JP6388812B2 - Quartz glass fiber sizing agent, quartz glass fiber, quartz glass yarn, and quartz glass cloth - Google Patents

Description

  The present invention relates to a sizing agent for quartz glass fiber, quartz glass fiber or quartz glass yarn and quartz glass cloth coated with the sizing agent, prepreg for printed wiring board, product using the quartz glass fiber, and production of quartz glass cloth. Regarding the method.

  Conventionally, as a glass cloth used for a multilayer printed wiring board, an E glass cloth, a D glass cloth, or the like obtained by weaving E glass fiber, D glass fiber, or the like has been used.

  However, in recent years, as the high-performance mobile terminals such as smartphones and tablet PCs are becoming lighter, thinner, and more multifunctional, multilayer printed wiring boards on which various electronic components are mounted have high-density wiring, excellent high-frequency characteristics, and high multi-layer. Downsizing and thinning are required. Under such a background, there is a strong demand for low thermal expansion, low dielectric constant, and thinning of glass cloth, which is a substrate constituting a printed wiring board.

  For this reason, quartz glass fibers having a low coefficient of linear expansion and a low dielectric constant and dielectric loss tangent are attracting attention among glass fibers. The specific thickness of the quartz glass cloth using the quartz glass fiber is required to be 20 μm or less.

  By the way, glass cloth is generally woven using glass fibers coated with a sizing agent having starch as a main component of a film forming agent. However, in the final process of glass cloth production, silane treatment is performed for the purpose of improving the adhesion to the matrix resin used for the laminate, so if starch remains on the glass cloth, the silane coupling agent and glass The adhesiveness of the cloth deteriorates. In order to prevent this, heating deoiling is usually performed by burning off the sizing agent for starch-based glass fibers at a high temperature for a long time before the silane treatment.

  However, this deoiling process not only entails energy costs, but also damages the glass cloth, so that the strength of the glass cloth is extremely reduced. In particular, this decrease in strength becomes a serious problem in the production of ultrafine glass yarns of 3 to 5 μm and the production of ultrathin glass cloths of 20 μm or less using the same.

  In addition, as described in Patent Document 1, in quartz glass fibers having a silica content of 99% or more, the quartz glass fibers have a lower thermal expansion coefficient than the iron core around which the cloth is wound. It is easy to enter, and the strength reduction due to heat deoiling is more remarkable.

  On the other hand, development of a sizing agent having a synthetic resin that does not require heat deoiling as a main component of a film forming agent has been attempted. The glass fiber sizing agent disclosed in Patent Literature 2 and Patent Literature 3 uses a water-soluble epoxy resin as a main component of the film forming agent. However, since the focusing power is insufficient, a secondary for glass fiber is used. Polyoxyethylene nonyl phenyl ether is used as a sizing agent. Although this agent can improve focusing and soldering heat resistance, it is not desirable to use it because of environmental hormone problems.

  Moreover, the sizing agent for glass fibers disclosed in Patent Document 4 and Patent Document 5 uses a water-soluble urethane resin and a water-soluble epoxy-modified product as the main component of the film forming agent, but the film formation is insufficient. For this reason, fluff cannot be suppressed, and the strength of the resulting quartz glass cloth is not satisfactory. Further, when a water-soluble epoxy resin is used, since it has an epoxy group with high reactivity, a part of the reaction with the silane coupling agent added to the glass fiber sizing agent occurs, and the yarn quality changes. In addition, when water-soluble epoxy resin is used, the yarn tends to harden. When applied to hard quartz glass fiber, the flexibility is insufficient, and the filament breaks at the intersection of the warp and weft of the quartz glass cloth. Will occur.

The chargeability of quartz glass can be cited as a cause of insufficient strength caused by insufficient film formation when a conventional glass fiber sizing agent is applied to quartz glass cloth. A multi-component glass such as E glass used as a general-purpose product is electrically conductive in a molten state, and is also hardly charged because it is spun from a platinum-based nozzle during spinning. In addition, it is disclosed in Patent Document 6 that electric conductivity is exhibited in a molten state even in an alkali-free glass having an alkali metal oxide (Li ₂ O, Na ₂ O, K ₂ O) of 0.2% by weight or less. It is clear from the fact that is used.

