JPH0841129A - Polymerizable composition - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Low viscosity, excellent UV curability, molded products obtained by curing have low water absorption, excellent heat resistance and chemical resistance, and high strength. There is provided a polymerizable composition containing the (meth) acrylate compound. [Structure] A polymerizable composition comprising a tetrafunctional (meth) acrylate compound having the following structural formula (1), a polymerizable monomer, and a radical polymerization initiator or a photopolymerization initiator. In the formula (1), the position of the substituent of —CH ₂ N (R) ₂ is the 1,3 position or the 1,4 position of the cyclohexane ring, and R is Represents Here, R ₁ represents hydrogen or a methyl group.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel tetrafunctional (meta)
The present invention relates to a polymerizable composition including an acrylate compound, a polymerizable monomer, and an initiator (radical polymerization initiator or photopolymerization initiator). The polymerizable composition of the present invention can be cured by heat, ultraviolet rays and electron beams,
It is extremely useful in a wide range of applications such as moldings, paints, printing inks, adhesives and resists.

[0002]

2. Description of the Related Art Generally, as a polyfunctional (meth) acrylate compound used in a polymerizable composition, an epoxy compound obtained by reacting an epoxy compound obtained from bisphenol A and epihalohydrin with (meth) acrylic acid is representative. (Meth) acrylate, adipic acid and 1,6
-Polyesters (meth) in which a diol compound obtained from hexanediol is reacted with (meth) acrylic acid, and a triol compound obtained from trimellitic acid and diethylene glycol is reacted with (meth) acrylic acid ) There is acrylate.

As the bis (aminomethyl) cyclohexane-based polyfunctional (meth) acrylate, an epoxy compound obtained by reacting 1,3-bis (aminomethyl) cyclohexane with epihalohydrin is reacted with acrylic acid or methacrylic acid. The compound obtained by this is known. Further, a methacrylate compound obtained by reacting 1,3-bis (aminomethyl) cyclohexane with glycidyl methacrylate is also known.

The above-mentioned epoxy (meth) acrylate has a drawback that the cured product thereof has both hardness and flexibility, but it has a high viscosity, is difficult to handle alone at room temperature, and has a low crosslink density and poor heat resistance. Have. The above-mentioned polyester (meth) acrylate compounds have low viscosity, are easy to handle, and have excellent reactivity,
In the case of curing by ultraviolet rays, surface curing is slow due to strong anaerobic property, so it is necessary to add a sensitizer such as triethylamine or diethylaminoethyl methacrylate.

The above-mentioned (meth) acrylate compound and the above-mentioned compound have an active aliphatic tertiary amino group in the molecule and have four polymerization-reactive double bonds. Therefore, it is possible to rapidly polymerize alone with a radical polymerization catalyst such as peroxides, and to copolymerize with vinyl compounds such as styrene and methyl methacrylate. Since it contains a cyclohexane ring and has a high cross-linking density, it has excellent heat resistance and also has excellent chemical resistance to organic solvents and alkalis. Further, these and their (meth) acrylate compounds have good adhesiveness and adhesion to glass fibers, carbon fibers, steel plates, etc., and composite materials using these as reinforcements have characteristics such as high elastic modulus and high hardness. ing. However, since the (meth) acrylate compound of and has four hydroxyl groups in one molecule, when it is used in a polymerizable composition, it has a very high viscosity and is inferior in workability, and a cured product has a drawback that it has a high water absorption rate.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of conventional (meth) acrylate compounds, to have a very low viscosity and excellent ultraviolet curability, and the cured product thereof has a water absorption rate. It is intended to provide a polymerizable composition containing a (meth) acrylate compound having low heat resistance, good heat resistance, chemical resistance and high strength.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a novel bis (aminomethyl) cyclohexane-based tetrafunctional (meth) acrylate compound represented by a specific structural formula as a (meth) acrylate compound. The inventors have found that the above problems can be solved by using, and have completed the present invention.

