JP2000169665A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a thermoplastic resin composition excellent in impact resistance and transparency by including a methacrylic resin and a specific block copolymer. SOLUTION: The objective thermoplastic resin composition is prepared by including (A) 99.5-30 wt.% (preferably 99.5-50 wt.%) methacrylic resin and (B) 0.5-70 wt.% (preferably 0.5-50 wt.%) block copolymer consisting of (i) a methacrylic polymer block, (ii) an acrylic polymer block and (iii) an isobutylene- based polymer block. The difference between refractive indices of the ingredients B and A preferably is within 0.01 at 20 deg.C. The ingredient B preferably has 30,000-500,000 number average molecular weight (Mn) and <=1.8 (Mw/Mn) (wherein, Mw shows weight average molecular weight; Mw/Mn is measured by gel permeation chromatography). The ingredient B preferably consists of 5-90 wt.% component (i) and 95-10 wt.% the total of components (ii) and (iii).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a methacrylic resin composition having excellent impact resistance. More specifically, the present invention relates to a methacrylic resin composition comprising a methacrylic resin, a methacrylic polymer, and a block copolymer containing an acrylic polymer and an isobutylene polymer, and having excellent impact resistance and transparency.

[0002]

2. Description of the Related Art Methacrylic resins are used in various fields because they have excellent transparency, have a beautiful appearance and weather resistance, and are easy to mold, but their strength against impact is not always sufficient. In general, when sufficient performance cannot be obtained with a single resin alone, a method of using the resin in combination with another resin or the like has been attempted. In particular, they are often used in combination with a polymer material having an elastomeric property for the purpose of improving impact resistance. A polymer material used for such a purpose is called an impact modifier.

For example, vinyl chloride resins include chlorinated polyethylene, ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), butyl Acrylate-methyl methacrylate copolymer, methacrylic resin, butyl acrylate-styrene-methyl methacrylate copolymer, etc., polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), butyl acrylate-methyl methacrylate An acrylate copolymer, etc., and a composition in which a prebutylene terephthalate resin is combined with an acrylonitrile-butadiene-styrene copolymer (ABS resin), an epoxy-modified ethylene-propylene copolymer, etc. It has been draft, example that is commercially available often. Among such impact modifiers, methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), butyl acrylate-methyl methacrylate copolymer Is a copolymer obtained by graft polymerization (forming a shell portion) of a vinyl monomer in the presence of crosslinked rubber particles (forming a core portion), and is called a core-shell type graft copolymer because of its particle structure. It is useful as an impact modifier. Among such core-shell type graft copolymers, the MBS resin and the ABS resin copolymerized with butadiene have a problem in weather resistance because unsaturated double bonds remain in the polymer main chain.
Therefore, when weather resistance is required, a butyl acrylate-methyl methacrylate copolymer is very often selected. However, although such a core-shell type graft copolymer is useful as an impact modifier, it is dispersed in a particle shape and affects fluidity, so in injection molding, molding conditions, mold gate shape, etc. It is pointed out that, depending on the situation, surface defects such as fogging may occur at the gate portion of the molded product, and unevenness in the sheet thickness or surface roughness may occur in the molding and processing of the sheet.

On the other hand, it is known that a block copolymer in which a hard segment and a soft segment (rubber component) are combined can be used as a composition in combination with a thermoplastic resin. Examples of such a block copolymer include a styrene-butadiene copolymer, a styrene-isoprene copolymer, and hydrogenated polymers thereof (styrene-ethylene-butylene copolymer, styrene-ethylene-propylene copolymer, respectively). (Called coalescence) is widely used. When such a block copolymer is used, in general, a composition having an excellent balance of impact resistance, rigidity, and molding fluidity can be obtained, but the thermoplastic resin to be combined is a polystyrene resin, a polyolefin resin, a polyphenylene ether. It is limited to those having low polarity such as resin.

[0005]

An object of the present invention is to provide a methacrylic resin composition having excellent impact resistance and transparency.

[0006]

Means for Solving the Problems The present inventors have found that a block copolymer containing a methacrylic polymer, an acrylic polymer and an isobutylene polymer functions as an excellent impact resistance modifier, By combining with a methacrylic resin, it has been found that a thermoplastic resin composition having excellent impact resistance can be obtained without substantially lowering transparency.
The present invention has been completed.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a methacrylic resin composition comprising a methacrylic resin and a block copolymer containing a methacrylic polymer block, an acrylic polymer block and an isobutylene polymer block. The thing is the content. The weight ratio of the methacrylic resin (a) and the block copolymer (b) in the methacrylic resin composition is not particularly limited, but from the viewpoint of impact resistance and transparency, (a) is preferably 99.5
-30% by weight and (b) 0.5-70% by weight, more preferably (a) 99.5-50% by weight and (b) 0.5-50% by weight. When (b) is 0.5% by weight or less, impact resistance tends to decrease,
When (b) is 70% by weight or more, transparency tends to decrease.