  On the other hand, quartz glass does not contain any ionic conductive species such as alkali metals, and has a low electrical conductivity even in a melt-softened state and is easily charged. In fact, quartz glass is spun using a known method such as Patent Documents 7 to 9, and at that time, the charging potential is remarkably -2.0 kV or more due to friction with a flame flow, flow friction inside the glass, and the like. Quartz glass fiber is negatively charged.

  By the way, in Patent Document 10, it is ideal that the charging potential of the glass fiber bundle and the glass fiber fabric in the weaving process is controlled to be ± 0 kV. However, these charging potentials depend on variations in temperature and humidity. In general, since there is a tendency to largely fluctuate to the minus side, it is more stable if the central value of the charging potential is controlled in advance to be slightly on the plus side, more specifically, +1.5 kV to -1.0 kV. There is a description that it can be operated.

  However, in the case of quartz glass fiber, since it tends to be remarkably negatively charged as described above, it is difficult to keep the charged potential in the range of +1.5 kV to -1.0 kV with the conventional nonpolar film forming agent. It is considered that the coating was not sufficiently covered and the strength was lowered.

Japanese Patent Publication 8-18853 JP-A-9-268034 JP-A-9-67757 JP-A-9-209233 JP2007-162171 JP-A-2005-132713 JP 2006-282401 JP 2004-99377 A JP 61-258043 JP2007-153706

  The present invention solves the above problems found in conventional sizing agents for glass fibers. In other words, it suppresses the charging of quartz glass fiber, can provide the focusing power necessary for weaving without using a secondary sizing agent for glass fiber, and can be used even in the pH range of 1 to 5 where heating deoiling is unnecessary. Stable sizing agent for quartz glass fiber, quartz glass fiber or quartz glass yarn and quartz glass cloth coated with the sizing agent, prepreg for printed wiring board, product using the quartz glass fiber, and production of quartz glass cloth It aims to provide a method.

  The sizing agent for quartz glass fibers of the present invention is composed of an aqueous solution containing a cationic water-soluble urethane resin, a cationic silane coupling agent, and a cationic softening agent, and has a pH of 1 to 5.

  The quartz glass fiber of the present invention is formed by applying the sizing agent for quartz glass fiber.

  In this specification, the quartz glass fiber refers to a thin thread-like shape obtained by stretching quartz glass, and quartz glass filaments, quartz glass strands, quartz glass yarns, quartz glass wool, and the like are obtained from the quartz glass fibers. Further, in this specification, a single fiber is defined as a quartz glass filament, a bundle of quartz glass filaments is defined as a quartz glass strand, and a bundle of quartz glass filaments that is twisted is defined as a quartz glass yarn.

  The quartz glass yarn of the present invention is formed by applying the sizing agent for quartz glass fibers.

  It is preferable that the quartz glass yarn is composed of quartz glass fibers made of quartz glass filaments having a diameter of 3 to 8 μm.

  It is preferable that the charged potential of the quartz glass yarn is +1.5 to -1.0 kV.

  The quartz glass cloth of the present invention includes the quartz glass yarn. The quartz glass cloth can be manufactured by weaving the quartz glass yarn.

  The prepreg for printed wiring boards of the present invention includes the quartz glass cloth. The printed wiring board prepreg can be manufactured by impregnating the quartz glass cloth with a synthetic resin.

  The quartz glass fiber product of the present invention includes the quartz glass fiber.

  The method for producing a quartz glass cloth of the present invention is a method for producing a quartz glass cloth using the quartz glass yarn coated with the sizing agent for quartz glass fiber, wherein the quartz glass yarn coated with the sizing agent for quartz glass fiber is used. This is a method in which heat deoiling is not performed after weaving. Therefore, in the method for producing a quartz glass cloth according to the present invention, since heat deoiling is not performed, strength reduction due to heat deoiling does not occur.

  According to the present invention, it is possible to suppress the charging of quartz glass fiber, and to impart a focusing force necessary for weaving without using a glass fiber secondary sizing agent, and to eliminate the need for heat deoiling. A chemically stable sizing agent for quartz glass fiber, a quartz glass fiber coated with the sizing agent or a quartz glass yarn and a quartz glass cloth, a prepreg for a printed wiring board, a product using the quartz glass fiber, and quartz There is a remarkable effect that a method for producing a glass cloth can be provided.

It is typical explanatory drawing which shows roughly one embodiment of the method of manufacturing the quartz glass filament used for this invention.

