JP2000103931A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of giving various molded products excellent in properties such as releasability, moldability, water repellency and oxygen permeability by using a vinyl polymer having a specific branched structure in the side chain. SOLUTION: This composition comprises (A) a vinyl polymer having in the side chain a carbosiloxane dendrimer structure, pref. a group of formula I [Z is a bivalent organic group; (p) is 0 or 1; R1 is a 1-10C alkyl or aryl; X1 is a silylalkyl of formula II (R2 is a 2-10C alkylene; R3 is a 1-10C alkyl; X1+i is H, a 1-10C alkyl, aryl or the like; (i) denotes the stratum of the silylalkyl group, being 1-10; ai is 0-3) when (i)=1] and (B) a thermoplastic resin other than the component A in the weight ratio A/B of (0.01-500):100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition capable of providing various molded articles having excellent properties such as mold releasability, moldability, water repellency and oxygen permeability. It is about things.

[0002]

2. Description of the Related Art Thermoplastic resins such as olefin resins, styrene resins, polyamide resins, polyester resins and vinyl halide resins have excellent physical properties and are widely used as materials for various molded articles. It is used. However, since this type of thermoplastic resin has a drawback that the releasability, moldability, water repellency and the like are inferior, various studies have been made for the purpose of improving them.

[0003] Among them, linear polyorganosiloxanes such as silicone oil and silicone raw rubber have excellent interfacial properties, and therefore, additives for improving the releasability, moldability, water repellency, etc. of thermoplastic resins. This kind of proposal is actually made by Japanese Patent Publication No. 57-10144.

However, in general, the compatibility between polyorganosiloxane and thermoplastic resin is inferior, for example, AS resin or AB resin.
It has been difficult to uniformly disperse the polyorganosiloxane in a fine form in a thermoplastic resin such as an S resin. For this reason, the thermoplastic resin to which the polyorganosiloxane is added and mixed has poor workability, and the molded product not only has problems such as bleed-out of the polyorganosiloxane and poor appearance due to separation, and furthermore, each molded product There is a problem that the mold releasability, moldability, water repellency and the like vary.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition which can provide various molded articles having excellent properties such as mold releasability, moldability, water repellency and oxygen permeability. It is in.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that, as an additive component to a thermoplastic resin, a specific branched polyorganosiloxane is used instead of a conventional linear polyorganosiloxane. By using a vinyl polymer having a structure, that is, a carbosiloxane dendrimer structure in the side chain, compatibility between the thermoplastic resin and the additive component is good, and lubricity, mold release, moldability, and water repellency are obtained. Various properties such as gas permeability and mechanical strength are well balanced,
In addition, the present inventors have found that a thermoplastic resin composition which does not cause bleed-out or separation of the additive component and can provide various molded articles having a good appearance can be obtained.

The thermoplastic resin composition of the present invention comprises a vinyl polymer (A) having a carbosiloxane dendrimer structure in a side chain and a thermoplastic resin (B) other than the component (A).
Consisting of 100 parts by weight of the component (B),
It is characterized by containing 0.01 to 500 parts by weight of the component.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition of the present invention will be specifically described below. One component of the thermoplastic resin composition of the present invention, a vinyl polymer (A)
Is a vinyl polymer having a carbosiloxane dendrimer structure in the side chain. Such a component (A) contains a carbosiloxane dendrimer structure in the side chain of the polymer. In the present invention, the dendrimer structure is highly regularly branched radially from one core. A high molecular weight group is meant. As a carbosiloxane dendrimer having such a structure, for example, there is a hyperbranched siloxane / silalkylene copolymer (Japanese Patent Application No. Hei 9 (1994) -19783).
171154). In the present invention, the carbosiloxane dendrimer structure in the vinyl polymer (A) is preferably a group represented by the following general formula.

[0009]

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In the above formula, Z is a divalent organic group, and includes an alkylene group, an arylene group, an aralkylene group, a divalent organic group containing an ester, a divalent organic group containing an ether, and a divalent organic group containing a ketone.
Examples thereof include a valent organic group and an amide group-containing divalent organic group, and among these, an organic group represented by the following formula is preferable.

