JP2015096573A - Graft copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a graft copolymer that is suitable as a material for thermoplastic resin composition capable of producing a formed article having excellent impact resistance, color development, transparency and scratch resistance.SOLUTION: Provided is a graft copolymer obtained by polymerizing a vinyl-type monomer mixture comprising an aromatic vinyl compound and a vinyl cyanide compound, in the presence of a crosslinked rubbery polymer (C) that is obtained by crosslink-treating a hydrogenated product of block copolymer comprising a block composed mainly of a constitutional unit based on an aromatic vinyl compound and a block composed mainly of a constitutional unit based on a conjugated diene-type compound.

Description

  The present invention relates to a graft copolymer.

  Improving the impact resistance of the molded product not only expands the applications of the molded product, but also makes it extremely useful for industrial applications, such as making it possible to reduce the thickness and size of the molded product. . Therefore, various techniques have been proposed so far for improving the impact resistance of the molded product. Among these methods, a method for increasing the impact resistance of a molded product by using a resin material in which a rubbery polymer and a hard resin are combined has already been industrialized. Examples of such resin materials include acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin, acrylonitrile-ethylene / propylene / non-conjugated diene copolymer-styrene (AES) resin, and the like. Can be mentioned.

Moreover, when high designability is calculated | required by a molded article, the coating process is performed to the molded article obtained from these resin materials, and high appearance quality is obtained. However, the coating process has problems such as a large environmental load, complicated processes, and high manufacturing costs. Therefore, the coating treatment of the molded product may be omitted. In this case, the molded product is required to have, for example, the following characteristics in addition to mechanical properties such as impact resistance.
-Hard to discolor even when exposed to direct sunlight (weather resistance).
-It has good color developability equivalent to paint.
・ No scratches or scratches are noticeable (scratch resistance).

Resin materials that can provide molded products with good weather resistance include ethylene-propylene-non-conjugated diene copolymers, acrylic ester rubbers, hydrogenated rubbers (hydrogenated butadiene rubbers, etc.) as rubbery polymers. ), And those using silicone rubber or the like are known.
As a molded product having good color development, one using a highly transparent resin material is known.
Molded products with good scratch resistance include those in which the ratio of the rubbery polymer is lowered to harden the surface of the molded product, and lubricant (silicone oil, olefin wax, etc.) is added to slip the surface of the molded product. Those with improved properties are known.

For example, the following materials have been proposed as highly transparent resin materials.
(1) A graft copolymer obtained by polymerizing a monomer component containing a (meth) acrylate ester in the presence of a rubbery polymer, or the graft copolymer and a (meth) acrylate ester A rubber-reinforced thermoplastic resin comprising a mixture of a monomer component containing (co) polymer and a copolymer of (meth) acrylic acid ester and maleimide compound, and co-polymerized with rubber-reinforced thermoplastic resin A thermoplastic resin composition having a small difference in refractive index from the coalescence (Patent Document 1).
(2) A graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer which is a styrene elastomer, and an aromatic vinyl compound And a styrene resin obtained by polymerizing a vinyl cyanide compound, and a thermoplastic resin composition having a small refractive index difference between the graft copolymer and the styrene resin (Patent Document 2).

For example, the following materials have been proposed as resin materials that can obtain a molded article having good scratch resistance.
(3) A rubbery material comprising a graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, and a hard resin. A thermoplastic resin composition having a low polymer ratio (Patent Document 3).

However, when the thermoplastic resin compositions (1) and (2) are used, the transparency of the molded product is improved, but the impact resistance of the molded product is low, and the use of the molded product is limited.
When the thermoplastic resin composition of (3) is used, the hardness of the surface of the molded product is increased, so that the scratch resistance against scratches is improved, but the ratio of the rubbery polymer is reduced, so Impact strength decreases.
As described above, it is difficult to achieve both the impact resistance of the molded article, the color developability (transparency), and the scratch resistance, and improvements are required.

International Publication No. 2003/080724 JP 2001-131369 A JP-A-11-001600

  An object of the present invention is to provide a graft copolymer suitable as a material for a thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance, color developability, transparency and scratch resistance.

The graft copolymer of the present invention cross-links a hydrogenated product of a block copolymer having a block mainly composed of a structural unit based on an aromatic vinyl compound and a block mainly composed of a structural unit based on a conjugated diene compound. It is obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the crosslinked rubbery polymer (C).
The conjugated diene compound is preferably isoprene.

  The graft copolymer of the present invention is suitable as a material for a thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance, color developability, transparency and scratch resistance.

It is the schematic explaining the abrasion-resistance test by gauze wear.

The following definitions of terms apply throughout this specification and the claims.
“Structural unit” means a unit composed of monomer molecules formed by polymerization of monomers.
The “block” means a part of a polymer that is composed of a plurality of structural units and has at least one characteristic that does not exist in the adjacent part.
“Mainly” means that the proportion of a specific structural unit in one block is 50 mol% or more of all the structural units constituting the block.
The “hydrogenated product” means a product obtained by hydrogenating at least a part of unsaturated bonds in a polymer.
“Aqueous dispersion” means a resin component dispersed in an aqueous medium.
“Aqueous medium” means water or water containing a water-soluble organic solvent.
“Lightness (L ^* )” means a lightness value (L ^* ) among color values in the L ^* a ^* b ^* color system adopted in JIS Z 8729.
The “SCE method” means a method of measuring a color by using a spectrocolorimeter in accordance with JIS Z 8722 and removing specularly reflected light with an optical trap.

"Graft copolymer"
The graft copolymer of the present invention (hereinafter also referred to as graft copolymer (D)) is obtained by polymerizing the vinyl monomer mixture (m) in the presence of the crosslinked rubbery polymer (C). It is a thing.

Specific examples of the crosslinked rubbery polymer (C) include the following.
(Α) A crosslinked rubbery polymer (C) obtained by crosslinking the rubbery polymer (A).
(Β) An aqueous dispersion containing a crosslinked rubber polymer (C) obtained by crosslinking the rubber polymer (A) in the aromatic vinyl resin aqueous dispersion (B).
Hereinafter, each component ((A)-(D), (m), etc.) is demonstrated.

<Rubber polymer (A)>
The rubbery polymer (A) is a hydrogenated product of a block copolymer having a block mainly composed of a structural unit based on an aromatic vinyl compound and a block mainly composed of a structural unit based on a conjugated diene compound.

