JPH05247139A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a mixture, obtained by a specific method, of divinyl compound and vinylbenzyl ether, giving a cured product excellent in mechanical characteristics, thermal stability, etc., and having high photosensitivity for sunlight. CONSTITUTION:The objective composition composed of a mixture of a divinylbenzene compound of formula I (X is a residue of diaminodiphenyl sulfone having less (y) atoms in its amino group; y is 2-4) obtained by subjecting diaminodiphenyl sulfone to react with chloromethylstyrene in the presence of an alkali and a divinyl benzyl ether compound of formula II. The mixture is preferably obtained by subjecting in the rate of 1 equivalent of diaminodiphenyl sulfone calculated from active hydrogen to react with 1-3 equivalents of chloromethylstyrene. The ratio of both compounds is preferably 54-82wt.% of formula I compound to 46-18wt.% of formula II compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which is easily cured by active energy rays such as ultraviolet rays and has a high photosensitivity to natural light (sunlight), mechanical properties and thermal stability. The present invention relates to a curable composition which gives a cured product having excellent properties, solvent resistance and alkali resistance.

[0002]

2. Description of the Related Art In recent years, research on curable compositions using active energy rays has advanced, and in the fields of printing inks, paints, adhesives, photoresists, etc., resin systems such as epoxy acrylate, polyester acrylate, urethane acrylate, etc. Practical application is progressing mainly in
However, all of these are technologies for curing by irradiating ultraviolet rays with an ultraviolet curing device, and it cannot be said that the method of curing with natural light (sunlight) is still sufficiently advanced.

[0003]

The object of the present invention is to overcome the drawbacks of the prior art and to have a high photosensitivity to active energy rays, especially sunlight, and to provide mechanical properties, thermal stability, chemical resistance, etc. It is to provide a curable composition which gives an excellent cured product.

[0004]

The present invention provides a curable composition that can achieve the above objects.

That is, the present invention is obtained by reacting diaminodiphenyl sulfone with chloromethylstyrene in the presence of an alkali, represented by the general formula (I)

[0006]

[Chemical 3] (In the formula, X represents a residue obtained by removing y hydrogen atoms from the amino group of diaminodiphenyl sulfone, and y is a number of 2 to 4.) and a vinylbenzyl compound represented by the general formula (I
I)

[0007]

[Chemical 4] And a curable composition comprising a mixture of divinylbenzyl ethers represented by:

Further, the present invention is a curable composition comprising a mixture of a vinylbenzyl compound represented by the above general formula (I) and a divinylbenzene ether represented by the above general formula (II) and a vinyl group-containing compound. Regarding things.

The general formula (I) used in the present invention

[0010]

[Chemical 5] (In the formula, X represents a residue obtained by removing y hydrogen atoms from the amino group of diaminodiphenyl sulfone, and y is a number of 2 to 4.) and a vinylbenzyl compound represented by the general formula (I
I)

[0011]

[Chemical 6] The mixture of divinylbenzyl ether represented by the following uses diaminodiphenylsulfone and chloromethylstyrene, and chloromethylstyrene is added to diaminodiphenylsulfone at a ratio of 2 to 4 vinylbenzyl groups or at a ratio higher than that. It can be easily synthesized by dehydrochlorination with an inorganic alkali using a solvent such as dimethyl sulfoxide as a solvent.

The production ratio of the vinylbenzyl compound represented by the general formula (I) and the divinylbenzyl ether represented by the general formula (II) varies depending on the use ratio of diaminodiphenylsulfone and chloromethylstyrene and the reaction conditions. The viscosity can be changed at the same time.

In the present invention, the mixture of the vinylbenzyl compound represented by the general formula (I) and the divinylbenzyl ether represented by the general formula (II) is chloro with respect to 1 equivalent of diaminodiphenylsulfone calculated from active hydrogen. It is suitable to react methyl styrene at a ratio of 0.5 to 5 equivalents, preferably 1 to 3 equivalents.

The ratio of the vinylbenzyl compound represented by the general formula (I) to the divinylbenzyl ether represented by the general formula (II) in the mixture is the vinylbenzyl compound 3
8 to 92% by weight and divinylbenzyl ether 62 to 8% by weight, preferably vinylbenzyl compound 54 to 8
2% by weight and divinylbenzyl ether 46-18% by weight
It is desirable to consist of

When the proportion of divinylbenzyl ether in the mixture is less than 8% by weight, the viscosity of the mixture becomes high and the workability becomes poor. When the proportion of divinylbenzyl ether in the mixture is more than 62% by weight, the viscosity of the mixture is lowered but the curability by sunlight is deteriorated.

The ratio of the vinylbenzyl compound represented by the general formula (I) to the divinylbenzyl ether represented by the general formula (II) in the mixture can be determined by GPC (gel permeation chromatography) by using the vinylbenzyl compound and the divinylbenzyl compound. It can be measured and calculated from the area ratio of each peak of ether.

Examples of the alkali used when reacting diaminodiphenyl sulfone with chloromethylstyrene include potassium hydroxide and sodium hydroxide.

Further, as diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 '
-Diaminodiphenyl sulfone.

