JP6104046B2 - Inorganic reinforcement compounding resin composition - Google Patents

Description

  The present invention relates to a resin composition for molding an inorganic reinforcing material. More specifically, the present invention relates to a resin composition for molding with an inorganic reinforcement material that has excellent impact resistance, and has excellent surface gloss and releasability.

  Thermoplastic resins or thermosetting resins such as polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyimide resin, epoxy resin, thermosetting unsaturated polyester resin and phenol resin have a melting point Alternatively, since it has a high softening point and excellent mechanical properties, it is widely used in various industrial fields such as the automobile industry, the electric and electronic industries.

In order to increase the rigidity and heat resistance of these thermoplastic resins or thermosetting resins,
Inorganic reinforcing materials such as carbon fibers are blended.

  However, when an inorganic reinforcing material is blended, there is a problem that high impact resistance of the thermoplastic resin or thermosetting resin is impaired.

  Therefore, in order to eliminate the problems caused by the blending of the inorganic reinforcing material, blending an olefin wax having a carboxyl group and / or a derivative group thereof (Patent Documents 1 and 2), and further adding a composite rubber graft copolymer Blending (Patent Document 3) is performed. However, since the olefin wax used in Patent Documents 1, 2, and 3 is generally poorly compatible with polycarbonate, which is a thermoplastic resin, the olefin wax is floated on the surface of the molded body by increasing the amount of the olefin wax. It is expected that the surface glossiness will be lowered. Although the impact resistance of the molded body is improved in Patent Documents 1, 2, and 3, surface gloss is not discussed. Resin modifiers obtained by adding silicon-modified oil wax as an olefin wax (Patent Document 4) or reacting a polyolefin having a functional group that reacts with a carbodiimide group and a carbodiimide group-containing compound have been proposed. (Patent Document 5). Patent Document 6 proposes a graft-modified polyethylene wax grafted with a monomer selected from a styrene monomer and an unsaturated carboxylic acid derivative monomer as a toner release agent. The unsaturated carboxylic acid derivative monomer of Patent Document 6 has been proposed as an ester derivative as a specific example, and a fumaric acid diester as a preferable specific example, but according to Patent Document 3, an olefin wax having no carboxyl group has impact resistance. Does not improve. Therefore, there is room for further improvement in order to achieve both the impact resistance and surface gloss of the molded body.

JP-A-8-188708 Japanese Examined Patent Publication No. 62-12814 JP 7-238213 A JP 2009-256655 A No. 2009/066649 Patent 2520892

    This invention provides the resin composition for inorganic reinforcement material compounding molding with favorable impact resistance, mold release property, and surface glossiness about the resin composition for inorganic reinforcement material compounding molding.

  The inventors of the present application grafted a styrene monomer and a specific unsaturated carboxylic acid derivative monomer onto at least one resin selected from the group consisting of a thermoplastic resin and a thermosetting resin containing an inorganic reinforcing agent. It has been found that a composition having good impact resistance, release and surface glossiness can be obtained by containing the modified olefin wax.

  The inorganic reinforcing material blending molding resin composition of the present invention comprises 95 to 50 parts by weight of at least one resin (A) selected from the group consisting of a thermoplastic resin and a thermosetting resin, and an inorganic reinforcing material (B). 5 to 50 parts by weight (provided that the total of component (A) and component (B) is 100 parts by weight) grafted with styrene monomer (a) and unsaturated carboxylic acid derivative monomer (b) The modified olefin wax (C) is contained in the range of 0.01 to 10 parts by weight.

  The thermoplastic resin is polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyimide resin, and the thermosetting resin is epoxy resin, thermosetting unsaturated polyester resin, and phenol. It is preferably at least one resin selected from the group consisting of resins.

  The inorganic reinforcing material (B) is preferably at least one filler selected from glass fibers and carbon fibers.

  The graft amount of the unsaturated carboxylic acid derivative monomer (b) in the modified olefin wax (C) is preferably 0.1 to 10% by weight.

  The graft amount of the styrene monomer (a) in the modified olefin wax (C) is preferably 5 to 80% by weight.