The ratio of the structural unit based on the aromatic vinyl compound in the block mainly composed of the structural unit based on the aromatic vinyl compound is 50 mol% or more, and 100 mol% is sufficient from the viewpoint of sufficiently exerting the effects of the present invention. Particularly preferred.
The proportion of the structural unit based on the conjugated diene compound in the block mainly composed of the structural unit based on the conjugated diene compound is 50 mol% or more, and 100 mol% is sufficient from the point of sufficiently exerting the effects of the present invention. Particularly preferred.

As block copolymer, AB type consisting of a block mainly composed of a structural unit based on an aromatic vinyl compound and a block mainly composed of a structural unit based on a conjugated diene compound; mainly composed of a structural unit based on an aromatic vinyl compound A block composed mainly of a structural unit based on a conjugated diene compound and a block composed mainly of a structural unit based on an aromatic vinyl compound; a block composed mainly of a structural unit based on an aromatic vinyl compound And (AB) _n- type in which a block mainly composed of a structural unit based on a conjugated diene compound is included.

Of the unsaturated bonds in the block copolymer, the ratio of hydrogenation (hydrogenation ratio) is preferably 95 to 100%, and 99 to 100% from the viewpoint of color development, transparency and scratch resistance of the molded product. Is more preferable.
The hydrogenation rate is measured by the method described in the examples.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-, m- or p-methylstyrene, ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminostyrene, N , N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, pt-butylstyrene, vinylnaphthalene and the like. . Styrene is particularly preferred from the viewpoint of impact resistance, color developability and transparency of the molded product. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The proportion of the structural unit based on the aromatic vinyl compound is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, out of all the structural units (100% by mass) constituting the block copolymer. 35% by mass is particularly preferred. When the proportion of the structural unit based on the aromatic vinyl compound is within the above range, the impact resistance, color developability and transparency of the molded product are further improved.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-pentadiene, , 3-hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene and the like. From the viewpoint of impact resistance and color developability of the molded product, 1,3-butadiene and isoprene are preferable, and isoprene is particularly preferable. A conjugated diene type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The method for producing the rubbery polymer (A) is not particularly limited. Examples of the method for producing the rubber polymer (A) include a method in which a block copolymer is produced by a known polymerization method such as an anionic polymerization method or a cationic polymerization method, and hydrogenated to the block copolymer. . Specifically, the method described in Japanese Patent No. 3310536, that is, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in a hydrocarbon solvent using an organolithium compound as a polymerization initiator to form a block copolymer. The method of manufacturing and hydrogenating this block copolymer is mentioned.

  Hydrocarbon solvents used for polymerization include aliphatic hydrocarbons (butane, pentane, hexane, isopentane, heptane, octane, isooctane, etc.), alicyclic hydrocarbons (cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Ethylcyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene, etc.) and the like. A hydrocarbon solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the organic lithium compound include lithium compounds having one or more lithium atoms in one molecule. Specific examples include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium. . An organic lithium compound may be used individually by 1 type, and may be used in combination of 2 or more type.

During polymerization, adjustment of the polymerization rate, adjustment of the microstructure of blocks composed of structural units based on conjugated diene compounds (cis, trans, vinyl bond content, etc.), reaction of aromatic vinyl compounds and conjugated diene compounds For the purpose of adjusting the sex ratio, a randomizing agent may be used.
Randomizing agents include ether compounds (dimethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, etc.), amine compounds (trimethylamine, triethylamine, tetramethylethylenediamine, cyclic tertiary amine, etc.), phosphorus compounds (triphenylphosphine, etc.) , Hexamethyl phosphoramide, etc.).

The polymerization time may be a time required for the polymerization of the aromatic vinyl compound and the conjugated diene compound.
The polymerization temperature is usually −10 to 150 ° C.

As the solvent used in the hydrogenation, the same hydrocarbon solvent as the hydrocarbon solvent used in the polymerization is preferable.
Examples of hydrogenation catalysts include supported heterogeneous catalysts in which metals (nickel, platinum, palladium, ruthenium, etc.) are supported on carriers (carbon, silica, alumina, diatomaceous earth, etc.), metals (nickel, cobalt, iron, chromium). Etc.) and a Ziegler type homogeneous catalyst in which a reducing agent (such as organoaluminum) is combined.

<Aromatic vinyl resin aqueous dispersion (B)>
The aromatic vinyl resin aqueous dispersion (B) is obtained by dispersing the rubber polymer (A) in an aqueous medium.

  The method for preparing the aromatic vinyl resin aqueous dispersion (B) is not particularly limited. As a preparation method, for example, the rubber polymer (A) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.), dispersed by applying mechanical shearing force, and an emulsifier is added. Method of adding to an aqueous medium containing; after the rubber polymer (A) is dissolved in a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with an emulsifier, and added to the aqueous medium to emulsify, The method etc. which stir fully and distill away a hydrocarbon solvent are mentioned. In preparing the aromatic vinyl resin aqueous dispersion (B), an emulsifier, an acid-modified olefin polymer and the like may be added as other components.

Examples of the emulsifier include known ones. For example, long chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, alkylbenzene sulfonates and the like can be mentioned.
In the case of using potassium oleate as an emulsifier, the added amount of the emulsifier can suppress thermal coloring of the resulting thermoplastic resin composition and can easily control the particle size of the aromatic vinyl resin aqueous dispersion (B). The amount of the rubber polymer (A) is preferably 1 to 15 parts by mass with respect to 100 parts by mass.

Examples of the acid-modified olefin polymer include those having a mass average molecular weight of 1,000 to 5,000, which is obtained by modifying an olefin polymer (polyethylene, polypropylene, etc.) with a compound having a functional group (such as an unsaturated carboxylic acid compound). preferable. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, and maleic acid monoamide.
The addition amount of the acid-modified olefin polymer is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the rubbery polymer (A). When the amount of the acid-modified olefin polymer added is within the above range, the balance of impact resistance, color development and scratch resistance of the molded product is further improved.
The method for mixing the rubbery polymer (A) and the acid-modified olefin polymer is not particularly limited. Examples of the mixing method include a kneader, a Banbury mixer, and a melt kneading method using a multi-screw extruder.

