not particularly limited, but is preferably 1,000 or less, preferably 500 or less, more preferably 200 or less. When the degree of polymerization increases, the compatibility with the rubber-modified aromatic vinyl-based copolymer resin decreases, the plastic effect also decreases, and the transparency of the sheet or film deteriorates. Escolets E of Tonex Corporation
CR231C (trade name of Tonex Corporation) and the like can be used.

The content of at least one resin selected from the group consisting of a terpene resin (a), a terpene hydrogenated resin (b) and a petroleum resin (c) is 1% based on the rubber-modified aromatic vinyl copolymer resin. -30% by weight (1% by weight ≦ a + b + c ≦ 30% by weight). Preferably, it is 2 to 20% by weight. More preferably, the content is 3 to 10% by weight. When the amount is less than 1 part by weight, the effect of improving the strength and moldability is not recognized, and when the amount exceeds 30 parts by weight, the rigidity is reduced, and the effect of improving the transparency and the effect of reinforcing the strength are saturated. It is not preferable because the cost is increased.

As a method of adding the terpene resin (a) and / or the terpene hydrogenated resin (b) and / or the petroleum resin (c), a styrene monomer or a styrene monomer and acrylic acid ( (Methacrylic acid) Either polymerize by dissolving in an ester monomer mixture, or terpene-based resin (a) and / or terpene-based hydrogenated resin during polymerization of styrene-based polymer.
(b) and / or petroleum resin (c) is added by melting or dissolving in a solvent, or after polymerization is completed and unreacted monomers and solvent are removed or before or after terpene-based resin (a ) And / or terpene-based hydrogenated resin (b) and / or petroleum resin
(c) can be mixed and kneaded with an extruder or a molding machine.

From the obtained resin composition, various molded articles can be formed by injection molding or extrusion molding. Further, it can be formed into a sheet or a film by using a T-die sheet extruder, a casting machine, a biaxial stretching machine, and an inflation machine. The resulting molded product is
Utilizing its excellent transparency and impact resistance, it is used for covers, cases, household goods, etc. In particular, it is useful as a styrene-based resin sheet and film material, and can be suitably used as a food packaging container, daily miscellaneous goods packaging, or lamination sheet film.

[0030]

Embodiments of the present invention will be described below. First, the rubber-modified aromatic vinyl copolymer resin containing a rubbery polymer as dispersed particles of the present invention can be produced by a conventionally known method. That is, the rubbery polymer is dissolved in a raw material solution composed of an aromatic vinyl compound and an alkyl (meth) acrylate compound, a polymerization solvent as needed, and a polymerization initiator, and is dissolved in the presence of a generally used radical catalyst. In the presence, the raw material is fed to a reactor equipped with a stirrer to carry out polymerization. The polymerization temperature can be determined in consideration of the fluidity and productivity of the rubber-modified aromatic vinyl copolymer resin, the heat removal capability of the reactor, and the like. After completion of the polymerization, a treatment under vacuum is performed to remove unreacted monomers, polymerization solvent, and the like, whereby a rubber-modified aromatic vinyl copolymer resin can be obtained.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The data shown in Examples and Comparative Examples were measured according to the following methods. The molecular weight distribution of the styrene-butadiene-based block copolymer rubber was measured by the GPC method under the following conditions. Solvent (mobile phase): TH
F, deaerator: ERC-3310 manufactured by ERMA, pump: PU-980 manufactured by JASCO Corporation, flow rate: 1.0 ml / min, autosampler: AS-8020 manufactured by Tosoh Corporation, column oven: L-5030 manufactured by Hitachi, Ltd. Set temperature 40 ° C, Column configuration: Tosoh TSKgurdcolumn MP (× L)
One 6.0mmID × 4.0cm and TSK-GE manufactured by Tosoh Corporation
L MULTIPORE HXL-M 7.8mmID × 30.0cm
Two, three in total, detector: RI Hitachi L-335
0, data processing: SIC480 data station.

