JP2002220778A - Selvedge-fixed glass cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a selvedge-fixed glass cloth useful for producing high-quality prepregs with high frayproofness and heat resistance, and environmentally favorable. SOLUTION: This selvedge-fixed glass cloth is obtained by coating a given width of each of both the selvedges of a glass cloth with an antioxidant- incorporated polyamide resin for preventing the selvedges from fraying at normal temperatures and even under heating conditions. By the way, since the main solvent of the resin liquid to be used for fixing the selvedges of the glass cloth is water, there occurs no workplace environmental pollution over the total process ranging from its preparation, coating to drying, therefore being also effective from the viewpoint of environmental protection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ear stopper glass cloth provided for use in a printed wiring board and provided with anti-fraying.

[0002]

2. Description of the Related Art A printed wiring board is made by coating a glass cloth with a varnish obtained by dissolving a synthetic resin such as an epoxy resin in an organic solvent such as methyl ethyl ketone, methyl cellosolve, toluene, hexane, acetone and dimethylformamide, drying and heating. The prepreg is manufactured through a heating and pressurizing process to produce a glass-cloth reinforced resin copper-clad laminate, followed by processes such as patterning, through-hole formation, and multilayering.

[0003] In recent years, glass cloth used as a material for printed wiring boards has been woven by fragmentary looms such as air jet looms instead of lyric looms such as fly shuttle looms. The glass cloth woven on a piece loom is characterized by the fact that the weft yarns are driven independently at a fixed length and cut slightly longer than the width of the cloth, so that the "tufts" remain in both ears ing. When the glass cloth having such a tuft is used as it is in the varnish coating process, cost and quality aspects such as excessive infiltration of the varnish by the tuft and sticking of the cut glass fiber to the prepreg surface are reduced. Will cause problems.

Conventionally, in order to prevent the harmful effects of the ears, a thermoplastic resin such as a polyester resin (for example, polybutylene terephthalate, polyethylene terephthalate, etc.) which is hardly soluble in an organic solvent used for the varnish is used. Used as a resin, the chlorine-based solvent solution,
Ear stopper processing is performed in which a fixed width is applied to the inside of a glass tuft, dried, and then cut while leaving a resin applied portion having a fixed width.
Since this method uses a chlorine-based solvent such as methylene chloride, there is a concern that the process environment may be deteriorated and the global environment may be adversely affected.

[0005] In recent years, in order to improve the productivity of prepregs and the performance of printed circuit boards, the amount of organic solvent in varnish has been reduced, the speed of the prepreg coating process, and the drying and heating temperature have been increased. I have. The reduction of the organic solvent in the varnish is accompanied by an increase in the varnish viscosity, and the glass cloth and the varnish may be preliminarily heated in order to reduce coating defects caused thereby. For this reason, the ear stopper resin is required to have a high-viscosity varnish coating, an adhesive property that withstands an increase in stress during varnish coating due to an increase in the coating speed, and a heat-resistant adhesive property that can withstand an increase in the preheating and drying / heating temperature of the prepreg. It has become. In the case of conventionally used polybutylene terephthalate and polyethylene terephthalate resins, such a severe use environment causes a phenomenon that the ear stoppers come off in the prepreg production process.

In order to solve this problem, an attempt has been made to use a thermosetting resin such as an epoxy-based or phenol-based resin as an ear stopper resin (Japanese Patent Laid-Open No. 19191/1992).
0, JP-A-6-2277, JP-A-5-22
2676, JP-A-6-192965, etc.).
However, it takes a considerable amount of time for the resin to cure during the coating process on the glass cloth, and there are problems in equipment and productivity.An organic solvent is required to dissolve the resin, Although it is somewhat reduced in comparison, there is a concern about adverse effects on the environment, and in addition, there is a concern about the risk of fire in the safety of work processes due to its flammability. Further, attempts have been made to cut the tufts or the ground of the glass cloth while melting and bonding the glass thread with a laser beam. However, its adhesive strength is weak, and there is a drawback that the adhesive part is easily peeled off even by a slight ironing, and there is a drawback that the molten ball at the end of the glass thread formed at the time of fusing falls into the varnish. Has not been reached.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a glass cloth which has been subjected to an ear-stopping process, which is preferable from the viewpoint of environmental hygiene and which can cope with the recent severe prepreg production process, and a method for producing the same. The purpose is to:

