JPS58217514A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful for forming heat-resistant, corrosion- resistant paint films of good mechanical properties, comprising a (meth)acrylate prepared by adding an alkylene oxide to a dihydric phenol and a polymerizable unsaturated monomer. CONSTITUTION:1.5-2.5 equiv. of an alkylene oxide is added to 1 equiv. of a dihydric phenol of the formula, wherein X is a 1-5C alkylene, -S- or the like. The purpose thermosetting resin composition is prepared from 100pts.wt. (meth) acrylate of the above reaction product and 10-100pts.wt. polymerizable unsaturated monomer (e.g., styrene).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an excellent radically polymerizable thermosetting resin composition.

As radically polymerizable thermosetting resins, unsaturated polyester resins have been widely used in paints, cast products, FRP (fiber reinforced plastics), etc.
°Recently, as their uses have expanded, the required performance has also become more diverse. Against this background, there has been a demand for resins with excellent heat resistance, corrosion resistance, mechanical properties, and the like. However, as is well known, it is extremely difficult to simultaneously realize antinomic properties such as heat resistance, corrosion resistance, and surf-like performance using a single type of unsaturated polyester resin. Therefore, a high-performance resin that compensated for this was introduced as EBOKI/resin, acrylic acid, and/or
Alternatively, epochino(meth)acrylate resin, which is a reaction product with methacrylic acid, is not always satisfactory in terms of performance due to drawbacks such as high water absorption.

Therefore, the inventors of the present invention completed the present invention as a result of intensive research in order to obtain a resin that has the above-mentioned antinomic properties. That is, the present invention can be obtained by adding an average of 15 to 25 equivalents of alkylene oxide (b) to 1 equivalent of dihydric phenol (a) represented by the general formula 110 (X-◎-OH (meth)acrylate of reaction product (c)
) (A) 100 parts by weight and polymerizable unsaturated monomer (Bi1
The present invention relates to a thermosetting resin composition comprising o to 100 parts by weight.

An example of divalent 7enr(a) is 2,2-bis(
4-hydroxyphenyl)propane, 2,2-bis(4
-hydroxyphenyl)pentane, bis(4-hydroquinphenyl)methane, bis(4-hydroquinphenyl)
Examples include sulfone, bis(4-hydroxyphenyl) sulfide, and the like. (meth)acrylate (5
), one or two of these compounds are used.
More than one species can be used as dihydric phenol (a).

Examples of alkylene oxide (b) include lower alkylene oxides such as ethylene oxide and propylene oxide, and one or two of these may be used.
More than one species can be used.

(Meth)acrylate (5) is dihydric phenol (a)
15 to 25 equivalents of alkylene oxide (
Acrylate and/or methacrylate of the reaction product (c) having two alcoholic hydroxyl groups per molecule obtained by adding 0) with at least 80 of the alcoholic hydroxyl groups in the reaction product (c) %, preferably 90% or more, is an ester of acrylic acid and/or methacrylic acid. If the amount of alkylene oxide, do(O), used is outside the above range, it will be difficult to satisfy all of the heat resistance, corrosion resistance, and mechanical properties of the resulting thermosetting resin composition. Still 2
Value.

If the degree of esterification of the alcoholic hydroxyl group of the addition reaction product (c) of phenol (a) and alkylene oxide (b) is less than 80%, a thermosetting resin composition with excellent performance cannot be obtained. . Such (meth)acrylate (A) can be easily produced according to a conventionally known method. A typical example thereof is a reaction method according to a two-step process as shown below.

1st step: Hydroquine alkyl etherification step of dihydric phenol (a) 2 3 to 5 mol of alkylene oxide (b) per 1 mol of dihydric phenol (a), optionally (1) triethylamine, triethanolamine , amine compounds such as benzyl ammonium chlorite; Lewis acids such as boron trifluoride and tin tetrachloride; sodium, lithium,
Compounds of alkali metals such as potassium; reaction catalysts such as compounds of alkaline earth metals such as potassium, macanediram, etc. (2) Acetone, trichlene, chlormethane, methyl ethyl ketone, methylinobutyl ketone, benzene, toluene, xylene, etc. A step of converting the hydroxyl group of dihydric phenol (a) into a hydroxy/alkyl ether in the presence of an organic solution or the like at room temperature or under heating.

