JP2001270963A - Filler for resin reinforcement and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filler for resin reinforcement, a resin composition compounded therewith, and a phenol resin molding material excellent in heat resistance, dimensional stability, moldability and in particular excellent in mechanical strength at a room and higher temperature. SOLUTION: This filler for resin reinforcement is prepared on 100 pts.wt. glass fiber by attaching 0.01-50 pts.wt. glass filler containing 30 wt.% or more SiO2 and having a particle diameter of 0.01-10 μm, and this resin composition is prepared by compounding the resin with the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filler for reinforcing a resin, a resin composition containing the filler, and excellent heat resistance, dimensional stability, moldability and the like. It relates to an excellent phenolic resin molding material.

[0002]

2. Description of the Related Art Many proposals have been made on a method of treating fibers and fillers for improving the strength of a composite material. For example, Japanese Patent Application Laid-Open No. 7-33963 discloses a method for achieving high strength by strengthening the adhesion to a matrix resin by using glass fibers surface-treated with a polycyclic or polynuclear aromatic thermosetting resin and an alkoxysilane compound. Is disclosed. Japanese Patent No. 1809895 discloses that mechanical properties and coloring properties of a thermoplastic resin such as polyether are improved by converging glass fibers with a sizing agent composition comprising an epoxy emulsion, a silane coupling agent, and a leveling agent. A sizing composition is disclosed.

[0003] JP-A-7-267690 discloses a sizing agent containing a polycondensate of a bisphenol-type epoxy resin and a polyhydric alcohol and a silane coupling agent, and a thermoplastic material such as PET, PBT, or PC made of sizing glass fibers. There is a description that it is effective for improving the mechanical strength of the resin. JP-A-62-8
No. 9734 discloses a thermosetting resin, a film forming agent such as urethane-modified polyester, and a glass fiber for improving the mechanical properties, thermal properties, and water resistance of a thermosetting resin treated with a surfactant. is there. Tokiohei 6-5054
No. 71 discloses glass fibers converged by a melamine-formaldehyde resin, a phenoxy resin, an epoxysilane coupling agent, and a sizing agent to which water is added as glass fibers for reinforcing an acetal resin.

[0004] Also, Japanese Patent Application Laid-Open No. 10-324544,
JP-A-7-223846 and JP-A-52-53
No. 972 also discloses a treatment method using a coupling agent, a sizing agent, a resin, or the like for the purpose of reinforcing a thermoplastic resin. However, these treatments all relate to the composition of the coupling agent and the sizing agent and the treatment method. Therefore, this is completely different from the present invention in which a glass filler is attached to the surface of a glass fiber and the filler has a structural change.
Further, there is no invention relating to a resin composition reinforced by a filler having such structural characteristics.

In order to achieve high strength, many methods have been proposed for phenolic resin molding materials in which glass fibers are treated with a coupling agent to increase the adhesion to a matrix resin. However, there is a limit to the effect of improving strength by only the coupling agent alone. Then, several methods have been proposed for further improving the adhesion between the glass fiber and the matrix resin.

Japanese Patent Application Laid-Open No. 52-12278 discloses a glass fiber to be mixed with a thermosetting resin, a processing resin or a processing resin compatible with the thermosetting resin on the surface of the glass fiber. A method for treating glass fiber in which a treating agent such as a silane coupling agent is closely adhered is disclosed, and it is described that the strength is increased by dispersing the fiber in a resin. However, this technique is not economical because not only is the strength-improving effect of the molding material small, but it is also necessary to perform autoclave treatment at the stage of treating the glass fiber. In addition, glass fibers treated with a diallyl phthalate polymer and a silane coupling agent are used for the diallyl phthalate polymer matrix, and only the strength improvement effect due to the reaction and interaction effect between these diallyl phthalate resins is shown. There is no description about the resin molding material.

[0007] Japanese Patent Application Laid-Open No. 10-7883 discloses that a glass fiber obtained by first sizing a glass fiber with a phenol resin of the same type as the phenol resin of the matrix and further treating the glass fiber with a coupling agent is used as a phenol resin composition. A method for improving the rotational breaking strength by blending is disclosed. However, in this method, the glass fiber surface is directly treated with the phenol resin. Generally, the chemical bonding force between the phenolic resin and the glass fiber is poor, and strong adhesion between the fiber and the matrix resin cannot be obtained. Therefore, this method cannot provide a sufficient effect of improving the strength of the molding material.

JP-A-5-86260 discloses that a semi-cured or fully cured thermosetting resin in a solid content of 10 to 200 parts by weight based on 100 parts by weight of a fibrous base material is treated.
There is disclosed a method for obtaining a thermosetting resin molded article having high strength by using this. However, in this method, since a large amount of thermosetting resin of 10 to 200 parts by weight, which is semi-cured or completely cured, is used, the fibers are converged with the thermosetting resin. Not only was not obtained, but also the reproducibility of characteristics was poor.

