WO2019017260A1

WO2019017260A1 - Coating resin composition, and molded article

Info

Publication number: WO2019017260A1
Application number: PCT/JP2018/026225
Authority: WO
Inventors: 豪教古谷; 和也江川
Original assignee: テクノＵｍｇ株式会社
Priority date: 2017-07-18
Filing date: 2018-07-11
Publication date: 2019-01-24
Also published as: JP7017333B2; JP2019019238A

Abstract

This coating resin composition contains: (A) a rubber-reinforced vinyl resin formed from a rubber component that is derived from an ethylene·α-olefin rubber polymer, and a resin component that includes a structural unit derived from an aromatic vinyl compound; (B) a polyolefin resin; and (C) a polycarbonate resin. The content ratios of the rubber-reinforced vinyl resin (A), the polyolefin resin (B), and the polycarbonate resin (C) are 3-40 mass%, 1-20 mass%, and 40-91 mass%, respectively, with respect to a total of 100 mass% of these components.

Description

Resin composition for coating and molded article

The present invention relates to a resin composition for coating suitable for producing a base-side molded product (a molded product for coating) which is coated on the surface thereof to give a coated molded product having a good appearance.

BACKGROUND ART Molded articles made of a rubber-reinforced vinyl resin such as ABS resin are conventionally used in a wide range of fields such as vehicles, home appliances, building materials, etc. because they are excellent in impact resistance and the like. Among them, in the field of vehicles, large-sized molded articles such as spoilers were generally manufactured by the blow molding method, but application of a more productive injection molding method is being studied . On the other hand, among articles to be used outdoors, those having a coating film are required from the viewpoint of designability, weather resistance improvement, etc. In particular, the surface of a molded article obtained by the injection molding method is coated In this case, residual distortion may cause coating defects, and in large-sized molded articles, coating defects may become significant, which may lower the productivity of the coated molded articles.

Here, molding materials which give moldings suitable for coating are disclosed, for example, in the following Patent Documents 1 to 3.
Patent Document 1 discloses a thermoplastic resin composition for coating comprising (A) a polyamide resin, (B) a styrene resin and (C) an olefin resin.

In Patent Document 2, a rubber-reinforced copolymer resin [A1] obtained by polymerizing a vinyl monomer [b1] in the presence of a rubbery polymer [a], or a rubbery polymer [a] Reinforcement containing a rubber-reinforced copolymer resin [A1] obtained by polymerizing a vinyl-based monomer [b1] in the presence of (A) and a (co) polymer [A2] of a vinyl-based monomer [b2] Vinyl-based resin [A] 84.9-98.9 parts by mass, polyester resin [B] 1-8 parts by mass, and ethylene (meth) acrylate ester / carbon monoxide copolymer [C] 0.1-7 There is disclosed a resin composition for coating characterized in that it comprises 1 part by mass (provided that [A] + [B] + [C] = 100 parts by mass).

Further, Patent Document 3 contains an aromatic polycarbonate resin (A), a rubbery polymer / aromatic vinyl / vinyl cyanide copolymer (B-1), and a polyolefin resin (C). An aromatic polycarbonate resin molded article characterized in that the aromatic polycarbonate resin composition is injection molded under the conditions of an injection rate of 10 to 100 cm ³ / s and a surface progression coefficient of 40 to 200 cm ³ / s · cm. It is disclosed.

JP 2007-327011 A JP 2011-256366 A JP, 2014-184720, A

An object of the present invention is to provide a resin composition for coating which gives a molded article for coating excellent in appearance by suppressing defects such as peeling, and also, for example, injection molding which tends to generate residual strain. Even if painting is performed on a molded article (ground-side molded article) by the method, coating defects such as cracks and wales are suppressed, and a ground-side molded article giving a coated molded article having a good appearance is produced. It is an object of the present invention to provide a coating resin composition suitable for Another object of the present invention is to provide a resin composition for coating which gives a molded article for coating excellent in impact resistance and heat resistance.

The present invention is shown below.
1. (A) A rubber-reinforced vinyl resin comprising a rubbery portion derived from an ethylene / α-olefin rubber polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound, (B) a polyolefin resin, And (C) a coating resin composition containing a polycarbonate resin, wherein the content ratio of the rubber-reinforced vinyl resin (A), the polyolefin resin (B) and the polycarbonate resin (C) is the total of these. The resin composition for coating which is 3 to 40% by mass, 1 to 20% by mass and 40 to 91% by mass, respectively, based on 100% by mass.
2. The coating resin composition according to item 1, wherein the content of the rubbery portion derived from the rubber-reinforced vinyl resin (A) is 2 to 30% by mass with respect to the entire coating resin composition.
3. The rubber-reinforced vinyl-based resin further comprises a rubber-reinforced vinyl-based resin comprising a rubber-like portion derived from a diene-based rubbery polymer (D) and a resin portion containing a structural unit derived from an aromatic vinyl compound The content ratio of (D) is 0.5 to 35 parts by mass when the total of the rubber reinforced vinyl resin (A), the polyolefin resin (B) and the polycarbonate resin (C) is 100 parts by mass. The resin composition for coating according to

