JPH0826779A - Production of glass fiber treating agent - Google Patents

Abstract

PURPOSE:To produce the treating agent with which the affinity of glass fiber for a composite material consisting of synthetic resins, etc., can be enhanced and thereby, the glass fiber is provided with an excellent improving effect on material quality by esterifying a polymerizable monomer contg. a phosphate group with an epoxy resin and then, cololymerizing the esterification reaction product with another polymerizable monomer. CONSTITUTION:In this production, a polymerizable monomer contg. a phosphate group is esterified in an amount to provide a 0.1 to 25wt.% ratio to the amount of the final copolymer with an epoxy resin which has a number average molecular weight of about >=900 and is present in an organic solvent in a ratio by weight to the amount of the polymerizable monomer contg. a phsphate group of 2:1 to 1:10. Thereafter, the esterification reaction product is copolymerized with a 9 to 91wt.% in terms of polymeric solid matter of a reactive emulsifier or polymerizable monomer contg. a carboxyl group based on the amount of the final copolymer. Preferably, then, an amono resin is mixed into the resulting polymer solution in a >=5 pts.wt. ratio to 100 pts.wt. of the raw material epoxy resin. The polymer organic solvent solution thus produced as it is or an aqueous liquid dispersion obtained by dispersing this polymer solution in water is used as the objective glass fiber treating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glass fiber treating agent, and more specifically, to various laminated boards for electrical insulation including printed circuit boards, reinforced plastics, reinforced cements, filtration materials, sound absorbing materials, and heat insulation. The present invention relates to a method for producing a glass fiber treating agent capable of increasing the affinity of a glass fiber used as a material or the like with a synthetic resin or other composite material or obtaining an excellent treatment efficiency.

[0002]

BACKGROUND OF THE INVENTION Glass fibers have traditionally been used in glass yarns,
In various forms such as glass cloth, glass roving, glass mat, glass chopped strand, alone or as a composite material, for electrical insulation including printed circuit boards, for reinforced plastics, for reinforced cement, for filter media,
It is used for sound absorbing materials, heat insulating materials, etc. However, since glass fibers have a poor affinity with thermosetting resins, thermoplastic resins, cement, etc. that are composited with the fibers, the affinity with them is increased, or glass fibers are used in the form of fiber sheet or paper. In order to enhance the physical properties when processed into, polyvinyl acetate resin, polyacrylic ester resin, water-soluble polymer, phenolic resin,
It is treated with various resins such as polyvinyl alcohol-based resin, melamine-based resin, urea-based resin, polyester-based resin and epoxy-based resin, or a glass fiber treating agent composed of an emulsion thereof. Further, in order to enhance the composite effect when it is used as a composite material after fiberization, the same treating agent may be used in combination with a so-called silane coupling agent.

However, these resin-based glass fiber treating agents are used as fiber composite materials exposed to severe conditions such as friction materials for electrical insulation, reinforced cement, engineering plastics, brake / clutch facings, etc. In such a case, it cannot be said that it has a sufficient modifying effect, and there is a demand for the development of a glass fiber treating agent that gives a more excellent modifying effect.

There are also attempts to enhance the modifying effect by using a carboxyl group-containing acrylated epoxy resin (Japanese Patent Laid-Open Nos. 63-35440 and 63-35).
No. 441, No. 63-50599, etc.), however, a satisfactory modifying effect has not yet been obtained in the above applications. Moreover, it has been pointed out that conventional glass fiber treating agents have a problem in that when the glass fiber is subjected to bake hardening treatment after the treatment, volatile low-molecular substances are generated to cause contamination (fumes) in the treatment furnace. Further, from the viewpoint of improving productivity and saving energy, there is an increasing demand for shortening the baking time, and there is a demand for the development of a glass fiber treatment agent capable of exhibiting an excellent modifying effect by baking for a short time.

[0005]

The present invention has been made by paying attention to the problems as described above, and its purpose is to:
Without causing contamination of the processing furnace due to volatilization of low molecular weight substances in the bake hardening process during glass fiber processing,
It is intended to establish a method for producing a glass fiber treating agent which can give an excellent modifying effect to glass fibers by a short-time treatment.

[0006]

The constitution of the method for producing a glass fiber treating agent according to the present invention, which has been capable of solving the above-mentioned problems, is obtained by subjecting an epoxy resin to an esterification reaction of a phosphoric acid group-containing polymerizable monomer. The gist resides in that the reaction product obtained is copolymerized with another polymerizable monomer. As the other polymerizable monomer used at this time, a reactive emulsifier or a carboxyl group-containing polymerizable monomer is preferable,
Further, the above-mentioned copolymerization is carried out in the presence of an organic solvent, and this is dispersed in an aqueous medium to obtain a reforming property (solvent resistance,
It is a very good treatment agent in terms of heat resistance, electrical characteristics, etc.), handleability, stability, etc. In addition, a copolymer obtained by the above copolymerization and mixed with an amino resin and then dispersed in an aqueous medium show a further excellent performance as a glass fiber treating agent.

