JPH0670184B2 - Composite material using thermosetting resin as matrix and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composite material using a novel thermosetting resin as a matrix and a method for producing the same.

[Conventional technology]

Various composite materials having a thermosetting resin as a matrix have been conventionally known. It is as follows when this is divided into a matrix and an aggregate.

Matrix: unsaturated polyester resin, epoxy resin, phenol resin, furan resin, diallyl phthalate resin, urea resin, melamine resin, xylene resin, polyimide resin, polyurethane resin, polyvinylbenzene resin, silicone resin, etc.

Aggregate: (granular and tabular) silica, mica, talc, stone powder, diatomaceous earth, clay, volcanic ash, graphite, carbon black, calcium carbonate, alumina, titanium oxide, aluminum powder, iron powder, wood powder, barium sulfate, Molybdenum disulfide,
etc.

(Fiber and cloth) Asbestos, glass fiber, carbon, graphite fiber, silicon carbide fiber, metal fiber, silica, alumina fiber, pulp, cellulose, vinylon, acrylic, tetron, cotton, hemp, etc.

Of these, the surface treatment of the aggregate has not been carried out except for glass fiber, carbon fiber and graphite fiber. Regarding glass fibers, Japanese Patent Publication Nos. Sho 36-17081 and Sho 37-2979 disclose that chromium aminoacetate and a silane coupling agent are effective aggregate surface-treating agents for epoxy resin matrix. For carbon and graphite fibers, Japanese Patent Publication Sho 52
It is disclosed in JP-A-53092 and JP-B-53-35630 that a pyrolysis gas of ammonium nitrate is an effective aggregate surface treatment method for matrices such as epoxy resin and phenol resin. On the other hand, the present inventors at the 51st Annual Meeting of the Chemical Society of Japan held in Kanazawa on October 4, 1960, mainly condensed polycyclic aromatic compounds of two or more rings, hydroxymethyl group and halomethyl group A thermosetting composition comprising a combination of an aromatic cross-linking material having one or more aromatic rings having two or more groups of at least one of the above and an acid catalyst (hereinafter CO
(Abbreviated as PNA resin matrix) and a composite material of COPNA resin matrix and carbon fiber paper. (Proceedings of symposium lectures I.p539-542) [Problems to be solved by the invention] First, in many conventional composite materials, the bond between the aggregate and the matrix depends on the physical adhesion (anchor effect). Therefore, few have actively introduced chemical bonds. For this reason, there is a drawback that it is difficult to say that the properties to be improved by combining aggregates such as heat resistance, dimensional stability, strength, elastic modulus, toughness, and abrasion resistance are sufficiently brought out. The Japanese Patent Publications Nos. 36-17081 and 37-2979 introduce chemical bonds, but the aggregate is limited to the glass composition and the matrix is limited to the epoxy resin, and various aggregates and matrixes are used. It is not applicable to. Also,
Regarding JP-B-52-53092 and JP-B-53-35630, the aggregate is limited to carbon fiber, and further, there is no description about a specific cross-linking agent or the like for chemically bonding the aggregate and the matrix, It has a drawback that the kind of aggregate to be used is limited.

[Means and Actions for Solving Problems]

The present invention is not limited to the heat resistance of the composite material made by using the carbon fiber paper as the aggregate and the COPNA resin as the matrix, which was announced by the present inventors, and further has strength, elastic modulus, toughness, and wear resistance. It is an object of the present invention to provide a composite material which has strong properties and is more strongly bonded to the aggregate having various surface functional groups as well as the carbon fiber paper and the matrix through a surface treatment material. The above object can be achieved by providing a composite material and a manufacturing method thereof according to the claims.

Next, the present invention will be described in detail.

That is, the first invention is a COPNA resin matrix, and the aggregate is a surface treated with a surface treatment agent containing 0.01 to 5 wt% of an aromatic cross-linking agent based on the aggregate. It is a composite material having a chemical bond at the interface of the matrix, which is rich in heat resistance, dimensional stability, strength, elastic modulus, toughness, and wear resistance.