[0011]

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[0012]

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[0013]

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In the above formula, R ⁹ is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. A methylene group and a propylene group are preferable, and R ¹⁰ is a carbon atom. A methyl group and an ethyl group are exemplified by a propyl group and a butyl group. Among them, a methyl group is preferable, and R ¹¹ is an alkylene group having a carbon number of 1 to 10, and a methylene group. ,
Examples thereof include an ethylene group, a propylene group, and a butylene group. Among them, an ethylene group is preferable, d is an integer of 0 to 4, and e is 0 or 1. R ¹ has ^{1 to 1} carbon atoms
10 alkyl groups or aryl groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples thereof include a phenyl group and a naphthyl group. Of these, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred. X ¹ is a silylalkyl group represented by the following formula when i = 1.

[0015]

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(Wherein, R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as an ethylene group, a propylene group, a butylene group, and a hexylene group; Examples include a branched alkylene group such as a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group, etc. Among these, an ethylene group, a methylethylene group, a hexylene group,
A 1-methylpentylene group and a 1,4-dimethylbutylene group are preferred. R ³ is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is 0 to 3
Is an integer. ).

In the thermoplastic resin composition of the present invention,
Among them, a branched organosiloxane polymer (A) having the following carbosiloxane dendrimer structure is preferably used. That is, (a) 0 to 99.9 parts by weight of a vinyl monomer and (b) a general formula:

[0018]

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In the formula, Y is an organic group capable of undergoing radical polymerization, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and the alkyl group includes a methyl group, an ethyl group, a propyl group, A butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group and a cyclohexyl group are exemplified. As the aryl group, a phenyl group,
An example is a naphthyl group. Of these, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred. X ¹ is a silylalkyl group represented by the following formula when i = 1.

[0020]

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(Wherein R ¹ is the same as above, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 10 carbon atoms, methylene group, ethylene X, propylene, and butylene.
^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is an integer of 0 to 3. A) a vinyl polymer having a carbosiloxane dendrimer structure in the side chain obtained by polymerizing 100 to 0.1 parts by weight of a carbosiloxane dendrimer containing an organic group capable of undergoing radical polymerization represented by (1). The vinyl polymer (A) will be further described. The vinyl monomer as the component (a) may be any one having a radically polymerizable vinyl group, and its type is not particularly limited. Such vinyl monomers include, for example, (meth)
Lower alkyl (meth) acrylates such as methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate; glycidyl (meth) acrylate; n-butyl (meth) acrylate , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, Higher (meth) acrylates such as (meth) lauryl acrylate and stearyl (meth) acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, and vinyl laurate , Higher fatty acid esters such as vinyl stearate; Styrene, vinyltoluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, aromatic vinyl-type monomers such as vinyl pyrrolidone; (meth) acrylamide, N- methylol (meth) acrylamide, N- methoxymethyl (meth)
Amide group-containing vinyl monomers such as acrylamide, isobutoxymethoxy (meth) acrylamide, N, N-dimethyl (meth) acrylamide; hydroxyl-containing vinyl such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate Carboxylic acid-containing vinyl monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol Ether bond-containing vinyl such as (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether Monomers: (meth) acryloxypropyltrimethoxysilane, (meth) acrylic group-containing (branched or linear) polydimethylsiloxane at one end, polydimethylsiloxane containing styryl group at one end, etc. Butadiene; vinyl chloride; vinylidene chloride; (meth) acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; (meth) acrylic glycidyl ether: (meth) acrylic acid; Alkali metal salts, ammonium salts, organic amine salts of radically polymerizable unsaturated carboxylic acids such as acids, crotonic acid, fumaric acid, and maleic acid;
Radical polymerizable unsaturated monomers having a sulfonic acid group such as styrenesulfonic acid, and their alkali metal salts, ammonium salts, organic amine salts;
Quaternary ammonium salts derived from (meth) acrylic acid, such as 3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of alcohols having tertiary amine groups, such as diethylamine methacrylate, and quaternary ammoniums thereof Salts are exemplified.

Polyfunctional vinyl monomers can also be used, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate. ) Acrylate, polyethylene glycol di (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetrioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (Meta)
Acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bisphenol A ethylene oxide or propylene oxide adduct diol di (meth) acrylate, hydrogenated bisphenol A ethylene oxide or propylene oxide adduct Examples include (meth) acryloyl group-containing monomers such as di (meth) acrylate and triethylene glycol divinyl ether of diols, divinylbenzene, and unsaturated group-containing silicone compounds such as polydimethylsiloxane capped at both ends with styryl groups. Is done.

