JP2003277450A - Polyorganosiloxane-based graft copolymer and thermoplastic resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an additive for a thermoplastic resin, developing high impact resistance and fluidity and a thermoplastic resin composition using the same. <P>SOLUTION: The polyorganosiloxane-based graft copolymer comprises a graft copolymer obtained by subjecting an epoxy group-containing vinyl-based monomer or a vinyl-based monomer mixture comprising the epoxy group- containing vinyl-based monomer to graft polymerization onto composite rubber composed of polyorganosiloxane rubber and polyalkyl (meth)acrylate rubber. The mass-average particle diameter of the composite rubber is 0.2 μm-1.0 μm and the ratio of the epoxy group-containing vinyl-based monomer component in the graft copolymer is 0.1-10 mass %. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyorganosiloxane-based graft copolymer used as an additive for a thermoplastic resin, and a thermoplastic resin composition containing the same, which is excellent in impact resistance and fluidity.

[0002]

2. Description of the Related Art Various methods have been proposed as a method for improving the impact resistance of a thermoplastic resin.
A method for blending a polyorganosiloxane-based graft copolymer grafted with an epoxy group-containing vinyl-based monomer is described.

[0003]

However, in the above method, since the epoxy group contained in the polyorganosiloxane-based graft copolymer has a chemical bondability with the polyester resin to be modified, the chain extension action is caused. This tends to reduce the fluidity of the entire composition. Therefore, there has been a problem that physical properties such as impact resistance are lowered in applications such as thin-wall molding requiring high fluidity.

[0004]

The present invention has been made in order to solve the above-mentioned problems, and is an additive for adding a thermoplastic resin exhibiting high impact resistance and fluidity, and a heat using the same. An object is to provide a plastic resin composition. That is, the gist of the present invention is to provide a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber with a vinyl monomer containing an epoxy group-containing vinyl monomer or an epoxy group-containing vinyl monomer. A graft copolymer obtained by graft polymerizing a monomer mixture, wherein the composite rubber has a mass average particle diameter of 0.2 μm to 1.0 μm, and the epoxy group-containing vinyl monomer occupies in the graft copolymer. The polyorganosiloxane-based graft copolymer is characterized in that the ratio of the components is 0.1 to 10% by mass.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyorganosiloxane rubber used in the present invention comprises a cross-linking agent for organosiloxane and polyorganosiloxane rubber [hereinafter referred to as cross-linking agent (I)] and, if desired, a graft crossing agent for polyorganosiloxane rubber [hereinafter referred to as graft The fine particles obtained by emulsion-polymerizing the crossing agent (I)] can be used. As the organosiloxane used for preparing the polyorganosiloxane rubber, a cyclic organosiloxane having 3 or more membered rings is used, and those having 3 to 6 membered rings are preferably used. Examples of such cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenyl. Examples thereof include cyclotetrasiloxane, which may be used alone or in combination of two or more kinds.

As the cross-linking agent (I) used for preparing the polyorganosiloxane rubber, trifunctional or tetrafunctional one, that is, trialkoxyalkyl or arylsilane or tetraalkoxysilane is used. Methoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like can be mentioned. The cross-linking agent (I) used in the present invention is preferably tetraalkoxysilane, and tetraethoxysilane is particularly preferably used among the above.

The graft cross-linking agent (I) used for preparing the polyorganosiloxane rubber does not react when preparing the polyorganosiloxane rubber, and is subsequently described in the presence of the polyorganosiloxane rubber for preparing the composite rubber. Is a siloxane having a functional group that reacts when polymerizing (meth) acrylate
Equation _CH 2 ⁼ CR 2 -COO- As specific examples ^{_{(CH 2) p -SiR 1 n}} O (3-n) / 2 ··· formula ^{_{1 CH 2 = CH-SiR 1}} n O (3-n) _/ 2 equation _{2 HS- (CH 2) p -SiR} 1 n O (3-n) / 2 Equation ^{_{3 CH 2 = CR 2 -C 6}} H 4 SiR 1 n O (3-n) / 2 ··· Equation 4 (each wherein R ¹ is a methyl group, an ethyl group, a propyl group or a phenyl group R ² represents a hydrogen atom or a methyl group,
n shows 0, 1 or 2 and p shows the integer of 1-6. )
The compound represented by

