JPH02258855A - Surface-treated inorganic filler and styrene resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact resistance, heat- resistance and mechanical properties and containing a filler firmly bonded to polymer by compounding a styrene polymer with an inorganic filler surface- treated with a silane compound, etc. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts. wt. of a styrene polymer free from functional group with (B) 0.01-30 pts.wt. of a styrene polymer having epoxy group and (C) 1-550 pts.wt. of an inorganic filler surface-treated with a silane compound or a titanium compound. The surface-treatment is carried out by treating 100 pts.wt. of an inorganic filler with a mixture of 0.1-5 pts.wt. of the component B and 0.05-1 pts.wt. of a silane compound or a titanium compound. The component A is a styrene polymer having mainly syndiotactic structure, an atactic polystyrene or a butadiene-modified polystyrene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a surface-treated inorganic filler and a styrenic resin composition, and more particularly to electrical and electronic materials.

The present invention relates to a styrenic resin composition useful for molding industrial structural materials, home appliances, miscellaneous goods, automobile parts, etc., and a surface-treated inorganic filler particularly suitable for filling into styrenic polymers.

[Prior Art and Problems to be Solved by the Invention] Hitherto, various synthetic resins have been blended with inorganic fillers such as glass fibers to improve their mechanical properties, particularly their rigidity and heat resistance. However, since styrenic polymers do not have sufficient adhesion to inorganic fillers, additives and surface treatment agents for inorganic fillers have been investigated to improve this adhesion. As a result, various aminosilane compounds, polyester-based, urethane-based, and epoxy-based surface treatment agents are used.

Combinations of acrylic and vinyl acetate resins, and maleic anhydride styrene copolymers as additives have been developed. Specifically, a styrene/maleic anhydride-styrene/glass fiber composition (Japanese Unexamined Patent Publication No. 161836/1983, Publication No. 49-19097) and the like are known. However, even with these, the improvement effects were still not sufficient.

Also, Japanese Patent Application Laid-Open No. 62-257948 and Japanese Patent Application No. 63
Specification No. 4923 discloses a resin composition with excellent heat resistance and mechanical properties by adding an inorganic filler to syndiotactic polystyrene and an inorganic filler to syndiotactic polystyrene/thermoplastic resin and/or rubber, respectively. Proposed. However, even in these compositions, the adhesion between the syndiotactic polystyrene and the inorganic filler was insufficient, and there was room for improvement.

In other words, the addition of various inorganic fillers and additives that have been surface-treated with various conventional surface treatment agents still has insufficient adhesion to styrenic polymers, especially syndiotactic polystyrene, and is particularly resistant to Low impact resistance, Izot impact value (with notch) is 6.0 kg-CIl/CI
There was no material that exceeded this, and improvements in impact resistance were desired.

Therefore, the present inventor has created a composition that has unprecedented impact resistance, heat resistance, 2 mechanical properties, and sufficient adhesion to styrenic polymers, and has developed a composition that has sufficient adhesion to styrene polymers. We have conducted extensive research to develop surface-treated inorganic fillers and additives that can provide superior strength.

[Means to solve the problem]

As a result, it has been found that the above problems can be solved by subjecting the inorganic filler to surface treatment with a specific surface treatment agent. Furthermore, it has been discovered that a styrenic resin composition with excellent impact resistance can be obtained by blending a specific additive and an inorganic filler into a styrenic polymer in a specific ratio.The present invention is based on this knowledge. It was then completed.

That is, the present invention provides (a) 100 parts by weight of a styrenic polymer having no functional groups, (b) 0.01 to 30 parts by weight of a styrenic polymer containing epoxy groups, and (c) a silane compound or a titanium compound on the surface. The present invention provides a styrenic resin composition characterized in that it consists of 1 to 550 parts by weight of a treated inorganic filler, and further, 100 parts by weight of the inorganic filler is replaced by (b) a styrene resin composition having an epoxy group. The present invention provides a surface-treated inorganic filler characterized in that the surface is treated with a mixture consisting of 0.1 to 5 parts by weight of a combined substance and 0.05 to 1 part by weight of (d) a silane compound or a titanium compound.

The styrenic polymer that does not have a functional group and is used in the present invention may be any of various styrenic polymers on the condition that it does not have a functional group. represents an alkyl group, Z represents hydrogen, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5. ] A polymer having at least 25% by weight of repeating structural units derived from a vinyl aromatic compound represented by the above formula can be used.