item

1 or 2 above.
4. The ratio of the total amount of the rubbery portion derived from the rubber reinforced vinyl resin (A) and the rubbery portion derived from the rubber reinforced vinyl resin (D) is relative to the whole of the resin composition for coating 4. The coating resin composition according to item 3, which has a weight of 2 to 35% by mass.
5. When the content ratio of the rubbery portion derived from the rubber reinforced vinyl resin (A) and the rubbery portion derived from the rubber reinforced vinyl resin (D) is 100% by mass of the total of both: 5. The resin composition for coating according to item 3 or 4, which is 15 to 90% by mass and 10 to 85% by mass, respectively.
6. The resin composition for coating according to any one of the above items 1 to 5, wherein the resin composition for coating contains at least one of a structural unit derived from a maleimide compound and a structural unit derived from α-methylstyrene object.
7. The molded article containing the resin composition for coating as described in any one of said claim | item 1 thru | or 6.
8. 8. A molded article according to item 7, wherein the molded article is an automobile part.
9. 9. A molded article according to item 8, wherein the part for automobile is a spoiler.

The resin composition for coating of the present invention gives a molded article for coating excellent in appearance by suppressing defects such as peeling. In addition, for example, after a molded article (base-side molded article) is produced by an injection molding method that tends to generate residual strain, even if painting is performed on this, the coating film has excellent adhesion and coating defects (cracks, It is suitable for the production of a base-side molded product which gives a coated molded product having a good appearance, which is suppressed, etc.).
Moreover, according to the resin composition for coating of this invention, the molded article for coating excellent in impact resistance and heat resistance can be manufactured.

Examples are test pieces used for the peeling test in [Example], (1) is a bottom view, (2) is a cross-sectional view taken along line XX in (1). It is a perspective view of the test piece used for the coating test in [Example]. FIG. 3 is a plan view (1), a side view (2) and a YY sectional view (3) of the test piece in FIG. 2; It is a figure explaining the crack formed in the coating film of the coating test piece obtained by the coating test in [Example].

Hereinafter, the present invention will be described in detail. In the present specification, “(meth) acrylic” refers to acrylic and methacrylic, “(meth) acrylate” refers to acrylate and methacrylate, and “(meth) acryloyl group” refers to acryloyl and methacryloyl groups. The (meth) allyl group means an allyl group and a methallyl group, and the "(co) polymer" means a homopolymer and a copolymer.

The resin composition for coating of the present invention comprises a rubber-reinforced vinyl comprising (A) a rubbery portion derived from an ethylene / α-olefin rubber polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound Base resin (hereinafter referred to as “component (A)”), (B) polyolefin resin (hereinafter referred to as “component (B)”), and (C) polycarbonate resin (hereinafter referred to as “component (C)”) It is a composition containing, Comprising: The content rate of the said component (A), (B), and (C) is respectively 3-40 mass% and 1-20 mass, when the sum total of these is made into 100 mass%. % And 40 to 91% by mass.
Although the resin composition for coating of the present invention essentially comprises the components (A), (B) and (C), it may further contain other thermoplastic resins and additives (all described later).

The component (A) is a rubbery weight in which a rubbery portion derived from an ethylene / α-olefin rubbery polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound are chemically bonded. It is united reinforced vinyl resin. The content ratio of the rubbery portion and the resin portion in the component (A) is not particularly limited, but preferably 45 to 90% by mass and 10 to 55% by mass, when the total of both is 100% by mass. More preferably, they are 50 to 80% by mass and 20 to 50% by mass.
The component (A) is preferably a rubbery portion obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of an ethylene / α-olefin rubbery polymer, and a resin portion And are chemically bonded graft resins.

The ethylene / α-olefin rubber polymer is a copolymer rubber comprising a structural unit derived from ethylene and a structural unit derived from α-olefin, or, in addition to these structural units, non-conjugated It is a copolymer rubber containing a structural unit derived from a diene. The ethylene unit content of the ethylene / α-olefin rubber polymer is preferably 30 to 85% by mass, more preferably 40 to 80, from the viewpoint of the appearance and impact resistance of a molded article for coating. % By mass, more preferably 45 to 75% by mass.

Examples of the α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1 -Eikosen etc. are mentioned. The number of carbon atoms of the α-olefin is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8, from the viewpoint of the appearance and impact resistance of the molded article for coating.