The carbosiloxane dendrimer of the component (b) has a general formula:

Embedded image Indicated by

In the above formula, Y is an organic group capable of undergoing radical polymerization, and may be any organic group capable of undergoing a radical addition reaction, and specifically, (meth) represented by the following general formula: Examples thereof include an acryloxy group-containing organic group, a (meth) acrylamide group-containing organic group, a styryl group-containing organic group, and an alkenyl group having 2 to 10 carbon atoms.

[0025]

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[0026]

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[0027]

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(In the above formula, R ⁴ and R 6 are a hydrogen atom or a methyl group, and R ⁵ and R ^{8 each} have 1 to 1 carbon atoms.
0 is an alkylene group, and R ⁷ is an alkyl group having 1 to 10 carbon atoms. b is an integer of 0 to 4, and c is 0 or 1. Examples of such radically polymerizable organic groups include acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, and 3-vinylphenyl. , 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl group, methallyl And 5-hexenyl groups. R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group and a cyclohexyl group. Illustrated, examples of the aryl group include a phenyl group,
An example is a naphthyl group. Of these, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred. Also,
X ¹ is a silylalkyl group represented by the following formula when i = 1.

[0029]

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In the above formula, R ² is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, Examples thereof include a branched alkylene group such as a 1-methylpentylene group and a 1,4-dimethylbutylene group. Among them, ethylene group, methylethylene group, hexylene group, 1-methylpentylene group,
A 1,4-dimethylbutylene group is preferred. R ³ is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. R ¹ is the same as described above. X ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group. a
ⁱ is an integer of 0 to 3. i is an integer of 1 to 10,
This indicates the number of levels of the silylalkyl group, that is, the number of repetitions of the silylalkyl group. Therefore, when the number of layers is 1, the carbosiloxane dendrimer of this component has the general formula:

[0031]

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(Wherein, Y, R ¹ , R ² and R ³ are the same as above, R ¹² is a hydrogen atom or the same as R1. A ¹ is the same as ^ai above, The average total number of a ^{1 in} the molecule is 0 to 7.) When the number of layers is 2, the carbosiloxane dendrimer of this component has the general formula:

[0033]

Embedded image (Wherein Y, R ¹ , R ² , R ³ and R ¹² are the same as above. A ¹ and a ² are the same as the above ^ai ,
The average total number of a ¹ and a ^{2 in} one molecule is 0 to 25. ), And when the number of layers is 3, the carboxydendrimer of this component has the general formula:

[0034]

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Wherein Y, R ¹ , R ² , R ³ and R ¹²
Is the same as above. a ¹ , a ² and a ³ are the same as ^ai , but the average total number of a ¹ , a ² and a ³ in one molecule is 0 to 79. ). As the carboxydendrimer containing an organic group capable of undergoing radical polymerization of this component, a carbosiloxane dendrimer represented by the following average composition formula is exemplified.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Such a carbosiloxane dendrimer can be produced according to the method for producing a branched siloxane / silalkylene copolymer described in Japanese Patent Application No. 9-171154. For example, the general formula:

[0051]

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(Wherein, R ¹ and Y are the same as those described above) by subjecting a silicon compound containing a silicon-bonded hydrogen atom represented by the formula and an organosilicon compound containing an alkenyl group to a hydrosilylation reaction. Can be. Examples of the silicon compound represented by the above formula include 3-
Methacryloxypropyltris (dimethylsiloxy) silane, 3-acryloxypropyltris (dimethylsiloxy) silane, and 4-vinylphenyltris (dimethylsiloxy) silane are used. As the alkenyl-containing organosilicon compound, vinyltris (trimethylsiloxy) is used. Silane, vinyltris (dimethylphenylsiloxy) silane, and 5-hexenyltris (trimethylsiloxy) silane are used. Note that this hydrosilylation reaction is preferably performed in the presence of a transition metal catalyst such as chloroplatinic acid or a platinum vinyl siloxane complex.

In the (A) birni polymer having a carbosiloxane dendrimer structure in the side chain used in the present invention, the polymerization ratio of the component (a) and the component (b) is as follows:
(A) component and (b) component are 0: 100-9 by weight ratio.
9.9: 0.1, preferably 1: 9
The range is 9 to 99: 1. The fact that the component (a) and the component (b) are 0: 100 means that the homopolymer of the component (b) may be used.