The block copolymer containing a methacrylic polymer block, an acrylic polymer block and an isobutylene polymer block which can be used in the present invention is a polymer block containing a methacrylic monomer as a main component. It is a block copolymer containing at least one each of (A), a polymer block (B) containing an acrylic monomer as a main component, and at least one polymer block (C) containing an isobutylene monomer as a main component. .

That is, the block copolymer (b) is, for example, an ABC type triblock copolymer, ABC
-BA type pentablock copolymer, (ABC
-) N-type (n is an integer of 3 or more) multi-block copolymers, etc., but not limited thereto, and the order of A, B, and C may be changed. Among these, an ABCBA type pentablock copolymer is preferable from the viewpoint of impact resistance. The structure of the block copolymer is a linear block copolymer or a branched (star) block copolymer, and may be a mixture thereof. The structure of such a block copolymer can be properly used depending on required characteristics such as processing characteristics and mechanical characteristics of the methacrylic resin composition.

The number average molecular weight of the block copolymer is not particularly limited, but is preferably 30,000 to 50,000.
0, more preferably 50,000 to 400,000. If the number average molecular weight is small, the viscosity tends to be low, and if the number average molecular weight is large, the viscosity tends to increase. Therefore, the viscosity may be set according to the required processing characteristics.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer (b) measured by gel permeation chromatography is not particularly limited, but is 1.8 or less. Is preferably
More preferably, it is 1.5 or less. When Mw / Mn is more than 1.8, the uniformity of the block copolymer tends to decrease. When Mw / Mn is 1.8 or less, more preferably 1.5 or less, it becomes easy to obtain higher impact resistance and transparency because the uniformity of the block copolymer is higher. Such a highly uniform block copolymer can be obtained by a living polymerization method described later, but the production method is not limited thereto.

The preferred composition ratio of the methacrylic polymer block (A), acrylic polymer block (B) and isobutylene polymer block (C) constituting the block copolymer (b) is as follows: 5 to 90% by weight, the total of (B) and (C) is 95 to 10% by weight, more preferably 10 to 80% by weight of (A), and 90 to 90% by weight of (B) and (C). 20% by weight, more preferably (A)
Is 20 to 50% by weight, and the total of (B) and (C) is 80 to 5%.
0% by weight. If (A) is less than 5% by weight, the compatibility with the methacrylic resin tends to decrease, and (B)
If the total proportion of (C) and (C) is less than 10% by weight, the impact resistance of the thermoplastic resin composition tends to decrease. (A)
The more preferable the weight fraction is, the higher the compatibility with the methacrylic resin is secured, so that desired physical properties such as impact resistance can be easily expressed. Also,
The more preferable the total weight fraction of (B) and (C) is, the more the impact resistance tends to be improved.

Further, in order to impart transparency to the methacrylic resin composition, the block copolymer (b) must be kept at 20 ° C.
It is preferable that the ratio between (A), (B) and (C) is such that the difference between the refractive index at 20 ° C. of the methacrylic resin (a) combined with the refractive index in (a) is 0.01 or less. When high transparency is required, the difference in refractive index is more preferably 0.005 or less, and 0.003 or less.
It is more preferred that: The calculated refractive index of the block copolymer (b) is calculated by the weight of each of the blocks (A), (B), and (C) described in the literature such as Polymer Handbook / Wiley interscience. It can be calculated by arithmetic mean multiplied by the ratio. Further, the actual refractive index of the block copolymer (b) can be measured by a refractometer by making (b) alone into a sheet by pressing.

The methacrylic polymer block (A) constituting the block copolymer (b) is a block obtained by polymerizing a monomer having a methacrylate ester as a main component. For the purpose of adjusting the refractive index, the glass transition temperature, the compatibility with the methacrylic resin, and the like, a vinyl monomer copolymerizable therewith may be copolymerized as long as the properties of the coalescence are not impaired. The methacrylic polymer block (A) preferably comprises 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of a vinyl monomer copolymerizable therewith.
When (A) is a copolymer type, it may be any of random copolymerization, alternating copolymerization, and block copolymer type. If the methacrylate is less than 50%, the glass transition temperature inherent in the methacrylate polymer and the compatibility with the methacrylic resin tend to be impaired.