The glass transition point of the styrene-butadiene-based block copolymer rubber (A) is determined by D
It measured using the SC-200 and SSC-5000 series under the following conditions. The temperature is raised from room temperature to the melting point of polystyrene plus the temperature of alpha, held at that temperature for about 10 minutes, and cooled at a cooling rate of 20 to 25 ° C / min to the glass transition temperature of polybutadiene minus the temperature of alpha (n
= 1), the temperature is raised again to the temperature of the melting point of polystyrene plus alpha, and the temperature is maintained for about 10 minutes,
The polybutadiene was cooled at a cooling rate of ° C./min to the glass transition temperature minus the temperature of alpha (n = 2) and the average of the two measurements was recorded. Rubber modified aromatic vinyl
The glass transition point of the dispersed particles dispersed in the alkyl (meth) acrylate copolymer was determined by measuring the rubber-modified aromatic vinyl copolymer resin sample a (accurately weighing about 1 g) to 4/6 (volume) of acetone / methyl ethyl ketone. Ratio) Dispersed in 30 cc of a mixed solvent, insoluble matter was separated by a centrifugal separation method, and dried to obtain DSC-200, SSC-5 manufactured by Seiko Denshi Kogyo KK
Using the 000 series, the measurement was performed under the following conditions. From room temperature, the temperature is raised to the temperature of the melting point of polystyrene plus the temperature of alpha, held at that temperature for about 10 minutes, and cooled at a cooling rate of 20 to 25 ° C./min to the glass transition temperature of polybutadiene minus the temperature of alpha (n = 1). ), Raise the temperature again to the melting point of polystyrene plus the temperature of alpha, hold at that temperature for about 10 minutes, and cool at a cooling rate of 20-25 ° C / min to the glass transition temperature of polybutadiene minus the temperature of alpha (n = 2) ) The average of the two measurements was recorded.

The microstructure of the styrene-butadiene-based block copolymer rubber, in particular, the vinyl bond content and styrene content of the butadiene portion were determined by infrared spectroscopy (Hampto).
n, Anal. Chem., 21, 923 (1949)), and the styrene solution viscosity was measured by an Ostwald viscometer. The graft ratio of the rubber-modified aromatic vinyl copolymer resin composition was determined by dispersing the sample S1 (approximately 1 g precisely) in 30 cc of a 4/6 (volume ratio) mixed solvent of acetone / methyl ethyl ketone, and centrifuging the insoluble matter. Separated and dried, and the weight of insoluble matter (S
2) is precisely weighed and calculated by the following equation 1. Here, S3 indicates the content of the rubbery polymer in the sample S1. {Formula 1} Graft rate (g) = [(S2 / S1) -S3]
/ S3 × 100 The swelling index was determined by measuring the sample S4 (approximately 1 g)
After stirring for 1 hour to dissolve, the supernatant was removed by centrifugation, the weight of the remaining swelled product (S5) was accurately weighed, and the remaining swelled product was then dried by vacuum drying. It is a characteristic value determined by the following formula 2 from the result of precisely weighing the weight (S6) of the dry solid content to be obtained. {Equation 2} Swelling index = S5 / S6

The surface gloss, total light transmittance and haze were determined by JI
S-K7105, Charpy impact strength is JIS K-7
111 (notched), flexural modulus and flexural stress are J
ISK-7203, JIS K-7113 for tensile strength, tensile modulus and elongation, JIS for Vicat softening point
K-7206 and the fluidity at high temperature are JISK-
It was measured according to 7210. Similarly, the falling weight impact strength is
A flat plate having a thickness of 2 mm is molded by an injection molding machine, and a heavy weight having a weight of 6.5 kg from a height of 62 cm is held by using a falling weight graphic impact tester (trademark of an instrumented falling weight impact tester manufactured by Toyo Seiki Seisaku-sho). (Diameter 40 mm) is dropped naturally on the plane of the test piece fixed, and the test piece is completely destroyed or penetrated by a striker (diameter 12.7 mm) provided at the lower part of the heavyweight, and the total energy required at this time (total absorbed energy and ) Was measured. Further, the amount of the polybutadiene rubber component in the rubber-modified styrene copolymer resin composition was determined by a halogen addition method in which iodine chloride was added to a double bond and measured.