The vinyl polymer (A) having a carbosiloxane dendrimer structure in the side chain used in the present invention comprises:
The component (a) and the component (b) are copolymerized, or only the component (b) is polymerized. As the polymerization method, a radical polymerization method or an ionic polymerization method is used, and among these, the radical polymerization method is particularly preferable. In this radical polymerization, a solution polymerization method is suitably used. In this solution polymerization, the components (a) and (b) are mixed with each other in a solvent in the presence of a radical initiator at 50 to 15 wt.
The reaction is preferably carried out at a temperature of 0 ° C. for 3 to 20 hours.

The solvent used at this time is hexane,
Aliphatic hydrocarbons such as octane, decane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; acetone, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone Ketones; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate; methanol,
Examples include alcohols such as ethanol, isopropyl alcohol, and butanol; and organosiloxane oligomers such as octamethyltecyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.

As the radical initiator, a conventionally known compound generally used in a radical polymerization method is used. Specifically, 2,2′-azobis (isobutyronitrile),
2,2'-azobis (2-methylbutyronitrile), 2,2
2'-Azobis (2,4-dimethylvaleronitrile)
Azobis compounds such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxybenzoate, t
Organic peroxides such as tert-butylperoxy-2-ethylhexanoate are exemplified. One of these radical initiators may be used alone, or two or more of them may be used in combination. The amount of the radical initiator used is preferably in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the total of the components (a) and (b).

At the time of polymerization, a chain transfer agent can be added. Specifically, as the chain transfer agent, 2
-Mercapto compounds such as mercaptoethanol, butylmercaptan, n-dodecylmercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyl And halides such as trimethoxysilane. In the case of producing the vinyl polymer of the present invention, it is preferable to remove the remaining unreacted vinyl monomer by performing a vacuum treatment under heating after polymerization.

The number average molecular weight of the vinyl polymer (A) having a carbosiloxane structure in a side chain used in the present invention is preferably from 3,000 to 2, from the viewpoint of ease of blending with a thermoplastic resin. 0,000, more preferably 5,000 to 800,000. The properties are liquid, gum, paste, solid,
A powder form is exemplified.

In the thermoplastic resin composition of the present invention, the other component, the thermoplastic resin (B) other than the component (A), is compatible with the component (A) or disperses the component (A). The property is not particularly limited as long as it is possible, and may be an elastomer at room temperature, for example.

The thermoplastic resin (B) comprises a homopolymer or a copolymer of an α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1pentene. Polyethylene, low-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, ethylene / propylene copolymer, copolymerization of these α-olefins with monomers other than α-olefins such as vinyl acetate, methyl methacrylate, and maleic acid. An ethylene / vinyl acetate copolymer comprising a polymer,
Olefinic resins such as ethylene (meth) acrylate copolymer; acrylic acid, methacrylic acid, (meth)
Methyl acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2
-(Meth) acrylates such as ethylcyclohexyl, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and diethylaminoethyl (meth) acrylate , Ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth)
Homopolymers or copolymers of acrylic monomers such as polyfunctional (meth) acrylates such as acrylates; these acrylic monomers and styrene monomers such as styrene and α-methylstyrene; vinyl acetate Acrylic resins such as copolymers with vinyl monomers such as vinyl chloride, vinylidene chloride and the like, and maleimide monomers such as phenylmaleimide, cyclohexylmaleimide and anhydrous maleimide; polyvinyl chloride, polyvinylidene chloride, polyfluorinated Vinyl halide resins such as vinyl and polyvinylidene fluoride; polystyrene, high impact polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene copolymer, acrylonitrile / acrylic rubber / styrene copolymer, Acrylonitrile / ethylene propylene rubber Styrene resin such as styrene copolymer; Polyester resin such as polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate; nylon 6, nylon 66, nylon 6/66, nylon 6
/ 12, nylon 610, nylon 612, nylon 1
Polyamide resins such as 1, nylon 12; polyvinyl alcohol resins; polyoxyalkylene resins such as polyacetal; polycarbonate resins; polyvinyl acetate resins; polysulfone resins; polyethersulfone resins; Arylene sulfide resin; polyarylate resin; polyimide resin; polyamideimide resin, polyetherimide resin; polyetheretherketone resin; liquid crystal polyester resin; polytetrafluoroethylene;
Thermoplastic resins such as fluorine-based resins such as ethylene / tetrafluoroethylene copolymers, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, fluorine-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, and polyester-based elastomers; and Mixtures and copolymers of two or more of these thermoplastic resins are exemplified.

