JPH09216951A - Housing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a housing having an excellent balance among heat resistance, rigidity and impact resistance. SOLUTION: This housing is made by molding a resin composition comprising at least three components of a thermoplastic resin (A), an inorganic filler (B) and an elastic polymer (C) having a glass transition temperature of -20 deg.C or below and being a resin composition which contains a thermoplastic resin (A) as the matrix resin, and in which at least 30% of the dispersed particles of the elastic polymer (C) in the composition are present in a state in which they and inorganic filler (B) have common interfaces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a housing having excellent rigidity, heat resistance, impact resistance, and toughness, and a housing used for electric appliances, electric / electronic equipment, office automation equipment, electric tools and the like.

[0002]

2. Description of the Related Art In recent years, O represented by electric products, electronic devices, copying machines, printers, facsimiles, and computers.
Various plastic materials have come to be used for the housing of the device A, but the demand for higher performance of these housings using plastic is increasing further. For example, in the case of printer housings, copier housings, etc., a high level of dimensional stability, impact resistance, heat resistance and rigidity are required. However, satisfying all of these characteristics at a high level is a difficult task.

For example, when a material mixed with an elastomer component is molded for the purpose of increasing the impact strength of a molded product, only a material having impaired heat resistance and rigidity is obtained, and conversely, the heat resistance and rigidity of the housing are improved. When molding materials mixed with various inorganic fillers and reinforcing agents in order to increase the strength, the Izod impact strength and surface impact strength are impaired, so it is not possible to obtain a housing with improved impact strength and heat resistance or rigidity at the same time. Have difficulty.

Further, by molding a material containing a fibrous reinforcing agent such as glass fiber, a component excellent in rigidity and heat resistance and at the same time improved in Izod impact strength can be obtained. However, a component obtained by this method is On the contrary, the surface impact strength is lower than that of the non-reinforced type, and the elongation is lowered, the anisotropy of mechanical properties is expressed, and the appearance is poor, which is not always preferable for the housing.

[0005]

SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned problems by simultaneously improving the contradictory properties of impact strength, elongation at break, heat resistance, and rigidity.
An object of the present invention is to obtain a housing having small mechanical property anisotropy and excellent in dimensional stability.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention provides at least (A) a thermoplastic resin, (B) an inorganic filler and (C) -20.
A resin composition comprising three components of an elastic polymer having a glass transition temperature of ℃ or less, wherein a thermoplastic resin (A) is used as a matrix resin, and the elastic polymer (C) is dispersed in the composition. 30% or more of which is the inorganic filler (B)
And a housing made of a resin composition characterized by being present in a state of being in contact with an interface with at least (A) a thermoplastic resin of 22 to 89.8% by weight, and (B) an inorganic filler 60.
A resin composition comprising 3 components of 10 to 10% by weight and (C) 18 to 0.2% by weight of an elastic polymer having a glass transition temperature of −20 ° C. or less, wherein the composition of the elastic polymer (C) is A housing made of a resin composition, characterized in that 30% or more of the dispersed particles in the product are present in a form in which the interface is in contact with the inorganic filler (B).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) used in the present invention means a resin which can be melt-molded by heating, and in the case of a resin having a melting point, the melting point is preferably 150 ° C. or higher, It is preferably 180 ° C or higher. When it has no melting point, it preferably has a glass transition temperature of 100 ° C. or higher.

The thermoplastic resin (A) itself is
According to the STM D790 method, it is preferable that the measured bending elastic modulus of the molded product is 1.5 GPa or more, and 2.0 GPa
The above are more preferred.

Preferred examples of the thermoplastic resin which can be used in the present invention include polyester resin, polyamide resin, polyarylene sulfide resin, polycarbonate resin, polyarylate resin, polyacetal resin, ABS resin, polyphenylene oxide resin, polystyrene resin. , Polyolefin resin, acrylic resin, etc., and two or more of these may be used in combination. Among them, polyester resin, polyamide resin, polyarylene sulfide resin and the like can be particularly preferably used.

The polyester resin as used herein is a thermoplastic polyester having an aromatic ring as a chain unit of a polymer, and is usually an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). And / or a polymer or copolymer obtained by a condensation reaction containing hydroxycarboxylic acid as a main component, and may be liquid crystalline or non-liquid crystalline.

Examples of the aromatic dicarboxylic acid used herein include terephthalic acid, isophthalic acid, orthophthalic acid and 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-
Diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid,
4,4'-diphenylisopropylidenedicarboxylic acid,
1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 4,4 "
-P-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid and the like, and among them, terephthalic acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, in the above preferable polyester, the aromatic dicarboxylic acid and
Adipic acid, azelaic acid, sebacic acid of less than mol%,
It is also preferable to use a mixture of one or more aliphatic dicarboxylic acids such as dodecanedioic acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

As the diol component, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3.
An aliphatic diol such as propanediol, diethylene glycol, triethylene glycol, decamethylene glycol, an alicyclic diol such as 1,4-cyclohexanedimethanol, 4,4′-dihydroxybiphenyl,
Examples thereof include aromatic diols such as 4,4′-dihydroxydiphenyl ether, hydroquinone, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene, and mixtures thereof. In addition, as long as it is a small amount, one or more long chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized.

As the hydroxycarboxylic acid, p is
-Hydroxybenzoic acid, m-hydroxybenzoic acid, 6-
Hydroxy-2-naphthoic acid, 4'-hydroxy-biphenyl-4-carboxylic acid and the like can be mentioned.

Specific examples of the polyester resin suitable for the purpose of the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate and polyethylene.
In addition to 2,6-naphthalene dicarboxylate, polybutylene-2,6-naphthalene dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, Polybutylene isophthalate /
Terephthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene-4,4′-dicarboxylate / terephthalate, p-oxybenzoic acid /
Polyethylene terephthalate, p-oxybenzoic acid / 6
-Copolymerized polyesters such as hydroxy-2-naphthoic acid. Among these, polybutylene terephthalate, polyethylene terephthalate, polyethylene-2, in terms of balance of mechanical properties and moldability,
6-naphthalene dicarboxylate is particularly preferably used.

Among the aromatic polyesters which can be particularly preferably used in the present invention, polybutylene terephthalate has an intrinsic viscosity of 0.80 to 1.9 measured at 25 ° C. in a 0.5 W / V% o-chlorophenol solution. , Especially in the range of 1.0 to 1.5, and in the case of polyethylene terephthalate, the intrinsic viscosity measured under the same conditions as above is 0.36 to 1.60, particularly 0.52 to 1.3.
The range of 5 is preferable.

Examples of the polyamide resin include ring-opening polymerization products of cyclic lactams, polycondensation products of aminocarboxylic acids, polycondensation products of dicarboxylic acids and diamines, and specifically, nylon 6 and nylon 4.6. , Nylon 6.6,
Nylon 6/10, Nylon 6/12, Nylon 11,
Aliphatic polyamides such as nylon 12, poly (meta-xylylene adipamide), poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide),
Aliphatic-aromatic polyamides such as poly (tetramethylene isophthalamide), and copolymers and mixtures thereof can be mentioned. Polyamide resins particularly suitable for the present invention include nylon 6 and nylon 6.6.

As the polyarylene sulfide resin, either a cross-linked type or a linear type can be used.

Examples of the inorganic filler (B) used in the present invention include fibrous, granular or plate-like inorganic substances which are usually used as resin fillers. Preferred examples of the fibrous inorganic filler include glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, copper fiber, steel fiber, boron whisker fiber, carbon fiber and the like. Further, as preferred examples of the granular, powdery and plate-like inorganic fillers, wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, and oxidation. Metal oxides such as magnesium, zirconium oxide and titanium oxide, calcium carbonate,
Magnesium carbonate, carbonates such as dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, glass milled fibers, boron nitride, silicon carbide, Saloyan, and the like, which may be hollow (for example, hollow glass Fiber, glass micro balloon, shirasu balloon, carbon balloon etc.).

The inorganic filler used in the present invention is preferably granular and / or plate-shaped, and examples of particularly preferable ones include plate-shaped talc, mica, clay and kaolin.

As the granular and / or plate-like inorganic filler, those having an average particle size of 2 μm or less measured by a sedimentation method can be particularly preferably used.

These inorganic fillers are preferably treated with a silane-based or titanate-based coupling agent or other surface-treating agent, and particularly those treated with a silane-based coupling agent can be preferably used.

Preferred silane coupling agents are γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-anilinopropyltrimethoxysilane,
γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be exemplified, and particularly γ
-Glycidoxypropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferred.

Next, the elastic polymer (C) having a glass transition temperature of -20 ° C. or lower used in the present invention has a glass transition temperature (here, a temperature rising rate of 10 ° C./min by a differential scanning calorimetry method). Defined as the value obtained) is -20 ° C
The following are JIS K-6 at 23 ° C.
100% modulus measured according to method 301 is 100M
Those having Pa or less are preferable, and those having 50 MPa or less are more preferable.

The weight average molecular weight of the elastic polymer (C) is preferably 5,000 or more.

As the weight average molecular weight of the elastic polymer (C), a value measured by gel permeation chromatography is used.

Examples of preferable elastic polymer (C) include:
Examples thereof include ethylene-based copolymers, conjugated diene-based polymers, conjugated diene-aromatic vinyl hydrocarbon-based copolymers, and polyester-based thermoplastic elastomers.

Examples of the ethylene-based polymer here include copolymers and multi-component copolymers of ethylene and other monomers, and other monomers copolymerized with ethylene have 3 carbon atoms. It can be selected from the above α-olefins, non-conjugated dienes, vinyl acetate, vinyl alcohol, α, β-unsaturated carboxylic acids and their derivatives.

The α-olefin having 3 or more carbon atoms includes propylene, butene-1, pentene-1, 3-methylpentene-1, octacene-1, and the like, and propylene and butene-1 can be preferably used. Non-conjugated dienes include 5-methylidene-2-norbornene and 5-ethylidene-
2-norbornene, 5-vinyl-2-norbornene, 5
-Propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-crotyl-2-norbornene, 5- (2-methyl-2-butenyl) -2-norbornene, 5- (2-ethyl-2-butenyl) ) -2-Norbornene, norbornene compounds such as 5-methyl-5-vinylnorbornene, dicyclopentadiene, methyltetrahydroindene, 4,7,8,9-tetrahydroindene, 1,5-cyclooctadiene, 1,4- Hexadiene, isoprene, 6-methyl-1,5-heptadiene, 11-ethyl-1,11-tridecadiene and the like can be mentioned, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene,
1,4-hexadiene and the like are preferable. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butene dicarboxylic acid, and the like, and derivatives thereof include alkyl esters and aryls. Esters, glycidyl esters, acid anhydrides and imides can be mentioned as examples.

The conjugated diene polymer is a polymer derived from at least one conjugated diene monomer, that is, a single conjugated diene, for example, a homopolymer of 1,3-butadiene, or two or more of them. Conjugated dienes, eg 1,3
-Butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene,
Examples thereof include copolymers of 1,3-pentadiene. Those in which a part or all of the unsaturated bonds of these polymers are reduced by hydrogenation can also be preferably used.

Examples of the conjugated diene-aromatic vinyl hydrocarbon-based copolymer include block copolymers and random copolymers having various ratios of conjugated diene and aromatic vinyl hydrocarbon, and the conjugated diene constituting the same. Examples of the above include the above-mentioned monomers, and 1,3-butadiene and isoprene are particularly preferable. Examples of aromatic vinyl hydrocarbons include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene,
Examples thereof include vinylnaphthalene, and among them, styrene can be preferably used. Further, those in which a part or all of unsaturated bonds other than double bonds other than the aromatic ring of the conjugated diene-aromatic vinyl hydrocarbon copolymer are reduced by hydrogenation can also be preferably used.

As the polyester thermoplastic elastomer, a polyether ester block copolymer or a polyester / ester block copolymer having an aromatic polyester as a hard segment and a poly (alkylene oxide) glycol and / or an aliphatic polyester as a soft segment is used. Examples thereof include coalesce and polyether ester / ester copolymers.

Specific examples of the hard segment aromatic polyester component include polyethylene terephthalate, polybutylene terephthalate, polyethylene (terephthalate / isophthalate) and polybutylene (terephthalate / isophthalate).

Specific examples of the poly (alkylene oxide) glycol and the aliphatic polyester constituting the soft segment here include polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, and poly (tetraoxide). Preferred examples include methylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, polyethylene adipate, poly-ε-caprolactone, polyethylene sebacate, polybutylene sebacate, and the like. The weight ratio of the polyester hard segment to the soft segment of the polyester thermoplastic elastomer is 95/5 to 10/90, particularly 90/10 to 30/70.
It is preferred that

Specific examples of the polyester thermoplastic elastomer include polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer,
Polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / decanedicarboxylate poly (tetramethylene oxide) Glycol block copolymer,
Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer,
Polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / decanedicarboxylate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (ethylene oxide) Glycol block copolymer, polyethylene terephthalate / poly (ethylene oxide) glycol block copolymer, polybutylene terephthalate / polyethylene adipate block copolymer, polybutylene terephthalate
Examples thereof include polybutylene adipate block copolymers, polybutylene terephthalate / polybutylene sebacate block copolymers, polybutylene terephthalate / poly-ε-caprolactone block copolymers, and the like.

The glass transition temperature of these elastic polymers is −
It needs to be 20 ° C or lower, and more preferably -30 ° C or lower. When the temperature is higher than -20 ° C, the impact resistance at low temperature is insufficient and the object of the present invention cannot be achieved.

The above-mentioned elastic polymers (C) having a glass transition temperature of -20 ° C. or less can be used in combination of two or more kinds, and a part or all of them are various unsaturated carboxylic acids and / or derivatives thereof. An elastomer obtained by grafting or copolymerizing a vinyl monomer can also be preferably used. In this case, the amount of unsaturated carboxylic acid and / or its derivative or vinyl monomer which has been graft-reacted or copolymerized with respect to the entire elastic polymer (C) is preferably 0.01 to 20% by weight. Examples of the unsaturated carboxylic acid used in the graft reaction or copolymerization include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid and the like. Further, as their derivatives, alkyl ester, glycidyl ester, di-
Further, mention may be made of an ester having a tri-alkoxysilyl group, an acid anhydride or an imide, and among these, a glycidyl ester, an unsaturated carboxylic acid ester having a di- or tri-alkoxysilyl group, an acid anhydride and an imide. More preferable.

Preferred examples of unsaturated carboxylic acids or their derivatives are maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, diglycidyl itaconic acid, diglycidyl citraconic acid,
Butenedicarboxylic acid diglycidyl ester, butenedicarboxylic acid monoglycidyl ester, γ-methacryloxypropyltrimethoxysilane, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid imide, itaconic acid imide, citraconic acid imide, etc., Particularly, glycidyl methacrylate, maleic anhydride, itaconic anhydride, and maleic imide can be preferably used. Examples of vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile,
Examples thereof include vinylsilane compounds such as vinyltrimethoxysilane, and these unsaturated carboxylic acids or their derivatives or vinyl monomers may be used in combination of two or more kinds.

The significance of grafting or copolymerizing an unsaturated carboxylic acid such as maleic acid is that the elastic polymer (C) is used.
To have an affinity with the resin to be strengthened,
Alternatively, it is possible to introduce a functional group for causing a chemical reaction. Therefore, preferable results can be obtained by appropriately using other than the above unsaturated carboxylic acid depending on the resin to be strengthened.

Known methods can be used for the graft reaction of these unsaturated carboxylic acids or their derivatives or vinyl monomers.

Composition ratio of the above-mentioned (A) thermoplastic resin, (B) inorganic filler and (C) elastic polymer having a glass transition temperature of -20 ° C. or lower, which constitutes the composition for obtaining the housing of the present invention. When the total composition is 100,
It is preferable that (A) the thermoplastic resin is 22 to 89.8% by weight, (B) the inorganic filler is 60 to 10% by weight, and (C) the elastic polymer is 18 to 0.2% by weight. It is preferable that (A) the thermoplastic resin is 45 to 86.5% by weight, (B) the inorganic filler is 45 to 12% by weight, and (C) the elastic polymer is 10 to 1.5% by weight.

Further, in the composition for obtaining the housing of the present invention, 30% or more of the dispersed particles of the elastic polymer (C) in the composition are present in the form of being in contact with the inorganic filler (B) at the interface. It is necessary to add 50% or more.
In the composition comprising (A), (B) and (C), the elastic polymer (C) is usually not completely compatible with the thermoplastic resin (A) and forms an independent dispersed phase. . Here, the thermoplastic resin (A) serves as a matrix resin, and the proportion of the dispersed phase (dispersed particles) of the component (C), in which at least a part of the dispersed particles is in contact with the inorganic filler (B) at the interface, It means that 30% or more (preferably 50% or more) of the entire component (C) is present. However, as an evaluation method, a transmission electron microscope (TEM) is used, and an ultrathin section of the composition is observed, and the number of dispersed particles of the elastic polymer (C) is at least 10
The visual field to be observed was observed and evaluated by the total dispersed particle area of the elastic polymer (C) and the area of the dispersed particles in contact with the interface with the inorganic filler (B).
At this time, examples of the dispersion form of the elastic polymer (C) existing in a form of contacting the interface with the inorganic filler (B) include the forms shown in FIGS. 1A to 1D are cross-sectional views showing various examples in which the interfaces of the component (B) and the component (C) are in contact with each other, and the inorganic filler 2 contacts the interface with the elastic polymer 3 in the matrix of the thermoplastic resin 1. It exists in a form. On the contrary, in the present invention, it is necessary that the dispersed particles of the elastic polymer (C) independently present in the thermoplastic resin are less than 70% without contacting the interface with the inorganic filler (B) at all. Yes, less than 50% is preferable.

From the viewpoint of the mechanical properties of the housing obtained in the composition for obtaining the housing of the present invention, the ratio of the elastic polymer to the total of the inorganic filler (B) and the elastic polymer (C). Is preferably 2 to 40% by weight,
5 to 35% by weight is more preferable.

The characteristic feature of the housing of the present invention is that impact strength and rigidity are well balanced, and a composition that provides a housing having typical effects of the present invention is one that satisfies the following characteristics. Particularly preferred.

Impact strength (AS) at room temperature (23 ° C.)
1/8 "thickness notched Izod impact strength Sc and flexural modulus (ASTM) measured according to TM D256 test method
It is preferable that the relationship of flexural modulus of elasticity (Mc) measured according to the test method of D790 satisfies the inequality of Equation 1.

(Equation 1) Mc> M0 Mc <0.07Sc -1.6 (where M0 is an injection molded product of the thermoplastic resin (A) alone, measured according to the test method of ASTM D790, 23 ° C.)
Shows the flexural modulus of elasticity, and the units of Mc and M0 are GP
The units of a and Sc are J / m. ) Furthermore, a resin composition in which the inorganic filler (B) component in the composition used in the present invention is replaced with an equal weight of the thermoplastic resin (A) component (substantially (A) thermoplastic resin and (C)) Impact strength (1/8 "thickness notched Izod impact strength measured according to the test method of ASTM D256) higher than that of a two-component composition of an elastic polymer, especially 200%
Those having high impact strength are preferable.

One of the features of the present invention is that the impact strength is increased by the addition of the above-mentioned inorganic filler, and the addition amount XB (% by weight) of the inorganic filler (B) and the injection-molded article at 23 ° C. are the same. It is desirable to satisfy the inequality of the following equation 2 during the Izod impact strength (SC) with the 1/8 "thickness notch by the measuring method, and it is more preferable to satisfy the inequality of the equation 3. Further, the equation 4 is more preferable. To satisfy the inequality of.

(Equation 2) Sc> 1.65XB + S0 (where S0 is 1 / measured by the test method of ASTM D256 at 23 ° C. of the thermoplastic resin (A) alone)
8 "shows Izod impact strength (J / m) with thickness notch. (Equation 3) Sc> 1.65XB + 1.2S0 (where S0 is a test of ASTM D256 at 23 ° C of thermoplastic resin (A) alone) 1 / measured according to the method
Izod impact strength (J / m) with 8 "thickness notch is shown.) (Formula 4) Sc> 1.65XB + 1.5S0 (where S0 is the test of ASTM D256 at 23 ° C of thermoplastic resin (A) alone) 1 / measured according to the method
Izod impact strength (J / m) with a 8 "thickness notch is shown.) The composition used in the present invention has an increased impact strength due to the addition of the elastic polymer (C), but the effect is obtained by a usual polymer blend. 1/8 "thick notched Izod measured according to ASTM D256 test method at 23 ° C for injection molded articles of composition greater than elastic polymer (C) XC (wt%) larger than high impact plastic It is preferable that the inequality of the following equation 5 is satisfied during the impact strength (SC), and it is more preferable that the inequality of the equation 6 is satisfied. Further, it is more preferable to satisfy the inequality of Expression 7, and the one that satisfies the inequality of Expression 8 is most preferable.

(Equation 5) Sc> 0.86XC + 1.3S0 (where S0 is the thermoplastic resin (A) alone measured at 23 ° C. according to the test method of ASTM D256 1 /
Izod impact strength (J / m) with 8 "thickness notch is shown. (Equation 6) Sc> 4.5XC + 1.3S0 (where S0 is a test of ASTM D256 of thermoplastic resin (A) alone at 23 ° C) 1 / measured according to the method
Izod impact strength (J / m) with 8 "thickness notch is shown. (Equation 7) Sc> 4.5XC + 1.8S0 (where S0 is a test of ASTM D256 of thermoplastic resin (A) alone at 23 ° C) 1 / measured according to the method
Izod impact strength (J / m) with 8 "thickness notch is shown.) (Equation 8) Sc> 4.5XC + 2.2S0 (where S0 is a test of ASTM D256 at 23 ° C of thermoplastic resin (A) alone) 1 / measured according to the method
8 "shows Izod impact strength (J / m) with thickness notch.) The method for producing the resin composition used in the present invention is not particularly limited, but as described above, it is necessary to obtain the housing of the present invention. In the composition, 30% or more, preferably 50% or more of the added amount of the elastic polymer (C) needs to be present in a form of contacting the interface with the inorganic filler (B),
A method capable of controlling the structure of each component as described above can be preferably used.

For example, a method of coating the surface of the inorganic filler (B) with the elastic polymer (C) component and then adding it to the thermoplastic resin (A), the inorganic filler (B) and the elastic polymer (C). ) Component is previously kneaded at a temperature at which the elastic polymer is in a molten state, and then the mixture is kneaded again with the thermoplastic resin (A), and the elastic polymer (C) component in the presence of the inorganic filler (B). Examples of the method include a method in which the thermoplastic resin (A) is kneaded after polymerizing and coating the monomer components constituting the.

When the surface of the inorganic filler (B) is coated with the elastic polymer (C) component, the surface of the inorganic filler (B) is coated with a solution of the elastic polymer (C) component in a solvent. A coating treatment is also preferable. When the inorganic filler (B) and the elastic polymer (C) components are melt-kneaded in advance, a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll is used. can do.

Further, an inorganic filler (B) which has been surface-coated with the elastic polymer (C) component in advance or a melt-kneaded mixture of the elastic polymer (C) component and the inorganic polymer (B) is thermoplastic. The same known method can be used when kneading with the resin (A).

In the composition used in the present invention, 30% by weight or more, preferably 50% by weight or more of the added amount of the elastic polymer (C) is in a form of contacting the interface with the inorganic filler (B). Inorganic filler (B) because it must be present
It is preferable that the surface and the elastic polymer (C) have high adhesiveness and adhesion.

As a method of enhancing the adhesiveness, it is effective to introduce various organic groups or reactive groups by subjecting the surface of the inorganic filler (B) to a coupling treatment with a silane coupling agent or the like. Furthermore, by using the elastic polymer (C) having a functional group having affinity and reactivity with the introduced organic group, more excellent adhesiveness at the interface can be obtained.

Also, as a coating treatment method, a method of polymerizing a monomer as a raw material of the elastic polymer in the presence of the inorganic filler (B) can also obtain excellent adhesiveness. In this case, the inorganic filler (B) may or may not be treated with the coupling agent. The polymerization can be performed by a method suitable for the type of elastic polymer, such as emulsion polymerization. At that time, it is preferable that the inorganic filler is uniformly dispersed in the reaction system. In particular, the inorganic filler (B) is emulsified in an aqueous solvent to give an elastic polymer (C).
The method of coating by emulsion-polymerizing the components is preferred. In this polymerization method, a radical generator, a surfactant and the like can be used appropriately.

When the inorganic filler coated with the elastic polymer is added to the thermoplastic resin, or both are melt-kneaded, it is preferable to carry out in the presence of a reactive compatibility modifier.

The above-mentioned reactive compatibility modifier means the compatibility between the elastic polymer (C) and the thermoplastic resin (A) which are in contact with the inorganic filler at the interface and are preferably adhered to the inorganic filler. It can be improved and has a functional group capable of forming a chemical bond with the thermoplastic resin (A) and the elastic polymer (C). The chemical bond is the same as that described for the elastic polymer (C). Specifically, a carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, an acid chloride group, an epoxy group, an isocyanate group, an ester group,
It contains a carbon-carbon unsaturated bond in the molecule. The reaction of these functional groups includes those requiring a catalyst. This reactive compatibility modifier has a carbon-
It preferably has a carbon double bond.

Preferred examples of such a reactive compatibility modifier include unsaturated carboxylic acids having one or more carbon-carbon double bonds in the molecule or derivatives thereof. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid, tetrahydrophthalic acid, and the like. Examples thereof include glycidyl ester, acid anhydride and acid chloride. Examples of the reactive compatibility modifier include maleic anhydride, itaconic anhydride, acid anhydrides such as tetrahydrophthalic anhydride, and glycidyl esters such as glycidyl methacrylate as particularly preferable examples.

When the inorganic filler coated with the elastic polymer is added to the thermoplastic resin and melt-kneaded, the reactive compatibility modifier is added by melt-mixing or melt-kneading. It may be carried out in the presence of the compatibility modifier.
In this step, an ordinary known melt-kneading device, that is, a single-screw or twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, or the like can be used.

In this step, it is preferable to add a compound and a catalyst that accelerate the reaction of the reactive compatibility modifier together with the reactive compatibility modifier. Specific examples thereof include so-called radical initiators, of which organic peroxides are preferable. The organic peroxide is preferably selected as appropriate depending on the melt-mixing and melt-kneading conditions of the thermoplastic resin (A) and the inorganic filler coated with the elastic polymer. Specific preferred examples thereof are 2,5 -Dimethyl-
2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-isopropylbenzene hydroperoxide, di-t-butylperoxide, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, cumene hydroperoxide, t-butyl hydroperoxide and the like can be disclosed.

The reactive compatibility modifier used is added in a total amount of 10 for the inorganic filler (B) and the elastic polymer (C).
0.1 to 10 parts by weight is preferable with respect to 0 parts by weight,
0.5 to 3.0 parts by weight is more preferable. Further, in particular, when the radical initiator is used together with the reactive compatibility improver in this step, 0.01 to 100 parts by weight of the total amount of the inorganic filler (B) and the elastic polymer (C) is used. 1 part by weight is preferable, and 0.05 to 0.5 part by weight is particularly preferable.

With respect to the composition used for the housing of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, lubricants, and release agents may be used as long as the characteristics of the composition for the purpose of the present invention are not impaired. One or more usual additives such as a mold agent, a colorant including a dye and a pigment, and a nucleating agent can be added.

The housing of the present invention is obtained by molding the above composition by a usual method such as injection molding or extrusion molding, and has high impact resistance, rigidity, and excellent heat resistance, and has small anisotropy. It has a characteristic that the warp is small,
It is extremely useful as a housing for electric appliances, electric / electronic equipment, office automation equipment, moving tools, and the like. Specifically, electric products such as shavers, dryers, vacuum cleaners, televisions, VCRs, audio equipment, electrical and electronic equipment, electronic calculators, copying machines, printers, facsimiles,
Examples include housings for computers, office automation equipment typified by word processors, floppy disks, cameras, watches, and various measuring instruments.

[0065]

The present invention will be described in more detail with reference to the following examples.

Reference Example 1 (Production of Maleic Anhydride Modified EPR) 2 parts by weight of maleic anhydride and 2,5-dimethyl-based on 100 parts by weight of ethylene / propylene copolymer (P0680 manufactured by Mitsui Petrochemical Co., Ltd.). 2,5-di-t-butylperoxyhexane (Perhexa 25 manufactured by NOF CORPORATION)
B) Add 0.7 parts by weight, mix evenly with a ribbon blender, and then set the cylinder temperature to 210 ° C.
Was supplied to the twin-screw extruder to obtain maleic anhydride-modified EPR pellets (C-1). The glass transition temperature of (C-1) was −42 ° C., the weight average molecular weight was 10,000 or more, and the 100% modulus was 3.8 MPa.

Example 1 1 to talc (LMS300 manufactured by Fuji Talc Co., Ltd.)
A coupling treatment was carried out by a conventional method using γ-glycidoxypropyltrimethoxysilane in a weight percentage. 70 parts by weight of talc (B-1) after coupling treatment and 30 parts by weight of maleic anhydride-modified EPR (C-1) were supplied to a twin-screw extruder set to a cylinder temperature of 200 ° C., and extruded from a die to form talc. A composition pellet (P-1) composed of maleic anhydride-modified EPR was obtained.

Next, the dried pellet (P-1) 2
5 parts by weight and 75 parts by weight of nylon 6 (relative viscosity measured at 25 ° C. in concentrated sulfuric acid: 2.75, flexural modulus measured according to ASTM D790 method: 2.7 GPa, melting point 221 ° C.), cylinder temperature 250 ° C. It was supplied to the twin-screw extruder set to and extruded from a die to obtain a composition pellet. When an ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM), about 6 out of the dispersed particles of maleic anhydride modified EPR used as an elastic polymer component were found.
It has been found that 0% is present either surrounding the talc particles or in contact with the talc particles.

After drying the obtained pellets, the pellets were subjected to an injection molding machine, and a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C.
2 "x 5" x 1/8 "thick rod specimens and 1/8" thick Izod impact specimens were molded.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 3.0 GPa and the bending strength was 93 MPa. In addition, a cut notch was added to the impact test piece, and Iz
When an od impact test was performed, the impact value was as high as 105 J / m.

Further, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 20
5 ° C.

Further, the printer cover (housing)
A printer cover was molded under the same temperature conditions as above using the mold of the above. The obtained printer cover had a good appearance and no warp was observed. A thin flat portion (2 mm thick) of the printer cover was cut out, and a servo pulser EHF-U2H-20L type high-speed surface impact tester manufactured by Shimadzu Corporation was used, and at 23 ° C., a punch tip diameter was 5/8 "and a collision speed was 2.
The test was conducted at 5 m / s. As a result, the breaking energy was 5.6 J and the maximum deflection was 13.5 mm.
7 out of 0 were ductile fractured. The term “ductile fracture” as used herein means a state in which a punch collision portion is plastically deformed and a through hole is generated, but no crack is generated in the entire test piece and the punch does not scatter.

Example 2 45 parts by weight of a composition pellet (P-1) composed of talc and maleic anhydride-modified EPR, which had been subjected to a coupling treatment under the same conditions as in Example 1, and the same nylon as used in Example 1 65 parts by weight of the composition was supplied to a twin-screw extruder having a cylinder temperature of 250 ° C. and extruded from a die to obtain a composition pellet. An ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM). As a result, it was confirmed that about 55% of the dispersed particles of the maleic anhydride modified EPR used as the elastic polymer component surround the talc particles. It was also found that they exist in the form of being in contact with talc particles.

The pellets thus obtained were dried and then subjected to an injection molding machine to carry out molding under the same conditions as in Example 1 to obtain 1/2 ″ ×.
5 "x 1/8" thick rod specimen and 1/8 "thick Iz
Molded od impact test pieces.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 2.8 GPa and the bending strength was 81 MPa. In addition, a cut notch was added to the impact test piece, and Iz
When an od impact test was conducted, the impact value was as high as 139 J / m.

Further, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 19
9 ° C.

Further, a printer cover was molded in the same manner as in Example 1, and its thin flat portion (2 mm thick) was cut out,
As a result of a high-speed surface impact test at 23 ° C., the breaking energy was 5.9 J, the maximum deflection was 13.6 mm, and 5 out of 10 tests were ductile failures.

Example 3 70 parts by weight of talc (LMS300 manufactured by Fuji Talc Co., Ltd.) and silane-modified EEA (HPR manufactured by Mitsui Polychemical Co., Ltd.)
30 parts by weight of AS252, glass transition temperature −34 ° C., 100% modulus 4.6 MPa (C-2) was supplied to a twin-screw extruder set to a cylinder temperature of 150 ° C., extruded from a die, and talc and silane-modified EEA were used. A composition pellet (P-2) was obtained.

Next, the dried pellet (P-2) 2
5 parts by weight and the same nylon 6 7 used in Example 1
5 parts by weight was supplied to a twin-screw extruder set to a cylinder temperature of 250 ° C. and extruded from a die to obtain a composition pellet. An ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM). As a result, it was confirmed that about 72% of the dispersed particles of the maleic anhydride modified EPR used as the elastic polymer component surround the talc particles. It was also found that they exist in the form of being in contact with talc particles.

After drying the obtained pellets, the pellets were subjected to an injection molding machine, and the cylinder temperature was 250 ° C. and the mold temperature was 80 ° C.
2 "x 5" x 1/8 "thick rod specimen and 1/8"
Thick Izod impact specimens were molded.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 2.9 GPa and the bending strength was 90 MPa. In addition, a cut notch was added to the impact test piece, and Iz
When an od impact test was conducted, the impact value was as high as 106 J / m.

Further, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 19
5 ° C.

Further, the printer cover was molded in the same manner as in Example 1 above, and the thin flat portion (2 mm thick) was cut out,
As a result of a high-speed surface impact test at 23 ° C., the breaking energy was 4.3 J, the maximum deflection was 11.5 mm, and 4 out of 10 tests were ductile failures.

Example 4 Maleic anhydride-modified EPR (C-obtained in Reference Example 1)
1) Xylene 2500 in which 125 parts by weight was heated to 60 ° C
The talc (B-1) 10 which has been subjected to the coupling treatment used in Example 1 was dissolved in a glass flask in an amount of 1 part by weight and the whole flask was irradiated with ultrasonic waves using an ultrasonic cleaner.
0 part by weight was gradually added, and stirring was continued at 100 ° C. for 1 hour.

The obtained mixed solution was centrifuged, and the precipitated talc-EPR composite was separated and dried. The EPR content in the obtained talc-EPR composite was determined by thermogravimetric analysis to be 6.5% by weight. 20 parts by weight of this dried talc-EPR composite and 680 parts by weight of the same nylon as used in Example 1 were fed to a twin-screw extruder set to a cylinder temperature of 250 ° C. and extruded from a die to obtain composition pellets. Obtained.

Next, an ultrathin section was cut from the obtained composition pellets and observed with a transmission electron microscope (TEM). As a result, it was confirmed that about 10% of the dispersed particles of the maleic anhydride modified EPR used as the elastic polymer component were obtained. It was found that 82% were present either surrounding the talc particles or in contact with the talc particles.

After drying the obtained pellets, the pellets were subjected to an injection molding machine and molded under the same conditions as in Example 1 to obtain 1/2 ″ ×.
5 "x 1/8" thick rod specimen and 1/8 "thick Iz
Molded od impact test pieces.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 3.7 GPa and the bending strength was 108 MPa.
Met. Furthermore, cut notch is attached to the impact test piece,
When the Izod impact test was conducted, the impact value was as high as 146 J / m.

Also, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 20
2 ° C.

Further, a printer cover was molded in the same manner as in Example 1, and its thin flat portion (2 mm thick) was cut out,
As a result of a high-speed surface impact test at 23 ° C., the breaking energy was 4.2 J, the maximum deflection was 12.2 mm, and 3 out of 10 tests were ductile failures.

Comparative Example 1 31.5 parts by weight of talc (B-1) subjected to the coupling treatment under the same conditions as in Example 1 and the maleic anhydride-modified EPR (C-1) 13.5 obtained in Reference Example 1 Parts by weight and 55 parts by weight of the same nylon 655 as used in Example 1 were simultaneously fed to a twin-screw extruder set at a cylinder temperature of 250 ° C.,
Extrusion through a die gave composition pellets. The composition ratio of each constituent in the pellet is substantially the same as that in Example 2.
When an ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM), the maleic anhydride-modified EPR used as the elastic polymer component was dispersed in Nylon 6 as a single particle, The area surrounding the talc particles or existing in contact with the talc particles was 10% or less in area.

After drying the obtained pellets, the pellets were subjected to an injection molding machine and injection-molded under the same conditions as in Example 1 to obtain 1/2 ″ × 5 ″.
X 1/8 "thick rod specimen and 1/8" thick Izod
Impact test pieces were molded.

When a bending test was carried out using the rod-shaped test piece, the bending elastic modulus was 4.1 GPa and the bending strength was 82 MPa. In addition, a cut notch was added to the impact test piece, and Iz
When an od impact test was conducted, it was found that the impact value was 60 J / m, which was lower than that of Example 2.

Also, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 19
Same as Example 2 at 9 ° C.

Further, a printer cover was molded in the same manner as in Example 1, the thin flat portion (2 mm thick) was cut out, and a high-speed surface impact test was conducted at 23 ° C., with the result that the breaking energy was 2.1 J and the maximum deflection was Was 6.9 mm, and all the tests were brittle and fractured, and the test pieces were scattered. It was found to be brittle as compared with Example 2.

Comparative Example 2 18.7 parts by weight of talc (B-1) subjected to coupling treatment under the same conditions as in Example 1, and maleic anhydride-modified EPR (C-1) 1.3 obtained in Reference Example 1 Parts by weight and Example 1
The same nylon 680 parts by weight as used in 1. was simultaneously supplied to a twin-screw extruder set to a cylinder temperature of 250 ° C. and extruded from a die to obtain a composition pellet. The composition ratio of each component in the pellet is substantially the same as in Example 4. When an ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM), the maleic anhydride-modified EPR used as the elastic polymer component was dispersed in Nylon 6 as a single particle, Almost none existed so as to surround or contact the talc particles.

After drying the obtained pellets, the pellets were subjected to an injection molding machine and injection-molded under the same conditions as in Example 1 to obtain 1/2 ″ × 5 ″.
A 1/8 "thick rod specimen and a 1/8" thick Izod impact specimen were molded.

A bending test was carried out using a rod-shaped test piece. The bending elastic modulus was 4.2 GPa and the bending strength was 113 MPa.
Met. Furthermore, cut notch is attached to the impact test piece,
The Izod impact test revealed that the impact value was 40 J / m, which was lower than that of Example 4.

Also, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 20
Same as Example 4 at 2 ° C.

Further, a printer cover was molded in the same manner as in Example 1, and its thin flat portion (2 mm thick) was cut out,
As a result of a high-speed surface impact test at 23 ° C., it was found that the fracture energy was 1.3 J, the maximum deflection was 6.1 mm, and all the tests were brittle fracture, which was brittle compared to Example 4.

Examples 5 to 10 and Comparative Examples 3 to 9 Compositions were prepared by compounding the various talcs, glass fibers, elastic polymers and thermoplastic resins shown in Table 1 by the method shown in Table 1. did. The flexural moduli of the nylon 6 and polybutylene terephthalate (PBT) used were 2.7 GPa and 2.5 GPa, respectively. Also PBT
Had a melting point of 225 ° C. These compositions were molded under the same conditions as in Example 1 and the physical properties of the molded products were evaluated. Table 2 shows the results.

Comparative Example 10 The PBT resin (A-2) used in Example 10 was put into an injection molding machine and injection-molded under the same conditions as in Example 1 to obtain 1/2 ″ ×.
5 ″ × 1/8 ″ thick rod-shaped test pieces and 1/8 ″ thick Izod impact test pieces were molded.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 2.5 GPa and the bending strength was 90 MPa. Further, when an Izod impact test was carried out with a cut notch on the impact test piece, the impact value was 45 J / m.

Also, using a rod-shaped test piece, a low load (455K
The load deflection temperature of Pa) was measured and found to be 172 ° C.

[0105]

[Table 1]

[0106]

[Table 2]

Example 11 Talc having an average particle size of 1.4 μm (LM manufactured by Fuji Talc Co., Ltd.)
S25) 1 kg, 14.25 g of γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning SZ-6030) and DBU as a catalyst.
A treatment solution prepared by diluting 0.75 g of (1,8-diazabicyclo [5.4.0] -7-undecene) with 100 g of methanol was uniformly sprayed, and a Henschel mixer was used to
After stirring for 0 minute, the obtained mixture was heat-treated at 130 ° C. for 12 hours to obtain a coupling-treated talc.