[0035]

EXAMPLE 1 A styrene-butadiene random copolymer (A) constituting the styrene-butadiene block copolymer rubber was prepared from styrene-butadiene random copolymer rubbers such as US Pat. No. 3,094,512. A method, that is, a production condition that generally satisfies the relationship of polymerization rate> styrene-butadiene mixed monomer supply rate under a certain condition, is generally used. The concrete implementation method is as follows. A stainless steel polymerization tank having an inner volume of 1000 L with a jacket, a coil and a stirrer is washed with cyclohexane dehydrated to a water content of 10 ppm or less, replaced with nitrogen, and then dehydrated to a water content of 10 ppm or less under a nitrogen gas atmosphere. Then, 540 kg of cyclohexane containing 35 ppm of trimethylethylenediamine was charged into the polymerization tank, and after raising the internal temperature to 80 ° C., 0.8 kg of a cyclohexane solution containing 10 wt% of n-butyllithium was added. Next, at a constant internal temperature of 80 ° C., a water content of 10
8.75 kg / h of styrene dehydrated to less than ppm and 35 k of butadiene dehydrated by passing through a molecular sieve
g / h were fed simultaneously for 4 hours to carry out polymerization. After that, styrene dehydrated to a water content of 10 ppm or less
kg, and the maximum temperature should not exceed 120 ° C.
The polymerization was carried out for minutes, and all of the charged styrene was polymerized.

Thereafter, the polymerization solution is transferred to the next reaction tank,
After 0.08 parts by weight of water was added to 100 parts by weight of the polymer to terminate the polymerization, carbon dioxide was added and neutralized during the transfer to the next reaction tank. Next, 2,4, -bis
[(Octylthio) methyl] -O-cresol was added at a rate of 0.2% to the polymer, the solvent was removed by steam stripping, dried with a hot roll at 100 ° C, and dried with a styrene-butadiene block copolymer. A united rubber was obtained. 7.9% by weight of the styrene butadiene block copolymer rubber was 46.6% by weight of styrene monomer, 32.5% by weight of methyl methacrylate, and butyl acrylate.
100 parts by weight of a solution dissolved in 6% by weight and 8.4% by weight of ethylbenzene and 0.01,1,1-bis (tert-butylperoxyl) 3,3,5-trimethylcyclohexane 0.0
The solution consisting of 15 parts by weight was continuously fed into the first polymerization machine, and after stirring polymerization reaction at a polymerization temperature of 125 ° C., the whole amount was continuously continuously charged into a plug flow type reactor to carry out polymerization. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time,
Terpene resin (YS resin TO-115 manufactured by Yashara Chemical Co., Ltd.) 5 per 100 parts by weight of rubber-modified styrene resin
Parts by weight were fed to a vented extruder. Tables 1 and 2 show various analytical values and evaluation results of solid physical properties.

[0037]

Example 2 The styrene-butadiene random copolymer (A) constituting the styrene-butadiene-based block copolymer rubber was produced from styrene-butadiene-based random copolymer rubbers such as US Pat. No. 3,094,512. A method, that is, a production condition that generally satisfies the relationship of polymerization rate> styrene-butadiene mixed monomer supply rate under a certain condition, is generally used. The concrete implementation method is as follows. A stainless steel polymerization tank having an inner volume of 1000 L with a jacket, a coil and a stirrer is washed with cyclohexane dehydrated to a water content of 10 ppm or less, replaced with nitrogen, and then dehydrated to a water content of 10 ppm or less under a nitrogen gas atmosphere. Then, 540 kg of cyclohexane containing 35 ppm of trimethylethylenediamine was charged into the polymerization tank, and after raising the internal temperature to 80 ° C., 0.8 kg of a cyclohexane solution containing 10 wt% of n-butyllithium was added. Next, at a constant internal temperature of 80 ° C., a water content of 10
3.89 kg / h of styrene dehydrated to less than ppm and 35 k of butadiene dehydrated by passing through a molecular sieve
g / h were fed simultaneously for 4 hours to carry out polymerization. Then, styrene dehydrated to a water content of 10 ppm or less at 80.degree.
kg, and the maximum temperature should not exceed 120 ° C.
The polymerization was carried out for minutes, and all of the charged styrene was polymerized.