The resin composition for molding an inorganic reinforcing material according to the present invention includes the styrene monomer (a) in the modified olefin wax (C), the unsaturated carboxylic acid derivative monomer (b), and an olefin monomer that is a modified precursor. The graft amount ratio of the wax (D) satisfies the following relationship.
0.01 <(b) / (a) <1
0.05 <(a) / (D) <3

  The modified olefin wax (C) of the present invention is excellent in mechanical properties such as tensile properties and bending properties, and impact resistance, and is also excellent in surface gloss of the molded product. The mechanism is considered as follows. . That is, the affinity between the unsaturated carboxylic acid derivative monomer (b) of the modified olefin wax (C) and the inorganic reinforcing material, or the effect that the modified olefin wax (C) having a low surface tension wets the surface of the inorganic reinforcing material, Shearing applied to the reinforcing material such as glass fiber at the time of molding is suppressed, and the reinforcing fiber length in the resin composition is kept long. Thereby, it is considered that excellent mechanical properties such as tensile properties and bending properties are exhibited. As for the improvement in impact resistance, the modified olefin wax (C) covers the surface of the inorganic reinforcing material, and when impact is applied, the modified resin covers the thermoplastic resin or thermosetting resin and the inorganic reinforcing material. It is considered that interfacial peeling occurs between the olefinic waxes (C), uniform voids (voids) are generated, and the impact is absorbed. The styrene monomer (a) of the modified olefin wax (C) is particularly excellent in compatibility with a thermoplastic resin or a thermosetting resin having an aromatic skeleton, so that it does not float on the surface of the molded product, and the surface gloss Is expressed.

Hereinafter, the present invention will be specifically described.
The present invention comprises at least one resin (A) selected from the group consisting of thermoplastic resins and thermosetting resins, an inorganic reinforcing material (B), and a modified olefin wax (C).
<At least one resin (A) selected from thermoplastic resins and thermosetting resins>

  The thermoplastic resin and thermosetting resin used in the present invention are polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, and polyimide resin, and the thermosetting resin is epoxy resin, heat resin. It is at least one resin selected from the group consisting of a curable unsaturated polyester resin and a phenol resin. That is, these thermoplastic resins and thermosetting resins can be used singly or in combination of two or more.

  The definitions and production methods for these thermoplastic resins or thermosetting resins are well known, and are described in publications such as “Practical Plastics Encyclopedia” (Edited by Practical Plastics Encyclopedia, published by Industrial Research Co., Ltd.). Has been.

The following resins (1) to (7) are thermoplastic resins.
(1) Polycarbonate resin

Typically, it is a resin obtained by reacting an aromatic diol (for example, bisphenol A) and phosgene. In the present invention, diethylene glycol diallyl carbonate is preferred.

Such polycarbonate resins are commercially available, and examples thereof include trade names such as NOVAREX (Mitsubishi Engineering Plastics), Panlite (Teijin Chemicals), Lexan (SABIC Innovative Plastics). Can be preferably used in the present invention.

(2) Thermoplastic polyester resin Typically a resin obtained by polycondensation of dicarboxylic acid and diol. In the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalene dicarboxylate Polycyclohexane terephthalate and the like are preferably used.

Such thermoplastic polyester resins are commercially available, and examples thereof include trade name Rynite (DuPont) and can be preferably used in the present invention.
(3) ABS resin

Typically, it is an impact resistant resin obtained by graft polymerization of acrylonitrile and styrene to polybutadiene. In the present invention, the polybutadiene component is 5 to 40% by weight, and the graft amount of the styrene component and the acrylonitrile component. The ratio (styrene / acrylonitrile) is preferably 70/30 to 80/20.

  Such ABS resins are commercially available, and examples thereof include trade names such as Stylac (Asahi Kasei Chemicals Co., Ltd.) and Psycolac (Ube Saikon Co., Ltd.), and can be preferably used in the present invention.

(4) Polyacetal resin Typically, a resin obtained by ring-opening polymerization of formalin or trioxane together with ethylene oxide as desired in the presence of a cationic catalyst, and having a polyoxymethylene chain as the main skeleton However, in the present invention, the copolymer type is preferable.

Such polyacetal resins are commercially available, and examples thereof include trade names such as Iupital (Mitsubishi Engineering Plastics Co., Ltd.) and can be preferably used in the present invention.
(5) Polyamide resin

  Typically, it is a resin obtained by polycondensation of diamine and dicarboxylic acid or ring-opening polymerization of caprolactam. In the present invention, it is a polycondensation reaction product of aliphatic diamine and aliphatic or aromatic dicarboxylic acid. Is preferred.