The mixing ratio of the two components (A) and (B) is such that the amount of the component (A) is 0.0 to 100 parts by weight of the component (B).
1 to 500 parts by weight, preferably 0.01 to 100 parts by weight.
Parts by weight, more preferably 0.1 to 50 parts by weight. When the proportion of the component (A) is less than 0.01 part by weight, the effect of improving the intended properties is small, and when it exceeds 500 parts by weight, the mechanical properties inherent to the thermoplastic resin (B) are lowered, which is preferable. Absent.

The mixing ratio of the two components (A) and (B) is appropriately selected according to the type of the thermoplastic resin of the component (B). That is, there is an optimum range according to the type of the thermoplastic resin of the component (B) in consideration of the compatibility of the component (A) and the component (B). The method for preparing the thermoplastic resin composition of the present invention is not particularly limited. For example, after the components (A) and (B) are preliminarily mixed by a mixing device such as a Henschel mixer, the mixture is mixed with a neater mixer.
A method of melt-mixing with a kneading device such as a Banbury mixer, a single-screw continuous kneader, a twin-screw continuous kneader, or a method of directly melting and kneading the two components by supplying the two components to the kneading device is used. A method of dissolving the two components in the above solvent and then removing the solvent can also be used.

In preparing the thermoplastic resin composition of the present invention, a reinforcing agent such as glass fiber, carbon fiber, thermoplastic resin fiber, graphite, mica, talc, silica fine powder, or a molding agent such as a filler or a lubricant is used. Stabilizers such as processability improvers, weathering agents, light stabilizers, antioxidants, UV inhibitors, flame retardants,
Conventional additives such as an antistatic agent, a coloring agent such as a pigment, a surfactant, and an antibacterial agent can be added as long as the effects of the present invention are not impaired.

Since the thermoplastic resin composition of the present invention has good compatibility of the vinyl polymer (A) with the thermoplastic resin (B), it can be used as it is by injection molding, extrusion molding, compression molding, blow molding and the like. It is possible to provide for various molding means. The molded product thus obtained has lubricity, release properties,
Since various properties such as moldability, water repellency, gas permeability and mechanical strength are excellent in balance, and there is no bleed out or separation of additive components, and it has good appearance characteristics,
It can be widely applied to various uses.

[0065]

The present invention will be described below in more detail with reference to examples. Me in the structural formulas in the examples represents a methyl group. The viscosity in the examples is a value measured at 25 ° C. In addition, each physical property value in the following Examples and Comparative Examples is a value measured by the following method.

[Molding conditions and releasability of molded article] 100 m
An appropriate amount of the resin composition is placed on a stainless steel mold from which one plate-shaped molded piece having a size of mx 100 mm x 3 mm can be taken,
Heat compression was performed at 220 ° C. for 10 minutes. Next, when the plate-shaped molded piece was taken out of the mold by hand after cooling, the releasability was relatively compared by touch. Here, the hot / cold press used was one made by Toyo Machinery.

[Appearance of Molded Article] The appearance of the obtained molded article was visually observed. [Lubricity] Molded from a cylindrical molded piece obtained by molding from a polypropylene resin (“Riprene Y101” manufactured by Sumitomo Chemical Co., Ltd.) and the thermoplastic resin compositions of the following Examples and Comparative Examples. Using the obtained disk-shaped molded piece,
Thrust friction and wear tester (Toyo Seiki Seisakusho)
The sliding friction coefficient when sliding under the conditions of a pressure of 1 kgf / cm and a sliding speed of 2.10 cm / sec was measured.

[Water repellency] The contact angle of the plate-like molded product to water was measured. Here, an automatic contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.) was used as the apparatus. [Oxygen permeability] According to the oxygen permeability test specified in JIS K-7126, the temperature was 23 ° C, the humidity was 0%, and the oxygen concentration was 5
% Oxygen permeability was measured. Here, an oxygen permeation tester (10/50 manufactured by Modern Control Co., Ltd.) was used as a measuring instrument, and a test piece having a coating area of 50 cm ² was used as a sample of the composition. The measured value P is a value of 10 billion times the oxygen permeability coefficient, and the unit is cm ³ · cm / (cm ² · sec · mm
Hg).

