JPH061907A - Unsaturated epoxy ester resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having an extremely short reaction time for impregnated decorative paper, providing a decorative sheet having excellent water resistance, alkali resistance and weather resistance by reacting a specific aliphatic epoxy compound with an unsaturated monobasic acid. CONSTITUTION:In an unsaturated epoxy ester resin obtained by reacting an epoxy compound containing one or more epoxy groups on the average in the molecule with an unsaturated monobasic acid, a composition contains 40-80wt.% based on the whole epoxy compounds of an aliphatic epoxy compound having 130-500/eq epoxy equivalent among epoxy compounds containing one or more epoxy groups on the average in the molecule. Hexahydrophthalic acid diglycidyl ester is used as the aliphatic epoxy compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an unsaturated epoxy ester resin composition for impregnated decorative paper. For more details,
The reaction time when hot-pressing the impregnated decorative paper on the plywood etc. is very short, that is, it has excellent reactivity, and the decorative board obtained by hot-pressing has excellent water resistance, alkali resistance and weather resistance. To an unsaturated epoxy ester resin composition for impregnated decorative paper, which is capable of obtaining

[0002]

2. Description of the Related Art Conventionally, to obtain an impregnated decorative paper, an unsaturated polyester resin is dissolved in an inert solvent such as acetone or toluene, and a high boiling point reaction such as a diallyl phthalate prepolymer is used. Mixed with a diluting solvent,
The intended decorative paper is impregnated with this solution, and the inert solvent is evaporated to make it non-tacky. When the impregnated decorative paper thus obtained is hot-pressed onto plywood or the like, the unsaturated polyester resin and the reactive diluting solvent are melted, and when heat is further applied, these cause a crosslinking reaction, so that the plywood and the impregnated decorative paper are An integrated decorative board can be obtained.

By the way, as the above-mentioned unsaturated polyester resin, for example, orthophthalic acid type unsaturated polyester resin, hydrogenated type unsaturated polyester resin, and unsaturated epoxy ester resin are used. However, among these unsaturated polyester resins, those using an orthophthalic acid type unsaturated polyester resin are excellent in reactivity, but have a drawback that they are inferior in water resistance, alkali resistance and weather resistance.
Further, the one using the hydrogenated unsaturated polyester resin is excellent in weather resistance, but has a drawback that it is inferior in reactivity, water resistance and alkali resistance. Further, those using an unsaturated epoxy ester resin are excellent in reactivity, water resistance and alkali resistance, but have a drawback that they are inferior in weather resistance.

In order to improve various properties such as reactivity, water resistance, alkali resistance and weather resistance of the unsaturated polyester resin for impregnated decorative paper, the components of acid and polyhydric alcohol which are raw materials of the unsaturated polyester resin are changed. Or, the above three kinds of resins for impregnated decorative paper are mixed, but none of them sufficiently satisfies all the properties.
An object of the present invention is to solve the above-mentioned problems of the prior art and to provide an unsaturated epoxy ester resin composition for impregnated decorative paper, which is excellent in various properties such as reactivity, water resistance, alkali resistance and weather resistance. is there.

[0005]

In order to solve the above problems, it is effective for the present inventors to select an unsaturated epoxy ester resin composition composed of a specific epoxy compound as a resin for impregnated decorative paper. That is, the present invention has been achieved. That is, the present invention is an unsaturated epoxy ester resin obtained by reacting an epoxy compound having an average of 1 or more epoxy groups in the molecule with an unsaturated monobasic acid, and an average of 1 or more epoxy groups in the molecule. Epoxy equivalent of 130 ~ 500g / eq
4 of the total epoxy compounds
The unsaturated epoxy ester resin composition for impregnated decorative paper is characterized by containing 0 to 80% by weight.

In the present invention, the epoxy compound having an average of one or more epoxy groups in the molecule is, for example,
General formula (1) (Formula 1) obtained from bisphenol A and epichlorohydrin

[Chemical 1] A general formula (2) (Chemical Formula 2) obtained by reacting a bisphenol A epoxy compound represented by or a novolac resin with epichlorohydrin

[0007]

[Chemical 2] The novolac-based epoxy compound represented by and other bisphenol F-based epoxy compounds are used. Two or more of these may be used in combination. Examples of the unsaturated monobasic acid to be reacted with the epoxy compound include (meth) acrylic acid and crotonic acid.

The fatty epoxy compound used in the present invention has an epoxy equivalent of 130 to 500 g / eq,
For example, hexahydrophthalic acid diglycidyl ester (epoxy equivalent 148-155 g / eq), cyclohexanedimethanol diglycidyl ether (epoxy equivalent 240-26
0 g / eq) and hydrogenated bisphenol A diglycidyl ether (epoxy equivalent: 470 to 490 g / eq). When the epoxy equivalent is less than 130 g / eq, the resulting impregnated decorative paper is tacky and impractical, and it is 500 g / e
If it exceeds q, the impregnated decorative paper after drying becomes brittle. In the present invention, the amount of these fatty epoxy compounds is usually 40 to 80% by weight, preferably 50 to 70% by weight, based on the total epoxy compounds having an average of one or more epoxy groups in the molecule. If the amount is less than 40% by weight, it is difficult to obtain a decorative board having excellent weather resistance, and if it exceeds 80% by weight, the resulting impregnated decorative paper has tackiness and is not practical.