Examples of the non-conjugated dienes include alkenyl norbornene, cyclic dienes and aliphatic dienes.
When the ethylene / α-olefin rubber-like polymer is an ethylene / α-olefin / non-conjugated diene copolymer rubber, the upper limit of the content ratio of structural units derived from non-conjugated diene is the above ethylene / α-olefin When the total amount of structural units constituting the rubber polymer is 100% by mass, it is preferably 15% by mass, more preferably 10% by mass, still more preferably 5% by mass.

The ethylene / α-olefin rubber polymer giving the rubbery portion is preferably an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer or the like.

On the other hand, the resin part which comprises the said component (A) contains the structural unit (henceforth "a structural unit (a1)") originating in an aromatic vinyl compound. The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyl toluene, vinyl xylene, vinyl naphthalene and the like. Of these, styrene is preferred.

The said resin part may contain only 1 type of said structural unit (a1), and 2 or more types may be included. The resin portion is composed of the structural unit (a1) and a structural unit derived from another vinyl monomer other than the aromatic vinyl compound (hereinafter referred to as "structural unit (a2)"). It may be. In this case, the lower limit of the content ratio of the structural unit (a1) contained in the resin portion is preferably 60% by mass, more preferably 65, when the total amount of structural units constituting the resin portion is 100% by mass. % By mass, more preferably 70% by mass.

Examples of the other vinyl monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, and amide groups Included unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, and the like.

Examples of the above-mentioned vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like.

Examples of the (meth) acrylic acid ester compounds 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, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate.

As the above maleimide compound, maleimide, N-methyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-dodecyl maleimide, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N- (4-methyl) And phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N-benzyl maleimide, N-naphthyl maleimide, N-cyclohexyl maleimide and the like. In addition, when introduce | transducing the structural unit originating in a maleimide-type compound into a polymer chain, the method of imidating after copolymerizing maleic anhydride is applicable, for example.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, 2,3-dimethylmaleic 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.

As the amino group-containing unsaturated compound, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminomethyl acrylate, diethylaminomethyl acrylate, 2-dimethylaminoethyl acrylate, aminoethyl methacrylate, propylaminoethyl methacrylate Dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, 2-dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, p-aminostyrene, N-vinyldiethylamine, N-acetylvinylamine, acrylamine, methacrylamine, N- Methyl acryl amine etc. are mentioned.
Examples of the amide group-containing unsaturated compound include acrylamide, N-methyl acrylamide, methacrylamide, N-methyl methacrylamide and the like.

Examples of the hydroxyl group-containing unsaturated compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) A hydroxyl group such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate ( M-) acrylic acid esters; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2- Hydroki Methyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxy Methyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 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.

As the epoxy group-containing unsaturated compound, (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-oxycyclohexyl, vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, monoglycidyl maleate, diglycidyl maleate And monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allylsuccinate, diglycidyl allylsuccinate, glycidyl p-styrenecarboxylate, 2-methylpropenyl glycidyl ether, styrene-p-glycidyl ether and the like.

As the above oxazoline group-containing unsaturated compound, vinyl oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline , 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Etc.

When the said resin part contains the said structural unit (a2), only 1 type of said structural unit (a2) may be included, and 2 or more types may be included.
The structural unit (a2) preferably contains a structural unit derived from a vinyl cyanide compound or a (meth) acrylic acid ester compound, from the viewpoint of the appearance, mechanical strength and chemical resistance of a molded article for coating.

The graft ratio of the component (A), which is a graft resin, is preferably 20% or more, more preferably 30% or more, and still more preferably 35 to 65%, from the viewpoint of appearance and mechanical strength of a molded article for coating is there.
The graft ratio can be determined by the following equation.
Graft ratio (%) = {(S−T) / T} × 100
In the above formula, S is charged with 1 g of the component (A) in 20 ml of acetone, shaken with a shaker for 2 hours, and then centrifuged to separate insolubles and insolubles, thereby obtaining insolubles And T is the mass (g) of the rubbery portion derived from the ethylene / α-olefin rubbery polymer contained in 1 g of the component (A). The mass of this rubbery portion can be obtained by the method of calculating from the polymerization formulation and the polymerization conversion rate, the method of obtaining by infrared absorption spectrum (IR), or the like.

The component (A) contained in the resin composition for coating of the present invention may be only one kind or two or more kinds.

The component (B) is a polyolefin resin, preferably a non-modified (co) polymer comprising at least one structural unit derived from an α-olefin having 2 or more carbon atoms. In the present invention, a particularly preferred component (B) is a polyolefin resin comprising at least one structural unit derived from an α-olefin having 2 to 10 carbon atoms.

Examples of the above α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1 and the like. Among these, ethylene, propylene, butene-1,3-methylbutene-1 and 4-methylpentene-1 are preferable, and propylene is particularly preferable.

