JPH09309930A - Aqueous acrylic resin for glass fiber sizing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin which is excellent in the adhesion to glass fibers and has flexibility, strength and a good heat cleanability. SOLUTION: A monomer (A) contg. an acrylic acid monomer and/or a methacrylic acid monomer (a), an acrylic acid monomer and/or a methacrylic acid monomer (b) having a hydroxyl group, and an acrylic acid monomer and/or a methacrylic acid monomer (c) having an ethylene oxide adduct and a monomer (B) having a difunctional divinyl type ethylene oxide adduct are polymerized in a wt. ratio of the component (A) to the component (B) in the range of (100:0.1) to (100:3.0) in the presence of an oleaginous radical reaction initiator in an alcohol or a mixed solvent composed of water and an alcohol, and the carboxylic acid is then neutralized with an alkali to improve the water solubility.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based acrylic resin for concentrating glass fibers, and more particularly to a glass for heat cleaning which has good adhesion to glass fibers, flexibility, and excellent thermal decomposability. The present invention relates to an aqueous acrylic resin for fiber focusing.

[0002]

2. Description of the Related Art Conventionally, a sizing agent containing a partially saponified polyvinyl alcohol as a main component has been widely used for bundling glass fibers because of its physical properties. However, polyvinyl alcohol resin has a poor thermal decomposability and is 400 to 600 ° C.
The heating agent is heated in the air for several days to remove the sizing agent. Further, there is a problem of heat cleaning property, and ash remains, and when used for an electronic substrate, the remaining ash causes energization, which causes a trouble such as a circuit not functioning normally. For these reasons, it has long been desired to improve the efficiency and performance of heat cleaning properties.

For this reason, acrylic acid ester-based polymers and methacrylic acid ester-based polymers have hitherto been investigated for their excellent thermal decomposability, but these polymers are not satisfied with physical properties such as flexibility and strength. In addition, due to the problem that tarified ash remains during heat cleaning, an acrylic resin suitable for glass fiber focusing has not been developed yet.

[0004]

SUMMARY OF THE INVENTION The present invention was devised in view of the present situation of such a heat cleaning-compatible glass fiber sizing agent, and its object is to provide excellent adhesion to a glass fiber as an adherend and to provide flexibility. An object of the present invention is to provide an acrylic resin having good heat-cleaning properties, which has properties and strength.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that an acrylic acid monomer, a methacrylic acid monomer and their ester derivatives are used as main components and a specific oily catalyst is used. We have found that the above object can be achieved by using an acrylic resin obtained by polymerizing a monomer in an alcohol or a mixed solvent of water and alcohol as an initiator, and have completed the present invention.

That is, the present invention relates to (a) an acrylic acid monomer and / or a methacrylic acid monomer, (b) an acrylic acid monomer and / or a methacrylic acid monomer having a hydroxyl group, and (c) an acrylic acid having an ethylene oxide adduct. (A) a monomer containing an acid monomer and / or a methacrylic acid monomer, and (B) a monomer having a bifunctional divinyl type ethylene oxide adduct,
When the weight ratio of (B) is 100 / 0.1 to 100 / 3.0, polymerization is carried out in an alcohol or in a mixed solvent of water and alcohol using an oily radical reaction initiator, and then the carboxylic acid is alkali-treated. Is a water-based acrylic resin, which is characterized by improving the water solubility.

It is well known that a polymer obtained by a polymerization reaction of an acrylic acid type monomer and a methacrylic acid type monomer is depolymerized into a monomer by heat. The acrylic polymer is manufactured by emulsion polymerization in which an emulsifier is used together to polymerize a monomer, or solution polymerization in which a monomer is polymerized in a solvent such as alcohol. In the case of emulsion polymerization,
When plasticized by internal plasticization, the toughness of the resin is lost. In addition, anionic emulsifiers and catalysts that are mainly used in emulsion polymerization, such as ammonium persulfate and potassium persulfate, cause tar formation in the heat cleaning step, and there is a risk of energizing the base of the product. Since the water-based acrylic resin of the present invention is produced by polymerization in alcohol or a mixed solvent of water and alcohol, it is possible to form a film without using a plasticizer even with a high glass transition point polymer composition having a hard polymer composition. It has a toughness and flexibility similar to the film physical properties of polyvinyl alcohol, which is mainly used as a sizing agent for glass fibers.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Monomers used in the water-based acrylic resin of the present invention include (a) acrylic acid monomer and / or methacrylic acid monomer, (b) hydroxyl group-containing acrylic acid monomer and / or methacrylic acid monomer, And (c) contains an acrylic acid monomer and / or a methacrylic acid monomer having an ethylene oxide adduct.
Examples include (A) monomers, and (B) difunctional monomers having a divinyl type ethylene oxide adduct.
The carboxylic acids of these monomers are used after polymerization to neutralize with an alkali to improve water solubility. To neutralize,
Although a general alkali can be used, neutralization with ammonia is preferable in terms of volatility. The (a) acrylic acid monomer and / or methacrylic acid monomer used in the present invention is (A)
1 to 35% by weight, preferably 5 to 25% by weight in the monomer
Is preferable. If the amount of the monomer (a) is less than the above range, the water solubility decreases, and if it exceeds the above range, the polymer film becomes hard and flexibility is difficult to obtain, which is not preferable.