Among these, the (meth) acryloyloxyalkylsiloxane capable of forming the unit represented by the formula (1) has a high grafting efficiency and therefore can efficiently form a grafted chain. The composition of the present invention used is preferred because it has more excellent impact resistance. Among the (meth) acryloyloxyalkylsiloxanes, methacryloyloxyalkylsiloxanes are preferable, and specific examples thereof include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, and γ- Methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethoxysilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-
Methacryloyloxybutyldiethoxymethylsilane and the like can be mentioned.

The vinyl siloxane capable of forming the unit represented by the formula (2) is vinylmethyldimethoxysilane,
Examples of the mercaptosiloxane capable of forming the unit represented by Chemical formula 3 include γ-.
Examples thereof include mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldiethoxyethylsilane. Examples of the compound capable of forming the unit represented by Chemical formula 4 include p-vinylphenylmethyldimethoxysilane and the like. In polyorganosiloxane rubber,
The amount of the component derived from the cyclic organosiloxane is 60% by mass or more, preferably 70% by mass or more, and the amount of the component derived from the crosslinking agent (I) is 0 to 30% by mass, which is derived from the graft crossing agent (I). The amount of the component to be added is preferably 0.1 to 10% by mass.

In producing the latex of the polyorganosiloxane rubber component, US Pat. No. 2,891,920 is used.
Known methods such as the method described in Japanese Patent No. 3294725 and the method described in Japanese Patent No. 3294725 can be used. For example, a mixture of an organosiloxane, a cross-linking agent (I) and a graft crossing agent (I) (hereinafter referred to as an organosiloxane-based mixture) in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid, for example, a homogenizer. A method of elevating the temperature of the condensation reaction after forming an emulsion by a method of shear mixing with water using, for example, an organosiloxane emulsion in an emulsified state by stirring an organosiloxane mixture, an emulsifier and water, The polyorganosiloxane rubber latex can be obtained by, for example, a method of admixing an acidic compound such as sulfuric acid having no micelle forming ability to allow the condensation reaction to proceed.

The polyalkyl (meth) acrylate rubber used in the present invention includes the following alkyl (meth) acrylates, crosslinking agents for polyalkyl (meth) acrylate rubbers (hereinafter referred to as crosslinking agents (II)) and polyalkyl (meth) acrylates.
It is obtained by copolymerizing an acrylic rubber raw material mixture comprising a graft crossing agent for acrylate rubber (hereinafter referred to as graft crossing agent (II)). Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, and the like. These may be used alone or in combination. Among these, n-butyl acrylate is particularly preferable.

The cross-linking agent (II) is a compound having two or more radically polymerizable double bonds in one molecule, and includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di (meth) acrylate,
Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol tetra (meth) acrylate, allyl (meth) acrylate, divinylbenzene and triallyl cyanurate. The amount of the crosslinking agent (II) used is 0 in the polyalkyl (meth) acrylate rubber component.
10 to 10% by mass. Since the polyalkyl (meth) acrylate rubber is used as a composite rubber with the polyorganosiloxane in the present invention, the crosslinking agent (II) is appropriately added. If it exceeds 10% by mass, the rubber tends to be too hard.

As the graft crossing agent (II), compounds having two kinds of unsaturated groups having different reactivities are used, and examples of such compounds include allyl methacrylate, triallyl cyanurate, triallyl isocyanate and the like. You can Triallyl cyanurate and triallyl isocyanate seem to have the same reactivity of the three allyl groups, but the reactivity when the second and third allyl groups react after the reaction of the first allyl group Since the reactivity of the first allyl group is different, it can be regarded as having an unsaturated group having different reactivity. In the case of allyl methacrylate, among the two unsaturated groups,
The less reactive one also acts as a crosslinking site by reacting during part of the polymerization, and since these do not react at all during the polymerization, the remaining unsaturated group acts as a graft site during the subsequent graft polymerization. is there. The amount of the graft crossing agent (II) used is preferably 0.01 to 10% by mass in the polyalkyl (meth) acrylate rubber component. If it is less than 0.01% by mass, the effect as a graft crossing agent tends to decrease, and if it exceeds 10% by mass, the performance as a rubber tends to decrease. These cross-linking agents (II) and graft cross-linking agents (II) can be used alone or in combination of two or more, and a compound such as allyl methacrylate can be used as both.