The methacrylate constituting the block (A) includes, for example, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate
-Butyl, isobutyl methacrylate, -t-butyl methacrylate, -n-pentyl methacrylate, -n-hexyl methacrylate, cyclohexyl methacrylate, -n-heptyl methacrylate, methacrylic acid-
n-octyl, 2-ethylhexyl methacrylate,
Nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, -3-methacrylic acid Methoxybutyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane , Γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, 2-trifluoromethylethyl methacrylate,
2-Perfluoroethyl methacrylate, 2-perfluoroethyl methacrylate-2-perfluorobutylethyl, 2-perfluoroethyl methacrylate, perfluoromethyl methacrylate, diper methacrylate Fluoromethylmethyl, methacrylic acid-2
-Perfluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate,
2-perfluorohexadecylethyl methacrylate and the like. These are used alone or in combination of two or more thereof. Of these, methyl methacrylate is preferred in terms of compatibility with the methacrylic resin to be combined and availability.

Examples of the vinyl monomer copolymerizable with the methacrylate ester constituting the block (A) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and acrylate -N-butyl, isobutyl acrylate, acrylic acid-
t-butyl, acrylic acid-n-pentyl, acrylic acid-
n-hexyl, 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, 2-hydroxypropyl acrylate, stearyl acrylate, acrylic acid Glycidyl, 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, acrylic acid- 2-trifluoromethylethyl, acrylate-2-perfluoroethylethyl, acrylate-2-perfluoroethyl-2-perfluorobutylethyl, acrylate-2-perfluoroethyl, perfluoroacrylate L-methyl, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, acrylate-2 Acrylates such as perfluorohexadecylethyl; styrene,
aromatic alkenyl compounds such as α-methylstyrene, p-methylstyrene and p-methoxystyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, and par Halogen-containing unsaturated compounds such as fluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl maleates Unsaturated dicarboxylic acid compounds such as esters, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; vinyl acetate;
Vinyl ester compounds such as vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide,
Various vinyl monomers such as maleimide compounds such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide are exemplified. These are used alone or in combination of two or more thereof. These vinyl monomers can be preferably selected depending on the compatibility with the methacrylic resin to be combined. For example, when the methacrylic resin (a) to be combined is a resin mainly composed of methyl methacrylate and copolymerized with methyl acrylate, the main constituents of the block (A) are methyl methacrylate and vinyl monomer. Is preferably methyl acrylate, and when the methacrylic resin (a) is a resin mainly composed of methyl methacrylate and copolymerized with styrene, the main constituents of the block (A) are methyl methacrylate and vinyl monomer. Styrene is preferable as the body, but the methacrylate and vinyl monomer used for the block (A) are not limited thereto.

The glass transition temperature of the block (A) is preferably 25 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher. When the glass transition temperature is lower than 25 ° C., the impact resistance of the thermoplastic resin composition tends to decrease. As the glass transition temperature becomes a more preferable value, the interaction with the methacrylic resin (a) is secured, so that the one-stage impact resistance tends to be higher.

The acrylic polymer block (B) constituting the block copolymer (b) is a block obtained by polymerizing a monomer mainly containing an acrylate ester. For the purpose of adjusting the refractive index, the glass transition temperature, the compatibility with the methacrylic resin (a), and the like, a vinyl monomer copolymerizable therewith may be copolymerized within a range not to impair the above. The acrylic polymer block (B) comprises 50 to 100% by weight of an acrylate ester and 0 to 50% of a vinyl monomer copolymerizable therewith.
% By weight. When (B) is a copolymer, any of random copolymerization, alternating copolymerization, and block copolymer may be used. 50 acrylate
%, The glass transition temperature inherent in the acrylate polymer and the compatibility with the methacrylic resin tend to be impaired.

Examples of the acrylate constituting the block (B) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate and acrylic acid. -T-butyl, -n-pentyl acrylate, -n-hexyl acrylate, cyclohexyl acrylate, -n-heptyl acrylate, -n-acrylic acid
Octyl, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, -3-acrylic acid Methoxybutyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ-
(Methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-peracrylic acid Fluoroethyl-
2-perfluorobutylethyl, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-acrylic acid
Perfluoromethyl-2-perfluoroethylmethyl,
2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, acrylic acid-2
-Perfluorohexadecylethyl and the like.
These are used alone or in combination of two or more thereof. Of these, butyl acrylate is preferred from the viewpoint of compatibility with the methacrylic resin to be combined and availability.

Examples of the vinyl monomer copolymerizable with the acrylate constituting the block (B) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate. N-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-heptyl methacrylate , N-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, methacrylic acid Isobornyl, methacrylic acid-2-methoxy Ethyl, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of methacrylic acid, trifluoromethylmethyl methacrylate, 2-trifluoromethylethyl methacrylate, methacrylic Acid-2-perfluoroethylethyl, methacrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, methacrylic acid-2-perfluoroethyl, perfluoromethyl methacrylate, diperfur methacrylate Romechirumechiru, methacrylic acid-2-perfluoromethyl-2
Methacrylates such as perfluoroethylmethyl, 2-perfluorohexylethyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate;
Styrene, α-methylstyrene, p-methylstyrene,
aromatic alkenyl compounds such as 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; vinyl trimethoxy Silicon-containing unsaturated compounds such as silane and vinyltriethoxysilane; unsaturated dicarboxylic acid compounds such as maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide; Chill maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, the various vinyl monomers such as maleimide compounds such as cyclohexyl maleimide and the like. These are used alone or in combination of two or more thereof. These vinyl monomers can be preferably selected depending on the compatibility with the methacrylic resin to be combined.