The volume average particle diameter of the rubber-like polymer (A) in the aromatic vinyl resin aqueous dispersion (B) is preferably 0.2 to 0.6 μm from the viewpoint of excellent physical properties of the molded product, 0.3 to 0.5 μm is more preferable. When the volume average particle diameter is within the above range, the impact resistance, color developability and transparency of the molded product are further improved.
As a method of controlling the volume average particle diameter of the rubber polymer (A) in the aromatic vinyl resin aqueous dispersion (B), the type or amount of the emulsifier, the type or content of the acid-modified olefin polymer, The method of adjusting the shear force, temperature conditions, etc. which are applied at the time of kneading is mentioned.
The volume average particle size of the rubber polymer (A) dispersed in the aromatic vinyl resin aqueous dispersion (B) is the same as the volume average particle size of the crosslinked rubber polymer (C) in the aqueous dispersion. It is confirmed by image processing of an electron micrograph that the volume average particle diameter of the crosslinked rubbery polymer (C) in the graft copolymer (D) is shown.

<Crosslinked rubber polymer (C)>
The crosslinked rubbery polymer (C) is obtained by crosslinking the rubbery polymer (A). By subjecting the rubber polymer (A) to a crosslinking treatment, the impact resistance, color developability, transparency and scratch resistance of the molded article are further improved.

3-80 mass% is preferable, as for the gel content rate of a crosslinked rubber-like polymer (C), 7-70 mass% is more preferable, and 15-50 mass% is further more preferable. When the gel content is within the above range, the impact resistance, color developability, transparency and scratch resistance of the molded product are further improved.
The gel content is measured by the method described in the examples.

  The crosslinking treatment of the rubber polymer (A) is performed by a known method. As a crosslinking treatment method, (a) a method in which an organic peroxide and, if necessary, a polyfunctional compound are added to the rubbery polymer (A) for crosslinking treatment; (b) crosslinking by ionizing radiation. The method of performing a process etc. are mentioned. From the viewpoint of impact resistance, color developability, transparency and scratch resistance of the molded product, the method (a) is preferred.

Specifically, as the method of (a), an organic peroxide and, if necessary, a polyfunctional compound are added to the rubber polymer (A) or the aromatic vinyl resin aqueous dispersion (B). The method of adding and heating is mentioned.
The gel content of the crosslinked rubbery polymer (C) can be adjusted by adjusting the addition amount of organic peroxide and polyfunctional compound, heating temperature, heating time and the like.
The heating temperature varies depending on the type of organic peroxide. The heating temperature is preferably −5 ° C. to + 30 ° C., which is the 10-hour half-life temperature of the organic peroxide.
The heating time is preferably 3 to 15 hours.

  The organic peroxide is for forming a crosslinked structure in the rubbery polymer (A). Examples of the organic peroxide include a peroxy ester compound, a peroxy ketal compound, a dialkyl peroxide compound, and the like. An organic peroxide may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of the peroxyester compound include α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexyl peroxy 2-hexyl Hexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexano Ate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl Peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoe , Bis (t-butylperoxy) isophthalate.

  Specific examples of the peroxyketal compound include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) Examples include butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, and the like.

  Specific examples of the dialkyl peroxide compound include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butyl. Examples include cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

  As the organic peroxide, dialkyl peroxide compounds such as dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide are particularly preferable because the gel content of the crosslinked rubbery polymer (C) can be easily adjusted. preferable.

  The amount of the organic peroxide added is 0 with respect to 100 parts by mass of the rubbery polymer (A) because the gel content of the crosslinked rubbery polymer (C) can be easily adjusted to a range of 3 to 80% by mass. .1 to 10 parts by mass is preferable.

  The polyfunctional compound is used in combination with an organic peroxide as necessary in order to adjust the gel content of the crosslinked rubbery polymer (C). Examples of the polyfunctional compound include divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetraacrylate, and the like. It is done. From the viewpoint of easily adjusting the gel content, divinylbenzene is preferable. A polyfunctional compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the polyfunctional compound is 10 parts by mass with respect to 100 parts by mass of the rubbery polymer (A) because the gel content of the crosslinked rubbery polymer (C) can be easily adjusted to 3 to 80% by mass. The following is preferred.

The volume average particle size of the crosslinked rubbery polymer (C) in the aqueous dispersion is preferably 0.2 to 0.6 μm, more preferably 0.3 to 0.5 μm, from the viewpoint of excellent physical properties of the molded product. When the volume average particle diameter is within the above range, the molded article is excellent in impact resistance, color development and transparency.
Volume average particles of the crosslinked rubbery polymer (C) in the aqueous dispersion obtained by crosslinking the rubbery polymer (A) in the aromatic vinyl resin aqueous dispersion (B) with an organic peroxide The diameter does not change with respect to the volume average particle diameter of the rubber polymer (A) in the aromatic vinyl resin aqueous dispersion (B).
The volume average particle diameter of the crosslinked rubber polymer (C) dispersed in the aqueous dispersion indicates the volume average particle diameter of the crosslinked rubber polymer (C) in the graft copolymer (D) as it is. This is confirmed by image processing of electron micrographs.

<Vinyl monomer mixture (m)>
The vinyl monomer mixture (m) is a monomer mixture containing at least an aromatic vinyl compound and a vinyl cyanide compound.

Examples of the aromatic vinyl compound include styrene, α-methyl styrene, o-, m- or p-methyl styrene, vinyl xylene, pt-butyl styrene, ethyl styrene, and the like. Styrene and α-methylstyrene are preferred from the viewpoint of color developability, transparency and impact resistance of the molded product. An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl compound is preferably 60 to 82% by mass, more preferably 73 to 80% by mass, and further preferably 75 to 80% by mass in 100% by mass of the vinyl monomer mixture (m). When the content of the aromatic vinyl compound is within the above range, the color developability, transparency and impact resistance of the molded product are further improved.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. A vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide compound is preferably 18 to 40% by mass, more preferably 20 to 27% by mass, and further preferably 20 to 25% by mass in 100% by mass of the vinyl monomer mixture (m). When the content of the vinyl cyanide compound is within the above range, the color developability, transparency and impact resistance of the molded product are further improved.

The vinyl monomer mixture (m) may contain, in addition to the aromatic vinyl compound and the vinyl cyanide compound, other monomers copolymerizable therewith within a range not impairing the effects of the present invention.
Other monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.) ), Maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.) and the like. Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.