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polyamide resin containing an antioxidant is effective as an ear stopper resin for glass cloth. Thus, the present invention has been completed. That is, the present invention provides: a) an ear-stopping glass cloth characterized by having a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more is added at an end portion of the glass cloth as an ear-stopping resin. provide. In addition, b) a fixed width of an ear stopper resin solution in which a polyamide resin containing an antioxidant having a melting point of 50 ° C. or more is dissolved or dispersed in a solvent is applied to both ears of the glass cloth or inside thereof, and dried. After that, a method for manufacturing a glass cloth is provided, wherein the ear cloth is cut by cutting the glass cloth while leaving a fixed width of the ear stopper resin in both ear portions. Further, c) the present invention is characterized in that the antioxidant contains an antioxidant comprising a phenol compound. Further, d) the polyamide resin is water-soluble. Also, e) the polyamide resin is a water-dispersion type resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (1) Ear stopper resin The polyamide resin used for the glass cloth of the present invention is not particularly limited. In addition to polycondensation of dicarboxylic acid and diamine, polycondensation of various acid derivatives with amine and lactam can be used. Including ring-opening polymerization, N-carboxy-
Ring-opening polymerization involving decarboxylation of α-amino acid anhydride, hydrogen transfer polymerization of acrylamide, solid-phase peptide synthesis by Merrifield method, anionic polymerization of isocyanate, Ritter polymerization of dinitrile and diester, ethyleneimine and carbon monoxide Resins obtained by copolymerization and the like can be mentioned. In particular, from the viewpoint of environmental health, it is preferable to use a water-soluble or water-dispersible polyamide resin with water as a solvent.

In order to obtain a water-soluble or water-dispersible polyamide resin, generally, an insoluble polyamide resin is made water-soluble. For example, a polyamide resin obtained by (a) ring-opening polymerization of lactam (for example, N-methoxymethylated nylon, N-ethoxymethylated nylon,
N-alkoxymethylated nylon such as N-butoxymethylated nylon) and hydrophilic polymer (acrylic acid, methacrylic acid, hydroxyethyl acrylate, polyethylene glycol monomethacrylate, itaconic acid, acrylamide, N-methylolamide, etc.) (1:
Graft polymerized (at 0.3 weight ratio)
No. 25854) and (a) lactam (for example, ε-
Caprolactam and mixtures thereof with small amounts of other lactams: other lactams include 2-pyrrolidone, δ-valerolactam, enanlactam, η-laurolactam, etc.
And a polyol (for example, a polyol mainly composed of oxyethylene units and having a molecular weight of 100 to 3000: Examples of the polyol include polypropylene glycol, polyoxyethylene / oxypropylene glycol copolymer, polytetramethylene glycol, polycaprolactone diol,
(Polybutadiene diol and its water additive, etc.) and anion-polymerized in the presence of a catalyst (JP-A-61-203128);

(C) Copolyamide prepared by copolymerizing polyalkylene glycol (eg, polyethylene glycol, polypropylene glycol, etc.), ε-caprolamide having a tertiary amino group, N-alkyl having a tertiary amino group in the main chain Copolyamides having urea units obtained by condensing iminobispropylamine and ε-caprolactam, or polyamides having water-solubility such as multi-component copolymerized polyamides (JP-A-59-78239); A) a diamine having a tertiary amino group and / or an oxyethylene group in the main chain [for example, N, N′-bis (γ-aminopropyl) piperazine, N- (β-aminoethyl) piperazine, etc. Monomers containing oxyethylene groups in the main chain, such as monomers containing secondary amino groups, oxyethylene alkylamines, etc. Min] with dicarboxylic acids (such as adipic acid, sebacic acid, etc.) which was allowed polycondensation or more other copolymerizable component (e.g., alpha-pyrrolidone,
α-piperidone, ε-caprolactam, etc.) (JP-A-5-4348).