The contents of the polymethyl methacrylate resin, polystyrene resin and polybutylene terephthalate resin used in the following Examples and Comparative Examples are as follows. Polymethyl methacrylate resin: "Acrypet MF" manufactured by Mitsubishi Rayon Co., Ltd. Polystyrene resin: "Stylon 666" manufactured by Asahi Kasei Kogyo Co., Ltd. Polybutylene terephthalate resin: "PBT1400 × 04" manufactured by Toray Industries, Inc.

Reference Example 1 A 200 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 24.0 g of methyl methacrylate monomer.

[0071]

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6.0 g of a “carbosiloxane dendrimer containing a methacrylic group” represented by the following formula:
0 g and stirring them under a nitrogen atmosphere.
Heated to 0 ° C. Further, α, α′-azobisisobutyronitrile (hereinafter referred to as AIBN) 0.3 is added thereto.
g was added and stirred for 6 hours.

Next, a part of the toluene was removed by heating and stirring under reduced pressure with an aspirator. The remaining reaction solution was poured into a large excess of methanol, stirred, and allowed to stand to separate a precipitate. The precipitate was dried under reduced pressure to obtain 26.2 g of a colorless transparent solid. This is designated as “Polymer-1”.

Reference Example 2 To a 200 ml four-necked flask equipped with a stirrer, thermometer and reflux condenser was charged 90 g of toluene, which was heated to 70 ° C. while stirring under a nitrogen atmosphere. Then, 21.0 g of methyl methacrylate monomer and 3.0 n-butyl acrylate monomer were added.
g, 6.0 g of “carbosiloxane dendrimer containing methacryl group” used in Reference Example 1 and AIBN
0.3 g of the mixture was heated to 75 ° C.
The solution was gradually dropped while controlling so as not to exceed.

After the completion of the dropwise addition, the heating and stirring were continued to carry out the polymerization for a total of 6 hours. Next, a part of toluene was removed by heating and stirring under reduced pressure with an aspirator. After pouring the remaining reaction solution into a large excess of methanol and stirring,
The precipitate was separated by standing, and dried under reduced pressure to obtain 25.8 g of a colorless transparent solid. This is designated as “Polymer-2”.

Example 1 25 g (100 parts by weight) of polymethyl methacrylate resin and 100.0 g (400 parts by weight) of “Polymer-1” obtained in Reference Example 1 were combined with “Laboplast” manufactured by Toyo Seiki Seisaku-sho, Ltd. Mill, 220 ° C, 10
The mixture was heated and mixed at 0 rpm for 10 minutes. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated.
The results are shown in Table 1.

Example 2 125 g (100 parts by weight) of a polymethyl methacrylate resin and 3.75 g (3.0 parts by weight) of “Polymer-1” obtained in Reference Example 1 were mixed with “Toyo Seiki Seisakusho” Labo Plast Mill ”, 220 ° C, 10
The mixture was heated and mixed at 0 rpm for 10 minutes to obtain a thermoplastic resin composition. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated. The results are shown in Table 1.

Example 3 75 g of polystyrene resin (1
00 parts by weight) and “Polymer-1” obtained in Reference Example 1.
5 g (50 parts by weight) was charged into “Laboplast Mill” manufactured by Toyo Seiki Seisaku-sho, and 10 g at 220 ° C. and 100 rpm.
Heat and mix for minutes. The appearance of the molded product obtained by molding this,
The water repellency and oxygen permeability were evaluated. The results are shown in Table 1.

Example 4 60 g (100 parts by weight) of polybutylene terephthalate resin and 60 g (100 parts by weight) of “Polymer-1” obtained in Reference Example 1 were combined with “Laboplast Mill” manufactured by Toyo Seiki Seisaku-Sho, Ltd. At 260 ° C, 100r
Heat mixing at pm for 10 minutes. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated. The results are shown in Table 1.

