JP2003128869A - Resin composition for acrylic cap stock - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for cap stock, which has high weather resistance, color retention, impact strength and hardness and which is excellent in workability, and heat resistance. SOLUTION: The resin composition for cap stock comprises (A) a block copolymer containing (a) a methacrylic polymer block in an amount of 5 to 95% by weight and (b) an acrylic polymer block in an amount of 95 to 5% by weight. To the resin composition, a graft copolymer or other thermoplastic resin can be further added. The block copolymer (A) can be obtained by atomic transfer radical polymerization.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The object of the present invention is to provide a resin composition for a capstock, which has weather resistance, high color retention, high impact strength, high hardness, as well as good workability and heat resistance. Especially.

[0002]

BACKGROUND OF THE INVENTION The present invention is a capstock.
ck) and for other uses. These compositions are especially extruded into articles, and polyvinyl chloride resins (PV
It is useful for structural composites such as C) to make composite materials. The invention also relates to the composite material produced thereby.

PVC has a combination of properties that makes it particularly suitable for use as a structural material. In applications where the impact strength of structural plastics is important, PVC can be compounded with impact modifier resins that improve the impact strength of the resulting resin composition. Such high impact strength PVC compositions are easily extruded or otherwise formed into a variety of articles including superior impact strength, toughness and other desirable mechanical and chemical properties. , For example,
Industrial profile for building siding, shutters, windows and door frames
e), a system for transporting rainwater, for example trenches and troughs, and fences. However, such PVC compositions have relatively poor weatherability, especially in darker grade colors such as brown and blue. Color is imparted to the PVC composition, for example by the use of colorants such as pigments or dyes, but exposure to sunlight changes the color in an unattractive manner. Such unattractive changes are more significant in dark colors than in light colors. Poor weather resistance also causes a drop in impact strength, leading to brittleness and cracking and / or mechanical failure of articles made from such compositions. Therefore, there is a need to improve the weather resistance of such materials. One remedy is to mix stabilizing additives such as UV absorbers, heat stabilizers and titanium dioxide into the PVC composition. However, the resulting weather resistance improvement is more important than the industry-wide standard (Vi
nyl Siding Institute, Janua
ry1999, adopted in ASTM D3679 work instructions). Another attempted remedy is to apply other resinous materials onto PVC to provide a surface that can withstand sunlight and other environmental conditions. Such surface material is called capstock. The capstock is generally thinner than the base plastic, typically about 10 to about 25% of the total composite (ie, capstock and base) plastic thickness.
Is. A suitable capstock material must have processing properties, hardness, and a specific combination of other physical, chemical, and aesthetic properties, including excellent color retention, high impact strength and excellent weatherability. I have to. Moreover, capstocks must not adversely affect their properties which make PVC such a widely used building material.

Various types of polymer-based compositions have been disclosed for use as capstock, including PVC-based compositions and acrylic resin-based compositions. Many of these polymer-based compositions are disclosed in EP-A-473379, the disclosure of which is incorporated herein by reference for its teaching of resin compositions for capstocks. This publication discloses a resin composition for a capstock containing a blend of PVC resin and an acrylic copolymer, which results in poor weatherability due to the presence of PVC in the capstock. On the other hand, as a resin composition for a capstock that can provide weather resistance, high color retention, and high impact strength,
There is a composition obtained by blending an acrylic polymer as disclosed in U.S. Pat. No. 5,318,737 with an impact resistance improving resin containing an acrylate as a main component, which is generally called a core shell. These have a low impact strength with a small amount of core-shell polymer consisting of a multilayer structure, and when a large amount of core-shell polymer is added to increase the impact strength, they do not exhibit the necessary mechanical properties and hardness, or the fluidity during melting. Lowers the workability, and distortion occurs during working, resulting in lower heat resistance (warpage of the sheet at high temperatures). Therefore,
In order to solve these problems, the present invention is directed to a methacrylic polymer block (a) and an acrylic polymer block (b).
Block copolymer (A) containing 5 to 95% by weight of a methacrylic polymer block (a) and 95 to 5% by weight of an acrylic polymer block (b). Provided is a resin composition for a capstock, which comprises (A).

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for capstock which has weather resistance, high color retention, high impact strength, high hardness, and good workability and heat resistance. To provide.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention comprise a block copolymer (A) containing a methacrylic polymer block (a) and an acrylic polymer block (b),
5 to 95% by weight of the methacrylic polymer block (a)
And 95 to 5% by weight of the acrylic polymer block (b)
A resin composition for a capstock characterized by containing a block copolymer (A)
The inventors have found that they have high impact strength, high hardness, and good workability and heat resistance, and have completed the present invention.

That is, the present invention is for a capstock containing a block copolymer (A) comprising 5 to 95% by weight of a methacrylic polymer block (a) and 95 to 5% by weight of an acrylic polymer block (b). A resin composition (claim 1) and a graft polymer (B) are further contained, and the resin composition for capstock (claim 2) according to claim 1 and a thermoplastic resin (C) are further contained. The resin composition for a capstock according to claim 1 or 2, wherein the graft copolymer (B) is
Is a core-shell particle type graft copolymer containing an inner layer portion (core portion) made of a polymer component having a glass transition temperature of less than 25 ° C. and an outer layer portion (shell portion) made of a polymer component having a glass transition temperature of 25 ° C. or more. The resin composition for a capstock according to claim 1, 2 or 3 (claim 4), wherein the thermoplastic resin (C) is a free polymer composed of an acrylic ester and a methacrylic ester. The resin composition for a capstock according to claim 1, 2, 3 or 4 (claim 5) and the block copolymer (A) are produced by atom transfer radical polymerization. The resin composition for a capstock according to 2, 3, 4 or 5 (claim 6), the block copolymer (A) is the methacrylic polymer block (a) 20.
˜50 wt% and acrylic polymer block (b) 80
% To 50% by weight,
The resin composition for a capstock according to 3, 4, 5 or 6 (claim 7), wherein the block copolymer (A) comprises 50 to 75% by weight of a methacrylic polymer block (a) and an acrylic polymer block. (B) 50 to 25% by weight of the resin composition for a capstock according to claim 1, 2, 3, 4, 5 or 6 (claim 8), of the block copolymer (A). The methacrylic polymer block contains methyl methacrylate as a main component, and the acrylic polymer block contains butyl acrylate as a main component. A resin composition for a capstock according to the above (claim 9) and claim 1,
The present invention relates to a synthetic resin composite material (claim 10) comprising a capstock layer containing the resin composition for capstock according to 2, 3, 4, 5, 6, 7, 8 or 9.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (A) containing a methacrylic polymer block and an acrylic polymer block which can be used in the present invention is an ab type diblock copolymer, a- b-a type triblock copolymer, b-
It is at least one type of block copolymer selected from an ab type triblock copolymer and an (ab) n type multiblock copolymer. Among these, from the viewpoints of processability of the resin composition for capstock and impact resistance and mechanical properties of the molded resin composition for capstock, an a-b-a type triblock copolymer, (a-b) ) N-type multiblock copolymers or mixtures thereof are preferred,
A -ba type triblock copolymer is more preferable.

The structure of the block copolymer (A) is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer is properly selected according to the required properties such as moldability, processing properties, mechanical properties and the like of the resin composition for a capstock.

