JP2008024839A - Thermosetting resin composite and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composite in which self-aggregation properties and dispersibility of a filler are improved; molding temperature is shortened and molding temperature is reduced; properties such as mechanical strength and heat resistance are improved, and to provide a method for producing the same. <P>SOLUTION: A phenol derivative, an amine, and an aldehyde are agitated, heated, and subjected to polycondensation in the state where a surface-treated filler is dispersed to obtain a thermosetting resin composite comprising at least the surface-treated filler. The surface-treated filler is preferably a filler which is surface-treated with a surface-treatment agent having an amine terminal. The method for producing a thermosetting resin composite containing a filler in a dispersed state comprises the steps of surface-treating the filler and agitating, heating, and subjecting to polycondensation a phenol derivative, an amine, and an aldehyde in the state where the surface-treated filler is dispersed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composite material. In particular, friction materials such as disc brake pads, brake linings, clutch facings, etc. used for braking of automobiles, railway vehicles, various industrial machines, molding materials, electrical / electronic equipment parts, communication equipment parts, machine parts, structural members, The present invention relates to a thermosetting resin composite material used for structural adhesives and the like.

Thermosetting resin composite materials are excellent in mechanical strength, heat resistance, electrical properties, etc., and are used in various applications. Thermosetting resins are used as binders, but are important components that affect the properties of molding materials.
Said thermosetting resin composite material is shape | molded by methods, such as compression molding, extrusion molding, injection molding, transfer molding. For example, the brake pad is molded by compression molding at a temperature of about 130 to 180 ° C. and then post-curing at a higher temperature.

On the other hand, fillers surface-treated with a surface treatment agent are filled into a thermosetting resin to improve the self-cohesiveness / dispersibility of the filler and improve the wettability between the resin / filler, and the thermosetting resin composite material Improvements have been made to the characteristics.
Usually, the surface treatment agent exists in a state separated from the thermosetting resin inside the thermosetting resin composite material, and the surface treatment agent is a low molecular weight component as compared with the thermosetting resin, and has strength and resistance. It is often inferior to maturity. Therefore, the properties (strength, heat resistance, etc.) of the thermosetting resin composite material may be reduced by the addition of the surface treatment agent.

For example, in “Patent Document 1”, a particulate inorganic substance is treated with a natural or synthetic latex composition, and the resulting mixture is dehydrated and dried to produce a surface-treated inorganic filler, and then thermoplastic. It describes that a thermoplastic resin or a thermosetting resin composition is produced through a step of dispersing the surface-treated inorganic filler in a resin or a thermosetting resin. However, it cannot be said that the above-described surface treatment has surely modified the particulate inorganic substance.
Also, in “Patent Document 2”, 5 to 25% by weight of thermosetting resin and 75 to 95% by weight of graphite as a base material with respect to the entire molding material, and the graphite has 10 to 32 carbon atoms. Although thermosetting resin molding materials that have been surface-treated with linear saturated fatty acids are described, there is a high probability that linear saturated fatty acids are ionically bonded to graphite, and fatty acids are liberated in the molding materials. There is a possibility of coming.
JP 7-173330 A JP 2002-294079 A

  The object of the present invention is that when the surface-treated filler is filled in the thermosetting resin, the surface treatment agent used for the surface treatment of the filler is not released inside the thermosetting resin composite material, and the thermosetting resin and It exists in a state of being chemically covalently bonded to improve the self-aggregation / dispersibility of the filler and the wettability between the resin / filler, shorten the molding time and lower the molding temperature, and improve the mechanical strength and resistance. It is to provide a thermosetting resin composite material having improved properties such as maturity and a method for producing the same.

  In the present invention, a filler is surface-treated with a surface-treating agent having an amine terminal, and the surface-treated agent and the phenol derivative are stirred and heated in a state where the surface-treated filler is dispersed and the phenol derivative, amines and aldehyde are stirred. A thermosetting resin is prepared by copolymerizing the filler and the filler is uniformly dispersed in the thermosetting resin so that the filler is uniformly dispersed in the thermosetting resin simultaneously with the polymerization operation. This is a resin composite material, and a thermosetting resin composite material having excellent strength and heat resistance can be obtained.