The glass transition temperature of the block (B) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably -20 ° C. or lower. If the glass transition temperature is higher than 25 ° C., the impact resistance of the thermoplastic resin composition tends to decrease. The more preferable the glass transition temperature is, the more easily it becomes easier to develop impact resistance.

The isobutylene-based polymer block (C) constituting the block copolymer (b) is a block obtained by polymerizing a monomer containing isobutylene as a main component, within a range that does not impair the properties of the isobutylene polymer. For the purpose of adjusting the refractive index, the glass transition temperature, and the compatibility with the thermoplastic resin, a monomer copolymerizable therewith may be copolymerized. The isobutylene-based polymer block (C) preferably comprises 50 to 100% by weight of an isobutylene monomer and 0 to 50% by weight of a monomer copolymerizable therewith.
When (C) is a copolymer type, any of random copolymerization, alternating copolymerization, and block copolymer type may be used. If the content of isobutylene is less than 50% by weight, the glass transition temperature inherent in the isobutylene polymer and the compatibility with the methacrylate resin tend to be impaired.

The monomer copolymerizable with the isobutylene monomer constituting the block (C) includes, for example, styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-
Methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6 -Dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6
-Dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m- or p-chlorostyrene, 2,6
-Dichlorostyrene, 2,4-dichlorostyrene, α-
Chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chloro Styrene, 2,4,6-
Trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-
Chloro-2,6-dichlorostyrene, β-chloro-2,
4-dichlorostyrene, o-, m- or pt-butylstyrene, o-, m- or p-methoxystyrene,
o-, m- or p-chloromethylstyrene, o-, m
-Or an aromatic alkenyl compound such as p-bromomethylstyrene, p-trimethoxysilylstyrene, p-dimethoxymethylsilylstyrene, indene, vinylnaphthalene; butadiene, isoprene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, Conjugated diene compounds such as ethylidene norbornene; methyl vinyl ether, ethyl vinyl ether, (n-, iso) propyl vinyl ether, (n
-, Sec-, t-, or iso) butyl vinyl ether, methyl propenyl ether, ethyl propenyl ether, and other vinyl ether compounds; cyclic ether compounds, such as tetrahydrofuran; ethylene, propylene, 1-butene, 2-methyl-1-butene , 3-methyl-1-butene, pentene, hexene, cyclohexene,
Aliphatic olefinic compounds such as 4-methyl-1-pentene, vinylcyclohexene, octene, norbornene; vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxy Silane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, γ-
Methacryloyloxypropyltrimethoxysilane, γ
-Various cationic polymerizable monomers such as silane compounds such as methacryloyloxypropylmethyldimethoxysilane. These are used alone or in combination of two or more thereof. These cationically polymerizable monomers can be suitably selected depending on the glass transition temperature required for the block (C).

The glass transition temperature of the block (C) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and further preferably -20 ° C. or lower. If the glass transition temperature is higher than 25 ° C., the impact resistance of the thermoplastic resin composition tends to decrease. The more preferable the glass transition temperature is, the more easily it becomes easier to develop impact resistance.

The method for producing the block copolymer (b) is not particularly limited, but it is preferable to use controlled polymerization using a polymer initiator. Controlled polymerization includes living anion polymerization, radical polymerization using a chain transfer agent,
Living radical polymerization has been developed in recent years. Living radical polymerization is preferred in terms of controlling the molecular weight and structure of the block copolymer, and moreover, since more types of monomers can be used than in the case of living anionic polymerization.

Living radical polymerization is radical polymerization in which the activity of the polymerization terminal is maintained without loss. In a narrow sense, living polymerization refers to 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 recent years by various groups. Examples thereof include those using a chain transfer agent such as polysulfide, and cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 1).
16, 7943) and those using a radical scavenger such as a nitroxide compound (Macromolecules,
1994, 27, 7228), atom transfer radical polymerization using an organic halide or the like as an initiator and a transition metal complex as a catalyst (AtomTransfer Radical Po).
lymerization: ATRP). In the present invention, which method is used is not particularly limited, but atom transfer radical polymerization is preferable in terms of easy control.