Such polyamide resins are commercially available, and examples thereof include trade names such as Leona (Asahi Kasei Chemicals Co., Ltd.), Zytel (Deyupon Co., Ltd.) and the like, and can be preferably used in the present invention.
(6) Polyphenylene oxide resin

  Typically, it is a resin obtained by oxidative coupling of 2,6-dimethylphenol in the presence of a copper catalyst, but a modified polyphenylene oxide resin modified by a technique such as blending this resin with another resin Can also be used in the present invention.

  In the present invention, blend-modified products of styrenic polymers are preferred. Such polyphenylene oxide resins are commercially available, and examples thereof include trade names such as Zylon (Asahi Kasei Chemicals Co., Ltd.) and Iupiace (Mitsubishi Engineering Plastics Co., Ltd.), and can be preferably used in the present invention.

(7) Polyimide resin Typically a resin obtained by polycondensation of tetracarboxylic acid and diamine to form an imide bond in the main skeleton, but in the present invention, from pyromellitic anhydride and diaminodiphenyl ether What is formed is preferred.

  Such a polyimide resin is commercially available, and examples thereof include trade name Vespel (DuPont Co., Ltd.), and can be preferably used in the present invention.

  Resin (8)-(10) demonstrated below is a thermosetting resin, and demonstrates the thing of the state before thermosetting.

(8) Epoxy resin Typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of an alkali. In the present invention, bisphenol having an epoxy equivalent of 170 to 5000 is used. A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are preferable.

  Such epoxy resins are commercially available, and examples thereof include Epomic (Mitsui Chemicals Co., Ltd.), Epicron (Dainippon Ink Chemical Co., Ltd.), Sumi Epoxy (Sumitomo Chemical Co., Ltd.) and the like. Can be preferably used in the present invention.

(9) Thermosetting unsaturated polyester resin Typically, it is a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the present invention, maleic acid or fumaric acid is used. A resin obtained by esterifying an unsaturated dicarboxylic acid such as ethylene glycol and a diol such as diethylene glycol is preferred.

  Such thermosetting unsaturated polyester resins are commercially available, and examples thereof include trade names such as Rigolac (Showa High Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite Co., Ltd.), and the like, which are preferably used in the present invention. Can do.

(10) Phenolic resin In the present invention, both so-called novolak type and resol type are included, but a novolak type cured with hexamethylenetetramine and a solid resol mainly composed of dimethylene ether bonds are preferable.

  Such a phenol resin is commercially available, and examples thereof include trade name Sumiko PM (Sumitomo Bakelite Co., Ltd.), Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.) and the like, and can be preferably used in the present invention. .

In the present invention, a combination of polycarbonate resin, polybutylene terephthalate, which is one of thermoplastic polyester resins, and a combination of polycarbonate resin and ABS resin is preferable.
<Inorganic reinforcement (B)>

The inorganic reinforcing material (B) used in the present invention refers to at least one selected from glass fibers, carbon fibers, and fillers. These inorganic reinforcing materials (B) can be used alone or in combination of two or more.

  The type of glass fiber is not particularly limited, and roving glass, chopped strand glass, milled glass, and the like can be used. These may be used alone or in combination of two or more.

  The length of the glass fiber may be broken when it is mixed with the resin with an extruder or the like, and is not particularly limited, but is preferably 0.3 mm to 10 mm, and preferably 2 mm to 7 mm from the viewpoint of workability. The length of the glass fiber in the composition of the present invention is 2 mm to 5 mm. Although the thickness of the glass fiber is not particularly limited, the average fiber diameter is 1 to 25 μm, preferably 5 to 17 μm. Further, the aspect ratio (average fiber length / fiber diameter) is preferably 25 or less, but glass fibers having different aspect ratios can be mixed and used at an appropriate ratio. There is no particular limitation on the cross-sectional shape of the glass fiber, and a circular shape, an eyebrows shape, a gourd shape, an ellipse shape, a cylindrical shape, and the like can be used.

  Moreover, the glass fiber may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. Examples of the silane coupling agent herein include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Examples include silane and γ-chloropropyltrimethoxysilane.

  In addition, the glass fiber may be subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In this case, the olefin resin or urethane resin used for the bundling treatment is used in a range that does not affect the physical properties of the entire composition.

  Further, the glass fiber may be coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a plating method or a vapor deposition method.

  There are no particular restrictions on the shape and type of the carbon fiber, and the shape may be a chopped strand, a roving strand, a milled fiber, or the like, and the type may be either pitch-based or polyacrylonitrile-based.

  In addition to those obtained by spinning or molding these raw material compositions and then carbonizing them, it is also possible to use carbon fibers obtained basically without passing through a spinning step as in the vapor phase growth method.

When such vapor grown carbon fibers are used, the fiber diameter is small and the L / D is large, so that it is possible to obtain a molded product having high rigidity and good appearance.
Further, the carbon fiber of the present invention can be used with a specific surface area increased by performing an activation treatment.

  These carbon fibers are preferably those surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.

  Examples of the sizing agent include epoxy resins, urethane resins, olefin resins, styrene resins, polyester resins, nylon resins, and the like. Epoxy resins and urethane resins are preferred.

  The fiber diameter is generally in the range of 6 to 18 μm, but in the present invention, the diameter is preferably 0.5 to 15 μm, particularly preferably 1 to 10 μm.

  The cut length of the chopped strand used in the present invention is preferably 1 to 15 mm, more preferably 2 to 10 mm, and most preferably 3 to 8 mm. In addition, the chopped strand is crushed during the molding.

  The aspect ratio (L / D), which is the ratio between the length L of the carbon fiber in the fiber axis direction and the fiber diameter D in the resin composition, is preferably in the range of 15 to 100, and more preferably in the range of 20 to 50.

  Fillers include calcium carbonate, silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, amorphous fillers such as aluminum hydroxide, alumina, magnesium hydroxide, plate shapes such as talc, mica, or glass flakes. Fillers, wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, acicular fillers such as aluminum borate, fillers such as metal powder, metal flakes, carbon black, and carbon fine particles are used. Other glass beads, glass powder, etc. are used. These fillers may be used alone or in combination, or those whose surfaces are subjected to carbon coating or silane coupling treatment may be used alone or in combination.

  In the present invention, among these inorganic reinforcing materials, glass fibers and carbon fibers are preferably used, and glass fibers are particularly preferable from the viewpoint of affinity with the modified olefin wax used in the present application.

The at least one resin (A) selected from the group consisting of the thermoplastic resin and thermosetting resin used in the present invention is 95 to 50% by weight, preferably 95 to 70% by weight, more preferably 95 to 80% by weight. When the resin (A) is within the above range, a molding resin composition having improved molding processability and excellent surface gloss and mechanical properties can be obtained.
The inorganic reinforcing material (B) used in the present invention is 5 to 50% by weight, preferably 5 to 30% by weight, and more preferably 5 to 20% by weight. When the inorganic reinforcing material (B) is within the above range, the molding processability is improved, and a molding resin composition having excellent surface gloss and mechanical properties can be obtained.

<Olefin wax (D)>
Examples of the olefin wax (D), which is a modified precursor of the modified olefin wax (C) used in the present invention, include polyethylene wax and polypropylene wax, and those obtained by polymerizing olefins. It may also be obtained by thermally decomposing high molecular weight polyethylene or polypropylene.
Manufacture of what is obtained by superposing | polymerizing an olefin can be performed by any conventionally well-known method, For example, it can superpose | polymerize using a titanium catalyst, a vanadium catalyst, a metallocene catalyst, etc. The olefin wax (D) is particularly preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The α-olefin may be linear or branched, and may be substituted or unsubstituted.

 The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, more preferably propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, 1-pentene having 5 carbon atoms, and carbon atoms. Examples thereof include 1-hexene, 4-methyl-1-pentene having 6 formulas, 1-octene having 8 carbon atoms, and particularly preferable examples include propylene, 1-butene, 1-hexene and 4-methyl-1-pentene. It is done.

  The form of the olefin wax (D) as described above may be any form of resin and elastomer, and any of the isotactic structure and syndiotactic structure can be used as the steric structure. There are no particular restrictions on regularity. Commercially available olefin waxes can be used as they are.

  The olefin wax (D) used in the present invention has a lower limit of density measured by JIS K7112 D method (density gradient tube method) of 870 kg / m 3 or more, preferably 890 kg / m 3 or more, more preferably 910 kg / m 3 or more. The upper limit is 980 kg / m 3 or less, preferably 970 kg / m 3 or less, more preferably 960 kg / m 3 or less. When the density of the olefinic wax (D) is within the above range, a resin composition for molding an inorganic reinforcing material can be obtained which has less surface tackiness and excellent mechanical properties and impact properties.

  The lower limit of the melting point of the pre-modified olefin wax (D) used in the present invention measured by a differential scanning calorimeter (DSC) is 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 100. The upper limit is 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 120 ° C. or lower. When the melting point of the olefinic wax (D) is within the above range, a molding resin composition having less surface tackiness and excellent mechanical properties and impact properties can be obtained.

  The pre-modified olefin wax (D) used in the present invention has a weight average molecular weight (Mw) and a number average molecular weight (Mn) determined by gel permeation chromatography (GPC). Measured as solvent. Number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 400 to 5,000, preferably 400 to 4,000, more preferably 400 to 3,000, particularly preferably 400 to 1,000. It is desirable to be in range. When the number average molecular weight (Mn) of the olefin wax (D) is within the above range, the dispersibility of the wax is improved, and a molding resin composition having excellent mechanical properties and impact resistance can be obtained.

  In the olefin wax (D) used in the present invention, the upper limit of the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) measured by GPC is 4.0 or less, preferably 3.5 or less, more preferably It is desirable that it is 3.0 or less. The lower limit value of Mw / Mn is 1.1 or more, preferably 1.3 or more, more preferably 1.5 or more. Molding resin composition having excellent mechanical properties and impact resistance when the ratio (Mw / Mn) of weight average molecular weight to number average molecular weight (Mw / Mn) of olefin wax (D) is within the above range. You can get things.

GPC measurement was performed under the following conditions. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / General calibration method

  In addition, the coefficient of the Mark-Houwink viscosity formula was used for calculation of general-purpose calibration. The values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)) are used for the Mark-Houwink coefficients of PS and PE, respectively. It was.

  The olefin wax (D) used in the present invention has a penetration hardness measured by JIS K2207 of 40 dmm (dmm = 0.1 mm) or less, preferably 35 dmm or less, more preferably 30 dmm or less. When the penetration hardness of the olefin wax (D) is within the above range, the mechanical properties of the molding resin composition are excellent.

  The olefin wax (D) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.04 to 0.47 dl · g−1, preferably 0.04 to 0.30 dl · g−. 1, more preferably 0.04 to 0.20 dl · g −1, particularly preferably 0.04 to 0.15 dl · g −1. When the intrinsic viscosity [η] of the olefin wax (D) is within the above range, a molding resin composition with less outgas during molding and excellent mechanical properties and impact resistance can be obtained.

<Styrene monomer (a)>
Specific examples of the styrene monomer (a) used together with the unsaturated carboxylic acid derivative monomer (b) in the present invention include, for example, styrene, methyl styrene, ethyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and the like. Of these, styrene is preferable from the viewpoint of removing unreacted substances.

<Unsaturated carboxylic acid derivative monomer (b)>
When the unsaturated carboxylic acid derivative monomer (b) used together with the styrenic monomer (a) in the present invention is used, an unsaturated compound having one or more carboxylic acid groups, an unsaturated compound having one or more carboxylic anhydride groups, and derivatives thereof Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specific examples of the derivatives include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept- Examples thereof include unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, and esters). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. An acid anhydride, monomethyl maleate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. can be mentioned.

  When using unsaturated carboxylic acid derivative monomer (b), it can also be used individually by 1 type and can also be used in combination of 2 or more type. Among these, maleic anhydride, (meth) acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Hydroxyethyl (meth) acrylate is preferred. Furthermore, it is a dicarboxylic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride. It is particularly preferred.

<Method for producing modified olefin wax (C)>
The modified olefin wax (C) of the present invention is obtained by reacting an olefin wax (D) with a styrene monomer (a) unsaturated carboxylic acid derivative monomer (b).

 The production method of the modified olefin wax (C) of the present invention is not particularly limited, and can be performed according to various conventionally known methods. The olefin wax (D), the styrene monomer (a), the unsaturated carboxylic acid derivative monomer (b), and the organic peroxide are simultaneously or sequentially used, for example, Henschel mixer, V-type blender, tumbler It can be obtained by charging into a blender, ribbon blender or the like and kneading, and then melt-kneading with a single screw extruder, multi-screw extruder, kneader, Banbury mixer or the like. Among these, when an apparatus excellent in batch-type melt kneading performance such as an autoclave is used, a modified olefin wax (C) in which each component is more uniformly dispersed and reacted can be obtained. Compared to the continuous type, the batch type is easy to adjust the residence time, and since the residence time can be made longer, it is relatively easy to increase the modification rate and modification efficiency, and is the most preferred embodiment in the present invention.

  The graft ratio (b) / (a) between the styrene monomer (a) and the unsaturated carboxylic acid derivative monomer (b) in the modified olefin wax (C) is preferably 0.01 to 1, 0.03 to 0.8 is more preferable, and 0.05 to 0.6 is particularly preferable. When the graft amount ratio (b) / (a) is smaller than 0.01, the interaction with the surface of the inorganic reinforcing material of the unsaturated carboxylic acid derivative monomer (b) is reduced, so that the impact resistance is not improved. On the other hand, when the graft amount ratio (b) / (a) is larger than 1, the melt viscosity of the modified olefin wax (C) becomes high, making it difficult to produce.

  The graft amount ratio (a) / (D) of the styrene monomer (a) and the olefin wax (D) in the modified olefin wax (C) is preferably 0.05 to 3, preferably 0.07 to 2. 0.5 is more preferable, and 0.1 to 2 is particularly preferable. When the graft ratio (a) / (D) is within the above range, the dispersibility of the modified olefin wax (C) in the thermoplastic resin and the thermosetting resin is improved, and the surface gloss and impact properties are excellent. A molding resin composition can be obtained.

  In addition, various additives can be blended with the wax of the present invention as necessary within a range not impairing the object of the present invention. For example, a softener, a stabilizer, a filler, an antioxidant and the like can be blended.

<Method for producing resin composition for molding compounded with inorganic reinforcing material>
Any method can be used as a method for producing the resin composition for molding an inorganic reinforcing material of the present invention. For example, at least one resin (A) selected from a thermoplastic resin or a thermosetting resin, an inorganic reinforcing material (B), a modified olefin wax (C), and other optional components may be simultaneously or in any order, A method of mixing with a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, a single-screw or twin-screw extruder, or the like is appropriately used.

 The resin composition thus obtained is molded by various known methods such as injection molding, extrusion molding and compression molding, and injection molding is preferred from the viewpoint of design and moldability.

<Optional component>
The resin composition for molding with an inorganic reinforcing material of the present invention may contain any additive, for example, brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, tricarbonate, as long as the object and effect of the present invention are not impaired. Flame retardants such as phenyl phosphate, phosphonic acid amide and red phosphorus, flame retardant aids such as antimony trioxide and sodium antimonate, heat stabilizers such as phosphate esters and phosphites, hindered phenols, etc. Such as antioxidants, heat-resistant agents, weathering agents, light stabilizers, mold release agents, flow modifiers, colorants, lubricants, antistatic agents, crystal nucleating agents, plasticizers and foaming agents as needed You may mix | blend the effective expression level.

  Currently, plastic materials are used in a wide range of applications from household goods to industrial goods. Use the inorganic reinforcing material compounding resin composition of this application as a material or molded article impact resistance or surface condition modifier. Can do. Examples of the molded body obtained by such a method include electrical parts, electronic parts, automotive parts, mechanical mechanism parts, food containers, films, sheets, fibers, and the like. More specifically, for example, printers, personal computers, and the like. , Word processor, keyboard, PDA (small information terminal), telephone, mobile phone, smartphone, tablet terminal, WiFi router, facsimile, copier, ECR (electronic cash register), calculator, electronic notebook, electronic dictionary, card, Office and office equipment such as holders and stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, bags, etc .; TVs, VTRs, video cameras, digital cameras, SLR cameras, mobile phones Audio terminal, radio cassette, tape recorder, mini disc, CD player, speaker, LCD disc Ray and other AV equipment; connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, and other electrical / electronic components and communication equipment It is done.

  In addition, seats (filling, dressing, etc.), belts, ceilings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, tires, mattress covers, airbags, insulation, hanging hands, Suspension band, wire covering material, electrical insulation material, paint, coating material, upholstery material, flooring, corner wall, deck panel, covers, plywood, ceiling plate, partition plate, side wall, carpet, wallpaper, wall covering material , Exterior materials, interior materials, roofing materials, sound insulation plates, heat insulation plates, window materials, etc., automobiles, vehicles, ships, aircraft and building materials; clothing, curtains, sheets, plywood, synthetic fibers, carpets, doormats, sheets, Life / sports goods such as buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and the like.