Examples of the component (B) include polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / butene-1 copolymer and the like. Among these, polyethylene, polypropylene and propylene / ethylene copolymer are preferable, and from the viewpoint of appearance and mechanical strength of a molded article for coating, a polypropylene resin containing 85 mass% or more of propylene units with respect to all structural units That is, polypropylene and ethylene / propylene copolymer are more preferable. Examples of the ethylene / propylene copolymer include a random copolymer, a block copolymer and the like, and a random copolymer is particularly preferable.

The component (B) may be crystalline or amorphous. Preferably, it has a crystallinity of 20% or more by X-ray diffraction at room temperature.
The molecular weight of the component (B) is not particularly limited, but from the viewpoint of the appearance and mechanical strength of a molded article for coating, the melt mass flow rate (hereinafter also referred to as "MFR") according to JIS K7210 is It is preferably 0.1 to 50 g / 10 min, more preferably 0.5 to 30 g / 10 min, and one having a molecular weight corresponding to each value is preferable.

The component (B) contained in the resin composition for coating of the present invention may be only one kind or two or more kinds.

Next, the component (C) is not particularly limited as long as it is a polycarbonate resin having a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, it may be an aliphatic carbonate containing an aromatic ring. In the present invention, aromatic polycarbonate is preferred from the viewpoints of impact resistance before coating and after coating, heat resistance and the like. In addition, even if this component (C) is terminally modified to R-CO- group or R'-O-CO- group (R and R 'both represent an organic group). Good.

As the above-mentioned aromatic polycarbonate, those obtained by transesterification (ester exchange reaction) of an aromatic dihydroxy compound and a carbonic diester by melting, those obtained by the interfacial polycondensation method using phosgene, pyridine and phosgene What was obtained by the pyridine method which used the reaction product, etc. can be used.

The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as hydroquinone, dihydroxybenzene such as resorcinol, 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter referred to as "bisphenol A"), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis p-hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-) Methylphenyl) fluorene, 4,4 '-(p-phenylenediisopropylidene) bisphenol, 4,4'-(m-phenylenediisopropylidene) bisphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxyphenyl) ) Ketone, bis (p-hydroxyphenyl) ether, bis (p-bis) Roxyphenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone And bis (p-hydroxyphenyl) sulfoxide and the like. These can be used alone or in combination of two or more.

Among the above aromatic hydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. The benzene ring may be one in which a hydrogen atom bonded to a carbon atom constituting the benzene ring is substituted by a halogen atom. Therefore, as the above compounds, bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like can be mentioned. Of these, bisphenol A is particularly preferred.

Dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, ditolyl carbonate and the like can be mentioned as a carbonic acid diester used to obtain an aromatic polycarbonate by transesterification. These can be used alone or in combination of two or more.

The average molecular weight and molecular weight distribution of the component (C) are not particularly limited as long as the composition has moldability. The molecular weight of this component (C) is preferably 10,000 to 50,000, more preferably 15,000, as a viscosity average molecular weight (Mv) converted from the solution viscosity measured at 25 ° C. using methylene chloride as a solvent. It is -30,000, more preferably 17,500-27,000.
The MFR (temperature 240 ° C., load 10 kg) of the component (C) is preferably 1 to 70 g / 10 min, more preferably 2.5 to 50 g / 10 min, still more preferably 4 to 30 g / 10 min. is there.

The component (C) contained in the resin composition for coating of the present invention may be only one kind or two or more kinds.

The content ratio of the components (A), (B) and (C) contained in the resin composition for coating of the present invention is remarkable when the effect of the present invention is remarkable, and therefore the total of these is 100 mass%. 3 to 40% by mass, 1 to 20% by mass and 40 to 91% by mass, preferably 7 to 35% by mass, 1 to 15% by mass and 50 to 87% by mass, more preferably 10 to 32% by mass %, 2 to 10% by mass and 60 to 85% by mass.

The resin composition for coating of the present invention may contain other thermoplastic resins in addition to the components (A), (B) and (C) as described above. When the other thermoplastic resin is contained, the upper limit of the content ratio is preferably 200 parts by mass, more preferably 150 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). It is a department.