In the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound is used as an initiator, and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst is used as a catalyst. Is done. (For example,
See Matyjaszewski et al. Am. Chem.
Soc. 1995, 117, 5614, Macromo
recules 1995, 28, 7901, Scie
nce 1996, 272, 866 or Sawa
Moto et al., Macromolecules 199
5, 28, 1721). According to these methods, the polymerization rate is generally very high, and although the termination polymerization such as coupling between radicals is likely to occur, the polymerization proceeds in a living manner and the molecular weight distribution is narrow.
Thus, a polymer having a ratio of / Mn 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 an organic halide or a sulfonyl halide compound used as an initiator, a monofunctional, difunctional or polyfunctional compound can be used. These may be properly used depending on the purpose, but when a diblock copolymer is produced, a monofunctional compound is preferable, and an ABA-type triblock copolymer and a BAB-type It is preferable to use a bifunctional compound when producing a triblock copolymer, and it is preferable to use a polyfunctional compound when producing a branched block copolymer. It is also possible to use a polymer initiator as the initiator. The polymer initiator is a compound of a polymer having a halogen atom bonded to a molecular chain terminal, among organic halides or halogenated sulfonyl compounds. Since such a polymer initiator can be produced by a living radical polymerization method, it is known that a block copolymer in which polymers having different properties are bonded can be easily produced. Since it can be produced by a controlled polymerization method other than the radical polymerization method, it is characterized in that a block copolymer in which polymers obtained by different polymerization methods are combined can be obtained. The isobutylene-based polymer constituting the block copolymer used in the present invention can be produced by a living cationic polymerization method described below, and the isobutylene-based polymer obtained by such a method is used as a polymer initiator. However, it is preferable in that the structure of the polymer can be easily controlled.

As the polymer initiator, for example, a compound represented by the following general formula:

[0030]

Embedded image Wherein X is chlorine, bromine or iodine, and R is carbon
~ 30 hydrocarbon groups, l is an integer of 1 ~ 10, m is 100
-10,000, n is an integer of 0-1,000) or a general formula:

[0031]

Embedded image Wherein X is chlorine, bromine or iodine, and R is carbon
~ 30 hydrocarbon groups, l is an integer of 1 ~ 10, m is 100
-10,000). As described above, such a polymer initiator can be produced by a living cationic polymerization method described below.

When an organic halide or a sulfonyl halide compound having a functional group other than the one which initiates the polymerization is used, a polymer having a functional group introduced into a terminal easily can be 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 halides or halogenated sulfonyl compounds which can be used as these initiators, the carbon to which the halogen is bonded is bonded to a carbonyl group or a phenyl group, and the carbon-halogen bond is activated. Polymerization starts. The amount of the initiator to be 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 by how many molecules of the monomer are used per one molecule of the initiator.

The transition metal complex used as a catalyst for the above atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zero-valent copper, divalent ruthenium, divalent iron and divalent nickel. Complexes. Among these, a copper complex is preferred from the viewpoint of cost and reaction control. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. When using a copper compound, to increase the catalytic activity,
2′-Bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, polyamines such as tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine and hexamethyl (2-aminoethyl) amine may be added as ligands. . Also,
Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as the catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides may be added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ) and bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PP
h _{3) 2),} and a divalent bis tributylphosphine complex nickel _{(NiBr 2 (PBu 3) 2} ) are also preferred as the catalyst. The amounts of the catalyst, ligand and activator to be used are not particularly limited, but may be appropriately determined from the relationship between the amounts of the initiator, monomer and 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. Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol and t-butanol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene Carbonate,
And carbonate-based solvents such as propylene carbonate. These can be used alone or in combination of two or more. As described above, when the reaction is carried out in the absence of a solvent, a bulk polymerization results. On the other hand, when using a solvent,
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 atom transfer radical polymerization can be carried out at room temperature to 200 ° C., preferably 50 to 200 ° C.
~ 150 ° C.

In order to produce a block copolymer by the above atom transfer radical polymerization, a method of sequentially adding monomers, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator, and a method of separately adding A method in which the polymerized polymer is bonded by a reaction is exemplified. These methods may be properly used depending on the purpose, but from the viewpoint that the structure of the polymer is easily controlled as described above, a method of polymerizing the next block using a polymer synthesized in advance as a polymer initiator is preferable. .

The method for producing the polymer initiator comprising the above-mentioned isobutylene-based polymer is not particularly limited, but living cationic polymerization is preferred from the viewpoint that the structure of the polymer is easily controlled. The living cationic polymerization is carried out by a general formula (1): (CR ¹ R ² X) n R ³ (where X is a substituent selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R ¹ , R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ¹ and R ² may be the same or different; and R ³ is a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic group. A hydrocarbon group, and n represents a natural number of 1 to 6) in the presence of a compound represented by the following formula:

The compound represented by the general formula (1) serves as an initiator and generates a carbon cation in the presence of a Lewis acid or the like, and is considered to be a starting point of cationic polymerization. Examples of the compound of the general formula (1) used in the present invention include:
Examples include the following compounds.