The number average molecular weight of the block copolymer (A) is not particularly limited, but is preferably 30,000 to 500,000, and more preferably 50,000 to 400,000. If the number average molecular weight is small, the viscosity is low, and if the number average molecular weight is large, the viscosity tends to be high, and therefore the viscosity is set according to the required processing characteristics. The molecular weight is measured in terms of polystyrene by gel permeation chromatography (GPC) using a polystyrene gel column with chloroform as the mobile phase.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the block copolymer (A) measured by GPC.
The ratio (Mw / Mn) is also not particularly limited, but is preferably 1.8 or less. If Mw / Mn exceeds 1.8, the homogeneity of the block copolymer is deteriorated, and the impact resistance, mechanical properties, hardness, etc. of the resin composition for capstock tend to be deteriorated.

The methacrylic polymer block (a) constituting the block copolymer (A) comprises 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. Consists of. Examples of the methacrylic acid ester constituting (a) include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate. , Methacrylic acid-tert-butyl, methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, methacrylic acid cyclohexyl, methacrylic acid-n-heptyl, methacrylic acid-n-octyl, methacrylic acid- 2-Ethylhexyl, Nonyl Methacrylate, Decyl Methacrylate, Dodecyl Methacrylate, Phenyl Methacrylate, Toluyl Methacrylate, Benzyl Methacrylate, Isobornyl Methacrylate, 2-Methoxyethyl Methacrylate, Methacrylic Acid-3-methoxybutyl, methacrylic acid-2-hi Droxyethyl, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid Acid-2-perfluoroethylethyl, methacrylic acid-
2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl-2 -Perfluoroethylmethyl, methacrylic acid-
2-perfluorohexylethyl, methacrylic acid-2-
Examples thereof include perfluorodecylethyl and methacrylic acid-2-perfluorohexadecylethyl. These may be used alone or in combinations of two or more. Among these, methyl methacrylate is preferable in terms of availability.

Examples of the vinyl monomer copolymerizable with the methacrylic acid ester constituting (a) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, acrylate- n-butyl, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, acrylate- 2-ethylhexyl,
Nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, acrylic acid
-2-methoxyethyl, acrylic acid-3-methoxybutyl,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxy Methylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutyl acrylate Ethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, Ak Le acid 2 perfluorodecyl ethyl, acrylate esters such as acrylic acid-2-perfluoroalkyl-hexadecyl ethyl; styrene, alpha-
Aromatic alkenyl compounds such as methylstyrene, p-methylstyrene and p-methoxystyrene; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Conjugated diene compounds such as butadiene and isoprene; halogen-containing unsaturated compounds such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane Compound;
Unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid; vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl ester compounds such as vinyl and vinyl cinnamate; various maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. Examples include vinyl monomers. These may be used alone or in combinations of two or more. As these vinyl-based monomers, preferred ones can be selected according to the processability of the resin composition for capstock, the required mechanical properties and the like.

The glass transition temperature of (a) is 25 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher. If the glass transition temperature is lower than 25 ° C., the processability, hardness, heat resistance and the like of the resin composition for capstock tend to be low.

The acrylic polymer block (b) constituting the block copolymer (A) comprises 50 to 100% by weight of an acrylic ester and 0 to 50% by weight of a vinyl monomer copolymerizable therewith. Is preferable from the viewpoint of the moldability of the film and the processability of the clothing laminate.

Examples of the acrylate ester constituting (b) include methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, acrylic acid- t-Butyl, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate , Dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, acrylate-2- Hydroxypropyl, stearyl acrylate, glycidyl acrylate , 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic acid-2 -Trifluoromethylethyl, acrylic acid-2-perfluoroethylethyl, acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, acrylic acid 2-perfluoroethyl, acrylic acid perfluoromethyl, acrylic acid diper Fluoromethylmethyl, acrylate-2-perfluoromethyl-2-perfluoroethylmethyl, acrylate-2-perfluorohexylethyl, acrylate-2-perfluorodecylethyl, acrylate-2-perfluorohexadecylethyl And so on. These may be used alone or in combinations of two or more. Among these, impact resistance of the molded resin composition for capstock, mechanical properties, flexibility,
From the viewpoint of easy availability, -n-butyl acrylate is preferable.

Examples of the vinyl monomer copolymerizable with the acrylic ester which constitutes the component (b) include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate,
Methacrylic acid-n-hexyl, cyclohexylmethacrylate, methacrylic acid-n-heptyl, methacrylic acid
-n-octyl, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, methacrylic acid Acid-2-methoxyethyl,
Methacrylic acid-3-methoxybutyl, methacrylic acid-
2-hydroxyethyl, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ-
(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, methacrylic acid-2-trifluoromethylethyl, methacrylic acid Acid-2-perfluoroethylethyl, methacrylic acid 2
-Perfluoroethyl-2-perfluorobutylethyl,
Methacrylic acid-2-perfluoroethyl, methacrylic acid perfluoromethyl, methacrylic acid diperfluoromethylmethyl, methacrylic acid-2-perfluoromethyl
-Methacrylic acid ester such as 2-perfluoroethylmethyl, methacrylic acid-2-perfluorohexylethyl, methacrylic acid-2-perfluorodecylethyl, methacrylic acid-2-perfluorohexadecylethyl; styrene, α-methylstyrene, p-methylstyrene, p-
Aromatic alkenyl compounds such as methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Halogen-containing unsaturated compounds; Silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid, and Unsaturated dicarboxylic acid compounds such as dialkyl esters; vinyl acetate,
Vinyl ester compounds such as vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,
Examples thereof include various vinyl-based monomers such as maleimide-based compounds such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. These may be used alone or in combinations of two or more. As these vinyl monomers, preferred ones can be selected depending on the glass transition temperature required for the block (b). The glass transition temperature of (b) is preferably 25 ° C or lower, more preferably 0 ° C or lower, and further preferably -20 ° C or lower. When the glass transition temperature is higher than 25 ° C, the impact resistance, mechanical properties, flexibility and the like of the molded resin composition for capstock tend to be lowered.

The method for producing the block copolymer (A) is not particularly limited, but controlled polymerization is preferably used. Examples of the controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and living radical polymerization recently developed, and living radical polymerization is preferable from the viewpoint of controlling the molecular weight and structure of the block copolymer.

Living radical polymerization is a radical polymerization in which the activity at the polymerization end is maintained without loss. In a narrow sense, living polymerization indicates polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the activated one is in an equilibrium state. . The definition in the present invention is also the latter. Living radical polymerization has been actively studied in various groups in recent years. Examples thereof include those using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc. 1994, 1).
16, 7943) or a radical scavenger such as a nitroxide compound (Macromolecules,
1994, 27, 7228), an atom transfer radical polymerization using an organic halide as an initiator and a transition metal complex as a catalyst (Atom Transfer Radical Po
lymerization: ATRP) and the like. In the present invention, which of these methods is used is not particularly limited, but atom transfer radical polymerization is preferable from the viewpoint of easy control.

Atom transfer radical polymerization is carried out by using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having an element of Group 8, 9, 10 or 11 of the periodic table as a central metal as a catalyst. To be done. (For example,
Matyjaszewski et al. Am. Chem.
Soc. 1995, 117, 5614, Macromo
leules 1995, 28, 7901, Scie
nce 1996, 272, 866, or Sawa
moto et al., Macromolecules 1995,
28, 1721). According to these methods, the polymerization rate is generally very high, and although the polymerization is a radical polymerization in which a termination reaction such as coupling between radicals is likely to occur, the polymerization proceeds in a living manner and has a narrow molecular weight distribution, Mw / M.
A polymer having n of about 1.1 to 1.5 is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In the atom transfer radical polymerization method, as the organic halide or sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These may be used properly according to the purpose, but in the case of producing a diblock copolymer, a monofunctional compound is preferable, and an ab-a type triblock copolymer or a b-a-b type triblock copolymer is preferable. When manufacturing a triblock copolymer, it is preferable to use a bifunctional compound, and when manufacturing a branched block copolymer, it is preferable to use a polyfunctional compound.

