JP4701726B2 - Glass paper - Google Patents

Description

  The present invention is a glass paper suitable as a base material of an electrically insulating laminate such as a printed wiring board, a base material of a vinyl chloride flooring material, a roofing material, a wall material, and a glass fiber processing suitable as an adhesive thereof. The present invention relates to a resin composition.

Conventionally, glass paper adhesives for electrical insulating laminates such as printed wiring boards in wet manufacturing methods, or glass paper adhesives suitable as base materials for vinyl chloride-based flooring materials, roofing materials, wall materials, etc. are acrylic. A method of impregnating a wet web with a glass fiber processing resin (adhesive) such as an epoxy resin (acrylic emulsion), an epoxy resin, a phenol resin, or a water-soluble silicone resin has been practiced.

  However, when these adhesives are processed into glass paper, they may be used at a high temperature after drying, at a high temperature after drying, or at a high temperature after curing. There was a problem that the paper was discolored (colored). Examples of the conditions under which the glass paper is exposed to high temperatures include a step of drying a glass fiber processing resin used as an adhesive and a curing step for accelerating a curing reaction when manufacturing the glass paper. When using paper, when used as glass paper for electrical insulation laminates, a process for producing a prepreg by impregnating glass paper with resin, and when used as glass paper for a substrate of vinyl chloride flooring, molten chloride The process which processes vinyl sol is mentioned, The solution of the problem that glass paper discolors by the heat history in these processes was desired.

  In particular, in a glass paper in a wet manufacturing method, when polyvinyl alcohol fiber is mixed with glass fiber to make paper, or when polyvinyl alcohol is used during or after paper making, a conventional glass fiber processing resin is used as an adhesive between fibers. When used as, the discoloration of the glass paper due to heat at a high temperature is remarkable, the appearance of the glass paper is deteriorated, and the commercial value is impaired.

  As a countermeasure against such discoloration due to heat, a binder composed of a polyvinyl alcohol resin and an organic acid having a pKa of 3.5 or less and a hydrazide compound is disclosed (for example, see Patent Document 1). However, when high strength and durability (heat resistance and warm water resistance) are required for the glass paper, there is a drawback that it is difficult to develop performance only with a binder of polyvinyl alcohol resin. In addition, when other water-dispersible resins are used in combination with the binder described in this publication in order to develop high strength and durability, the binder contains an organic acid, so that the mixing stability with the water-dispersible resin is improved. There is also a drawback that the binder is easy to solidify.

JP 2003-238922 A

  Therefore, the objective of this invention is providing the resin composition for glass fiber processing and glass paper for obtaining the glass paper with few discoloration by a heat | fever. In particular, it is to provide a glass paper that is excellent in heat discoloration at a high temperature of 120 ° C. or higher, and even at a high temperature of 200 ° C. or higher.

  As a result of intensive studies, the present inventors have obtained the following knowledge in order to solve the above problems. Glass fiber processing resin composition containing water-dispersible resin and alkali metal phosphate or alkaline earth metal phosphate has less discoloration due to heat as an adhesive between fibers of glass paper. I found it.

That is, the present invention provides a sheet-like glass fiber bundle, a water-dispersible acrylic resin, and sodium triphosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, potassium triphosphate, potassium tripolyphosphate or Provided is a glass paper obtained by spraying, coating or impregnating a resin composition containing a phosphate (A) which is potassium metaphosphate .

  ADVANTAGE OF THE INVENTION According to this invention, the glass paper excellent in heat-resistant discoloration property and the resin composition for glass fiber processing used for this can be provided.

  The water-dispersible resin of the present invention is not particularly limited, and examples thereof include acrylic resins, epoxy resins, styrene / butadiene resins, and urethane resins. Among these, acrylic resins and epoxy resins are particularly preferable because they are excellent in heat discoloration. Specific examples of the acrylic resin include an acrylic emulsion obtained by emulsion polymerization using an acrylic ester as a raw material monomer, and an acrylic / styrene emulsion obtained by emulsion polymerization of an acrylic ester and styrene. Epoxy resins include water-dispersible resins in which epoxy resins are dispersed in water with surfactants and protective colloids, water-dispersible resins in carboxy-modified epoxy resins, and water-dispersed amine-epoxide acidic salts. Resin etc. are mentioned. Among these, acrylic emulsions, acrylic / styrene emulsions, and water-dispersible resins such as carboxy-modified epoxy resins are preferable because they have excellent heat discoloration resistance.

  Specific examples of commercially available acrylic emulsions include “Dick Fine IV-3600” (manufactured by Dainippon Ink & Chemicals, Inc.). Specific examples of commercially available water-dispersible resins of carboxy-modified epoxy resins include “Dick Fine EN-0270” (manufactured by Dainippon Ink & Chemicals, Inc.).

  Moreover, you may add other water-dispersible resin and water-soluble resin as a crosslinking agent to the resin composition for glass fiber processing of this invention as needed. Specific examples include melamine crosslinking agents, isocyanate crosslinking agents, blocked isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, and the like.

  Moreover, in order to improve adhesiveness with glass fiber, it is also possible to add and use various silane coupling agents.

  In the present invention, in order to improve the heat discoloration resistance of the glass paper, it is essential to add the alkali metal phosphate and / or alkaline earth metal phosphate (A) as described above. Specifically, the alkali metal phosphate and / or alkaline earth metal phosphate (A) is, for example, primary sodium phosphate (anhydrous and / or crystals), dibasic sodium phosphate (anhydrous and / or). Crystals), sodium triphosphate (anhydrous and / or crystals), sodium pyrophosphate (anhydrous and / or crystals), acidic sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, sodium acid hexametaphosphate, Primary potassium phosphate, dibasic potassium phosphate, tribasic potassium phosphate, potassium pyrophosphate, potassium tripolyphosphate, potassium metaphosphate, primary calcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate, etc., one of these Or you can use a mixture of two or more . Among these, tribasic sodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, potassium tertiary phosphate, potassium pyrophosphate, potassium tripolyphosphate, potassium metaphosphate are water dispersible. This is preferable because of its excellent miscibility with the resin. Furthermore, sodium tripolyphosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate are preferred because they are remarkably excellent in miscibility with water-dispersible resins and heat discoloration.