That is, the present invention provides the following structural formula (1):
The invention relates to a polymerizable composition comprising a tetrafunctional (meth) acrylate compound represented by, a polymerizable monomer, and a radical polymerization initiator or a photopolymerization initiator.

[0009]

Embedded image

The compound of the structural formula (1) used in the present invention is a bis (aminomethyl) cyclohexane-based tetrafunctional (meth) acrylate compound modified with ethylene oxide, and has one cyclohexane ring in the molecule and an aliphatic group. It is a novel and useful tetrafunctional (meth) acrylate compound having two functional tertiary amino groups, and further four oxymethylene groups and four (meth) acrylate double bonds. Specifically, the tetrafunctional (meth) acrylate compound of the structural formula (1) is prepared by adding 4 mol of ethylene oxide to 1 mol of 1,3-bis (aminomethyl) cyclohexane or 1,4-bis (aminomethyl) cyclohexane. It is obtained by converting the above compound into an acrylic or methacrylic ester. This esterification method is carried out by a known transesterification reaction method.

The polymerizable monomer used in the present invention is used for the purpose of lowering the viscosity of the composition, imparting flexibility to the cured product, and improving the adhesion to the article to be coated. There are styrene, divinylbenzene, methyl acrylate, methyl methacrylate, and 2 as typical examples.
-Ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane Examples thereof include triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate and the like. The mixing ratio of the polymerizable monomer is 10 to 1 with respect to 100 parts by weight of the tetrafunctional (meth) acrylate compound represented by the structural formula (1).
It is desirable to add 000 parts by weight. In that range (meta)
The object of the present application can be achieved without impairing the characteristics of the acrylic compound.

As the radical polymerization initiator used in the present invention, any radical polymerization initiator that decomposes when heated to generate radicals and easily initiates a polymerization reaction can be used. Peroxide, tert-butyl hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, azobisisobutyronitrile, hydrogen peroxide-ferrous iron salt , Persulfate-sodium hydrogen sulfite, cumene hydroperoxide-ferrous iron salt, benzoyl peroxide-dimethylaniline, triethylboron, diethylzinc and the like. These radical polymerization initiators may be used alone or in combination of two or more.

As the photopolymerization initiator used in the present invention, any photoinitiator can be used as long as it is excited when irradiated with an actinic ray such as an ultraviolet ray or an electron beam to easily initiate a photopolymerization reaction. Examples include biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, tetramethyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, 1- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl 1-phenyl-propan-1-one, 1
-(4-Isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, 2-chlorothioxanthone, methylbenzoyl formate and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The proportion of the polymerization initiator used in the composition is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the tetrafunctional (meth) acrylate compound represented by the structural formula (1). It is desirable to blend in parts by weight. Use of the polymerization initiator in this range is a practically preferable polymerization rate and does not impair the properties of the cured product.

A polymerization inhibitor may be used in the polymerizable composition of the present invention. The polymerization inhibitor used in the present invention is for preventing gelation when the polymerizable composition of the present invention is stored, and typical examples thereof include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone and the like. be able to.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The blending ratio of each component in Examples and the like is a weight ratio. Example 1 No. 4 in 1,3-bis (aminomethyl) cyclohexane
A compound obtained by reacting methyl acrylate by transesterification reaction with a polyol compound obtained by adding twice the molar amount of ethylene oxide (hereinafter referred to as TETRAD-CEA) and 1,6-hexanediol diacrylate (hereinafter referred to as HDDA) : 8, 4: 6, 6: 4, 8:
To 100 parts of the mixture of 2 parts, 4 parts of benzophenone was added as a photoinitiator, and UV curing (conveyor speed was 1 m / min) by an ultraviolet irradiation device of 80 w / cm ozone type was performed at 200 ° C. for about 1 hour. Was heat-cured to prepare a film having a thickness of about 200 μm. Using the film, water absorption measurement based on JIS K 7209 and glass transition temperature measurement by a dynamic viscoelasticity measuring device were performed. The results are shown in Table 1.

