JP2009019315A - Method for producing surface-treated aromatic polyamide fiber woven fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a surface-treated aromatic polyamide fiber which can exhibit a practically sufficient heat resistance when preparing a fiber-reinforced resin. <P>SOLUTION: The method for producing the surface-treated aromatic polyamide fiber woven fabric comprises the attaching step of attaching a treating liquid containing a water-soluble epoxy compound, an organosilicon compound and water to an aromatic polyamide fiber woven fabric and the water-removing step of removing water in the attached treating liquid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a surface-treated aromatic polyamide fiber fabric.

  Since aromatic polyamide fibers are excellent in mechanical properties and electrical properties, the nonwoven fabrics and woven fabrics are used as reinforcing materials for laminated boards for printed wiring boards by being impregnated with a curable resin and cured. However, since the surface of the aromatic polyamide fiber is inactive, the adhesiveness with the curable resin is inferior, and the original performance of the aromatic polyamide fiber is not fully utilized.

For this reason, the processing method of an aromatic polyamide fiber for improving the adhesiveness of an aromatic polyamide fiber and curable resin has been examined (patent documents 1 and 2).
Japanese Patent Publication No. 07-1111030 JP 07-216112 A

  However, in the conventional treatment method, the heat resistance of the fiber reinforced resin obtained by impregnating the curable resin and then curing is not sufficient. Then, the objective of this invention is providing the manufacturing method of the surface treatment aromatic polyamide fiber fabric which can exhibit heat resistance practically sufficient, when a fiber reinforced resin is produced.

  The present invention includes an adhesion step of attaching a treatment liquid containing a water-soluble epoxy compound, an organosilicon compound and water to an aromatic polyamide fiber fabric, and a water removal step of removing moisture in the attached treatment liquid. A method for producing a treated aromatic polyamide fiber fabric is provided.

  The fiber reinforced resin (laminated board, etc.) obtained by impregnating and curing the surface-treated aromatic polyamide fiber fabric obtained by the production method of the present invention with a curable resin has excellent heat resistance compared to the conventional method. To demonstrate.

The production method of the present invention is characterized in that a treatment liquid in which a water-soluble epoxy compound and an organosilicon compound coexist in water is attached to an aromatic polyamide fiber fabric. If a woven fabric obtained by this production method is used, a fiber reinforced resin (laminated plate or the like) having particularly excellent heat resistance as compared with the case of using a woven fabric obtained by the following methods (1) to (2). It becomes possible to manufacture.
(1) Method of treating with a treatment liquid in which water-soluble epoxy compound is present in water after treatment with treatment liquid in which organic silicon compound is present in water (2) Treating with treatment liquid in which water-soluble epoxy compound is present in water Later, a method of treating with a treatment liquid in which an organosilicon compound is present in water

  The reason why such an effect is exhibited is that the surface-treated aromatic polyamide fiber woven fabric obtained by the production method of the present invention is superior in adhesiveness to a curable resin as compared with the conventional method. The It is also conceivable that the water-soluble epoxy compound and the organosilicon compound react in the treatment liquid, and this reaction product affects the heat resistance of the fiber reinforced resin.

  According to the method of the present invention, it is possible to shorten the processing step of the aromatic polyamide fiber fabric. That is, the conventional method in which the epoxy compound and the organosilicon compound are separately attached to the aromatic polyamide fiber fabric has many treatment steps, but the present invention provides a surface-treated aromatic polyamide fiber fabric with better performance. It can be provided in a short process.

  The adhesion amount of the treatment liquid after the moisture is removed is preferably 0.2 to 2 parts by mass per 100 parts by mass of the aromatic polyamide fiber fabric. The aromatic polyamide fiber fabric is sufficiently covered with the non-volatile component of the treatment liquid by adhering the above-mentioned weight of the treatment liquid after the moisture is removed (hereinafter sometimes referred to as “non-volatile component of the treatment liquid”). Therefore, the interfacial adhesiveness with the curable resin at the time of producing the fiber reinforced resin (laminated plate or the like) can be improved, and the heat resistance of the fiber reinforced resin (laminated plate or the like) can be remarkably improved.