  The weight ratio of the water-dispersible resin and the alkali metal phosphate and / or alkaline earth metal phosphate (A) is, for example, [water dispersible resin] / [(A)] = in solid content ratio. 100 / 0.05 to 100/3 is preferable because it is excellent in heat discoloration resistance and the water resistance of the glass paper is hardly lowered.

  The glass paper of the present invention can be produced by various methods. That is, either a wet method or a dry method may be used, but in order to obtain a higher density glass paper, it is preferable to employ a wet method. Specifically, water-dispersible glass fiber chopped strands are dispersed in water in which a dispersant is dissolved, and then paper is made with a paper machine and sprayed and sprayed with the resin composition for glass fiber processing of the present invention, or A method of impregnating a glass fiber processing resin composition liquid, or coating a glass fiber processing resin composition, or processing by combining these methods, and then drying and curing with a hot air dryer or a drum dryer. Is mentioned.

  The drying and curing step is usually performed at 100 to 250 ° C., more preferably at 150 to 200 ° C. for several seconds to several minutes with a hot air dryer or drum dryer, but by infrared, far infrared, or high frequency heating, or It can be implemented by a combination thereof.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples. In the following, unless otherwise specified, “%” represents “% by weight”, and “part” represents “part by weight”.

Example 1
The glass paper was formed into a sheet by the wet method with the following fiber configuration, and then pressed and dried at 105 ° C. for 10 minutes to obtain a sheet-like glass fiber bundle.
Glass fiber (average fiber diameter 9 μm, average fiber length 13 mm) 90 parts Vinylon fiber (polyvinyl alcohol fiber: manufactured by Kuraray Co., Ltd.) 10 parts [(average fiber diameter 10 μm, average fiber length 3.5 mm)]

  Next, a glass fiber processing resin composition having the following composition was adjusted to the sheet-like glass fiber bundle so that the solid content concentration was 5%, and 15% by weight (solid content) with respect to the sheet-like glass fiber bundle. Ratio) impregnation and drying at 160 ° C. for 10 minutes to obtain glass paper.

(Combination)
Dick Fine IV-3600 (acrylic emulsion: manufactured by Dainippon Ink & Chemicals, Inc.) 100 parts (solid content concentration: 20%)
2 parts of sodium tripolyphosphate aqueous solution (solid content concentration: 10%) The glass paper obtained in this way is placed in a hot-air circulating drier held at 210 ° C., and the discoloration state of the glass paper after holding for 10 minutes will be described later. Measured with a color difference meter. The results are listed in Table 1.

Example 2
A sheet-like glass fiber bundle was prepared in the same manner as in Example 1, and a glass fiber processing resin composition having the following composition was processed in the same manner as in Example 1 to obtain glass paper.

Dick Fine EN-0270 (carboxy-modified epoxy resin aqueous dispersion: manufactured by Dainippon Ink & Chemicals, Inc.) 100 parts (solid content concentration: 20%)
2 parts of sodium tripolyphosphate aqueous solution (solid content concentration: 10%) The glass paper obtained in this way is placed in a hot-air circulating drier held at 210 ° C., and the discoloration state of the glass paper after holding for 10 minutes will be described later. Measured with a color difference meter. The results are listed in Table 1.

Comparative Example 1
A sheet-like glass fiber bundle was prepared in the same manner as in Example 1, and a glass fiber processing resin composition having the following composition was processed in the same manner as in Example 1 to obtain glass paper.

Dick Fine IV-3600 (acrylic emulsion: manufactured by Dainippon Ink & Chemicals, Inc.) 100 parts (solid content concentration: 20%)
The glass paper thus obtained was placed in a hot-air circulating drier maintained at 210 ° C., and the color change state of the glass paper after being held for 10 minutes was measured with a color difference meter described later. The results are listed in Table 1. In addition, the preparation amount of the water-dispersible resin and phosphate (A) in Table 1 is described in solid parts by weight.

[Measure color difference]
The color difference of the glass paper was measured using a color difference meter CR-300 manufactured by Minolta. As a color difference comparison standard, the color difference of a sheet-like glass fiber bundle alone prepared in the same manner as in Example 1, and the color difference after holding for 10 minutes in a hot-air circulating drier holding the glass fiber bundle at 210 ° C. Was measured. The sheet-like glass fiber bundles used in Examples and Comparative Examples were heat treated at 210 ° C. without impregnating the water-dispersible resin and phosphate, and the color difference without impregnating the water-dispersible resin and phosphate. The color difference of the glass fiber bundle was also measured as a comparison.

Claims (2)

A sheet-like glass fiber bundle is coated with water-dispersible acrylic resin and phosphorus tribasic sodium phosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, potassium triphosphate, potassium tripolyphosphate or potassium metaphosphate. A glass paper obtained by spraying, coating or impregnating a resin composition containing an acid salt (A). A sheet-like glass fiber bundle is coated with water-dispersible acrylic resin and phosphorus tribasic sodium phosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, potassium triphosphate, potassium tripolyphosphate or potassium metaphosphate. A vinyl chloride floor base material or glass paper for roofing or wall material obtained by spraying, coating or impregnating a resin composition containing an acid salt (A).