Example 2 Part 1 of 1,3-bis (aminomethyl) cyclohexane
A compound (hereinafter referred to as TETRAD-CEM) obtained by reacting methyl polyol by a transesterification reaction with a polyol compound obtained by adding a double mole of ethylene oxide and HDDA are 2: 8, 4: 6, 6: 4, 8: To 100 parts of the mixture of 2 parts, 4 parts of benzophenone was added as a photoinitiator, and ultraviolet curing was carried out by an ultraviolet irradiation device of 80 w / cm ozone type (conveyor speed was 1
m / min) and heat curing at 200 ° C. for about 1 hour to produce a film having a thickness of about 200 μm. Using the film, water absorption measurement based on JISK 7209 and glass transition temperature measurement by a dynamic viscoelasticity measuring device were performed. Table 2 shows the results.

Comparative Example 1 187.4 g of acrylic acid and 3.1 of triphenylstibine
g, copper naphthenate 0.04 g, hydroquinone monomethyl ether 0.05 g, and a tetrafunctional epoxy resin (1,3-bis (aminomethyl) cyclohexane to which 4 times the mole of epichlorohydrin was added are subjected to a ring closure reaction by caustic soda treatment. 4 functional epoxy resin, manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: TETRAD-
C) 286.1 g was charged into a three-necked flask equipped with a stirrer, a thermometer, and a condenser, and the reaction temperature was 80.
The temperature was kept at 0 ° C. and the reaction was performed for 2 hours. The product was a yellow transparent viscous liquid with a viscosity of 348,000 cps at a temperature of 40 ° C. and a color number (Gardner) of 9 (hereinafter, TET
RAD-CA).

Next, TETRAD-CA and HDDA are set to 2:
Mixing in the ratio of 8, 4: 6, 6: 4, 8: 2 10
To 0 parts, 4 parts of benzophenone was added as a photoinitiator, and ultraviolet curing (conveyor speed was 1 m / min) by an 80 w / cm ozone type ultraviolet irradiation device and heat curing at 200 ° C. for about 1 hour were performed to obtain a thick film. About 200 μm
The film of was produced. Using the film, JIS
The water absorption rate measurement based on K 7209 and the glass transition temperature measurement using a dynamic viscoelasticity measuring device were performed. The results are shown in Table 3.

Table 1 Composition Ratio Composition Water absorption (wt%) Glass transition temperature (℃) TETRAD-CEA / HDDA = 2/8 0.6 109 TETRAD-CEA / HDDA = 4/6 0.6 113 TETRAD-CEA / HDDA = 6/4 0.5 120 TETRAD-CEA / HDDA = 8/2 0.5 125

Table 2 Composition Ratio Composition Water absorption (wt%) Glass transition temperature (℃) TETRAD-CEM / HDDA = 2/8 0.7 115 TETRAD-CEM / HDDA = 4/6 0.5 120 TETRAD-CEM / HDDA = 6/4 0.6 122 TETRAD-CEM / HDDA = 8/2 0.5 129

Table 3 Composition Ratio Composition Water absorption (wt%) Glass transition temperature (℃) TETRAD-CA / HDDA = 2/8 2.3 115 TETRAD-CA / HDDA = 4/6 3.5 119 TETRAD-CA / HDDA = 6/4 4.6 124 TETRAD-CA / HDDA = 8/2 5.9 127

[0023]

When the novel bis (aminomethyl) cyclohexane-based tetrafunctional (meth) acrylate compound of the present invention is used in a polymerizable composition, a composition having a very low viscosity and excellent curability can be obtained. it can. A molded article obtained by curing the composition has a low water absorption rate and excellent heat resistance.

Claims (2)

[Claims] 1. A polymerizable composition comprising a tetrafunctional (meth) acrylate compound represented by the following structural formula (1), a polymerizable monomer, and a radical polymerization initiator or a photopolymerization initiator. Embedded image 2. A tetrafunctional (meth) acrylate compound 10
10 parts by weight to 100 parts by weight of the polymerizable monomer, and 0.1 part by weight of the radical polymerization initiator or the photopolymerization initiator.
The polymerizable composition according to claim 1, which is compounded in an amount of 1 to 10 parts by weight.