JPH0733963A - Glass fiber reinforced resin composition - Google Patents

Abstract

(57) [Abstract] [Purpose] A condensed polycyclic polynuclear aromatic resin (obtained by reacting a condensed ring aromatic compound such as naphthalene with dihydroxymethylbenzene as a crosslinking agent in the presence of an acid catalyst,
(A thermosetting resin having a basic structure in which an aromatic ring containing a condensed aromatic ring is crosslinked by a methylene bond) and a glass fiber, in a fiber reinforced resin composition, the adhesiveness between the resin and the glass fiber is increased, and the resin-fiber layer Prevents peeling and enhances strength. [Structure] The glass fiber is surface-treated with an alkoxysilane compound having at least one amino group in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a glass fiber reinforced resin composition comprising a surface-treated glass fiber and an aromatic thermosetting resin having excellent heat resistance.

[0002]

BACKGROUND OF THE INVENTION Condensed polycyclic polynuclear aromatic resin (COPNA)
(Also called a resin) is an acid-based catalyst containing an aromatic raw material containing a condensed ring aromatic compound such as naphthalene as a main component, and a crosslinking agent containing an aromatic compound having at least two hydroxymethyl groups or halomethyl groups. It is a thermosetting resin obtained by reacting in the presence of, and has a basic structure in which an aromatic ring including a condensed aromatic ring is cross-linked through a methylene chain. The condensed aromatic ring means a condensed ring type aromatic ring represented by naphthalene, anthracene, phenanthrene, pyrene and the like.

Since this resin is superior in heat resistance to phenol resin and epoxy resin and can be manufactured at a lower cost than polyimide resin, its use is expanding to manufacture fiber reinforced plastics (FRP) in place of these resins. Is expected to do. FRP pipes and prepregs using this condensed polycyclic aromatic resin as a matrix resin are disclosed in JP-A-3-
No. 393 and No. 4-189827.

The fused polycyclic polynuclear aromatic resin has a long-term heat resistance temperature of about 260 ° C. and a long-term heat resistance temperature of the polyimide resin (about 200 ° C.).
℃), low dielectric constant and low water absorption,
In particular, it is very suitable as a substrate material for a printed wiring board that requires these characteristics. This type of substrate includes a flexible substrate made of a resin-only film and a rigid substrate (laminated substrate) manufactured by laminating and molding a prepreg obtained by impregnating glass fiber with a resin.

In the rigid substrate, the adhesiveness between the reinforcing glass fiber and the resin is required in order to secure the bending strength and the reliability of the substrate performance. This adhesion between the glass fiber and the resin is a necessary or desirable property in any other FRP.

Surface treatment of glass fibers has generally been carried out in order to improve the adhesion between the glass fibers and the matrix resin. Various silane coupling agents have been used as this type of surface treatment agent.

[0007]

The silane coupling agents generally used for the surface treatment of glass fibers such as glass cloth are mostly trialkoxysilane type compounds represented by (RO) ₃ SiR ′. However, one in which a halogen atom (X) is bonded to a Si atom instead of the alkoxyl group (RO) and one of the three alkoxyl groups (RO)
Some are substituted with an alkyl group. R'is an alkyl group having a functional group such as an amino group, an epoxy group or a methacryloxy group; or a vinyl group, a phenyl group or the like.

However, a glass fiber (eg, glass cloth) is surface-treated with some silane coupling agents, and the surface-treated glass fiber is impregnated with a condensed polycyclic polynuclear aromatic resin to produce an FRP product. As a result, the bending strength of the product was unexpectedly low. Moreover, when the cross section of the test material that has been subjected to the bending test is observed by SEM (scanning electron microscope), the delamination phenomenon between the glass and the resin, which is not observed in the case of the FRP product using other resin as the matrix resin, is observed. Was observed.

That is, the condensed polycyclic polynuclear aromatic resin has insufficient adhesiveness with the glass fiber even when the glass fiber is surface-treated with the silane coupling agent, and when a large force is applied, the glass fiber and the resin are Therefore, various FRP products using this resin as a matrix resin could not exhibit their performance sufficiently.

An object of the present invention is to provide a glass fiber reinforced resin composition which uses a condensed polycyclic polynuclear aromatic resin as a matrix resin and which does not cause delamination during a bending test and has excellent adhesiveness between the resin and the glass fiber. Is to provide.

[0011]

Means for Solving the Problems The present inventors have found that among various silane coupling agents, only the silane coupling agent having an amino group significantly improves the adhesiveness between the condensed polycyclic polynuclear aromatic resin and the glass fiber. It was found that the above-mentioned object can be achieved and the above-mentioned object can be achieved, and the present invention has been completed.

