JPS63183936A - Resin-impregnated sheet for molded-laminated article and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled sheet of good quality containing inorganic fiber cloth as a substrate without loosening of end parts, by filling a matrix resin onto a coating part, consisting of copolyester resin particles having a specific particle size and formed near both selvedge parts of the sheet. CONSTITUTION:An aqueous dispersion of a copolyester resin having 150-220 deg.C melting point, 0.2-0.7dl/g reduced viscosity and an average particle diameter of <=1/5 based on the single fiber diameter of inorganic fiber cloth, e.g. glass fiber cloth, etc., woven by a reedless loom is applied to the inside of fringed selvedge parts thereof and water is then evaporated. The polyester is melted above the softening point thereof, cooled and solidified to cut and remove the fringed selvedge parts along the coated parts. A matrix resin varnish, e.g. epoxy resin, etc., is then impregnated in the whole inorganic fiber cloth and dried.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to a resin-impregnated laminate molded article having an inorganic fiber fabric woven on a shuttleless loom as a base material and a thermosetting or thermoplastic resin as a matrix. Concerning sheets and their manufacturing methods.

[Conventional technology]

A laminated molded product using inorganic fiber fabric as a reinforcing material is produced by impregnating a glass, quartz or ceramic fiber fabric with a thermosetting or thermoplastic resin varnish diluted with a solvent or a reactive monomer, and then drying it. At the same time as the solvent is volatilized, thermosetting resins are B-staged (semi-cured) and resin-impregnated sheets (ie prepregs) obtained are laminated and molded.

In recent years, when inorganic fiber fabrics are used for the resin-impregnated sheet, fabrics woven on shuttleless looms have been increasingly used from the viewpoints of cost and fabric quality.

[Problem that the invention seeks to solve]

However, since fabrics woven using shuttleless looms have tassels, the following problems occur. That is, (a) the warp yarns at the ends easily fray, causing trouble in the resin impregnation process.

(b) Since the tufts absorb a large amount of resin, both ends of the impregnated sheet become abnormally thick, making it difficult to stack and store or wind up into a roll.

(c) A large amount of resin adhering to the tufted portion easily separates, scatters during lamination molding, and adheres to various places, causing a defective molded product.

In order to solve these problems, attempts have been made to cut and remove the tufts before impregnating them with resin. The first method is to fuse the inside of the tufted part with a laser beam, but since the adhesive force at the fused part is weak and brittle, strong ironing may cause the fibers to become frayed or when cut. It has drawbacks such as the generated minute fiber balls falling into the varnish, making it difficult to put it into practical use.

The second method is the method disclosed in JP-A No. 52-34094, in which the cut portion is coated with an adhesive such as acrylic, polyvinyl acetate, rubber, or polyvinyl chloride, particularly preferably compatible with polyester. This is a method in which a soluble polyvinyl acetate adhesive is applied as an anti-stick agent. However, in this method, since the adhesive has poor heat resistance and solvent resistance, there is a risk that the fabric warp threads may become frayed during the resin varnish impregnation step, or that the adhesive may dissolve into the resin varnish and alter the performance of the matrix resin.

As another method to solve these problems,
No. 9-15563, JP-A-60-15111, and JP-A-60-194182 propose a method in which a certain type of polyester resin is dissolved in a halogenated lower hydrocarbon and applied as a solution. This method solved problems such as fraying of threads caused by dissolution of the adhesive into the resin varnish or melting due to insufficient heat resistance of the adhesive, but on the other hand, as mentioned above, this method also Since hydrogen is used as a solvent, it causes serious problems in the working environment, hygiene, and production process control.

In other words, as is well known, halogenated lower carbons such as methylene chloride, trichloroethane, and chloroform are concerned about their effects on the human body, and strict control is required when using them. Problems include that it is not easy to achieve complete sealing, that if it evaporates into the atmosphere, it is likely to cause groundwater contamination due to its heavy specific gravity, and that complete recovery of the solvent requires serious investment. .

The present invention solves the problems of the conventional technology as described above, and provides a high-quality resin-impregnated sheet for a laminated molded product in which the influence of tufts is reliably removed and the edges do not fray, and it is environmentally hygienic. It is an object of the present invention to provide a manufacturing method that is also preferable and that can inexpensively manufacture a high-quality resin-impregnated sheet for laminated molded materials.

[Means for solving problems]

The object of the present invention is to provide a resin-impregnated sheet for a laminated molded product, which is made of an inorganic fiber fabric as a base material and filled with a matrix resin, wherein the average particle diameter of the inorganic fiber fabric is smaller in the vicinity of both sides of the sheet. This is achieved by a resin-impregnated sheet for a laminated molded product, characterized in that a coated part is formed of copolymerized polyester resin particles having a diameter of 115 or less than the diameter of the single fiber filament constituting the sheet, and is filled with a matrix resin. Ru.