  The water-soluble epoxy compound is preferably a water-soluble polyepoxy compound having an epoxy equivalent of 80 to 200. An epoxy compound having an epoxy equivalent in the above range is excellent in water solubility and also has good adhesion to an aromatic polyamide fiber fabric. The water-soluble epoxy compound may be chemically or physically bonded to the surface of the organosilicon compound or the aromatic polyamide fiber fabric in the treatment liquid. However, the mobility of the molecule increases when the epoxy equivalent is within the above range. It is considered that the reactivity is improved. In addition, since the water-soluble epoxy compound is a polyfunctional epoxy compound, that is, a water-soluble polyepoxy compound, the chemical or physical bonding point increases, adhesion to an aromatic polyamide fiber fabric, fiber reinforced resin (lamination) Interfacial adhesion at the time of producing a board etc. can be improved, and for this reason, the heat resistance of the fiber reinforced resin (laminated board etc.) obtained is also excellent.

  In the present invention, a fiber opening step of opening the aromatic polyamide fiber fabric can be further provided before the attaching step. Opening exposes the gaps in the aromatic polyamide fiber fabric, resulting in improved impregnation, increasing the surface treatment efficiency of the surface-treated aromatic polyamide fiber fabric and further improving the adhesiveness of the curable resin. Can be made. In general, aromatic polyamide fibers are attached with a sizing agent for weaving, and this is a factor that reduces heat resistance, but the fiber opening process not only makes the fabric uniform but also removes the sizing agent. Can do. Therefore, the heat resistance of fiber reinforced resin (laminated board etc.) improves more.

  By the above production method, a surface-treated aromatic polyamide fiber fabric can be obtained, and a prepreg can be produced using this surface-treated aromatic polyamide fiber fabric. That is, the manufacturing method of a prepreg provided with the process of making a surface treatment aromatic polyamide fiber fabric impregnate curable resin is provided. As a result, it is possible to manufacture a prepreg that fully utilizes the original mechanical properties and electrical properties of the aromatic polyamide fiber using the aromatic polyamide fiber fabric having higher adhesion to the curable resin as compared with the prior art as a reinforcing material. .

  This invention also provides the manufacturing method of a laminated board provided with the process of laminating | stacking one or more layers of the said prepreg, and making it harden | cure. Although a laminated board is obtained by this manufacturing method, since this laminated board contains the surface treatment aromatic polyamide fiber fabric obtained by the above-mentioned manufacturing method as a reinforced fiber, it is excellent in heat resistance. The laminated board thus obtained can be used as a laminated board for printed wiring boards.

  Provided is a method for producing a surface-treated aromatic polyamide fiber that can exhibit practically sufficient heat resistance when a fiber-reinforced resin is produced.

  The method for producing a surface-treated aromatic polyamide fiber fabric of the present invention essentially comprises an adhesion step and a water removal step. First, the adhesion process will be described.

  In the attaching step, the object to which the treatment liquid is attached is an aromatic polyamide fiber. Here, the aromatic polyamide is a polymer in which a monomer having an aromatic skeleton is bonded by an amide bond. For example, an aromatic polyamine (aromatic diamine etc.) and an aromatic polycarboxylic acid (aromatic dicarboxylic acid etc.) It can be obtained by polycondensation. At least one of the polyamine and the polycarboxylic acid used as the raw material for the aromatic polyamide needs to be an aromatic compound, but is preferably a wholly aromatic polyamide in which both are aromatic compounds. Examples of such aromatic polyamides include Kevlar (trade name, manufactured by DuPont), Technora (trade name, manufactured by Teijin), Conex (trade name, manufactured by Teijin), and Twaron (trade name, manufactured by Akzo). Can be mentioned.

The aromatic polyamide fiber fabric is preferably woven with 3 to 50 tex (more preferably 5 to 25 tex) aromatic polyamide fiber yarn as warp and weft. Although the method of weaving is not limited, it is preferable to use plain weaving because the workability is good and the thickness of the prepreg or laminate can be reduced. The weave density is preferably 10/25 mm to 70/25 mm (more preferably 15/25 mm to 30/25 mm). Moreover, since the effect of the present invention is remarkably recognized when the thickness of the aromatic polyamide fiber fabric is relatively thin, the mass per unit area of the aromatic polyamide fiber fabric is 5 to 100 g / m ² (more preferably 10 to 50 g / m ² ) is preferable. A sizing agent for weaving may be attached to the warp and weft of the aromatic polyamide fiber fabric.