  The cationic water-soluble urethane resin used in the present invention is not particularly limited as long as it is a water-soluble urethane resin having a cationic site in its structure.

  The water-soluble urethane resin having a cation moiety in the structure means having a positively charged moiety in the water-soluble urethane resin molecular structure, and can be produced, for example, by the following method. That is, a part of the tertiary amine of the urethane prepolymer composed of polyisocyanate and polyester polyol or polyether polyol or polycarbonate polyol and a chain extender having a tertiary amino group in the molecular structure is neutralized with acid or 4 A cationic water-soluble polyurethane resin is obtained by subjecting a cationic prepolymer quaternized with a secondary amine agent to chain extension using water or a polyamine compound. Polyester polyol, polyether polyol, and polycarbonate polyol can be used alone or in combination of two or more.

  As the polyisocyanate, polyisocyanates such as aliphatic, alicyclic, aromatic, and araliphatic can be used.

  The aliphatic polyisocyanate is not particularly limited, and examples thereof include tetramethylene diisocyanate, hexamethylene dicyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and trimethylhexamethylene dicyanate. These aliphatic polyisocyanates can be used alone or in combination of two or more.

  The alicyclic polyisocyanate is not particularly limited. For example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis ( And isocyanatomethyl) cyclohexane. These alicyclic polyisocyanates can be used alone or in combination of two or more.

  The aromatic polyisocyanate is not particularly limited. For example, tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, xylylene diisocyanate, 1 , 4-phenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate and the like. These aromatic polyisocyanates can be used alone or in combination of two or more.

  The aromatic aliphatic polyisocyanate is not particularly limited, and examples thereof include dialkyldiphenylmethane, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate. These araliphatic polyisocyanates can be used alone or in combination of two or more.

  Polyester polyol is not particularly limited, but for example, polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, poly -Ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate, 1,6-hexanediol and dimer acid polycondensate, 1,6-hexanediol, adipic acid and dimer acid copolycondensation Products, polycondensates of nonanediol and dimer acid, and copolycondensates of ethylene glycol, adipic acid and dimer acid. These polyester polyols can be used alone or in combination of two or more.

  The polyether polyol is not particularly limited. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol homopolymer, block copolymer, random copolymer, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random Examples thereof include a copolymer and a block copolymer. These polyether polyols can be used alone or in combination of two or more.

  The polycarbonate polyol is not particularly limited, and examples thereof include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, and 1,6-hexanediol carbonate polyol. These polycarbonate polyols can be used alone or in combination of two or more.

  The chain extender having a tertiary amino group in the molecular structure used for introducing the tertiary amino group is not particularly limited, and examples thereof include N-alkyl dialkanolamine, N-alkyldiaminoalkylamine and the like. Can be mentioned. These chain extenders having a tertiary amino group can be used alone or in combination of two or more.

  A cationic urethane prepolymer is produced by neutralizing part of the tertiary amino group introduced by the chain extender with an acid or quaternizing with a quaternizing agent.

  The acid used when neutralizing a part of the tertiary amino group with an acid is not particularly limited. For example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, malic acid, malonic acid, adipic acid, etc. Examples include organic acids and inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and the like. These acids can be used alone or in combination of two or more.

  Although it does not specifically limit as a quaternizing agent used in order to quaternize a part of tertiary amino group with a quaternizing agent, For example, an alkyl halide, a dialkyl sulfuric acid, etc. are mentioned. These quaternizing agents can be used alone or in combination of two or more.

  Next, a cationic water-soluble urethane resin is obtained by dispersing the cationic urethane prepolymer in which some of the tertiary amino groups are neutralized or quaternized in water and performing chain extension with a polyamine compound. Can do.

  Although it does not specifically limit as a polyamine compound, For example, it has 2 or more amino groups, such as hydrazides, such as ethylenediamine, propylenediamine, hexylenediamine, tetraethylenepentamine, isophoronediamine, piperazine, hydrazine, adipic acid dihydrazide Compounds.

  Examples of the cationic water-soluble urethane resin include Parazole PC-88 (manufactured by Ohara Palladium Chemical Co., Ltd.), Superflex 600, Superflex 610, Superflex 620, Superflex 650, Elastron M1064 (Daiichi Kogyo Seiyaku), TR-420. , TR-440, TR-2000 (manufactured by Kao), Brian UK-200, Brian WET-09 (manufactured by Matsumoto Yushi), Hydran CP-7020, Hydran CP-7030, Hydran CP-7040, Hydran CP-7050 (manufactured by DIC) ), Hair roll UC-4 (manufactured by Sanyo Kasei) and the like are commercially available.