The water-soluble polyamide resin thus obtained generally has rubber elasticity and is flexible, and the heat resistance and the solvent resistance are remarkably improved as the crosslinking reaction proceeds.
Such a polyamide resin is applied to a portion of the glass cloth to be cut at a constant width. In this case, the polyamide resin is 300 Pa · s or less, preferably 100 Pa
S or less, more preferably from 5 Pa · s to 50 Pa · s with a solvent. If the viscosity of the polyamide resin is 300 Pa · s or more, it is not preferable because the single yarn of the glass cloth is not sufficiently impregnated. As a solvent for lowering the viscosity of the polyamide resin, methylene chloride,
Halogenated lower hydrocarbon solvents such as carbon tetrachloride, chloroform, and trichloroethylene, as well as alcohols, ethers, and ketones are used, but water is used to reduce the effects on the human body or prevent environmental pollution. Is most desirable. On the other hand, use with other resins such as melamine resin, epoxy resin and urethane resin, or use in combination with a curing agent such as citric acid or lactic acid or a curing accelerator therefor is completely acceptable.

(2) Antioxidant The addition of an antioxidant improves the heating stability of the polyamide resin used for the ear stopper resin, and heats the coating and drying of the ear stopper resin liquid in the ear stopper processing on the glass cloth. This has the effect of preventing thermal deterioration of the ear stopper resin in glass cloth preheating and prepreg drying and heating in the prepreg production process. For this reason, it is possible to apply an ear stopper process to the glass cloth that can withstand severe heat and stress. The antioxidant has a melting point of 50 ° C. or higher, preferably 60 ° C. or higher.
Any antioxidant having a temperature of less than 50 ° C., more preferably 90 ° C. or more and less than 200 ° C. can be blended, and can be used alone or in combination with various antioxidants. When the melting point is less than 50 ° C, the glass cloth preheating during prepreg production, due to the heat during heating varnish coating,
Only the antioxidant melts and separates from the ear stopper resin,
The effect of the antioxidant is not sufficiently exhibited.

The antioxidant can be added by a method such as a step of synthesizing a polyamide resin, a step of diluting a solvent, a method of directly mixing the resin liquid after diluting the solvent, and the like. Further, at the time of the addition, an addition method such as adding an antioxidant at room temperature solid, liquid by heat melting, dissolving in an organic solvent in advance, or dispersing in water, etc. is possible, and is not particularly limited. The antioxidant can be used alone or in combination of two or more. In order to improve dispersibility and compatibility with the polyamide resin, an antioxidant having a melting point of less than 50 ° C. is added. If it is 25% by weight or less of the total amount of the antioxidant, it can be added.

As the antioxidant, an antioxidant composed of a phenol compound which captures radicals generated by heating the polyamide resin and causing deterioration is particularly effective (hereinafter referred to as phenolic antioxidant). Other antioxidants include an antioxidant based on an organic sulfur compound (hereinafter referred to as an organic sulfur-based antioxidant) having an effect of decomposing a peroxide accompanying radical oxidation during heating, and an antioxidant based on a phosphorus compound (hereinafter referred to as phosphorus). An antioxidant such as an antioxidant having a lactone structure (a lactone antioxidant) or an antioxidant having a lactone structure can be used.