Here, the present invention is a thermosetting condensed polycyclic polynuclear aromatic resin having a basic structure in which an aromatic ring containing a condensed aromatic ring is cross-linked through a methylene chain, and at least one in the molecule. A glass fiber reinforced resin composition comprising a glass fiber surface-treated with an alkoxysilane compound having an amino group.

The condensed polycyclic polynuclear aromatic resin used in the present invention is a raw material containing a condensed ring aromatic compound as a main component and an aromatic compound having at least two hydroxymethyl groups or halomethyl groups bonded to an aromatic ring. A thermosetting resin produced by reacting a crosslinking agent composed of a compound in the presence of an acid catalyst.

The condensed ring aromatic compound as the raw material is
Condensed ring aromatic hydrocarbons such as naphthalene, acenaphthene, phenanthrene, anthracene, and pyrene, their alkyl derivatives and hydroxy-substituted derivatives, and polynuclear structures in which these are linked by linking groups such as methylene group, phenylene group, ether group, and xylylene group. In addition, coal-based or petroleum-based heavy oils, tar, pitch, and the like containing these compounds as main components can be used. The raw material may partially contain a monocyclic aromatic compound. In this case, it is preferable that the fused ring aromatic compound occupy more than half of the mixture in molar ratio.

The aromatic compound having at least two hydroxymethyl groups or halomethyl groups bonded to an aromatic ring, which is used as a cross-linking agent, includes benzene, naphthalene, anthracene, pyrene and alkyl derivatives thereof.
Hydroxymethyl and halomethyl derivatives such as (eg, toluene, xylene) are included. Preferred cross-linking agents are dihydroxymethyl derivatives such as dihydroxymethylbenzene, dihydroxymethylxylene and dihydroxymethylnaphthalene.

As the acid catalyst, any of Lewis acids such as aluminum chloride and boron fluoride, and protic acids such as sulfuric acid, phosphoric acid, organic sulfonic acid and carboxylic acid can be used, and a mixture of two or more kinds of acids can also be used. Can be used. Preferred acid catalysts are organic sulfonic acids such as toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid and naphthalene sulfonic acid.

The ratio of the cross-linking agent used to the raw material is appropriately in the range of 0.7 to 6 in terms of molar ratio, and the addition amount of the acid catalyst is 0.2 to 20 relative to the total weight of the raw material and the cross-linking agent.
The weight ratio is preferably in the range of 0.5 to 10% by weight. The reaction temperature is about 50 to 300 ° C, preferably about 80 to 200 ° C. The reaction pressure is usually normal pressure or slightly increased pressure, but the reaction can be carried out under reduced pressure in order to accelerate the removal of condensed water by-produced in the reaction from the reaction system and enhance the reaction efficiency. The reaction is easy to carry out in the molten state, but it can also be carried out in a suitable solvent or dispersion medium.

The viscosity of the reaction product increases with the progress of the reaction, and an intermediate condensate in a semi-cured state (B stage state) is obtained. For use in impregnation of glass fiber, heating is stopped in the B stage state to stop the reaction and the resin is used as a thermosetting resin. The melt viscosity of the condensed polycyclic polynuclear aromatic resin in the B stage state is generally 10 ¹ to 10 ⁸ poise at 80 ° C.
Is the range.

When the B-stage resin is further heated, crosslinking proceeds to form an insoluble and infusible thermosetting material. This thermosetting product is a resin having a basic structure in which aromatic rings containing condensed aromatic rings derived from a raw material and a cross-linking agent are cross-linked through a methylene chain, and this is a matrix of the fiber-reinforced resin composition of the present invention. It becomes a resin.

The reinforcing fibers used in the resin composition of the present invention are glass fibers surface-treated with an alkoxysilane compound having at least one amino group in the molecule. The form of the glass fiber is not particularly limited, for example, long fiber (roving), short fiber (chopped strand),
It may be in any form conventionally used in the manufacture of FRP products, such as cloth, mat, or tape.

The amino group-containing alkoxysilane compound used for the surface treatment of glass fiber is generally represented by the formula (RO) ₃ SiR '. One of the three alkoxyl groups (RO) is an alkyl group (R). ), R ′ is an alkyl group having at least one amino group or a phenyl group. The amino group may be a primary, secondary or tertiary amino group, but is preferably a primary amino group.

Representative examples of such amino group-containing alkoxysilanes include commercially available silane coupling agents containing amino groups, such as 3-aminopropyltriethoxysilane and N- (2-aminoethyl) -3-amino. Examples include propyltrimethoxysilane and N- (2-aminoethyl) -2-aminopropylmethyldimethoxysilane.

