Thermoplastic resin composition and molded article

Abstract

To provide a thermoplastic resin composition from which a resin molded article excellent in moldability, impact resistance, rigidity, weather resistance and adhesion of a deoxime type silicone-based sealing material cured product is given.SOLUTION: A thermoplastic resin composition contains a graft copolymer obtained by polymerization of a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, a vinyl-based copolymer which contains a unit derived from an aromatic vinyl compound and a unit derived from a vinyl cyanide compound, and contains no unit of formula (1), and a modified vinyl-based copolymer containing a unit derived from an aromatic vinyl compound, a unit derived from a vinyl cyanide compound, and a unit of Formula (1), and when the total of the units is 100 mass%, a content ratio of the rubbery polymer is 5 to 25 mass%, and a content ratio of the unit of Formula (1) in the modified vinyl-based copolymer is 1 to 20 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition that provides a molded article for use in adhesion, sealing, etc. using a deoxime-type silicone-based sealing material.

Background Art

[0002] Since rubber-reinforced styrene resins are excellent in various physical properties, they are widely used in various parts used in sanitary, housing and household products such as bathrooms, and various parts used in vehicles, building materials, etc. In the case of various parts made of such rubber-reinforced styrene resins, when airtightness and waterproofness are required at the joints, etc., it is generally common to use a silicone-based sealing material.

[0003] Silicone-based sealing materials are roughly classified into one-component sealing materials that utilize a condensation-type curing mechanism, are put into a sealed container such as a tube or a cartridge, and start to cure by reacting with moisture in the air when taken out of the container during use, and two-component sealing materials that mix the main agent and the curing agent before use to generate a curing reaction. However, due to reasons such as handleability and cost, one-component sealing materials are widely used in the market. One-component sealing materials cure by reacting with moisture in the air. When the hydrolyzable functional groups in the sealing material come into contact with moisture, a hydrolysis condensation reaction occurs and crosslinking takes place. Examples of hydrolyzable functional groups include methyl ethyl ketoxime groups (deoxime type), acetoxy groups (deacetic acid type), alkoxy groups (dealcohol type), isopropenoxy groups (deacetone type), etc.

[0004] Generally, as a thermoplastic resin composition that has excellent adhesiveness to a low-odor deoxime-type silicone-based sealing material and gives molded products with good physical properties such as weather resistance, chemical resistance, and impact resistance, a composite rubber composed of a polyorganosiloxane and an alkyl (meth)acrylate rubber is graft polymerized with one or more selected from the group consisting of an aromatic vinyl compound, a methacrylic acid ester, an acrylic acid ester, and a vinyl cyanide compound to obtain a graft copolymer (I) having a mass average particle diameter of 0.08 to 0.2 μm, and a resin component composed of a vinyl-based copolymer (II) containing at least an aromatic vinyl compound and a vinyl cyanide compound as constituent units is known (see Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] When applying a deoxime-type silicone-based sealing material to an adherend, primer treatment may be required. However, there is a demand for a thermoplastic resin composition that can directly apply such a silicone-based sealing material to the surface of a resin molded product and obtain adhesiveness of the cured product of the silicone-based sealing material after curing. An object of the present invention is to provide a thermoplastic resin composition that gives molded products excellent in adhesiveness, impact resistance, rigidity, weather resistance, and molding appearance of a cured product of a silicone-based sealing material and has excellent molding processability.

Means for Solving the Problems

[0007] The present inventors have found that a thermoplastic resin composition containing a graft copolymer and a vinyl copolymer, wherein the vinyl copolymer contains, in particular, a modified vinyl copolymer having a (meth)acrylic acid ester compound having a carbon chain in which the ester moiety has a polar group as a structural unit, can provide a molded article excellent in adhesion, impact resistance, rigidity, weather resistance, and molding appearance of a silicone-based sealing material cured product, and also has excellent moldability, and thus have completed the present invention.

[0008] The present invention is as follows. 1. A graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, (B) A vinyl copolymer containing a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a vinyl cyanide compound, and not containing a structural unit represented by the following general formula (1), and (C) A modified vinyl copolymer containing a structural unit (c1) derived from an aromatic vinyl compound, a structural unit (c2) derived from a vinyl cyanide compound, and a structural unit (c3) represented by the following general formula (1) [Chemical formula] (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a substituted alkyl group containing a polar group) In a thermoplastic resin composition containing the content ratio of the rubbery polymer is 5 to 25% by mass based on the total amount of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C), A thermoplastic resin composition characterized in that the content ratio of the structural unit (c3) in the modified vinyl copolymer (C) is 1 to 20% by mass. 2. The thermoplastic resin composition according to item 1 above, wherein the content ratio of the structural unit derived from a vinyl cyanide compound in the acetone-soluble component obtained by contacting with acetone is 20 to 40% by mass. 3. In the general formula (1) representing the above structural unit (c3), R 2 The thermoplastic resin composition according to item 1 above, wherein the number of carbon atoms of is 1 to 4. 4. The thermoplastic resin composition according to item 1 above, wherein the polar group contained in the above structural unit (c3) is a hydroxy group. 5. The thermoplastic resin composition according to item 1 above, wherein the content ratio of the above structural unit (c3) is 0.1 to 3.5% by mass based on the total amount of the above graft copolymer (A), the above vinyl copolymer (B), and the above modified vinyl copolymer (C). 6. The plastic resin composition according to item 1 above, wherein the above rubber polymer is an acrylic rubber or an ethylene-α-olefin rubber. 7. The thermoplastic resin composition according to item 1 above, which is used for forming a molded article to which a deoxime-type silicone-based sealing material is applied. 8. A molded article comprising the thermoplastic resin composition according to item 1 above.

Advantages of the Invention

[0009] The thermoplastic resin composition of the present invention is excellent in molding processability, and the obtained molded article can be preferably adhered to a cured product by applying a deoxime-type silicone-based sealing material without being subjected to a primer treatment, and is excellent in impact resistance, rigidity, weather resistance, and molding appearance. Therefore, the thermoplastic resin composition of the present invention is suitable as a molding material for resin products that need to be made watertight and airtight with a deoxime-type silicone-based sealing material and require molding appearance, weather resistance, etc.

Modes for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. In this specification, "(co)polymer" means a homopolymer and a copolymer. Also, "(meth)acrylic" means acrylic and methacrylic, and "(meth)acrylate" means acrylate and methacrylate.

[0011] The thermoplastic resin composition of the present invention contains a graft copolymer (A), two vinyl copolymers (B), and a modified vinyl copolymer (C), and is used for forming a molded article to which a deoxime-type silicone sealing material is applied and the cured product thereof is adhered.

[0012] The graft copolymer (A) is a resin obtained by polymerizing (graft-polymerizing) vinyl monomers including an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer.

