JP2006002257A - Glass nonwoven fabric by wet process and prepreg and composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass nonwoven fabric suitable for decorative laminate uses, i.e. the glass nonwoven fabric without lowering tensile strength even when dipped in water or a mixture liquid of water and an alcohol. <P>SOLUTION: The glass nonwoven fabric by a wet process is composed of glass fibers and a binder component binding the glass fibers. A component having sulfur atoms and a rubber component are contained in the binder. γ-Mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane and bis(triethoxysilylpropyl) tetrasulfide are suitable for the component having the sulfur atoms. BR, SBR, NBR, ABS or the rubber component in which an acrylic monomer is copolymerized in the molecule thereof is suitable for the rubber component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wet method glass nonwoven fabric using glass fibers, a prepreg using the same, and a composite material. More specifically, the present invention relates to a wet method glass nonwoven fabric having a high tensile strength, a prepreg using the same, and a composite material.

FRP (Fiber Reinforced Plastics) improves the strength of the resin itself by including fibers in a resin (plastic) serving as a matrix, as called fiber reinforced plastics. One type of FRP is a wet glass nonwoven fabric used as a fiber, and in a plate-shaped composite material obtained by press molding a prepreg impregnated or coated with a resin component, printed wiring boards or building materials used for electric circuit boards There is a decorative board used for.
When the prepreg is produced, if the wet strength of the wet glass nonwoven fabric is insufficient, it becomes easy to break the paper in an impregnation machine or a coating machine, resulting in a problem of reducing productivity. Particularly in recent years, in order to improve productivity, the tensile strength required for wet method glass nonwoven fabrics has been required to be stronger than before.

Conventionally, as a technique for adding a silane coupling agent to the binder component of a wet glass nonwoven fabric, an epoxy resin, an aliphatic amine, and a silane coupling agent reactive with these components are proposed as essential components (patent) Reference 1). Another proposal has been proposed (Patent Document 2) in which cationic silane is surface-treated on the glass fiber itself or added to the binder component. These proposals all relate to wet method glass nonwoven fabrics used for printed wiring boards for the purpose of improving the heat-resistant and moisture-insulating properties of the laminate after press molding and the migration between the through holes.
In addition, in Patent Document 2, the conventional wet method glass nonwoven fabric technology is described and introduced as “treatment with a glass woven fabric as a coupling agent treatment has been conventionally performed with epoxysilane”.
Patent Document 3 proposes that a component composed of a rubber emulsion and an aminosilane coupling agent is attached to the glass fiber surface. However, even when this component is used as a binder component, the bond between the rubber emulsion and the aminosilane coupling agent is mainly a hydrogen bond, so that sufficient tensile strength cannot be obtained.
Patent No. 2778399 JP 7-1113016 A Shoko 62-4344

As described above, none of the conventional techniques is satisfactory in improving the tensile strength of the glass nonwoven fabric.
In particular, for decorative board applications, it is important that the tensile strength of the wet glass nonwoven fabric does not decrease even when immersed in water and alcohol mixed solution, but none of the properties can be satisfied.

In order to solve the above problems, the present invention employs the following configurations (1) to (6).
(1) A wet method glass nonwoven fabric comprising a glass fiber and a binder component that binds the glass fiber, wherein the binder includes a component having a sulfur atom and a rubber component.
(2) The component having a sulfur atom is at least one of γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and bis (triethoxysilylpropyl) tetrasulfad (1) The wet method glass nonwoven fabric described in).
(3) The wet process glass according to (1) or (2), wherein the rubber component is BR, SBR, NBR, ABS, or a rubber component in which an acrylic monomer is copolymerized in these molecules. Non-woven fabric.
(4) A prepreg having a resin component attached to the wet method glass nonwoven fabric according to any one of (1) to (3).
(5) A composite material characterized by being press-molded using at least one prepreg according to (4).
(6) The composite material according to (5), wherein the composite material is a decorative board.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a wet method glass nonwoven fabric having a high tensile strength, in particular, a high tensile strength when immersed in water and / or alcohol, and a prepreg and a composite material using the same, which are extremely useful industrially. .