As another thermoplastic resin, a rubbery polymer reinforced vinyl-based resin (hereinafter referred to as “rubber-based polymer reinforced vinyl resin comprising a rubbery portion derived from a diene-based rubbery polymer and a resin portion including a structural unit derived from an aromatic vinyl compound Component (D) "); rubbery polymer reinforced vinyl resin comprising a rubbery portion derived from an acrylic rubbery polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound; hydrogenated diene Rubbery polymer reinforced vinyl resin comprising a rubbery portion derived from a rubbery polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound; a rubbery portion derived from a silicone rubbery polymer A rubbery polymer reinforced vinyl resin comprising a resin portion containing a structural unit derived from an aromatic vinyl compound; one or two or more kinds of a structural unit derived from an aromatic vinyl compound ( ) Polymers (excluding the above components (A) and (D)); Structural units derived from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acids Structural units derived from at least one selected from an anhydride, a carboxyl group-containing unsaturated compound, an amino group-containing unsaturated compound, an amide group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound and an oxazoline group-containing unsaturated compound Aromatic vinyl-containing copolymers (excluding the above components (A) and (D), hereinafter referred to as "component (E)"); modified polyolefin resins; polyamide resins; polyester resins; polyvinyl chloride resins; Polyvinylidene chloride resin; fluorine resin etc. may be mentioned. Among these, components (D) and (E) are preferred.

The component (D) is a rubbery polymer-reinforced vinyl polymer in which a rubbery portion derived from a diene rubbery polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound are chemically bonded. It is a resin. The content ratio of the rubbery portion and the resin portion in the component (D) is not particularly limited, but preferably 45 to 95% by mass and 5 to 55% by mass, when the total of both is 100% by mass. More preferably, they are 50 to 80% by mass and 20 to 50% by mass.
The component (D) is preferably prepared by polymerizing a vinyl-based monomer containing an aromatic vinyl compound in the presence of a diene-based rubber-like polymer, and the rubber-like portion and the resin portion are chemically Is a graft resin bonded to The grafting rate in this component (D) can be the same grafting rate as the above-mentioned component (A).

Examples of the diene-based rubbery polymer giving the rubbery portion constituting the above component (D) include homopolymers such as polybutadiene, polyisoprene and polychloroprene; styrene / butadiene copolymer, styrene / butadiene / styrene copolymer Styrene / butadiene copolymer rubbers such as acrylonitrile / butadiene copolymer, acrylonitrile / styrene / butadiene copolymer, etc .; styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer Examples thereof include styrene / isoprene copolymer rubbers such as coalescence. These copolymers may be block copolymers or random copolymers.

Although the resin part which comprises the said component (D) will not be specifically limited if it is a thing containing the structural unit originating in an aromatic vinyl compound, The structure illustrated as a resin part which comprises the said component (A) is applied be able to.

When the resin composition for coating of the present invention contains the component (D), the content ratio of the component (D) is determined from the above-mentioned components (A), (B) and When the total of (C) is 100 parts by mass, it is preferably 0.5 to 30 parts by mass, and more preferably 1 to 25 parts by mass. Preferably, it is 3 to 20 parts by mass.

The component (E) is a structural unit derived from an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound, a maleimide compound, an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, an amino group A copolymer comprising at least one structural unit derived from at least one selected from an unsaturated compound having an amide group, an unsaturated compound having an amido group, an unsaturated compound having a hydroxyl group and an unsaturated compound having an oxazoline group, and a copolymer of acrylonitrile and styrene Combination, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, acrylonitrile / α-methylstyrene / methyl methacrylate copolymer, acrylonitrile・ Styrene ・ N-phenyl Reimido copolymer, styrene-methyl methacrylate copolymer, a styrene-N-phenylmaleimide copolymer, styrene-maleic anhydride-N-phenylmaleimide copolymer, and the like.

When the resin composition for coating of the present invention contains the component (E), the content ratio of the component (E) is the above component (A), (E) from the viewpoint of the appearance and mechanical strength of the molded article for coating When the total of B) and (C) is 100 parts by mass, it is preferably 10 to 150 parts by mass, more preferably 20 to 120 parts by mass. Preferably, it is 25 to 70 parts by mass.

The resin composition for coating of the present invention may be derived from any of the above resin components, but at least one of a structural unit derived from a maleimide compound and a structural unit derived from α-methylstyrene It is preferable to include. In particular, when the component (E) contains these structural units, a molded article having excellent heat resistance can be obtained, and deformation or the like occurs indoors or in a car where a high temperature environment is obtained or outdoors where the temperature is high. Can be suppressed.

The resin composition for coating of the present invention may contain an additive as described above. As this additive, fillers, plasticizers, antioxidants, UV absorbers, anti-aging agents, flame retardants, stabilizers, weathering agents, light stabilizers, heat stabilizers, antistatic agents, water repellents, water repellents Oil agents, antibacterial agents, preservatives, coloring agents (pigments, dyes, etc.) and the like can be mentioned.

The resin composition for coating of the present invention can be manufactured by kneading the raw material components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders, etc. it can. The set temperature of the apparatus at the time of kneading is selected depending on the type, amount and the like of the raw material components, and is usually 220 ° C. to 270 ° C. The method of using the raw material components is not particularly limited, and the respective components may be mixed together and kneaded, or may be divided and mixed in multiple stages and mixed.