  Furthermore, bottles for shampoos and detergents, seasoning bottles for edible oil and soy sauce, beverage bottles for mineral water and juice, lunch boxes, containers for heat-resistant food such as bowls for steaming tea, dishes such as dishes and chopsticks Other various food containers, packaging films, packaging bags and the like.

<Production Example 1>
420 g of “High Wax 110P” (Mitsui Chemicals, Inc.) as an olefin wax (D) was charged into a glass reactor and dissolved at 160 ° C. in a nitrogen atmosphere. Subsequently, 180 g of styrene, 15.0 g of maleic anhydride, and 18.1 g of di-t-butyl peroxide (hereinafter abbreviated as DTBPO) were continuously supplied to the above reaction system (temperature 160 ° C.) over 5 hours. Thereafter, the mixture was further reacted by heating for 1 hour, and then degassed in a 10 mmHg vacuum for 0.5 hours in a molten state to remove volatile components, then cooled, and styrene maleic anhydride co-modified olefin wax (a- 1) got. Table 1 shows the physical properties.

<Production Example 2>
Styrene maleic anhydride co-modified olefin wax (a-2) was obtained in the same manner as in Production Example 1 except that 240 g of “High Wax 110P”, 360 g of styrene, 30.0 g of maleic anhydride, and 36.2 g of DTBPO were changed. It was. Table 1 shows the physical properties.

<Production Example 3>
Styrene maleic anhydride co-modified olefin wax (a-3) in the same manner as in Production Example 1 except that 540 g of “High Wax 110P”, 60.0 g of styrene, 30.0 g of maleic anhydride, and 11.3 g of DTBPO were changed. Got. Table 1 shows the physical properties.

<Production Example 4>
A maleic anhydride-modified olefin wax (a-5) was obtained in the same manner as in Production Example 1, except that 570 g of “High Wax 110P”, 30.0 g of maleic anhydride, and DTBPO were changed to 6.0 g. Thereafter, styrene maleic anhydride co-modified olefin wax (a-) was prepared in the same manner as in Production Example 1 except that 540 g of maleic anhydride-modified olefin wax (a-5), 60.0 g of styrene, and 5.3 g of DTBPO were changed. 4) got. Table 1 shows the physical properties.

<Production Example 5>
A maleic anhydride-modified olefin wax (a-5) was obtained in the same manner as in Production Example 1, except that 570 g of “High Wax 110P”, 30.0 g of maleic anhydride, and DTBPO were changed to 6.0 g. Table 1 shows the physical properties.

<Production Example 6>
A styrene-modified olefin wax (a-6) was obtained in the same manner as in Production Example 1, except that 240 g of “High Wax 110P”, 360.0 g of styrene, and 30.2 g of DTBPO were changed. Table 1 shows the physical properties.

<Example 1>
90 parts by weight of aromatic polycarbonate resin (Teijin Kasei Co., Ltd .: Panlite L-1225Y MVR11), 10 parts by weight of glass fiber for polycarbonate (Nittobo Co., Ltd .: chopped strand CS3PE455S), and styrene maleic anhydride co-modified olefin type Inorganic obtained by extruding 3.0 parts by weight of wax (a-1) using a unidirectional rotating twin screw extruder HK25D (φ25mm L / D = 41, Parker Corporation) at a cylinder temperature of 280 ° C. A reinforcing material blend composition was obtained.

  The pellets were dried at 120 ° C. for 8 hours and then injected using an injection molding machine Niigata NN100 (Niigata Machine Techno Co., Ltd.) under conditions of a cylinder temperature of 280 ° C., a screw rotation speed of 60 rpm, an injection pressure of 130 MPa, and a mold temperature of 90 ° C. It shape | molded and the test piece was created according to each JIS test. A high speed surface impact test, Charpy impact test, and surface gloss evaluation were performed by the following methods. Table 2 shows the composition of the inorganic reinforcing material-compounding resin composition and its physical properties.

<Example 2>
A test piece was prepared and tested in the same manner as in Example 1 except that the styrene maleic anhydride co-modified olefin wax (a-2) was used instead of the styrene maleic anhydride co-modified olefin wax (a-1). did.