<Graft copolymer (D)>
The graft copolymer (D) is obtained by polymerizing the vinyl monomer mixture (m) in the presence of the crosslinked rubbery polymer (C).

  The graft copolymer (D) is a vinyl-based monomer mixture (m) 20 to 50% by mass (provided that the crosslinked rubbery polymer (C) is in the presence of 50 to 80% by mass of the crosslinked rubbery polymer (C). A product obtained by polymerizing C) and the vinyl monomer mixture (m) is preferably 100% by mass). If the amount of the crosslinked rubbery polymer (C) is 50 to 80% by mass, the balance of physical properties of the molded article with respect to impact resistance, color developability and transparency is further improved.

The graft ratio of the graft copolymer (D) is preferably 20 to 100% by mass from the viewpoint of the balance of impact resistance, color developability and transparency of the molded product.
The graft rate is measured by the method described in the examples.

  Examples of the polymerization method include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.). The emulsion polymerization method is particularly preferred from the viewpoint that the impact resistance, color developability and transparency of the molded product are further improved.

  As a method for producing the graft copolymer (D) by the emulsion polymerization method, for example, an organic peroxide is mixed into the vinyl monomer mixture (m), and then the vinyl monomer mixture (m) is crosslinked. The method of adding continuously to the aqueous dispersion of rubber-like polymer (C) is mentioned. The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent. In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.

The redox initiator does not require the polymerization reaction conditions to be at a high temperature, avoids deterioration of the cross-linked rubber polymer (C), and avoids deterioration of impact resistance of the molded product. A combination of a product and a ferrous sulfate-chelating agent-reducing agent is preferred.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butyl hydroperoxide.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid, these Sodium salt, etc.), α-methylstyrene dimer, and the like. Mercaptans are preferred from the viewpoint of easy adjustment of the molecular weight. A chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The addition amount of the emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m).

The graft copolymer (D) obtained by the emulsion polymerization method is in a state of being dispersed in water. As a method for recovering the graft copolymer (D) from the aqueous dispersion containing the graft copolymer (D), for example, a precipitation agent is added to the aqueous dispersion, and after heating and stirring, the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (D) is washed with water, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (D) as necessary.

<Function and effect>
In the graft copolymer of the present invention described above, a block copolymer having a block mainly composed of a structural unit based on an aromatic vinyl compound and a block mainly composed of a structural unit based on a conjugated diene compound. A vinyl monomer mixture (m) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a crosslinked rubbery polymer (C) obtained by crosslinking a rubbery polymer (A) as a hydrogenated product. Since it is obtained by polymerization, it is suitable as a material for a thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance, color development, transparency and scratch resistance.

"Thermoplastic resin composition"
The thermoplastic resin composition includes a graft copolymer (D) and a hard resin (E). The thermoplastic resin composition may contain various additives as necessary within a range not impairing the effects of the present invention.

<Hard resin (E)>
The hard resin (E) is not particularly limited. As the hard resin (E), styrene polymer, polycarbonate, polymethyl methacrylate, polybutylene terephthalate, polyethylene terephthalate, polyvinyl chloride, methyl methacrylate / styrene copolymer, methyl methacrylate / styrene / N-phenylmaleimide Copolymers, modified polyphenylene ether, polyamide and the like can be mentioned. From the viewpoint of impact resistance, color developability and transparency of the molded product, styrene polymers and polycarbonate are preferred.
Hard resin (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

Styrenic polymers are obtained by polymerizing a monomer component containing an aromatic vinyl compound as an essential component and a vinyl cyanide compound and other monomers copolymerizable with these as optional components. It is a coalescence.
Specific examples of the aromatic vinyl compound, the vinyl cyanide compound, and other monomers include the aromatic vinyl compounds, vinyl cyanide compounds, and other single monomers exemplified above in the description of the vinyl monomer mixture (m). A monomer is mentioned.

  Of the monomer component 100% by mass, the content of the aromatic vinyl compound is preferably 25 to 100% by mass, and the content of the vinyl cyanide compound is preferably 0 to 40% by mass. The content is preferably 0 to 65 mass (however, the total of the aromatic vinyl compound, the vinyl cyanide compound and other monomers is 100 mass%).

The styrenic polymer can be produced by a known polymerization method (emulsion polymerization method, suspension polymerization method, etc.).
In the case of producing by an emulsion polymerization method, a monomer component, an emulsifier, a polymerization initiator and a chain transfer agent are charged in a reactor, and the monomer component is polymerized by heating, and an aqueous solution containing the resulting styrene polymer. A styrene polymer is recovered from the dispersion by a precipitation method.
Examples of the emulsifier include ordinary emulsifiers (potassium rosinate, sodium alkylbenzenesulfonate, etc.) used in the emulsion polymerization method.
Examples of the polymerization initiator include organic peroxides and inorganic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.
As the precipitation method, a method similar to that used when recovering the graft copolymer (D) from the aqueous dispersion can be employed.

In the case of producing by the suspension polymerization method, the monomer component, suspending agent, suspending aid, polymerization initiator and chain transfer agent are charged in the reactor and heated to polymerize the monomer component. The resulting slurry is dehydrated and dried to recover the styrenic polymer.
Examples of the suspending agent include tricalcium phosphite and polyvinyl alcohol.
Examples of the suspension aid include sodium alkylbenzene sulfonate.
Examples of the polymerization initiator include organic peroxides.
Examples of chain transfer agents include mercaptans, α-methylstyrene dimers, terpenes and the like.

Examples of the polycarbonate include those obtained by reaction of one or more bisphenols with phosgene or a carbonic acid diester.
Examples of bisphenols include hydroquinone, 4,4-dihydroxyphenyl, bis- (4-hydroxyphenyl) -alkane, bis- (4-hydroxyphenyl) -cycloalkane, bis- (4-hydroxyphenyl) -sulfide, Examples include bis- (4-hydroxyphenyl) -ether, bis- (4-hydroxyphenyl) -ketone, bis- (4-hydroxyphenyl) -sulfone, alkyl substitution products thereof, aryl substitution products, halogen substitution products, and the like. . From the viewpoint of easy availability, 2,2-bis- (4-hydroxyphenyl) propane, so-called bisphenol A is preferred. Bisphenol may be used individually by 1 type, and may be used in combination of 2 or more type.

<Various additives>
Examples of various additives include antioxidants, lubricants, processing aids, pigments, fillers, silicone oils, paraffin oils, and the like.