The composite rubber used in the present invention comprises a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber, and the acrylic rubber raw material mixture is emulsion-polymerized in the presence of the above-mentioned polyorganosiloxane rubber latex. Obtainable. Alkyl (meta)
Acrylate, crosslinking agent (II) and graft crossing agent (II)
The acrylic rubber raw material mixture consisting of (1) may be added to the polyorganosiloxane rubber latex all at once or continuously. As the polymerization progresses, the polyalkyl (meth) acrylate rubber component forms a cross-linked network in which the polyorganosiloxane rubber component and the polyorganosiloxane rubber component are intertwined with each other, and the presence of the graft crossing agent (I) causes the polyorganosiloxane rubber component to become Alkyl (meta)
Grafting of the acrylate rubber component also occurs, resulting in a composite rubber latex that is substantially inseparable from each other.

The composition of the composite rubber used in the present invention is such that the polyorganosiloxane rubber component is 1 to 99% by mass, and the polyalkyl (meth) acrylate rubber component is 99.
1% by mass (the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component is 10
0 mass%) is preferred, 5 to 95 mass% of polyorganosiloxane rubber component, polyalkyl (meth)
More preferably, the acrylate rubber component is 95 to 5 mass%. Polyorganosiloxane rubber component is 99
If the content of the polyalkyl (meth) acrylate rubber component exceeds 99% by mass, the surface appearance of the resulting composition tends to deteriorate, and the impact resistance of the composition obtained tends to decrease.

The weight average particle size of the composite rubber used in the present invention must be in the range of 0.2 μm to 1.0 μm,
A more preferable lower limit is 0.3 μm and an upper limit is 0.7 μm. The weight average particle diameter is, for example, 0.1 ml obtained by diluting latex with distilled water to a solid content concentration of about 3%, and using a CHDF2000 type particle size distribution meter manufactured by MATEC, USA, a flow rate of 1.4 ml / min and a pressure of about 2.76 MPa. (About 4
The measurement can be performed using a capillary type cartridge for particle separation and a carrier liquid under the conditions of 000 psi) and a temperature of 35 ° C. The calibration curve of particle size is, for example, DUK
It can be prepared by measuring a total of 13 particle diameters from 0.02 μm to 1.0 μm using a monodisperse polystyrene with a known particle diameter manufactured by Company E as a standard particle diameter substance. If the weight average particle size is less than 0.2 μm, the total surface area of the rubber when compounded with the thermoplastic resin increases, so that the amount of epoxy groups required for improving impact resistance increases, and the fluidity of the composition increases. It tends to decrease. On the other hand, if it exceeds 1.0 μm, the rubber addition efficiency with respect to the development of impact resistance tends to decrease.

In the present invention, in addition to the above-mentioned composite rubber,
Graft-polymerize an epoxy group-containing vinyl monomer or a vinyl monomer mixture containing an epoxy group-containing vinyl monomer. The epoxy group-containing vinyl monomer used in the present invention, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, Examples thereof include glycidyl itaconate, and of these, it is more preferable to use glycidyl methacrylate. These may be used alone or in combination of two or more. The proportion of the epoxy group-containing vinyl-based monomer component in the entire graft copolymer needs to be in the range of 0.1 to 10% by mass. A more preferable lower limit is 0.5% by mass and an upper limit is 8% by mass. If it is less than 0.1% by mass, impact resistance tends to decrease, and if it exceeds 10% by mass, fluidity tends to decrease.