Thereafter, the polymerization solution is transferred to the next reaction tank,
After 0.08 parts by weight of water was added to 100 parts by weight of the polymer to terminate the polymerization, carbon dioxide was added and neutralized during the transfer to the next reaction tank. Next, 2,4, -bis
[(Octylthio) methyl] -O-cresol was added at a rate of 0.2% to the polymer, the solvent was removed by steam stripping, and the mixture was dried on a hot roll at 100 ° C., and dried with a styrene butadiene block copolymer. I got the rubber. 7.9% by weight of the styrene butadiene block copolymer rubber was 46.6% by weight of styrene monomer, 32.5% by weight of methyl methacrylate, and butyl acrylate.
100 parts by weight of a solution dissolved in 6% by weight and 8.4% by weight of ethylbenzene and 0.01,1,1-bis (tert-butylperoxyl) 3,3,5-trimethylcyclohexane 0.0
The solution consisting of 15 parts by weight was continuously fed into the first polymerization machine, and after stirring polymerization reaction at a polymerization temperature of 125 ° C., the whole amount was continuously continuously charged into a plug flow type reactor to carry out polymerization. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time,
Terpene resin (YS resin TO-115 manufactured by Yashara Chemical Co., Ltd.) 5 per 100 parts by weight of rubber-modified styrene resin
Parts by weight were fed to a vented extruder. Tables 1 and 2 show various analytical values and evaluation results of solid physical properties.

[0039]

Example 3 The styrene-butadiene tapered copolymer block portion (A) constituting the styrene-butadiene block copolymer rubber is a styrene-butadiene random copolymer rubber such as US Pat. No. 3,094,512. In other words, it can be obtained by applying a production method that satisfies the relationship of polymerization rate> supply rate of styrene-butadiene mixed monomer under certain conditions. That is, polymerization is performed while supplying a monomer mixture having a desired butadiene and styrene composition ratio at a polymerization rate or lower, and then supplying a monomer mixture having a different butadiene and styrene composition ratio at a polymerization rate or lower, By repeating this operation at least once, the styrene-butadiene tapered copolymer block (A) constituting the styrene-butadiene-based block copolymer rubber used in the present invention can be synthesized. A specific implementation method will be described. A stainless steel polymerization tank equipped with a jacket, coil, and stirrer with an inner volume of 1000 L was filled with a water content of 10 ppm.
After washing with dehydrated cyclohexane and purging with nitrogen, dehydrate to a water content of 10 ppm or less under a nitrogen gas atmosphere, charge 540 kg of cyclohexane containing 35 ppm of trimethylethylenediamine in a polymerization tank, raise the internal temperature to 80 ° C., and then add n-butyllithium. 0.8 kg of a 10 wt% cyclohexane solution was added.

Next, styrene dehydrated to a water content of 10 ppm or less and butadiene dehydrated by passing through a molecular sieve at a constant internal temperature of 80 ° C. are converted into six stages at a specific feed rate and polymerization time. Feeding and polymerization were carried out simultaneously while changing them. The feeding rate and the polymerization time at this time were as follows. First stage: 2.6 kg / h of styrene, 32.9 kg / h of butadiene, 1.3 hours of polymerization time. Second stage: styrene 6.1 kg / h, butadiene 32.8 k
g / h, polymerization time 1.2 hours. Third stage: Styrene8.
7 kg / h, butadiene 25.9 kg / h, polymerization time 1.0 hour. Fourth stage: styrene 8.1 kg / h, butadiene 14.9 kg / h, polymerization time 1.0 hour. Fifth stage: styrene 8.7 kg / h, butadiene 10.5 kg
/ H, polymerization time 1.2 hours. Sixth stage: styrene 7.8
kg / h, butadiene 5.0 kg / h, polymerization time 0.9
time.