In addition, JP-A-57-90049, JP-A-3-52934, and JP-A-7-26
No. 7690 discloses a method for reinforcing various thermoplastic resins and polyimide resins by blending fibers obtained by adhering a resin and a coupling agent to glass fibers, but these publications disclose phenol resin molding. No description of the material is found. In any of these publications, there is no description of improvement in characteristics by a filler having a structural feature as in the present invention.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin reinforcing filler for imparting excellent strength to a resin composition, and further to have excellent heat resistance, dimensional stability, moldability, etc. An object of the present invention is to provide a resin composition such as a phenol resin molding material having excellent mechanical strength at the time.

[0011]

That is, the first invention of the present invention comprises a glass filler having a composition of 30 wt% or more of SiO ₂ and a particle size of 0.01 μm to 10 μm per 100 parts by weight of glass fiber. It is a resin reinforcing filler deposited in an amount of from 0.01 to 50 parts by weight, and the second invention is a resin composition containing the resin reinforcing filler.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION (Glass fiber) The glass fiber used for the phenolic resin reinforcing glass fiber of the present invention includes E glass, S glass, D glass, and high modulus glass conventionally used as a reinforcing glass fiber. And other glass fibers can be used. Among them, it is preferable to use E glass from the viewpoint of strength improvement and cost. The glass may be long fibers or short fibers. The shape of the glass fiber is not particularly limited, and examples thereof include chopped strand, milled fiber, chopped mat, roving, woven fabric, and nonwoven fabric.

(SiO ₂ ) As a glass filler having a particle diameter of 0.01 μm to 10 μm containing at least 30 wt% of SiO ₂ to be adhered to the glass fiber used in the present invention,
E glass, S glass, A glass, C glass, L glass,
Any of general-purpose glass fillers such as D glass, high modulus glass, silica, glass powder, and low melting point glass can be used. Preferably, the particle size is from 0.1 μm to 10 μm, more preferably from 0.5 μm to 8 μm. The average particle size is 0.
When the thickness is less than 01 μm, the anchor effect of the glass filler attached to the glass fiber is not sufficiently exhibited, and the strength improving effect is reduced. When the average particle size is 10 μm or more,
In some cases, the effect of improving the strength by the adhesion treatment with the glass fiber is not exhibited.

(Preparation method of resin reinforcing filler) The preparation method of the resin reinforcing filler used in the present invention includes:
A method of simultaneously treating and integrating glass fiber and glass filler with a coupling agent or the like can be used. Conventionally known coupling agents such as silane-based and titanium-based coupling agents can be appropriately used. In addition, those which are not usually used for coupling agent applications can be used as long as they can integrate glass fiber and glass filler by reaction.

Examples of such compounds include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycid Xypropyltrimethoxysilane, 3
(Or 2) a hydrolysis-condensation product of -triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine,
γ-ureidopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, aminosilane having an alkoxysilyl group at both terminals, tetraethoxysilane, tetramethoxysilane and the like. Any of these compounds may be used alone or in combination of two or more.

These compounds are used as an aqueous solution or a solution of an organic solvent such as alcohols, ketones, glycols and hydrocarbons, or a mixed solvent of water and these organic solvents. If necessary, the pH of the above solution may be adjusted with an acid such as acetic acid or hydrochloric acid, or an alkali. Further, a lubricant, an antistatic agent, a softener, and the like may be used in combination as long as the effects of the present invention are not impaired. It is preferable that the filler for resin reinforcement in which the glass fiber and the glass filler are integrated does not lose the attachment point during kneading and molding.

The resin reinforcing filler of the present invention may be coated with a resin compatible or reactive with the matrix resin, if necessary, in order to improve the adhesiveness and reactivity with the matrix resin. For example, when used for the purpose of reinforcing a phenolic resin, a further improvement in strength can be expected if a novolak-type phenolic resin or a resol-type phenolic resin is further applied to glass fibers to which a glass filler has been attached.

In the present invention, the amount of the glass filler attached to the glass fiber is such that the glass filler is 0.01 to 50 parts by weight based on 100 parts by weight of the glass fiber. Preferably it is 0.1 to 10 parts by weight. 0.
If the amount is less than 01 parts by weight, the amount of glass filler adhering to the surface of the glass fiber becomes insufficient, the anchor effect on the matrix resin becomes insufficient, and the strength improving effect decreases. On the other hand, if the amount exceeds 50 parts by weight, the effect on the strength is not seen even if the amount of adhesion is further increased. Variations may occur or workability may deteriorate. As a method for attaching the glass filler to the glass fiber with the compound such as the coupling agent described above, various known treatment methods such as a wet treatment by immersion and a dry treatment by spraying can be appropriately used.

(Phenolic resin) The phenolic resin of the matrix used in the phenolic resin molding material of the present invention is not particularly limited, and may be any resin having a phenolic hydroxyl group. For example, a random novolak type phenol resin, a high ortho novolak type phenol resin, a resol type phenol resin, and a modified phenol resin such as an epoxy-modified phenol resin and a melamine-modified phenol resin are exemplified. Any of these may be used alone or in combination of two or more.