Further, as the monomer other than the epoxy group-containing vinyl monomer contained in the vinyl monomer mixture,
There is no particular limitation as long as it can be radically polymerized under the same conditions as the epoxy group-containing vinyl monomer, and an appropriate monomer can be selected and used according to the purpose. For example,
(Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate Unsaturated acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, maleic anhydride, acid anhydrides such as itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide and the like. Maleimide derivative, 2-hydroxypropyl (meth) acrylate,
Hydroxy group-containing monomer such as 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, (meth)
Acrylonitrile, diacetone acrylamide, nitrogen-containing substances such as dimethylaminoethyl methacrylate, butadiene, isoprene, chloroprene and other diene-based monomers, styrene, α-methylstyrene and other styrene-based monomers, and the like. They can be used alone or in combination of two or more.

The amount of the epoxy group-containing vinyl monomer or the vinyl group monomer mixture containing the epoxy group-containing vinyl monomer grafted in the graft copolymer is 100 mass% of the graft copolymer. When it is defined as mass%, it is preferably 5 to 50 mass%, and more preferably 10 to 30 mass%. The polyorganosiloxane-based graft copolymer is obtained by emulsifying a vinyl-based monomer mixture containing an epoxy group-containing vinyl-based monomer in a single stage or multiple stages in the presence of the composite rubber latex described above. It can be obtained by graft polymerization. In the graft polymerization, the component corresponding to the branch of the graft copolymer (here, the component derived from the vinyl monomer containing the epoxy group-containing vinyl monomer) is not grafted to the trunk component (here, the composite rubber). In addition, a so-called free polymer obtained by polymerizing only a branch component is obtained as a by-product and is obtained as a mixture of a graft copolymer and a free polymer. In the present invention, both of them are referred to as a graft copolymer. .

The thermoplastic resin used in the present invention is not particularly limited, but one containing at least one thermoplastic resin selected from polyester resin, polyamide resin, polyarylene sulfide resin and polyolefin resin as a main component is preferable. The polyester resin used in the present invention means terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipine as a resin constituent component. Acid, sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid and other dicarboxylic acids, or ester-forming derivatives thereof
One or more, and ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol,
One or two of hydroquinone, bisphenol A, 2,2-bis (4'-hydroxyethoxyphenyl) propane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends.
It is a polyester resin obtained by a polycondensation reaction with a glycol selected from one or more species, and may be either a homopolyester or a copolyester. As a comonomer component for constituting the copolyester, other than the above,
Glycolic acid, hydroxy acid, hydroxybenzoic acid, hydroxyphenylacetic acid, hydroxycarboxylic acid such as naphthyl glycolic acid, lactone compounds such as propiolactone, butyrolactone, caprolactone, and valerolactone can also be used. Trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid, a branched or crosslinked polyester using a polyfunctional ester-forming component such as pyromellitic acid within a range that can be retained. good. Also, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrachloroterephthalic acid,
1,4-Dimethylol tetrabromobenzene, tetrabromobisphenol A, tetrabromobisphenol A
Also included are polyester copolymers having a halogen compound as a substitution machine in an aromatic nucleus such as ethylene or propionoxyside adduct and having a halogen using a compound having an ester forming group. Further, a polyester-based elastomer that constitutes a block copolymer of a high melting point hard segment and a low melting point soft segment can also be used. Examples of this polyester-based elastomer include a block copolymer of a hard segment mainly containing an alkylene terephthalate unit and a soft segment consisting of an aliphatic polyester or polyether. These polyester resins can be used alone or in combination of two or more. Particularly preferred polyester resins are polybutylene terephthalate, polyethylene terephthalate and copolymers containing these as the main repeating units. As the comonomer component forming the copolymer, isophthalic acid, bisphenol A, 2,2 are particularly preferred. -Bis (β-hydroxyethoxyphenyl) propane, 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane and the like.