<Example 3>
A test piece was prepared and tested in the same manner as in Example 1 except that the styrene maleic anhydride co-modified olefin wax (a-3) was used instead of the styrene maleic anhydride co-modified olefin wax (a-1). did.

<Example 4>
A test piece was prepared and tested in the same manner as in Example 1 except that the styrene maleic anhydride co-modified olefin wax (a-4) was used instead of the styrene maleic anhydride co-modified olefin wax (a-1). did.

<Comparative Example 1>
Instead of styrene maleic anhydride co-modified olefin wax (a-1), 1.5 parts by weight of maleic anhydride modified olefin wax (a-5) and styrene modified olefin wax (a-6) were used. Except that, a test piece was prepared and tested in the same manner as in Example 1.

<Comparative example 2>
A test piece was prepared and tested in the same manner as in Example 1 except that the maleic anhydride-modified olefin wax (a-5) was used instead of the styrene maleic anhydride co-modified olefin wax (a-1).

<Comparative Example 3>
A test piece was prepared and tested in the same manner as in Example 1 except that the styrene-modified olefin wax (a-6) was used instead of the styrene maleic anhydride co-modified olefin wax (a-1).

<Maleic anhydride graft amount, styrene graft amount>
A film having a thickness of 100 μm was prepared by hot pressing the modified olefin wax (C), the infrared absorption spectrum was measured, and the amount of maleic anhydride grafted was calculated from the absorption intensity near 1785 cm −1. The amount of styrene grafted was determined as the amount of styrene added because styrene was not recovered by the deaeration treatment after the completion of the reaction. The graft amount ratio of maleic anhydride and styrene was (b) / (a). The weight ratio of grafted styrene and olefin wax was defined as (a) / (D).

<Appearance>
A test piece of 100 mm × 100 mm × 4 mm was prepared using an injection molding machine, and 60 ° reflectance was measured using GLOSS METER GM-3D (manufactured by MURAKAMI Color Lab.). The average value was calculated by measuring a total of 5 points near the gate and far from the gate.

<High-speed surface impact test>
A test piece of 100 mm × 100 mm × 4 mm was prepared using an injection molding machine, and a high-speed surface impact test was performed at a striker diameter of 1/2, a support base diameter of 3, and 3 m / sec at 23 ° C.

<Charpy impact test>
Specimens were prepared using an injection molding machine. Based on JIS K-7111, hammer weight 2J, hammer rotation moment 1.08 N · J, hammer lifting angle 50 °, impact speed 2.9 m / S, rotation axis The Charpy impact value was measured under the condition of a distance of 0.23 m from the impact point to the impact point.

Claims (6)

95-50 parts by weight of at least one resin (A) selected from the group consisting of thermoplastic resins and thermosetting resins;
5 to 50 parts by weight of the inorganic reinforcing material (B) (however, the total of the component (A) and the component (B) is 100 parts by weight) ;
Modified olefin wax (C 2 ) 0 ... Grafted with styrene monomer (a) and unsaturated carboxylic acid derivative monomer (b). 01 to 10 parts by weight ,
The resin (A) is a polycarbonate resin,
The number average molecular weight (Mn) of the olefin wax (D), which is a modified precursor of the modified olefin wax (C), measured by gel permeation chromatography (GPC) is in the range of 400 to 3,000. A resin composition for molding with an inorganic reinforcing material characterized by the above.   The inorganic reinforcing material-compounding resin composition according to claim 1, wherein the inorganic reinforcing material (B) is at least one filler selected from glass fiber and carbon fiber.   2. The resin composition for molding an inorganic reinforcing material according to claim 1, wherein the graft amount of the unsaturated carboxylic acid derivative monomer (b) in the modified olefin wax (C) is 0.1 to 10% by weight. object.   The resin composition for molding an inorganic reinforcing material according to claim 1, wherein the graft amount of the styrene monomer (a) in the modified olefin wax (C) is 5 to 80% by weight. The graft amount ratio of the styrene-based monomer (a), the unsaturated carboxylic acid derivative-based monomer (b), and the modified precursor olefin-based wax (D) in the modified olefin-based wax (C) satisfies the following relationship: 2. The resin composition for molding an inorganic reinforcing material according to claim 1 characterized by the above.
0.01 <(b) / (a) <1
0.05 <(a) / (D) <3   2. The inorganic reinforcement compounded molding according to claim 1, wherein the olefin wax (D) has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) in the range of 400 to 1,000. Resin composition.