(Others) The amount of the resin reinforcing filler obtained by adhering the above-mentioned glass filler to the phenol resin molding material is 40 to 300 parts by weight based on 100 parts by weight of the phenol resin. Preferably, it is 60 to 200 parts by weight based on 100 parts by weight of the phenol resin. If the amount is less than 40 parts by weight, the mechanical strength of the molding material is insufficiently improved.

The phenolic resin molding material of the present invention contains a coloring agent, a release agent, a conductive agent, an inorganic base material, a coupling agent, a solvent, etc., depending on the purpose and application within a range not to impair the effects of the present invention. can do. As a kneading method, kneading can be performed alone or in combination using a kneader such as a roll, a co-kneader or a twin-screw extruder. As a molding method, molding can be performed by a molding method such as transfer molding, compression molding, or injection molding.

[0022]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The raw materials used in Examples and Comparative Examples include (1) a matrix resin of a phenolic resin composition: a novolak-type phenolic resin (2) a coupling agent: an aminosilane X-12-5263 having an alkoxysilyl group at both terminals. [Made by Shin-Etsu Silicone] (3) Glass fiber: Glass milled fiber [Nitto Boseki standard fiber diameter 10 ± 1.5 μm Average fiber length 90 μ]
m] (4) Glass filler: average particle size 5 μm [Nippon Frit surface-untreated product] (5) Filler processing phenolic resin: number average molecular weight about 210, monomer charge ratio, ie, formaldehyde / phenols (F / P) = 1.5 Les
Sol resin (6) phenol resin curing agent: hexamethylenetetramine

The methods of treating and adding the glass fibers and glass fillers described in the examples and comparative examples in Table 1 are as follows. Example 1 90 parts by weight of the above-mentioned glass milled fiber and 10 parts by weight of a glass filler were immersed in a 1% by weight aqueous solution of the above-mentioned coupling agent hydrolyzed at room temperature for 30 minutes while mixing for 5 minutes, and then 30 ° C. at 100 ° C. Heat for a minute,
Further drying was performed at 35 ° C. for 24 hours to obtain a target filler (F1) for resin reinforcement. The filler for resin reinforcement was mixed in the ratio shown in Table 1 and kneaded with a roll. A transfer molding machine was used for producing a bending test piece.

Example 2 90 parts by weight of the above-mentioned glass-milled fiber and 10 parts by weight of a glass filler were immersed in a 1% by weight aqueous solution of the above-mentioned coupling agent which had been hydrolyzed at room temperature for 30 minutes while mixing for 5 minutes. 30 ° C
Heated for 35 minutes and dried at 35 ° C. for 24 hours. This filler is further added to a 1% by weight phenol resin for filler treatment.
The resultant was immersed in a methanol solution for 5 minutes while mixing, then heated at 100 ° C. for 20 minutes, and further dried at 35 ° C. for 24 hours to obtain an intended resin reinforcing filler (F2). The filler for resin reinforcement was mixed in the ratio shown in Table 1 and kneaded with a roll. A transfer molding machine was used for producing a bending test piece.

(Comparative Example 1) The above-mentioned glass milled fiber was blended in the untreated state at the ratio shown in Table 1 and kneaded with a roll. A transfer molding machine was used for producing a bending test piece.

(Comparative Example 2) The above glass milled fiber was immersed in the 1% by weight aqueous solution of the coupling agent for 5 minutes while mixing, then heated at 100 ° C. for 30 minutes, and further dried at 35 ° C. for 24 hours. (F3) was obtained. This filler was blended in the ratio shown in Table 1 and kneaded with a roll. A transfer molding machine was used for producing a bending test piece.

Comparative Example 3 The above-mentioned glass milled fiber and glass filler were blended in the untreated state at the ratio shown in Table 1, and kneaded with a roll. A transfer molding machine was used for producing a bending test piece.

Various characteristics were evaluated based on the following. (1) Bending test: Room temperature test: Measured according to JIS K7203 standard. Heat test: 120 ° C environment other than temperature JIS
Measured according to K7203 standard. (2) Mold appearance test: Judged visually. (○: good,
×: defective)

[0029]

[Table 1]

[0030]

According to the present invention, a filler for reinforcing resin,
A resin composition comprising the resin reinforcing filler is further provided with a phenolic resin molding material which is excellent in heat resistance, dimensional stability, moldability, etc., and particularly excellent in mechanical strength at normal temperature and heat, and is used for automobile, electric It greatly facilitates the replacement of metal parts in the electronics field.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 F term (Reference) 4J002 CC041 CC071 CC181 CD041 DJ017 DL006 DL007 FA046 FB136 FB137 FB146 FB147 FD016 FD017

Claims (3)

[Claims] 1. A method according to claim 1, wherein 100 parts by weight of glass fiber is SiO
₂ containing 30% by weight or more of the composition and having a particle size of 0.01 μm to 10
A filler for reinforcing a resin, wherein 0.01 to 50 parts by weight of a glass filler of μm is attached. 2. A resin composition comprising the resin reinforcing filler according to claim 1. 3. The base resin of the resin composition is a phenol resin, and the filler for reinforcing the resin is a phenol resin.
3. The resin composition according to claim 2, wherein 40 to 300 parts by weight is blended with respect to 0 parts by weight.