Examples of the monofunctional compound include compounds represented by the formula: C ₆ H ₅ -CH ₂ X, C ₆ H ₅ -C (H) (X) -CH ₃ , C ₆ H ₅ -C (X) (CH ₃ ) ₂ , R ¹ -C (H) (X) -COOR ² , R ¹ -C (CH ₃ ) (X) -COOR ² , R ¹ -C (H) (X) -CO-R ² , R during _{^{1 -C (CH 3) (X}} ) -CO-R 2, R 1 -C 6 H 4 -SO 2 X ( wherein, C ₆ H ₄ is a phenylene group (ortho-substituted, meta-substituted, any para-substituted R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms.
Or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine, or iodine. R ² represents a monovalent organic group having 1 to 20 carbon atoms. ) And the like.

Examples of the bifunctional compound include compounds of the formula: X-CH ₂ -C ₆ H ₄ -CH ₂ -X, X-CH (CH ₃ ) -C ₆ H ₄ -CH (CH ₃ ) -X, _{X-C (CH 3) 2} -C 6 H 4 -C (CH 3) 2 -X, X-CH (COOR 3) - (CH 2) n -CH (COOR 3) -
_{X, X-C (CH 3} ) (COOR 3) - (CH 2) n -C (CH 3)
^{(COOR 3) -X, X-} CH (COR 3) - (CH 2) n -CH (COR 3) -X, X-C (CH 3) (COR 3) - (CH 2) n -C (CH ₃ )
^{(COR 3) -X, X-} CH 2 -CO-CH 2 -X, X-CH (CH 3) -CO-CH (CH 3) -X, X-C (CH 3) 2 -CO-C ( _{CH 3) 2 -X, X-} CH (C 6 H 5) -CO-CH (C 6 H 5) -X, X-CH 2 -COO- (CH 2) n -OCO-CH 2 -X, X _{-CH (CH 3) -COO- (CH} 2) n -OCO-CH (C
_{H 3) -X, X-C} (CH 3) 2 -COO- (CH 2) n -OCO-C (C
_{H 3) 2 -X, X-} CH 2 -CO-CO-CH 2 -X, X-CH (CH 3) -CO-CO-CH (CH 3) -X, X-C (CH 3) 2 - _{CO-CO-C (CH 3} ) 2 -X, X-CH 2 -COO-C 6 H 4 -OCO-CH 2 -X, X-CH (CH 3) -COO-C 6 H 4 -OCO-CH (C
_{H 3) -X, X-C} (CH 3) 2 -COO-C 6 H 4 -OCO-C (CH 3) 2 -
_{X, X-SO 2 -C 6} H 4 -SO 2 -X ( wherein, R ³ is an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
~ 20 aryl group or a C7-20 aralkyl group. C ₆ H ₄ represents a phenylene group (which may be ortho-substituted, meta-substituted or para-substituted). C ₆ H ₅ represents a phenyl group. n represents an integer of 0 to 20. X is chlorine,
Represents bromine or iodine. ) And the like.

Examples of the polyfunctional compound include compounds represented by the formula: C ₆ H _3- (CH ₂ -X) ₃ , C ₆ H _3- (CH (CH ₃ ) -X) ₃ , C ₆ H _3- (C (CH ₃ ) ₂ -X) ₃ , C ₆ H _3- (OCO-CH ₂ -X) ₃ , C ₆ H _3- (OCO-CH (CH ₃ ) -X) ₃ , C ₆ H _3- (OCO _{-C (CH 3) 2 -X)} 3, C 6 H 3 - (SO 2 -X) 3 ( wherein, C ₆ H ₃ is the position of the trisubstituted phenyl group (the substituent is 1
It may be any of the 6th to 6th positions). X is chlorine, bromine,
Or represents iodine. ) And the like.

If an organic halide having a functional group other than the one that initiates the polymerization or a sulfonyl halide compound is used, a polymer having a functional group introduced at the terminal can be easily obtained. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group and a silyl group.

In the organic halide or sulfonyl halide compound which can be used as the initiator, the carbon to which the halogen is bonded is bonded to the carbonyl group or the phenyl group, and the carbon-halogen bond is activated. Polymerization begins. The amount of the initiator used may be determined from the ratio with the monomer in accordance with the required molecular weight of the block copolymer. That is, the molecular weight of the block copolymer can be controlled depending on the number of molecules of the monomer used per one molecule of the initiator.

The transition metal complex used as a catalyst for the atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zero valent copper, divalent ruthenium, divalent iron and divalent nickel. The complex of is mentioned. Among these, a copper complex is more preferable in terms of cost and reaction control.

As the monovalent copper compound, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,
Examples include cuprous oxide and cuprous perchlorate. When using a copper compound, in order to increase the catalytic activity 2,2'-
Bipyridyl and its derivative, 1,10-phenanthroline and its derivative, polyamine such as tetramethylethylenetriamine (TMEDA), pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine may be added as a ligand. Also, 2
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst.
When using a ruthenium compound as a catalyst, you may add aluminum alkoxide as an activator.
Further, divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistriphenylphosphine complex (NiCl ₂ (PP
h ₃ ) ₂ ) and a bivalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) are also preferable as the catalyst. The amounts of the catalyst, the ligand and the activator used are not particularly limited, but may be appropriately determined depending on the relationship between the amount of the initiator, the monomer and the solvent used and the required reaction rate.

The atom transfer radical polymerization can be carried out without solvent (bulk polymerization) or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ester solvents such as ethyl acetate, butyl acetate; ethylene Examples thereof include carbonate solvents such as carbonate and propylene carbonate. These may be used alone or in combination of two or more. As described above, when the polymerization is carried out without a solvent, bulk polymerization is performed. On the other hand, when a solvent is used, the amount to be used may be appropriately determined from the relationship between the viscosity of the entire system and the required stirring efficiency (that is, reaction rate).

The above-mentioned polymerization can be carried out at room temperature to 200 ° C, preferably 50 to 150 ° C. In order to produce a block copolymer by the above-mentioned polymerization, a method of sequentially adding monomers, a method of polymerizing the next block by using a pre-synthesized polymer as a polymer initiator, and a reaction of separately polymerized polymers The method of combining by etc. is mentioned. These methods may be selectively used according to the purpose, but from the viewpoint of simplicity of the production process, the method of sequentially adding the monomers is preferable.

The methacrylic polymer block (a) constituting the block copolymer (A) used in the present invention
The composition ratio of the acrylic polymer block (b) and the acrylic polymer block (b) is not particularly limited, but it is preferable that the block (a) is 5 to 95% by weight and the block (b) is 95 to 5% by weight. It is preferable in terms of the balance of impact resistance, mechanical properties, hardness, workability, etc., and more preferably (a) 20 to 7
5% by weight and (b) 80 to 25% by weight. If the proportion of (a) is less than 5% by weight, the processability, surface hardness, etc. of the resin composition for capstock tend to decrease,
If the proportion of (b) is less than 10% by weight, the impact resistance of the resin composition for capstock tends to decrease. However, the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the block copolymer (A) used in the present invention is, in a specific case, a resin for capstock. It is preferable to set the composition ratio according to the desired physical properties such as the processability of the composition, the secondary processability of the molded resin composition for capstock, and the required mechanical properties. Although the scope of the invention is not limited thereto, for example, a composition obtained by blending an acrylic polymer as described in U.S. Pat. No. 5,318,737 with a core-shell particle type graft copolymer containing acrylate as a main component has high impact resistance. Alternatively, when the processability is improved by improving the fluidity at the time of melting without lowering the surface hardness and mechanical properties, the methacrylic polymer block (a) is 20 to 50% by weight, It is preferable to use the block copolymer (A) containing 80 to 50% by weight of the acrylic polymer block (b). In this case, the content of the block copolymer (A) is preferably 1 to 80% by weight, more preferably 1 to 60% by weight, in terms of surface hardness, based on the weight of the entire resin composition for capstock. , And more preferably 1 to 40% by weight.