Examples of such styrenic polymers include homopolymers of styrene or its derivatives, as well as polybutadiene, polyisoprene, and butyl rubber.

EPDM, ethylene-propylene copolymer, natural rubber,
Examples include styrenic polymers modified with natural or synthetic elastomeric materials such as epichlorohydrin, as well as styrene-containing copolymers such as styrene-methylstyrene copolymers, styrene-butadiene copolymers, and the like. Among these, in particular, styrenic polymers having a syndiotactic structure, atactic polystyrene, isotactic polystyrene, polybutadiene-modified styrene polymers, and butadiene-styrene copolymers.

Isoprene-styrene copolymers are preferred.

Here, a styrenic polymer with a mainly syndiotactic structure is a styrenic polymer whose stereochemical structure is mainly a syndiotactic structure, that is, a phenyl group or substituted phenyl group that is a side chain with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure in which carbon atoms are alternately located in opposite directions, and its toughness can be determined by nuclear magnetic resonance method (13C) using carbon isotope.
-NMR method). Toughness measured by the C-NMR method is expressed by the proportion of consecutive constituent units, e.g. 2 in the case of diats, 3 in the case of triats, and 5 in the case of pentads. However, in the present invention, the styrenic polymer mainly having a syndiotactic structure is usually 75% or more diad, preferably 85% or more, or 30% or more pentad (racemic pentad), preferably is a polystyrene or poly(alkylstyrene) having syndiotacticity of 50% or more.

Refers to poly(halogenated styrene), poly(alkoxystyrene), poly(vinyl benzoate), mixtures thereof, or copolymers having these as main components. Note that poly(alkylstyrene) here includes poly(methylstyrene), poly(ethylstyrene),
Examples of poly(isopropylstyrene) and poly(tert-butylstyrene) include poly(halogenated styrene) such as poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene).

Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene). Among these, particularly preferred styrenic polymers include polystyrene, poly(P-methylstyrene), and poly(m - methylstyrene).

Poly(p-tert-butylstyrene), poly(p-
chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and copolymers of styrene and p-methylstyrene.

Furthermore, the molecular weight of the styrenic polymer used in the present invention is not limited, but those having a weight average molecular weight of 10,000 or more are preferred, and those of 50,000 or more are particularly optimal. Further, there is no restriction on the width or narrowness of the molecular weight distribution, and various types can be used. If the weight average molecular weight is less than 10,000, the thermal properties or mechanical properties of the obtained composition or molded article will deteriorate, which is undesirable.

Such styrenic polymers having a mainly syndiotactic structure can be produced by using a titanium compound and a condensation product of water and trialkylaluminum as catalysts, for example, in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing monomers (monomers corresponding to the above-mentioned styrene polymers) (Japanese Patent Application Laid-Open No. 1983-1999).
187708).

The styrene polymer having an epoxy group, which is component (2), is used for surface treatment of this inorganic filler and for addition to the resin. This component (c) is soluble in various solvents like the silane compound or titanium compound that is component (d) described below, and is also compatible with the styrene polymer used to fill the surface-treated inorganic filler. be. Specific examples of the above component (b) include a copolymer of styrene or a styrene derivative and a vinyl compound having an epoxy group, or a copolymer of a styrene polymer and a vinyl compound having an epoxy group. I can do it.

Here, examples of the vinyl compound having an epoxy group include glycidyl methacrylate and glycidyl acrylate vinyl glycidyl ether.

Examples include glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate, and glycidyl itaconate. Among these, glycidyl methacrylate is particularly preferred. Styrenic polymers obtained by copolymerizing these vinyl compounds can be produced by various known methods, such as copolymerizing a vinyl compound having an epoxy group and styrene or a styrene derivative in the presence of a radical initiator. Alternatively, it can be produced by graft polymerizing a vinyl compound having an epoxy group and a styrene polymer in the presence of an organic peroxide.

Specific examples of styrenic polymers copolymerized with vinyl compounds having epoxy groups include vinyl compounds having epoxy groups, styrene polymers mainly having a syndiotactic structure, atactic polystyrene, isotactic polystyrene, and polybutadiene-modified polystyrene. Styrenic polymer, butadiene-styrene copolymer or isoprene-
These include polymers obtained by reacting styrene copolymers with heat or in the presence of peroxides, and styrene-glycidyl methacrylate copolymers obtained by polymerizing styrene and glycidyl methacrylate in the presence of a radical initiator. Among these, styrene-glycidyl methacrylate copolymer is particularly preferred.