The phenolic antioxidants which can be used in the present invention include: a) pentaerythritol tetrakis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate],

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B) Thiodioxyethylenebis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

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C) Octadecyl-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate,

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D) N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide],

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E) Diethyl [[3,5-bis (1,1
-Dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate,

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F) 3,3 ′, 3 ″, 5,5 ′, 5 ″ −
Hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol,

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G) Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m
-Tolyl) propionate],

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H) Hexamethylenebis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate],

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I) 1,3,5-tris (3,5-di-
tert-butyl-4-hydroxylbenzyl) -1,
3,5-triazine-2,4,6 (1H, 3H, 5H)
-Trion,

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J) 1,3,5-tris [(4-ter
t-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3
H, 5H) -trione,

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K) 3,9-bis [2- [3- (3-t
tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] 1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane

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L) 2,6-di-tert-butyl-4
-Methylphenol

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M) 2,2'-methylene bis (6-di-tert-butyl-4-methylphenol)

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Examples of the organic sulfur antioxidants include: a) distearyl 3,3'-thiodipropionate

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B) 2-mercaptobenzimidazole

Embedded image Are exemplified.

Examples of the phosphorus antioxidants include: a) Tris (2,4-di-tert-butylphenyl) phosphite

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B) bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid

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C) Tetrakis (2,4-di-tert)
-Butylphenyl) [1,1-biphenyl] -4,4 ′
-Diylbisphosphonite

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D) bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphonite

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E) 10-decyloxy-9,10-dihydro-9-oxa-10-phosphananthrene

Embedded image Are exemplified.

The addition amount of the antioxidant is 0.1% by weight or more and 5.0% by weight or less, preferably 0.2% by weight or more and 3.0% by weight or less based on the polyamide resin. When the amount is less than 0.1% by weight, an antioxidant effect cannot be obtained.

(3) Ear stopper processing of glass cloth As a method of applying the ear stopper resin liquid, a die coater, a spray coater, a roll coater and the like can be mentioned. The coating width is preferably as narrow as the bonding strength allows, but in industrial production, 4 to 10 mm is desirable in consideration of variations. It is important to adjust the application amount so that the resin solid content is 1 to 10% by weight based on the application portion of the glass cloth. At this time, if it is less than 1% by weight, a sufficient effect of preventing fraying cannot be obtained, and if it exceeds 10% by weight, the applied portion becomes thicker than other portions, causing abnormalities such as ear height.

According to the method of the present invention, a polyamide resin containing an antioxidant having a melting point of 50 ° C. or more is applied to both ears of a glass cloth or the inside thereof, and dried, and then applied to both ears. The present invention relates to a method for manufacturing a glass cloth, which comprises cutting the glass cloth while leaving a predetermined width of the ear stopper resin. In the method of the present invention, the glass cloth coated with the ear stopper resin liquid is further dried in a dryer, under the condition that the solvent component contained in the ear stopper resin liquid is heated within a predetermined time. There is no particular limitation as long as it is dried without drying, but for example, 100 to 200 ° C. and 3 to 30 seconds are suitable.

To heat the ear stopper resin liquid applied to the glass cloth, any heating method may be used, and examples thereof include a hot air drying method, an infrared drying method, a microwave drying method, and a cylindrical drying method. Infrared drying and microwave drying are preferred because it is desirable to avoid heating other than the ear stopper. After drying,
A melting step at a temperature of 00 to 300 ° C. may be added.
After the drying and melting processes, the glass cloth is cut with a slitter at a substantially central portion of the applied anti-fraying agent.
As the cutting position, it is desirable to cut the center of the application width, but it is preferable that the center of the application width ± 20% of the application width be taken into account in the industrial production in consideration of the variation. Therefore, the glass cloth after cutting has a width of 7 mm or less, preferably 2 to 5 mm, at both ears.
The ear stopper resin having a width of mm is applied, and the ears including the tuft are removed from the cloth.