Further, when the fluidity during melting is higher and the ease of handling during processing is required, the methacrylic polymer block (a) is 50 to 75% by weight, and the acrylic polymer is It is preferable to use the block copolymer (A) in which the block (b) is 50 to 25% by weight. Further, in this case, when higher impact resistance and surface hardness are required, the graft copolymer and the thermoplastic resin can be appropriately added to the capstock resin composition. In this case, the content of the block copolymer (A) is
From the viewpoint of impact resistance, 40 to 100% by weight is preferable, based on the total weight of the resin composition for capstock, and 4
0 to 90% by weight is more preferable, and 40 is more preferable.
~ 80% by weight. The resin composition for capstock of the present invention may further contain at least one graft polymer (B).

Graft polymer (B) used in the present invention
The form of is a comb-shaped graft copolymer containing a trunk composed of the component (c) and a branch composed of the component (d), and a comb-shaped graft containing a branch composed of the component (c) and a trunk composed of the component (d). Core-shell particle type graft copolymer containing a copolymer, an inner layer portion (core portion) composed of the component (c) and an outer layer portion (shell portion) composed of the component (d), 2
A core-shell particle type graft copolymer containing an inner layer portion (core portion) composed of the component (c) and an outer layer portion (shell portion) composed of the component (d), the inner layer portion forming a salami structure, A three-layer particle type graft copolymer comprising a central part composed of the component c), an intermediate layer part composed of the component (c) different from the component constituting the central part, and an outer layer part composed of the component (d), (d). A three-layer particle type graft copolymer containing a central part composed of the component, an intermediate layer part composed of the component (c) and an outer layer part composed of the component (d), which may be the same as or different from the component composing the central part. Polymer, a plurality of particles composed of component (c) (unit particles are composed of one kind or two or more kinds of component (c), and each particle may be the same or different) are aggregated And the inner layer part (core part) that constitutes one particle And (d) an outer layer portion consisting of components such as aggregating and enlarging system shell particles type graft copolymer containing (shell portion) thereof. These are a block copolymer (A) and a thermoplastic resin (C) to be combined.
The block copolymer (A) is used depending on the properties of
Further, the core-shell particle type graft copolymer is preferable because the dispersed particle diameter after mixing with the thermoplastic resin (C) is easily controlled and the impact resistance is easily improved. When the graft polymer (B) is a core-shell particle type graft polymer, a polymer component (c) having a glass transition temperature of less than 25 ° C and a polymer component (d) having a glass transition temperature of 25 ° C or more. It is preferable that it is a graft polymer containing a. The component (c) plays a role of improving impact resistance,
The component (d) has a role of improving the dispersibility in the block copolymer (A) and the thermoplastic resin (C). The glass transition temperature of the component (c) constituting the graft copolymer (B) is lower than 25 ° C, preferably 0 ° C or lower, and more preferably -20 ° C or lower.
When the glass transition temperature of the component (c) is 25 ° C. or higher, the effect of improving impact resistance tends to be low. The glass transition temperature of the component (d) constituting the graft copolymer (B) is 25 ° C. or higher, preferably 40 ° C. or lower, and more preferably 50 ° C. or lower. When the glass transition temperature of the component (c) is less than 25 ° C., the dispersibility in the block copolymer (A) and the thermoplastic resin (C) and the interfacial adhesion are lowered, and further, the resin composition for a capstock is The surface hardness tends to decrease.

The glass transition temperature (Tg) of the polymer can be set by setting the weight ratio of the monomers in each polymer portion according to the following Fox equation. The glass transition temperature (Tg) can be measured by DSC (differential scanning calorimetry) or tanδ peak of dynamic viscoelasticity. 1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... +
(Wm / Tgm) W1 + W2 + ... + Wm = 1 [wherein Tg represents the glass transition temperature of the polymer portion, and Tg1, Tg2, ..., Tgm represent the glass transition temperature of each polymerized monomer. Also, W1, W
2, ..., Wm represent the weight ratio of each polymerized monomer. When the graft copolymer (B) is a particle-type graft copolymer, the average particle diameter thereof is 0.05 to 30 μm, preferably 0.05 to 25 μm. If the average particle size is less than 0.05 μm, the effect of improving impact resistance tends to be insufficient, and if it exceeds 30 μm, the effect of improving impact resistance tends to be insufficient.

When the graft copolymer (B) is a particle type graft copolymer, the gel content is 20 to 10
It is 0% by weight, preferably 40 to 100% by weight, and more preferably 70 to 100% by weight. If the gel content is less than 20% by weight, the impact resistance improving effect and processability tend to be insufficient. The ratio of the component (c) to the component (d) in the graft copolymer (B) is not particularly limited, but the ratio of the component (c) to the component (c) is 30 based on the total weight of the graft copolymer (B). ~ 95% by weight,
The component (d) is preferably 5 to 70% by weight,
Component (c) is 40 to 90% by weight, component (d) is 10 to 6
It is more preferably 0% by weight. If the component (d) is less than 5% by weight, dispersion tends to be insufficient when mixed with the block copolymer (A) and the thermoplastic resin (C), and if it exceeds 70% by weight, impact resistance is increased. The imparting effect tends to decrease. The graft efficiency of the components (c) and (d) in the graft copolymer (B) is not particularly limited, but is preferably 25% by weight or more,
It is more preferably 50% by weight or more. If the grafting efficiency is less than 25% by weight, the dispersion tends to be insufficient when mixed with the block copolymer (A) and the thermoplastic resin (C). The component (c) constituting the graft copolymer (B) is not particularly limited as long as it is a polymer component having a glass transition temperature of less than 25 ° C., but a vinyl monomer and /
Alternatively, a polymer obtained by polymerizing an organosiloxane-based monomer is preferable.

The vinyl monomer is a compound which undergoes addition polymerization to form a vinyl polymer, and specific examples thereof include ethylene, propylene, n-butene, isobutylene, n-hexene and n-octene. Olefin: Acrylic acid ester such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Methacrylic acid esters such as benzyl methacrylate and isobornyl methacrylate; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene and vinyltoluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; butadiene and isoprene Examples of the conjugated diene compound include a halogen-containing unsaturated compound such as vinyl chloride and vinylidene chloride. These may be used alone or in combination of two or more. Of these, n-butyl acrylate, butadiene, styrene / butadiene, and isobutylene are preferred because they are general-purpose, inexpensive, and easy to handle, and more preferably n-butyl acrylate from the viewpoint of weather resistance.

The above-mentioned organosiloxane monomer is a compound which becomes a siloxane polymer by condensation polymerization or ring-opening polymerization, and specific examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethyl. Cyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octaethylcyclotetrasiloxane, dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, Examples thereof include diphenyldimethoxysilane, and these may be used alone or in combination of two or more kinds. Of these, octamethylcyclotetrasiloxane is preferable because it is versatile, inexpensive, and easy to handle.