The polyamide resin used in the present invention is not particularly limited, and means all polymers which are composed of amino acid lactam or diamine and dicarboxylic acid and which can be melt-polymerized and melt-molded. Specific examples of the polyamide resin used in the present invention include the following resins. (1) Polyhexamethylene adipamide which is a polycondensation product of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms, for example, a polycondensation product of hexamethylenediamine and adipic acid. [6, 6
Nylon], polyhexamethylene azamide [6, which is a polycondensation product of hexamethylenediamine and azelaic acid]
9 Nylon], polyhexamethylene sebacamide [6, which is a polycondensation product of hexamethylenediamine and sebacic acid]
10 nylon], polyhexamethylene dodecanoamide [6,12 nylon] which is a polycondensation product of hexamethylenediamine and dodecanedioic acid, and polybis which is a polycondensation product of bis-p-aminocyclohexylmethane and dodecanedioic acid. (4-aminocyclohexyl) methandodecane,
(2) Polyundecanamide [1] which is a polycondensation product of ω-amino acid, for example, ω-aminoundecanoic acid
1 nylon], (3) ring-opening polymer of lactam, for example, polycapramide [6 nylon] which is a ring-opening polymer of ε-aminocaprolactam, polylauric lactam [12 nylon] which is a ring-opening polymer of ε-amino laurolactam. And so on. Among them, polyhexamethylene adipamide (6,6 nylon), polyhexamethylene azeramide (6,9 nylon), polycaprolamide (6 nylon)
Is preferably used. Further, in the present invention, for example, a polyamide resin produced from adipic acid, isophthalic acid and hexamethylenediamine can be used, and two or more kinds such as a mixture of 6 nylon and 6,6 nylon can be used. It is also possible to use a blended product containing the above polyamide resin.

The polyamide resin (1) is, for example, an organic dicarboxylic acid having 4 to 12 carbon atoms and 2 carbon atoms.
It can be prepared by polycondensation with the organic diamine contained in -13. Further, if necessary, the organic dicarboxylic acid can be used in a larger amount than the organic diamine so that the carboxy group in the polyamide resin is in excess of the amino group, and conversely, the amino group in the polyamide resin is carboxy. It is also possible to use the organic dicarboxylic acid in a smaller amount than the organic diamine so that it is in excess of the groups. Specific examples of the organic dicarboxylic acid include adipic acid, pimelic acid, suberic acid, sebacic acid, and dodecanedioic acid. Specific examples of the organic diamine include hexamethylenediamine and octamethylenediamine. The polyamide resin (1) may be prepared from a derivative capable of generating a carboxylic acid such as an ester or an acid chloride and a derivative capable of generating an amine such as an amine salt in the same manner as in the above method. it can.

The polyamide resin (2) can be prepared, for example, by heating an ω-amino acid in the presence of a small amount of water to cause polycondensation. Often, small amounts of viscosity stabilizers such as acetic acid are added. The polyamide resin (3) can be prepared, for example, by heating a lactam in the presence of a small amount of water to cause ring-opening polymerization. Often, small amounts of viscosity stabilizers such as acetic acid are added.
With the polyarylene sulfide resin used in the present invention,
Repeating unit represented by the general formula (Ar-S) [in the formula, A
r is (where X is —SO ₂ —, —CO—, —O—, or 1 carbon atom in the main chain which may have a lower alkyl side chain.
The alkylene groups of 5 are shown. ) And those having 1 to 8 halogens or substituents such as a methyl group on these aromatic rings. ] As a main constituent unit, may be a polymer having only a linear structure, and may have a crosslinked structure as long as it has melt processability.