[0013] The rubbery polymer may be a homopolymer or a copolymer as long as it is rubbery at room temperature. Further, the rubbery polymer may be a crosslinked polymer or a non-crosslinked polymer. In the present invention, either a diene polymer (diene rubber) or a non-diene polymer (non-diene rubber) may be used, and a diene rubber, an ethylene-α-olefin rubber, or an acrylic rubber is preferably used. These can be used alone or in combination of two or more. When an acrylic rubber and an ethylene-α-olefin rubber are used as the rubbery polymer, a molded article excellent in weather resistance can be obtained by using the thermoplastic resin composition containing the graft copolymer. Further, when a diene rubber and an ethylene-α-olefin rubber are used as the rubbery polymer, a molded article excellent in impact resistance can be obtained by using the thermoplastic resin composition containing the graft copolymer.

[0014] The acrylic rubber is preferably a copolymer rubber produced by polymerizing an alkyl (meth)acrylate and a polyfunctional alkyl (meth)acrylate.

[0015] Examples of the alkyl (meth)acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Among these, n-butyl acrylate is preferred. The alkyl (meth)acrylate can be used alone or in combination of two or more.

[0016] Examples of the polyfunctional alkyl (meth)acrylate include allyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,4-butylene glycol di(meth)acrylate. Among these, allyl methacrylate is preferred. The polyfunctional alkyl (meth)acrylate can be used alone or in combination of two or more.

[0017] When synthesizing an acrylic rubber using an alkyl (meth)acrylate and a polyfunctional alkyl (meth)acrylate, when the total of these is 100% by mass, their respective usage ratios are preferably 80 to 99.9% by mass and 0.1 to 20% by mass, more preferably 95 to 99.8% by mass and 0.2 to 5% by mass, and still more preferably 99 to 99.8% by mass and 0.2 to 1% by mass. In addition, an acrylic rubber may be synthesized by reacting an alkyl (meth)acrylate, a polyfunctional alkyl (meth)acrylate, and further, triallyl cyanurate, triallyl isocyanurate, or the like.

[0018] The ethylene·α-olefin rubber is a copolymer rubber that includes a structural unit derived from ethylene and a structural unit derived from an α-olefin, and may further include a structural unit derived from another monomer.

[0019] Examples of the α-olefin include α-olefins having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicosene and the like. Among these, from the viewpoint of the surface appearance of the molded article obtained using the thermoplastic resin composition of the present invention, the number of carbon atoms of the α-olefin is preferably 3 to 12, more preferably 3 to 8. Further, the α-olefin can be used alone or in combination of two or more. As the ethylene·α-olefin rubber, an ethylene·propylene copolymer, an ethylene·1-butene copolymer and an ethylene·1-octene copolymer are preferable, and an ethylene·propylene copolymer is more preferable. The ethylene·α-olefin rubber can be used alone or in combination of two or more.

[0020] When the ethylene·α-olefin rubber is an ethylene·α-olefin copolymer, from the viewpoint of the impact resistance of the molded article obtained using the thermoplastic resin composition of the present invention, the content ratio of the structural unit derived from ethylene is preferably 5 to 95% by mass, more preferably 50 to 95% by mass, still more preferably 60 to 95% by mass, particularly preferably 70 to 90% by mass, based on 100% by mass of the total of the structural unit derived from ethylene and the structural unit derived from α-olefin.

[0021] When the ethylene·α-olefin rubber further contains a structural unit derived from another monomer, the other structural unit can be a structural unit derived from a non-conjugated diene. Examples of the non-conjugated diene include 1,4-hexadiene, 1,5-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene and the like. The non-conjugated diene can be used alone or in combination of two or more.

[0022] Examples of the diene rubber include homopolymers such as polybutadiene and polyisoprene; butadiene copolymers such as styrene-butadiene copolymer, styrene-butadiene-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer; and isoprene copolymers such as styrene-isoprene copolymer, styrene-isoprene-styrene copolymer, and acrylonitrile-styrene-isoprene copolymer. These may be random copolymers or block copolymers. Alternatively, the diene rubber may be a hydrogenated (co)polymer obtained by hydrogenating a (co)polymer containing a structural unit derived from a conjugated diene compound. In this case, the hydrogenation rate with respect to the (co)polymer before hydrogenation is preferably 95% or more, more preferably 98% or more.

[0023] The shape of the rubbery polymer is not particularly limited, and may be particulate (spherical, substantially spherical), linear, curved, or the like. When it is particulate, the volume average particle diameter is preferably 0.10 to 0.60 μm, more preferably 0.15 to 0.45 μm, and still more preferably 0.20 to 0.40 μm. The volume average particle diameter can be measured by image analysis using an electron micrograph, laser diffraction method, light scattering method, or the like.

[0024] The vinyl monomer to be graft-polymerized in the presence of the rubbery polymer includes aromatic vinyl compounds and vinyl cyanide compounds, and may further contain other monomers (described later) if necessary. The amount of the vinyl monomer used is not particularly limited, but from the viewpoints of impact resistance, weather resistance, etc. of the molded article obtained using the thermoplastic resin composition of the present invention, when the total amount of the graft copolymer (A) is 100% by mass, it is preferably 25 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 50 to 60% by mass.

[0025] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, and the like. These compounds can be used alone or in combination of two or more. Among these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, and the like. These compounds can be used alone or in combination of two or more. Among these, acrylonitrile is preferred.

[0026] As described above, the vinyl monomer to be graft-polymerized in the presence of the rubbery polymer may contain other monomers. Examples of the other monomers include (meth)acrylic acid ester compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, maleimide compounds, and the like. When the vinyl monomer contains other monomers, the ratio of the total amount of the aromatic vinyl compound and the vinyl cyanide compound to the total amount of the vinyl monomer is preferably 85% by mass or more, more preferably 95% by mass or more.

[0027] When the vinyl monomer consists of an aromatic vinyl compound and a vinyl cyanide compound, when the total of both is 100% by mass, the respective ratios of the amounts used of the aromatic vinyl compound and the vinyl cyanide compound are preferably 60 to 74% by mass and 26 to 40% by mass, more preferably 65 to 70% by mass and 30 to 35% by mass. When the thermoplastic resin composition of the present invention contains the graft copolymer (A) obtained by using the aromatic vinyl compound and the vinyl cyanide compound in the above ratios, the resulting molded article is excellent in chemical resistance, weather resistance, impact resistance, and thermal stability, and also excellent in adhesiveness to the cured product of the deoxime-type silicone-based sealing material.

[0028] The method for producing the graft copolymer (A) is not particularly limited, and emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization can be applied.

[0029] In the case of emulsion polymerization, a vinyl monomer is added to a latex of a rubbery polymer, graft polymerization is carried out by radical polymerization, and then the latex containing the obtained graft copolymer (A) is brought into contact with a coagulant to make the resin component powdery. Thereafter, the graft copolymer (A) can be recovered by washing this with water and drying. Examples of the polymerization initiator used here include organic peroxides, azo compounds, inorganic peroxides, redox-type polymerization initiators, and the like. Examples of the coagulant include inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid; and inorganic salts such as calcium chloride, calcium acetate, calcium nitrate, calcium bromide, magnesium sulfate, magnesium chloride, and sodium chloride. For example, in the case of a latex containing the graft copolymer (A) obtained when the rubbery polymer is a diene rubber, the graft copolymer (A) can be recovered from the latex by charging it into an aqueous solution of a calcium salt and salting out. As the calcium salt for salting out, calcium chloride and calcium acetate are preferable from the viewpoints of coagulability and economy.