This styrenic polymer copolymerized with a vinyl compound having an epoxy group is produced as described above, but preferably the vinyl compound unit having an epoxy group is contained in the copolymer in an amount of 0.01 to 40. It contains mol%, particularly preferably 0.1 to 20 mol%, and has a weight average molecular weight of 1.
000 to 500,000, particularly preferably 5,000 to 30
0000 is used. Here, if the vinyl compound unit having an epoxy group is less than 0.01 mol% in the copolymer, the adhesion between the styrene polymer, which is component (a) and does not have a functional group, and the inorganic filler is improved. If the amount exceeds 40 mol%, the compatibility with component (a), a styrenic polymer that does not have a functional group, may deteriorate, and the mechanical properties may deteriorate instead. . Furthermore, if the weight average molecular weight of the styrenic polymer having an epoxy group is less than 1,000, the adhesion improvement effect may not be observed, and if it exceeds 500,000, the dispersibility in the composition may deteriorate. be. The content of vinyl compound units having epoxy groups is determined according to JIS K
It is calculated from the epoxy equivalent measured according to 7236.

Next, the silane compound or titanium compound that is component (d) and the compound used for surface treatment of the inorganic filler that is component (c) are the inorganic filler and the epoxy group-containing styrene compound that is component (b). It is used as a coupling agent to improve adhesion with polymers, and can be selected from any conventionally known coupling agent as a silane coupling agent or titanium coupling agent. I can do it. Specific examples of this silane coupling agent include triethoxysilane, vinyl tris (β
-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, β-(1,1-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)- γ-aminopropyltrimethoxysilane, N-
β-(aminoethyl)-di-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane.

N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, T-chloropropyltrimethoxysilane.

T-aminopropyltrimethoxysilane, γ-aminopro and lutris(2-methoxy-ethoxy)silane, N
-Methyl-γ-aminopropyltrimethoxysilane, N
-vinylbenzyl-T-aminopropyltriethoxysilane, triaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4.5 dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N,O-(bis Examples include trimethylsilyl)amide, N,N-bis(trimethylsilyl)urea, and the like. Among these, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Aminosilanes such as trimethoxysilane and epoxysilanes are preferred.

Specific examples of titanium-based coupling agents include isopropyl triisostearoyl titanate 5 isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate.

Bis(dioctyl pyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-amidoethyl) aminoethyl) titanate, dicumylphenyloxyacetate titanate,
Examples include diisostearoyl ethylene titanate. Among these, isopropyl tri(N-amidoethyl, aminoethyl) titanate is preferred.

The inorganic filler used in the present invention may be fibrous, granular, or powdery. Examples of the fibrous inorganic filler include glass fiber, carbon fiber, alumina fiber, etc. Glass fibers and carbon fibers are particularly preferred.The shapes of glass fibers include cross-like shapes, mat-like shapes, bundle-cut shapes, short fibers, and filament shapes. is 0.05am~50
aaa.

Preferably, the fiber diameter is 5 to 20 pm. Further, as the carbon fiber, polyacrylonitrile (PAN) type carbon fiber is preferable.

On the other hand, examples of granular and powdery inorganic fillers include talc, carbon black, graphite titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, and magnesium carbonate.

Examples include magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, and the like. Particularly preferred are talc, calcium carbonate, and mica, and the preferred average particle size of talc is 0.3 to 2.
0 um %, more preferably 0.6 to 10 um, and the preferred average particle size of calcium carbonate is 0.1
~20am. Further, the average particle size of mica is preferably 40 to 250 am, more preferably 50 to 150 t.
Im.

Among the various inorganic fillers mentioned above, glass fillers such as glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass lobings, and glass mats are particularly preferred.

In the present invention, the above-mentioned components are blended, and the blending ratio is 1 to 550 parts by weight, preferably 5 to 550 parts by weight, of the surface-treated inorganic filler per 100 parts by weight of the styrene polymer that does not contain functional groups. If the amount of the zero-surface treated inorganic filler blended in 200 parts by weight is less than 1 part by weight, a sufficient blending effect as a filler will not be recognized. On the other hand, if it exceeds 550 parts by weight, there will be problems such as poor dispersibility and difficulty in molding.