That is, the present invention has solved the above problems by the following means.
(1) In a thermosetting resin composite material containing at least a surface-treated filler, a phenol derivative, an amine and an aldehyde are stirred, heated, and polycondensed in a state where the surface-treated filler is dispersed. A thermosetting resin composite material.
(2) The thermosetting resin composite material according to (1), wherein the surface-treated filler is surface-treated with a surface treatment agent having an amine terminal.
(3) The thermosetting resin composite material according to (1) or (2), wherein the surface-treated filler is contained in an amount of 1 to 95% by mass with respect to the entire thermosetting resin composite material. .
(4) In the method for producing a thermosetting resin composite material in which a filler is dispersed and contained, in the state in which the filler is surface-treated, and in the state in which the surface-treated filler is dispersed, A method for producing a thermosetting resin composite material comprising the steps of stirring, heating and polycondensation of an aldehyde.
(5) The method for producing a thermosetting resin composite material according to (4), wherein the filler is subjected to a surface treatment with a surface treatment agent having an amine terminal.

Since the filler constituting the thermosetting resin composite material of the present invention has an amino group introduced on the filler surface, the self-aggregation and dispersibility of the filler are improved, and the wettability between the resin and the filler is further improved. Moreover, since the dispersibility of the filler is improved by simultaneously performing the dispersion of the filler and the polycondensation reaction of the thermosetting resin, a thermosetting resin composite material in which the filler is uniformly dispersed can be obtained.
In addition, since the filler is rendered reactive with the phenol derivative by introducing an amino group on the filler surface, the surface treatment agent is copolymerized with the thermosetting resin, so the surface treatment agent is thermosetting. A composite material excellent in various properties (strength, heat resistance, etc.) that is not liberated in the resin composite material and does not deteriorate due to the surface treatment agent can be obtained. In addition, the reactivity of the thermosetting resin is accelerated by the reactivity of the amino terminal of the surface treatment agent and the functional group of the filler surface, which is effective in shortening the molding time and lowering the molding temperature.

Hereinafter, the present invention will be described in detail. The thermosetting resin used in the present invention is not particularly limited.
The thermosetting resin composite material of the present invention is a thermosetting resin composite material comprising at least a surface-treated filler and a thermosetting resin. The addition amount of the thermosetting resin in the composite material is preferably 1 to 95% by mass in the composite material. More preferably, it is 1-50 mass%. If the resin is insufficient, the bonding of the molding material becomes weak and the strength becomes insufficient. Moreover, when there is too much resin, a composite material will become hard too much.

  As the phenol derivative, a compound having a phenolic hydroxyl group can be used. For example, phenol, o-cresol, m-cresol, p-cresol, xylenol, alkyl-substituted phenols such as pt-butylphenol, aromatic-substituted phenols such as p-phenylphenol, catechol, resorcinol, bisphenol F, bisphenol Examples thereof include divalent phenols such as A, and naphthols such as α-naphthol and β-naphthol. Of these, bisphenol A is preferred.

  Examples of the filler used in the present invention include calcium carbonate, barium sulfate, magnesia, alumina, zirconia, alumina, aluminum powder, copper powder, zinc powder, graphite, and molybdenum disulfide. Use. The surface-treated graphite can be suitably used in the present invention. The type of graphite to be used is not particularly limited, and examples thereof include natural scale graphite, artificial graphite, and expanded graphite. The surface treatment can be performed by a well-known method as will be described later, but in the present invention, when the composite material is used, the surface-treated graphite is chemically covalently bonded to the thermosetting resin. It is desirable to introduce a functional group by surface treatment with a surface treatment agent.

  Although there are many surface treatment agents having a functional group capable of chemically forming a covalent bond, it is preferable to use an amine having an amino group at the terminal in the present invention. The amine compound as the surface treatment agent can be used as long as it is an amine containing an alkyl group, aryl group or the like having about 10 to 35 carbon atoms. The alkyl group may be linear or branched, but a linear alkylamine is preferred. An amine having less than 10 carbon atoms has a low melting point and a strong pungent odor, making it difficult to work. Specific examples of the amine compound include n-dodecylamine, n-hexadecylamine, n-octadecylamine, n-nonadecylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- Although a coupling agent having an amine terminal such as phenyl-3-aminopropyltrimethoxysilane can be mentioned, it is preferable to use dodecylamine in the present invention.