The polyolefin resin used in the present invention is, for example, a homopolymer or copolymer of an olefinic monomer obtained by radical polymerization, ionic polymerization, etc., a predominant amount of the olefinic monomer and an inferior amount of the vinylic monomer. Copolymer with a polymer,
Examples thereof include those containing a copolymer of an olefin-based monomer and a diene-based monomer as a main component, and these may be used alone or in 2
Used in combination of two or more species. As the catalyst, known catalysts such as Ziegler catalyst, chromium catalyst and metallocene catalyst are used. Examples of the olefin-based monomer here include:
Examples thereof include ethylene, propylene, butene-1, hexene-1, decene-1, octene-1, 4-methyl-pentene-1 and the like, with ethylene and propylene being particularly preferred. Specific examples of homopolymers or copolymers of the above-mentioned olefinic monomers include low density polyethylene, ultra low density polyethylene, ultra low density polyethylene, linear low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene. , Ethylene-propylene copolymer, polymethylpentene, polybutene and the like. Moreover, these olefin polymers are used individually or in combination of 2 or more types. Among these, a polyolefin resin containing, as a main component, one or a mixture of two or more selected from the group consisting of polyethylene, polypropylene and an ethylene-propylene copolymer is particularly preferable.

The resin composition of the present invention contains pigments, dyes, glass fibers, metal fibers, and
Reinforcing agents and fillers such as metal flakes and carbon fibers, 2,6
-Phenolic antioxidants such as di-butyl-4-methylphenol, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), tris (mixed, mono and dinylphenyl) phosphite, diphenyl・ Phosphite antioxidants such as isodecyl phosphite, sulfur antioxidants such as dilauryl thiodipropionate and dimyristyl thiodipropionate diasterial thiodipropionate, 2-hydroxy-4-octoxybenzophenone , A benzotriazole-based ultraviolet absorber such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, bis (2,2,6,
6) -light stabilizer such as tetramethyl-4-piperidinyl, antistatic agent such as hydroxylalkylamine, sulfonate, lubricant such as ethylenebisstearylamide, metal soap, and tetrabromophenol A, decabromophenol oxide, By appropriately blending various additives such as a flame retardant such as TBA epoxy oligomer, TBA polycarbonate oligomer, antimony trioxide, etc., more desirable physical properties and characteristics can be adjusted.

[0026]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In each description, "part" and "%" all indicate "part by mass" and "% by mass". The evaluations in Examples and Comparative Examples were carried out according to the following methods. (1) Solid content concentration: determined by drying the particle dispersion at 170 ° C. for 30 minutes. (2) Particle size distribution, weight average particle size: 0.1 ml of latex diluted with distilled water to a solid content concentration of about 3% was used as a sample, and a flow rate of 1.4 ml / min was measured with a CHDF2000 type particle size distribution meter manufactured by MATEC, USA. , Pressure about 2.76MP
a (about 4000 psi) and a temperature of 35 ° C., using a capillary type cartridge for particle separation and a neutral carrier liquid. The calibration curve of the particle diameter was prepared by measuring 13 particle diameters in total of 0.02 μm to 1.0 μm using monodisperse polystyrene with a known particle diameter manufactured by DUKE, USA as a standard particle diameter substance. (3) Izod impact strength: Using a test piece obtained by injection molding, according to ASTM D256, a thickness of 3.2 mm,
It measured at 23 degreeC with a notch. (4) MFR: using pellets, 250 ° C., load 325
It was measured under the condition of g.