The molded article of the present invention is characterized by containing a resin composition for coating. The molded article of the present invention comprises a resin composition for coating, injection molding method, injection compression molding method, press molding method, extrusion molding method, coextrusion molding method, sheet extrusion molding method, profile extrusion molding method, vacuum molding method, It can manufacture by using for conventional, well-known shaping | molding methods, such as a blow molding method, a compression molding method, a cast molding method, and a roll-forming method. The resin composition for coating of the present invention is suitable for an injection molding method which has high productivity and tends to generate residual strain when it is formed into a large-sized molded product.

Since the molded article of the present invention has high compatibility with the components (A), (B) and (C) which are essential components, defects such as peeling are suppressed, and the shape stability and appearance of the molded article are excellent. Furthermore, it is excellent in impact resistance and heat resistance. Therefore, when the molded article of the present invention is used as a base-side molded article for coating and the surface thereof is coated, a coated molded article excellent in the adhesion of the coating film and the coating appearance can be obtained.

The method for coating the molded article of the present invention is not particularly limited, and conventionally known coating methods such as spray coating, electrostatic coating, powder coating, electrodeposition coating and the like can be applied. The paint used for coating is also not particularly limited, and may be either a liquid paint or a powder paint, preferably a liquid paint, and particularly preferably an oil paint. Moreover, as a base resin, acrylic resin, phenol resin, alkyd resin, amino alkyd resin, vinyl chloride resin, silicone resin, fluorine resin, unsaturated resin, epoxy resin, polyurethane resin, melamine resin, acrylic urethane resin, acrylic melamine resin And polyester melamine resins.
The thickness of the coating film in the resulting coated molded product depends on the type of paint and the like, but is usually 10 to 100 μm from the viewpoint of coating appearance.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples unless the gist of the present invention is exceeded. In the following, parts and% are based on mass unless otherwise specified.

1. Raw Material Components The raw materials used in Examples 1 to 16 and Comparative Examples 1 to 9 are as follows. In addition, the measurement of the graft ratio was performed according to the method of the said description.

1-1. Raw material (P)
The raw material (P) has an ethylene unit content of 63%, a propylene unit content of 32%, a dicyclopentadiene unit content of 5%, and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 33 in a toluene solvent. A rubbery polymer reinforced resin obtained by polymerizing styrene and acrylonitrile in the presence of an ethylene / propylene / dicyclopentadiene copolymer rubber, which is an ethylene / α-olefin rubber corresponding to the component (A) It is a mixed resin composed of a polymer-reinforced vinyl resin and an acrylonitrile / styrene copolymer corresponding to another thermoplastic resin.
The graft ratio of ethylene / α-olefin rubber polymer reinforced vinyl resin is 60%, the content of ethylene / propylene / dicyclopentadiene copolymer rubber contained in rubber polymer reinforced resin is 30%, acrylonitrile unit The amount was 24.5%, and the styrene unit amount was 45.5%. The ungrafted acrylonitrile-styrene copolymer (acetone-soluble component) contains 35% and 65% of acrylonitrile units and styrene units, respectively, and has an intrinsic viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) ) Is 0.4 dl / g.

1-2. Raw material (Q)
The raw material (Q) is a polypropylene resin corresponding to the component (B).
(Q-1) is polypropylene “Novatec FY4” (trade name) manufactured by Japan Polypropylene Corporation, and the MFR (temperature 190 ° C., load 2.16 kg) is 5.0 g / 10 min.
(Q-2) is polypropylene “Novatech FY6C” (trade name) manufactured by Japan Polypropylene Corporation, and MFR (temperature 190 ° C., load 2.16 kg) is 2.4 g / 10 min.

1-3. Raw material (R)
The raw material (R) is a polycarbonate resin corresponding to the component (C), and a polycarbonate "NOVAREX 7022PJ" (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. The viscosity average molecular weight (Mv) is 18,700, and the MFR (temperature 240 ° C., load 10 kg) is 7.7 g / 10 min.

1-4. Raw material (S)
The raw material (S) corresponds to another thermoplastic resin.
(S-1) is a rubber polymer reinforced resin obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber having a gel fraction of 86% and an average particle diameter of 290 nm, and corresponds to the component (D) It is a mixed resin comprising a diene rubber polymer reinforced vinyl resin and an acrylonitrile / styrene copolymer (ungrafted copolymer).
The graft ratio in diene rubber polymer reinforced vinyl resin is 53%, the content of polybutadiene rubber contained in rubber polymer reinforced resin is 60%, the amount of acrylonitrile unit is 10%, the amount of styrene unit is 30% there were. The ungrafted acrylonitrile-styrene copolymer (acetone-soluble component) contains acrylonitrile units and styrene units at 25% and 75%, respectively, and has an intrinsic viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) ) Is 0.37 dl / g. The weight average molecular weight (in terms of polystyrene) is 77000.