The component (c) constituting the graft copolymer (B) used in the present invention may contain a cross-linking agent described below and / or a moiety derived from a graft crossing agent.

The content of the crosslinking agent and / or the portion derived from the graft crossing agent in the component (c) is 0 to 20%, more preferably 0 to 10% of the portion derived from the crosslinking agent. 0 to 20% of the part derived from
It is preferably 10% from the viewpoint of the balance between impact resistance improving effect and workability.

The cross-linking agent is a compound having a plurality of functional groups in one molecule, and the reactivity of the plurality of functional groups is the same. The graft crossing agent is a compound having a plurality of functional groups in one molecule. And a compound having different reactivity of a plurality of functional groups. The cross-linking agent is used for the purpose of forming cross-linking in the same polymer component, and the graft crossing agent is used for forming cross-linking between different polymer components. In some cases, cross-linking may occur between different polymer components, and in other cases, the graft crossing agent may cause cross-linking in the same polymer component.

When a vinyl monomer is used as the crosslinking agent, for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,
Examples thereof include bifunctional vinyl compounds such as 3-butylene glycol dimethacrylate, 1,4-butylene dimethacrylate and divinylbenzene, and trifunctional vinyl compounds such as triallyl cyanurate and triallyl isocyanurate. If you use the body,
Examples thereof include trifunctional silane compounds such as trimethoxymethylsilane and triethoxyphenylsilane; tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. These may be used alone or in combination of two or more. These crosslinkers are
A preferable one can be selected depending on the kind of the polymer to be crosslinked.

Examples of the graft crossing agent include vinyl compounds such as allyl methacrylate and allyl acrylate when vinyl monomers are used, and β-type compounds when organosiloxane monomers are used. Methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxy Methylsilane, γ-methacryloyloxypropyltriethoxysilane, δ-methacryloyloxybutyldiethoxymethylsilane, γ-acryloyloxypropyl dimethyl Carboxymethyl silane, .gamma.
(Meth) acryl-functional silane compounds such as acryloyloxypropyltrimethoxysilane; such as vinyltrimethoxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyldimethoxymethylsilane Ethylene functional silane compounds; mercapto functional silane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane. These may be used alone or in combination of two or more. As these graft crossing agents, preferred ones can be selected depending on the kind of the polymer desired to form a crosslinkage.

The component (d) constituting the graft copolymer (B) is not particularly limited as long as it is a polymer component having a glass transition temperature of 25 ° C. or higher, but it is formed by polymerizing a vinyl monomer. Vinyl polymers are preferred.

Examples of such vinyl monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate; methyl methacrylate, ethyl. Methacrylic acid esters such as methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate; aromatic alkenyl compounds such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene; acrylonitrile, methacrylic acid. Vinyl cyanide compounds such as ronitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride Which compounds such as halogen-containing unsaturated compounds. These may be used alone or in combination of two or more. As these vinyl-based monomers, preferred ones can be selected depending on the combination with the block copolymer (A) and the thermoplastic resin (C). Of these, n-butyl acrylate, methyl methacrylate, styrene, and acrylonitrile are preferred because they are versatile, inexpensive, and easy to handle, and more preferred are methyl methacrylate from the viewpoint of weather resistance.

Blocked by using at least one vinyl monomer selected from the above-mentioned acrylic acid ester, methacrylic acid ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound and halogen-containing unsaturated compound. It exhibits the effect of improving dispersibility in the copolymer (A) and various thermoplastic resins (C) and interfacial adhesion.

The method for producing the graft copolymer (B) is not particularly limited, but polymerization in an emulsion system using an aqueous dispersion medium and an emulsifier is preferable because the production cost is low and the heat of reaction is easily removed. .

When the radical-polymerizable vinyl-based monomer is used as the component (c), ordinary emulsion radical polymerization can be applied, and when the vinyl-based monomer having poor radical-polymerizable property is used, the cationic polymerization, A method of emulsifying and dispersing a prepolymer obtained by ionic polymerization such as anionic polymerization and coordination polymerization in an aqueous dispersion medium can be applied. When an organosiloxane-based monomer is used as the component (c), the organosiloxane-based monomer is emulsified and dispersed in an aqueous dispersion medium to obtain an acid,
A method of conducting condensation polymerization or ring-opening polymerization in the presence of a catalyst such as a base or an organometallic compound can be applied. Further, in the case of producing a particle-type graft copolymer containing a plurality of polymer components in the same particle, a method of uniformly mixing the respective monomer components in advance and then emulsifying and dispersing the reaction, a single weight A method of additional polymerization (seed polymerization) of other components to seed particles composed of coalescing components, mixing particles composed of a single polymer component, and adding an acid such as hydrochloric acid or a salt such as sodium sulfate to agglomerate It can be produced using a method of enlarging. At this time, the morphology (phase structure) inside the obtained particles can be controlled by the production method, the ratio of each component, the reaction sequence, and the like.

To graft-polymerize the component (d),
A method in which a vinyl monomer is added to the emulsion dispersion (latex) of the component (c) in one step or in multiple steps and polymerization is carried out by a radical polymerization technique can be applied.

The emulsion dispersion (latex) of the graft copolymer (B) obtained by the above-mentioned production method can be used by separating and recovering the graft copolymer (B) by salting out.

Specific examples of the graft copolymer (B) include Kaneace FM series (Kanefuchi Chemical Co., Ltd.), Metabrene S-2001 (Mitsubishi Rayon Co., Ltd.), Dura Strength (Elf Atchem Co., Ltd.), K
M334 (made by Rohm and Haas), Blendex (made by General Electric), and the like are available as industrial products.

The graft polymer (B) can be further added in an amount of 0 to 100 parts by weight with respect to the block polymer (A). The total weight of the capstock resin composition need not add up to 100. Addition of other ingredients follows this gravimetric fractionation protocol.

The capstock resin composition of the present invention may further contain at least one thermoplastic resin (C).

The thermoplastic resin (C) is selected from the group consisting of polyacrylic resins, polyvinyl chloride resins, polyethylene resins, polypropylene resins, cyclic olefin copolymer resins, aromatic alkenyl compounds and vinyl cyanide compounds. 70 to 100% by weight of at least one vinyl-based monomer and other vinyl-based monomer copolymerizable with these vinyl-based monomers, such as ethylene, propylene, vinyl acetate and / or butadiene, isoprene Homopolymers or copolymers obtained by polymerizing 0 to 30% by weight of diene-based monomers such as, polystyrene resin, polyphenylene ether resin, mixture of polystyrene resin and polyphenylene ether resin, polycarbonate resin, polyester resin, Polycarbonate resin and polys Resin mixtures, polyamide resins, polyacetal resins, polyphenylene sulfide resins, polysulfone resins, polyimide resins, polyetherimide resins, polyetherketone resins, polyetheretherketone resins, polyamideimide resins and polyarylate resins. Is alone or 2
A mixture of two or more species can be used. In the present invention, the thermoplastic resin is not limited to these, and various thermoplastic resins can be widely used. Among these, a polyacrylic resin and a polyvinyl chloride resin are excellent in compatibility with the block copolymer (A) and the graft polymer (B) used in the present invention and can easily obtain high impact resistance. , Polymethylmethacrylate resin, acrylonitrile-styrene copolymer resin, methylmethacrylate-styrene copolymer resin, polycarbonate resin, polyester resin and polyamide resin are preferable, and polyacrylic resin is more preferable in terms of weather resistance. preferable.