  The blending ratio of the cationic water-soluble urethane resin to the sizing agent is not particularly limited, but for example, 0.01 to 50% by weight may be mentioned with respect to 100% by weight of the sizing agent for quartz glass fiber. , Preferably 0.01 to 30% by weight, more preferably 0.01 to 20% by weight.

  The cationic silane coupling agent used in the present invention is not particularly limited as long as it is an organic silicon compound that exhibits a cationic system and has a condensation reactive group. For example, from the viewpoint of heat resistance, N- (vinylbenzyl) ) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and the like.

  The blending ratio of the cationic silane coupling agent to the sizing agent is not particularly limited. Examples thereof include 0.01 to 5% by weight with respect to 100% by weight of the sizing agent for quartz glass fibers. , Preferably 0.01 to 3% by weight, more preferably 0.01 to 2% by weight.

  The cationic softening agent used in the present invention is not particularly limited, and examples of the softening agent include amide or imidazoline obtained by reacting tetraethylenepentamine and stearic acid.

  The blending ratio of the cationic softening agent to the sizing agent is not particularly limited, and for example, 0.01 to 10% by weight is preferable with respect to 100% by weight of the total amount of sizing agent for quartz glass fiber, preferably Is 0.01 to 5% by weight, more preferably 0.01 to 3% by weight.

  The sizing agent for quartz glass fibers of the present invention has a pH of 1 to 5, more preferably 1 or more and less than 3. A pH greater than 5 is not preferable because the stability of the hydrolysis state of the cationic silane coupling agent is deteriorated. When the pH is in the range of 1 or more and less than 3, the dehydration condensation reaction between the cationic silane coupling agent and the quartz glass fiber is more likely to proceed. Strength and solder heat resistance are improved. On the other hand, if the pH is less than 1, the surface of the quartz glass is eroded, and the strength of the quartz glass fiber may be weak, which is not preferable.

  Although it does not specifically limit as an acid used in order to make it fall in the range of the said pH 1-5, For example, organic acids and hydrochloric acid, such as formic acid, an acetic acid, propionic acid, a butyric acid, lactic acid, malic acid, malonic acid, adipic acid, hydrochloric acid, Examples include inorganic acids such as nitric acid and phosphoric acid.

  The sizing agent for quartz glass fibers of the present invention may contain other components other than the above cationic water-soluble urethane resin, cationic silane coupling agent, and cationic softening agent as long as the effects of the present invention are not impaired. it can. Examples of other components include lubricants, emulsifiers, preservatives, and the like. In addition, a small amount of alcohol such as methanol, ethanol, isopropanol or other organic solvent may be added to the sizing agent for quartz glass fiber of the present invention.

  The quartz glass fiber of the present invention has a pH of 1 to 5 and is coated with a quartz glass fiber sizing agent characterized by containing a cationic water-soluble urethane resin, a cationic silane coupling agent, and a cationic softening agent It is. Thereby, the charged potential of the quartz glass fiber can be stored in the range of +1.5 kV to -1.0 kV, and a focusing force necessary for weaving can be imparted without using a secondary sizing agent for glass fiber, and Heat deoiling can be omitted.

  As a method of attaching the sizing agent for quartz glass fiber of the present invention to the quartz glass fiber, a known method can be applied. For example, a dipping method, a roller type or belt type applicator, a spraying method, and the like can be given.

  The quartz glass cloth of the present invention has a charging potential in the range of +1.5 kV to -1.0 kV, does not require a secondary sizing agent for glass fibers, and is intended to suppress fuzz and improve heat resistance. It is preferable to contain the glass yarn of this, and it is more preferable to consist only of the glass yarn of this invention.

  The woven structure, woven density and the like of the quartz glass cloth of the present invention are not particularly limited, and examples of the woven structure include plain weave, satin weave, Nanako weave, twill weave and the like. Moreover, as a woven density, 10-150 piece / 25mm is mentioned, for example.

  The method for weaving the quartz glass cloth of the present invention is not particularly limited, and examples thereof include an air jet loom, a water jet loom, a rapier loom, and a shuttle loom.