  The nonwoven fabric of the present invention is produced by making glass fibers by a wet method and comprises a binder component that bonds the glass fibers and the glass fibers. A known papermaking technique can be used as a wet method. For example, a well-known paper machine such as a long net, a round net, an inclined wire, and a twin wire, and a hand-making machine used by a person skilled in the art at the laboratory level can be preferably cited. In the case of a wet method glass nonwoven fabric, an inclined wire is particularly preferable, and the paper at the laboratory level is a handmade machine.

  When the binder component used in the present invention uses a binder fiber or a powder binder, it is preferably included in advance in a fiber dispersion containing bundles of bundled fibers. When a liquid binder is used as the binder component, it is preferable to produce a nonwoven fabric by supplying and attaching the binder component to a wet sheet formed with a wire part and drying it with a dryer part. Such liquid binder supply methods include, for example, impregnation method, spray method, Mayer bar method, gravure method, micro gravure method, die method, blade method, micro rod method, air knife method, curtain method, slide method, A known coating method such as a roll method can be preferably exemplified. Of course, the examples are not limited to these examples.

Preferred examples of the glass fiber used in the present invention include E glass fiber, D glass fiber, S glass fiber, NE glass fiber, C glass fiber, quartz glass fiber, and high silicate glass fiber, and particularly preferably E glass. Fiber.
The glass fiber of the present invention preferably has an average fiber diameter (the average fiber diameter is an average fiber diameter when converted into a perfect circle) of 4 μm to 20 μm and an average fiber length of 1 mm to 25 mm. More preferably, the average fiber diameter is 4 μm to 15 μm, and the average fiber length is 3 mm to 20 mm. If the average fiber diameter is less than 4 μm and / or the average fiber length is less than 1 mm, it is not preferable because it may be harmful to health as with asbestos. If the average fiber diameter is greater than 20 μm and / or the average fiber length is 25 mm. If it is larger, there is a problem that the nonwoven fabric tends to be poorly formed.

  The glass fiber used in the present invention may have a surface treated with a silane coupling agent. As the silane coupling agent for surface treatment, known ones can be preferably mentioned. For example, vinyl silane coupling agent, epoxy silane coupling agent, styryl silane coupling agent, methacryloxy silane coupling agent, acryloxy silane coupling agent, amino silane coupling agent, ureido silane coupling agent More preferred are chloropropylsilane coupling agents, mercaprosilane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, and the like.

As a result of intensive investigations for improving the tensile strength of the wet method glass nonwoven fabric, the revolutionary present invention has been invented by using a component having a sulfur atom and a rubber component in combination as a binder component. The mechanism for improving the tensile strength of the wet method glass nonwoven fabric of the present invention is not clear, but vulcanization is considered to be one important mechanism.
When considering the required amount of the component having sulfur atoms in the binder component of the present invention, it is appropriate to evaluate the amount of sulfur atoms. The sulfur atom in the binder component is preferably contained in an amount of 0.0001% by mass to 10% by mass, more preferably 0.001% by mass to 3% by mass, and still more preferably 100% by mass of the binder component. It is 0.05 mass%-0.5 mass%.

  The component having a sulfur atom in the binder component in the present invention is preferably a component in which a sulfur atom is contained in the silane coupling agent molecule. The reason why the silane coupling agent containing a sulfur atom in the molecule is preferable is that the glass fiber and the hydrolyzed silane coupling agent are bonded, and the sulfur atom in the coupling agent and the rubber component in the polymer component This is because vulcanization occurs and the glass fiber and the binder component are firmly bonded. When aminosilane is used as the silane coupling agent, the bond with the polymer component is considered to have many hydrogen bonds, so the tensile strength improvement effect is small, especially when immersed in water, alcohol, etc. It is hard to get.

  Specific examples of such a silane coupling agent containing a sulfur atom include γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfade, and alkoxides thereof. Oligomers are preferred, and γ-mercaptopropyltrimethoxysilane is more preferred. In the present invention, one or a plurality of silane coupling agents containing sulfur atoms can be used, and it is preferably blended at 0.01% by mass to 10% by mass with respect to 100% by mass of the binder component. Preferably they are 0.1 mass%-6 mass%, More preferably, they are 0.3 mass%-3 mass%.