The glass cloth of the present invention has a number of warps or wefts per unit length, a thickness, and a weight per unit area,
Those which correspond to the Japanese Industrial Standards (JIS) R-3414 and the United States Military Standards (MIL Standards) are preferred, but not limited thereto, and any ones can be used. For example, the glass fiber may have various component compositions such as S glass, H glass, and D glass in addition to E glass and C glass. Further, a glass cloth having a sizing agent necessary for weaving adhered thereto, a glass cloth having a sizing agent removed therefrom, or a glass cloth having a silane coupling agent or the like already treated by a known surface treatment method. Either may be used. Further, a glass cloth opened by a columnar flow, a high frequency wave, or the like in each of the above steps or any one of the steps may be used. Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[0041]

Example 1 (1) Preparation of an ear stopper resin solution using a polyamide resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ears were prepared. The stop resin solution was adjusted. (2) Addition of antioxidant Pentaerythrol tetrakis [3- (3,5-di-te) which is a phenolic antioxidant as an antioxidant
rt-butyl-4-hydroxyphenyl) propione
G] (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGANOX1010 (registered trademark), melting point 11)
(0 ° C. to 125 ° C.) in an amount of 1.0% by weight of the solid content of the polyamide resin.

(3) Ear stopper processing The ear stopper resin solution was applied to the inside of both ears of the glass cloth with a width of 10 mm along a warp yarn by a roll coater, and then dried at 170 ° C. for 20 seconds. At this time, the adhesion amount of the anti-fraying agent was 3% by weight based on the coated portion of the glass cloth (7628, manufactured by Asahi Schwebel Co., Ltd.). Further, the glass cloth is a glass cloth of the present invention in which a central portion of a coating portion of the applied ear stopper resin liquid is cut with a slitter, and a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more is added is used as an ear stopper resin. I got

[0043]

Example 2 (1) Preparation of Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ears were removed. The stop resin solution was adjusted. (2) Addition of antioxidant N, which is a phenolic antioxidant as an antioxidant,
N'-hexane-1,6-diylbis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionamide] (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGANOX1098 (registered trademark), melting point: 156 ° C. to 161 ° C.), 1.0 wt. % Was added. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0044]

Example 3 (1) Preparation of Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ear was removed. The stop resin solution was adjusted. (2) Addition of antioxidant A phenol-based antioxidant as an antioxidant,
9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer-GA-80 (registered trademark), melting point 110 ° C.) To 120 ° C.) in an amount of 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0045]

Example 4 (1) Preparation of Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ear was removed. The stop resin solution was adjusted. (2) Addition of antioxidant 2-mercaptobenzimidazole (manufactured by Sumitomo Chemical Co., Ltd.) which is an organic sulfur-based antioxidant as an antioxidant
Trade name: Sumilizer-MB (registered trademark), melting point 285 ° C
Was added in an amount of 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0046]

Example 5 (1) Preparation of an Ear Stop Resin Liquid Using Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water to give 10% by weight of ear. The stop resin solution was adjusted. (2) Antioxidant addition Tris (2,2) which is a phosphorus-based antioxidant as an antioxidant
4-di-tert-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: I)
RGAFOS168®, melting point 183 ° C-18
6 ° C.) was added in an amount of 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0047]

Example 6 (1) Preparation of an Ear Stop Resin Liquid Using Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water to obtain 10% by weight of ear. The stop resin solution was adjusted. (2) Addition of antioxidant (A) As an antioxidant, phenol-based antioxidant, pentaerythritoltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione- G] (Ciba Specialty Chemicals Co., Ltd.)
(Trade name: IRGANOX1010 (registered trademark), melting point: 110 ° C. to 125 ° C.); and (B) a phosphorus-based antioxidant, tris (2,4-di-tert-butylphenyl)
Phosphite (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGAFOS168 (registered trademark), melting point: 183 ° C. to 186 ° C.), (A) and (B), (A) :( B) = 2: 1 Was added at a weight ratio of 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0048]

Example 7 (1) Preparation of Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ears were removed. The stop resin solution was adjusted. (2) Addition of antioxidant (A) As an antioxidant, phenol-based antioxidant, pentaerythritoltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione- G] (Ciba Specialty Chemicals Co., Ltd.)
(Trade name: IRGANOX1010 (registered trademark), melting point: 110 ° C. to 125 ° C.), and (B) 2-mercaptobenzimidazole (manufactured by Sumitomo Chemical Co., Ltd.) : (A) and (B) (A) with Sumilizer-MB (registered trademark, melting point 285 ° C. or more):
(B) A combined antioxidant mixed at a weight ratio of 2: 1 was added to 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, a glass cloth of the present invention using a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more was added as an ear stopper resin was obtained.