(S-2) is an acrylonitrile-styrene copolymer containing acrylonitrile units and styrene units at 23.5% and 76.5%, respectively, and having a weight average molecular weight (in terms of polystyrene) of 78,000. The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is 0.42 dl / g.
(S-3) contains acrylonitrile unit, styrene unit and phenyl maleimide unit at 9%, 51% and 40%, respectively, and has a weight average molecular weight (in terms of polystyrene) of 124,000. It is a copolymer.

1-5. Raw material (T)
Raw material (T) is an additive.
(T-1) is a stabilizer, manufactured by Sumitomo Chemical Co., Ltd. 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl Acrylate "Sumilyzer GS" (trade name).
(T-2) is an antioxidant and is tris (2,4-di-tert-butylphenyl) phosphite “ADEKA STAB 2112” (trade name) manufactured by ADEKA Corporation.

2. Production and Evaluation of Coating Resin Composition Examples 1 to 16 and Comparative Examples 1 to 9
After the raw materials (P), (Q), (R), (S) and (T) are mixed by the Henschel mixer in the proportions described in Tables 1 to 3, this mixture is The mixture was supplied to a shaft extruder "TEX 44 α II" (model name) and melt-kneaded (cylinder set temperature: 220 ° C. to 270 ° C.) to obtain pellets composed of a thermoplastic resin composition. Then, the melt mass flow rate was measured under the conditions of a temperature of 240 ° C. and a load of 98 N according to ISO 1133 using this pellet, and evaluation of fluidity (molding processability) was performed. In addition, the pellet was subjected to injection molding, a test piece for evaluation was prepared, and was subjected to the following evaluation. The results are shown in Tables 1 to 3.

2-1. Impact Resistance In accordance with ISO 179, Charpy impact strength was measured under conditions of temperatures of 23 ° C and -30 ° C.
2-2. Heat resistance In accordance with ISO 75, the heat distortion temperature was measured under a load of 1.80 MPa.

2-3. Molded Appearance A plate-shaped test piece having a convex portion 2 using a gate was obtained using an injection molding machine “α-150” (model name) manufactured by FANUC. The resin temperature at the time of injection molding was 260 ° C., the mold temperature was 50 ° C., and the injection speed was 80 mm / s.
Subsequently, cuts 3 (cut length: 2 mm) were inserted at two positions on the left and right of the convex portion 2 of the plate-like test piece to obtain a test piece 1 shown in FIG. The dimensions in the figure are as follows. L = 150 mm, W = 70 mm, T = 3 mm, L ₁ = 45 mm, L ₀ = 6 mm, W ₁ = 3 mm, T ₀ = 2 mm. Then, the convex portion 2 is pinched by pliers and pulled in the direction indicated by the arrow in FIG. 1 (2), and at that time, it is observed whether or not peeling occurs on the surface of the test piece 1 did.

<Evaluation of molding appearance>
◎: Peeling did not occur in the vicinity of the convex portion 2
Good: Peeling occurred from the convex portion 2 toward the main body of the test piece. The peeling length was 2 mm or less from the root of the convex portion 2.
Fair: Peeling occurred from the convex portion 2 toward the main body of the test piece. The peeling length was 2 mm or more from the root of the

convex portion

2 and 5 mm or less.
X: Peeling occurred from the convex portion 2 toward the main body of the test piece. The peeling length exceeded 5 mm from the root of the convex portion 2.

2-4. Paintability Evaluation A test piece 5 shown in FIG. 2 and FIG. 3 was obtained using an injection molding machine “α-150” (type name) manufactured by FANUC. The resin temperature at the time of injection molding was 260 ° C., the mold temperature was 50 ° C., and the injection speed was 20 mm / s. Then, according to the following procedure, a test piece (painting test piece) for paintability evaluation is produced, and the presence or absence of the occurrence of paint defects (cracks indicated by symbol 7 in FIG. 4) is visually observed, and the following evaluation criteria The paintability was judged based on.
(1) Condition Control Condition control was performed by leaving the test piece 5 shown in FIG. 2 in a thermostat controlled at 23 ° C. for 12 hours or more.
(2) Coating Spraying of a paint for coating comprising 80 parts of an acrylic resin base paint, 85 parts of a thinner for synthetic resin paint, and 10 parts of a curing agent on the surface indicated by symbol P of the test piece 5 shown in FIGS. The paint was applied (film thickness: 20 to 30 μm) and left at 23 ° C. for 5 minutes.
(3) Drying Thereafter, it was dried at 80 ° C. for 30 minutes to obtain a coated test piece.