  The quartz glass cloth of the present invention may be washed with water or opened as necessary. Heat deoiling is performed for the purpose of completely removing the silica glass fiber sizing agent adhering to the surface of the quartz glass cloth, while water washing is intended to remove only the silica glass fiber sizing agent adhering excessively to the surface of the quartz glass cloth. Done in Compared to heat deoiling in which the glass cloth is treated at a high temperature for a long period of time, washing with water is a process at a low temperature, so that a decrease in strength of the quartz glass cloth can be suppressed.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

  Measurement and evaluation in the following examples and comparative examples were performed by the following methods.

1. PH of sizing agent for quartz glass fiber
The pH of the sizing agent for quartz glass fibers was measured using a pH meter D-51 manufactured by HORIBA, Ltd. and a pH electrode 9625-10D manufactured by HORIBA, Ltd.

2. Focusing force of glass yarn Using DI-200, a DI type yarn friction conjugation force tester manufactured by Daiei Kagaku Seiki Seisakusho, with a yarn crossing angle of 30 °, a reciprocating speed of 150 rpm, and a load of 50 g. It was confirmed visually. In this example, “◯” or more was regarded as acceptable.
<Evaluation criteria>
No breakage of yarn ... ◎
There are some yarn cracks ...
Yarn cracking small ... △
Yarn cracking size, fluff ... ×
In the above evaluation criteria, the yarn cracking as a whole and the degree of cracking being small is defined as “low yarn cracking”, and the yarn cracking as a whole and the degree of cracking is large as “yarn cracking large”. It was.

3. Charging potential of glass yarn Static electricity measuring device STATILON DX-01 made by SHICIDO static electricity Co., Ltd. was set at a distance of 5 cm from the bobbin, and the bobbin charging potential was measured while continuously flying the yarn with an air pressure of 0.1 MPa. .

4). Tensile strength of glass cloth Measured according to JIS R 3420 2013 7.4.2.

5. Loss on ignition of glass yarn and glass cloth Measured and calculated according to JIS R 3420 2013 7.3.2.

6). Fluff of glass cloth While applying side light to the glass cloth, the range of 3 mm square was visually confirmed with an optical microscope at five places, and the number of fluff was measured.

7). Solder heat resistance of glass cloth The glass cloth was immersed in an epoxy resin varnish, and the varnish-coated glass cloth was dried in a hot air dryer at 150 ° C. for 5 minutes to obtain a prepreg. Next, the glass cloth / epoxy resin composite sheet was obtained by heating and curing at 170 ° C. for 90 minutes. A test piece cut out to 5 cm × 5 cm from the composite sheet was subjected to moisture absorption heat treatment (1.05 kg / cm ² (G), 121 ° C.) for a predetermined time using a pressure cooker, and then immersed in water at 25 ° C. for 15 minutes. Thereafter, the test piece was dipped in a solder bath at 260 ° C. for 25 seconds, and after pulling up, excess solder stuck to the test piece was scraped off to obtain the same form as before solder dipping. The surface of the test piece from which the solder was shaved was visually observed to evaluate the heat resistance. In this example, “◯” or more was regarded as acceptable.
<Evaluation criteria>
Small interfacial peeling ・ ・ ・ ◎
Interfacial peeling ... ○
Full surface peeling ・ ・ ・ ×

[Composition of varnish]
Epoxy resin: jER5046B80 manufactured by Mitsubishi Chemical Corporation 100 parts by weight Curing agent: Dicyandiamide manufactured by Kanto Chemical Co., Ltd. 3.2 parts by weight Accelerator: N, N-dimethylbenzylamine manufactured by Kanto Chemical Co., Ltd. 0.2 parts by weight Diluting solvent: 30 parts by weight of dimethylformamide manufactured by Kanto Chemical Co., Inc.

Example 1
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, acetate softener of polyethylenepentamine and stearic acid as cationic softening agent 0.4% by weight, and other components 0.06% by weight lauryldimethylethylammonium ethyl sulfate, polyethyleneimine Was prepared, and a sizing agent for quartz glass fiber containing 0.1% by weight of hydrochloric acid, 3.6% by weight of hydrochloric acid, and the remainder comprising water was prepared. The pH of the sizing agent for quartz glass fibers was measured using the sizing agent for quartz glass fibers.