[0007]

As described above, in the present invention, the glass fiber is obtained by copolymerizing the reaction product obtained by esterifying the epoxy resin with the phosphoric acid group-containing polymerizable monomer and the other polymerizable monomer. The type of epoxy resin used for producing a treating agent is not particularly limited, but a bisphenol type epoxy resin is particularly preferable, and has 1 to 2 epoxy groups per molecule, A number average molecular weight of 900 or more is preferable. Commercially available products of such an epoxy resin include, for example, "Epicoat # 1001" and "Same 10" manufactured by Yuka Shell Epoxy Co., Ltd.
04 ”,“ 1007 ”,“ 1009 ”,“ 101 ”
0 ”and the like. When the number average molecular weight of the epoxy resin is less than 900, the solvent resistance, alkali resistance, acid resistance, heat resistance, electrical characteristics, etc. of the finally obtained glass fiber treating agent may be insufficient.

The amount of the above epoxy resin used depends on the solvent resistance,
From the viewpoint of enhancing acid resistance, alkali resistance, water resistance, heat resistance and the like, and more effectively preventing contamination of the processing furnace by volatile low molecular weight substances during baking and curing treatment after glass fiber treatment, the phosphate group described below is used. It is desirable to select from the range of 2: 1 to 1:10 in terms of solid content in terms of weight ratio with respect to the contained polymerizable monomer.

Next, as the phosphoric acid group-containing polymerizable monomer,
(Meth) acryloyloxyethyl acid phosphate and other (meth) acryloyloxyalkyl acid phosphates or alkylene oxide adducts thereof,
Of (meth) acryloyloxyalkyl acid phosphites or their alkylene oxide adducts, epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate, and phosphoric acid, phosphorous acid or their acidic esters Examples thereof include ester compounds, which may be used alone or 2
One or more species can be used in combination as appropriate.

The amount of the phosphoric acid group-containing polymerizable monomer used is 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, based on the solid content in terms of the proportion in the obtained copolymer. The range is preferable, and if it is less than 0.1% by weight, heat resistance, solvent resistance, electrical characteristics, dispersion stability of resin, etc. when used as a glass fiber treating agent may be insufficient, and glass fiber treatment In doing so, there is a tendency that volatile low-molecular substances are generated during the bake-curing process to cause contamination (fumes) in the processing furnace, insufficient low-temperature curability, and a long curing time. On the other hand, if the amount exceeds 25% by weight, flexibility tends to decrease when producing modified glass fiber paper or the like, and water resistance and electrical characteristics tend to deteriorate.

Next, other polymerizable monomers used in the present invention include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like, a carmboxyl group-containing polymerizable monomer, and (meth) acryl. Methyl acid, ethyl (meth) acrylate, propyl (meth) acrylate, n-isobutyl (meth) acrylate, isobutyl (meth) acrylate,
T-butyl (meth) acrylate, n (meth) acrylate
-Amyl, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate,
(Meth) acrylic acid ester such as dodecyl (meth) acrylate, styrene-based polymerizable monomer such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, chlorostyrene, hydroxyethyl (meth) acrylate, Hydroxyl group-containing (meth) acrylic acid ester-based monomer such as hydroxypropyl (meth) acrylate, N
-N-substituted (meth) acrylamide-based monomers such as methylol (meth) acrylamide, acrylonitrile,
Furthermore, a reactive emulsifying agent or the like can be used, and these can be used alone, or two or more kinds can be appropriately used in combination as necessary.

Of the above-mentioned other polymerizable monomers, particularly preferable are the carboxyl group-containing polymerizable monomer and the reactive emulsifier, and when these are used alone or in combination of two kinds, solvent resistance and heat resistance are improved. It is possible to obtain a treating agent which is much more excellent in the properties, the dispersion stability of the resin, and the like. Among them, the reactive emulsifier is effective in enhancing the dispersion stability when it is used as an aqueous dispersion type glass fiber treating agent. Specific examples of such a reactive emulsifier include the following general formula (a),
A sulfosuccinate-based reactive emulsifier represented by (b),

[0013]

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For example, "Ramtel S-12" manufactured by Kao Corporation
0 "," S-180, "S-180A", "Eleminol JS-2" manufactured by Sanyo Kasei Co., Ltd., or an alkylphenol ether-based reactive emulsifier represented by the following general formula (c):

[0015]

Embedded image

For example, "Aqualon H" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
"S-10", "RN-20" and the like.