[0030] Next, the two vinyl copolymers (B) and modified vinyl copolymers (C) contained in the thermoplastic resin composition of the present invention will be described.

[0031] Both the vinyl copolymer (B) and the modified vinyl copolymer (C) contain a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound. The difference between them is that the latter is a copolymer containing a structural unit represented by the following general formula (1), while the former is a copolymer not containing this structural unit.

Chemical formula

[0032] The vinyl copolymer (B) contains at least a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a vinyl cyanide compound, and may contain, if necessary, a structural unit (hereinafter referred to as "structural unit (b3)") derived from other monomers. The vinyl copolymer (B) is a component obtained by copolymerization by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, or a combination thereof.

[0033] As the aromatic vinyl compound and vinyl cyanide compound that give the vinyl copolymer (B), each compound contained in the vinyl monomer that gives the graft copolymer (A) can be applied.

[0034] As the aromatic vinyl compound that forms the structural unit (b1), styrene and α-methylstyrene are preferable, and the structural unit (b1) contained in the vinyl copolymer (B) can be only one kind or two or more kinds. As the vinyl cyanide compound that forms the structural unit (b2), acrylonitrile and methacrylonitrile are preferable, and the structural unit (b2) contained in the vinyl copolymer (B) can be only one kind or two or more kinds.

[0035] Further, examples of other monomers that form the structural unit (b3) include (meth)acrylic acid alkyl esters, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds (excluding monomers that form the structural unit represented by the above general formula (1)), amino group-containing unsaturated compounds (excluding monomers that form the structural unit represented by the above general formula (1)), maleimide compounds, and the like.

[0036] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and the like.

[0037] Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Examples of the carboxyl group-containing unsaturated compound include (meth)acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like.

[0038] Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, and the like.

[0039] Examples of the amino group-containing unsaturated compound include N-vinyldiethylamine, N-acetylvinylamine, (meth)acrylamine, N-methyl(meth)acrylamine, (meth)acrylamide, 3-dimethylaminopropyl(meth)acrylamide, and the like.

[0040] When the vinyl copolymer (B) contains the structural unit (b3), the structural unit (b3) can be only one kind or two or more kinds.

[0041] The total content ratio of structural units (b1) and (b2) constituting the vinyl copolymer (B) according to the present invention is preferably 25% by mass or more, more preferably 85% by mass or more. The upper limit is 100% by mass. Further, when the vinyl copolymer (B) consists of structural units (b1) and (b2), and also in the case of consisting of structural units (b1), (b2) and (b3), the content ratios of structural units (b1) and (b2) are preferably 60 to 80% by mass and 20 to 40% by mass, more preferably 65 to 75% by mass and 25 to 35% by mass, respectively, when the total of both is 100% by mass. When the content ratios of structural units (b1) and (b2) are within this range, the molded article obtained using the thermoplastic resin composition of the present invention is excellent in adhesiveness and impact resistance to the cured product of the deoxime-type silicone-based sealing material, and further, the balance between the fluidity and chemical resistance of the thermoplastic resin composition is excellent.

[0042] The weight average molecular weight of the vinyl copolymer (B) is not particularly limited, but considering the balance between the impact resistance and fluidity of the thermoplastic resin composition, it is preferably 50,000 to 200,000, more preferably 60,000 to 110,000.

[0043] The modified vinyl copolymer (C) contained as a resin component in the thermoplastic resin composition contains at least a structural unit (c1) derived from an aromatic vinyl compound, a structural unit (c2) derived from a vinyl cyanide compound, and a structural unit (c3) represented by the above general formula (1), and may contain, if necessary, a structural unit (hereinafter referred to as "structural unit (c4)") derived from another monomer. The modified vinyl copolymer (C) is a component obtained by copolymerization by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization, or a combination thereof.

[0044] As the aromatic vinyl compound and vinyl cyanide compound that give the modified vinyl copolymer (C), each compound contained in the vinyl monomer that gives the graft copolymer (A) can be applied.

[0045] As the aromatic vinyl compound forming the structural unit (c1), styrene and α-methylstyrene are preferred, and the structural unit (c1) contained in the modified vinyl copolymer (C) can be only one kind or two or more kinds. As the vinyl cyanide compound forming the structural unit (c2), acrylonitrile and methacrylonitrile are preferred, and the structural unit (c2) contained in the modified vinyl copolymer (C) can be only one kind or two or more kinds.

[0046] The structural unit (c3) is a structural unit represented by the general formula (1) having an R 2 which is a substituted alkyl group containing a polar group. The polar group is not particularly limited, and examples thereof include a hydroxy group, a carboxy group, a sulfo group, an amino group, a thio group, a halogen atom, etc. Among these, a hydroxy group is preferred because it is easily incorporated into the hydrolysis condensation reaction of the deoxime type silicone-based sealing material. Further, the number of carbon atoms in the substituted alkyl group is usually 4 or less, preferably 2 - 3, and more preferably 2.

[0047] The substituted alkyl group containing a hydroxy group preferably has 1 - 4 carbon atoms in R 2 and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxy-n-propyl group, a 2-hydroxy-n-propyl group, a 3-hydroxy-n-propyl group, a 1-hydroxy-isopropyl group, a 2-hydroxy-isopropyl group, a 2,2'-dihydroxy-isopropyl group, a 1-hydroxy-n-butyl group, a 2-hydroxy-n-butyl group, a 3-hydroxy-n-butyl group, a 4-hydroxy-n-butyl group, a 1-hydroxy-1-methyl-propyl group, a 1-hydroxy-2-methyl-propyl group, a 2-hydroxy-1-methyl-propyl group, a 2-hydroxy-2-methyl-propyl group, a 3-hydroxy-1-methyl-propyl group, a 3-hydroxy-2-methyl-propyl group, a 3-hydroxy-3-methyl-propyl group, etc.

[0048] Examples of the compound that forms the structural unit (c3) containing a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like.

[0049] Examples of the substituted alkyl group containing an amino group include monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, monophenylamino group, diphenylamino group, and the like.

[0050] Examples of the compound that forms the structural unit (c3) containing an amino group include aminoethyl (meth)acrylate, propylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, phenylaminoethyl (meth)acrylate, and the like.

[0051] The structural unit (c3) contained in the modified vinyl copolymer (C) can be either only one kind or two or more kinds. The content ratio of the structural unit (c3) is 1 to 20% by mass, preferably 5 to 15% by mass, and more preferably 8 to 12% by mass with respect to the modified vinyl copolymer (C) because the molded product obtained using the thermoplastic resin composition of the present invention is excellent in adhesion, impact resistance, rigidity, weather resistance, and molding appearance to the cured product of the deoxime type silicone-based sealing material.

[0052] In addition, examples of other monomers that form the structural unit (c4) include (meth)acrylic acid alkyl esters, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds (excluding the monomers that form the structural unit represented by the general formula (1) above), amino group-containing unsaturated compounds (excluding the monomers that form the structural unit represented by the general formula (1) above), maleimide-based compounds, and the like.

[0053] When the modified vinyl-based copolymer (C) contains the structural unit (c4), the structural unit (c4) can be either only one kind or two or more kinds.

[0054] The total content ratio of the structural units (c1), (c2), and (c3) constituting the modified vinyl-based copolymer (C) according to the present invention is preferably 85% by mass or more, more preferably 95% by mass or more. The upper limit is 100% by mass. Also, when the total of the content ratios of the structural units (c1), (c2), and (c3) is 100% by mass, they are preferably 55 to 80% by mass, 14 to 40% by mass, and 1 to 20% by mass, more preferably 60 to 75% by mass, 20 to 35% by mass, and 5 to 15% by mass, and even more preferably 65 to 70% by mass, 20 to 25% by mass, and 8 to 12% by mass. When the content ratios of the structural units (c1), (c2), and (c3) are within this range, the molded article obtained using the thermoplastic resin composition of the present invention is excellent in adhesiveness and impact resistance to the cured product of the deoxime-type silicone-based sealing material, and further, has an excellent balance of fluidity, chemical resistance, and adhesiveness to the cured product of the deoxime-type silicone-based sealing material suitable for injection molding.

[0055] The weight average molecular weight of the modified vinyl-based copolymer (C) is not particularly limited, but considering the balance between the impact resistance and fluidity of the thermoplastic resin composition, it is preferably 50,000 to 200,000, more preferably 60,000 to 110,000.

[0056] In the thermoplastic resin composition of the present invention, when the total of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C) is 100% by mass, the content ratio of the graft copolymer (A) is preferably 8 to 45% by mass, more preferably 10 to 40% by mass. When the content ratio of the graft copolymer (A) is within this range, the molded article obtained using the thermoplastic resin composition of the present invention is excellent in impact resistance, mechanical strength, and molding appearance, and furthermore, both the balance of these physical properties and the adhesiveness to the cured product of the deoxime-type silicone-based sealing material are excellent.

[0057] In the thermoplastic resin composition of the present invention, the content ratios of the vinyl copolymer (B) and the modified vinyl copolymer (C) are not particularly limited. Since the molded article obtained using the thermoplastic resin composition of the present invention is excellent in adhesiveness and impact resistance to the cured product of the deoxime-type silicone-based sealing material, when the total of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C) is 100% by mass, the content ratio of the structural unit (c3) is preferably 0.1 to 3.5% by mass, more preferably 0.5 to 2.5% by mass.

[0058] The thermoplastic resin composition of the present invention may contain other polymers (resins) or various additives as necessary, in addition to the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C).

[0059] Examples of other polymers (resins) include acrylic resins, polycarbonate resins, polyamide resins, polyester resins, and the like.

[0060] When the thermoplastic resin composition of the present invention contains other polymers (resins), the upper limit of the content ratio is preferably 20 parts by mass, more preferably 10 parts by mass, when the total of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C) is 100 parts by mass.

[0061] Examples of additives include anti-aging agents, antioxidants, ultraviolet absorbers, lubricants, plasticizers, fillers, heat stabilizers, flame retardants, antistatic agents, colorants, etc.

[0062] Examples of anti-aging agents include naphthylamine-based compounds, diphenylamine-based compounds, p-phenylenediamine-based compounds, quinoline-based compounds, hydroquinone derivative-based compounds, monophenol-based compounds, bisphenol-based compounds, tris-phenol-based compounds, polyphenol-based compounds, thiobisphenol-based compounds, hindered phenol-based compounds, phosphite ester-based compounds, imidazole-based compounds, nickel dithiocarbamate-based compounds, etc.

[0063] Examples of antioxidants include hindered amine-based compounds, hydroquinone-based compounds, hindered phenol-based compounds, sulfur-containing compounds, phosphorus-containing compounds, etc. Examples of ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, triazine-based compounds, etc.

[0064] Examples of lubricants include waxes, silicones, lipids, etc. Examples of plasticizers include phthalate esters, trimellitate esters, pyromellitate esters, aliphatic monobasic acid esters, aliphatic dibasic acid esters, phosphate esters, esters of polyhydric alcohols, epoxy plasticizers, polymer-type plasticizers, chlorinated paraffins, etc.

[0065] Examples of fillers include calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran balloon, phenol balloon, etc. Examples of heat stabilizers include phosphite-based heat stabilizers, lactone-based heat stabilizers, hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, amine-based heat stabilizers, and the like.

[0066] Examples of flame retardants include organic flame retardants, inorganic flame retardants, and the like.

[0067] Examples of organic flame retardants include halogen-based flame retardants such as brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol-based epoxy resins, brominated bisphenol-based phenoxy resins, brominated bisphenol-based polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins, brominated bisphenol cyanurate resins, brominated polyphenylene ethers, decabromodiphenyl oxide, tetrabromobisphenol A, and its oligomers; phosphate esters such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethylethyl phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, hydroxyphenyl diphenyl phosphate, and their modified compounds, condensed phosphate ester compounds, phosphazene derivatives containing phosphorus and nitrogen elements, and other phosphorus-based flame retardants; guanidine salts, silicone-based compounds, phosphazene-based compounds, and the like.

[0068] Examples of inorganic flame retardants include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium-based compounds, molybdenum-based compounds, zinc stannate, and the like.

[0069] The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and it can be produced by mixing the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C) with other polymers (resins) and various additives that can be contained as necessary. When mixing the raw material components, it is preferable to carry out melt kneading using a Banbury mixer, a kneader, a single-screw or twin-screw extruder. During kneading, the raw material components may be kneaded all at once, or may be kneaded by a multi-stage addition method. The kneading temperature (cylinder set temperature) is preferably 200°C to 250°C.

[0070] In the present invention, the acetone-soluble component obtained by bringing the thermoplastic resin composition into contact with acetone and dissolving in acetone is usually the vinyl copolymer (B) and the modified vinyl copolymer (C). The content ratio of the structural unit derived from the vinyl cyanide compound in this acetone-soluble component is preferably 20 to 40% by mass, more preferably 25 to 35% by mass, because the molded product obtained using the thermoplastic resin composition of the present invention is excellent in impact resistance and thermal stability, and the adhesiveness of the cured product of the deoxime-type silicone-based sealing material is also excellent.

[0071] As described above, the thermoplastic resin composition of the present invention contains the graft copolymer (A) obtained by polymerizing a specific vinyl monomer with a rubbery polymer, the specific vinyl copolymer (B), and the specific modified vinyl copolymer (C). Furthermore, since both the content ratio of the rubbery polymer to the total amount of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C) and the content ratio of the structural unit (c3) in the modified vinyl copolymer (C) are specific amounts, it has excellent molding processability, and the impact resistance, rigidity, weather resistance, and molding appearance of the obtained molded product are very excellent, and it also has an excellent adhesiveness of the cured product of the deoxime-type silicone-based sealing material that has never existed before.

[0072] The molded article of the present invention can be manufactured by processing the above-mentioned thermoplastic resin composition of the present invention or raw material components that will form its constituent components with a known molding device such as an injection molding device, a sheet extrusion molding device, a profile extrusion molding device, a hollow molding device, or a compression molding device. That is, the molded article of the present invention contains the above-mentioned thermoplastic resin composition of the present invention.

[0073] When manufacturing a molded article using the above molding device, the molding temperature and the mold temperature are appropriately selected depending on the type of raw material components used, etc.

[0074] The shape of the molded article of the present invention is not particularly limited and is appropriately selected depending on the use, etc. As described above, the thermoplastic resin composition of the present invention provides molded articles with excellent various performances. Therefore, the molded article of the present invention is useful for the manufacture of a composite structure that is adhesively bonded, sealed, etc. using a deoxime-type silicone-based sealing material without subjecting it to primer treatment, and is subjected to watertight and airtight treatment. Furthermore, since the molded article of the present invention has excellent weather resistance, it is suitable for outdoor use. Examples of the molded article of the present invention include window frame covers such as residential sashes and doors, door leaves, fences, joints of resin parts of carports, and various molded articles such as storage cabinets, dressing shelves, and counter products around bathrooms and washrooms where contact with detergents, etc. is extremely high. Such molded articles are distributed and used as they are or as resin products with a sealing material such as a deoxime type adhered to the molded article.

Examples

[0075] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following, "parts" indicates parts by mass, and "%" indicates mass%.

[0076] 1. Raw materials for the thermoplastic resin composition The raw materials used for the production of the thermoplastic resin composition were obtained by the following synthesis methods.

[0077] Synthesis Example 1 (Synthesis of Graft Copolymer (P-1)) 1.4 parts of sodium alkylbenzenesulfonate, 120 parts of ion-exchanged water, 6 parts of n-butyl acrylate, 0.03 part of triallyl isocyanurate, and 0.012 part of cumene hydroperoxide were charged under stirring. The inside of the reactor was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60°C. When the internal temperature reached 60°C, an aqueous solution consisting of 0.0036 part of ferrous sulfate heptahydrate, 0.0072 part of disodium ethylenediaminetetraacetate, 0.054 part of Rongalit, and 3 parts of ion-exchanged water was added to initiate polymerization. After the polymerization exotherm was confirmed, the internal temperature was maintained at 60°C for an additional 1 hour in this state. Next, a mixed solution consisting of 54 parts of n-butyl acrylate, 0.3 part of triallyl isocyanurate, and 0.12 part of cumene hydroperoxide was introduced at a rate of 1.1 liters / hour, an aqueous solution consisting of 1.5 parts of sodium alkylbenzenesulfonate and 69 parts of water was introduced at a rate of 1.4 liters / hour, and an aqueous solution consisting of 0.054 part of sodium formaldehyde sulfoxylate, 0.0036 part of ferrous sulfate heptahydrate, 0.072 part of disodium ethylenediaminetetraacetate, and 3 parts of water was introduced at a rate of 60 milliliters / hour over 10 hours. Continuous polymerization was carried out at a polymerization temperature of 60°C to obtain a latex containing a rubbery polymer (r-1) with a volume average particle diameter of 0.28 μm. Thereafter, while maintaining the temperature of the latex in the reactor at 60°C, 135 parts of ion-exchanged water was added. To 60 parts (as solid content) of the rubbery polymer (r-1), 0.5 part of sodium alkylbenzene sulfonate was added, and an aqueous solution consisting of 0.2 part of Rongalit, 0.003 part of ferrous sulfate heptahydrate, 0.017 part of disodium ethylenediaminetetraacetate, and 10 parts of water was added. Subsequently, a mixture of 15 parts of acrylonitrile, 25 parts of styrene, and 0.2 part of cumene hydroperoxide was added dropwise over 2 hours for graft polymerization. After completion of the dropwise addition, the internal temperature was maintained at 60°C for 30 minutes and then cooled. When the internal temperature reached 60°C, 330 parts of a 1% aqueous calcium acetate (Ca acetate) solution was heated to 75°C, and while stirring the aqueous solution, the graft copolymer latex was gradually added dropwise to the aqueous solution to solidify the graft copolymer, and the temperature was further raised to 90°C and held for 5 minutes. Subsequently, the solidified product was dehydrated, washed, and dried to obtain a graft copolymer (P-1) composed of an ASA resin. The graft ratio of the graft copolymer (P-1) was 35%, and the weight-average molecular weight by GPC was 116,000.

[0078] Synthesis Example 2 (Synthesis of graft copolymer (P-2)) A mixture of 2 parts of potassium oleate, 4 parts of sodium dioctylsulfosuccinate, 200 parts of ion-exchanged water, 0.003 part of ferrous sulfate heptahydrate, 0.009 part of disodium ethylenediaminetetraacetate, and 0.3 part of sodium formaldehyde sulfoxylate was charged into the reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen and heated to 60°C. From the time when the temperature reached 60°C, a mixture consisting of 82 parts of n-butyl acrylate, 18 parts of methacrylic acid, and 0.5 part of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, aging was further carried out at 60°C for 2 hours to obtain an acid group-containing copolymer latex (L-1) having a solid content of 33%, a polymerization conversion rate of 96%, and a volume average particle diameter of the acid group-containing copolymer of 150 nm. Except that 82 parts of n-butyl acrylate and 18 parts of methacrylic acid as monomers were changed to 86 parts of n-butyl acrylate and 14 parts of methacrylic acid, the same operations as above were carried out to obtain an acid group-containing copolymer latex (L-2) with a solid content of 33%, a polymerization conversion rate of 95%, and a weight-average particle diameter of the acid group-containing copolymer of 110 nm. Next, a mixture of 0.85 part of dipotassium alkenyl succinate, 170 parts of ion-exchanged water, 50 parts of n-butyl acrylate, 0.25 part of triallyl isocyanurate, and 0.17 part of tert-butyl hydroperoxide was charged into a reactor. By passing a nitrogen stream through the reactor, the inside of the reactor was purged with nitrogen and heated to 55°C. An aqueous solution consisting of 0.00025 part of ferrous sulfate heptahydrate, 0.00075 part of disodium ethylenediaminetetraacetate, 0.17 part of Rongalit, and 5 parts of ion-exchanged water was added to initiate polymerization. After polymerization exotherm was confirmed, the internal temperature was set to 60°C and this state was maintained for 1 hour. Then, the internal temperature was set to 30°C, 0.4 part of sodium pyrophosphate was added into the reactor as a 2.5% aqueous solution, and after sufficient stirring, 1.5 parts (solid content: 0.5 part) of the acid group-containing copolymer latex (L-1) and 0.45 part (solid content: 0.15 part) of the acid group-containing copolymer latex (L-2) were added. Stirring was carried out for 30 minutes while maintaining the internal temperature at 30°C to obtain a latex containing a swollen rubbery polymer (r-2) with a volume-average particle diameter of 0.36 μm of the swollen rubber. Thereafter, the temperature of the latex in the reactor was raised to 60°C. To 50 parts (as solids) of the swollen rubbery polymer (r-2), 220 parts of ion-exchanged water (including the water in the rubber latex) and 0.25 part of dipotassium alkenyl succinate were added. After raising the liquid temperature inside the reactor to 70°C, an aqueous solution consisting of 0.38 part of Rongalit, 0.0013 part of ferrous sulfate heptahydrate, 0.038 part of disodium ethylenediaminetetraacetate, and 10 parts of ion-exchanged water was added. Then, 12.5 parts of acrylonitrile, 37.5 parts of styrene, and 0.25 part of t-butyl hydroperoxide were added dropwise over 2 hours for graft polymerization. After completion of the dropwise addition, the internal temperature was maintained at 60°C for 30 minutes and then cooled. Next, the polymer component contained in the obtained reaction solution was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (P-2) composed of an ASA resin. The graft ratio of the graft copolymer (P-2) was 40%, and the weight-average molecular weight by GPC was 158,000.

[0079] Synthesis Example 3 (Synthesis of graft copolymer (P-3)) Into a stainless steel autoclave equipped with a ribbon-type stirring blade, an auxiliary agent continuous addition device, a thermometer, etc., ethylene-propylene copolymer rubber (ethylene / propylene = 78 / 22 (%), Mooney viscosity (ML 1+4, 100 °C): 20, melting point (Tm): 40 °C, glass transition temperature (Tg): -50 °C, volume average particle diameter: 0.45 μm) 50 parts, styrene 30 parts, acrylonitrile 20 parts, tert-dodecyl mercaptan 0.5 part and toluene 110 parts were charged, and the internal temperature was raised to 75 °C, and the autoclave contents were stirred for 1 hour to obtain a uniform solution. Then, 0.45 part of tert-butyl peroxyisopropyl monocarbonate was added, and the internal temperature was further raised. After reaching 100 °C, the polymerization reaction was carried out at a stirring rotation speed of 100 rpm while maintaining this temperature. From the 4th hour after the start of the polymerization reaction, the internal temperature was raised to 120 °C, and the reaction was further carried out for 2 hours while maintaining this temperature to complete the polymerization reaction. Then, the internal temperature was cooled to 100 °C, and 0.2 part of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenol)-propionate and 0.02 part of dimethyl silicone oil "KF-96-100 cSt" (trade name) manufactured by Shin-Etsu Silicone Co., Ltd. were added. Next, the obtained reaction solution was taken out from the autoclave, and unreacted substances and the solvent were distilled off by steam distillation. Further, the volatile components were substantially degassed using a 40 mmφ extruder with a vent (cylinder temperature: 220 °C, vacuum degree: 760 mmHg) and pelletized to obtain a graft copolymer (P-3) composed of an AES resin. The graft ratio of the graft copolymer (P-3) was 44%, and the weight average molecular weight by GPC was 85,000.

[0080] Synthesis Example 4 (Synthesis of Graft Copolymer (P-4)) Into a polymerizer equipped with a stirrer, 280 parts of water, 65 parts (in terms of solid content) of a latex containing polybutadiene rubber with a volume average particle diameter of 0.30 μm and a gel fraction of 90%, 0.3 part of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate, and 0.01 part of disodium ethylenediaminetetraacetate were charged. After deoxygenation, it was heated to 60°C with stirring in a nitrogen stream. Then, while maintaining 60°C, a monomer mixture consisting of 10 parts of acrylonitrile, 25 parts of styrene, 0.2 part of tert-dodecyl mercaptan, and 0.3 part of cumene hydroperoxide was continuously added dropwise over 5 hours. After completion of the addition, the polymerization temperature was raised to 65°C, and stirring was continued for 1 hour, and then the polymerization was terminated to obtain a latex of a graft copolymer. The polymerization conversion rate was 98%. Next, 0.2 part of 2,2′-methylene-bis(4-ethyl-6-tert-butylphenol) was added to the obtained latex, and further, calcium chloride was added for coagulation, followed by washing, filtration, and drying to obtain a powdery graft copolymer (P-4) composed of an ABS resin. The graft ratio of the graft copolymer (P-4) was 39%, and the weight average molecular weight by GPC was 115,000.

[0081] Synthesis Example 5 (Synthesis of vinyl copolymer (Q-1)) Into a nitrogen-substituted reactor equipped with a stirrer, 120 parts of water, 0.002 part of sodium alkylbenzenesulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyronitrile, 0.65 part of tertiary-dodecyl mercaptan, 32 parts of acrylonitrile, and 68 parts of styrene were put. While stirring, the temperature of the raw material mixture was maintained at 60°C for 5 hours and then raised to 120°C. After reacting for 4 hours, the polymer was taken out. The polymerization conversion rate was 96%. The obtained polymer was a styrene-acrylonitrile copolymer, and the weight average molecular weight by GPC was 75,000. Hereinafter, this styrene-acrylonitrile copolymer is referred to as "vinyl copolymer (Q-1)".

[0082] Synthesis Example 6 (Synthesis of vinyl copolymer (Q-2)) Into a nitrogen-substituted reactor equipped with a stirrer, 120 parts of water, 0.002 part of sodium alkylbenzenesulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyronitrile, 0.60 part of tertiary dodecyl mercaptan, 23 parts of acrylonitrile and 77 parts of styrene were added. While stirring, the temperature of the raw material mixture was maintained at 60 °C for 5 hours and then raised to 120 °C. After reacting for 4 hours, the polymer was taken out. The polymerization conversion rate was 98%. The obtained polymer was a styrene-acrylonitrile copolymer, and the weight average molecular weight by GPC was 98,000. Hereinafter, this styrene-acrylonitrile copolymer is referred to as "vinyl copolymer (Q-2)".