The surface treatment of the glass fiber may be carried out by a conventional method. For example, prepare a solution in which the amino group-containing alkoxysilane compound to be used is dissolved in an appropriate solvent (eg, lower alcohol such as methanol, water, or a mixed solvent of lower alcohol and water), and spray or dip the solution. It can be carried out by applying to the glass fiber by the means described above and removing the solvent. It is preferable to heat the glass fiber after coating to remove the solvent and at the same time, to hydrolyze the silane compound to form a film and to form a bond between the fiber and the silane compound. This heating may be performed at a temperature of 80 to 130 ° C. for about 5 to 120 minutes, for example. The amount of the silane compound attached in this treatment is not particularly limited and may be selected by experiment so that the object of the present invention can be achieved.

By this surface treatment, the alkoxyl group of the silane compound is hydrolyzed by the solvent or the water in the air, and the generated hydroxyl group causes a condensation reaction or a hydrogen bond with the hydroxyl group or oxygen atom on the glass surface, and the silane compound itself is also generated. Polycondensation produces a polysiloxane type film. Thus
The surface of the glass fiber is at least partially coated with a polysiloxane type coating bonded to the glass fiber, and the polysiloxane type coating contains an amino group as a functional group.

The resin composition of the present invention is produced by impregnating the glass fiber thus surface-treated with the above condensed polycyclic polynuclear aromatic resin in the B stage. Then, the matrix resin is cured by heating after molding or by heating at the same time as molding, resulting in a thermosetting product.
(FRP product) can be obtained. These resin impregnation and molding
Curing can be performed by any method conventionally used for manufacturing FRP products, such as a filament winding method and a prepreg method.

The thermosetting product obtained by molding and thermosetting the resin composition of the present invention is excellent in the adhesion between the condensed polycyclic polynuclear aromatic resin of the matrix and the glass fiber, and the resin-fiber is also used in the bending test. No delamination between layers is observed, and cohesive failure of the resin occurs due to mechanical stress, so high strength can be exhibited. It is considered that this is because the amino group in the film bonded to the surface of the glass fiber exhibits high adhesiveness with the condensed polycyclic polynuclear aromatic resin.

On the other hand, when the glass fiber surface-treated with an alkoxysilane compound containing another functional group such as an acrylic group or an epoxy group is used, the adhesiveness between the glass fiber and the condensed polycyclic polynuclear aromatic resin Is small and breakage occurs due to delamination between the resin and the fiber, so that sufficient strength cannot be exhibited.

The glass fiber reinforced resin composition of the present invention comprises a moldable composition in which the condensed polycyclic polynuclear aromatic resin of the matrix resin is in an uncured state, and a thermosetting product in which the curing of the matrix resin is completed. Both compositions of matter are included. As described above, production of the resin composition of the present invention (method of impregnating glass fiber with resin) and molding / thermosetting of the uncured resin composition may be carried out in the same manner as in conventional FRP.

The blending ratio of the glass fiber and the resin in the composition of the present invention is not particularly limited, but is usually within the range of 20 to 60% by weight based on the total weight of the resin and the glass fiber. In addition to the condensed polycyclic polynuclear aromatic resin and the glass fiber, the composition of the present invention may contain one kind or two or more kinds of various additives that can be added to the FRP.
Examples of such additives include fillers such as talc and mica, colorants, ultraviolet absorbers, antioxidants, flame retardants, and plasticizers.

In order to manufacture a rigid substrate from the glass fiber reinforced resin composition of the present invention, it is convenient to use the resin composition in the form of prepreg. The prepreg may be obtained by either a solvent method or a hot melt method.
The glass fiber is preferably a glass fiber having a low dielectric constant, and the form thereof may be cloth, mat, tape or the like, but is usually glass cloth. Also in this case, the resin content in the prepreg is appropriately in the range of 20 to 60% by weight.

If necessary, several tens of prepregs comprising the resin composition of the present invention are laminated to a predetermined thickness, and the laminate is thermocompression-bonded by a hot pressing method and at the same time the resin is cured to a desired degree. When laminated and formed by, a rigid laminated plate (laminated substrate) is obtained. Suitable hot pressing conditions are a temperature of 100 to 300 ° C., a pressing force of 5 to ²⁰⁰ kgf / cm ² , and a holding time of 10 to 300 minutes. This hot pressing is usually performed after sandwiching the laminate between two copper foils. As a result, a rigid copper clad laminate having both sides coated with copper foil is directly manufactured. Thereafter, the surface of the copper foil is subjected to imaging, etching, and metal plating processing to manufacture a rigid printed wiring board.