Further, the second and third inventions are heat resistance, dimensional stability, and strength in which a COPNA resin matrix and an aggregate having a surface functional group are chemically bonded by a surface treatment agent mainly composed of an aromatic crosslinking agent. , A method for producing a composite material rich in elastic modulus, toughness, wear resistance and the like.

By the way, the difference between the present invention and the composite material of the carbon fiber paper which was previously announced by the present inventors is as follows. That is, in the composite material using the carbon fiber paper as an aggregate previously announced by the present inventors, the carbon fiber paper as an aggregate and the COPNA resin matrix are merely physical bonds. In contrast, those of the present invention are hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group,
COPNA resin matrix is directly bonded to an aggregate surface functional group such as an aldehyde group, an epoxy structure, a lactone structure, an ether structure and an acid anhydride structure by a surface treatment agent.

Hereinafter, the condensed polycyclic aromatic compound, the cross-linking agent, the acid catalyst, the surface treatment agent, and the aggregate that constitute the COPNA resin matrix that constitutes this composite material will be described.

The condensed polycyclic aromatic compound of the present invention includes naphthalene, anthracene,
One or more mixtures selected from phenanthrene, pyrene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as the main skeletons, or coal-based and petroleum-based heavy oils, tars, pitches Etc. can be used.

Next, the cross-linking agent of the present invention includes an aromatic compound having one or more aromatic rings having at least one group selected from the group consisting of hydroxymethyl group and halomethyl group, for example, p-xylylene dichloride, 1 For example, 4,4-benzenedimethanol (p-xylylene glycol) and 9,10-anthracene dimethanol can be used.

The acid catalyst of the present invention is a Lewis acid such as aluminum chloride or boron fluoride, or sulfuric acid, phosphoric acid, organic sulfonic acid,
One or a mixture of two or more selected from protic acids such as carboxylic acids and derivatives thereof can be used.

Regarding the mixing ratio for using the COPNA resin matrix as the condensed polycyclic aromatic, the cross-linking agent and the acid catalyst, the range of cross-linking agent / condensed polycyclic aromatic = 0.5 to 4.0 (molar ratio): , 0.5 to 10 wt% was experimentally confirmed to be a preferable range.

The reaction temperature range for obtaining a thermosetting intermediate reaction product (B-stage resin) having substantially thermoplasticity, which is obtained by reacting a COPNA resin composition with heating, is 60 to 300.
It was confirmed experimentally that the temperature was in a suitable range. As described above, a so-called B-stage resin is obtained by heating and reacting the COPNA resin composition.

Next, regarding the surface treatment agent in the present invention, an aromatic cross-linking agent consisting of one or two or more aromatic rings having at least one group of at least one of a hydroxymethyl group and a halomethyl group, or the above aromatic cross-linking agent It is a mixture of the agent and the acid catalyst, and can be used as a solution by heating and melting the mixture at a temperature higher than the melting point of the mixture to form a liquid, or by dissolving it in a solvent. Further, regarding the aromatic cross-linking agent of the surface treatment agent, the addition amount is 0.
A range of 01-5 wt% is preferred. When the surface treatment agent contains two or more kinds of the aromatic cross-linking agents, it is preferable to add each aromatic cross-linking agent in the range of 0.01 to 5 wt% with respect to the aggregate.

The reason for this is that if the amount is less than 0.01 wt%, the surface of the aggregate is not sufficiently covered with the aromatic cross-linking agent, so that the chemical bond between the COPNA resin matrix and the aggregate is insufficient, and sufficient bond strength is obtained. Because there is no. On the other hand, if it exceeds 5 wt%, it is uneconomical to add an extra aromatic crosslinking agent that does not contribute to the improvement of the strength.

In the present invention, as the aggregate, carbon, graphite, metal, metal oxide, metal carbide, metal silicide, metal boride, metal nitride, metal salt, glass composition, natural and synthetic polymers, and precursors thereof Can be used.