  In the state schematically shown in FIG. 1, a quartz glass fiber made of a quartz glass filament having a diameter of 4 μm is introduced into the nozzle of the burner 1 by introducing a quartz glass material 2 which is a quartz glass fiber having a diameter of 0.2 mm and heating and stretching. 3 was produced. Then, the quartz glass fiber sizing agent shown in Example 1 was applied to each quartz glass fiber by the applicator 4, then focused by the sizing machine 5, wound by the winder 6, and quartz having 50 quartz glass filaments. Glass strand 7 was produced. The wound quartz glass strand 7 was twisted once per 25 mm to produce a quartz glass yarn having a count of 1.38 tex. Measurement of the focusing force, charging potential and loss on ignition of the quartz glass yarn was performed using the quartz glass yarn.

  Warping was performed using the obtained quartz glass yarn, and beaming was performed without applying the secondary sizing agent for glass fiber to obtain a warp beam. The obtained warp beam was set on an air jet loom, and a quartz glass cloth of plain weave having a warp density of 95/25 mm and a weft density of 95/25 mm was obtained using the quartz glass yarn obtained as the weft. .

  The obtained quartz glass cloth was washed with water and opened. The quartz glass cloth was measured for tensile strength, loss on ignition, fluff and solder heat resistance.

(Example 2)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a cationic softening agent, 0.06% by weight of octyldimethylethylammonium ethyl sulfate as another component, polyethyleneimine A sizing agent for quartz glass fiber containing 0.1% by weight, 30% by weight of acetic acid and the balance being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Example 3)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, 0.4% by weight of the acetate of a condensation product of polyethylenepentamine and stearic acid as a cationic softening agent, 0.46% by weight of stearyltrimethylammonium chloride as other components, and 0% of polyethyleneimine A sizing agent for quartz glass fiber containing 1% by weight, 4% by weight of acetic acid, and the remainder being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Example 4)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, 0.4% by weight of acetate of a condensation product of polyethylenepentamine and stearic acid as a cationic softening agent, 0.46% by weight of distearyldimethylammonium chloride as other components, and polyethyleneimine A sizing agent for quartz glass fiber containing 0.1% by weight, 4% by weight of acetic acid, and the remainder being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Example 5)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a cationic softening agent, 0.46% by weight of laurylmethylammonium chloride as the other component, and 0% of polyethyleneimine A sizing agent for quartz glass fiber containing 1% by weight, 0.15% by weight of acetic acid, and the balance being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Example 6)
The sizing agent for quartz glass fiber of Example 2 was prepared. The pH of the sizing agent for quartz glass fibers was measured using the sizing agent for quartz glass fibers.

  In the state schematically shown in FIG. 1, a quartz glass material 2 which is a quartz glass fiber having a diameter of 0.2 mm is introduced into the nozzle of the burner 1 and is heated and stretched to produce quartz made of a quartz glass filament having a diameter of 3.5 μm. Glass fiber 3 was produced. Then, after applying the glass fiber sizing agent shown in Example 6 to each quartz glass fiber with the applicator 4, the glass fiber is focused by the sizing machine 5, wound by the winder 6, and the quartz glass strand having 50 single fibers. 7 was produced. The wound quartz glass strand 7 was twisted once per 25 mm to produce a quartz glass yarn having a count of 1.07 tex. Measurement of the focusing force, charging potential and loss on ignition of the quartz glass yarn was performed using the quartz glass yarn.

  Warping was performed using the obtained quartz glass yarn, and beaming was performed without applying the secondary sizing agent for glass fiber to obtain a warp beam. The obtained warp beam was set on an air jet loom, and a quartz glass cloth of plain weave having a warp density of 105/25 mm and a weft density of 105/25 mm was obtained using the quartz glass yarn obtained as the weft. .

  The obtained quartz glass cloth was washed with water and opened. The quartz glass cloth was measured for tensile strength, loss on ignition, fluff and solder heat resistance.

(Example 7)
The sizing agent for quartz glass fiber of Example 2 was prepared. The pH of the sizing agent for quartz glass fibers was measured using the sizing agent for quartz glass fibers.