For a resin composition consisting of a styrene polymer having no functional group, which is component (a), and an inorganic filler whose surface has been treated with a silane compound or a titanium compound, (
In addition to the method of adding the epoxy group-containing styrenic polymer as component (b), surface treatment is performed in advance with the epoxy group-containing styrenic polymer as component (b) and the silane compound or titanium compound as component (d). There is a method of adding a surface-treated inorganic filler to a styrenic polymer having no functional group, and the latter is also preferred since it is effective in improving the adhesion between the resin and the inorganic filler.

Examples of methods for surface treatment of inorganic fillers include Q)).

A surface-treated inorganic filler can be obtained by applying a solution consisting of component (d) and various solvents and/or water to the inorganic filler.

At this time, the amount of components (b) and (d) applied to the inorganic filler is 0.1 to 100 parts by weight based on 100 parts by weight of the inorganic filler.
It is applied in an amount of 5 parts by weight, preferably 0.5 to 2 parts by weight. When the coating ratio of component (b) is less than 0.1 part by weight,
The inorganic filler cannot be uniformly coated, and sufficient adhesive strength cannot be obtained when the inorganic filler is filled into the resin. As a result, the strength of the resin product may decrease. Moreover, if it exceeds 5 parts by weight, the inorganic filler will cause poor dispersion in the m-acid, which will similarly reduce the strength of the resin product.

The silane compound or titanium compound as component (d) is 0.05 parts by weight per 100 parts by weight of the inorganic filler.
~1.0 part by weight, preferably 0.1 to 0.5 part by weight is applied. If the coating ratio of component (a) is less than 0.05 part by weight, the adhesiveness will be significantly reduced, and even if it is blended in an amount exceeding 1 part by weight, no particular increase in the adhesiveness can be expected.

Surface treatment of the inorganic filler with the above components (b) and (d) can be carried out by a conventional method, and there are no particular limitations. For example, a sizing treatment in which an organic solvent solution or suspension of components (b) and (d) is applied as a so-called sizing agent to an inorganic filler, or a Henschel mixer, a super mixer, a Loedige mixer, a V
Depending on the shape of the inorganic filler, it can be carried out using an appropriate method such as dry mixing using a mold blender, spray method, integral blend method, dry concentrate method, etc.; It is desirable to do so.

Further, a film-forming substance for glass can be used in combination with the above-mentioned silane coupling agent. This film-forming substance is not particularly limited, and includes, for example, polyester-based, urethane-based, epoxy-based, acrylic-based, and vinyl acetate-based polymers.

Furthermore, various known lubricants may be added to prevent wear of the inorganic filler.

Thereby, the surface-treated inorganic filler of the present invention can be obtained.9 This surface-treated inorganic filler is made of polypropylene,
Although it can be used as a filler for various resins such as polycarbonate and polyethylene, it is particularly suitable as a filler for styrenic polymers that do not have functional groups. In order to improve the mechanical properties of styrenic polymers that do not have functional groups by filling them with this surface-treated inorganic filler,
In the same way as when filling the inorganic filler whose surface was treated with the silane compound or titanium compound which is the component (c), for 100 parts by weight of the component (a), Φ), which was surface treated with the component (d) The inorganic filler should be filled in an amount of 1 to 550 parts by weight; if the amount is less than this, or if it is too much, sufficient effects cannot be obtained as described above.

The resin composition of the present invention is composed of the above-mentioned styrenic polymer and surface-treated inorganic filler, but various additives or other synthetic resins may be added as necessary as long as they do not impede the purpose of the present invention. Can be blended. Here, the additives include, for example, sulfite ester-based, phosphate ester-based antioxidants, ultraviolet absorbers, aliphatic carboxylic acid ester-based, paraffin-based external lubricants, commonly used organic acid metal salts, organic Examples include nucleating agents such as phosphorus compounds, mold release agents, antistatic agents, coloring agents, and the like.

The resin composition of the present invention can be obtained by blending the above-mentioned components and, if necessary, various desired components, and kneading at an appropriate temperature. The blending and kneading at this time may be carried out by conventional methods. Specifically, a melt-kneading method using a Nigu, mixing roll, extruder, Banbury mixer, Henschel mixer, or kneading roll, or a solution blending method may be used.

Various molded articles can be manufactured using the resin composition of the present invention. Shape and molding method of molded products.

There are no particular restrictions on the degree of crystallinity, and it can be determined as appropriate depending on the characteristics required for the intended molded product. For example, the shape may be a sheet or a three-dimensional structure such as a container, and the molding method may be extrusion molding, injection molding, compression molding, blow molding, etc. depending on the shape of the molded product. I can do it. Furthermore, the degree of crystallinity may be either crystalline or non-crystalline.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Reference Example 1 (Production of polystyrene having a syndiotactic structure) To a reaction vessel, 2f toluene as a solvent, 5 mmol of tetraethoxytitanium as a catalyst component, and 500 mmol of methylaluminoxane as an aluminum atom were added.
Styrene 151 was added to this at 5°C, and a polymerization reaction was carried out for 4 hours.

After the reaction, the product was washed with a hydrochloric acid-methanol mixture, the catalyst component was decomposed and removed, and then dried and styrene/methanol was removed.
Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue of 97% by weight. The weight average molecular weight of this product is 400.000, the number average molecular weight is 180,
000, and the melting point was 269°C. In addition, analysis by 13C-NMR (solvent: 1,2-dichlorobenzene) showed that this polymer had an absorption at 145.35 ppm due to its syndiotactic structure, and the racemic pentad was calculated from the peak area. The syndiotactic rate was 98%.

Example 1 To 100 parts by weight of the syndiotactic polystyrene obtained in Reference Example 1 above, (2,6-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (trade name: PEP- 36i manufactured by Adeca Argus) 0.7 parts by weight, and 2.6-sheet t
Add 0.1 part by weight of ert-butyl-4-phenol (product name: Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), and further add p(tert-butyl)aluminum benzoate (product name: 2PTBBA-A1, Dainippon Ink Chemical Industry Co., Ltd.). company)
1 part by weight and styrene-glycidyl methacrylate (5 parts by weight)
mol%) copolymer (trade name: Blenmar CP10053:
Add 5 parts by weight of Mw-10XIO' manufactured by NOF Corporation,
After triblending, 43 parts by weight of glass fibers surface-treated with T-aminopropyltrimethoxysilane (aminosilane coupling agent) were pelletized using a twin-screw kneader while side-feeding.

Using the obtained pellet, injection molding was performed to obtain a bending test piece and an isot test piece. A bending test, a heat distortion temperature test, and an Izot test were conducted using the obtained test piece. The results are shown in Table 2.

Examples 2 to 9 and Comparative Examples 1 to 5 The same operations as in Example 1 were performed except that the types and amounts of each component were as shown in Table 1. The results are shown in Table 2.

In Example 10, 0.3 parts by weight of T-aminopropyltriethoxylan was atomized to 1001 parts of talc in a 20 f Henschel mixer at a temperature of 60 to 100°C and a rotation speed of 1100 rpm. The procedure of Example 1 was repeated, except that 50 parts by weight of talc after mixing for 5 minutes under the following conditions was added to 100 fE parts of syndiotactic polystyrene at the time of triblending.

Further, in Example 11, the same procedure as in Example 10 was carried out except that talc was replaced with calcium carbonate.

(Left below) *1 Reference example *2 Idemitsu Polystyrene HH30E Idemitsu Petrochemical ■
Manufactured by *3 Idemitsu Polystyrene IT40 Idemitsu Petrochemical ■
Umbrella manufactured by Nippon Oil & Fats Corporation 4 Blenmar CP10053 Styrene-glycidyl methacrylate (5 mol%) copolymer *5 manufactured by Nippon Oil & Fats Corporation BLEMMER CP2O3 Styrene-glycidyl methacrylate (20 mol%) copolymer manufactured by NOF Corporation *6 Blenmar CP503 Styrene-glycidyl methacrylate (50 mol%) copolymer *7 manufactured by Nippon Oil & Fats Co., Ltd. Chimachi Tsubuto strand, γ-aminoprobilt ethoxylan treatment Average fiber diameter 13 μm Average fiber length 311I
l *8 Chipped strand, N-β-(aminoethyl)γ-aminopropyltrimethoxylan treatment, average fiber diameter 13 μm, average fiber length 31 m *9 Glass powder, γ-aminopropyltriethoxylan treatment, average fiber diameter 9 μm Average fiber length 70IIm *10 Talc FFR Asada Seifun ■ Co., Ltd. γ-aminopropyltriethoxylan treatment average particle size 0.6 μm *11 Calcium carbonate KS'l 300' Kinpei Mining ■ Co., Ltd. γ-aminopropyltriethoxylan treatment average Particle size 3 μm (hereinafter referred to as margin) Examples 12 to 19 and Comparative Examples 6 to 10 Surface treatment Surface treatment base material with diameter 13 μm and average fiber length 3
After applying the surface treatment agent shown in Table 3 to the glass fibers of the cabinet by spraying, it was dried and subjected to kneading with a styrenic polymer.