The aggregate has one or more selected from the group consisting of hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure and acid anhydride structure on its surface. It is desirable to have at least. The reason for this is to complete the chemical bond between the aggregate and the COPNA resin matrix. For the surface functional groups of the aggregate, the glass composition,
Natural and synthetic polymers, carbon precursors, etc., in which they are present in advance, as they are, in addition to them, if they are present in small amounts, wet oxidation with an oxidant and dry oxidation with oxygen, or hydrogen It is effective to introduce by reduction treatment such as liquefaction.

Regarding aggregates, the present inventors previously announced carbon fiber paper that has not been subjected to any special surface treatment. The COPNA resin matrix composite material using this as a aggregate is
The mechanical properties did not change even after heat treatment at ℃ for 10 hours.

In this respect, in the present invention, the aggregate is an aromatic compound consisting of one or two or more aromatic rings having at least one group of at least one of a hydroxymethyl group and a halomethyl group, such as P-xylylene dichloride, It is treated with a surface treatment agent mainly composed of an aromatic crosslinking agent such as 9,10-anthracene dimethanol. Therefore, aggregate and COPNA
It can be chemically and strongly bonded to the resin matrix, and in addition to heat resistance, it also has excellent dimensional stability, strength, and
A composite material having elastic modulus, toughness, wear resistance and the like can be manufactured.

The binding mechanism at the aggregate interface is presumed to be as follows. That is, in the surface treatment agent or COPNA
Due to the action of the acid catalyst contained in the resin matrix, the bifunctional or higher cross-linking agent in the surface treatment agent causes hydrogen on the aggregate surface,
Chemically bonds with halogens, hydroxyl groups, carbonyl groups, carboxyl groups, aldehyde groups, epoxy structures, lactone structures, ether structures, acid anhydride structures, etc. by reactions such as dehydration, dehalogenation, dehydrohalogenation, etc. By reacting in the same manner as aromatic hydrogen, halogen, hydroxyl group, etc. in COPNA resin matrix,
As a result, the aggregate and the COPNA resin matrix are strongly chemically bonded.

In the method of the present invention, the surface treatment of the aggregate uses a method of treating the aggregate with a surface treatment agent in advance, and a method of simultaneously adding the surface treatment agent when the aggregate and the COPNA resin matrix are combined. It is possible to heat and melt the surface treatment agent to a temperature above their melting point to form a liquid,
Alternatively, it can be dissolved in a solvent and used as a solution, but among these, it is preferable to use a method of dissolving in a solvent and pretreating the surface of the aggregate as a solution with a surface treatment agent.

According to the invention, the COPNA resin matrix is: (1) as an unreacted powder mixture, (2) as so-called B-stage resin powder, (3) as a so-called B-stage resin by heating and melting, or (4) so-called B-stage resin. The stage resin can be used as a liquid by dissolving it in a solvent. The form of the aggregate is: (3) or (4) in the case of continuous fiber, woven fabric, non-woven fabric, or porous body Method such as impregnation method, filament winding method, prepreg method, etc .; in the case of short fiber shape, granular shape, flat plate shape, lump shape, etc., kneading method, production method, etc. by the method of (1) or (2). It is preferable to employ a grain method or the like; and to combine each.

In addition, as the molding method, select a molding method suitable for the purpose from hot press, molding, hydrostatic pressure, vibration, extrusion, injection, transfer, vacuum, blowing, winding, laminating, etc. Thermoset molding. At this time, the molding temperature range is preferably 100 to 400 ° C., and it is important to set the molding temperature and time so that the composite is thermoset after softening.

Next, according to the present invention, the post-curing temperature is preferably in the range of 100 to 400 ° C, and the post-curing time is preferably in the range of 10 to 30 hours.

As described above, a composite material rich in heat resistance, dimensional stability, strength, elastic modulus, toughness, wear resistance and the like can be obtained.

By the way, in the present invention, a composite material using carbon, graphite, or a carbon precursor as an aggregate is fired and graphitized to obtain heat resistance, dimensional stability, strength, elastic modulus, toughness, and abrasion resistance. It can also be used as a carbon material or graphite material rich in the like. Further, materials treated with the surface treating agent of the present invention, having hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, acid anhydride structure, etc. on the surface, When bonded with COPNA resin matrix, it showed excellent adhesive strength. In particular, it was confirmed that when the graphite materials were adhered to each other with the COPNA resin matrix made from pitch, the adhered part showed conductivity.