  In the state schematically shown in FIG. 1, a quartz glass material 2 which is a quartz glass fiber having a diameter of 0.3 mm is introduced into the nozzle of the burner 1 and is heated and stretched to produce quartz composed of a quartz glass filament having a diameter of 7.3 μm. Glass fiber 3 was produced. Then, the glass fiber sizing agent shown in Example 7 was applied to each quartz glass fiber by the applicator 4, and then focused by the squeezing machine 5, wound up by the winder 6, and quartz glass filaments having 200 quartz glass filaments. Strand 7 was produced. The wound quartz glass strand 7 was twisted once per 25 mm to produce a quartz glass yarn having a count of 18.4 tex. Measurement of the focusing force, charging potential and loss on ignition of the quartz glass yarn was performed using the quartz glass yarn.

  Warping was performed using the obtained quartz glass yarn, and beaming was performed without applying the secondary sizing agent for glass fiber to obtain a warp beam. The obtained warp beam was set on an air jet loom and a plain glass quartz glass cloth having a warp density of 65/25 mm and a weft density of 62/25 mm was obtained using the quartz glass yarn obtained as the weft. .

  The resulting quartz glass cloth was not washed with water and opened. The quartz glass cloth was measured for tensile strength, loss on ignition, fluff and solder heat resistance.

  Table 1 shows the results obtained in Examples 1-7.

(Comparative Example 1)
1.2% by weight of high amylose corn starch, 2.8% by weight of regular corn starch, 0.8% by weight of beef tallow, 0.08% by weight of polyoxyethylene alkyl ether, a condensate of polyethylene pentamine and stearic acid 0.24 wt% acetate, 0.24 wt% distearyldimethylammonium chloride, 0.1 wt% N-2- (aminoethyl) -3-aminopropylmethoxysilane, 0.01% preservative Then, a sizing agent for quartz glass fiber, the remainder being water, was prepared. The pH of the sizing agent for quartz glass fibers was measured using the sizing agent for quartz glass fibers.

  In the state schematically shown in FIG. 1, a quartz glass fiber made of a quartz glass filament having a diameter of 4 μm is introduced into the nozzle of the burner 1 by introducing a quartz glass material 2 which is a quartz glass fiber having a diameter of 0.2 mm and heating and stretching. 3 was produced. Then, after applying the glass fiber sizing agent shown in Comparative Example 1 to each quartz glass fiber by the applicator 4, the glass fiber sizing agent is focused by the sizing machine 5, wound by the winder 6, and the quartz glass strand having 50 quartz glass filaments. 7 was produced. The wound quartz glass strand 7 was twisted once per 25 mm to produce a quartz glass yarn having a count of 1.38 tex. Measurement of the focusing power, charging potential and loss on ignition of the glass yarn was performed using the glass yarn.

  Warping was performed using the obtained quartz glass yarn, a secondary sizing agent for starch-based glass fibers was applied, and beaming was performed while drying to obtain a warp beam. The obtained warp beam was set on an air jet loom, and a quartz glass cloth of plain weave having a warp density of 95/25 mm and a weft density of 95/25 mm was obtained using the quartz glass yarn obtained as the weft. .

  The obtained quartz glass cloth was subjected to heat deoiling and fiber opening treatment, and further silane treatment. Measurements of tensile strength, loss on ignition, fluff and solder heat resistance of the quartz glass cloth were evaluated using the quartz glass cloth.

(Comparative Example 2)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, 0.45% by weight of N-2- (aminoethyl) -3-aminopropylmethoxysilane as the aminosilane coupling agent, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a softening agent, 0.46% by weight of laurylmethylammonium chloride, 0.1% by weight of polyethyleneimine, and 0% of acetic acid A sizing agent for quartz glass fiber containing 15% by weight and the balance being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Comparative Example 3)
2% by weight of Superflex 500 (Daiichi Kogyo Seiyaku) as a nonionic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as a cationic silane coupling agent 0.45% by weight, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a cationic softening agent, 0.06% by weight of octyldimethylethylammonium ethyl sulfate as another component, polyethyleneimine A sizing agent for quartz glass fiber containing 0.1% by weight, 30% by weight of acetic acid and the balance being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Comparative Example 4)
2% by weight of Superflex 600 (Daiichi Kogyo Seiyaku) as the cationic water-soluble urethane resin, and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as the cationic silane coupling agent 0.45% by weight, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a cationic softening agent, 0.06% by weight of octyldimethylethylammonium ethyl sulfate as another component, polyethyleneimine The sizing agent containing 0.1% by weight and 0.02% by weight of acetic acid and the remainder being water was prepared, but the sizing agent was not stable and could not be applied uniformly.