<Content of each component>
As for content of a graft copolymer (D), 0.1-99 mass% is preferable among the total 100 mass% of a graft copolymer (D) and a hard resin (E). When the content of the graft copolymer (D) is within the above range, the molded article has an excellent balance of physical properties such as impact resistance, color developability, transparency and scratch resistance.
The content of the hard resin (E) is preferably 99.9 to 1% by mass in the total 100% by mass of the graft copolymer (D) and the hard resin (E).

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition is obtained by mixing the graft copolymer (D), the hard resin (E), and various additives as necessary. You may pelletize with an extruder, a Banbury mixer, a kneading roll, etc.

<Function and effect>
In the thermoplastic resin composition demonstrated above, since the graft copolymer (D) is included, the molded article excellent in impact resistance, coloring property, transparency, and scratch resistance can be obtained.

"Molding"
The molded product is formed by molding a thermoplastic resin composition.
Examples of the molding method include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
Applications of molded products include vehicle interior parts, vehicle exterior parts, office equipment, home appliances, building materials, and the like.
In the thermoplastic resin composition demonstrated above, since the thermoplastic resin composition containing a graft copolymer (D) is used, it is excellent in impact resistance, coloring property, transparency, and scratch resistance.

Hereinafter, an example is shown concretely. However, the present invention is not limited to these examples.
In the following, “%” means “mass%” and “part” means “part by mass”.
Various measurements and evaluation methods in the following examples and comparative examples are as follows.

<Hydrogenation rate>
The block copolymer before hydrogenation was dissolved in chloroform, and then the iodine value was measured with potassium iodide. Moreover, after dissolving the rubber-like polymer (A) after hydrogenation in chloroform, the iodine value was measured with potassium iodide. The hydrogenation rate was calculated from the following formula (1).
Hydrogenation rate (%) = 100− (iodine value of rubbery polymer (A) / iodine value of block copolymer × 100) (1)

<Volume average particle diameter>
The volume average particle diameter (MV) of the rubber polymer in the aromatic vinyl resin aqueous dispersion was measured using Microtrac (manufactured by Nikkiso Co., Ltd., “Nanotrack 150”) using pure water as a measurement solvent. .

<Gel content>
A coagulated powder sample [D1] obtained by coagulating an aqueous or solvent dispersion of a crosslinked rubbery polymer with dilute sulfuric acid, washing with water and drying is immersed in 200 mL of 110 ° C. toluene for 5 hours, and then The residue was dried, the mass of the dried product [D2] was measured, and the gel content of the crosslinked rubbery polymer was calculated from the following formula (2).
Gel content rate (%) = dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g) × 100 (2)

<Graft ratio>
1 g of the graft copolymer was added to 80 mL of acetone, heated to reflux at 65 to 70 ° C. for 3 hours, and the obtained suspension acetone solution was centrifuged with a centrifuge (“CR21E” manufactured by Hitachi Koki Co., Ltd.). Centrifugation was carried out at 14,000 rpm for 30 minutes to separate a precipitation component (acetone insoluble component) and an acetone solution (acetone soluble component). And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed from following formula (3). In Formula (3), Y is the mass (g) of the acetone-insoluble component of the graft copolymer, X is the total mass (g) of the graft copolymer (D) used to determine Y, and the rubber fraction. Is a content ratio in terms of solid content of rubber components (crosslinked rubber polymer (C), rubber polymer (A), etc.) in the graft copolymer.
Graft rate (%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100 (3)

<Melt-kneading 1>
The graft copolymer and hard resin are mixed, melt kneaded at a cylinder temperature of 200 to 260 ° C. and 93.325 kPa vacuum using a 30 mmφ twin-screw extruder with a vacuum vent (“Ikegai Co., Ltd.,“ PCM30 ”). A plastic resin composition (1) was obtained. Moreover, after melt-kneading as needed, pelletization was performed using a pelletizer ("SH type pelletizer" manufactured by Souken Co., Ltd.).

<Melting and kneading 2>
Carbon black (Mitsubishi Chemical Co., Ltd., “Mitsubishi Carbon Black # 960”) 0.5 part is added to and mixed with 100 parts of the total amount of the graft copolymer and the hard resin. Using an extruder ("PCM30" manufactured by Ikegai Co., Ltd.), melt kneading was performed at a cylinder temperature of 200 to 260 ° C and a vacuum of 93.325 kPa to obtain a thermoplastic resin composition (2). About the obtained thermoplastic resin composition (2), it pelletized using the pelletizer (The Soken company make, "SH type pelletizer").

<Melt volume rate (MVR)>
About the thermoplastic resin composition (1), MVR was measured according to the ISO 1133 standard. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

<Injection molding 1>
The pellet of the thermoplastic resin composition (1) is 80 mm in length under the conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. using an injection molding machine (Toshiba Machine Co., Ltd., “IS55FP-1.5A”). The molded product (Ma1) having a width of 10 cm and a thickness of 4 mm was formed. The molded product (Ma1) was used as a molded product for Charpy impact test.

<Injection molding 2>
The pellet of the thermoplastic resin composition (1) is 10 cm long under the conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). The flat plate (molded product (Ma2)) having a width of 10 cm and a thickness of 2 mm was formed. The molded product (Ma2) was used as a molded product for transparency evaluation.

<Injection molding 3>
The pellet of the thermoplastic resin composition (2) is 10 cm long under conditions of a cylinder temperature of 200 to 260 ° C. and a mold temperature of 60 ° C. using an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.). Then, it was molded into a black colored flat plate (molded product (Ma3)) having a width of 10 cm and a thickness of 2 mm. The molded product (Ma3) was used as a molded product for evaluating color development and a molded product for evaluating scratch resistance.

<Bending elastic modulus>
The flexural modulus of the molded product (Ma1) was measured according to the ISO 178 standard.

<Impact resistance>
The molded product (Ma1) was subjected to a Charpy impact test (notched) at 23 ° C. according to ISO 179 standard, and the Charpy impact strength was measured.

<Color development>
For the molded product (Ma3), a spectral colorimeter (manufactured by Konica Minolta Optics, “CM-3500d”) is used, and the lightness L ^{* is changed} to the SCE method with a d / 8 (diffuse illumination / 8-degree light receiving) optical system. Measured. The L ^* measured in this way is referred to as “L ^* (ma)”. A lower L ^* means better color developability.