Example 5 75 g (100 parts by weight) of a polymethyl methacrylate resin and 37.5 g (50 parts by weight) of "Polymer-2" obtained in Reference Example 2 were combined with "Laboplast" manufactured by Toyo Seiki Seisaku-sho, Ltd. Mill, 220 ° C, 100r
Heat mixing at pm for 10 minutes. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated. The results are shown in Table 1.

[Comparative Example 1] 75 g (100 parts by weight) of polymethyl methacrylate resin and 37.5 g (50 parts by weight) of polydimethylsiloxane having a viscosity of 1,000,000 centistokes were mixed in a “Laboplast Mill” manufactured by Toyo Seiki Seisaku-sho, Ltd. The mixture was mixed and heated and mixed at 220 ° C. and 100 rpm for 10 minutes. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated. The results are shown in Table 1.

Comparative Example 2 75 g (100 parts by weight) of polymethyl methacrylate resin and polymethyl methacrylate / polydimethylsiloxane-graft copolymer 3
7.5 g (50 parts by weight) was charged into “Laboplast Mill” manufactured by Toyo Seiki Seisaku-sho, and mixed by heating at 220 ° C. and 100 rpm for 10 minutes. The appearance, water repellency, and oxygen permeability of a molded product obtained by molding this were evaluated. The results are shown in Table 1.

[0083]

[Table 1] (Note) The unit of (*) is “cm ³ · cm / (cm ² · sec · mmHg)”

[0084]

As described above, the thermoplastic resin composition of the present invention is excellent in properties such as mold releasability, moldability, water repellency, oxygen permeability, and bleed-out and separation of additive components. Since it has no good appearance and good characteristics, it can be applied to various molding means, and the obtained molded product can be widely applied to various uses by utilizing the above characteristics.

Continued on the front page (72) Inventor Makoto Yoshitake 2-2 Chigusa Coast, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. R & D Division (72) Inventor Takayuki Aso 2-2 Chigusa Coast, Ichihara City, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Research and Development Headquarters (72) Inventor Yoshiji Morita 2-2 Chigusa Coast, Ichihara-shi, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd. Research and Development Headquarters F-term (reference) BB122 BB142 BB152 BB172 BC002 BC021 BD002 BF011 BF021 BG011 BG041 BG051 BG071 BG131 BJ001 CB002 CF002 CG002 CL002 CM042 CN012 CP161 CP171 FD010

Claims (4)

[Claims] 1. A composition comprising a vinyl polymer (A) having a carbosiloxane dendrimer structure in a side chain and a thermoplastic resin (B) other than the component (A), wherein the component (B) 100
A thermoplastic resin composition containing 0.01 to 500 parts by weight of the component (A) based on parts by weight. 2. The thermoplastic resin composition according to claim 1, wherein the carbosiloxane dendrimer structure in the component (A) is a group represented by the following formula (I). Embedded image In the formula, Z is a divalent organic group, p is 0 or 1, and R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms. X ¹ is a silylalkyl group represented by the following formula when i = 1. Embedded image (Wherein, R ¹ is the same as above, and R ² has ² carbon atoms.
10 to 10 alkylene groups, and R ³ has 1 to 1 carbon atoms.
And X ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is an integer of 0 to 3. )｝. 3. The vinyl polymer (A) comprises (a) 0 to 99.9 parts by weight of a vinyl monomer and (b) a radical polymerizable organic group represented by the following general formula (II). The thermoplastic resin composition according to claim 1 or 2, which is obtained by polymerizing a carbosiloxane dendrimer containing 100 to 0.1 parts by weight. Embedded image Wherein Y is an organic group capable of undergoing radical polymerization, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and X ¹ is a silylalkyl represented by the following formula when i = 1: Group. Embedded image (Wherein, R ¹ is the same as above, and R ² has ² carbon atoms.
10 to 10 alkylene groups, and R ³ has 1 to 1 carbon atoms.
And X ^{i + 1} is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a ⁱ is an integer of 0 to 3. )｝. 4. The radical-polymerizable organic group in the component (b) has a general formula: Or (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ⁵
Is an alkylene group having 1 to 10 carbon atoms. An acrylic or methacrylic group-containing organic group represented by formula (1): (Wherein, R ⁶ is a hydrogen atom or a methyl group, R ⁷
Is an alkyl group having 1 to 10 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms, b is an integer of 0 to 4, and c is 0 or 1. The thermoplastic resin composition according to claim 3, which is a group selected from the group consisting of a styryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms.