JP2009227827A - Inorganic composite resin material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic composite resin material having high dispersibility of a filler and high heat resistance, and especially capable of using as a friction material suitably, and to provide a method for manufacturing the inorganic composite resin material efficiently. <P>SOLUTION: This inorganic composite resin material comprises the filler dispersed in the resin, wherein the filler contains a thin layer product composed of a layer clay mineral, and has a thickness of 0.1-300 nm. The method for manufacturing the composite resin material is also disclosed, which comprises swell-processing the layer clay mineral before freeze-drying, and melt-blending it with a resin to manufacture the inorganic composite resin material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an inorganic composite resin material and a method for producing the same.

  Conventionally, resin materials such as plastic materials and rubber materials, various fillers such as organic clay, talc, diatomaceous earth, mica, silica, calcium carbonate, carbon black and other inorganic materials, organic fibers, inorganic fibers, etc. A resin material obtained by compounding a fibrous substance or the like has been known. These resin materials contain various fillers to improve various mechanical, electrical, and chemical properties of the molded body. For example, the composite resin disclosed in Patent Document 1 In the material, the mechanical properties of the molded body are improved by dispersing the organically modified layered polysilicate in the resin.

Thus, the resin material formed by combining various fillers is widely used for automobile parts, aircraft parts, electronic / electronic equipment parts, building members, and the like. For example, as a friction material widely used for brake pads, brake linings, clutch facings, etc. in various vehicles and industrial machines, resin binder materials made of thermosetting resin powder, inorganic fillers, organic fillers, friction adjustment A resin material in which a material and a fiber material such as a heat-resistant organic fiber are mixed and compounded is known. The resin material is molded (preliminarily molded) at a predetermined pressure at room temperature and then thermoformed at a predetermined temperature. The desired molded body is manufactured by curing (aftercuring) and finishing.
JP 2000-119535 A

  When the composite resin material contains a filler with a high aspect ratio having a size of submicron or less, it is a big problem to uniformly disperse the filler while suppressing aggregation in the manufacturing process of the composite resin material. It has become.

  In Patent Document 1, the organically treated layered polysilicate is melt-kneaded with a resin to separate and disperse the polysilicate in layers, but it is necessary to apply a high shear force to the layered polysilicate. In addition, the obtained composite resin material has a problem that the dispersion state of the filler is not sufficient.

  Furthermore, the composite resin material obtained by the method described in Patent Document 1 is used as a friction material because the organic agent in the production stage remains, which may cause deterioration in performance and function, and has low heat resistance. In some cases, the desired performance cannot be obtained.

  Under such circumstances, the present invention efficiently produces an inorganic composite resin material having high dispersibility and heat resistance of the filler, and particularly suitable for use as a friction material, and the inorganic composite resin material. It is intended to provide a method.

  As a result of intensive research to achieve the above object, the present inventors have swelled the layered clay mineral, freeze-dried, and then melt-kneaded with the resin, thereby forming the layered clay mineral and having a thickness of It has been found that an inorganic composite resin material obtained by dispersing a filler containing a thin layered product having a thickness of 0.1 to 300 nm in a resin can be efficiently produced, and the present invention has been completed based on this finding.

That is, the present invention
(1) An inorganic composite resin material comprising a layered clay mineral and a filler containing a thinned product having a thickness of 0.1 to 300 nm dispersed in a resin,
(2) In the above (1), the layered clay mineral is one or more selected from smectite and synthetic fluorine mica, and the resin is one or more selected from a phenol resin, an epoxy resin, and a polybenzoxazine resin. The inorganic composite resin material described,
(3) The inorganic composite resin material according to the above (1) or (2), wherein the layered product of the layered clay mineral is processed with a coupling agent,
(4) The inorganic composite resin material according to any one of (1) to (3) above, wherein the layered clay mineral thinned product is treated with a water-soluble polymer compound.
(5) The inorganic composite resin material according to any one of (1) to (4), wherein the filler further contains ceramic particles,
(6) The layered clay mineral is swelled, freeze-dried, and then melt-kneaded with the resin, whereby a filler including a layered clay mineral having a thickness of 0.1 to 300 nm is contained in the resin. A method for producing an inorganic composite resin material, characterized by producing an inorganic composite resin material dispersed;
(7) In the above (6), the layered clay mineral is one or more selected from smectite and synthetic fluorine mica, and the resin is one or more selected from a phenol resin, an epoxy resin, and a polybenzoxazine resin. A method for producing the inorganic composite resin material described
(8) The method for producing an inorganic composite resin material according to (6) or (7), wherein the layered clay mineral is swollen together with a coupling agent,
(9) The method for producing an inorganic composite resin material according to any one of (6) to (8), wherein the layered clay mineral is swollen together with ceramic particles.

  According to the present invention, the layered clay mineral is swelled and thinned, and then freeze-dried to maintain the three-dimensional structure of the layered clay mineral, while the layered clay mineral is melted with the resin. It becomes possible to disperse easily by kneading. For this reason, according to the present invention, it is possible to provide an inorganic composite resin material that has high dispersibility and heat resistance, and can be suitably used particularly as a friction material. A method of manufacturing can be provided.

First, the inorganic composite resin material of the present invention will be described.
The inorganic composite resin material of the present invention is characterized in that a filler containing a thin layered product having a thickness of 0.1 to 300 nm is dispersed in a resin, which is made of a layered clay mineral.

In the inorganic composite resin material of the present invention, the layered clay mineral used as a raw material for the filler is not particularly limited as long as it has swelling properties. For example, natural clay minerals and synthetic clay minerals having cation exchange ability are used. Can be mentioned. Examples of the natural clay mineral and the synthetic clay mineral include smectite, kaolinite, vermiculite, mica, brittle mica, chlorite, and the like. Examples of the smectite include montmorillonite, saponite, piderite, and nontronite. it can. In addition, synthetic fluorine mica in which mica is treated with fluorine can also be mentioned, and this synthetic fluorine mica is suitable as a layered clay mineral because of small variations in quality. As the synthetic fluorine mica, sodium tetrasilicate fluorine mica is preferable. (NaMg _2.5 Si ₄ O ₁₀ F ₂ ) can be exemplified. These layered clay minerals may be used alone or in combination of two or more.

  In the inorganic composite resin material of the present invention, the layered clay mineral thinned product constituting the filler has a thickness in the range of 0.1 to 300 nm, preferably in the range of 0.1 to 200 nm. More preferably, it is in the range of 1 to 100 nm. The thickness of the thin layered product is difficult to be less than 0.1 nm in relation to the thickness of the layer constituting the layered clay mineral, and if it exceeds 300 nm, the effect of improving the mechanical properties is diminished.

  The layered clay mineral thinned product constituting the filler preferably has a layer length (length in the longitudinal direction) of 1 to 10 μm. It becomes possible to disperse | distribute suitably in resin because the layer length of a thin layered product is 1-10 micrometers.

  In the present specification, the thickness and the layer length of the thin layered product can be measured by observing the cut surface of the inorganic composite resin material according to the present invention with an electron microscope (SEM).

  In the inorganic composite resin material of the present invention, the layered clay mineral thinned product constituting the filler is preferably processed with a coupling agent.

  Examples of coupling agents include silane coupling agents, alumina coupling agents, titanate coupling agents, and the like. Examples of such coupling agents include Si, Al, Ti inorganic salts, and organic salts. Alternatively, an organic compound having one or more hydrophobic alkoxyl groups such as an alkylalkoxyl group can be given. Among these, it is preferable to use a silane coupling agent.

For silane coupling agents, the formula
R _n SiX _4-n
(In the formula, n is an integer of 0 to 3, R is a hydrocarbon group, may contain a functional group, X is a hydrolyzable group or a hydroxyl group, and there are a plurality of R and X, respectively. R and X may be the same or different when
It is preferable to use what is represented by these.

In the silane coupling agent represented by R _n SiX _4-n , n is an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. .

In the silane coupling agent represented by R _n SiX _4-n , R is a hydrocarbon group. Examples of the hydrocarbon group include a saturated or unsaturated aliphatic hydrocarbon group having a straight chain or a branched chain, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. These hydrocarbon groups are monovalent. Or multivalent.

  The number of carbon atoms of the hydrocarbon group is preferably 1 to 25, particularly 1 to 3 in the case of an aliphatic hydrocarbon group, and 6 to 25, particularly 6 to 10 in the case of an aromatic hydrocarbon group. When it is an alicyclic hydrocarbon, 3 to 25, particularly 3 to 6 are preferable.

  The hydrocarbon group may contain a functional group, and examples of the functional group include a vinyl group, an ester group, an ether group, an epoxy group, an amino group, a carboxyl group, a carbonyl group, an amide group, a mercapto group, Examples include a sulfonyl group, a sulfenyl group, a nitro group, a nitroso group, a nitrile group, a halogen atom, and a hydroxyl group.

  In the silane coupling agent, when there are a plurality of R, R may be the same or different.

In the silane coupling agent represented by R _n SiX _4-n , X is a hydrolyzable group or a hydroxyl group. Examples of the hydrolyzable group include an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group. Groups, aminoxy groups, amide groups and halogen atoms.

  In the silane coupling agent, when there are a plurality of Xs, Xs may be the same or different.

Specific examples of the silane coupling agent represented by R _n SiX _4-n include methyltrimethoxysilane, methyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-hexenyltrimethoxysilane, and phenyltrimethoxysilane. , Phenyltriethoxysilane, 3-β-naphthylpropyltrimethoxysilane, p-vinylbenzyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ- (2 -Aminoethyl) aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane and the like.

  The said coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content ratio of the layered clay mineral to the coupling agent in the filler is a mass ratio, and the layered clay mineral / coupling agent is preferably 1 / 0.5 to 1/4, and 1 / 0.5 to 1 More preferably, it is / 2.

  When the layered clay mineral thinned product constituting the filler is processed with a coupling agent, the hydroxyl group or hydrolyzable group of the coupling agent introduced between the layers of the layered clay mineral is hydrolyzed. The resulting hydroxyl group undergoes dehydration condensation, and the coupling agent is fixed between the layers of the layered clay mineral to form a structure having micropores having a diameter of 2 nm or less and mesopores having a diameter of more than 2 nm and not more than 50 nm. It is considered that macropores having a diameter of more than 50 nm are also formed between the structures when the structures are sterically bonded. When such a porous filler is used, a large number of pores can be introduced into the inorganic composite resin material. For example, it can be suitably used as a friction material.

  In the inorganic composite resin material of the present invention, the layered clay mineral thinned product constituting the filler is preferably processed with a water-soluble polymer compound.

  Examples of the water-soluble polymer compound include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyethylene glycol, carboxymethyl cellulose (CMC), alkyl cellulose, gelatin, agar, mannose, pectin, guar gum, xanthan gum, sodium alginate, and starch. be able to.

  The content of the water-soluble polymer compound in the filler is preferably 25 to 80% by mass and more preferably 50 to 80% by mass with respect to the total amount of the filler.

  When the layered clay mineral thinned product constituting the filler is treated with a water-soluble polymer compound, the filler is given flexibility and can be modified to be more hydrophobic.

  In the inorganic composite resin material of the present invention, it is preferable that the filler further contains ceramic particles. Examples of the ceramic particles include alumina, zirconia, and silica.

  The average particle diameter of the ceramic particles is preferably 3 to 20 μm, more preferably 5 to 15 μm, and still more preferably 5 to 10 μm.

  In addition, in this specification, an average particle diameter means a volume average particle diameter, and a volume average particle diameter can be measured with a particle size distribution measuring device etc., for example.

  The content of the ceramic particles in the filler is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass with respect to the total amount of the filler. preferable.

  When the layered clay mineral thinned product includes ceramic particles, it is preferable to take a form in which the ceramic particles are inserted between the thinned layers of the layered clay mineral.

  When the layered clay mineral layered product includes ceramic particles, the heat resistance and strength of the inorganic composite resin material can be improved by dispersing the filler containing the layered product.

  The inorganic composite resin material of the present invention is obtained by dispersing the filler in a resin. As resin which disperse | distributes a filler, 1 or more types chosen from a thermoplastic resin and a thermosetting resin can be mentioned.

  Examples of such resins include phenol resins, epoxy resins, polybenzoxazine resins, polyester resins, acrylic resins, and the like.

  Examples of the phenol resin include a polymer of a phenol monomer and formaldehyde, and examples thereof include a resol type and a novolac type, and any of them may be used.

  Epoxy resins include glycidyl ether type resins such as condensation reaction products of bisphenol A and epichlorohydrin, condensation reaction products of bisphenol F and epichlorohydrin, glycidyl ester resins, alicyclic epoxy resins, aliphatic epoxies. Resin, bromine-containing epoxy resin, phenol-novolak type or cresol-novolak type epoxy resin, and the like. Among these epoxy resins, a condensation reaction product of bisphenol A and epichlorohydrin, or bisphenol F and Glycidyl ether type resins such as condensation reaction products with epichlorohydrin are preferred.

  Specifically, “Epototo YD903N, YD128, YD14, PN639, CN701, NT114, ST-5080, ST-5100, ST-4100D” manufactured by Toto Kasei Co., Ltd., “EITPA3150” manufactured by Daicel Chemical Industries, manufactured by Ciba-Geigy “Aldite CY179, PT810, PT910, GY6084”, “Teconal EX711” manufactured by Nagase Kasei Co., Ltd., “Epicron 4055RP, N680, HP4032, N-695, HP7200H” manufactured by Dainippon Ink, Inc. “Epicoat 1001,” manufactured by Yuka Shell Epoxy 1002, 1003, 1004, 1007 "," DER 662 "manufactured by Dow Chemical Company," EPPN 201, 202, EOCN 1020, 102S "manufactured by Nippon Kayaku Co., Ltd., and the like.

  Examples of the polybenzoxazine resin include a reaction product of a compound having a phenolic hydroxyl group, a primary amine and formaldehyde.

  As the polybenzoxazine resin raw material having a phenolic hydroxyl group, monovalent or divalent or higher polyhydric phenols having a hydrogen atom in at least one of the ortho positions of the hydroxyl group on the aromatic ring can be used. Specifically, monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, p-tert-butylphenol, α-naphthol, β-naphthol, p-phenylphenol; catechol, resorcinol, 4 , 4'-dihydroxydiphenylmethane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and other dihydric phenols; trisphenol compounds, tetraphenol compounds, phenol resins and more Of polyphenols, etc. I can make it. Among these, bisphenol A is preferable from the viewpoint of the performance of the obtained polybenzoxazine resin.

  As primary amines which are raw materials for polybenzoxazine resins, there are aliphatic amines and aromatic amines. When aliphatic amines are used, the resulting polybenzoxazine resins have poor heat resistance. Group amines are preferred. Examples of the aromatic amine include aniline, toluidine, xylidine, and anisidine.

  Examples of formaldehydes that are raw materials for polybenzoxazine resins include formalin, paraformaldehyde, and trioxane.

  Examples of polyester resins include polyhydric alcohols such as ethylene glycol, propanediol, hexanediol, neopentylglycol, trimethylolpropane, pentaerythritol, maleic acid, terephthalic acid, isophthalic acid, phthalic acid, succinic acid, and glutaric acid. And those obtained by polymerizing carboxylic acids such as adipic acid, sebacic acid, and β-oxypropionic acid according to a conventional method.

  The number average molecular weight of the polyester resin is preferably 500 to 100,000, and more preferably 2,000 to 80,000. The hydroxyl value of the polyester resin is preferably 0 to 300 mgKOH / g, more preferably 30 to 120 mgKOH / g. Moreover, 0-200 mgKOH / g is preferable and the acid value of a polyester resin has more preferable 10-100 mgKOH / g. The melting point of the polyester resin is preferably 50 to 200 ° C, more preferably 80 to 150 ° C.

  Specifically, “Crill coat 341, 7620, 7630” manufactured by Daicel UCB, “Fine Dick M-8010, 8020, 8024, 8710” manufactured by Dainippon Ink, “Iupica Coat GV110, 230” manufactured by Iupika Japan, Japan Examples thereof include “ER6570” manufactured by Esther, “VESTAGON EP-P100” manufactured by Huls, and the like.

  Examples of the acrylic resin include a polymer of acrylic acid or a derivative thereof, and a copolymer of acrylic acid or a derivative thereof and another monomer, such as acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, glycidyl. A monomer comprising acrylic acid such as acrylate or n-butyl acrylate or a derivative thereof, or another monomer such as styrene was radically polymerized using a radical initiator such as azobisisobutyronitrile or benzoyl peroxide. Things can be mentioned. Specific examples include “Sanpex PA-70” manufactured by Sanyo Chemical Industries.

  In the inorganic composite resin material of the present invention, when a thermosetting resin is used as the resin for dispersing the thinned product, the inorganic composite resin material may further contain a curing agent, and examples of the curing agent include polyamines and dicyandiamide. Type, phenol type, aminoamide type, blocked isocyanate type, triglycidyl isocyanurate (TGIC) type, epoxy type (polyepoxide, epoxy resin) and the like, and polyamine type, dicyandiamide type and phenol type are particularly preferable. .

  In the inorganic composite resin material of the present invention, the filler content is preferably 1 to 30% by mass.

Next, the manufacturing method of the inorganic composite resin material of this invention is demonstrated.
The method for producing an inorganic composite resin material of the present invention comprises a layered clay mineral, which is swelled, freeze-dried and then melt-kneaded with a resin to form a layered clay mineral having a thickness of 0.1 to 300 nm. It is characterized by producing an inorganic composite resin material in which a filler containing a thin layered product is dispersed in a resin.

  In the method of the present invention, as the layered clay mineral, the same ones as described above can be used.

  The swelling treatment of the layered clay mineral can be performed by bringing the layered clay mineral into contact with the dispersion, for example, by immersing the layered clay mineral in the dispersion. Examples of the dispersion include water, and the contact time between the layered clay mineral and the dispersion is preferably about 5 to 24 hours, and the contact temperature is preferably about room temperature.

  The swelling treatment of the layered clay mineral may be performed in the presence of a coupling agent, a water-soluble polymer compound, ceramic particles, etc., and specific examples and blending ratios of the coupling agent, the water-soluble polymer compound, and ceramic particles are as follows: As described above.

  When the layered clay mineral is swollen in the presence of a coupling agent, a water-soluble polymer compound, ceramic particles, etc., the layered clay mineral may be swollen at a predetermined temperature in order to cause the layered clay mineral to react with the coupling agent. preferable. The layered clay mineral has a fibrous or flat crystal structure, and the structure is maintained up to about 1000 ° C. When the layered clay mineral is reacted with a coupling agent or the like by the method described above. Since it is necessary to determine the temperature during the reaction in consideration of the heat resistance of the hydrophobic group of the coupling agent, the reaction temperature of the layered clay mineral and the coupling agent is about room temperature to about 100 ° C. preferable. The reaction time is preferably 2 to 48 hours.

  The swollen layered clay mineral is then lyophilized. The lyophilization preferably includes a preliminary freezing treatment step, and the preliminary freezing treatment is preferably performed at −45 to −20 ° C. for 24 hours or more. After the preliminary freezing step, it is preferable to freeze-dry without dissolving the pre-freeze, and the freeze-drying conditions may be adjusted as appropriate so that no ice blocks are observed inside and the ice is not melted. In a reduced pressure atmosphere of 80 Pa or less, it is preferably performed at 20 ° C. or less for about 72 to 96 hours.

  In the method of the present invention, the freeze-dried layered clay mineral is melt kneaded with a resin. Melt kneading can be performed using a suitable kneader, for example, at a kneading temperature of 80 to 120 ° C.

  Prior to the present invention, a method of peeling and dispersing the clay mineral by melting and kneading a layered clay mineral and a resin was known. However, this method requires a high shear force for peeling and dispersing the clay mineral. It was a thing. In contrast, in the method of the present invention, since the layered clay mineral is subjected to a swelling treatment to make it thin, dispersibility can be improved without applying a high shearing force during melt kneading. In addition, when the layered clay mineral is subjected to swelling treatment and then dried by heating, the thin layer structure of the layered clay mineral is lost. Therefore, in the method of the present invention, the solvent is removed by lyophilization. In addition, dispersion in the resin is possible while maintaining a thin layer structure.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1
(A) 10 g of synthetic fluorine mica (ME-100, manufactured by Corp Chemical Co.), which is a layered clay mineral, was added to 600 mL of distilled water and stirred well to prepare a synthetic fluorine mica dispersion.
(B) The synthetic fluorine mica dispersion was stirred while being concentrated at 75 ° C. for 5 hours to swell the synthetic fluorine mica.
(C) After swollen the liquid containing swollen synthetic fluoromica obtained in (b) at −20 ° C. for 24 hours, 80 Pa or less using a freeze dryer (freeze dryer FD-5N manufactured by EYELA) After being freeze-dried at 20 ° C. for 72 hours under reduced pressure conditions of the above, pulverization and classification were performed to obtain a thin layer of synthetic fluoromica.
(D) 12 g of the layered clay mineral obtained in (c) was melted with 190 g of a novolak type phenolic resin (manufactured by Cashew) at a kneading temperature of 120 ° C. using a biaxial kneader (S1KRC kneader manufactured by Kurimoto Iron Works). By kneading, an inorganic composite resin material in which a filler made of a layered product of layered clay mineral was dispersed in a novolac type phenol resin was obtained.
When the cross section of the obtained inorganic composite resin material was observed with an electron microscope (FE-SEM), the thin layered product of synthetic fluorine mica was well dispersed in the resin, and the thickness was 200 to 300 nm. The layer length was 1-5 μm.

Example 2
(A) 10 g of synthetic fluorine mica (ME-100, manufactured by Co-op Chemical Co.), which is a layered clay mineral, and 15 g of acetic acid were added to 600 mL of distilled water and stirred well to prepare a synthetic fluorine mica dispersion.
(B) 20 g of triethoxymethylsilane as a coupling agent was diluted with 300 mL of ethanol and stirred well to obtain a coupling agent dispersion.
(C) The coupling agent dispersion obtained in (b) above is added to the synthetic fluorine mica dispersion obtained in (a) above, and the resultant mixture is stirred for 5 hours while concentrating at 75 ° C. to swell the synthetic fluorine mica. Reaction with a coupling agent.
(D) After swollen the liquid containing swollen synthetic fluoromica obtained in (c) at −20 ° C. for 24 hours, 80 Pa or less using a freeze dryer (freeze dryer FD-5N manufactured by EYELA) After being freeze-dried at 20 ° C. for 72 hours under reduced pressure conditions of the above, pulverization and classification were performed to obtain a thin layer of synthetic fluoromica.
(E) Using a biaxial kneader (S1 KRC kneader manufactured by Kurimoto Iron Works), the layered clay mineral thinned product obtained in (d) was subjected to a torque of 0.39 to 0.8 Nm, a biaxial rotation of 43 rpm, and a kneading temperature of 75 ° C. Then, 190 g of novolak type phenol resin (manufactured by Cashew Co.) was melt kneaded to obtain a dispersion material in which a filler composed of a layered clay mineral was dispersed in 6% by mass in the novolak type phenol resin.
When the cross section of the obtained dispersion material was observed with an electron microscope (FE-SEM), the thin layer of the synthetic fluorine mica was well dispersed in the resin, the thickness was 5 to 200 nm, and the layer length was It was 1-5 μm.
The dispersion material was pulverized and powdered, and then mixed so that the content of hexamethylenetetramine as a curing agent was 10% by mass to obtain an inorganic composite resin material.

Example 3
(A) 20 g of synthetic fluorine mica (ME-100 manufactured by Co-op Chemical Co., Ltd.), which is a layered clay mineral, was added to 2 L of distilled water and stirred at room temperature for 24 hours to prepare a synthetic fluorine mica dispersion.
(B) As a raw material for synthesizing titania particles as ceramic particles, 56 g of tetraisopropoxytitanium was charged into 500 mL of 80% aqueous acetic acid and mixed at 50 ° C. for 1 hour to obtain a titania particle-containing liquid.
(C) The titania particle-containing liquid obtained in (b) above was added to the synthetic fluoric mica dispersion obtained in (a) above, and stirred while being concentrated at 75 ° C. for 5 hours to swell the synthetic fluoric mica. .
(D) After swollen the liquid containing swollen synthetic fluoromica obtained in (c) at −20 ° C. for 24 hours, 80 Pa or less using a freeze dryer (freeze dryer FD-5N manufactured by EYELA) After lyophilization at 20 ° C. for 72 hours under the reduced pressure conditions of the above, heating at 150 ° C. for 2 hours yielded a thin layer of synthetic fluoromica.
(E) Using a biaxial kneader (S1 KRC kneader manufactured by Kurimoto Iron Works), the layered clay mineral thinned product obtained in (d) was subjected to a torque of 0.39 to 0.8 Nm, a biaxial rotation of 43 rpm, and a kneading temperature of 75 ° C. Then, 190 g of novolak type phenol resin (manufactured by Cashew Co.) was melt kneaded to obtain a dispersion material in which a filler composed of a layered clay mineral was dispersed in 6% by mass in the novolak type phenol resin.

  When the cross section of the obtained dispersion material was observed with an electron microscope (FE-SEM), the thin layered product of synthetic fluorine mica was well dispersed in the resin, the thickness was 5 to 300 nm, and the layer length was It was 1-5 μm. The electron micrograph is shown in FIG. Moreover, the electron micrograph in the surface of the obtained dispersion material is shown in FIG.1 (2). FIG. 1 (1) shows that the synthetic fluorine mica is thinned, and FIG. 1 (2) shows that the surface of the obtained dispersion material is porous.

  The dispersion material was pulverized to form a powder, and then mixed so that the content of hexamethylenetetramine as a curing agent was 10% by mass to obtain an inorganic composite resin material.

Example 4
In Example 3 (e), an inorganic composite resin material was obtained in the same manner as in Example 3 except that a polybenzoxazine resin was used instead of the novolac-type phenol resin.
When the cross section of the obtained inorganic composite resin material was observed with an electron microscope, the layered product of synthetic fluorine mica had a thickness of 5 to 200 nm and a layer length of 1 to 5 μm.

Comparative Example 1
(A) 50 g of synthetic fluorine mica (ME-100, manufactured by Corp Chemical Co.), which is a layered clay mineral, was added to 10 L of distilled water and stirred well to prepare a synthetic fluorine mica dispersion.
(B) 100 g of dodecyltrimethylammonium salt was added to the above synthetic fluorine mica dispersion, stirred for 30 minutes, filtered, and dried at 110 ° C. for 2 hours. After drying, the resulting mass was pulverized to obtain a filler made of synthetic fluoromica organized with dodecyltrimethylammonium.
(C) A novolac type phenolic resin obtained by using a biaxial kneader (S1KRC kneader manufactured by Kurimoto Iron Works) and a torque of 0.39 to 0.8 Nm, a biaxial rotation speed of 43 rpm, and a kneading temperature of 75 ° C. By melt-kneading with 190 g (manufactured by Cashew Co., Ltd.), a mixture obtained by dispersing 6% by mass of a filler made of a layered clay mineral thin layer in a novolac type phenol resin was obtained.
The obtained mixture was pulverized to form a powder, and then mixed so that the content of hexamethylenetetramine as a curing agent was 10% by mass to obtain a composite resin material.