  The treatment liquid used in the attaching step includes a water-soluble epoxy resin. Here, “water-soluble” means a property in which 50% by mass or more of the epoxy compound dissolves when 10 parts by mass of the epoxy compound is dissolved in 90 parts by mass of water at room temperature. The water-soluble epoxy resin is preferably dissolved in water in the treatment liquid, but may be present in a dispersed state in water.

The water-soluble epoxy compound preferably has two or more epoxy groups and has an epoxy equivalent of 80 to 200. As such a water-soluble epoxy compound, polyglycidyl ether of a polyhydric alcohol is preferable, glycerin is preferable as the polyhydric alcohol, and diglycidyl ether and / or triglycidyl ether is preferable. That is, a water-soluble epoxy compound having a structure represented by the following chemical formula (1) and / or (2) is preferable, and the water-soluble epoxy compound represented by the chemical formula (1) and (2) is used in combination. More preferred.

  The treatment liquid used in the attaching step includes an organic silicon compound in addition to the above-described water-soluble epoxy resin. As the organosilicon compound, an organosilane compound is preferable, and a silane coupling agent such as alkoxysilane is particularly preferable. Examples of such organosilicon compounds include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropylmethyl. Diethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane or its hydrochloride, N-β -(N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane or its hydrochloride, N-β- (N-benzylaminoethylaminopropyl) trimethoxysilane or its hydrochloride, N-β- (N- Benzylaminoethylaminopropyl) methyldimethyl Kishishiran or its hydrochloride salt, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropyl dimethoxysilane and the like. An amino group-containing alkoxysilane compound capable of reacting with a water-soluble epoxy compound is particularly preferred in order to improve the adhesion to the matrix resin (curable resin or a cured product thereof).

The treatment liquid preferably contains a surfactant. Usable surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants, with nonionic surfactants being preferred. Nonionic surfactants include polyoxyalkylene surfactants, acetylene glycol surfactants, and the like, and acetylene glycol surfactants include surfactants represented by the following chemical formula (3). preferable.

  The treatment liquid may contain a softener, a preservative, an antistatic agent and the like in addition to the above components. Moreover, alcohol, such as methanol, ethanol, and isopropanol, and other organic solvents may be contained in a small amount.

  The content of the water-soluble epoxy resin in the treatment liquid is preferably 1 to 10% by mass, more preferably 2 to 5% by mass based on the total amount of the treatment liquid. Further, the content of the organosilicon compound is preferably 0.1 to 1.0% by mass, and more preferably 0.2 to 0.5% by mass based on the total amount of the treatment liquid. The organosilicon compound is also preferably contained in an amount of 3 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the water-soluble epoxy resin. When a processing liquid contains surface activity, 0.01-0.5 mass% is preferable on the basis of the processing liquid whole quantity, and 0.05-0.2 mass% is more preferable.

  Examples of the method of attaching the treatment liquid to the aromatic polyamide fiber fabric include a method of immersing the aromatic polyamide fiber fabric in the treatment liquid, a method of applying the treatment liquid of the aromatic polyamide fiber fabric (roll coating, spray coating, etc.), and the like. Although it mentions, application methods other than these are also employable. After attaching the treatment liquid of the aromatic polyamide fiber fabric, the excess treatment liquid may be removed by squeezing.

  Next, the moisture removal process will be described. In the present invention, a water removal step is performed after the above-described attachment step. In the moisture removal step, moisture is removed from the treatment liquid adhering to the aromatic polyamide fiber fabric. What is necessary is just to determine the quantity of the water | moisture content to remove suitably according to the processing content after a water | moisture-content removal process. When manufacturing laminates by impregnating with a curable resin after the moisture removal process, remove as much moisture as possible in the moisture removal process to prevent moisture from being taken in during laminate production and causing swelling during curing. It is preferable to do. From such a viewpoint, it is preferable to heat the aromatic polyamide fiber fabric adhered to the treatment liquid at 100 to 140 ° C. What is necessary is just to determine a heating time suitably according to the quantity of the aromatic polyamide fiber fabric heat-processed at once.