(1-Chloro-1-methylethyl) benzene [C ₆ H ₅ C (CH ₃ ) ₂ Cl], 1,4-bis (1-
Chloro-1-methylethyl) benzene [1,4-Cl
_{(CH 3) 2 CC 6 H} 4 C (CH 3) 2 Cl ], 1,3-bis (1-chloro-1-methylethyl) benzene [1,3
Cl (CH ₃ ) ₂ CC ₆ H ₄ C (CH ₃ ) ₂ Cl], 1,3
5- tris (1-chloro-1-methylethyl) benzene _{[1,3,5- (ClC (CH 3) 2} ) 3 C 6 H 3 ], 1,
3-bis (1-chloro-1-methylethyl) -5- (t
ert- butyl) benzene _{[1,3- (C (CH 3) 2} C
_{l) 2 -5- (C (CH} 3) 3) C 6 H 3 ] Among them, a difunctional initiator, linear polymers are obtained therefrom starts the polymerization both ends is growing terminal In particular, bis (1-chloro-1-methylethyl) benzene [C ₆ H ₄ (C (CH ₃ ) ₂ C]
l) ₂ ] [bis (1-chloro-1-methylethyl) benzene is also referred to as bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride].

In the polymerization of the isobutylene-based polymer block, a Lewis acid catalyst may be additionally used. Such a Lewis acid may be any as long as it can be used for cationic polymerization. TiCl ₄ , TiBr ₄ , BCl ₃ , BF ₃ ,
BF ₃ OEt ₂ , SnCl ₄ , SbCl ₅ , SbF ₅ , WCl ₆ ,
TaCl ₅ , VCl ₅ , FeCl ₃ , ZnBr ₂ , AlCl ₃ , A
metal halides such as lBr ₃ ; Et ₂ AlCl, EtA
Organometallic halides such as 1Cl ₂ can be suitably used. Among them, TiCl ₄ , BCl ₃ , and SnCl ₄ are preferable in view of the ability as a catalyst and industrial availability. The amount of the Lewis acid used is not particularly limited,
It can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it can be used in an amount of 0.1 to 100 molar equivalents, preferably 1 to 60 molar equivalents, based on the compound represented by the formula (1).

In the polymerization of the isobutylene-based polymer block, an electron donor component can be further added, if necessary. This electron donor component is considered to have an effect of stabilizing the growing carbon cation during cation polymerization, and the addition of the electron donor produces a polymer whose structure with a narrow molecular weight distribution is controlled. The usable electron donor component is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.

The amount of each component can be appropriately designed depending on the characteristics of the target polymer.

The present invention can be carried out in a solvent, if necessary, and any such solvent can be used without any particular limitation as long as it does not substantially inhibit cationic polymerization. Specifically, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride and chlorobenzene; benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene and the like Alkylbenzenes; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane; 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, Branched aliphatic hydrocarbons such as 1,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane;
Examples include paraffin oil obtained by hydrorefining a petroleum fraction. Among these, a mixed solvent of toluene is preferable from the viewpoint of environmental safety and polymer properties. Also, primary and / or secondary monohalogenated hydrocarbons having 3 to 8 carbon atoms can be suitably used. As a specific example, for example, 1
-Chloropropane, 1-chloro-2-methylpropane,
1-chlorobutane, 1-chloro-2-methylbutane, 1
-Chloro-3-methylbutane, 1-chloro-2,2-dimethylbutane, 1-chloro-3,3-dimethylbutane,
1-chloro-2,3-dimethylbutane, 1-chloropentane, 1-chloro-2-methylpentane, 1-chloro-
3-methylpentane, 1-chloro-4-methylpentane, 1-chlorohexane, 1-chloro-2-methylhexane, 1-chloro-3-methylhexane, 1-chloro-
4-methylhexane, 1-chloro-5-methylhexane, 1-chloroheptane, 1-chlorooctane, 2-chloropropane, 2-chlorobutane, 2-chloropentane, 2-chloropentane, 2-chlorohexane, 2-chloro Heptane, 2-chlorooctane, chlorobenzene and the like can be used, and these can be used alone or in combination of two or more. Among these, 1-chlorobutane can be preferably used in view of the balance between the solubility of the isobutylene-based block copolymer, the ease of detoxification by decomposition, and the cost.

These solvents are used alone or in combination of two or more in consideration of the balance between the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer.

The amount of the solvent used is adjusted so that the concentration of the polymer is 1 to 50 in consideration of the viscosity of the obtained polymer solution and the ease of heat removal.
%, Preferably 5 to 35% by weight.