Further, 240 g of this talc having undergone the coupling treatment, 900 g of pure water (ion-exchanged water) and a nonionic surfactant (“Phosphanol” RS-610 manufactured by Toho Chemical Co., Ltd.) having the structural formula shown below were used. A mechanical homogenizer (IKA) was added with 30 g of a 10 wt% aqueous solution.
Made by "Ultra Turrax" T-50 type), 6,
The mixture was emulsified and dispersed at 000 rpm for 5 minutes and further at 10,000 rpm for 5 minutes to obtain an emulsion mixture having a low viscosity and uniform particle dispersion. The pH of this mixture was 6.39 at 23 ° C.

[0109]

Embedded image

While keeping this mixture at 70 ° C. in a polymerization reaction vessel equipped with a stirrer and a dropping device, about 300 rpm
After stirring, the monomer mixture in which 6 g of maleic anhydride was dissolved in 54 g of butyl acrylate as a monomer component and 15 g of a 10 wt% aqueous solution of potassium persulfate as a polymerization initiator were both used for about 2 hours. After the completion of the supply, stirring was continued for about 1 hour while maintaining the temperature.

The obtained polymerization reaction mixture was put into 2000 g of a 0.75% by weight aqueous solution of aluminum sulfate with stirring, coagulation was performed, filtration and washing were repeated, and vacuum drying was carried out at 70 ° C. for 12 hours. Then, an inorganic filler coated with an elastic polymer was obtained.

Thermogravimetric analysis of the obtained elastic polymer-coated inorganic filler revealed that 16.5% of the elastic copolymer component was present in the solid content, and thus the elastic polymer (C) component The reaction rate was found to be about 79%.
Furthermore, the obtained composite particles were extracted using a Soxhlet extractor using toluene as a solvent. The sample after extraction for 10 hours was again measured by thermogravimetric analysis, and it was found that about 75% of the elastic copolymer in the solid content was not extracted and was supported and fixed on the inorganic particles. Also,
As a result of differential scanning calorimetry, the glass transition temperature of the elastic polymer (C) component was -47 ° C.

20 parts by weight of this elastic copolymer-coated inorganic filler and nylon 6 (ηr = 2.70, flexural modulus:
80 parts by weight of (2.7 GPa) was supplied to a twin-screw extruder set to a cylinder temperature of 250 ° C. and extruded from a die to obtain a composition pellet.

After drying the obtained pellets, the pellets were subjected to an injection molding machine and injection-molded under the same conditions as in Example 1 to obtain 1/2 ″ × 5 ″.
X 1/8 "thick rod specimen and 1/8" thick Izo
d Impact test pieces were molded.

When a bending test was performed using a rod-shaped test piece, the bending elastic modulus was 3.7 GPa. Furthermore, when a cut notch was attached to the impact test piece and an Izod impact test was performed, the impact value was as high as 140 J / m.

Also, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 20
3 ° C.

Further, as in Example 1, the printer cover was molded, the thin flat portion (2 mm thick) was cut out, and a high-speed surface impact test was performed at 23 ° C. As a result, the average breaking energy was 5.3 J, and the average breaking energy was 5.3 J. The maximum deflection was 14.5 mm, and 4 out of 10 tests had ductile fracture.

Further, when an ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM),
Less than about 10% of the elastic polymer (C) component is present as independent particles, in other words, about 90% or more of the elastic polymer (C) component surrounds the talc particles or becomes talc particles. It turned out that they existed in contact with each other.

Example 12 Talc having an average particle size of 1.4 μm (LM manufactured by Fuji Talc Co., Ltd.)
S25) 1 kg, 14.25 g of γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning SZ-6030) and DBU as a catalyst.
A treatment solution prepared by diluting 0.75 g of (1,8-diazabicyclo [5.4.0] -7-undecene) with 100 g of methanol was uniformly sprayed, and a Henschel mixer was used to
After stirring for 0 minute, the obtained mixture was heat-treated at 130 ° C. for 12 hours to obtain a coupling-treated talc.

Furthermore, 240 g of this talc subjected to the coupling treatment, 900 g of pure water (ion-exchanged water) and 36 g of a 10% by weight aqueous solution of sodium lauryl sulfate (“Emar 10” manufactured by Kao Corporation) as an anionic surfactant.
Was added and a mechanical homogenizer ("Ultra Turrax" T-50 type, manufactured by IKA Co., Ltd.) was used to emulsify and disperse at 6,000 rpm for 5 minutes, and further at 10,000 rpm for 5 minutes to obtain a low-viscosity uniform particle dispersion state. To obtain an emulsified mixture of. The pH of this mixture was 6.39 at 23 ° C.

While maintaining this mixture at 70 ° C. in a polymerization reaction vessel equipped with a stirrer and a dropping device, about 300 rpm
After stirring, the monomer mixture in which 6 g of maleic anhydride was dissolved in 54 g of butyl acrylate as a monomer component and 15 g of a 10 wt% aqueous solution of potassium persulfate as a polymerization initiator were both used for about 2 hours. After the completion of the supply, stirring was continued for about 1 hour while maintaining the temperature.

The obtained polymerization reaction mixture was poured into 2000 g of a 0.75 wt% aqueous solution of aluminum sulfate while stirring, coagulation was carried out, filtration and washing were repeated, and vacuum drying was carried out at 70 ° C. for 12 hours. Then, an inorganic filler coated with an elastic polymer was obtained.

By thermogravimetric analysis of the obtained elastic polymer-coated inorganic filler, it was found that 16.9% of the elastic polymer component was present in the solid content, and the reaction of the elastic polymer (C) component obtained from this was determined. The rate was found to be about 85%.
Furthermore, the obtained inorganic filler coated with the elastic polymer was extracted using toluene as a solvent using a Soxhlet extractor. The sample after extraction for 10 hours was again measured by thermogravimetric analysis, and it was found that about 86% of the elastic polymer in the solid content was not extracted and was supported and fixed on the inorganic particles. As a result of differential scanning calorimetry, the glass transition temperature of the elastic polymer (C) component was -45 ° C.

20 parts by weight of the inorganic polymer-coated inorganic filler prepared above and nylon 6 (ηr = 2.
70, 80 parts by weight of flexural modulus 2.7 GPa), 0.3 parts by weight of maleic anhydride and 0.03 of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as a radical initiator. Cylinder temperature 2 after mixing parts by weight
The composition was fed into a twin-screw extruder set at 50 ° C. and extruded through a die to obtain a composition pellet.

After drying the obtained pellets, the pellets were subjected to an injection molding machine and injection-molded under the same conditions as in Example 1 to obtain 1/2 ″ × 5 ″.
X 1/8 "thick rod specimen and 1/8" thick Izo
d Impact test pieces were molded.