[0083] Synthesis Example 7 (Synthesis of modified vinyl copolymer (R-1)) Two polymerization reaction vessels with jackets equipped with ribbon blades were connected, purged with nitrogen, and then a monomer-containing raw material with a ratio of 68 parts of styrene, 22 parts of acrylonitrile, 10 parts of 2-hydroxyethyl methacrylate, and 20 parts of toluene was continuously supplied to the first reaction vessel. At the same time, a solution with a ratio of 0.21 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution with a ratio of 0.1 part of 1,1′-azobis(cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator were continuously supplied, and polymerization was carried out under stirring. In the first reaction vessel, the polymerization temperature was controlled at 110 °C and the average residence time was 2.0 hours. The polymerization conversion rate by this was 57%. The polymer solution obtained in the first reaction vessel was continuously taken out by a pump provided outside thereof and supplied to the second reaction vessel. The amount of the polymer solution taken out from the first reaction vessel was the same as the total amount of the supply amounts of styrene, acrylonitrile, 2-hydroxyethyl methacrylate, toluene, molecular weight regulator, and polymerization initiator supplied to the first reaction vessel. In the second reaction vessel, the polymerization temperature was 130 °C. The polymerization conversion rate by this was 75%. Then, the polymer solution obtained in the second reaction vessel was directly devolatilized of unreacted monomers and solvents using a twin-screw extruder with a three-stage vent to obtain a styrene·acrylonitrile·2-hydroxyethyl methacrylate copolymer. The weight-average molecular weight by GPC was 192,000. Hereinafter, this styrene·acrylonitrile·2-hydroxyethyl methacrylate copolymer is referred to as "modified vinyl copolymer (R-1)".

[0084] Synthesis Example 8 (Synthesis of modified vinyl copolymer (R-2)) Two polymerization reaction vessels equipped with ribbon blades and jackets were connected, purged with nitrogen, and then a monomer-containing raw material with a ratio of 68 parts of styrene, 22 parts of acrylonitrile, 10 parts of hydroxypropyl methacrylate, and 20 parts of toluene was continuously supplied to the first reaction vessel. At the same time, a solution with a ratio of 0.24 parts of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution with a ratio of 0.1 part of 1,1′-azobis(cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator were continuously supplied, and polymerization was carried out under stirring. In the first reaction vessel, the polymerization temperature was controlled at 110 °C and the average residence time was 2.0 hours. The polymerization conversion rate was 55%. The polymer solution obtained in the first reaction vessel was continuously taken out by a pump provided outside and supplied to the second reaction vessel. The amount of the polymer solution taken out from the first reaction vessel was the same as the total amount of the supply amounts of styrene, acrylonitrile, hydroxypropyl methacrylate, toluene, molecular weight regulator, and polymerization initiator supplied to the first reaction vessel. In the second reaction vessel, the polymerization temperature was 130 °C. The polymerization conversion rate was 73%. Then, the polymer solution obtained in the second reaction vessel was directly devolatilized of unreacted monomers and solvents using a twin-screw extruder with three-stage vents to obtain a styrene·acrylonitrile·hydroxypropyl methacrylate copolymer. The weight-average molecular weight by GPC was 180,000. Hereinafter, this styrene·acrylonitrile·hydroxypropyl methacrylate copolymer is referred to as "modified vinyl copolymer (R-2)".

[0085] Synthesis Example 9 (Synthesis of modified vinyl copolymer (T-1)) Two polymerization reaction vessels with jackets equipped with ribbon blades were connected, purged with nitrogen, and then a monomer-containing raw material with a ratio of 75 parts of styrene, 20 parts of acrylonitrile, 5 parts of methacrylic acid, and 20 parts of toluene was continuously supplied to the first reaction vessel. At the same time, a solution with a ratio of 0.50 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution with a ratio of 0.1 part of 1,1′-azobis(cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator were continuously supplied, and polymerization was carried out under stirring. In the first reaction vessel, the polymerization temperature was controlled at 110 °C, and the average residence time was 2.0 hours. The polymerization conversion rate by this was 55%. The polymer solution obtained in the first reaction vessel was continuously taken out by a pump provided outside thereof and supplied to the second reaction vessel. The amount of the polymer solution taken out from the first reaction vessel was the same as the total amount of the supply amounts of styrene, acrylonitrile, methacrylic acid, toluene, molecular weight regulator, and polymerization initiator supplied to the first reaction vessel. In the second reaction vessel, the polymerization temperature was set at 130 °C. The polymerization conversion rate by this was 77%. Then, the polymer solution obtained in the second reaction vessel was directly devolatilized of unreacted monomers and solvents using a twin-screw extruder with a three-stage vent to obtain a styrene·acrylonitrile·methacrylic acid copolymer. The weight-average molecular weight by GPC was 90,000. Hereinafter, this styrene·acrylonitrile·methacrylic acid copolymer is referred to as "modified vinyl copolymer (T-1)".

[0086] Synthesis Example 10 (Synthesis of modified vinyl copolymer (T-2)) Two polymerization reaction vessels with jackets equipped with ribbon blades were connected, purged with nitrogen, and then a monomer-containing raw material in the ratio of 65 parts of methyl methacrylate, 10 parts of acrylonitrile, and 25 parts of styrene was continuously supplied to the first reaction vessel. At the same time, a solution in the ratio of 0.50 part of tert-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution in the ratio of 0.1 part of 1,1′-azobis(cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator were continuously supplied, and polymerization was carried out under stirring. In the first reaction vessel, the polymerization temperature was controlled at 110 °C and the average residence time was 2.0 hours. The polymerization conversion rate thereby was 56%. The polymer solution obtained in the first reaction vessel was continuously taken out by a pump provided outside thereof and supplied to the second reaction vessel. The amount of the polymer solution taken out from the first reaction vessel was the same as the total amount of the supply amounts of styrene, acrylonitrile, methacrylic acid, toluene, molecular weight regulator, and polymerization initiator supplied to the first reaction vessel. In the second reaction vessel, the polymerization temperature was 130 °C. The polymerization conversion rate thereby was 76%. Thereafter, the polymer solution obtained in the second reaction vessel was directly devolatilized of unreacted monomers and solvents using a twin-screw extruder with three-stage vents to obtain a methyl methacrylate·acrylonitrile·styrene copolymer. The weight average molecular weight by GPC was 86,000. Hereinafter, this methyl methacrylate·acrylonitrile·styrene copolymer is referred to as "modified vinyl copolymer (T-2)".

[0087] 2. Production and Evaluation of Thermoplastic Resin Composition Examples 1 to 11 and Comparative Examples 1 to 5 The above raw materials were used in the amounts shown in Tables 1 and 2, and melt-kneaded at a cylinder set temperature of 200 °C to 250 °C using a twin-screw extruder "TEX44αII" (model name) manufactured by Japan Steel Works, Ltd. to produce a thermoplastic resin composition. Then, the following various evaluations were carried out, and the results are also shown in Tables 1 and 2.