The main component of the binder component of the present invention is a rubber component, preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 80% by mass or more with respect to 100% by mass of the binder component.
As such a rubber component, natural rubber, BR (butadiene rubber), SBR (styrene / butadiene copolymer rubber), NBR (acrylonitrile / butadiene copolymer rubber), ABS (acrylonitrile / butadiene / styrene copolymer weight) are preferable. (Unified rubber), chloropropylene rubber, ethylene propylene rubber, polyisoprene rubber, butyl rubber, silicone rubber, urethane rubber, polysulfide, neoprene rubber, epichlorohydrin rubber, nitrile rubber, and acrylic monomers were copolymerized in the molecules of these rubber components The thing etc. can be mentioned.
More preferred are polymer components having a butadiene group, and even more preferred are BR, SBR, NBR, ABS, or those obtained by copolymerizing acrylic monomers in the molecules of these components. An acrylic monomer means an acrylate monomer.

  It is preferable that the binder amount of the wet method glass nonwoven fabric of this invention is 3 mass%-25 mass% with respect to 100 mass% of wet method glass nonwoven fabrics. When the amount is less than 3% by mass, the strength of the nonwoven fabric is weak and easily torn, and when it is more than 25% by mass, the resin component used in making the prepreg may be difficult to adhere. More preferably, the amount of the binder is 4% by mass to 20% by mass, and even more preferably 6% by mass to 15% by mass.

  As the binder component used in the present invention, a component having a sulfur atom and a component other than the rubber component can be used in combination. Examples of such a combination component include, in addition to known liquid binders such as acrylic resin, polyimide resin, urethane resin, polyvinyl alcohol, polyacrylamide, water-soluble cellulose, starch, melamine resin, epoxy resin, phenol resin, and meta-aramid. Fibers, liquid crystal polymer fibers, thermoplastic polyimide fibers, polypropylene fibers, polyethylene terephthalate fibers, acrylic fibers, polyvinyl alcohol fibers, polystyrene fibers and other known thermoplastic fibers, and KP, GP, TMP and other binder fibers such as wood pulp Preferable examples can be given. A pigment can also be contained in the binder component of the present invention. Preferred examples of the pigment include kaolin, silica, calcium carbonate, calcium silicate, aluminum hydroxide, talc, mica powder, zeolite, mica powder, and titanium oxide.

  The wet method glass nonwoven fabric of the present invention comprises a glass fiber and a binder component for binding the glass fiber, but auxiliary additives necessary for the production of the wet method glass nonwoven fabric, for example, a glass fiber dispersant, a sticking agent, etc. are preferably used. be able to.

  The prepreg of the present invention has a resin component attached to the wet glass nonwoven fabric of the present invention. As the resin component of the prepreg, a known thermoplastic resin or thermosetting resin can be used, and in general, a thermosetting resin is preferably used. For example, epoxy resin, phenol resin, melamine resin, urea resin Polyimide resins, cyanate resins, thermosetting polyphenylene oxide resins, and the like are more preferably used, and among these resin components, those that are stable with respect to a water / alcohol mixed dilution are more preferable.

  A pigment can be contained in the resin component of the prepreg of the present invention. By including the pigment, the quality of the composite material produced by press-molding the prepreg can be improved, such as incombustibility and moisture absorption. The pigment is preferably contained in an amount of 30% by mass or more, more preferably 50% by mass or more, based on 100% by mass of the resin component. Examples of the pigment include known inorganic pigments and organic pigments. Preferred examples of inorganic pigments include kaolin, silica, calcium carbonate, calcium silicate, aluminum hydroxide, talc, mica powder, zeolite, mica powder, and titanium oxide. Aluminum hydroxide is particularly preferable in terms of nonflammability. Is suitable. At least one kind of pigment can be used.

The method for producing a prepreg of the present invention can be applied by applying a resin component paint using a known method, such as an impregnation method, a spray method, a die method, and a roll method. The diluent for the resin component paint is preferably water and / or alcohol. As the alcohol, known ones can be preferably used, and methanol, ethanol, IPA (isopropyl alcohol), and methyl cellosolve are more preferable.
The composite material of the present invention is formed by press molding using at least one of the above prepregs. It is good also as a composite material of the type which mixed prepregs other than the said prepreg.

  The composite material of the present invention may be any material, but for example, a printed wiring board and a decorative board can be preferably mentioned, and a decorative board is more preferable.

  The present invention will be described more specifically with reference to the following examples. However, the scope of the present invention is not limited to these examples. In Examples, “%” and “parts” indicate “% by mass” and “parts by mass” unless otherwise specified.