The amount of the above-mentioned other polymerizable monomer used is 9 to 91 in terms of solid content in terms of the ratio in the copolymer obtained.
%, More preferably 15 to 60% by weight, and if the blending amount is insufficient, the furnace is likely to be contaminated (fumes) during bake-hardening treatment, and solvent resistance, alkali resistance, and acid resistance are also high. Insufficient properties, and conversely, if too much, electrical properties, etc. tend to be insufficient.

In carrying out the present invention, first, the above epoxy resin is subjected to an esterification reaction with a phosphoric acid group-containing polymerizable monomer, and the resulting reaction product (epoxy phosphoric acid ester group-containing polymerizable monomer) is converted into another product. It is carried out by copolymerizing with a polymerizable monomer.

This esterification reaction is usually carried out under an atmosphere of non-oxidizing gas such as nitrogen, generally an organic solvent, preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-. Butanol, alkyl alcohols such as isobutanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, propylene glycol methyl ether,
50 to 1 in the presence of ether ester such as propylene glycol ethyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, etc., and other dioxane, dimethylformamide, diacetone alcohol, etc., alone or in a mixed solvent of two or more kinds.
It is carried out by heating and stirring at about 50 ° C. for about 1 to 10 hours, and successively removing the produced water out of the reaction system. By this reaction, the epoxy group in the epoxy resin and the phosphoric acid group in the phosphoric acid group-containing polymerizable monomer undergo an esterification reaction to obtain an epoxy phosphoric acid ester group-containing polymerizable monomer. That is, this monomer is one in which the phosphoric acid group in the molecule is bonded to the epoxy group of the epoxy resin by an esterification reaction while leaving a polymerizable double bond, and a part of the epoxy group is bonded by an esterification reaction. However, it is considered that some of the epoxy groups remain in a reactive state.

Next, the obtained reaction product and other polymerizable monomers are copolymerized with a radical polymerization initiator such as an azo compound such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide. Polymerize. This reaction may be carried out continuously by adding other co-polymerizable monomers and radical polymerization initiators to the same reaction vessel, or the esterification reaction product is once taken out and placed in another reaction vessel. It is also possible to carry out a copolymerization reaction.

The conditions of the copolymerization reaction are not particularly limited, but generally, the same organic solvent as that used in the above esterification reaction is used alone or as a mixed solvent of two or more kinds, and further in these. Using a solvent mixed with a small amount of water, in the presence of about 0.1 to 10% by weight of a polymerization initiator,
It is carried out in the range of 0 to 150 ° C. Although the reaction time is not particularly limited, the reaction proceeds sufficiently in about 1 to 10 hours.

The copolymer solution thus obtained is used as a glass fiber treating agent as it is as an organic solvent solution, or a small amount of an amino resin is added to this as a curing agent to further enhance the performance as a glass fiber treating agent. Can be used. As the amino resin used here,
For example, alkyl etherified melamine-based resin, alkyl etherified benzoguanamine-based resin, alkyl etherified urea-based resin and the like can be used singly or in a suitable combination of two or more kinds. When these amino resins are used in combination, a glass fiber treating agent can be used. When used as, the reaction between the epoxy group remaining in the copolymer and the amino resin makes it possible to obtain more excellent effects in solvent resistance, water resistance, heat resistance, alkali resistance and the like. The effect of using the amino resin in combination is 5 in terms of solid content based on 100 parts by weight of the epoxy resin used as the raw material for the esterification reaction.
It can be effectively used by using more than 1 part by weight,
If the blending amount is too large, there will be a problem that the furnace is likely to be contaminated (fumes) during the bake hardening treatment.
It is desirable to limit the amount to 50 parts by weight or less.

As described above, the glass fiber treating agent of the present invention is
A treatment agent for glass fiber, which is used for electrical insulation, reinforced plastics, reinforced cement, etc. in an organic solvent solution as it is or by adding an amino resin to the organic solvent solution obtained by the copolymerization reaction. However, it is more preferable to disperse the obtained organic solvent solution in water and to use it as an aqueous dispersion in order to further enhance the treatment effect on the glass fiber and the handleability, and such an aqueous dispersion. The liquid is easily obtained by dispersing the reaction liquid obtained by the above copolymerization reaction in an appropriate amount of water. At this time, those using a carboxyl group-containing monomer or a reactive emulsifying agent as the other polymerizable monomer can be more easily dispersed in water, and a more stable aqueous dispersion can be obtained. It is possible to do so, which is preferable. It is of course possible to further mix a modification aid such as a silane coupling agent with the aqueous dispersion within a range not impairing the features of the present invention, if necessary.