<Evaluation of paintability>
◎: no crack was generated on the surface of the coated test piece.
○: A crack less than 5 mm in length was generated on the surface of the coated test piece.
Fair: A crack of 5 mm or more and less than 10 mm in length was generated on the surface of the coated test piece.
X: A crack of 10 mm or more in length was generated on the surface of the coated test piece.

The following can be understood from Tables 1 to 3.
The comparative example 1 is an example using the resin composition for coating which does not contain component (A) and (B), and was inferior to paintability. The comparative example 2 is an example using the resin composition for coating which does not contain a component (A), and was inferior to shaping | molding external appearance property and paintability. Comparative Example 3 is an example in which the content ratio of the component (A) is outside the range of the present invention (too little) and the content ratio of the component (C) is outside the range of the present invention (too much). And it was inferior to paintability. Comparative Example 4 is an example in which the content ratio of the component (A) is out of the range of the present invention (excessive), and the paintability was inferior. The comparative example 5 is an example using the resin composition for coating which does not contain a component (B), and was inferior to paintability. Comparative Example 6 is an example in which the content ratio of the component (B) is outside the range of the present invention (too little), and the paintability was inferior. Comparative Example 7 was an example in which the content ratio of the component (B) was out of the range of the present invention (excessive), and was inferior in molding appearance and paintability. The comparative example 8 is an example in which the content ratio of the component (A) is outside the range of the present invention (excessive) and the content ratio of the component (C) is outside the range of the invention (too low). And it was inferior to heat resistance. Comparative Example 9 was an example in which the content ratio of the component (C) was outside the range of the present invention (excessive), and was inferior in molding appearance and paintability.
On the other hand, Examples 1 to 16 were all excellent in impact resistance, heat resistance, molding appearance and paintability.

Molded articles obtained by the resin composition for paints according to the present invention have applications requiring impact resistance, heat resistance, molding appearance, paintability, etc. For example, glazing such as window members for vehicles, bonnets, pillars, trunk lids , Vehicle exterior parts such as canopy, spoiler and trim, cup holders, vehicle interior parts such as bezel of vehicle equipment and instrument panel, (mobile) phone, smart phone, PDA, (portable) DVD player, (portable) personal computer, (Portable type) game consoles, (portable type) touch panels, enclosures and parts of electric and electronic devices such as cameras, OA related parts such as printers and copiers, lighting equipment parts, signboards, display boards, window frames, sash, It is suitable for building material parts, such as a decorative board, etc.

1: Test specimen for evaluation of molded appearance, 2: convex, 3: cut, 5: test specimen for evaluation of paintability, 7: crack, P: coated surface

Claims

(A) A rubber-reinforced vinyl resin comprising a rubbery portion derived from an ethylene / α-olefin rubber polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound,
(B) Polyolefin resin,
as well as,
(C) A coating resin composition containing a polycarbonate resin,
The content ratio of the rubber-reinforced vinyl resin (A), the polyolefin resin (B) and the polycarbonate resin (C) is 3 to 40% by mass and 1 to 10%, respectively, when the total of these is 100% by mass. Resin composition for coating which is 20% by mass and 40 to 91% by mass.
The coating resin composition according to claim 1, wherein a content ratio of the rubbery portion derived from the rubber-reinforced vinyl resin (A) is 2 to 30% by mass with respect to the whole of the coating resin composition.
And (D) a rubber-reinforced vinyl resin comprising a rubbery portion derived from a diene rubber-like polymer and a resin portion containing a structural unit derived from an aromatic vinyl compound,
When the content ratio of the rubber-reinforced vinyl resin (D) is 100 parts by mass of the total of the rubber-reinforced vinyl resin (A), the polyolefin resin (B) and the polycarbonate resin (C), 0. The resin composition for coating according to claim 1 or 2, which is 5 to 35 parts by mass.
The ratio of the total amount of the rubbery portion derived from the rubber reinforced vinyl resin (A) and the rubbery portion derived from the rubber reinforced vinyl resin (D) is relative to the entire resin composition for coating The resin composition for coating according to claim 3, which is 2 to 35% by mass.
When the content ratio of the rubbery portion derived from the rubber reinforced vinyl resin (A) and the rubbery portion derived from the rubber reinforced vinyl resin (D) is 100% by mass of the total of both 5. The resin composition for coating according to claim 3, which is 15 to 90% by mass and 10 to 85% by mass, respectively.
The resin composition for coating according to any one of claims 1 to 5, wherein the coating resin composition contains at least one of a structural unit derived from a maleimide compound and a structural unit derived from α-methylstyrene. object.
The molded article containing the resin composition for coating as described in any one of Claims 1 thru | or 6.
The molded article according to claim 7, wherein the molded article is an automobile part.
9. The molded article according to claim 8, wherein the automotive part is a spoiler.