Examples of the acrylic resin include polymethacrylic acid ester, polyacrylic acid ester, methacrylic acid ester-acrylic acid ester copolymer, methacrylic acid ester-methacrylic acid copolymer, methacrylic acid ester-maleic anhydride. Copolymer, methacrylic acid ester-styrene copolymer, methacrylic acid ester-
Examples thereof include, but are not limited to, styrene-substituted maleimide copolymers and methacrylic acid ester-substituted maleimide copolymers. These may be used alone or in combination of two or more. Among these, compatibility with the block copolymer (A) and the graft polymer (B) used in the present invention, and mechanical properties when combined with the block copolymer (A) and the graft polymer (B) Although it may be selected depending on the conditions, polymethacrylic acid ester and methacrylic acid ester-acrylic acid ester copolymer are preferable from the viewpoint of availability and ease of polymerization. From the viewpoint of availability and ease of polymerization, polymethyl methacrylate is preferable as the polymethacrylic acid ester, and as the methacrylic acid ester-acrylic acid ester copolymer, a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms- Acrylic acid alkyl ester copolymers are preferred.

As a specific example of the acrylic resin, acrylite (manufactured by Silo Co., Ltd.) is available as an industrial product.

The thermoplastic resin (C) can be further added in an amount of 0 to 100 parts by weight with respect to the block polymer (A). As in the case where the graft polymer (B) was added, the total weight of the resin composition for capstock was 10 in total.
It doesn't need to be zero. Addition of other ingredients follows this gravimetric fractionation protocol.

The polymer composition constituting the resin composition for a capstock of the present invention is, if necessary, a block copolymer (A) or a graft polymer with the block copolymer (A) as long as the effect of the present invention is not impaired. In addition to (B) or it and the thermoplastic resin (C), other polymers, stabilizers, matting agents, plasticizers, lubricants, flame retardants, pigments, fillers, release agents, antistatic agents, antibacterial and antibacterial agents. A mold agent or the like may be added. Specifically, styrene-butadiene rubber (SBR), butadiene rubber (B
R), isoprene rubber (IR), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, butyl rubber (IIR), urethane Rubber, silicone rubber, polysulfide rubber, hydrogenated nitrile rubber, fluororubber, tetrafluoroethylene-propylene rubber, tetrafluoroethylene-propylene-vinylidene fluoride rubber, acrylic rubber (ACM), chlorosulfonated polyethylene rubber, epi Chlorohydrin rubber (CO), ethylene-acrylic rubber, norbornene rubber, styrene-based thermoplastic elastomer (SBC), olefin-based thermoplastic elastomer (TPO), urethane-based thermoplastic elastomer (TPU), polyester-based thermoplastic elastomer (TPEE), polyamide-based thermoplastic elastomer (TPAE), 1,2-polybutadiene-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer (TPVC), fluorine-based thermoplastic elastomer, or other synthetic rubber or thermoplastic elastomer; triphenylphos Stabilizers such as phyto, hindered phenol, dibutyltin maleate; paraffin oil, polybutene oil, light oil, spindle oil, machine oil, linseed oil, sesame oil, castor oil, camellia oil, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, Plasticizers such as tricresyl phosphate; lubricants such as polyethylene wax, polypropylene wax, montanic acid type wax; triphenyl phosphate, tricresyl phosphate, decabromobiphenyl Decabromobiphenyl ether, flame retardants such as antimony trioxide; titanium oxide, zinc sulfide, pigments such as zinc oxide; glass fibers,
Examples include fillers such as metal fibers, potassium whisker titanate, asbestos, wollastonite, mica, talc, calcium carbonate, glass flakes, milled fibers and metal powders. Although not particularly limited, it is preferable to include a UV light stabilizer, a pigment, a matting agent, and an external lubricant from the above in view of the required characteristics of the capstock.

In the above case, the UV light stabilizer is 0 to
5, preferably 0.1-3, most preferably 0.2-2
It may further include parts by weight. "Plastics
Additives and Modifiers Ha
ndbook, Ch. 16 Environmenta
I Protective Agents ", J. Am. Ede
nbaum, Ed. , Van Nostrand (19
92) pp. 208-271 describes a number of suitable UV light stabilizers, a description of which is incorporated herein by reference. Preferred UV light stabilizers are compounds of HALS-, benzotriazole- and benzophenone-type. These compounds further improve the weatherability of the capstock composition. Many of such compounds are Ciba Specialty Chem
icals (Tarrytown, New York)
Commercially available under the trade name TINUVIN.

Further, in the above case, the pigment may be preferably contained in an amount of 0 to 20 parts by weight, more preferably 2 to 10 parts by weight. "Plastics Addit
ives and Modifiers Handboo
k, Section VIII, Colorant
s ", J. Edenbaum, Ed. , Van Nos
land (1992) pp. A number of suitable pigments are described in 884-954, the disclosure of various pigments useful for coloring plastics is referenced herein. For example, it includes organic and inorganic pigments, the preferred ones of which are resistant to UV and visible light exposure, such as titanium dioxide (white), clay (beige) and slate blue pigments (blue). ).

Further, in the above case, a matting agent may be contained in an amount of 0 to 15 parts by weight. Suitable matting agents include relatively large organic and inorganic particles (eg, glass, ceramics and polymers) used to modify light scattering properties within plastic resins. Many inorganic and polymeric matting agents for acrylics are disclosed in US Pat. No. 5,346,954, the disclosure of which is useful herein for matting agents useful in blending with acrylics.

Further, in the above-mentioned case, an external lubricant such as a lubricant such as polyethylene wax, polypropylene wax or montanic acid wax can be contained in an amount of 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, which is preferable. Polyethylene wax is used for this.

When the resin composition for a capstock of the present invention is composed of a polymer composition, the method of blending and manufacturing the polymer composition is not particularly limited, and a Banbury mixer, a roll mill, a twin-screw extruder are used. It is possible to use an existing method such as a method of mechanically mixing and shaping into pellets using a known device such as. The temperature at the time of kneading may be adjusted according to the melting temperature of the block copolymer (A) used or the graft polymer (B) or the thermoplastic resin (C) and the like, for example, 130 to 300.
It can be produced by melt-kneading at ℃. The ideal operating temperature for melt-kneading is preferably a temperature at which the resin composition for capstock can be effectively processed and the appearance of low gloss can be produced while maintaining the impact strength, and the processing temperature is lower. Preferably.

For the production of capstock, it is optimal to form the melt to a thickness of 0.1 to 1.0 mm, which is suitable for building PVC products (eg PVC siding, window frames, fences). , Decks and gutters) are useful as protective layers. For molding the capstock, the polymer composition can be molded by any molding method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, injection molding,
From the viewpoints of manufacturing processability, cost, etc., it is preferable to mold the capstock by an extrusion molding method. The extrusion molding can be performed by melt-extruding from a die having a desired shape and size such as a T die or a ring die and cooling. It is also possible to stretch in the uniaxial or biaxial direction simultaneously with the extrusion or after the extrusion.

The capstock and substrate can be prepared by various methods, such as by heating them in contact under pressure, by using a suitable adhesive, or by coextruding the capstock and substrate. , Can be combined. When utilizing the coextrusion method, the capstock and substrate are compatible or miscible with each other and a strong interfacial adhesion between these two layers is achieved without the additional use of an adhesive tie layer. , Should be achieved. The term "compatibility" is used to describe good interfacial adhesion between the constituent polymers, while the term "miscibility" is used to describe exhibiting a monolayer behaviour. . These terms are well known to those skilled in the art and are
si) et al .: “Polymer-polymer miscibility (Po
polymer-Polymer Miscibilit
y) ”, Academic Press, NY, 1979. Lamination of the capstock and substrate is
Generally, in the polymer processing industry, it is preferable from the viewpoint of workability that it is formed by a layered multilayer flow, which is called coextrusion. In this case, known flat-sheet forming dies are provided, where the various layers are assembled.