Examples of the (b) hydroxyl group-containing acrylic acid monomer and methacrylic acid monomer used in the present invention include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, Examples thereof include monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate. (C) used in the present invention
The acrylic acid monomer having a polyethylene oxide adduct is light acrylate 130A (manufactured by Kyoeisha Chemical Co., Ltd., methoxy polyethylene glycol acrylate, ethylene oxide mole number n = 9), and the methacrylic acid monomer is light ester 130MA (light acrylate 130A. Methacrylic acid monomer),
Examples include monomers such as light ester 041MA (manufactured by Kyoeisha Chemical Co., Ltd., methoxy polyethylene glycol methacrylate, ethylene oxide mole number n = 30). Further, an alkylphenol EO-added acrylate or methacrylate can be used in combination to the extent that water solubility is not impaired.

The (b) acrylic acid monomer and / or methacrylic acid monomer having a hydroxyl group used in the present invention is 20 to 90% by weight, preferably 3% in the (A) monomer.
5 to 85% by weight. If the amount of the monomer (b) is less than the above range, the film will not have sufficient strength, and if it exceeds the above range, the film will be too hard, which is not preferable. The (c) acrylic acid monomer and / or methacrylic acid monomer having an ethylene oxide adduct used in the present invention is 5 to 60% by weight, preferably 10 to 40% by weight in the (A) monomer.
It is. (c) When the amount of the monomer is less than the above range, the film becomes hard, and when the amount of the monomer exceeds the above range, stickiness due to humidity occurs, which is not preferable.

The (B) difunctional divinyl-type ethylene oxide adduct monomer used in the present invention is used to impart flexibility to the polymer film. Examples of such a monomer include divinyl type acrylates and methacrylates having a polyethylene oxide adduct, PEG # 200 diacrylate,
PEG # 400 diacrylate, PEG # 600 diacrylate and their methacrylates can be used. The (B) monomer is used in an amount of 0.1 to 3.0 parts by weight, preferably 0.5 to 2.5 parts by weight, based on 100 parts by weight of the (A) monomer. If the content of the monomer (B) is less than the above range, the film cannot have flexibility, and if it exceeds the above range, the crosslinking density becomes high and gelation occurs.

The (A) monomer of the water-based acrylic resin of the present invention includes, in addition to the (a), (b) and (c) monomers, general hydrophobic monomers, methyl acrylate and ethyl acrylate, to the extent that they do not impair the water solubility of the polymer. , Butyl acrylate, 2-ethylhexyl acrylate and their methacrylates can also be used.

As the oily radical reaction initiator used in the present invention, azobisisobutyronitrile (AIB
N), benzoyl peroxide (BPO), and
IBN is preferred. The oily radical reaction initiator is preferably used in the range of 0.3 to 1.0% by weight based on the (A) monomer + (B) monomer.

As a method for producing the water-based acrylic resin of the present invention, a general method for producing a water-soluble polymer is used. For example, a monomer solution in which AIBN is dissolved is dropped into an alcohol or a mixed solvent of water and an alcohol to polymerize, and after cooling, neutralized with ammonia water to obtain a polymer solution, and then the alcohol is removed under reduced pressure. And replace with water. Alternatively, it is used as a mixed solution of water and alcohol.

[0015]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. Parts and% are based on weight.

Example 1 A round bottom flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 180 parts of ion-exchanged water and 165 parts of isopropyl alcohol, and nitrogen was blown into it.
The temperature was raised to 0 ° C. Methacrylic acid 10 parts, 2-hydroxyethyl methacrylate 65 parts, light acrylate 1
30 A of 24 parts, light acrylate 14 EGA (manufactured by Kyoeisha Chemical Co., Ltd., PEG # 600 diacrylate) 1 part of a monomer were mixed, and a solution of 0.4 parts of AIBN was dissolved into a flask from a dropping funnel at 80 ° C. for 2 hours. The solution was dropped for a period of time to carry out a polymerization reaction. After dropping, maintain at 80 ° C for 3
After 0 minutes and 1 hour 30 minutes, isopropyl alcohol 5
A solution in which 0.05 part of AIBN was dissolved was added to each part, polymerization of residual monomers was continued, and aging was carried out at 80 ° C. for 1 hour and 30 minutes to complete the reaction. After cooling the reaction to 40 ° C., 2
Methacrylic acid was neutralized by adding 9 parts of 5% aqueous ammonia. This flask is equipped with a condenser and a receiver, heated under reduced pressure to collect isopropyl alcohol, and water 1
75 parts were added. The obtained polymer solution was a transparent solution having a heating residue of 21%, a viscosity of 180 mpa.sec / 25 ° C. and a pH of 6.5.