The condensed polycyclic polynuclear aromatic resin used as the matrix resin has a long-term heat resistance temperature higher than that of a typical heat-resistant polyimide resin, although it can be easily produced from inexpensive raw materials. It has the excellent property that other electrical and mechanical properties are also high. Therefore, the resin composition of the present invention is useful for the production of various FRP products including rigid printed wiring boards, particularly FRP products that require heat resistance, and has a long-term heat resistance as compared with the case of using a polyimide resin. It becomes possible to manufacture an FRP product having higher properties at a lower cost.

[0033]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are parts by weight and% by weight, unless otherwise specified.

A 1% aqueous solution of various alkoxysilane compounds commercially available as a silane coupling agent was prepared,
T glass cloth (plain weave, thickness 0.1 mm, bulk density 104.5 g / m ² ) was immersed in this aqueous solution for 5 minutes, then taken out and heated at a temperature of 110 ° C. for 20 minutes to surface-treat the glass cloth. By this heating, a surface-treated glass cloth in which the polysiloxane type hydrolyzate of the used silane compound was firmly bonded to the glass fiber surface was obtained.

The alkoxysilane compounds used in this example were as follows. Amino-based silane: 3-aminopropyltriethoxysilane, Acrylic-based silane: 3-methacryloxypropyltrimethoxysilane, Epoxy-based silane: 4-glycidylbutyltrimethoxysilane, Phenyl-based silane: Benzyltriethoxysilane.

On the other hand, a mixture of 100 parts of naphthalene, 173 parts of 1,4-dihydroxybenzene, and 8.3 parts of β-naphthalenesulfonic acid as a catalyst was heated and stirred at 110 ° C. for 3 hours to carry out an addition condensation reaction to obtain B. A condensed polycyclic polynuclear aromatic resin in a stage state was obtained. This resin has a brown transparent appearance and a melt viscosity at 70 ° C of 16,500 cP,
The number average molecular weight was 580. This resin is dissolved in tetrahydrofuran to give a resin solid content of 50% and a room temperature viscosity of 50 cP.
The resin varnish of was prepared.

The glass fiber was impregnated with the resin by passing the surface-treated glass cloth through the resin varnish. Then, the glass cloth was dried at 60 ° C. for 1 hour to remove the solvent, and a glass cloth prepreg having a resin content of about 40% was produced. This glass cloth prepreg, 1.
Stack the sheets so that a 6 mm thick molded body can be obtained, and sandwich between two electrolytic copper foils (35 μm thick each), 100 kgf / cm ²
By hot pressing at 230 ° C. for 60 minutes under pressure to laminate-form, a rigid copper-clad laminate having a thickness of about 1.6 mm was obtained.

The bending strength of the obtained double-sided copper-clad laminate was measured according to JIS
The results measured according to C6481 are shown in Table 1 below. As can be seen from this table, when the glass fiber was surface-treated with amino silane according to the present invention, the bending strength was increased by 100% as compared with the case where the untreated glass fiber was used. When the surface treatment was performed with the alkoxysilane, the rate of increase in bending strength was 50% or less. That is, the amino group-containing alkoxysilane was more than twice as effective in increasing flexural strength as other alkoxysilanes.

[0039]

[Table 1]

Further, when the bending fracture surface of the test piece after the bending test was observed by a cross-section SEM, when the glass fiber was surface-treated with the amino-based silane, the fracture was cohesive failure of the resin, and While no delamination phenomenon was observed between the fibers, the resin-fiber delamination phenomenon was remarkably observed in the cases of to.

[0041]

The fiber-reinforced resin composition of the present invention is produced by subjecting the glass fiber of the reinforcing material to a surface treatment with an amino-group-containing alkoxysilane compound to obtain a condensed polycyclic polynuclear aromatic resin of the glass fiber and the matrix resin. Adhesive strength is increased, resin-fiber delamination does not occur when external stress is applied, and FRP products having higher strength than conventional products can be manufactured. The condensed polycyclic polynuclear aromatic resin used in the present invention can be produced from an inexpensive raw material, is excellent in long-term heat resistance, and has other mechanical and
Since the resin composition of the present invention has good thermal and electrical properties, the resin composition of the present invention can be used in various types of F, including rigid printed wiring boards.
It is useful for manufacturing RP products.

Claims (1)

[Claims] 1. A thermosetting condensed polycyclic polynuclear aromatic resin having a basic structure in which an aromatic ring containing a condensed aromatic ring is cross-linked through a methylene chain, and an alkoxy having at least one amino group in the molecule. A glass fiber reinforced resin composition comprising a glass fiber surface-treated with a silane compound.