〔Example〕

 Next, the present invention will be described in more detail with reference to Examples.

Example 1. Commercially available glass cloth was mixed with p-xylylene glycol: 5 wt.
%, P-toluenesulfonic acid: 1% by weight, the solution was immersed in a surface treatment agent consisting of an ethanol solution and then heat-treated in air at 150 ° C. for 30 minutes to obtain an aggregate. COPNA resin matrix is a mixture of pyrene-phenanthrene (molar ratio 7: 3)
And p-xylylene glycol were mixed at a molar ratio of 1: 1.5, and a mixture obtained by adding 3 wt% of p-toluenesulfonic acid thereto was reacted at 130 ° C. for 40 minutes to use a B-stage resin.

The B-stage resin was heated and melted at 140 ° C., and applied on a surface-treated glass cloth to form a composite. Five composites thus obtained were laminated and hot pressed at 180 ° C. For comparison, a glass cloth surface-treated with a commercially available silane coupling agent was also compounded and molded using the same matrix. After these were post-cured at 200 ° C. for 15 hours, the flexural strength and flexural modulus were measured. The results are shown in Table 1.

In addition, the composite material of Example 1 exhibited an electrical insulation characteristic that was comparable to or higher than that of a commercially available glass epoxy resin composite material.

Example 2. Commercially available 0.2 μm or less crushed calcine pictoke coke was heated in air at 400 ° C. for 3 hours to introduce a functional group containing oxygen on the surface, which was then used as an aggregate. As COPNA resin matrix, coal-based pitch (average molecular weight 300) with softening point 49 ° C and p-xylylene dichloride in molar ratio of 1: 2
5% by weight of anhydrous aluminum chloride.
The added mixture was used. This mixture and aggregate by volume ratio
A 1: 1 mixture was added, and 1.0 wt% of p-xylylene dichloride was added as a surface treatment agent to the aggregate, and then the mixture was kneaded with a kneader at 140 ° C for 30 minutes. The kneaded product is 20 × 50 × 100 at a mold temperature of 200 ° C.
After molding to a size of mm, it was post-cured at 200 ° C. for 20 hours. For the purpose of checking the heat resistance, this molded body was placed in nitrogen at 20 ° C.
When heated at a heating rate of / min, there was no deformation up to 520 ° C.

Example 4. Commercially available carbon fiber cloth (satin weave) was heat-treated in air at 500 ° C. for 30 minutes to introduce a functional group containing oxygen on the surface, and then p-xylylene glycol: 5 wt%, p-toluene sulfone. Acid: After soaking in a surface treatment agent consisting of a 1 wt% ethanol solution, it was heat-treated in air at 150 ° C. for 30 minutes to obtain an aggregate. The COPNA resin matrix is naphthalene and P-xylylene glycol at a molar ratio of 1: 1.75.
A B-stage resin was used which was prepared by mixing a mixture of 1 wt% of p-toluenesulfonic acid and reacting the mixture at 130 ° C. for 40 minutes. The matrix was melted at 150 ° C., impregnated with carbon fiber cloth as an aggregate under reduced pressure, three sheets were laminated, and hot pressed at 200 ° C. The molded body was post-cured at 250 ° C. for 10 hours. For the purpose of examining dimensional stability, when this molded product was heated in nitrogen at a heating rate of 10 ° C / min, it showed no weight loss up to 450 ° C, and
When the size of the heat-treated product at ℃ was returned to normal temperature and the dimensions were measured, there was no change compared with that before the heat treatment.

Example 5. Commercially available mesocarbon microbeads (average particle size 10μ
m) as an aggregate and COPNA resin matrix, coal-based pitch (average molecular weight 300) having a softening point of 49 ° C and p-xylylene glycol are mixed at a molar ratio of 1: 2, and p-toluene sulfone is mixed therein. A mixture containing 5 wt% of acid was used. The mixture and the aggregate were mixed in a volume ratio of 1: 2, and p-xylylene glycol was used as a surface treatment agent for the aggregate 2.
After adding 0 wt%, the mixture was kneaded with a kneader at 130 ° C for 40 minutes. When the kneading was molded by an extrusion molding machine and an injection molding machine, good moldability was exhibited.