  In the surface treatment of the filler, the addition amount of the surface treatment agent is preferably 0.05 to 500 parts by mass with respect to 100 parts by mass of the filler. Surface treatment includes a method of melt-mixing a treatment agent and a filler (for example, graphite) at a temperature exceeding the melting point or softening point of the surface treatment agent, a method of spraying a treatment agent at a temperature exceeding the melting point or softening point, etc. There is. In addition, a method of filtering, washing, drying, and pulverizing the product after mixing and surface-treating a treatment agent dissolved in a solvent with a filler can also be employed. Thus, the surface-treated filler can improve the self-aggregation and dispersibility and improve the wettability between the resin and the filler.

The compounding amount of the surface-treated filler (graphite) in the composite material is preferably 1 to 95% by mass in the composite material. Considering the strength, it is more preferably 1 to 50% by mass. Further, the particle diameter of the filler to be used is not particularly limited. However, since the particle diameter affects the fluidity of the composite material and the moldability of the composite material, it may be appropriately selected according to the characteristics of the molded product.
As a more preferred embodiment, the amount of the thermosetting resin in the composite material is 5 to 99% by mass, and the amount of filler (graphite) added is preferably 1 to 95% by mass in the composite material.

  The thermosetting resin composite material of the present invention can be produced by a conventional method. That is, a surface-treated filler (graphite) as a raw material, a phenol derivative as a raw material for a thermosetting resin, an amine such as aniline, an aldehyde such as paraformaldehyde and acetaldehyde, a solvent such as water, methyl ethyl ketone (MEK), and methanol The reaction mixture is placed in a reaction vessel and stirred at a predetermined temperature for several hours to perform an addition condensation reaction. After completion of the reaction, it is filtered, washed and dried. Further, the solvent may be removed under reduced pressure.

  In order to obtain a molded product of the thermosetting resin composite material obtained as described above, for example, the thermosetting resin composite material is filled in a mold or the like, and the conditions are 130 to 180 ° C. and 10 to 100 MPa. It is preferable to form by heating and compression molding for 5 to 35 minutes, and then post-cure treatment at 160 to 270 ° C. for 1 to 10 hours as necessary.

As the reinforcing fibers, inorganic fibers such as glass fibers, ceramic fibers, carbon fibers and mineral fibers, organic fibers such as aramid fibers, polyamide fibers and polyimide fibers, and metal fibers such as copper fibers, brass fibers and steel fibers are used.
As a normal filler, cashew dust, rubber dust, barium sulfate, calcium carbonate, magnesium carbonate, silica, metal powder and the like can be used singly or in combination.
When the thermosetting resin composite material of the present invention is used as a friction material or the like, a lubricant such as antimony sulfide or molybdenum sulfide may be added.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, the scope of the present invention is not limited by those Examples.

1. Production of thermosetting resin composite materials, etc. (Types of production materials)
In order to make it easier to understand the difference in the materials produced for the test, it will be explained first.
Example 1: Thermosetting resin composite material obtained by reacting a thermosetting resin raw material with dispersion of amine-treated graphite with a surface-treating agent having an amino group at the terminal Comparative Example 1: Surface having no amino group at the terminal Thermosetting resin composite material obtained by reacting surface-treated graphite with a treatment agent while dispersing the thermosetting resin raw material Comparative example 2: Thermosetting resin with dispersion of graphite not surface-treated with a surface treatment agent Thermosetting resin composite material obtained by reacting raw materials Comparative Example 3: Thermosetting resin obtained by melt-kneading an amine-treated graphite with a surface treating agent having an amino group at the end with a thermosetting resin synthesized separately Composite Material Comparative Example 4: Thermosetting resin composite material obtained by melt-kneading graphite not surface-treated with a surface treatment agent with a separately synthesized thermosetting resin Comparative Example 5: Separately synthesized thermosetting resin Alone

Example 1
1) Surface treatment of filler 20 g of phosphorus-like graphite was immersed in a mixed acid of 300 g of sulfuric acid and 20 g of nitric acid for 24 hours, washed with water three times, and suction filtered to collect graphite. The above graphite was added to 60 g of dodecylamine dissolved in 2 liters of water at 80 ° C., stirred for 3 hours, and then suction filtered to recover amine-treated graphite. The amine-treated graphite was coarsely pulverized after drying at 120 ° C. for 5 hours to obtain 80 g of amine-treated graphite.
2) Synthesis of thermosetting resin composite material Amine-treated graphite 80 g, bisphenol A 150 g, methyl ethyl ketone (MEK) 150 g, aniline 92 g, and paraformaldehyde 84 g are added to a four-necked flask, and 40 ° C. for 1 hour and 50 ° C. for 1 hour. The polycondensation reaction was carried out at 80 ° C. for 4 hours. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin composite material of Example 1.