When a bending test was conducted using a rod-shaped test piece, the bending elastic modulus was 3.8 GPa. Furthermore, when a cut notch was attached to the impact test piece and an Izod impact test was performed, the impact value was as high as 148 J / m.

Further, using a rod-shaped test piece, a low load (455
When the load deflection temperature of kPa) was measured, it was 20
3 ° C.

Further, as in Example 1, the printer cover was molded, the thin flat portion (2 mm thick) was cut out, and a high-speed surface impact test was conducted at 23 ° C. As a result, the average breaking energy was 5.8 J, and the average breaking energy was 5.8 J. The maximum deflection was 16.5 mm, and 9 out of 10 tests showed ductile fracture.

Further, when an ultrathin section was cut from the obtained pellet and observed with a transmission electron microscope (TEM),
Less than about 10% of the elastic polymer (C) component is present as independent particles, in other words, about 90% or more of the elastic polymer (C) component surrounds the talc particles or becomes talc particles. It turned out that they existed in contact with each other.

[0130]

It was found that the housing of the present invention has an excellent balance of heat resistance, rigidity and impact resistance.

[Brief description of drawings]

1A to 1D are cross-sectional views showing various examples in which an interface between a component (B) and a component (C) in a composition used in the present invention is in contact with each other.

[Explanation of symbols]

 1. Thermoplastic resin 2. Inorganic filler 3. Elastic polymer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 77/00 LQR C08L 77/00 LQR 81/02 LRK 81/02 LRK 101/00 LTB 101/00 LTB // B29K 67:00 77:00 81:00 105: 18 B29L 22:00 31:34

Claims (19)

[Claims] 1. At least (A) a thermoplastic resin and (B)
A resin composition comprising three components, an inorganic filler and (C) an elastic polymer having a glass transition temperature of −20 ° C. or lower, wherein the thermoplastic resin (A) is used as a matrix resin, and the elastic polymer (C) is used. Of the dispersed particles in the composition of
A housing made of a resin composition, characterized in that 0% or more is present in a form in which the interface with the inorganic filler (B) is in contact. 2. At least (A) thermoplastic resin 22 to 8
9.8% by weight, and (B) inorganic filler 60 to 10% by weight
And (C) a resin composition comprising 3 components of 18 to 0.2% by weight of an elastic polymer having a glass transition temperature of -20 ° C or less, wherein the elastic polymer (C) is dispersed in the composition. A housing made of a resin composition, characterized in that 30% or more of the particles are present in a form of contacting the interface with the inorganic filler (B). 3. The ratio of the elastic polymer (C) to the total of the inorganic filler (B) and the elastic polymer (C) is 2 to 40.
A housing according to claim 1 or 2, which is in weight%. 4. The housing according to claim 1 or 2, wherein 50% or more of the dispersed particles of the elastic polymer (C) in the composition are present in a form of contacting the interface with the inorganic filler (B). 5. The thermoplastic resin (A) is ASTM D79.
The housing according to claim 1 or 2, wherein the thermoplastic resin (A) alone has a flexural modulus of 1.5 GPa or more measured according to the 0 method. 6. The housing according to claim 1, wherein the thermoplastic resin (A) is a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature of 100 ° C. or higher. 7. The thermoplastic resin (A) is a polyester resin,
The housing according to claim 1 or 2, which is at least one resin selected from a polyamide resin and a polyarylene sulfide resin. 8. A flexural modulus Mc and 23 at 23.degree.
The housing according to claim 1 or 2, which is formed by molding a resin composition that gives an injection-molded article that simultaneously satisfies the following inequalities within the Izod impact strength Sc with a 1/8 "thickness notch at ° C. Mc> M0 Mc < 0.07Sc -1.6 (where M0 is the flexural modulus of the thermoplastic resin (A) alone at 23 ° C, and the units of Mc and M0 are GPa,
The unit of Sc is J / m. ) 9. A resin composition (substantially (A) thermoplastic resin and (C) -20, wherein the inorganic filler (B) component in the resin composition is replaced by an equal weight of the thermoplastic resin (A) component. The housing according to claim 1 or 2, which is formed by molding a resin composition having a 1/8 "thickness notched Izod impact strength higher than (comprising two components of an elastic polymer having a glass transition temperature of ℃ or less). 10. Amount XB of the inorganic filler (B) component added
(Wt%) and Iz with 1/8 "thickness notch at 23 ° C
The housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality within the od impact strength Sc (J / m). Sc> 1.65XB + S0 (where S0 represents Izod impact strength (J / m) with 1/8 "thickness notch of thermoplastic resin (A) alone at 23 ° C) 11. An addition amount XB of an inorganic filler (B) component
(Wt%) and Iz with 1/8 "thickness notch at 23 ° C
The housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality within the od impact strength Sc (J / m). Sc> 1.65XB + 1.2S0 (where S0 is the Izod impact strength (J / m) with 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 12. Amount XB of the inorganic filler (B) component added
(Wt%) and Iz with 1/8 "thickness notch at 23 ° C
The housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality within the od impact strength Sc (J / m). Sc> 1.65XB + 1.5S0 (where S0 is the Izod impact strength (J / m) with the 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 13. An addition amount XC (% by weight) of an elastic polymer (C) component having a glass transition temperature of -20 ° C. or lower and 23 ° C.
1/8 "thickness notched Izod impact strength Sc (J
/ M), the housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality. Sc> 0.86Xc + 1.3S0 (where S0 is the Izod impact strength (J / m) with 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 14. An addition amount XC (% by weight) of an elastic polymer (C) component having a glass transition temperature of -20 ° C. or lower and 23 ° C.
1/8 "thickness notched Izod impact strength Sc (J
/ M), the housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality. Sc> 4.5Xc + 1.3S0 (where S0 is the Izod impact strength (J / m) with a 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 15. An addition amount XC (% by weight) of an elastic polymer (C) component having a glass transition temperature of -20 ° C. or lower and 23 ° C.
1/8 "thickness notched Izod impact strength Sc (J
/ M), the housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality. Sc> 4.5Xc + 1.8S0 (where S0 is the Izod impact strength (J / m) with a 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 16. An addition amount XC (% by weight) of an elastic polymer (C) component having a glass transition temperature of -20 ° C. or lower and 23 ° C.
1/8 "thickness notched Izod impact strength Sc (J
/ M), the housing according to claim 1 or 2, which is formed by molding a resin composition which gives an injection-molded article satisfying the following inequality. Sc> 4.5Xc + 2.2S0 (where S0 is the Izod impact strength (J / m) with the 1/8 "thickness notch of the thermoplastic resin (A) alone at 23 ° C.) 17. The housing according to claim 1, wherein the inorganic filler (B) is plate-shaped and / or granular. 18. The inorganic filler (B) has an average particle diameter of 2 μm.
18. The housing according to claim 17, which is less than or equal to m. 19. The housing according to claim 1, wherein the elastic polymer (C) having a glass transition temperature of −20 ° C. or lower has a weight average molecular weight of 5000 or more.