Thereafter, 45 kg of styrene dehydrated to a water content of 10 ppm or less was added at 80 ° C.
Polymerization was performed for 10 minutes at a temperature not exceeding ℃, and all of the charged styrene was polymerized. Thereafter, the polymerization solution was transferred to the next reaction vessel, water was added to 0.08 parts by weight with respect to 100 parts by weight of the polymer to stop the polymerization, and then carbon dioxide was added during the transfer to the next reaction vessel. Summed up. Next, 2,4,-
After adding bis [(octylthio) methyl] -O-cresol at a rate of 0.2% to the polymer, the solvent was removed by steam stripping, and the mixture was dried with a hot roll at 100 ° C. to obtain a styrene-butadiene block. A heavy rubber was obtained. 7.9% by weight of this styrene-butadiene block copolymer rubber was dissolved in 46.6% by weight of a styrene monomer, 32.5% by weight of methyl methacrylate, 4.6% by weight of butyl acrylate, and 8.4% by weight of ethylbenzene. A solution consisting of 100 parts by weight of the solution and 0.015 parts by weight of 1,1-bis (tert-butylperoxyl) 3,3,5-trimethylcyclohexane was continuously fed into the first polymerization machine, and a polymerization temperature of 125 ° C. , And then continuously charged in a plug flow type reactor to carry out polymerization. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time, the terpene resin (YS Resin TO-11 manufactured by Yashara Chemical Co., Ltd.) was used per 100 parts by weight of the rubber-modified styrene resin.
5) 5 parts by weight were supplied to a vent type extruder. Tables 1 and 2 show various analytical values and evaluation results of solid physical properties.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

Example 4 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The procedure is the same as in Example 1, except that 5 parts by weight of CLEARON M115) are supplied to the vented extruder. Table 3 shows the results of the evaluation of solid physical properties.

[0045]

Example 5 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The procedure is the same as in Example 2, except that 5 parts by weight of Clearon M115) are supplied to the vented extruder. Table 3 shows the results of the evaluation of solid physical properties.

[0046]

Example 6 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The procedure is the same as in Example 3, except that 5 parts by weight of Clearon M115) are supplied to the vented extruder. Table 3 shows the results of the evaluation of solid physical properties.

[0047]

[Table 3]

[0048]

Example 7 Petroleum resin (Escolez ECR manufactured by Tonex Corporation) was used per 100 parts by weight of rubber-modified styrene resin.
231C) The same operation as in Example 1 is performed, except that 5 parts by weight is supplied to the vented extruder. Table 4 shows the results of the evaluation of solid physical properties.

[0049]

Example 8 A petroleum resin (Escolets ECR manufactured by Tonex Corporation) was used per 100 parts by weight of the rubber-modified styrenic resin.
231C) The same operation as in Example 2 is performed, except that 5 parts by weight is supplied to the vented extruder. Table 4 shows the results of the evaluation of solid physical properties.

[0050]

Example 9 A petroleum resin (Escolets ECR manufactured by Tonex Corporation) was used per 100 parts by weight of the rubber-modified styrene resin.
231C) The procedure is the same as in Example 3, except that 5 parts by weight are fed to the vented extruder. Table 4 shows the results of the evaluation of solid physical properties.

[0051]

[Table 4]

[0052]

Comparative Example 1 Terpene resin (Yasuhara Chemical Co., Ltd.)
Example 1 was repeated except that YS resin TO-115) was not used. Table 5 shows the results of the evaluation of solid physical properties.

[0053]

Comparative Example 2 Terpene resin (Yasuhara Chemical Co., Ltd.)
YS resin TO-115) was used, except that it was not used. Table 5 shows the results of the evaluation of solid physical properties.

[0054]

Comparative Example 3 Terpene resin (Yasuhara Chemical Co., Ltd.)
Example 3 is the same as that of Example 3 except that YS resin (TO-115) is not used. Table 5 shows the results of the evaluation of solid physical properties.

[0055]

[Table 5]

[0056]

Comparative Example 4 Styrene butadiene block copolymer rubber (NS-316S, manufactured by Zeon Corporation) was 7.9% by weight, styrene monomer was 46.6% by weight, and methyl methacrylate 3 was used.
100% by weight of a solution of 2.5% by weight, 4.6% by weight of butyl acrylate and 8.4% by weight of ethylbenzene, and 1,1-bis (tert-butylperoxyl) 3;
A solution consisting of 0.015 parts by weight of 3,5-trimethylcyclohexane was continuously fed into the first polymerization machine, and a polymerization reaction with stirring was carried out at a polymerization temperature of 125 ° C., and then the whole amount was continuously fed to a plug flow reactor. It was charged and polymerized. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time, 5 parts by weight of a terpene-based resin (YS resin TO-115 manufactured by Yashara Chemical Co., Ltd.) was supplied to the vented extruder per 100 parts by weight of the rubber-modified styrene-based resin. Tables 6 and 7 show various analytical values and solid physical property evaluation results.