The unsaturated epoxy ester used in the present invention is obtained by polyadding an epoxy compound having an average of one or more epoxy groups in the molecule with an unsaturated monobasic acid in an air atmosphere at 100 to 140 ° C. Is obtained by On this occasion,
The ratio of (total epoxy group mole number / unsaturated monobasic acid mole number) is preferably in the range of 1.0 to 1.2. The progress of the polyaddition reaction can be known by measuring the acid value, and the acid value at the end of the reaction is usually 1 to 40 mg-KOH / g-
Solids, preferably in the range 1-10 mg-KOH / g-solids.

After completion of the above polyaddition reaction, the reaction product is diluted with an inert solvent. As the solvent, for example, a low boiling point solvent such as toluene, acetone, or isopropyl alcohol, which is easily dried, is used. If necessary, a polymerization inhibitor such as hydroquinone may be added to these unsaturated epoxy esters. The resin composition thus obtained, a reactive diluent solvent, for example, a diallyl phthalate prepolymer, a curing agent, for example, benzoyl peroxide, and, if necessary, various other additives are mixed to obtain a decorative paper. Impregnated with, evaporate the inert solvent,
An impregnated decorative paper is obtained by drying. Then, the impregnated decorative paper is hot pressed onto a plywood to obtain a desired decorative board excellent in various properties such as reactivity, water resistance, alkali resistance and weather resistance.

[0011]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. In the following, “part” is based on weight. The resulting impregnated decorative paper and decorative board were evaluated by the following methods. -Non-adhesiveness: The surface condition of the obtained impregnated decorative paper is evaluated by touching it with a finger in three levels.・ Reactivity: Impregnated decorative paper on plywood at 150 ℃ × 5Kg / cm ²・
Heat press at G for 1 minute. At that time, the state of adhesion between the impregnated decorative paper and the plywood is visually evaluated in three levels. -Water resistance: After the obtained decorative board is immersed in tap water for 24 hours, the appearance change is visually observed and evaluated in three stages. -Alkali resistance: The obtained decorative board is evaluated in three levels according to JIS-A-5420.・ Weather resistance: The obtained decorative board is measured for color difference change (ΔE) at an irradiation time of 200 hours according to JIS-A-1415.

Example 1 70 parts of hydrogenated bisphenol A diglycidyl ether (epoxy equivalent 470-490 g / eq), bisphenol A type epoxy resin (in a four-necked flask (with a stirrer, condenser, thermometer and air inlet)) Product name Epicote 82
8; Yuka Shell Epoxy Co., epoxy equivalent 330-350g
/ eq) 30 parts, and 0.01 parts of hydroquinone are charged, and 17 parts of methacrylic acid is added dropwise at 130 ° C. over 2 hours while passing air while paying attention to heat generation. An acid value of 10 mg-KOH / g-solid was reacted, cooled to 80 ° C., and diluted with 50 parts of toluene to obtain an unsaturated epoxy ester resin. To 100 parts of this unsaturated epoxy ester resin, 30 parts of diallyl phthalate prepolymer and 1.5 parts of benzoyl peroxide as a peroxide are added and mixed to impregnate the decorative paper.
It was dried at ℃ for 30 minutes to obtain an impregnated decorative paper. This impregnated decorative paper was hot pressed on plywood at 150 ° C. for 1 minute to obtain a decorative board. The properties of the resulting impregnated decorative paper and decorative board are shown in Table 1 (Table 1).

Examples 2 to 4 and Comparative Examples 1 to 4 The procedure of Example 1 was repeated except that the type and amount of each compound shown in Table 1 (Table 1) were used. Saturated epoxy ester resin, impregnated decorative paper and decorative board were obtained. The characteristics of the obtained impregnated decorative paper and decorative board are shown in Table 1.
It shows in (Table 1).

[0014]

[Table 1] * 1; Hydrogenated bisphenol A diglycidyl ether (epoxy equivalent 470 to 490 g / eq) * 2: Cyclohexanedimethanol diglycidyl ether (epoxy equivalent 240 to 260 g / eq) * 3; Bisphenol A epoxy resin (epoxy equivalent)
330-350g / eq) * 4; Bisphenol A type epoxy resin (epoxy equivalent)
900-1000g / eq)

[0015]

According to the present invention, it is possible to obtain an unsaturated epoxy ester resin composition for impregnated decorative paper, which is excellent in reactivity, water resistance, alkali resistance and weather resistance, which cannot be achieved by the prior art.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location C08J 5/18 CEZ 9267-4F D21H 19/24 27/18 (72) Inventor Kazuyoshi Tominaga Chiba Prefecture 1900 Togo, Mobara-shi Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. An unsaturated epoxy ester resin obtained by reacting an epoxy compound having an average of 1 or more epoxy groups in the molecule with an unsaturated monobasic acid, wherein an average of 1 or more epoxy groups is included in the molecule. An unsaturated epoxy ester resin composition for impregnated decorative paper, which comprises 40 to 80% by weight of the total epoxy compounds of a fatty epoxy compound having an epoxy equivalent of 130 to 500 g / eq.