As an antioxidant, (2,6-
tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name PEP-36:
0.7 parts by weight (manufactured by Adeka Argus) and 0.1 parts by weight of 2,6-di-tert-butyl-4-phenol (trade name Sumilizer BHT; manufactured by Sumitomo Chemical ■) were added.
Furthermore, 1 part by weight of p-(tert-butyl)aluminum benzoate (trade name: PTBBA-AI manufactured by Dainippon Ink & Chemicals Co., Ltd.) was added, and triblending was performed.
43 parts by weight of the glass fibers treated above (Example 19
(100 parts by weight) was side-fed and pelletized using a twin-screw kneader.

Using the obtained pellet, injection molding was performed to obtain a bending test piece and an isot test piece. Table 3 shows the formulation of the surface treatment agent used in the bending test, heat distortion temperature, and Izot test using the obtained test piece, and Table 4 shows the results of the obtained physical properties.
Shown in the table.

In addition, the preparation method of the surface treatment agent used here will be described.

Styrene-glycidyl methacrylate (5 mol%) in advance
Copolymer brand name (Blemmer CP10053 NOF■
Mw-10XIO') manufactured by Co., Ltd. was dissolved in toluene to obtain a 40 wt% solution.

7.5 parts by weight of the above solution, γ-aminopropyltriethoxysilane (silane coupling agent A manufactured by Nippon Unicar Co., Ltd.)
-1100) 1.0 parts by weight, 0.1 parts by weight of a nonionic lubricant (Chemitylene 5GF-6 manufactured by Sanyo Chemical Co., Ltd.) as a lubricant, and 95.9 parts by weight of water to prepare a surface treatment agent. .

Blenmar CP10053 Styrene-glycidyl methacrylate (5 mol%) copolymer manufactured by NOF ■, Mw = 10XIO'
) Dissolved in toluene and used as a 40wt% toluene solution Bremmer CP2O3 Styrene-glycidyl methacrylate (20mol%) copolymer manufactured by NOF ■, dissolved in toluene and used as a 40wt% toluene solution
Emulsion containing 56% by weight of polyvinyl acetate used as a toluene solution, Movinyl DC manufactured by Hoechst Synthesis Polyurethane emulsion Bondic 1310P manufactured by Dainippon Ink ■ γ-Aminopropyltriethoxysilane Nippon Unicar
Silane coupling agent A-1100 manufactured by Toray Silicone Inc. N-phenyl-T-aminopropyltriethoxysilane Silane coupling agent 5Z manufactured by Toray Silicone Inc.
6083* 7 Reference Example 1 * 8 Idemitsu Polystyrene HH30E Manufactured by Idemitsu Petrochemical Company *9 Idemitsu Polystyrene IT40 Manufactured by Idemitsu Petrochemical Company Four *10 Non-ionic lubricant Chemitylene 5 manufactured by Sanyo Chemical Company
GF-6 (Hereinafter, blank) [Effects of the Invention] As explained above, the resin composition of the present invention has excellent contact properties between the inorganic filler and the styrene polymer, and has good physical properties.

Furthermore, the surface-treated inorganic filler of the present invention has particularly excellent adhesion to styrenic polymers, and can improve the mechanical properties of styrenic polymers.

Therefore, the present invention is expected to be widely used in the production of various molded products such as electrical/electronic materials, industrial structural materials, home appliances, miscellaneous goods, and automobile parts.

Claims (4)

[Claims] (1) (a) Styrenic polymer 100 without functional groups
Part by weight, (b) Styrenic polymer having epoxy group 0
．． (c) 1 to 550 parts by weight of an inorganic filler whose surface has been treated with a silane compound or a titanium compound. (2) 100 parts by weight of an inorganic filler is coated with a mixture consisting of (b) 0.1 to 5 parts by weight of a styrene polymer having an epoxy group and (d) 0.05 to 1 part by weight of a silane compound or titanium compound. A surface-treated inorganic filler characterized by being treated. (3) (a) Styrenic polymer 100 without functional groups
Parts by weight and surface-treated inorganic fillers 1 to 55 according to claim 2
A styrenic resin composition comprising 0 parts by weight. (4) The styrenic resin according to claim 1 or 3, wherein the styrenic polymer having no functional group (a) is primarily a styrenic polymer having a syndiotactic structure, atactic polystyrene, or butadiene-modified polystyrene. Composition.