  After carrying out the water removal step, the surface of the aromatic polyamide fiber fabric is coated with the nonvolatile component of the treatment liquid, and the weight of the nonvolatile component is 0.2 to 5 parts by mass per 100 parts by mass of the aromatic polyamide fiber fabric. Is preferable, and 0.5 to 2 parts by mass is more preferable. Moreover, it is preferable that 0.01-1.0 mass part (more preferably 0.02-0.5 mass part) is attached as an organosilicon compound, and 0.1-4 mass as a water-soluble epoxy compound. Parts (more preferably 0.5 to 2 parts by mass) are preferably attached. When the value is less than the lower limit, the improvement of the interfacial adhesion with the curable resin when the fiber reinforced resin (laminate) is produced becomes insufficient, and the heat resistance of the fiber reinforced resin (laminate) is insufficient. There is. On the other hand, if the above upper limit is exceeded, when a fiber reinforced resin (laminated plate or the like) is produced, the amount of the non-volatile component present at the curable resin interface is too large, and the heat resistance may decrease.

  Next, the fiber opening process will be described. In this invention, you may implement the fiber opening process which opens an aromatic polyamide fiber fabric before an adhesion process. The opening of the aromatic polyamide fiber fabric is preferably performed by a method suitable for removing the sizing agent, such as water jetting, water flow, or treatment by vibration in water. In general, aromatic polyamide fibers are attached with a sizing agent for weaving, and this is a factor that lowers heat resistance. However, opening the fiber not only makes the fabric uniform but also removes the sizing agent. be able to. As a result, the gaps in the aromatic polyamide fiber fabric are exposed, and as a result, the impregnation property is improved. Therefore, the surface treatment efficiency of the surface-treated aromatic polyamide fiber fabric is increased, and the adhesiveness of the curable resin can be further improved. it can. Thereby, the heat resistance of fiber reinforced resin (laminated board etc.) can be improved more.

  The preferred embodiments of the method for producing the surface-treated aromatic polyamide fiber fabric have been described above. Next, the manufacturing method of the prepreg using the surface treatment aromatic polyamide fiber fabric obtained by the manufacturing method of this invention is demonstrated. A prepreg can be produced by impregnating a curable resin into a surface-treated aromatic polyamide fiber fabric obtained by the above-described production method and semi-curing it if necessary. As the curable resin, conventionally known thermosetting resins and photocurable resins can be used, but epoxy resins, polyimide resins, phenol resins, vinyl ester resins, unsaturated polyester resins, etc., which are thermosetting resins, etc. Is preferably used. When using a thermosetting resin, it is preferable to contain a hardening | curing agent. In addition, as conditions in case a thermosetting resin is semi-hardened by heating, it can be 100-200 degreeC and 1 to 30 minutes, for example.

  Examples of the epoxy resin include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, brominated epoxy resins thereof, novolac type polyglycidyl ether, and the like. In the case of an epoxy resin, a curing agent is usually used in combination. Examples of the curing agent include amine-based, acid anhydride-based, and epoxy-based curing agents. Examples of amine-based curing agents include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, dicyandiamide, 4,4'-methylenedianiline, m-phenylenediamine, and the like. Examples of the acid anhydride curing agent include phthalic anhydride, hexahydrophthalic anhydride, nadic methyl anhydride, dodecyl succinic anhydride, and the like. Furthermore, examples of the epoxy curing agent include butyl glycidyl ether, heptyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether.

  In the case of a polyimide resin, a polyimide resin having an imide skeleton used as a base resin for a printed wiring board can be used. A representative example is Kelimide 601 (trade name, manufactured by RHONE-POULENC). Moreover, in the case of a phenol resin, a novolak type phenol resin, a resol type phenol resin, a hydrocarbon modified phenol resin, a silicone resin modified phenol resin, an epoxy resin modified phenol resin and the like can be mentioned.

  A curable resin varnish can be used as the curable resin. The curable resin varnish means an organic solvent solution of a curable resin. Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and aromatic carbonization such as toluene, xylene, and mesitylene. Hydrogen, alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, carbitol, butyl carbitol, methoxyethyl acetate, ethoxy Esters such as ethyl acetate, butoxyethyl acetate, ethyl acetate, ether acetates such as methyl ether acetate of propylene glycol, N, N- Methylformamide, N, N- dimethylacetamide, a solvent may be used nitrogen-Motorui such as N- methyl-2-pyrrolidone. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In addition, when the curable resin used for a prepreg itself has fluidity | liquidity, it is not necessary to varnish using an organic solvent. In this case, after the surface-treated aromatic polyamide fiber fabric is impregnated with the curable resin, it is preferably semi-cured until the curable resin does not flow.