A preferred method for manufacturing the resin-impregnated sheet for a laminate molded body is a method of manufacturing a resin-impregnated sheet for a laminate molded body by impregnating and drying an inorganic fiber fabric woven using a shuttleless loom with a matrix resin varnish. On the inside of the ear part of the cell, the melting point is 150°C to 220°C and the reduced viscosity is 0.2 to 0.
7d! /g of a copolymerized polyester resin, and the average particle diameter of the dispersed particles is one-fifth or less of the diameter of the single fiber filament constituting the fabric, The water is volatilized, the copolymerized polyester resin is melted above its softening point, and after cooling and solidifying, the tassel edges are cut and removed along the applied area, and then the entire inorganic fiber fabric from which the tassel edges have been removed is coated with the It is characterized by being impregnated with matrix resin varnish and dried.

Since the copolymerized polyester resin used in the present invention is applied to the inorganic fiber fabric in the form of an aqueous dispersion, it must be a resin capable of forming a stable aqueous dispersion. In addition, in the present invention, as described above, the selvedge portions are cut and removed before the inorganic fiber fabric is dipped in the matrix resin varnish, and at that time,
Since a copolyester resin is applied to maintain the shape of the cut portion, this resin must be heat resistant to the drying temperature of the impregnated sheet.

The copolymerized polyester resin must be sufficiently impregnated and filled between the filaments of the inorganic fibers to completely adhere the filaments to each other. If this is insufficient, filament fuzz will be generated from the cut part, which may scatter or adhere to the resin-impregnated sheet or fall into the resin varnish, causing defects, so a small amount is sufficient. It must be able to impregnate between the filaments and bond and hold the filaments and the fabric structure together. Therefore, it is more preferable that the average particle diameter of the polymer particles in the filtrate dispersion used in the present invention is one-fifth or less of the diameter of the filaments constituting the inorganic fibers. For example, when used in a fabric made of fibers consisting of filaments with a diameter of 5 μm, the particle size is 1 μm or less. If a polymer particle size larger than this is used, the dispersed particles of the copolyester resin will not be sufficiently impregnated between the filaments and will tend to adhere to the fiber surface, thus increasing the thickness of the fabric, but not adhesion between the filaments. However, if it is less than 1μ, the polymer particles will be smoothly impregnated into the fiber bundle, achieving good adhesion between the filaments, and forming a good resin-impregnated sheet substrate after the matrix resin treatment. Become.

Furthermore, the higher the melting point of the copolymerized polyester resin used in the present invention, the better, but if it exceeds 220 t, a lot of energy will be required to melt the polyester resin after coating and drying, and the high temperature will damage the surface of the inorganic fibers. There is also a risk of causing decomposition of the applied surface treatment agent. In addition, since the resin-impregnated sheet is normally dried at 200°C or lower, the melting point of the copolyester is 150'C, ~
The drying temperature is preferably 220 t, more preferably 180°C to 220°C, which is about 20°C higher than the drying temperature of the resin-impregnated sheet. Further, the reduced viscosity of the copolymerized polyester resin of the present invention is 0.
．． Preferably, the range is 0.7 dl/g. If the reduced viscosity is less than 0.2 a/g, the copolymerized polyester resin itself will have a weak cohesive force and lack flexibility, which will easily cause earring etc. during handling. Also 0.7dI/
When it is larger than g, the molecular weight is large and problems arise in dispersibility in water.

As the copolymerized polyester resin used in the present invention,
Any copolyester resin may be used as long as it has the above-mentioned properties, but it has the following composition: (a) 60 to 95 mol% of terephthalic acid, (b) 20 mol% of sulfonic acid metal base-containing dicarboxylic acid 5N, (h) ) It is preferable to use a saturated copolymerized polyester resin comprising a dicarboxylic acid component other than (a) and (b) and an alkylene glycol having 2 to 10 carbon atoms. If the content of the tylphthalic acid component is less than 60 mol%, the solvent resistance of the resulting resin will decrease, which is not preferable. Furthermore, in this case, the heat resistance also decreases, making it difficult to maintain adhesive strength when drying the resin-impregnated sheet. Further, the dicarboxylic acid containing a sulfonic acid metal group is important in that it determines the water dispersibility of the resulting copolyester resin and the adhesion to inorganic fibers. Examples of sulfonic acid metal base-containing dicarboxylic acids include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxyisophthalic acid. I can give you some salt. Metal salts include Li, Na, and K.