〔The invention's effect〕

As described above, the composite material of the present invention contains hydrogen, halogen, a hydroxyl group, a carbonyl group, a carboxyl group,
COPNA resin matrix or functional group of aggregate such as aldehyde group, epoxy structure, lactone structure, ether structure, acid anhydride structure etc. and hydroxymethyl group, halomethyl group, or a part or bicycle having at least one group By chemically strongly bonding with a surface treating agent mainly composed of an aromatic cross-linking agent consisting of the above aromatic ring,
It is a composite material that has excellent heat resistance, dimensional stability, strength, elastic modulus, toughness, wear resistance, insulation, etc. that are not found in conventional composite materials.

This excellent heat resistance, dimensional stability, strength, elastic modulus, toughness,
Composite materials with abrasion resistance, insulation, etc. can be used for structural materials, heat resistant materials, heat insulating materials, electrical and electronic materials, sliding materials, etc., and are considered to have a significant effect on industry. To be

Claims (18)

[Claims] 1. An aromatic cross-linking agent comprising a condensed polycyclic aromatic compound having two or more rings and a mono- or bi- or more-ring aromatic having two or more groups of at least one of a hydroxymethyl group and a halomethyl group. And a thermosetting composition matrix formed by the reaction of an acid catalyst with the surface of the aggregate against the aggregate.
A heat-curing method, characterized in that an aggregate treated with a surface-treating agent containing 0.01 to 5 wt% of an aromatic crosslinking agent has a chemical bond at the interface between the aggregate and the matrix. A composite material with a resin matrix. 2. The composite material according to claim 1, wherein the matrix is a mixture of the condensed polycyclic aromatic compound, the aromatic crosslinking agent and the acid catalyst, or a thermosetting intermediate reaction product thereof. A composite material, characterized in that at least one selected from the objects is thermally cured by a reaction. 3. The composite material according to claim 1, wherein the fused polycyclic aromatic compound having two or more rings constituting the matrix is naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, acenaphthene, acenaphthylene. Or a mixture of one or more selected from perylene, coronene, and derivatives having these as the main skeleton, or a heavy oil of coal or petroleum, tar, or pitch, which is a composite material. 4. The composite material according to claim 1, wherein the acid catalyst constituting the matrix is aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and derivatives thereof. A composite material, which is one kind or a mixture of two or more kinds selected from the above. 5. The composite material according to claim 1, wherein the aggregate is carbon, graphite, metal, metal oxide, metal carbide, metal silicide, metal boride, metal nitride, metal salt. A composite material comprising one or more compounds or mixtures selected from glass compositions, natural and synthetic polymers, and precursors thereof. 6. The composite material according to claim 1, wherein the surface treatment agent is composed of one or more aromatic rings having at least two groups selected from hydroxymethyl groups and halomethyl groups. A composite material comprising the aromatic cross-linking agent or a mixture of the aromatic cross-linking agent and the acid catalyst having cross-linking ability. 7. The composite material according to claim 5, wherein the aggregate is at least one of amorphous and crystalline, and the form is continuous fibrous, short fibrous, granular, A composite material characterized by comprising one kind or a combination of two or more kinds selected from a flat plate shape, a block shape, a porous body shape, a woven cloth shape, and a non-woven cloth shape. 8. A method for producing a composite material using a thermosetting resin as a matrix, which comprises the following sequences (a) to (d). (A) The surface of the aggregate is 0.01 to 5w with respect to the aggregate composed of one or two or more aromatic rings having two or more groups of at least one of hydroxymethyl group and halomethyl group.
a step of performing heat treatment after coating with a surface treatment agent mainly containing t% of aromatic cross-linking agent; (b) a condensed polycyclic aromatic compound mainly having two or more rings, the aromatic cross-linking agent, and an acid catalyst A step of complexing a thermosetting composition matrix composed of a combination of the above and the bone agent coated in the step (a); (c) the composite obtained in the step (b) is oxidized or non-oxidized. Molding and curing step of heating in an oxidizing atmosphere to a temperature range of 100 to 400 ° C., plasticizing, and then thermosetting molding into a predetermined shape; (d) curing the molded and cured product in an oxidizing or non-oxidizing atmosphere