2nd step: Esterification step If necessary, acrylic acid and/or methacrylic acid or their acid chlorides are added in an amount larger than 0 g equivalent per 091 equivalent of the reaction product obtained in the first step. para-toluenesulfonic acid, sulfuric acid, Louis,',
Reaction catalysts such as acids and titanate esters (2) Organic solvents such as those exemplified in the first step (3)
The reaction obtained in the first step at room temperature or under heating in the presence of a deoxidizing agent such as tertiary amyl 7 such as triethylamine and pyridine; sulfur and lithium carbonate, weak acid salts of alkali metals such as potassium carbonate, etc. A step of converting the hydroxyl group of the product (c) into an ester of acrylic acid and/or methacrylic acid.

However, such (meta)acrylic.

The present invention is not dependent on the manufacturing method of item (5).

The polymerizable unsaturated monomer (B) refers to a compound that has at least one polymerizable unsaturated bond in one molecule, has a molecular weight of about 300 or less, and is liquid at room temperature. Such compounds include, for example, methyl/, divinylbenze/, vinylhyridine, p-methylstyrene, α-methylstyrene, p-
Examples include chlorstyrene, methyl methacrylate, diallyl phthalate, and the like. Among these, monovalent aromatic vinyl compounds and, more preferably, styrene are particularly preferred in terms of physical properties.

The thermosetting resin composition according to the present invention comprises 100 parts by weight of (meth)acrylate (5) and a polymerizable unsaturated monomer (B
) 10 to 100 parts by weight.

If the usage ratio of (meth)acrylate (5) and polymerizable unsaturated monomer (g)) is out of the above range,
This is not preferable because physical properties (particularly mechanical properties) deteriorate.

The thermosetting resin composition according to the present invention can be used in the same manner as conventionally known unsaturated polyester resins, and can be used in coating films, cast products, gel coats, FRP, etc., which have heat resistance, corrosion resistance, and mechanical performance. It provides molded products, etc.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the scope of these examples.

In addition, unless otherwise specified, "department" in the examples refers to "department".
"AO/BPJ" means "parts by weight" and "AO/BPJ" means the number of equivalents of alkylene oxide added per equivalent of dihydric phenol.

Example 1 Flask 12"°Uniol DB-400'" (manufactured by NOF Corporation, addition reaction product of bisphenol A and ≦ropylene oxide, hydroxyl-275, AO/BP = 1.
6) 204 parts, toluene 500 parts, methacrylic acid 13
0 parts of hydroquino, 701 parts of hydroquino, and 4 parts of paratoluene sulfonic acid were charged, and the mixture was esterified at 105 to 110°C while removing the toluene-water azeotrope in a fractionating tube, and then washed with water to remove volatile components. A methacrylic acid ester of Uniol DB-400 (hereinafter referred to as (meth)acrylate (A-)) was obtained. (meth)acrylate (
A-t) had a hydroxyl value of 159 and an ester value of 182, and 92% of the hydroxyl groups in 11 Uniol DB-400°'' were esterified.

Next, 100 parts of (meth)acrylate (A-1) and 40 parts of styrene were mutually dissolved to obtain resin (1). Resin (1) was a light brown liquid with a viscosity of 45 cp (25°C).

Cobalt octenoate (metal content: 8 parts by weight, hereinafter referred to as 0cCO (8%)) and f thyl ethyl ketone peroxide (peroxide content: 55% by weight, hereinafter referred to as MEKPO (55%)) were added to 0 parts of resin (ll I O). )) was blended and injected between two glass plates and cured. The physical properties of the resulting resin plate are shown in Table 1.

Comparative Example 1 A resin plate was produced in the same manner as in Example 1 using a resin (ratio -1) obtained by mutually dissolving 10.0 parts of (meth)acrylate (A-1) and 5 parts of styrene. We tested its physical properties. The results are shown in Table 1.

Comparative Example 2 In Example 1, “Uniol DB-400”20
Instead of 4 parts, "Uniol I) B-360" (manufactured by Nippon Oil & Fats Co., Ltd., addition reaction product of bisphenol A and propylene oxide, hydroxyl value 3]), AO/BP-1,
+4) Same as Example 1 except that 180 parts were used,
°゛Unior DB-360'' methacrylate (
Hereinafter, it will be referred to as (meth)acrylate (ratio -1). ) was obtained. (meth)acrylate (ratio-1) hydroxyl value 151,
With an ester value of 201, ``,:l: All DB-360
The 93rd hydroxyl group of ゛ had been esterified.

Next, a resin plate was made in the same manner as in Example 1 using a resin (ratio -2) derived from 100 parts of (meth)acrylate (ratio -1) and 40 parts of styrene, and its properties were tested. The results are shown in Table 1.