Reference Example 1 <Production of polyorganosiloxane-based graft copolymer (A-1)> 97.5 parts of octamethylcyclotetrasiloxane (hereinafter referred to as D4) and tetraethoxysilane 2 as a crosslinking agent.
Parts and 0.5 parts of γ-methacryloyloxypropyldimethoxymethylsilane which is a graft crossing agent, 150 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate is dissolved is added, and a homomixer is used for 10000r.
After stirring at pm for 2 minutes, add 20 MPa to the homogenizer.
At a pressure of 2 times to obtain a stable premixed organosiloxane latex. On the other hand, a separable flask equipped with a condenser and a stirring blade was charged with 251 parts of the above organosiloxane latex, and a 0.4% by mass aqueous sulfuric acid solution 5 was added.
0 part was added. With this mixed solution heated to 80 ° C., the temperature was maintained for 7 hours to polymerize octamethylcyclotetrasiloxane. The resulting reaction is then cooled,
After being kept at room temperature for 12 hours, it was neutralized with a 5% aqueous sodium hydroxide solution. The latex (L
The solid content concentration of -1) was 29.3%, the particle size distribution showed a single peak, and the weight average particle size was 350 nm. 27.3 parts of silicone latex (L-1) was collected, placed in a separable flask equipped with a stirring blade, 167.7 parts of distilled water was added, and after nitrogen replacement, the temperature was raised to 50 ° C.,
A mixed solution of 74 parts of n-butyl acrylate, 0.4 part of allyl methacrylate and 0.4 part of diisopropylbenzene hydroperoxide was added. Then, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of Rongalit and 5 parts of distilled water was added to start radical polymerization, and then the internal temperature was adjusted to 50
The temperature was kept at 1 ° C for 1 hour to obtain a silicone / acrylic composite rubber latex (S-1). The solid content concentration of S-1 was 29.
At 8%, the particle size distribution showed a single peak and the weight average molecular weight was 650 nm. To 275.2 parts of the composite rubber latex (S-1), a mixed solution of 2 parts of glycidyl methacrylate, 6 parts of methyl methacrylate and 0.5 part of diisopropylbenzene hydroperoxide was added dropwise over 12 minutes, and the internal temperature was 50 ° C for 1 hour. After holding and performing the first stage graft polymerization, a mixed solution of 10 parts of methyl methacrylate and 0.5 part of diisopropylbenzene hydroperoxide was added dropwise over 15 minutes, and the inside temperature was kept at 50 ° C. for 1 hour. Graft polymerization on the composite rubber was completed by carrying out the second stage graft polymerization to obtain a latex of a polyorganosiloxane-based graft copolymer (A-1). The solid content concentration of the latex was 33.3%, the particle size distribution showed a single peak, and the weight average particle size was 660 nm. (A-1)
Was added to a calcium chloride aqueous solution having a concentration of 5% by mass at 40 ° C. so that the mass ratio of the latex and the aqueous solution was 1: 2, and then the temperature was raised to 90 ° C. to coagulate and washing with water. After repeating, the solid content is separated and
It was dried at ℃ for 24 hours to obtain a dry powder of (A-1).

Reference Examples 2 and 3 <Production of Polyorganosiloxane-Based Graft Copolymer (A-2, A-3)> First graft-polymerized on composite rubber latex (S-1)
Polyorganosiloxane-based graft copolymers (A-2) and (A-3) were prepared in the same manner as in Reference Example 1, except that the compositions of the second and second stage monomers were changed as shown in Table 1. Synthesized.

[0029]

[Table 1]

Reference Example 4 <Production of Polyorganosiloxane Graft Copolymer (B-1)> Octamethylcyclotetrasiloxane 97.5 parts, tetraethoxysilane 2 parts, γ-methacryloyloxypropyldimethoxymethylsilane 0.5 The parts were mixed to obtain 100 parts of a siloxane mixture. 300 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate was dissolved was added thereto, and the mixture was stirred with a homomixer at 10,000 rpm for 2 minutes, and then passed through a homogenizer twice at a pressure of 30 MPa to obtain a stable premixed organosiloxane latex. Obtained. On the other hand, a separable flask equipped with a condenser and a stirring blade was charged with 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water to prepare a 10 mass% dodecylbenzenesulfonic acid aqueous solution. With this aqueous solution heated to 85 ° C., the premixed organosiloxane latex
The solution was added dropwise over a period of time, and after the completion of the addition, the temperature was maintained for 3 hours and then cooled. The reaction was then kept at room temperature for 12 hours and then neutralized with aqueous sodium hydroxide. The latex (L-2) thus obtained had a solid content concentration of 18.
Further, the particle size distribution showed a single peak and the mass average particle size was 32 nm. Silicone latex (L
24.2) was sampled, put in a separable flask equipped with a stirring blade, 153 parts of distilled water was added, and after nitrogen substitution, the temperature was raised to 50 ° C. and n-butyl acrylate 74 was added.
Part, allyl methacrylate 0.4 part and diisopropylbenzene hydroperoxide 0.4 part were added. Then, a mixed solution of 0.001 part of ferrous sulfate, 0.003 part of disodium salt of ethylenediaminetetraacetic acid, 0.2 part of Rongalit and 5 parts of distilled water was added to start radical polymerization, and then the internal temperature was 50 ° C. for 1 hour. By holding for a period of time, a silicone / acrylic composite rubber latex (S-2) was obtained. S
-2, the solid content concentration was 29.7%, the particle size distribution showed a single peak, and the weight average molecular weight was 73 nm.
Graft polymerization was performed in the same manner as in Reference Examples 1 to 3 except that (S-2) was used instead of (S-1), and polyorganosiloxane-based graft copolymers (B-1) to
(B-3) was synthesized.