A post-curing step of heating to a temperature range of 0 to 400 ° C. and holding the temperature range for 30 minutes or more and 100 hours or less; 9. The production method according to claim 8, wherein the surface treatment agent is a mono- or bi- or more-aromatic ring having two or more groups selected from at least one of a hydroxymethyl group and a halomethyl group. A method for producing a composite material, which is characterized in that it is used as a solution by being heated and melted at a temperature equal to or higher than the melting point of the cross-linking agent to be a liquid, or dissolved in a solvent. 10. The manufacturing method according to claim 8, wherein the surface treatment agent is a mixture of the aromatic crosslinking agent and the acid catalyst, and is heated and melted at a temperature equal to or higher than the melting point of the mixture to form a liquid. Alternatively, the method for producing a composite material, characterized in that the surface functional groups of the aggregate and the crosslinking agent are reacted by the heat treatment by dissolving in a solvent and used as a solution. 11. The method according to claim 8, wherein the matrix is mainly a combination of a fused polycyclic aromatic compound having two or more rings, the aromatic cross-linking agent, and an acid catalyst. A method for producing a composite material, which is a powder mixture of a curable composition. 12. The manufacturing method according to claim 8, wherein the matrix is obtained by heating and reacting the thermosetting composition in an oxidizing or non-oxidizing atmosphere in a temperature range of 60 to 300 ° C. Is a thermosetting intermediate reaction product having a thermoplastic property, and is made into a powder or in a liquid form by being heated and melted at a temperature higher than the softening point of the thermosetting intermediate reaction product in an oxidizing or non-oxidizing atmosphere. A method for producing a composite material, which is used. 13. The method for producing a composite material according to claim 8, wherein the thermosetting intermediate reaction product is dissolved in a solvent and used as a solution. 14. A method for producing a composite material using a thermosetting resin as a matrix, which comprises the following sequences (a) to (c). (A) a condensed polycyclic aromatic compound mainly having two or more rings, and an aromatic cross-linking agent consisting of one or more aromatic rings having two or more at least one group selected from a hydroxymethyl group and a halomethyl group; A thermosetting composition matrix comprising a combination of an acid catalyst, an aggregate, and 0.
A step of compounding 01 to 5 wt% of the aromatic cross-linking agent or the surface-treating agent comprising a mixture of the cross-linking agent and an acid catalyst; (b) oxidizing the composite obtained by the step (a) or Molding and curing step of heating in a temperature range of 100 to 400 ° C. in a non-oxidizing atmosphere, plasticizing, and then thermosetting molding into a predetermined shape; (c) Oxidizing the molded and cured product obtained in the above step (b) Or a post-curing step performed by heating in a temperature range of 100 to 400 ° C. in a non-oxidizing atmosphere and maintaining the temperature range for 30 minutes or more and 100 hours or less; 15. The thermosetting composition according to claim 14, wherein the matrix is a combination of the condensed polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst. A method for producing a composite material, which is a powder mixture of 16. The manufacturing method according to claim 14, wherein the matrix is formed by heating and reacting the thermosetting composition in a temperature range of 60 to 300 ° C. in an oxidizing or non-oxidizing atmosphere. Is a thermosetting intermediate reaction product having a thermoplastic property, and is made into a powder or in a liquid form by being heated and melted at a temperature higher than the softening point of the thermosetting intermediate reaction product in an oxidizing or non-oxidizing atmosphere. A method for producing a composite material, which is used. 17. The method for producing a composite material according to claim 14, wherein the thermosetting intermediate reaction product is dissolved in a solvent and used as a solution. 18. The composite material according to claim 14, wherein the surface treatment agent is heated and melted at a temperature equal to or higher than a melting point to be liquid, or is dissolved in a solvent to be used as a solution. Manufacturing method.