<transparency>
About the molded product (Ma2), the haze value was measured using a Haze meter. A lower haze value means higher transparency. When the haze value is less than 50%, the transparency is excellent, and when the haze value is less than 25%, the transparency is sufficiently excellent.

<Scratch resistance>
As shown in FIG. 1, a rod-like jig 10 having a tip portion 11 formed in a hemispherical shape was prepared, and the tip portion 11 was covered with a laminated sheet 12 in which eight sheets of gauze were stacked. The tip portion 11 covered with the laminated sheet 12 is brought into contact with the surface of the molded product (Ma3) 13 so that the rod-shaped jig 10 is at a right angle, and the tip portion 11 is brought into contact with the surface of the molded product (Ma3) 13. Were slid in the horizontal direction (arrow direction in the figure) and reciprocated 100 times. At that time, the applied load was 9.8 N. After reciprocating 100 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured by the SCE method using a spectrocolorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.

A determination index ΔL ^* of the degree of conspicuousness of scratches on the molded article (Mc) was calculated from the following formula (4). As the absolute value of ΔL ^* (mc−ma) is larger, scratches are more conspicuous.
ΔL ^* (mc−ma) = L ^* (mc) −L ^* (ma) (4)

When the absolute value of ΔL ^* (mc−ma) is 3 or less, scratches are not noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is 3.1 to 9.0, scratches are hardly noticeable and the design of the molded product is not impaired.
When the absolute value of ΔL ^* (mc−ma) is 9.1 or more, scratches are conspicuous and the design of the molded product is impaired.

<Each component>
In the following examples, the following rubber polymer (A), aromatic vinyl resin aqueous dispersion (B), crosslinked rubber polymer (C), graft copolymer (D), hard resin (E), etc. Was used.

<Rubber polymer (A), other rubber polymer (A ')>
(Rubber polymer (A-1))
Into an autoclave, 400 parts of degassed and dehydrated cyclohexane, 2 parts of styrene, 0.05 part of tetrahydrofuran and 0.04 part of n-butyllithium were added, polymerized at 60 ° C. for 4 hours, and 96 parts of isoprene were further added. Polymerization was carried out at 60 ° C. for 4 hours, and finally 2 parts of styrene was added, followed by polymerization at 60 ° C. for 4 hours. The obtained active polymer was deactivated with methanol, the polymer solution was transferred to a jacketed reactor, and 0.15 part of 2,6-di-t-butyl-p-cresol, bis ( Cyclopentadienyl) titanium dichloride 0.07 part, n-butyllithium 0.15 part, ethylaluminum chloride 0.28 part was added, and hydrogenation reaction was carried out at 100 ° C. and hydrogen gas pressure of 0.98 MPa for 1 hour. went. The solvent was removed by steam stripping to obtain a rubbery polymer (A-1) which is a hydrogenated product of a styrene-isoprene-styrene block copolymer (hereinafter referred to as SIS). The results are shown in Table 1.

(Rubber polymer (A-2) to (A-13))
Rubber polymers (A-2) to (A-13) were obtained in the same manner as the rubber polymer (A-1) except that the amount of styrene charged was changed. The results are shown in Tables 1 and 2.

(Rubber polymer (A-14))
In an autoclave, 400 parts of degassed and dehydrated cyclohexane, 15 parts of styrene, 0.05 part of tetrahydrofuran and 0.04 part of n-butyllithium were added, polymerized at 60 ° C. for 4 hours, and 1,3-butadiene was further added. 70 parts were added and polymerized at 60 ° C. for 4 hours, and finally 15 parts of styrene was added and polymerized at 60 ° C. for 4 hours. The obtained active polymer was deactivated with methanol, the polymer solution was transferred to a jacketed reactor, and 0.15 part of 2,6-di-t-butyl-p-cresol, bis ( Cyclopentadienyl) titanium dichloride 0.07 part, n-butyllithium 0.15 part, ethylaluminum chloride 0.28 part was added, and hydrogenation reaction was carried out at 100 ° C. and hydrogen gas pressure of 0.98 MPa for 1 hour. went. The solvent was removed by steam stripping to obtain a rubber polymer (A-14) which is a hydrogenated product of a styrene-butadiene-styrene block copolymer (hereinafter referred to as SBS). The results are shown in Table 2.

(Other rubbery polymer (A'-15))
Into an autoclave, 400 parts of degassed and dehydrated cyclohexane, 15 parts of styrene, 0.05 part of tetrahydrofuran and 0.04 part of n-butyllithium were added, polymerized at 60 ° C. for 4 hours, and further 70 parts of isoprene were added. Polymerization was carried out at 60 ° C. for 4 hours, and finally 15 parts of styrene was added, followed by polymerization at 60 ° C. for 4 hours. The obtained active polymer was deactivated with methanol to obtain a polymer solution. The solvent was removed by steam stripping to obtain another rubbery polymer (A′-15) which was SIS. The results are shown in Table 2.

(Other rubbery polymer (A'-16))
Other rubbery polymer (A′-16) which is SBS was obtained in the same manner as other rubbery polymer (A-15) except that isoprene was changed to 1,3-butadiene. The results are shown in Table 2.

(Other rubbery polymer (A'-17))
After fully replacing the 20 L stainless steel polymerization tank equipped with a stirrer with nitrogen, 10 L of dehydrated and purified hexane was added to prepare ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl ₁ adjusted to 8.0 mmol / L. ₅ ) was continuously supplied at a rate of 5 L / h for 1 hour, and then a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ prepared to 0.8 mmol / L as a catalyst was further added to 5 L / h. Hexane was continuously fed in an amount of 5 L / h. On the other hand, from the upper part of the polymerization tank, the polymerization liquid was continuously extracted so that the polymerization liquid in the polymerization tank was always 10 L. A bubbling tube was used to supply ethylene in an amount of 2000 L / h, propylene in an amount of 1000 L / h, and hydrogen in an amount of 8 L / h, and a polymerization reaction was performed at 35 ° C. to obtain a polymerization solution. The resulting polymer solution was deashed with hydrochloric acid, and then poured into methanol to precipitate a polymer, followed by drying, and another rubbery material that was an ethylene / propylene copolymer (hereinafter referred to as EPR). A polymer (A′-17) was obtained. The results are shown in Table 2.