[0049]

Example 8 (1) Preparation of an Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water, and 10% by weight of ear was removed. The stop resin solution was adjusted. (2) Addition of antioxidant (A) As an antioxidant, phenol-based antioxidant, pentaerythritoltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione- G] (Ciba Specialty Chemicals Co., Ltd.)
(Trade name: IRGANOX1010 (registered trademark), melting point: 110 ° C. to 125 ° C.) and (B) dilauryl 3,3′-thiodipropionate (reagent, melting point: 38 ° C.), which is an organic sulfur-based antioxidant, A) and (B) to (A):
(B) A combined antioxidant mixed at a weight ratio of 4: 1 was added to 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in Example 1, an antioxidant having a melting point of 50 ° C. or more and an antioxidant having a melting point of less than 50 ° C. were used. The glass cloth of the present invention was prepared by mixing the following antioxidants and using the added polyamide resin as an ear stopper resin.

[0050]

[Comparative Example 1] (1) Preparation of an ear stopper resin solution using a polyester resin A polyester resin (Vylon GA-1300 (registered trademark), manufactured by Toyobo Co., Ltd.) was dissolved in trichlorethylene, and 10% by weight of an ear stopper resin was prepared. The liquid was adjusted. (2) Ear stopper processing In the same manner as in (3) of Example 1, a glass cloth using a polyester resin as the ear stopper resin was obtained.

[0051]

[Comparative Example 2] (1) Preparation of an ear stopper resin solution using a polyamide resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water to obtain 10% by weight of ears. The stop resin solution was adjusted. (2) Ear stopper processing In the same manner as in (3) of Example 1, a glass cloth using a polyamide resin to which no antioxidant was added as an ear stopper resin was obtained.

[0052]

[Comparative Example 3] (1) Preparation of an ear stopper resin solution using a polyamide resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water to obtain 10% by weight of ears. The stop resin solution was adjusted. (2) Addition of antioxidant As an antioxidant, a phenolic antioxidant,
6-Di-tert-butyl-4-ethylphenol (reagent, melting point 43 ° C.) was added in an amount of 1.0% by weight of solid polyamide resin. (3) Ear stopper processing In the same manner as (3) of Example 1, a glass cloth using a polyamide resin to which an antioxidant having a melting point of less than 50 ° C. was added as an ear stopper resin was obtained.

[0053]

Comparative Example 4 (1) Preparation of an Ear Stop Resin Liquid with Polyamide Resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water and 10% by weight of ears were prepared. The stop resin solution was adjusted. (2) Addition of antioxidant Triphenylphosphite (reagent, melting point: 15 ° C.), which is a phosphorus-based antioxidant, was added as an antioxidant in an amount of 1.0% by weight of the solid content of the polyamide resin. (3) Ear stopper processing In the same manner as in (3) of Example 1, a glass cloth using a polyamide resin containing an antioxidant having a melting point of less than 50 ° C. as an ear stopper resin was obtained.

[0054]

[Comparative Example 5] (1) Preparation of an ear stopper resin solution using a polyamide resin A water-soluble polyamide resin (Toresin FS-350 (registered trademark), manufactured by Teikoku Chemical Industry Co., Ltd.) was diluted with water to obtain 10% by weight of ears. The stop resin solution was adjusted. (2) Addition of antioxidant dilauryl 3,3'-thiodipropionate (reagent, melting point 38), which is an organic sulfur-based antioxidant as an antioxidant
C) was added in an amount of 1.0% by weight based on the polyamide resin solids. (3) Ear stopper processing In the same manner as (3) of Example 1, a glass cloth using a polyamide resin to which an antioxidant having a melting point of less than 50 ° C. was added as an ear stopper resin was obtained.