In conducting the actual polymerization, the respective components are mixed under cooling at a temperature of, for example, -100 ° C. or more and less than 0 ° C. A particularly preferred temperature range is from -30C to -80C in order to balance the energy cost with the stability of the polymerization.

The polymer obtained by such living cationic polymerization can be used as it is as a polymer initiator for atom transfer radical polymerization, but the terminal is activated by reacting with styrene or diphenylethylene. Is preferred.

The amounts of the methacrylic resin (a) and the block copolymer (b) used in the present invention are not particularly limited. The combined amount is preferably 0.5 to 70% by weight, the methacrylic resin is more preferably 99.5 to 50% by weight, and the block copolymer is more preferably 0.5 to 50% by weight. Most preferred is 70% by weight and 0.5 to 30% by weight of the block copolymer. If the blending amount of the block copolymer is 0.5% by weight or less, the effect of improving the impact resistance tends to be low. As the compounding amount of the block copolymer becomes more preferable, it becomes easier to achieve both the effect of improving the impact resistance and the characteristics of the methacrylic resin.

As the method for producing the thermoplastic resin composition of the present invention, existing methods such as a method of mechanically mixing and shaping into a pellet using a known apparatus such as a Banbury mixer, a roll mill, and a twin-screw extruder are used. Method can be used. The shaped pellets can be molded in a wide temperature range, and a usual injection molding machine, blow molding machine, extrusion molding machine, compression molding machine or the like is used for molding.

Further, the thermoplastic resin composition may contain, if necessary, an impact modifier, a stabilizer, a plasticizer, a lubricant, a flame retardant, a pigment, a filler, and the like. Specifically, methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylic graft copolymer, acrylic-silicone composite rubber-based graft copolymer, isobutylene-based graft copolymer, isobutylene-acrylic composite rubber-based Impact modifiers such as graft copolymers, isobutylene-silicone composite rubber-based graft copolymers; stabilizers such as triphenyl phosphite, hindered phenol, and dibutyltin maleate; paraffinic oils, polybutene-based oils, light oils, 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 and montanic acid wax; flame retardants such as triphenyl phosphate, tricresyl phosphate, decabromobiphenyl, decabromobiphenyl ether, antimony trioxide;
Pigments such as titanium oxide, zinc sulfide and zinc oxide; glass fiber, asbestos, wollastonite, mica, talc,
And fillers such as calcium carbonate.

As the methacrylic resin (a),
It is not particularly limited as long as it can be melt-mixed with the block copolymer (b), but it is mainly composed of a commercially available hard methacrylic resin mainly containing methyl methacrylate and a small amount of methyl acrylate or the like, or mainly methyl methacrylate. Methyl methacrylate-styrene resin copolymerized with styrene etc. can be used,
Those bead-like or pellet-like molding materials are preferably used, but are not limited thereto. Hard methacrylic resin is usually composed mainly of a methyl methacrylate unit, and 20% by weight or less of a copolymer monomer unit such as methyl acrylate and ethyl acrylate, and has a weight average molecular weight of about 70,000 to 300,000. belongs to.

[0053]

The thermoplastic resin composition of the present invention can provide a molded article having particularly excellent impact resistance while maintaining, for example, transparency and weather resistance inherently possessed by a methacrylic resin. it can.

Accordingly, the thermoplastic resin composition of the present invention can be used as a sheet, film, board, or sheet useful in the fields of, for example, packaging materials, construction materials, civil engineering materials, automobile materials, home appliance materials, and other miscellaneous goods materials. Extruded products such as irregular shapes,
It can be suitably used for the production of calender molded products, blow molded products such as bottles, various injection molded products used for automobiles and home electric appliances, and the industrial value thereof is very large.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BG05W BG06W BG07W BP03X 4J015 DA23 DA26 EA00 EA05 EA06 EA07 4J026 HA02 HA03 HA04 HA05 HA06 HA07 HA08 HA10 HA11 HA14 HA15 HA16 HA19 HA27 HA32 HA35 HA39 H48 HB06 HB HB H09 HB HB35 HB39 HB45 HB48 HC06 HC09 HC10 HC11 HC12 HC15 HC16 HC19 HC32 HC35 HC39 HE03 HE04 HE05

Claims (27)