Examples 1 and 2, Comparative Examples 1 to 5 Polybutylene terephthalate resin (Tufpet PBT, N130 manufactured by Mitsubishi Rayon Co., Ltd.) as a thermoplastic resin.
0) was blended with the polyorganosiloxane-based graft copolymers obtained in the respective reference examples in the proportions shown in Table 2, and the twin-screw extruder (ZSK3 manufactured by WERNER & PFLEIDERER) was used.
0) barrel temperature 240 ℃, screw rotation speed 2
The pellets were prepared by extrusion at 00 rpm. Next, a test piece for measuring physical properties was prepared with an injection molding machine, and impact strength was evaluated. The results are shown in Table 2.

[0032]

[Table 2]

When a polyorganosiloxane-based graft copolymer in which the particle size of the composite rubber and the amount of the epoxy group-containing monomer are within the range of the present invention is used (Examples 1 and 2), both impact resistance and fluidity are excellent. Resin composition. A resin composition using a polyorganosiloxane-based graft polymer in which the mass average particle diameter of the composite rubber is outside the specified range of the present invention,
The impact resistance was poor. Further, the resin composition using a graft polymer in which the amount of the epoxy group-containing monomer was outside the range specified by the present invention was poor in fluidity.

Examples 3 to 5 and Comparative Examples 6 to 8 Polyethylene terephthalate resin (Dyanite PA-210 manufactured by Mitsubishi Rayon) was used as the thermoplastic resin.
The polyorganosiloxane-based graft copolymer obtained in Reference Example, glass fiber, and talc were mixed in the proportions shown in Table 3, and a twin-screw extruder (WERNER & PFLEIDERER was used.
ZSK30) manufactured by the company was used to extrude the pellets at a barrel temperature of 280 ° C. and a screw rotation speed of 200 rpm to prepare pellets. Next, a test piece for measuring physical properties was prepared using an injection molding machine, and impact strength and HDT (method of ASTM D648, high load 18.6 Kg / cm2) were evaluated. The results are shown in Table 3.

[0035]

[Table 3]

When the polyorganosiloxane-based graft copolymer in which the particle size of the composite rubber and the amount of the epoxy group-containing monomer are within the range of the present invention is used, not only excellent flowability but also high impact resistance and heat resistance are obtained. The resin composition is developed.

[0037]

The polyorganosiloxane-based graft copolymer of the present invention, when added to a thermoplastic resin, becomes a thermoplastic resin composition excellent in both impact resistance and fluidity, and has various uses. Can be widely used in.

Continued front page    F term (reference) 4J002 AA011 BB001 BN212 BQ001                       CF001 CL001 FD01 FD04                       FD05 FD07 FD09 FD13 FD17                 4J026 AA45 AB44 AC09 AC15 BA08                       GA01 GA09

Claims (2)

[Claims] 1. A composite rubber comprising a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber,
A graft copolymer obtained by graft-polymerizing a vinyl monomer mixture containing an epoxy group-containing vinyl monomer or an epoxy group-containing vinyl monomer, wherein the composite rubber has a mass average particle diameter of 0.2 μm to A polyorganosiloxane-based graft copolymer having a thickness of 1.0 μm and a proportion of an epoxy group-containing vinyl-based monomer component in the graft copolymer of 0.1 to 10% by mass. 2. A thermoplastic resin composition containing the polyorganosiloxane-based graft copolymer according to claim 1 and a thermoplastic resin.