Example 2 Polymerization was carried out using the same reactor and polymerization method as in Example 1. However, the monomer composition used was as follows: methacrylic acid 10 parts, 2-hydroxyethyl methacrylate 40 parts, 2-hydroxybutyl methacrylate 19
Parts, 10 parts of light acrylate 130A, 20 parts of light acrylate NP-4EA (nonylphenol 4EO acrylate manufactured by Kyoeisha Chemical Co., Ltd.), 1 part of light acrylate 14EGA. In addition, after the neutralization by adding the same ammonia water as in Example 1, isopropyl alcohol was not recovered, and a mixed solvent of water and isopropyl alcohol was used for the test. The obtained polymer solution has a heating residue of 21
%, Viscosity 320 mpa.sec / 25 ° C., pH 8.8 transparent solution.

Comparative Example 1 2 of partially saponified Poval GH-17 manufactured by Nippon Gosei Co., Ltd.
A 0% aqueous solution, viscosity 800 mpa.sec / 25 ° C. was used for the test.

Comparative Example 2 40 parts of an acrylamide monomer (40% aqueous solution) and 1 part of isopropyl alcohol were placed in the same reactor as in Example 1.
0 part and 360 parts of ion-exchanged water were charged, the temperature was raised to 65 ° C. under nitrogen blowing, 1 part of ammonium persulfate was added, and the reaction was carried out at 70 ° C. for 1 hour. Methacrylic acid 20
Parts, 60 parts of 2-hydroxypropyl methacrylate, and 20 parts of light acrylate 130A were mixed, and a solution having 0.4 parts of AIBN dissolved therein was added dropwise from a dropping funnel to the flask at 80 ° C. for 2 hours to carry out a polymerization reaction.
After the dropping, the temperature was maintained at 80 ° C., and after 30 minutes and 1 hour and 30 minutes, 5 parts of isopropyl alcohol had AIBN 0.0.
A solution in which 5 parts was dissolved was added, polymerization of the remaining monomer was continued, and aging was carried out at 80 ° C. for 1 hour and 30 minutes to complete the reaction. After cooling the reaction product to 40 ° C., 25% ammonia water 1
Methacrylic acid was neutralized by adding 7 parts. The obtained polymer solution had a heating residue of 21% and a viscosity of 190 mpa.sec.
It was a semi-transparent cloudy solution at / 25 ° C and pH 7.8.

With respect to Examples 1 and 2 and Comparative Examples 1 and 2, heat cleaning properties and film physical properties were tested by the following methods. About 10 samples of heat cleaning test
mg is collected in an aluminum pan with a diameter of 5 mm, and the thermogravimetric analyzer's differential thermobalance T manufactured by Rigaku Denki Co., Ltd. in an air atmosphere.
Using G-DTA (standard type) TG-8110, temperature rise 5
Heat up to 500 ℃ at ℃ / minute, and set the thermal decomposition point (℃) to TG.
It was determined from the intersection of the tangent to the curve and the weight of 0%. The state of ash in the aluminum pan was evaluated as follows, and the presence or absence of tar was visually observed. State of ash ○: There is a residue having a diameter of 0.5 mm or less. Δ: Residue adheres to an area of 20 to 50% of the aluminum pan. X: Residue is attached to an area exceeding 50% of the aluminum pan.

The physical properties of the film were tested by coating each 20% polymer solution on a glass plate and a polyester plate with a thickness of 36.
After coating with 0 micron, a dry film was prepared in a dryer at 50 ° C., and the film was evaluated for adhesion to a glass plate and flexibility / strength of the film. The glass adhesion was evaluated as follows in the situation when the film was peeled from the glass plate: Good: No peeling. Δ: Peeling off slightly easily. X: Easy to peel off.

The flexibility and strength of the film were evaluated as follows by comparing the state of the film peeled off from the polyester plate with a finger with bending or pulling, and evaluated as follows: ◯: Almost the same as polyvinyl alcohol There are physical properties of. Δ: Physical properties are slightly inferior to polyvinyl alcohol. X: The film has no flexibility and is broken.

Table 1 shows the test results of Examples 1-2 and Comparative Examples 1-2.

As is clear from the test results of Table 1, according to the present invention, there is no ash residue, the heat cleaning property is good, and the glass fiber has good adhesion, flexibility and strength. An acrylic resin is provided.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 71/02 LQA C08L 71/02 LQA D06M 15/31 D06M 15/31 // D01F 11/00 D01F 11/00

Claims (2)

[Claims] 1. (a) Acrylic acid monomer and / or methacrylic acid monomer, (b) Acrylic acid monomer and / or methacrylic acid monomer having a hydroxyl group, and
(c) (A) a monomer containing an acrylic acid monomer and / or a methacrylic acid monomer having an ethylene oxide adduct, and (B) a monomer having a bifunctional divinyl type ethylene oxide adduct, (A) / (B ) In the range of 100 / 0.1 to 100 / 3.0, using an oily radical reaction initiator, after polymerization in alcohol or in a mixed solvent of water and alcohol, carboxylic acid in an alkali A water-based acrylic resin characterized by being softened and having improved water solubility. 2. The water-based acrylic resin according to claim 1, wherein the oily radical reaction initiator is azobisisobutyronitrile (AIBN).