Comparative Example 1
1) Surface treatment of filler 20 g of phosphorus-like graphite was immersed in a mixed acid of sulfuric acid: 300 g and nitric acid 20 g for 24 hours, washed with water three times, and then suction filtered to collect graphite. The above graphite was added to 88 g of sodium dodecyl sulfate dissolved in 2 liters of water at 80 ° C., stirred for 3 hours, and suction filtered to recover surface-treated graphite. The surface-treated graphite was coarsely pulverized after drying at 120 ° C. for 5 hours to obtain 108 g of surface-treated graphite.
2) Synthesis of thermosetting resin composite material 108 g of surface-treated graphite, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), and 84 g of aniline paraformaldehyde were added to a four-necked flask. A polycondensation reaction was carried out at 80 ° C. for 4 hours. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin composite material.

Comparative Example 2
1) Surface treatment of filler 20 g of phosphorus-like graphite was immersed in a mixed acid of 300 g of sulfuric acid and 20 g of nitric acid for 24 hours, washed with water three times, and suction filtered to recover 20 g of graphite.
2) Synthesis of thermosetting resin composite material 20 g of graphite, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), 122 g of aniline, and 84 g of paraformaldehyde are added to a four-necked flask, at 40 ° C for 1 hour, at 50 ° C for 1 hour, A polycondensation reaction was carried out at 80 ° C. for 4 hours. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin composite material.

Comparative Example 3
1) Surface treatment of filler 20 g of phosphorus-like graphite was immersed in a mixed acid of 300 g of sulfuric acid and 20 g of nitric acid for 24 hours, washed with water three times, and suction filtered to collect graphite. The above graphite was added to 60 g of dodecylamine dissolved in 2 L of water at 80 ° C., stirred for 3 hours, and suction filtered to recover amine-treated graphite. The amine-treated graphite was coarsely pulverized after drying at 120 ° C. for 5 hours to obtain 80 g of amine-treated graphite.
2) Synthesis of mature curable resin Add 115 g of bisphenol A, 115 g of methyl ethyl ketone (MEK), 94 g of aniline, and 65 g of paraformaldehyde to a four-necked flask, and add 1 hour at 40 ° C, 1 hour at 50 ° C, 4 hours at 80 ° C. A condensation reaction was performed. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin.
3) Melt kneading of filler and thermosetting resin The coarsely pulverized products of the above 1) and 2) were mixed and co-ground to produce a mixed powder. The mixed powder was melted and kneaded at 100 ° C. using a biaxial kneader to obtain a thermosetting resin composite material.

Comparative Example 4
1) Surface treatment of filler 20 g of phosphorus-like graphite was immersed in a mixed acid of 300 g of sulfuric acid and 20 g of nitric acid for 24 hours, washed with water three times, and suction filtered to recover 20 g of graphite.
2) Synthesis of thermosetting resin In a four-necked flask, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), 122 g of aniline, and 84 g of paraformaldehyde are added, and the weight is 1 hour at 40 ° C, 1 hour at 50 ° C, and 4 hours at 80 ° C. A condensation reaction was performed. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin.
3) Melt kneading of filler and thermosetting resin The coarsely pulverized products of the above 1) and 2) were mixed and co-ground to produce a mixed powder. The mixed powder was melted and kneaded at 100 ° C. using a biaxial kneader to obtain a thermosetting resin composite material.

Comparative Example 5
1) Synthesis of thermosetting resin In a four-necked flask, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), 122 g of aniline, and 84 g of paraformaldehyde are added, and the mixture is heated at 40 ° C for 1 hour, at 50 ° C for 1 hour, and at 80 ° C for 4 hours. A condensation reaction was performed. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin.