In the present invention, although not particularly limited, a typical capstock can have a thickness of 0.1 to 1.0 mm, while structural plastics can be 0.8 to 1.2 mm for PVC siding. Thickness for PVC profiles (eg window frames, fences, decks and gutters) can be from 1.2 to 3.0 mm. If the capstock and substrate are very thick, the articles made from them will be very costly, and if they are very thin, they tend to lack strength.

The substrate layer can also be formed by extrusion of a thermoplastic resin. The thermoplastic resin can be any known extrudable thermoplastic resin, an example of which is disclosed in US Pat. No. 5,318,737, the disclosure of which is related to the extrudable resin and extrusion process herein. Referenced.

Among the preferred extrudable thermoplastics which are particularly useful for making architectural products, but which require protection with a capstock layer for weatherability and physical impact resistance, , PVC, chlorinated polyvinyl chloride (CPVC), high impact polystyrene (HI
PS), polypropylene (PP) and acrylonitrile-butadiene-styrene (ABS). The extrudable thermoplastic capstock and the substrate layer adhere to each other and are delaminated in the composite material.
on) is preferred. Adhesion is a selection of resins that are compatible and / or miscible with each other (eg, polymethylmethacrylate-based resins and chlorinated resins).
Can be promoted through. Various known methods are included to improve the adhesion between the composite substrate and the capstock layer, such as surface treatment with an adhesion promoter (ie corona discharge) and / or application of an adhesive.

When the capstock of the present invention is bonded to the substrate by an adhesive, any known adhesive may be used as long as the capstock is suitable for bonding to the substrate of the selected type. May be. Although not particularly limited, examples of the adhesive include JP-A-60-12.
Polyester resin-based water-based dispersants disclosed in JP-A-233233, epoxy-based adhesives disclosed in JP-A-63-12233, and heavy resins having various functional groups disclosed in JP-A-61-149341. Examples include coalescing.

The synthetic resin composite material may have a base layer of extrudable thermoplastic resin and a capstock layer of a capstock composition according to an embodiment of the present invention. The composite material can be formed, for example, by laminating preformed sheet or film PVC structural plastics and capstock together by heat melting or gluing.

[0070]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In the following description, the abbreviation BA represents butyl acrylate and MMA represents methyl methacrylate.

Production Example 1 (MMA-BA Block Copolymer) The following procedure was performed to obtain an MMA-BA-MMA type block copolymer (A). After replacing the inside of the polymerization vessel of a 5-liter separable flask with nitrogen, copper bromide 1 was added.
1.4 g (79.3 mmol) was weighed out, and 100 mL of acetonitrile (dried with molecular sieves and then bubbled with nitrogen) was added. After heating and stirring at 70 ° C. for 5 minutes, the mixture was cooled to room temperature again, and initiator 5.7 g (15.9 mmol) of diethyl 2,5-dibromoadipate, BA 4
47.0 g (500.0 ml) was added. The mixture was heated and stirred at 80 ° C., and 1.7 ml of the ligand diethylenetriamine (7.
(9 mmol) was added to initiate polymerization. About 0.2 ml of the polymerization solution for sampling was sampled from the polymerization solution at regular intervals after the initiation of the polymerization, and the conversion rate of butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine from time to time. When the conversion rate of BA exceeds 90%, MMA
1333.2 g (1424.3 ml), copper chloride 7.8 g
(79.3 mmol), diethylenetriamine 1.7 m
l (7.9 mmol), toluene (after drying with molecular sieves and bubbling nitrogen) 1424.3 ml
Was added. Similarly, the conversion rate of MMA was determined. B
The conversion ratio of A and MMA is the composition ratio (for example, B
To obtain a polymer of A / MMA = 40/60 (wt%), 1500 ml of toluene was added and reacted in a water bath so that if the BA addition rate was 100%, the MMA addition rate was 50%). The reactor was cooled to complete the reaction. The polymerization solution was always green during the reaction. The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate the polymer, and the obtained polymer was vacuum dried at 60 ° C. for 24 hours,
The block copolymer used in the following Examples 1-2 was obtained.

Production Example 2 (MMA-BA Block Copolymer) The following procedure was performed to obtain an MMA-BA-MMA type block copolymer (A). After replacing the inside of the polymerization vessel of a 5-liter separable flask with nitrogen, copper bromide 1 was added.
1.3 g (78.5 mmol) was weighed out, and 180 ml of acetonitrile (dried with molecular sieves and then bubbled with nitrogen) was added thereto. After heating and stirring at 70 ° C. for 5 minutes, the mixture was cooled to room temperature again, and 5.7 g (15.7 mmol) of diethyl 2,5-dibromoadipate as an initiator and 804.6 g (900.0 ml) of butyl acrylate were added. . The mixture was heated and stirred at 80 ° C., and 1.6 ml (7.9 mmol) of the ligand diethylenetriamine was added to initiate polymerization. About 0.2 ml of the polymerization solution for sampling was sampled from the polymerization solution at regular intervals after the initiation of the polymerization, and the conversion rate of butyl acrylate was determined by gas chromatogram analysis of the sampling solution. The polymerization rate was controlled by adding triamine from time to time. When the conversion of butyl acrylate is 95%, 345.7 g of methyl methacrylate
(369.3 ml), copper chloride 7.8 g (78.5 mmol), diethylenetriamine 1.6 ml (7.9 mmol), and toluene (dried with molecular sieves and then nitrogen bubbling) 1107.9 ml were added. Similarly, the conversion rate of methyl methacrylate was determined. When the conversion rate of methyl methacrylate was 85% and the conversion rate of butyl acrylate was 98%, 1500 ml of toluene was added,
The reaction was terminated by cooling the reactor with a water bath.

The polymerization solution was green throughout the reaction. The copper complex was removed by filtering the reaction solution through activated alumina. The obtained filtrate was added to a large amount of methanol to precipitate the polymer, and the obtained polymer was vacuum dried at 60 ° C. for 24 hours to obtain a block copolymer used in Example 3 below.

(Molecular weight / molecular weight distribution) GPC using polystyrene gel column with chloroform as mobile phase
The measurement was performed to determine the polystyrene-equivalent molecular weight.

(Composition ratio of BA and MMA (% by weight)) ¹ H-
The weight fractions of polybutyl acrylate and methyl polymethacrylate in the block copolymer were confirmed by NMR.

Example 1 1.0 part by weight of TINUVIN 234 (manufactured by Ciba-Geigy Co., Ltd.) as a stabilizer and 100 parts by weight of acrylic block manufactured in Manufacturing Example 1 and polyethylene wax (PED191 (manufactured by Clariant Japan Co., Ltd.) )
0.2 parts were blended and mechanically mixed using a twin screw extruder,
It was shaped into pellets. Shaped pellets with a twin-screw extruder and T-die to a thickness of 0.15 mm and 1.0 m
m sheets were obtained. Impact strength, hardness of the obtained composition,
Tensile properties, fluidity and heat resistance were examined according to the following methods. The results are shown in Table 1.

(Impact strength) ASTM-D3029, D5
According to the method described in 420, it was measured at 23 ° C. using a Gardner tester. The measurement was performed using a sheet having a thickness of 1 mm.