<Aromatic vinyl-based resin aqueous dispersion (B), other rubbery polymer aqueous dispersion (B ')>
(Aromatic vinyl resin aqueous dispersion (B-1))
100 parts of rubbery polymer (A-1) and maleic anhydride-modified polyethylene (Mitsui Chemicals, "Mitsui High Wax 2203A", weight average molecular weight: 2,700, acid value: 30 mg / mg as acid-modified olefin polymer) g) 15 parts and 3 parts of potassium oleate as an anionic emulsifier were mixed.
While supplying this mixture at 4 kg / h from a hopper of a twin screw extruder (Ikegai, “PCM30”, L / D = 40) and continuously supplying a 14% potassium hydroxide aqueous solution at 240 g / h. The mixture was melt-kneaded by heating to 220 ° C., and the resulting melt-kneaded product was extruded. The melt-kneaded product was continuously supplied to a cooling device attached to the tip of the extruder and cooled to 90 ° C. The taken-out solid was thrown into 80 degreeC warm water, and was continuously disperse | distributed, and the aromatic vinyl resin aqueous dispersion (B-1) whose volume average particle diameter is 0.40 micrometer was obtained. The results are shown in Table 3.

(Aromatic vinyl resin aqueous dispersions (B-2) to (B-14), other rubbery polymer aqueous dispersions (B′-15) to (B′-17))
Except for changing the rubbery polymer (A-1) to rubbery polymers (A-2) to (A-14) and other rubbery polymers (A′-15) to (A′-17). In the same manner as the aromatic vinyl resin aqueous dispersion (B-1), aromatic vinyl resin aqueous dispersions (B-2) to (B-14), other rubber polymer aqueous dispersions ( B'-15) to (B'-17) were obtained. The results are shown in Tables 3 and 4.

(Aromatic vinyl resin aqueous dispersions (B-18) to (B-21)
The aromatic vinyl resin aqueous dispersion (B-18) is the same as the aromatic vinyl resin aqueous dispersion (B-1) except that the amount of potassium hydroxide and the amount of ion exchange water are changed. To (B-21) were obtained. The results are shown in Table 4.

<Crosslinked rubbery polymer (C), other crosslinked rubbery polymer (C ′)>
(Crosslinked rubber polymer (C-1))
Aromatic vinyl resin aqueous dispersion (B-7) (100 parts as solid content), 0.1 part of t-butylcumyl peroxide as organic peroxide and 1.0 part of divinylbenzene as polyfunctional compound The mixture was added and reacted at 130 ° C. for 5 hours to prepare an aqueous dispersion of a crosslinked rubbery polymer (C-1). The results are shown in Table 5.

(Crosslinked rubber polymer (C-2) to (C-7))
Except having changed the addition amount of t-butyl cumyl peroxide, it was carried out similarly to the manufacturing method of a crosslinked rubber-like polymer (C-1), and the crosslinked rubber-like polymers (C-2)-(C-7). An aqueous dispersion was obtained. The results are shown in Table 5.

(Crosslinked rubbery polymers (C-8) to (C-20), other crosslinked rubbery polymers (C′-21) to (C′-23), crosslinked rubbery polymers (C-24) to (C-27))
Aromatic vinyl resin aqueous dispersions (B-7), aromatic vinyl resin aqueous dispersions (B-1) to (B-6), (B-8) to (B-14), other rubbers Polymeric Aqueous Dispersions (B′-15) to (B′-17) and Aromatic Vinyl Resin Aqueous Dispersions (B-18) to (B-21) In the same manner as in the production method of (C-1), crosslinked rubbery polymers (C-8) to (C-20), other crosslinked rubbery polymers (C'-21) to (C'-23) An aqueous dispersion of crosslinked rubbery polymers (C-24) to (C-27) was obtained. The results are shown in Tables 6-8.

(Crosslinked rubber polymer (C-28))
To 100 parts of rubbery polymer (A-7), 0.5 part of α, α'-bis (t-butylperoxy) diisopropylbenzene and 1.0 part of divinylbenzene are added as an organic peroxide, and a vacuum vent of 30 mmφ is added. A cross-linked rubber polymer (C-28) is obtained by carrying out melt kneading at 220 ° C. and 93.325 kPa vacuum with a twin screw extruder (Ikegai Co., Ltd., “PCM30”) and finely pulverizing. It was. The results are shown in Table 8.

(Crosslinked rubber polymer (C-29), (C-30))
A crosslinked rubber polymer (C-29) was produced in the same manner as the method for producing a crosslinked rubber polymer (C-28) except that the amount of α, α'-bis (t-butylperoxy) diisopropylbenzene was changed. ) And (C-30) were obtained. The results are shown in Table 8.

<Graft Copolymer (D), Other Graft Copolymer (D ′)>
(Graft copolymer (D-1))
In a stainless polymerization tank equipped with a stirrer, 180 parts of ion-exchanged water, an aqueous dispersion of a crosslinked rubbery polymer (C-1) (40 parts as solid content), 0.006 parts of ferrous sulfate, sodium pyrophosphate 0. 3 parts and 0.35 part of dextrose were charged and the temperature was 80 ° C. Acrylonitrile (13.2 parts), styrene (46.8 parts) and cumene hydroperoxide (0.6 parts) were continuously added for 150 minutes, and the polymerization temperature was kept constant at 80 ° C. to carry out emulsion polymerization. After the polymerization, an antioxidant is added to the aqueous dispersion containing the graft copolymer (D-1), solids are precipitated with sulfuric acid, and after washing, dehydration and drying, A polymer (D-1) was obtained. The results are shown in Table 9.

(Graft Copolymers (D-2) to (D-5))
The graft copolymer was produced in the same manner as the method for producing the graft copolymer (D-1) except that the charged amount of the aqueous dispersion of the crosslinked rubber polymer (C) and the vinyl monomer mixture (m) was changed. Polymers (D-2) to (D-5) were obtained. The results are shown in Table 9.

(Graft Copolymers (D-6) to (D-24), Other Graft Copolymers (D′-25) to (D′-27), Graft Copolymers (D-28) to (D- 31))
The graft copolymers (D-6) to (D-) were prepared in the same manner as the method for producing the graft copolymer (D-4) except that the type of the aqueous dispersion of the crosslinked rubbery polymer (C) was changed. 24) Other graft copolymers (D′-25) to (D′-27) and graft copolymers (D-28) to (D-31) were obtained. The results are shown in Tables 10 to 13.