<Example 1>
It is a nonionic surfactant for fibers adjusted to a mass ratio of E glass fiber chop with round cross-section fiber diameter φ13μm fiber length 6mm and E glass fiber chop with round cross-section fiber diameter φ6μm fiber length 15mm. Polyethylene glycol stearate (Emanon 3299, manufactured by Kao Corporation) was mixed at 1% to fiber and stirred in water at a fiber concentration of 0.02% using a three-one motor. In this fiber dispersion, an anionic polyacrylamide (Sumifloc FA40H, manufactured by Sumitomo Chemical Co., Ltd.) 0.1% solution, which is an anionic water-soluble polymer, was stirred as a viscous agent at a ratio of 0.5 part to 100 parts of the dispersion. A fiber dispersion was prepared. The fiber dispersion containing the bundle of fiber dispersions was wet-made with a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh. Subsequently, the binder component A was attached to the obtained wet sheet by spraying and dried for 10 minutes with a dryer at 160 ° C., and the basis weight was 100 g / m ² , the binder amount was 10% (10 g / m ² ), A wet glass nonwoven fabric having a sulfur atom component of about 0.08% was obtained. The wet strength glass nonwoven fabric was measured for tensile strength based on JIS P8113. Further, after the sheet was immersed in water for 15 minutes, the tensile strength measured in accordance with JIS P 8113 (referred to as water-resistant tensile strength in this specification) was measured. The results are shown in Table 1.

<< Binder A >>
SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon)
99.5 parts γ-mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts

<Example 2>
Round cross-section fiber diameter φ13μm E glass fiber chop with a fiber length of 10mm, nonionic surfactant polyethylene glycol stearate (Emanon 3299, manufactured by Kao Corporation) is mixed at 1% of the fiber, and the fiber concentration using a three-one motor Stir in water at 0.02%. In this fiber dispersion, an anionic polyacrylamide (Sumifloc FA40H, manufactured by Sumitomo Chemical Co., Ltd.) 0.1% solution, which is an anionic water-soluble polymer, was stirred as a viscous agent at a ratio of 0.5 part to 100 parts of the dispersion. A fiber dispersion was prepared. The fiber dispersion containing the bundle of fiber dispersions was wet-made with a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh. Subsequently, binder component B is attached to the obtained wet sheet by spraying and dried for 10 minutes in a dryer at 160 ° C., basis weight 100 g / m ² , binder amount 10% (10 g / m ² ), in binder A wet glass nonwoven fabric having a sulfur atom content of about 0.33% was obtained. Table 1 shows the results of evaluation in the same manner as in Example 1.

<< Binder B >>
Acrylic (trade name: A-104, manufactured by Toagosei Co., Ltd.) 18 parts SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon Co., Ltd.)
80 parts γ-mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

<Example 3>
Round cross-section fiber diameter φ13μm E glass fiber chop with a fiber length of 10mm, nonionic surfactant polyethylene glycol stearate (Emanon 3299, manufactured by Kao Corporation) is mixed at 1% of the fiber, and the fiber concentration using a three-one motor Stir in water at 0.02%. In this fiber dispersion, an anionic polyacrylamide (Sumifloc FA40H, manufactured by Sumitomo Chemical Co., Ltd.) 0.1% solution, which is an anionic water-soluble polymer, was stirred as a viscous agent at a ratio of 0.5 part to 100 parts of the dispersion. A fiber dispersion was prepared. The fiber dispersion containing the bundle of fiber dispersions was wet-made with a square hand-making machine using a plastic wire having a wire mesh number of 80 mesh. Subsequently, binder component C was attached to the obtained wet sheet by spraying and dried for 10 minutes in a dryer at 160 ° C., basis weight 100 g / m ² , binder amount 10% (10 g / m ² ), in binder A wet glass nonwoven fabric having a sulfur atom content of about 0.42% was obtained. Evaluation was performed in the same manner as in Example 1 except that the tensile strength against water was measured by immersing in a water / methanol solution having a water / methanol mass ratio of 1: 1 for 5 minutes. The results are shown in Table 1.