(Hardness) The surface hardness of the sheet is determined by ASTM-D.
According to the method described in 2240, it was measured at 23 ° C. using a type D durometer hardness tester. Measurement is 1m
This was done using a m-thick sheet.

(Fluidity) Melt flow rate (MFR) was measured using shaped pellets by applying the method described in JIS K7210. The measurement was performed at 230 ° C. and a load of 3.8 kg.

Example 2 30 parts by weight of FM-10 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) as an impact resistance improver and 70% by weight of TINUVIN 234 as a stabilizer were added to 70 parts by weight of the acrylic block body prepared in Production Example 1.
(Ciba Geigy Co., Ltd.) 1.0 part and polyethylene wax (PED191 (Clariant Japan Co., Ltd.) 0.2 part as a lubricant were mixed, mechanically mixed using a twin-screw extruder, and shaped into pellets. Thickness of shaped pellets is 0.15mm using a twin-screw extruder and T-die.
And a 1.0 mm sheet was obtained. The impact strength, hardness, tensile properties, fluidity, and heat resistance of the obtained composition were measured in Example 1
I went the same way. The results are shown in Table 1.

Example 3 With respect to 10 parts by weight of the acrylic block body produced in Production Example 1, a methacrylic resin (M30, manufactured by Silo Co., Ltd.) was used.
25 parts by weight FM-10 (Kanefuchi Chemical Co., Ltd.) 65 parts by weight as an impact resistance improver, and tinuvin 2 as a stabilizer.
34 (manufactured by Ciba Geigy Co., Ltd.) and 0.2 part of polyethylene wax (PED191 (manufactured by Clariant Japan Co., Ltd.) as a lubricant are mixed and mechanically mixed using a twin-screw extruder, and shaped into pellets The shaped pellets were made to have a thickness of 0.15 using a twin-screw extruder and a T-die.
mm and 1.0 mm sheets were obtained. The impact strength, hardness, tensile properties, fluidity and heat resistance of the obtained composition were the same as in Example 1. The results are shown in Table 1.

Comparative Example 1 To 25 parts by weight of a methacrylic resin (M30, manufactured by Silo Co., Ltd.), 85 parts by weight of FM-10 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) as an impact resistance improver and Tinuvin 234 as a stabilizer. (Ciba Geigy Co., Ltd.) 1.0 part and polyethylene wax (PED191 (Clariant Japan Co., Ltd.) 0.2 part as a lubricant were mixed, mechanically mixed using a twin-screw extruder, and shaped into pellets. The shaped pellets have a thickness of 0.1 using a twin-screw extruder and a T-die.
Sheets of 5 mm and 1.0 mm were obtained. The impact strength, hardness, tensile properties, fluidity and heat resistance of the obtained composition were the same as in Example 1. The results are shown in Table 1.

Comparative Example 2 50 parts by weight of a methacrylic resin (M30, manufactured by Silo Co., Ltd.), 50 parts by weight of FM-10 (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) as an impact resistance improver, and Tinuvin 234 as a stabilizer. (Ciba Geigy Co., Ltd.) 1.0 part and polyethylene wax (PED191 (Clariant Japan Co., Ltd.) 0.2 part as a lubricant were mixed, mechanically mixed using a twin-screw extruder, and shaped into pellets. The shaped pellets have a thickness of 0.1 using a twin-screw extruder and a T-die.
Sheets of 5 mm and 1.0 mm were obtained. The impact strength, hardness, tensile properties, fluidity and heat resistance of the obtained composition were the same as in Example 1. The results are shown in Table 1.

Comparative Example 3 90 parts by weight of FM-10 (produced by Kanegafuchi Chemical Industry Co., Ltd.) as an impact resistance improver, and Tinuvin 234 as a stabilizer, based on 10 parts by weight of a methacrylic resin (M30, produced by Silo Co., Ltd.). (Ciba Geigy Co., Ltd.) 1.0 part and polyethylene wax (PED191 (Clariant Japan Co., Ltd.) 0.2 part as a lubricant were mixed, mechanically mixed using a twin-screw extruder, and shaped into pellets. The shaped pellets have a thickness of 0.1 using a twin-screw extruder and a T-die.
Sheets of 5 mm and 1.0 mm were obtained. The impact strength, hardness, tensile properties, fluidity and heat resistance of the obtained composition were the same as in Example 1. The results are shown in Table 1.

[0086]

[Table 1] As is clear from Table 1 (represented in Examples 1 to 3 and Comparative Examples 1 to 3), the resin composition for a capstock of the present invention represented by Examples has weather resistance, high color retention,
It can be suitably used as a synthetic resin composite material characterized by having a capstock layer and a resin composition for capstock which have high impact strength and high hardness, and further have good processability and heat resistance. .

[0087]

EFFECT OF THE INVENTION The resin composition for capstock of the present invention has weather resistance, high color retention, high impact strength, high hardness, and further has good processability and heat resistance as a resin composition for capstock. It can be used preferably. Further, a composite material in which a capstock layer made of the resin composition for the present capstock is bonded to a substrate is used as an industrial profile for building siding, shutters, windows and door frames (technical profile), and a system for rainwater transportation (for example, It is widely used as a groove and a gutter) and a fence, and can be preferably used.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BB03Y BB12Y BC03Y BG04W                       BG04Y BG05W BL00Y BL01Y                       BN00X BN06X BN10X BN12X                       BN14X BP00W CB00Y CF00Y                       CG00Y CH00Y CH07Y CH09Y                       CL00Y CM04Y CN02Y FD01                       FD02 FD03 FD05 FD09 FD13                       FD17 GL00

Claims (10)

[Claims] 1. A methacrylic polymer block (a) 5
˜95% by weight and acrylic polymer block (b) 95
A resin composition for a capstock, which comprises the block copolymer (A) in an amount of 5 wt%. 2. The resin composition for a capstock according to claim 1, further comprising a graft polymer (B). 3. The resin composition for a capstock according to claim 1 or 2, further comprising a thermoplastic resin (C). 4. An inner layer portion (core portion) in which the graft copolymer (B) is composed of a polymer component having a glass transition temperature of less than 25 ° C.
The resin composition for a capstock according to claim 1, 2 or 3, which is a core-shell particle type graft copolymer containing an outer layer portion (shell portion) composed of a polymer component having a glass transition temperature of 25 ° C or higher. object. 5. The resin composition for a capstock according to claim 1, 2, 3 or 4, wherein the thermoplastic resin (C) is a free polymer composed of acrylic acid ester and methacrylic acid ester. 6. The resin composition for a capstock according to claim 1, 2, 3, 4 or 5, wherein the block copolymer (A) is produced by atom transfer radical polymerization. 7. The block copolymer (A) comprises 20 to 50% by weight of a methacrylic polymer block (a) and 80 to 50% by weight of an acrylic polymer block (b). Item 7. A resin composition for a capstock according to Item 1, 2, 3, 4, 5 or 6. 8. The block copolymer (A) comprises 50 to 75% by weight of a methacrylic polymer block (a) and 50 to 25% by weight of an acrylic polymer block (b). Item 7. A resin composition for a capstock according to Item 1, 2, 3, 4, 5 or 6. 9. The methacrylic polymer block of the block copolymer (A) has methyl methacrylate as a main component, and the acrylic polymer block has butyl acrylate as a main component. 2, 3, 4, 5,
The resin composition for capstock according to 6, 7, or 8. 10. Claims 1, 2, 3, 4, 5, 6, 7, 8
Or a capstock layer containing the resin composition for a capstock according to item 9.