Examples include salts such as Mg+Ca+Cu+Fe.

The sulfonic acid metal group-containing dicarboxylic acid is preferably in a range of 5 to 20 mol % based on the total dicarboxylic acid components.

If the amount is less than this, the dispersibility in water will be very poor and the resulting dispersion will have a large particle size. On the other hand, if the amount is higher than this, the softening point of the copolymerized polyester resin will be lowered,
cause problems. Since the composition ratio of these components is closely related to the dispersed particle diameter, it is necessary to determine the optimum amount while taking other properties into consideration. The glycol component is mainly composed of alkylene glycol having 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and diethylene glycol.

These alkylene glycols may be used alone or as a mixture of two or more.

In order to achieve the object of the present invention, the amount of copolymerized polyester resin applied is important. After cutting and removing the selvage of the inorganic fiber fabric, it is wound up into a roll and transferred to the next step, the resin varnish impregnation process. However, if the amount of application is insufficient, the fixing force of the cut surface is insufficient, and the application is delayed. If the amount is too large, the roll will become too high and the edges will be damaged, which is undesirable. Therefore, although the optimum amount of coating varies depending on the type of yarn of the fabric and the implantation density, it must be selected within a range that allows the thickness of the coated area to be maintained substantially equal to that of the non-coated area.

In the method of the present invention, known methods such as roller coating, printing, and nozzle methods can be used to apply the aqueous copolyester resin dispersion to the inorganic fiber fabric. In this case, the coating amount is adjusted by controlling the concentration of the aqueous dispersion.

In the present invention, after applying and impregnating the copolymerized polyester resin aqueous dispersion on the inside of the tassel portion of the inorganic fiber fabric, the water is volatilized by drying, and then the resin is melted at a temperature higher than the softening point. desirable.

If the water in the dispersion is simply volatilized, the grain boundaries of the dispersed particles will remain as they are, and a sufficient polymer film will not be formed, resulting in insufficient adhesion and fiber fraying during the cutting process and resin varnish impregnated sheet manufacturing process. There is a possibility that the powder may fall off or the powder of the resin may fall off.

In the present invention, thermosetting resins such as epoxy resins, unsaturated polyester resins, polyimide resins, triazine resins, and bismaleimide/triazine resins are generally used as matrix resins for producing resin-impregnated sheets, but polyphenylene sulfide Thermoplastic resins such as resins and polyetheretherketone resins can also be used. Solvents and reactive diluents for forming varnishes of these resins include acetone, ketones such as methyl ethyl ketone, alcohols such as methanol and isopropyl alcohol, cellosolves such as methyl cellosolve and methyl ethyl cellosolve, dimethyl formamide, N- Polar solvents such as methylpyrrolidone or reactive diluents such as styrene, divinylbenzene and many others are contemplated, but the copolyester resin used in the present invention must be resistant to these solvents.

Examples of the inorganic fiber fabrics used in the present invention include glass fiber fabrics, quartz fiber fabrics, and ceramic fiber fabrics such as alumina fibers.

Further, as the shuttleless loom, an air jet loom, a water jet loom, a gripper loom, etc. can be used. After inorganic fiber fabrics are usually woven, the adhesive is removed by heat cleaning and the surface is cleaned, then silane coupling agents, titanium coupling agents, etc. are applied to bond and wettability between the inorganic fiber base material and matrix resin. It can be obtained by applying 5 surface treatments effective for improving.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples unless it departs from the gist thereof.

After heat cleaning a glass fiber fabric style 7628 (filament diameter 9μ) woven on an air-jet loom and surface-treating it with aminosilane, the inside of the selvedge part of the fabric was coated with a material with a melting point of 212℃ and a reduced viscosity of 0.4d1. /g, copolymerized polyester resin aqueous dispersion with a dispersed particle size of 0.1μ (
8% solids concentration, terephthalic acid, 5-sodium sulfoisophthalic acid, ethylene glycol copolymer) was applied using a roll coater with a width of 7 cranes, and after drying with a hot air dryer,
The resin was melted in a far-infrared dryer. Next, the coated area was cut in the center with a cutter to obtain a glass fiber fabric of a constant width with the tufted edges removed. The obtained glass fiber fabric was coated with epoxy resin varnish (AER-711 manufactured by Asahi Kasei Corporation).
An epoxy prepreg was prepared by impregnating it with 125 parts of EK80, 20 parts of dimethylformamide, 20 parts of methyl cellosolve, 10 parts of methyl ethyl ketone, 5 parts of acetone, 3.0 parts of dicyandiamide, and 0.2 parts of benzyldimethylamine and drying.