Example 2
1) Filler surface treatment Into 1 g of an amine-based silane coupling agent (aminopropyltriethoxysilane) dissolved in 100 g of distilled water, 20 g of silica powder (average particle size: 5 μm) was added and stirred for 3 hours, followed by suction filtration. Thereafter, it was dried at 120 ° C. for 5 hours to obtain an amine-treated silica powder.
2) Synthesis of thermosetting resin composite material 20 g of amine-treated silica powder, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), 92 g of aniline, and 84 g of paraformaldehyde are added to a four-necked flask, and 1 hour at 40 ° C. and 1 at 50 ° C. The polycondensation reaction was carried out at 80 ° C. for 4 hours. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin composite material.

Comparative Example 6
1) Synthesis of thermosetting resin composite material In a four-necked flask, 20 g of untreated silica powder, 150 g of bisphenol A, 150 g of methyl ethyl ketone (MEK), 122 g of aniline, and 84 g of paraformaldehyde were added, and 1 hour at 40 ° C. and 1 at 50 ° C. The polycondensation reaction was carried out at 80 ° C. for 4 hours. Thereafter, the solvent was removed by reducing the pressure at 0.06 MPa for 1 hour to obtain a thermosetting resin composite material.

2. Evaluation 1) Test piece bending strength test i) Preparation of test piece Powder such as thermosetting resin composite material: Calcium carbonate powder = 40: 60 vol% Blended powder obtained by dry blending is filled into a mold and molded. Thermoforming was performed at a pressure of 10 MPa and 180 ° C. for a predetermined time (300 seconds for Example 1 and Comparative Example 3, 960 seconds for Comparative Examples 2 and 4, and 1800 seconds for Comparative Examples 1 and 5). Thereafter, heat treatment was performed at 250 ° C. for 3 hours. A test piece of 10 mm × 50 mm × 2 mm was cut out from the obtained molded body in a direction parallel and perpendicular to the compression direction to obtain a test piece.

ii) Bending test Using the above test pieces, the test was performed five times at a distance between supporting points of 40 mm and a test speed of 1 mm / min, and the average values were compared.
2) Gel time test In accordance with JIS K6910 7.11 D method (flat plate method), the hot plate temperature was 180 ± 1 ° C.
3) DSC measurement Temperature rising rate: 10 ° C / min, in air, at a scanning temperature of 25 ° C to 300 ° C.
4) TG-DTA measurement The sample was heated at 180 ° C. for 1 hour and then at 250 ° C. for 3 hours and ground to an average particle size of about 50 μm. Temperature increase rate: 100 ° C./min, in air, at a scanning temperature of 25 ° C. to 1050 ° C. The weight retention at 550 ° C. was compared.

3. Evaluation results The evaluation results are shown in Table 1.

  The test pieces of Examples 1 and 2 showed good strength characteristics with little strength anisotropy. A thermosetting resin composite material having good curing characteristics and heat resistance and high overall performance was obtained.

  The thermosetting resin composite material of the present invention can provide a thermosetting resin composite material having a reduced molding time and a reduced molding temperature, and improved properties such as mechanical strength and ripening resistance, and a method for producing the same. Greatly increases the production efficiency of molding materials such as friction materials such as disc brake pads, brake linings, clutch facings, electrical / electronic equipment parts, communication equipment parts, mechanical parts, etc. used for braking automobiles, railway vehicles, various industrial machines, etc. Can be improved.

Claims (5)

  In a thermosetting resin composite material containing at least a surface-treated filler, a phenol derivative, an amine and an aldehyde are stirred, heated, and polycondensed in a state in which the surface-treated filler is dispersed. Characteristic thermosetting resin composite material.   The thermosetting resin composite material according to claim 1, wherein the surface-treated filler is surface-treated with a surface treatment agent having an amine terminal.   The thermosetting resin composite material according to claim 1, wherein the surface-treated filler is contained in an amount of 1 to 95% by mass with respect to the entire thermosetting resin composite material.   In the method for producing a thermosetting resin composite material containing dispersed fillers, the step of surface-treating the filler and stirring the phenol derivative, amines and aldehyde in a state where the surface-treated filler is dispersed -The manufacturing method of the thermosetting resin composite material characterized by including the process of heating and polycondensation.   The method for producing a thermosetting resin composite material according to claim 4, wherein the surface treatment of the filler is performed with a surface treatment agent having an amine terminal.