[0088] [Evaluation Method] 1) Content Ratio of Vinyl Cyanide Unit in Acetone-Soluble Component The thermoplastic resin composition was mixed with chloroform to dissolve all the resin components, and then reprecipitated with methanol, filtered, and the insoluble matter was recovered. Next, the obtained insoluble matter was dissolved in acetone, left standing at room temperature for 24 hours, and then centrifuged at 30,000 revolutions per minute to separate into an acetone solution in which the acetone-soluble component was dissolved and an acetone-insoluble component. Next, methanol was added to the acetone solution for reprecipitation and filtration to obtain the acetone-soluble component. Then, the acetone-soluble component and the acetone-insoluble component were vacuum-dried and weighed to determine the mass of the acetone-soluble component and the mass of the acetone-insoluble component. Thereafter, the acetone-soluble component was subjected to elemental analysis using a C.H.N.O coder "CHN CORDER MT-3" (model name) manufactured by Yanako to determine the nitrogen content (N value), and the amount of vinyl cyanide units was calculated by converting the N value. Regarding the acetone-insoluble component as well, the amount of vinyl cyanide units was determined by conversion from the nitrogen content (N value) obtained by performing elemental analysis in the same manner using a C.H.N.O coder "CHN CORDER MT-w3" (model name) manufactured by Yanako.

[0089] 2) Content ratio of the rubber polymer to the total of the resin components It was determined from the synthesis formulation of the graft copolymer, its grafting rate, and the compounding formulation of the graft copolymer and the copolymer.

[0090] 3) Melt volume rate It was measured in accordance with ISO 1133 (temperature: 220 °C, load: 98 N). The unit is "cm 3 / 10 min."

[0091] 4) Adhesion test using a deoxime-type silicone-based sealing material Each thermoplastic resin composition was injection molded to produce a flat molded product with a thickness of 2.5 mm. Then, a deoxime-type silicone-based sealing material "Sealant 45 D-Brown" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. was applied to a 20 mm × 60 mm area on the surface of this molded product, and it was cured in an atmosphere at a temperature of 23 °C and a relative humidity of 50% for 14 days. Next, in order to evaluate the adhesiveness of the cured product, that is, the sealing adhesion, the cured product of the sealing material was manually pulled in a direction of 180° with respect to the surface of the molded product. At this time, those in a state of adhesion (cohesive failure) were rated 4 points, those with slight peeling were rated 3 points, those with about 50% peeling were rated 2 points, those with slight adhesion were rated 1 point, and those with peeling were rated 0 points. This was performed 5 times for each thermoplastic resin composition, and the total score of the 5 times was shown.

[0092] 5) Charpy impact strength In accordance with ISO 179, with the thickness of the test piece being 4 mm, it was measured at room temperature. The unit is "kJ / m 2 ".

[0093] 6) Flexural modulus In accordance with ISO 178, with the thickness of the test piece being 4 mm, it was measured. The unit is "MPa".

[0094] 7) Weather resistance In order to artificially reproduce the indoor and outdoor conditions such as sunlight, temperature, humidity, and rainfall and promote the deterioration of the resin molded body to evaluate the weather resistance, using "Sunshine Super Long Life Weather Ometer WEL-6XS-HCH-B" manufactured by Suga Test Instruments Co., Ltd., a weather resistance test was carried out at 63 ± 3 °C with spraying for 1000 hours, and the color tone change (ΔE) before and after the accelerated test was measured.

[0095] 8) Molding appearance (surface gloss) To evaluate the surface gloss of the molded article, a resin molded article colored black was prepared by the following method. 100 parts of the pellets of each thermoplastic resin composition shown in Table 1 or Table 2 and 0.8 part of carbon black were mixed using a Henschel mixer, and this mixture was supplied to an extruder heated to 240°C and kneaded to obtain black pellets. Then, the black pellets were injection-molded under the conditions of a cylinder temperature of 240°C, a mold temperature of 60°C, and an injection rate of 20 g / sec to obtain a plate-shaped black molded article having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm. Next, using a digital variable-angle gloss meter "UGV-5D" (model name) manufactured by Suga Test Instruments Co., Ltd., in accordance with JIS K 7105, the reflectance (%) of light from the surface of the molded article when the incident angle and the reflection angle were both 60° was measured. A higher reflectance means better surface appearance.

[0096]

Table 1

[0097]

Table 2

[0098] From Tables 1 and 2, the following can be understood. Comparative Example 1 is an example of a thermoplastic resin composition in which the content ratio of the rubbery polymer is low outside the scope of the present invention, and the impact resistance was not sufficient. Comparative Example 2 is an example of a thermoplastic resin composition in which the content ratio of the rubbery polymer is high outside the scope of the present invention, and the moldability and the rigidity and weather resistance of the obtained molded article were not sufficient. Comparative Example 3 is an example of a thermoplastic resin composition that does not contain the modified vinyl-based copolymer (C) according to the present invention, and the sealing adhesion was not sufficient. Comparative Examples 4 and 5 are examples of thermoplastic resin compositions that do not contain the modified vinyl-based copolymer (C) according to the present invention, and instead contain modified vinyl-based copolymers (T-1) and (T-2) as other copolymers, respectively, and the sealing adhesion was not sufficient. On the one hand, Examples 1 to 11 are examples of the thermoplastic resin composition of the present invention, which are excellent in molding processability, and the obtained molded articles are excellent in sealing adhesion, impact resistance, rigidity, weather resistance, and molding appearance.

Industrial Applicability

[0099] The molded article containing the thermoplastic resin composition of the present invention is suitable as a material for adhesion, sealing, etc. using a deoxime type silicone-based sealing material.

Claims

1. (A) A graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, (B) A vinyl copolymer containing a structural unit (b1) derived from an aromatic vinyl compound and a structural unit (b2) derived from a vinyl cyanide compound, and not containing a structural unit represented by the following general formula (1), and (C) A modified vinyl copolymer containing a structural unit (c1) derived from an aromatic vinyl compound, a structural unit (c2) derived from a vinyl cyanide compound, and a structural unit (c3) represented by the following general formula (1) 【Chemical Formula 1】 (wherein, R １ is a hydrogen atom or a methyl group, and R ２ is a substituted alkyl group containing a polar group) In a thermoplastic resin composition containing, The content ratio of the rubbery polymer is 5 to 25% by mass based on the total amount of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C), A thermoplastic resin composition characterized in that the content ratio of the structural unit (c3) in the modified vinyl copolymer (C) is 1 to 20% by mass.

2. The thermoplastic resin composition according to claim 1, wherein the content ratio of the structural unit derived from the vinyl cyanide compound in the acetone-soluble component obtained by contacting with acetone is 20 to 40% by mass.

3. R in the general formula (1) representing the structural unit (c3) ２ The thermoplastic resin composition according to claim 1, wherein the number of carbon atoms of is 1 to 4.

4. The thermoplastic resin composition according to claim 1, wherein the polar group contained in the structural unit (c3) is a hydroxy group.

5. The thermoplastic resin composition according to claim 1, wherein the content ratio of the structural unit (c3) is 0.1 to 3.5% by mass based on the total amount of the graft copolymer (A), the vinyl copolymer (B), and the modified vinyl copolymer (C).

6. The plastic resin composition according to claim 1, wherein the rubbery polymer is an acrylic rubber or an ethylene-α-olefin rubber.

7. The thermoplastic resin composition according to claim 1, which is used for forming a molded article to which a deoxime-type silicone-based sealing material is applied.

8. A molded article characterized by containing the thermoplastic resin composition according to claim 1.

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