[Evaluation of characteristics of ear stopper processing] (a) A tensile tester (Autograph AGS) was used to measure the strength when one warp yarn at the end of the ear stopper of a glass cloth was peeled perpendicular to the warp yarn. -500D, manufactured by Shimadzu Corporation), and the dry ear strength was used as an index of the adhesive force for the ear-stopping process of the normal glass cloth. (B) After immersion in N, N'-dimethylformamide for 5 minutes, air-dried for 12 hours, dry ear strength evaluation glass cloth was measured in the same manner, and it was used as an index of adhesive force at the time of varnish coating of ear closure processing of glass cloth. Wet ear strength.

(C) After heating the glass cloth in an oven at 210 ° C. for 3 minutes, the dry ear strength glass cloth was measured in the same manner, and this was used as an index of the heat resistance deterioration of the adhesive strength of the ear stopper processing of the glass cloth. The ear strength was determined after heating. In addition, the degree of discoloration due to deterioration was visually observed to determine the heat-resistant discoloration. (D) Dry ear strength evaluation A glass cloth was similarly measured under a heating condition of 80 ° C., and the hot ear strength was used as an index of heat resistance of the adhesive strength of the ear stopper processing of the glass cloth. The results are shown in Table 1.

[0057]

[Table 1]

As shown in Table 1, the glass cloth of the present invention in Examples 1 to 8 and the ear-closure glass cloth produced by the method for producing the same were the same as the conventional ear-closure glass cloth of polyester resin of Comparative Example 1. In comparison, adhesive strength, solvent resistance, heat deterioration resistance, and heat resistance are superior, and the use of a chlorine-based solvent reduces adverse effects on the environment. Further, the glass cloth of the present invention of Examples 1 to 8 and the ear-stoppered glass cloth by the manufacturing method thereof were the polyamide resin of Comparative Example 2 to which the antioxidant was not added, and Comparative Examples 3 to 4.
Compared with the ear-closure glass cloth made of a polyamide resin to which an antioxidant having a melting point of less than 50 ° C. is added, an improvement in adhesive strength, which is considered to be due to the prevention of heat deterioration during coating and drying of the ear-closing resin liquid, was observed. Improvements in heat deterioration resistance and heat discoloration, which are considered to be caused by prevention of heat deterioration by post-heating, are also observed.

[0059]

The ear-stop glass cloth of the present invention is superior in adhesive strength and solvent resistance to the ear-stop glass cloth made of the conventional polyester resin, and the ear-stop processed part is removed during the prepreg manufacturing process. There is no. Furthermore, since the ear stopper glass cloth of the present invention is excellent in heat deterioration resistance and heat resistance, the prepreg which is severe in recent years, such as a reduction in the amount of the organic solvent compounded in the varnish, the speed of the prepreg coating process, an increase in the drying heating temperature, etc. Also in the manufacturing process of (1), a defect phenomenon such as a detachment of the ear stopper processed portion does not occur. In addition, in the ear-stopping process, no chlorinated solvent that has an adverse effect on the environment is used, so there is very little adverse effect on the working environment and the global environment, and water can be used as a solvent, so explosions, fires, etc. The danger of is also reduced.

Continued on the front page F term (reference) 3B154 AA13 AB20 BA31 BB31 BD17 BD18 BF01 DA21 4L031 AA26 CA08 DA00 4L033 AA09 AC15 CA55 4L048 AA03 DA43 EB00

Claims (1)

[Claims] 1. An ear-stopping glass cloth comprising a polyamide resin to which an antioxidant having a melting point of 50 ° C. or more is added as an ear-stopping resin at a fixed width at the end of the glass cloth.