[Claims] 1. A thermoplastic resin composition comprising (a) a methacrylic resin and (b) a block copolymer containing a methacrylic polymer block, an acrylic polymer block and an isobutylene polymer block. 2. The method according to claim 1, wherein the methacrylic resin (a) is 99.5 to
30% by weight and 0.5 to 7 of the block copolymer (b)
2. The thermoplastic resin composition according to claim 1, comprising 0% by weight. 3. The method according to claim 1, wherein the methacrylic resin (a) is 99.5 to 99.5.
50% by weight and 0.5 to 5 of the block copolymer (b)
2. The thermoplastic resin composition according to claim 1, comprising 0% by weight. 4. The thermoplastic resin according to claim 1, wherein the difference between the refractive index of the block copolymer (b) at 20 ° C. and the refractive index of the methacrylic resin (b) at 20 ° C. is within 0.01. Composition. 5. The thermoplastic resin composition according to claim 1, wherein the number of blocks of the block copolymer (b) is 5. 6. The thermoplastic resin composition according to claim 1, wherein the number average molecular weight of the block copolymer (b) is 30,000 to 500,000. 7. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer (b) measured by gel permeation chromatography is 1.8 or less. 2. The thermoplastic resin composition according to 1. 8. The methacrylic polymer block is a polymer comprising 50 to 100% by weight of a methacrylic acid ester and 0 to 50% by weight of another vinyl monomer copolymerizable therewith. The thermoplastic resin composition according to the above. 9. The thermoplastic resin composition according to claim 8, wherein the methacrylate is methyl methacrylate. 10. The monomer according to claim 1, wherein the other vinyl monomer is an acrylate ester, a methacrylate ester, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound or a halogen-containing unsaturated compound. 9. The thermoplastic resin composition according to 8. 11. The thermoplastic resin composition according to claim 1, wherein the methacrylic polymer block has a glass transition temperature of 25 ° C. or higher. 12. The polymer according to claim 1, wherein the acrylic polymer block is composed of 50 to 100% by weight of an acrylate ester and 0 to 50% by weight of another vinyl monomer copolymerizable therewith. Thermoplastic resin composition. 13. The thermoplastic resin composition according to claim 12, wherein the acrylate is butyl acrylate. 14. The monomer according to claim 1, wherein the other vinyl monomer is an acrylate ester, a methacrylate ester, an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound or a halogen-containing unsaturated compound. 13. The thermoplastic resin composition according to item 12. 15. The thermoplastic resin composition according to claim 1, wherein the glass transition temperature of the acrylic polymer block is 25 ° C. or less. 16. The thermoplastic resin according to claim 1, wherein the isobutylene-based polymer block comprises 50 to 100% by weight of isobutylene and 0 to 50% by weight of another monomer copolymerizable therewith. Composition. 17. The thermoplastic resin composition according to claim 16, wherein the other monomer is a monomer of an aromatic alkenyl compound, a conjugated diene compound, a vinyl ether compound or a cyclic ether compound. 18. The thermoplastic resin composition according to claim 1, wherein the glass transition temperature of the isobutylene-based polymer block is 25 ° C. or less. 19. The thermoplastic resin composition according to claim 1, wherein the block copolymer (b) is a block copolymer produced by controlled radical polymerization using a polymer initiator. 20. The thermoplastic resin composition according to claim 19, wherein the block copolymer (b) is a block copolymer produced using an isobutylene-based polymer block having a halogen at a terminal as a polymer initiator. . 21. An isobutylene-based polymer in which the block copolymer (b) has a halogen at a terminal is a polymer initiator, and a group 8 element, 9 group, 10 group, or 11 group element of the periodic table as a central metal. 21. The thermoplastic resin composition according to claim 20, which is a block copolymer produced using a metal complex as a catalyst. 22. The thermoplastic resin composition according to claim 21, wherein the catalyst for producing the block copolymer (b) is a metal complex having copper, nickel, ruthenium, and iron as central metals. 23. The catalyst for producing the block copolymer (b) is a metal complex having copper as a central metal.
The thermoplastic resin composition according to the above. 24. The thermoplastic according to claim 21, wherein the block copolymer (b) is a block copolymer produced using an isobutylene-based polymer having a chain transfer functional group at a terminal as a polymer initiator. Resin composition. 25. An isobutylene-based polymer having a halogen at the terminal is represented by the following general formula: Wherein X is chlorine, bromine or iodine, and R is carbon
~ 30 hydrocarbon groups, l is an integer of 1 ~ 10, m is 100
The thermoplastic resin composition according to claim 22, wherein the thermoplastic resin composition is represented by an integer of from 10,000 to 10,000, and n is an integer of from 0 to 1,000). 26. An isobutylene-based polymer having a halogen at a terminal is represented by the following general formula: Wherein X is chlorine, bromine or iodine, and R is carbon
~ 30 hydrocarbon groups, l is an integer of 1 ~ 10, m is 100
22. The thermoplastic resin composition according to claim 21, wherein the thermoplastic resin composition is represented by the following formula: 27. The thermoplastic resin composition according to claim 20, 25 or 26, wherein the isobutylene-based polymer having a terminal halogen is produced by living cationic polymerization.