(Comparative Example 5)
2% by weight of Adeka Resin EM-0436F (made by ADEKA) as a cationic water-soluble epoxy resin, and 0% of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as a cationic silane coupling agent .45% by weight, 0.4% by weight of a condensate of polyethylenepentamine and stearic acid as a cationic softening agent, 0.06% by weight of octyldimethylethylammonium ethyl sulfate, and 0% of polyethyleneimine A sizing agent for quartz glass fiber containing 1% by weight, 30% by weight of acetic acid and the balance being water was prepared. Other than that was carried out similarly to Example 1, and obtained the quartz glass cloth.

(Comparative Example 6)
The sizing agent for quartz glass fiber of Example 2 was prepared. An E glass cloth was obtained in the same manner as in Example 1 except that this was applied to an E glass yarn composed of an E glass filament having a diameter of 4 μm.

  Table 2 shows the results obtained in Comparative Examples 1-6.

  The quartz glass yarn obtained in Examples 1 to 7 has a pH of 1 to 5, and a sizing agent for quartz glass fibers containing a cationic water-soluble urethane resin, a cationic silane coupling agent, and a cationic softening agent. Because it is coated, the charged potential of quartz glass fiber is within the range of +1.5 kV to -1.0 kV, and it has sufficient focusing force required for weaving without using a secondary sizing agent for glass fiber. Met. Moreover, since the quartz glass cloth obtained by weaving this quartz glass yarn does not require heat deoiling, it has a higher strength than the comparative example 1 using the conventional sizing agent for starch-based glass fibers. In particular, since the quartz glass yarn pH obtained in Examples 1 to 3 is 1 or more and less than 3, the charged potential becomes around ± 0 kV because the cationic silane coupling agent and the quartz glass fiber are firmly bonded. Fluffing during weaving could be effectively suppressed, and a quartz glass cloth with higher cross strength could be obtained. Furthermore, N-2- (aminoethyl)-, which is an aminosilane coupling agent, is obtained by using N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride as a cationic silane coupling agent. Better heat resistance than Comparative Example 2 using 3-aminopropylmethoxysilane was obtained.

  On the other hand, since the glass yarn coated with the glass fiber sizing agent of Comparative Example 3 using a nonionic urethane resin was negatively charged, the sizing power of the yarn deteriorated, and fluff generation during weaving could not be suppressed. It was. Since the pH of the sizing agent for quartz glass fibers of Comparative Example 4 was 5 or more, a stable sizing agent for quartz glass fibers could not be obtained, and uniform coating could not be performed. Since the glass yarn coated with the glass fiber sizing agent of Comparative Example 5 using a cationic epoxy resin was hard, it was poor in flexibility and could not suppress the occurrence of fluff during weaving. In Comparative Example 6 in which the sizing agent for quartz glass fiber was applied to the E glass yarn, the pH was as low as 1 or more and less than 3, so the E glass fiber was damaged and the strength was lowered.

1: Burner, 2: Quartz glass material, 3: Quartz glass fiber, 4: Applicator, 5: Focusing machine, 6: Winding machine, 7: Quartz glass strand.

Claims (9)

  A sizing agent for quartz glass fibers comprising an aqueous solution containing a cationic water-soluble urethane resin, a cationic silane coupling agent, and a cationic softening agent, and having a pH of 1 to 5.   A quartz glass fiber obtained by applying the sizing agent for quartz glass fiber according to claim 1.   A quartz glass yarn coated with the sizing agent for quartz glass fibers according to claim 1.   The quartz glass yarn according to claim 3, wherein the quartz glass yarn is composed of quartz glass fibers made of quartz glass filaments having a diameter of 3 to 8 µm.   The quartz glass yarn according to claim 3 or 4, wherein a charging potential of the quartz glass yarn is +1.5 to -1.0 kV.   A quartz glass cloth comprising the quartz glass yarn according to any one of claims 3 to 5.   A prepreg for a printed wiring board comprising the quartz glass cloth according to claim 6.   A quartz glass fiber product comprising the quartz glass fiber according to claim 2.   A method for producing a quartz glass cloth using a quartz glass yarn coated with the sizing agent for quartz glass fibers according to claim 1, comprising weaving with the quartz glass yarn coated with the sizing agent for quartz glass fibers, A method for producing quartz glass cloth in which no oil is used.

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