  Next, the manufacturing method of the laminated board using the prepreg obtained by the manufacturing method of this invention is demonstrated. A laminated board can be obtained by laminating one or more prepregs and curing them. In the prepreg, the curable resin is usually semi-cured, and when a laminated board is obtained, it is further cured and preferably completely cured. Complete curing can be judged by the absence of a peak based on reaction heat when thermal analysis is performed with a differential scanning calorimeter (DSC). This can be achieved by stopping in a state where a peak based on the heat of reaction appears in the analysis. For example, when FR-4 grade epoxy resin is used as the curable resin, complete curing can be achieved by curing at 175 ° C. for about 90 minutes. Thus, the laminated board obtained can be used as a printed wiring board, for example.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. However, the present invention is not limited to these examples, and various modifications can be made without departing from the technical idea of the present invention. Can be changed.

<Preparation of treatment solution>
Aqueous treatment liquids (A) to (C) having mass% shown in Table 1 were prepared and used as treatment liquids. The silane compound used here is an aromatic aminosilane which is a cationic silane, specifically, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane (AY43-038 manufactured by Toray Dow Corning). ). Moreover, EX-313 (made by Nagase ChemteX) was used for the water-soluble epoxy compound. Further, Olphine PD-001 (main component acetylene glycol, manufactured by Nissin Chemical Industry Co., Ltd.) was used as the surfactant.

<Creation of aromatic polyamide fiber fabric>
Using an aromatic polyamide fiber yarn having a count of 21.5 tex as a warp and a weft, weaving into a plain weave with a weft density of 25 warps / 25 mm yielded an aromatic polyamide fiber fabric (1). Prior to weaving, secondary warp processing was performed with an acrylic warp glue to obtain warps.
Subsequently, the aromatic polyamide fiber woven fabric (1) was subjected to fiber opening treatment with spray water having a pressure of 1.5 MPa to obtain an aromatic polyamide fiber woven fabric (2). The yarn width of the aromatic polyamide fiber fabric (1) was warp: 400 to 500 μm, and weft: 550 to 650 μm. The yarn width of the aromatic polyamide fiber fabric (2) was warp: 700 to 750 μm, and weft: 850 to 1050 μm.

<Surface treatment of aromatic polyamide fiber fabric>
(Example 1)
After impregnating the aromatic polyamide fiber woven fabric (1) in the treatment liquid (A), the solution was squeezed and dried at 130 ° C. for 2 minutes to obtain the treated aromatic polyamide fiber woven fabric of Example 1.

(Example 2)
After impregnating the aromatic polyamide fiber woven fabric (2) in the treatment liquid (A), the solution was squeezed and dried at 130 ° C. for 2 minutes to obtain a treated aromatic polyamide fiber woven fabric of Example 2.

(Comparative Example 1)
After impregnating the aromatic polyamide fiber woven fabric (2) in the treatment liquid (B), the solution was squeezed and dried at 130 ° C. for 2 minutes to obtain a treated aromatic polyamide fiber woven fabric of Comparative Example 1.

(Comparative Example 2)
After impregnating the aromatic polyamide fiber fabric (2) in the treatment liquid (B), squeezed and dried at 130 ° C for 2 minutes, then impregnated in the treatment liquid (C), squeezed and dried at 130 ° C for 2 minutes for comparison The treated aromatic polyamide fiber fabric of Example 2 was obtained.

(Comparative Example 3)
The aromatic polyamide fiber fabric (1) was used as the aromatic polyamide fiber fabric of Comparative Example 3.

(Comparative Example 4)
The aromatic polyamide fiber fabric (2) was used as the aromatic polyamide fiber fabric of Comparative Example 4.

<Evaluation of water absorption of surface-treated aromatic polyamide fiber fabric>
1. Amount of coating on the aromatic polyamide fiber fabric (1), the aromatic polyamide fiber fabric (2), and the treated aromatic polyamide fiber fabric of Example 2 were extracted with acetone using a Soxhlet extractor. Then, the adhesion amount of the coating was measured. Each sample was measured at 20 locations, and the average value of the results was obtained. The evaluation results are summarized in Table 2.
2. Measurement of water absorption rate The surface-treated aromatic polyamide fiber fabrics of Examples 1 and 2 and Comparative Examples 1 and 2 and the aromatic polyamide fiber fabrics of Comparative Examples 3 and 4 were placed in an atmosphere of 121 ° C. for 1 hour, before and after The water content was measured to determine the water absorption rate. Each measurement was performed 10 times, and an average value was obtained. The evaluation results are summarized in Table 2.