<< Binder C >>
SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon)
49 parts NBR (Brand name: NipolLX1577, manufactured by Nippon Zeon)
49 parts Bis (triethoxysilylpropyl) tetrasulfad (trade name: KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part γ-mercaptopropylmethyldimethoxysilane (trade name: KBM-802, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 Part

<Comparative Example 1>
Except for the binder D, the same examination as in Example 1 was performed. The results are shown in Table 1.
<< Binder D >>
SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon)
99.5 parts N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part

<Comparative Example 2>
Except for the binder E, the same examination as in Example 1 was performed. The results are shown in Table 1.
<< Binder E >>
Acrylic (trade name: A-104, manufactured by Toagosei Co., Ltd.) 18 parts SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon Co., Ltd.)
80 parts N-β (aminoethyl) γ-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

<Comparative Example 3>
Except for the binder F, the same examination as in Example 1 was performed. The results are shown in Table 1.
<< Binder F >>
SBR (trade name: Nipol LX433C, manufactured by Nippon Zeon)
49 parts NBR (Brand name: NipolLX1577, manufactured by Nippon Zeon)
49 parts γ-aminopropyltrimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts

<Example 4>
Resin component paint (100% solids content 50%) mixed with 50 parts of aluminum hydroxide with an average particle size of 5 μm, 10 parts of water, and 10 parts of IPA is applied to the wet glass nonwoven fabric of Example 1 using an impregnation machine. It was impregnated so as to have a solid content of 800 g / m ² (solid content) and dried to obtain a prepreg. Seven sheets of this prepreg were stacked and press-molded under the conditions of 150 ° C., 80 kgf / m ² , and 20 minutes to prepare a decorative board as a composite material. In the prepreg manufacturing process, the wet method glass nonwoven fabric did not break.

<Example 5>
Resin component paint (100% solids content 50%) mixed with 50 parts of aluminum hydroxide with an average particle size of 5 μm, 10 parts of water, and 10 parts of IPA is applied to the wet glass nonwoven fabric of Example 1 using an impregnation machine. It was impregnated so as to have a solid content of 800 g / m ² (solid content) and dried to obtain a prepreg. 7 sheets of this prepreg are stacked, impregnated paper with 130g / m ² solid impregnated melamine resin on gravure-printed paper with basis weight of 64g / m ² and dried at 150 ° C, 80kgf / m ² , 20 It was press-molded under the condition of minutes, and a decorative board as a composite material was prepared. In the prepreg manufacturing process, the wet method glass nonwoven fabric did not break.

<Example 6>
Resin component paint obtained by mixing 50 parts of aluminum hydroxide with an average particle size of 5 μm, 10 parts of water and 10 parts of methanol into 100 parts of resol type phenol resin (solid content 50%) is applied to the wet method glass nonwoven fabric of Example 1 in an impregnation machine. So that the solid content was 800 g / m ² (solid content) and dried to obtain a prepreg. 7 sheets of this prepreg are stacked, impregnated paper with 130g / m ² solid impregnated melamine resin on gravure-printed paper with basis weight of 64g / m ² and dried at 150 ° C, 80kgf / m ² , 20 It was press-molded under the condition of minutes, and a decorative board as a composite material was prepared. In the prepreg manufacturing process, the wet method glass nonwoven fabric did not break.

<Comparative example 4>
The same examination as in Example 4 was performed except that the wet method glass nonwoven fabric of Comparative Example 1 was used. Paper was cut during the prepreg manufacturing process.

<Comparative Example 5>
The same examination as in Example 5 was performed except that the wet method glass nonwoven fabric of Comparative Example 2 was used. Paper was cut during the prepreg manufacturing process.

<Comparative Example 6>
The same examination as in Example 6 was performed except that the wet method glass nonwoven fabric of Comparative Example 3 was used. Paper was cut during the prepreg manufacturing process.

Claims (6)

A wet-processed glass nonwoven fabric comprising a glass fiber and a binder component that bonds the glass fibers, wherein the first binder contains a component having a sulfur atom and a rubber component. 2. The component having a sulfur atom is at least one of γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, and bis (triethoxysilylpropyl) tetrasulfad. Wet method glass nonwoven fabric. The wet glass nonwoven fabric according to claim 1 or 2, wherein the rubber component is BR, SBR, NBR, ABS, or a rubber component in which an acrylic monomer is copolymerized in these molecules. A prepreg comprising a resin component attached to the wet method glass nonwoven fabric according to claim 1. A composite material obtained by press molding using at least one prepreg according to claim 4. The composite material according to claim 5, wherein the composite material is a decorative board.