<Thermal characteristics evaluation>
Using the TG / DTA apparatus (manufactured by Seiko Instruments Inc. (SII)), the composite resin materials obtained in Examples 1 to 4 and Comparative Example 1 were increased from room temperature to 900 ° C. at a rate of 10 ° C./min. The mass retention when heated ((mass at 900 ° C./mass at room temperature) × 100) was determined. The results are shown in Table 1.

＜強度評価＞
実施例１〜４および比較例１で得た複合樹脂材料を、炭酸カルシウムと複合樹脂材料が、体積比で、炭酸カルシウム：複合樹脂材料＝７０：３０となるように混合し、熱成形して、縦５０ｍｍ×横６５ｍｍ×厚さ１０ｍｍのテストピースを作製した。得られた各テストピースに対し、ＪＩＳＤ４３１１に準じて曲げ強度試験を行った結果を表２に示す。

<Strength evaluation>
The composite resin materials obtained in Examples 1 to 4 and Comparative Example 1 were mixed and thermoformed so that calcium carbonate and composite resin material were in a volume ratio of calcium carbonate: composite resin material = 70: 30. A test piece having a length of 50 mm, a width of 65 mm, and a thickness of 10 mm was produced. Table 2 shows the results of a bending strength test performed on each of the obtained test pieces in accordance with JIS D4311.

表１、表２より、実施例１〜実施例４で得られた無機複合化樹脂材料は、耐熱性や強度が高く、摩擦材として好適に使用し得るものであることが分かる。

From Tables 1 and 2, it can be seen that the inorganic composite resin materials obtained in Examples 1 to 4 have high heat resistance and strength and can be suitably used as friction materials.

  ADVANTAGE OF THE INVENTION According to this invention, the dispersibility and heat resistance of a filler are high, and especially the inorganic composite resin material which can be used suitably as a friction material, and the method of manufacturing this inorganic composite resin material efficiently can be provided. .

It is a cross-sectional photograph (1) and surface photograph (2) of the material obtained in the Example of this invention.

Claims (9)

  An inorganic composite resin material comprising a layered clay mineral and a filler containing a thinned product having a thickness of 0.1 to 300 nm dispersed in a resin.   2. The inorganic composite according to claim 1, wherein the layered clay mineral is one or more selected from smectite and synthetic fluorine mica, and the resin is one or more selected from a phenol resin, an epoxy resin, and a polybenzoxazine resin. Resin material.   The inorganic composite resin material according to claim 1 or 2, wherein the layered product of the layered clay mineral is processed with a coupling agent.   The inorganic composite resin material according to any one of claims 1 to 3, wherein the layered product of the layered clay mineral is processed with a water-soluble polymer compound.   The inorganic composite resin material according to claim 1, wherein the filler further contains ceramic particles.   The layered clay mineral is swelled, freeze-dried, and melt-kneaded with the resin to disperse the filler containing the layered clay mineral having a thickness of 0.1 to 300 nm in the resin. The manufacturing method of the inorganic composite resin material characterized by manufacturing the inorganic composite resin material which becomes.   The inorganic composite according to claim 6, wherein the layered clay mineral is one or more selected from smectite and synthetic fluorine mica, and the resin is one or more selected from a phenol resin, an epoxy resin, and a polybenzoxazine resin. Method for producing a fluorinated resin material.   The method for producing an inorganic composite resin material according to claim 6 or 7, wherein the layered clay mineral is swollen together with a coupling agent.   The method for producing an inorganic composite resin material according to any one of claims 6 to 8, wherein the layered clay mineral is swollen together with ceramic particles.

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