[0057]

Comparative Example 5 7.9% by weight of styrene butadiene block copolymer rubber (NS-312S manufactured by Zeon Corporation) was used in an amount of 46.6% by weight of a styrene monomer, and methyl methacrylate 3 was used.
100% by weight of a solution of 2.5% by weight, 4.6% by weight of butyl acrylate and 8.4% by weight of ethylbenzene, and 1,1-bis (tert-butylperoxyl) 3;
A solution consisting of 0.015 parts by weight of 3,5-trimethylcyclohexane was continuously fed into the first polymerization machine, and a polymerization reaction with stirring was carried out at a polymerization temperature of 125 ° C., and then the whole amount was continuously fed to a plug flow reactor. It was charged and polymerized. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time, 5 parts by weight of a terpene-based resin (YS resin TO-115 manufactured by Yashara Chemical Co., Ltd.) was supplied to the vented extruder per 100 parts by weight of the rubber-modified styrene-based resin. Tables 6 and 7 show various analytical values and solid physical property evaluation results.

[0058]

Comparative Example 6 7.9% by weight of styrene butadiene block copolymer rubber (670A manufactured by Nippon Elastomer Co.) was added to 46.6% by weight of a styrene monomer, and methyl methacrylate 3 was used.
100% by weight of a solution of 2.5% by weight, 4.6% by weight of butyl acrylate and 8.4% by weight of ethylbenzene, and 1,1-bis (tert-butylperoxyl) 3;
A solution consisting of 0.015 parts by weight of 3,5-trimethylcyclohexane was continuously fed into the first polymerization machine, and a polymerization reaction with stirring was carried out at a polymerization temperature of 125 ° C., and then the whole amount was continuously fed to a plug flow reactor. It was charged and polymerized. Thereafter, the mixture was polymerized to a polymerization rate of 85%, and the solution was fed to a vented extruder to remove volatile components at 230 ° C. under reduced pressure, to draw out a molten strand from a die, water-cooled, cut with a cutter, and pelletized. Resin was obtained. At this time, 5 parts by weight of a terpene-based resin (YS resin TO-115 manufactured by Yashara Chemical Co., Ltd.) was supplied to the vented extruder per 100 parts by weight of the rubber-modified styrene-based resin. Tables 6 and 7 show various analytical values and solid physical property evaluation results.

[0059]

[Table 6]

[0060]

[Table 7]

[0061]

Comparative Example 7 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The same operation as in Comparative Example 4 was carried out except that 5 parts by weight of Clearon M115) was not supplied to the vented extruder. Table 8 shows the results of the evaluation of solid physical properties.

[0062]

Comparative Example 8 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The same operation as in Comparative Example 5 was performed except that 5 parts by weight of Clearon M115) was not supplied to the vented extruder. Table 8 shows the results of the evaluation of solid physical properties.

[0063]

Comparative Example 9 Terpene-based hydrogenated resin (Yasuhara Chemical Co., Ltd.) per 100 parts by weight of rubber-modified styrene-based resin
The same operation as in Comparative Example 6 was performed except that 5 parts by weight of Clearon M115) was not supplied to the vented extruder. Table 8 shows the results of the evaluation of solid physical properties.