The obtained impregnated sheet did not cause any problems such as thread fraying during the varnish impregnation process or drying process, and the thickness of the impregnated sheet was the same in both the copolymer resin coated area and the non-coated area, and there was no problem even when 2000 sheets were stacked. Ta.

Example 1 An epoxy resin-impregnated sheet of glass fiber fabric was prepared in the same manner as in Example 1 except that glass fiber fabric style 1080 (filament diameter 5 μm) woven on an air jet loom was used, and a good target object was obtained.

By changing the monomer component ratio, type, and dispersion method, various copolymerized polyester aqueous dispersions shown in Table 1 were obtained and treated in the same manner as in Examples 1 and 2 to prepare glass fiber fabrics and A good epoxy resin-impregnated sheet of quartz fiber fabric was obtained.

Comparison ■Soil melting point is 207℃, reduced viscosity 0.75, dispersed particle size 5~
When a copolymerized polyester resin aqueous dispersion of 10μ was used in the same manner as in Example 1, the polyester resin particles were not sufficiently impregnated between the fiber filaments, and when the tuft edges were cut,
Fuzz appeared on the cut part and fell off into the resin varnish bath.

A copolymerized polyester resin aqueous dispersion having a melting point of 212°C, a reduced viscosity of 0.40, and a dispersed particle size of 1 to 2 μm (average particle size of 1.7 μm) was used in the same manner as in Example 2, and a comparative example was obtained. The same drawbacks as 1 occurred.

The melting point is 142°C, the reduced viscosity is 0.43, and the dispersed particle size is 0.
Example 1 Copolymerized polyester resin aqueous dispersion of 1μ or less
When used in the same manner as above, the edges of the adhesive part frayed during the drying process (drying temperature: 140° C.) after impregnating with resin varnish, and a good sheet could not be obtained.

Melting point: 174℃, reduced viscosity: 0.18, dispersed particle size: 0.1μ
When the following copolymerized polyester resin aqueous dispersion was used in the same manner as in Example 1, the selvage of the fabric at the cut portion of the tassel selvage was brittle and easily broke, producing selvage.

Table 1 shows the performance comparison results according to the type of copolyester resin used in the resin-impregnated sheets in Examples 1 to 6 and Comparative Examples 1 to 4.

The following margins are used as a resin of aqueous copolymerized polyester resin dispersion with a melting point of approximately 1.
Example 1 except that a polyester resin (terephthalic acid, 5-sodium sulfoisophthalic acid, ethylene glycol, diethylene copolymer: trade name [Gapsen ES 915J]) was used at 91°C and a reduced viscosity of about 0.35 dl/g. Epoxy prepreg was made under the same conditions as above. The results were the same as in Example 1.

〔Effect of the invention〕

Since the resin-impregnated sheet for laminated molded products and the method for producing the same according to the present invention are configured as described above, the inorganic sheet from which tufts have been removed is suitable as a base material for resin varnish impregnation without using harmful organic solvents. A fiber fabric is obtained, and since the tassels are surely removed from the inorganic fibers, the inorganic fibers are not cut and mixed into the resin varnish when impregnated with the resin varnish, and therefore, the product is good. A resin-impregnated sheet is obtained. Furthermore, since the thickness of the obtained resin-impregnated sheet can be made equal between the ends and the center, there is no problem when laminating a plurality of resin-impregnated sheets.

Claims (1)

[Scope of Claims] 1. A resin-impregnated sheet for a laminate molded product, which is formed by using an inorganic fiber fabric as a base material and filling the material with a matrix resin, wherein the average particle diameter near both sides of the sheet is as follows. 1 of the diameter of the single fiber filaments that make up the inorganic fiber fabric
1. A resin-impregnated sheet for a laminate molded article, characterized in that a coated portion is formed of copolymerized polyester resin particles having a particle size of 0.25% or less, and is filled with a matrix resin. 2. In a method of manufacturing a resin-impregnated sheet for a laminated molded product by impregnating and drying an inorganic fiber fabric woven with a shuttleless loom with a matrix resin varnish, the melting point is 150°C inside the tassel portion of the fabric. ~220℃, reduced viscosity 0.2~
0.7 dl/g of a copolymerized polyester resin, and the average particle diameter of the dispersed particles is one-fifth or less of the diameter of the single fiber filaments constituting the fabric. The inorganic fiber fabric is coated, water is volatilized, melted at a temperature equal to or higher than the softening point of the copolymerized polyester resin, and after cooling and solidifying, the tassel edges are cut and removed along the coated area, and then the tassel edges are removed. 1. A method for producing a resin-impregnated sheet for a laminated molded article, which comprises impregnating the entire body with the matrix resin varnish and drying it.