In preparing the aqueous dispersion, a basic compound such as ammonia or amine is added to the copolymerization reaction solution in an amount such that the pH of the aqueous dispersion is 4 to 11 beforehand. It is preferable to mix them, because they can be more easily dispersed in water.

When compounding the amino resin,
It is preferable to disperse the copolymerization reaction liquid in water, which allows even a relatively high molecular weight amino resin that is poorly soluble in water (hardly dispersible) to be easily dispersed. You can enjoy the benefits. That is, when a method of mixing an amino resin with the copolymerization reaction liquid obtained as described above and then dispersing it in water is employed, the coexistence with the copolymerization reaction product remarkably enhances the water dispersibility of the amino resin. However, even a relatively high molecular weight amino resin can be easily dispersed without any trouble, and as a result, contamination of the processing furnace due to volatile low molecular weight substances during the baking process when used as a glass fiber processing agent is more effective. It is possible to obtain a glass fiber treating agent which is effectively suppressed and exhibits further excellent performance in terms of solvent resistance, heat resistance, water resistance, alkali resistance and the like.

[0026]

EXAMPLES The constitutions and effects of the present invention will be described below in more detail with reference to Examples. However, the present invention is not limited by the following Examples, and is within a range applicable to the points of the preceding and following statements. It is also possible to carry out by appropriately changing the above, and all of them are included in the technical scope of the present invention. In the following examples,% and parts mean
Unless otherwise specified, it means% by weight and part by weight.

Example 1 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas blowing tube was charged with 300 epoxy resin (“Epicoat # 1009” manufactured by Yuka Shell Epoxy Co., Ltd.).
Part, mono (2-methacryloyloxyethyl) acid phosphate (“Light Ester PM” manufactured by Kyoei Chemical Co., Ltd.)
40 parts, butyl cellosolve 300 parts, N-butanol 7
After 3 parts were charged and the atmosphere was replaced with nitrogen, the temperature was raised to 105 ° C., and the mixture was kept under stirring for 2 hours to carry out an esterification reaction.

Next, 40 parts of methyl methacrylate, 40 parts of butyl acrylate and 80 parts of styrene were added to this reaction solution.
Part, and a mixed solution of 6 parts of azobisisobutyronitrile were added dropwise over 1.5 hours with stirring, and the mixture was continuously stirred at 105 ° C. for 2 hours for copolymerization, and then diluted with 500 parts of butyl cellosolve. Then, the mixture was cooled to 50 ° C. or lower, and then 306 parts of melamine resin [“NICALAC MX-706” manufactured by Sanwa Chemical Co., Ltd.] was added, and the mixture was stirred for 1 hour to obtain a glass fiber treatment agent A.

Example 2 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas blowing tube was charged with 300 epoxy resin (“Epicoat # 1009” manufactured by Yuka Shell Epoxy Co., Ltd.).
Part, mono (2-methacryloyloxyethyl) acid phosphate (“Light Ester PM” manufactured by Kyoei Chemical Co., Ltd.)
40 parts, butyl cellosolve 300 parts, N-butanol 7
After 3 parts were charged and the atmosphere was replaced with nitrogen, the temperature was raised to 105 ° C. and the mixture was kept under stirring for 2 hours to carry out an esterification reaction.

Then, 40 parts of methyl methacrylate, 40 parts of butyl acrylate and 80 parts of styrene were added to the reaction solution.
Part, and a mixed solution of 6 parts of azobisisobutyronitrile were added dropwise with stirring over 1.5 hours, and the mixture was continuously stirred at 105 ° C. for 2 hours to perform copolymerization, and then 15 parts of triethylamine was added, After stirring and mixing, 535 parts of deionized water was added dropwise with stirring over 30 minutes. Then, the mixture was further stirred for 60 minutes to obtain a water-dispersible resin liquid.

To the above water-dispersed resin solution, 306 parts of melamine resin ["Nikalac MX-706" manufactured by Sanwa Chemical Co., Ltd.] was added, and after stirring for 1 hour, 122 parts of deionized water was added and uniformly mixed to obtain a glass. A fiber treatment agent B was obtained.