[0064]

[Table 8]

[0065]

Comparative Example 10 Petroleum resin (Escolez ECR manufactured by Tonex Corporation) was used per 100 parts by weight of rubber-modified styrene resin.
231C) except that 5 parts by weight are not fed to the vented extruder
The same operation as in the fourth embodiment is performed. Table 9 shows the results of the evaluation of solid physical properties.
Shown in

[0066]

Comparative Example 11 A petroleum resin (Escolets ECR manufactured by Tonex Corporation) was used per 100 parts by weight of the rubber-modified styrene resin.
231C) except that 5 parts by weight are not fed to the vented extruder
The same operation as in the fifth embodiment is performed. Table 9 shows the results of the evaluation of solid physical properties.
Shown in

[0067]

Comparative Example 12 A petroleum resin (Escolets ECR manufactured by Tonex Corporation) was used per 100 parts by weight of the rubber-modified styrene resin.
231C) except that 5 parts by weight are not fed to the vented extruder
The same operation as in the sixth embodiment is performed. Table 9 shows the results of the evaluation of solid physical properties.
Shown in

[0068]

[Table 9]

[0069]

Comparative Example 13 Terpene resin (Yasuhara Chemical)
Comparative Example 4 was used except that YS resin TO-115 manufactured by Co., Ltd. was not used. Table 10 shows the results of the solid physical property evaluation.

[0070]

Comparative Example 14 Terpene-based resin (Yasuhara Chemical
Comparative Example 5 was used except that YS resin TO-115 manufactured by Co., Ltd. was not used. Table 10 shows the results of the solid physical property evaluation.

[0071]

Comparative Example 15 Terpene resin (Yasuhara Chemical
Comparative Example 6 was used except that YS resin TO-115 manufactured by Co., Ltd. was not used. Table 10 shows the results of the solid physical property evaluation.

[0072]

[Table 10]

[0073]

As described above, the present invention provides a rubber-modified aromatic vinyl resin using a rubber-like polymer having a specific glass transition point, selected from terpene resins, terpene hydrogenated resins, and petroleum resins. By containing at least one compound, the composition has transparency without lowering the heat resistance, and the physical properties, particularly the Charpy impact strength and the falling weight impact strength, are remarkably improved. Furthermore, it has excellent moldability and is suitable for molding, sheet processing, foam molding and the like. Further, the present invention provides a production method that can utilize a known production method, and its industrial value is extremely large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 65:00) C08L 65:00) (C08L 25/00 (C08L 25/00 57:02) 57:02 (C08L 25/00 (C08L 25/00 9:06) 9:06) (C08L 25/00 (C08L 25/00 53:02) 53:02) F-term (reference) 4J002 AC082 BA013 BC052 BC071 BC081 BC091 BG041 BG051 BG061 BK003 BP012 CE003 FA082

Claims (3)

[Claims] 1. A rubber-modified aromatic vinyl copolymer resin containing a rubbery polymer as dispersed particles in a continuous matrix resin, wherein (1) the continuous matrix has a refractive index substantially equal to that of the rubbery polymer. Having a structural unit of 20 to 80% by weight of at least one aromatic vinyl compound and at least one alkyl (meth) acrylate compound 20 to
A mixed solution consisting of 80% by weight is copolymerized,
(2) The content of the rubbery polymer is 3 to 20% by weight based on the rubber-modified aromatic vinyl copolymer resin, and (3) the average particle diameter of the rubbery polymer dispersed particles is 0.3 to (4) and the glass transition point of the dispersed particles is -75.
At least one selected from terpene-based resins (a), terpene-based hydrogenated resins (b), and petroleum resins (c) with respect to the rubber-modified aromatic vinyl-based copolymer resin in a temperature range of from −30 ° C. 1 to 30% by weight of the above resin (1% by weight ≦ a + b + c ≦ 30% by weight)
A mixed composition of a rubber-modified aromatic vinyl copolymer resin, characterized by comprising: 2. The aromatic vinyl compound is styrene,
The transparent rubber-modified aromatic vinyl copolymer resin composition according to claim 1, wherein the alkyl (meth) acrylate compound is methyl methacrylate alone or a mixture of methyl methacrylate and butyl acrylate. 3. The rubbery polymer dispersed in the rubber-modified aromatic vinyl copolymer resin component in the form of particles is a block portion (A) composed of a random or tapered copolymer of styrene and butadiene, and a styrene homopolymer. 2. The rubber-modified aromatic vinyl copolymer resin composition according to claim 1, wherein the copolymer is a block copolymer comprising a styrene-butadiene random copolymer block part (B) which is mostly composed of styrene. object.