<Creation of molded body and its evaluation>
The treated aromatic polyamide fiber fabric of each example and the aromatic polyamide fiber fabric of each comparative example were impregnated with FR-4 grade epoxy resin, heated at 130 ° C. for 2 minutes to be semi-cured, and the epoxy resin content was 50 mass. % Prepregs of respective examples and comparative examples were prepared.
Four prepregs were laminated and cured by heating and pressing at 175 ° C. for 90 minutes to obtain molded bodies (laminates) corresponding to the respective examples and comparative examples. 20 pieces of each test piece of the molded body were immersed in a solder bath at 260 ° C. for 1 minute, and bulges and measling on the surface of the test piece were visually observed. The swelling is a phenomenon in which a part of the molded body expands, and the “measuring” is a phenomenon in which a part of the molded body is peeled off mainly due to thermal stress. The evaluation results are summarized in Table 2. In the table, heat resistance was evaluated in four stages from 0 to 3. '0' indicates that the resin was peeled off and could not be evaluated, '1' indicates that a fuzzy measling that would cause a practical problem occurred, and '2' did not cause a practical problem. “3” indicates that there was almost no occurrence of swelling.

  The coating adhesion amount in Comparative Example 3 is the total amount of the primary size and the secondary size of the warp and weft. Moreover, from the comparison of the amount of coating deposits of Comparative Example 3 (without opening process) and Comparative Example 4 (with opening process), the sizing agent was 0.4% by mass (1.1-0.7 by opening process). (Mass%) It can be seen that it was washed away. From a comparison of the amount of coating deposit in Comparative Example 1 (with (B) liquid treatment) and Comparative Example 4 (without (B) liquid treatment), 0.1 mass% (0. (8-0.7% by mass). From the comparison of the coating amount of Example 2 (with (A) liquid treatment) and Comparative Example 4 (without (A) liquid treatment), the non-volatile component of the treatment liquid was 1.2 mass by (A) liquid treatment. % (1.9-0.7% by mass).

  From the heat resistance evaluation results of Examples 1 and 2 (with (A) liquid treatment) and Comparative Examples 1, 2, 3, 4 (without (A) liquid treatment), the heat resistance was improved by (A) liquid treatment. I understand. This is considered to be because the adhesiveness between the aromatic polyamide fiber and the epoxy resin was improved by the liquid treatment (A), and as a result, the water absorption rate of the molded body was reduced and the heat resistance was improved. In addition, from the evaluation results of the heat resistance of Example 1 (without opening process) and Example 2 (with opening process), or Comparative Example 3 (without opening process) and Comparative Example 4 (with opening process), It can be seen that the heat resistance is improved by the opening process. This is presumably because the amount of adhesion of the sizing agent was reduced by the fiber-opening treatment, resulting in a gap in the aromatic polyamide fiber and improved impregnation.

Claims (7)

An attaching step of attaching a treatment liquid containing a water-soluble epoxy compound, an organosilicon compound and water to an aromatic polyamide fiber fabric;
A moisture removal step of removing moisture in the treatment liquid that has adhered,
A method for producing a surface-treated aromatic polyamide fiber fabric.   The manufacturing method of Claim 1 whose adhesion amount of the process liquid after a water | moisture content was removed is 0.2-2 mass parts per 100 mass parts of said aromatic polyamide fiber fabrics.   The manufacturing method according to claim 1 or 2, wherein the water-soluble epoxy compound is a water-soluble polyepoxy compound having an epoxy equivalent of 80 to 200.   The manufacturing method according to any one of claims 1 to 3, further comprising a fiber-opening step of opening the aromatic polyamide fiber fabric before the attaching step.   A surface-treated aromatic polyamide fiber woven fabric obtainable by the production method according to any one of claims 1 to 4.   A method for producing a prepreg, comprising a step of impregnating the surface-treated aromatic polyamide fiber fabric according to claim 5 with a curable resin.   The manufacturing method of a laminated board provided with the process of laminating | stacking one or more prepregs which can be obtained with the manufacturing method of the prepreg of Claim 6, and making it harden | cure.