Example 2 In Example 1, 'Uniol DB-400''.

Instead of 204 parts, "°Uniol DA-400" (manufactured by Nippon Oil & Fats Co., Ltd., addition reaction product of bisphenol A and ethylene oxide, hydroxyl value 280, AO/BP = 2.0
) was used in the same manner as in Example 1 except that 200 parts of ``Uniol DA-400'' methacrylate (hereinafter referred to as (
It is called meth)acrylate (A-2). ). The (meth)acrylate (A-2) had a hydroxyl value of 93 and an ester value of 177, and 95% of the hydroxyl groups in Uniol DA-400'' were esterified.

Next, (meth)acrylate) (A-2) too much and 30 parts of styrene were mutually dissolved to obtain resin (2).

Resin (2) was a light brown liquid with a viscosity of 90 CI (25° C.).

Resin (21,100 parts) was mixed with 0.3 parts of 0cCO (8%) and 10 parts of MEKPO (55%).A resin plate was prepared using the resin liquid in the same manner as in Example 1, and its physical properties were tested. The results are shown in Table 1.

Example 3 “Uniall DB-36Q”]80 in an autoclave
300 parts of methyl isobutyl ketone and hydroxide)
l) 03 parts of ram was charged, the air in the system was replaced with nitrogen gas, and then the system was sealed. Next, 57 parts of ethylene oxide was continuously introduced and reacted while keeping the inside of the system at 130 to 150°C, and then the volatile components were removed under reduced pressure to form the reaction product (
Hereinafter, it will be referred to as diol (1). ). Diol (1
) has a hydroxyl value of 24], and is an addition reaction of 114 equivalents of propylene oxide and 1.1 g equivalent of ethylene oxide per equivalent of bisphenol A.

Next, 233 parts of diol (1), 15 parts of methacrylic acid
The methacrylate of diol (1) (hereinafter referred to as (meth)acrylate (A-3)) was prepared in the same manner as in Example 1 using 0.0 parts of toluene, 500 parts of toluene, 0.1 parts of hydroquinone, and 5 parts of para-toluenesulfonic acid. ) was obtained. The (meth)acrylate (A-3) had a hydroxyl value of 9 and an ester value of 169, and the 95th hydroxyl group of diol (1) was esterified.

(meth)acrylate (A-3) 100 parts and styrene 3
0 parts were mutually dissolved to obtain a resin (3).

Resin (3) was a dark brown liquid with a viscosity of 110 cp (25°C).

Table 1 shows the physical properties of a resin plate obtained using resin (3) in the same manner as in Example 1.

Comparative Example 3 Uniol DB-3 was prepared in the same manner as in Example 3 except that 100 parts of ethylene oxide was used.
A reaction product with 60° ethylene oxide (hereinafter referred to as diol (ratio-1)) was obtained. Diol (ratio -1
) has a hydroxyl value of 207, and is an addition reaction of 114 equivalents of propylene oxide and 206 equivalents of ethylene oxide per equivalent of bisphenol AI.

Next, 271 parts of diol (ratio -1), 1 part of methacrylic acid
Methacrylate of diol (ratio-2) (hereinafter referred to as (meth)acrylate (ratio-2)) was prepared in the same manner as in Example 1 using 50 parts of toluene, 500 parts of toluene, 0.1 part of hydroquinone, and 5 parts of para-toluenesulfonic acid. (Meth)acrylate (ratio -2) has a hydroxyl value of 96 and an ester value of 50.
94% of the hydroxyl groups in the diol (ratio -2) were esterified.

The physical properties of the resin (ratio-3) obtained in the same manner as in Example 3 using (meth)acrylate (ratio-2) are shown in Table 1.

Table 1 (Note) Tensile strength, elongation, heat distortion temperature JIS K 6
I followed 911.

Water Resistance A casting plate of 75 x 25 x 3 mm was boiled in ion-exchanged water, and the time until cracks appeared was measured.

As is clear from the results shown in Table 1, the thermosetting resin composition of the present invention has excellent performance in all of heat resistance, corrosion resistance, and mechanical strength.

Patent applicant: Agent of Nippon Shokubai Chemical Co., Ltd.
Tsuyoshi Yamaguchi

Claims (1)

[Claims], ■ A reaction product obtained by adding on average 15 to 2.5 parts of alkylene oxide (b) per equivalent of dihydric phenol (a) represented by the general formula ( c) 100 parts by weight of (meth)acrylate (5) and polymerizable unsaturated monomer (B)
A thermosetting resin composition comprising 10 to 100 parts by weight.