Examples 3 to 7 As shown in Table 1, glass fiber treating agents C to G were obtained in the same manner as in Example 2 except that the kind and amount of raw materials used were changed. Example 8 After performing an esterification reaction and a copolymerization reaction in exactly the same manner as in Example 2, 6 parts of triethylamine was added, and then 306 parts of a melamine resin (same as above) was added and mixed with stirring, and then, with stirring. Deionized water (657 parts) was added dropwise over 30 minutes, followed by vigorous stirring for 60 minutes to obtain a glass fiber treating agent H.

[0033]

[Table 1]

(Performance Evaluation Test) Commercially available glass filament paper (basis weight: 60 g / m ² ) was heated in an electric furnace at 550 ° C. for 2 minutes to decompose and remove the binder,
The glass fiber treating agents A to G obtained in Examples 1 to 7 were impregnated into the glass filament paper so as to be 10%, and then heated at 140 ° C. for 30 minutes to be dried and cured. The solvent resistance and heat resistance of this glass fiber treated paper were measured by the following methods, and the results shown in Table 2 were obtained.

In addition, each glass fiber treated paper obtained above,
An epoxy resin impregnating solution having the following composition is impregnated and dried to form a prepreg, 16 prepregs and a copper foil are stacked on one side, pressed at a temperature of 170 ° C. and a pressure of 50 kg / cm ² for 60 minutes, and laminated to have a thickness of 1 A copper-clad laminate having a thickness of 0.6 mm was obtained, its insulation resistance and the appearance of the laminate were examined, and the results are also shown in Table 2. (Epoxy resin impregnating liquid composition) Epicoat # 1001-B-80 50 parts Methyl ethyl ketone 32 parts Dicyandiamide 1.6 parts Methyl cellosolve 16 parts Benzyldimethylamine 0.008 parts

(Physical property test method) Solvent resistance: Immersed in methyl cellosolve at 50 ° C. for 5 minutes and then immediately measured the tensile strength according to JISP 8113. Heat resistance: JIS tensile strength in an atmosphere of 120 ° C
Measure according to P 8113. Insulation resistance: Measured according to the copper clad laminate test method for printed circuits specified in JIS C 6481. Fume resistance: 0.23 mm thick tin plate 15 x 2
Cut to 0 cm and precisely weigh (this is W ₁ ), apply glass fiber treating agent to 10 g / m ² , dry at 100 ° C. for 60 minutes, and weigh accurately (this is W ₂ ). ). Further, it is dried at 160 ° C. for 20 minutes and precisely weighed (this is referred to as W ₃ ), and the heating weight loss rate M (%) is calculated by the following formula and used as the standard of fume generation amount. _{M = [(W 2 -W 3} ) / (W 2 -W 1)] × 100

[0037]

[Table 2]

Comparative Examples 1 to 6 Comparative glass fiber treating agents a to f having the raw material compositions shown in Table 3 were produced according to the above-mentioned Examples. Using each of the obtained comparative glass fiber treating agents, a performance test was conducted in the same manner as above, and the results shown in Table 4 were obtained.

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

EFFECTS OF THE INVENTION The present invention is constituted as described above, has excellent affinity with glass fibers and various thermoplastic / thermosetting resins, has a high curing rate, and has excellent solvent resistance after curing. Therefore, it has become possible to provide a glass fiber treating agent having excellent performance, which exhibits acid resistance, alkali resistance, water resistance, heat resistance, and electrical characteristics. Moreover, the glass fiber treating agent obtained by compounding the amino resin further enhances the performance as the glass fiber treating agent by the action of the amino resin as a curing agent for the epoxy resin, and at the same time, has a volatility at the time of bake hardening treatment. The effect that the generation of low molecular weight substances is reduced and the pollution of the furnace is suppressed can also be enjoyed. Further, when a carboxyl group-containing monomer or a reactive emulsifying agent is used as the other polymerizable monomer, it is possible to obtain one having very good dispersibility in water and dispersion stability.

Claims (5)

[Claims] 1. A glass fiber treating agent comprising a reaction product obtained by subjecting an epoxy resin to an esterification reaction of a phosphoric acid group-containing polymerizable monomer with another polymerizable monomer. Manufacturing method. 2. A reaction product obtained by subjecting an epoxy resin to an esterification reaction of a phosphoric acid group-containing polymerizable monomer, with another polymerizable monomer in the presence of an organic solvent to obtain a copolymer. The method according to claim 1, wherein the product is dispersed in an aqueous medium. 3. The production method according to claim 2, wherein a reactive emulsifier is used as the other polymerizable monomer. 4. The method according to claim 2, wherein a carboxyl group-containing polymerizable monomer is used as the other polymerizable monomer. 5. The production method according to claim 4, wherein the amino resin is mixed with the product copolymerized in the presence of an organic solvent and then dispersed in an aqueous medium.