(Graft copolymer (D-32))
In a polymerization tank equipped with a stirrer, 70 parts of a crosslinked rubbery polymer (C-28), 180 parts of xylene, 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate, and 0.35 part of dextrose are charged, The temperature was 80 ° C. 6.6 parts of acrylonitrile, 23.4 parts of styrene and 0.6 part of cumene hydroperoxide were continuously added for 200 minutes, and solution polymerization was carried out while maintaining the polymerization temperature at 80 ° C. After the polymerization, an antioxidant was added, and after volatile components such as residual monomers and solvent were distilled off by steam distillation, finely pulverized to obtain a powdery graft copolymer (D-32). . The results are shown in Table 13.

(Graft Copolymer (D-33), (D-34), Other Graft Copolymer (D′-35))
The graft copolymer (D-D) was changed except that the cross-linked rubber polymer (C-28) was changed to a cross-linked rubber polymer (C-29), (C-30), and a rubber polymer (A-7). -32) In the same manner as in the production method, graft copolymers (D-33) and (D-34) and other graft copolymers (D'-35) were obtained. The results are shown in Table 13.

(Other graft copolymer (D'-36))
Except for changing the aqueous dispersion of the cross-linked rubber polymer (C-4) to the aromatic vinyl resin aqueous dispersion (B-7), the same procedure as in the production method of the graft copolymer (D-4) was performed. Thus, another graft copolymer (D′-36) was obtained. The results are shown in Table 13.

<Hard resin (E)>
(Styrene polymer (E-1))
In a stainless steel polymerization tank equipped with a stirrer purged with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of azobisisobutyronitrile, 25 parts of acrylonitrile, 75 parts of styrene, 0.35 of t-dodecyl mercaptan The reaction was carried out at a starting temperature of 60 ° C. for 5 hours. After heating up to 120 degreeC and making it react for 4 hours, the powdery styrene-type polymer (E-1) was obtained by taking out the content, wash | cleaning, and drying.

(Styrene polymer (E-2))
In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 0.003 part of sodium dodecylbenzenesulfonate, 28 parts of acrylonitrile, 26 parts of styrene, 36 parts of α-methylstyrene, 10 parts of N-phenylmaleimide, 0.7 part of benzoyl peroxide, 0.07 part of t-butylperoxybenzoate, 0.6 part of calcium phosphate, 0.4 part of t-dodecyl mercaptan, and 120 parts of ion-exchanged water were charged. The temperature of the polymerization tank was raised to 80 ° C. and polymerized at this temperature for 8 hours, and then heated to 120 ° C. and polymerized for 2 hours. The contents were extracted, washed, and dried to obtain a powdery styrene polymer (E-2).

(Polycarbonate (E-3))
As the polycarbonate (E-3), polycarbonate ("Iupilon S-3000F" manufactured by Mitsubishi Engineering Plastics) was used.

Example 1
Graft copolymer (D-1) 35 parts and styrene polymer (E-1) 65 parts are mixed, and cylinder temperature is 220 ° C. in a twin screw extruder with a 30 mmφ vacuum vent (“PCM30” manufactured by Ikegai Co., Ltd.). A thermoplastic resin composition (1) was prepared by melting and kneading in a vacuum of 93.325 kPa. Table 14 shows the MVR of the thermoplastic resin composition (1).
Graft copolymer (D-1) 35 parts, styrene polymer (E-1) 65 parts, carbon black (Mitsubishi Chemical Co., Ltd., “# 966”) 0.5 part are mixed and equipped with a 30 mmφ vacuum vent. A thermoplastic resin composition (2) was prepared by melt kneading at a cylinder temperature of 220 ° C. and a vacuum of 93.325 kPa using a twin-screw extruder (manufactured by Ikekai Co., Ltd., “PCM30”).
The thermoplastic resin compositions (1) and (2) were each pelletized, molded into various molded products, the flexural modulus was measured, and the impact resistance, color development, transparency, and scratch resistance were evaluated. The results are shown in Table 14.

(Examples 2-33)
Example 1 except that at least one of the type of graft copolymer (D), the charged amount of graft copolymer (D), the type of hard resin (E), and the charged amount of hard resin (E) was changed. The thermoplastic resin compositions (1) and (2) were prepared in the same manner as described above, and the MVR was measured. Further, the thermoplastic resin compositions (1) and (2) were molded into various molded products, the flexural modulus was measured, and the impact resistance, color developability, transparency and scratch resistance were evaluated. The results are shown in Tables 14-18.

(Comparative Examples 1-5)
Except having changed the kind of graft copolymer (D), the thermoplastic resin composition (1) and (2) was prepared like Example 4, and MVR was measured. In addition, the thermoplastic resin compositions (1) and (2) were molded into various molded products, the flexural modulus was measured, and the impact resistance, glossiness, color developability, and scratch resistance were evaluated. The results are shown in Table 19.

  As is apparent from the results in the table, the molded articles of the examples were excellent in impact resistance, color development, transparency and scratch resistance. Therefore, by using the graft copolymer of the present invention, it is possible to obtain a molded product excellent in impact resistance, color developability, transparency, and scratch resistance, and the molded product can be used for vehicle interior parts, vehicle exterior parts, office work. Applicable to equipment, home appliances, building materials, etc.

  On the other hand, Comparative Examples 1 and 2 using a graft copolymer made of a rubbery polymer that was not hydrogenated had low impact resistance, color development, transparency, and scratch resistance. Further, Comparative Example 3 using a graft copolymer made of a rubbery polymer having no aromatic vinyl compound unit had low color development and transparency. In Examples 4 and 5 using the graft copolymer made of the uncrosslinked rubber polymer (A), impact resistance and scratch resistance were low.

  The graft copolymer of the present invention is useful as a material for a thermoplastic resin composition used for vehicle interior parts, vehicle exterior parts, office equipment, home appliances, building materials and the like.

10 Jig 11 Tip 12 Laminated Sheet 13 Molded Product (Ma3)

Claims (2)

  Crosslinked rubber polymer (C) obtained by crosslinking a hydrogenated product of a block copolymer having a block composed mainly of a structural unit based on an aromatic vinyl compound and a block composed mainly of a structural unit based on a conjugated diene compound A graft copolymer obtained by polymerizing a vinyl monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of.   The graft copolymer according to claim 1, wherein the conjugated diene compound is isoprene.

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