A vinyl group-containing compound may be added to the mixture of the vinylbenzyl compound represented by the general formula (I) and the divinylbenzyl ether represented by the general formula (II). Examples of the vinyl group-containing compound include epoxy (meth) acrylate, urethane (meth) acrylate, oligomer such as unsaturated polyester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate. , Butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, alkylene oxide adduct of alkylphenol (meth) acrylate, cyclohexyl (meth) acrylate, styrene , Vinyltoluene, allylphenol, allyloxybenzene, vinylpyrrolidone and other monofunctional monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, pentyl glycol di (meth)
Acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate,
(Di) glycerin poly (meth) acrylate, trimethylol (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl terephthalate, etc. Examples include monomers.

The mixing ratio of the mixture of the vinylbenzyl compound and divinylbenzyl ether and the vinyl group-containing compound is 2-98% by weight of the mixture and the vinyl group-containing compound 98-.
2% by weight, preferably 5 to 95% by weight of the mixture and 95 to 5% by weight of the vinyl group-containing compound.

The curable composition comprising a mixture of a vinylbenzyl compound and a divinylbenzyl ether and a vinyl group-containing compound has excellent mechanical properties, thermal stability, solvent resistance and alkali resistance of the mixture, and the vinyl used. The characteristics inherent to the group-containing compound are also expressed.

When the mixing ratio of the vinyl group-containing compound is more than 98% by weight, it takes too long to cure.
Further, when the mixing ratio of the vinyl group-containing compound is less than 2% by weight, the characteristics originally possessed by the vinyl group-containing compound cannot be sufficiently exhibited.

A curable composition comprising a mixture of a vinylbenzyl compound and divinylbenzyl ether of the present invention, or a curable composition obtained by mixing a vinyl group-containing compound with a mixture of a divinylbenzyl compound and divinylbenzyl ether is photopolymerized. It can be cured with active energy rays, such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet rays or electron beams, such as sunlight without adding a catalyst such as an initiator. The feature is that it can be hardened.

In the curable composition of the present invention containing a vinyl group-containing compound in a mixture of a vinylbenzyl compound and divinylbenzyl ether, the greater the amount of the vinyl group-containing compound mixed, the more the photopolymerization initiator is not added. Curing is slow, and particularly if the vinyl group-containing compound is 95% by weight or more, it takes a long time to cure. In such a case, a photopolymerization initiator may be added to the curable composition to accelerate curing. Similarly, a photopolymerization initiator may be added to a curable composition composed of a mixture of a vinylbenzyl compound and divinylbenzyl ether to accelerate curing.

As the photopolymerization initiator, benzophenone,
Hydroxyisobutylphenone, acetophenone, 2,
Typical examples are carbonyl compounds such as 2-diethoxyacetophenone, benzoin, benzoin ethyl ether, benzyl, benzylmethyl ketal, benzoyldiphenylphosphine oxide and ethylanthraquinone, thioxanthone, chlorothioxanthone and azobisisobutylnitrile. The amount used is 0.2 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of the curable composition.

A cured product obtained by curing a curable composition comprising a mixture of the vinylbenzyl compound and divinylbenzyl ether of the present invention with active energy rays has excellent mechanical properties, thermal stability, solvent resistance, and Shows alkali resistance,
Further, a cured product obtained by curing a curable composition obtained by mixing a vinyl group-containing compound in a mixture of a vinylbenzyl compound and divinylbenzyl ether with an active energy ray is
The performance can be freely adjusted by selecting a vinyl group-containing compound having the desired performance.

The curable composition of the present invention can be widely used for adhesives, insulating materials, paints, printing inks, photoresists, prepreg materials, etc. by selecting the composition. Needless to say, hydroquinone, benzoquinone, copper salt, etc. may be added for adjusting the curing, and radical initiators may be added for promoting the curing.

The curable composition of the present invention is prepared by a kneader, a blender, a roll or the like, a filler such as talc, barium sulfate, silica powder, glass beads or aerial, a defoaming agent such as silicone oil, a leveling agent or a dyeing agent. As a molding material by blending pigments, etc. and as a varnish, paint, adhesive by dissolving in a solvent, and impregnating glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber which are reinforcing fibers, prepreg It is also possible to make a molding material or structural material useful as a filament winding.

[0029]

The present invention will be described in more detail with reference to Examples and Comparative Examples. The parts in the examples and comparative examples are parts by weight unless otherwise specified.

Synthesis Example 1 4,4'-diaminodiphenyl sulfone (1.0 equivalent)
Synthesis of a mixture by the reaction of chloromethylstyrene (1.0 equivalent) with 4,4'-diaminodiphenylsulfone 62.1 parts (1.0 equivalent) dimethylsulfoxide (DMSO) 1
To 50 parts of dissolved solution, 30 parts of aluminum salt of N-nitrosophenylhydroxylamine (Q-1301) is added.
Commercially available chloromethylstyrene 152.5 with 0 ppm added
Part (1.0 equivalent) was added, and an aqueous potassium hydroxide solution consisting of 56.1 parts of potassium hydroxide (1.0 equivalent) and 35 parts of water was added dropwise at 60 ± 2 ° C. over 40 minutes, and further 60 ±.
The reaction was continued at 2 ° C for 4 hours.

Next, a large excess of water was added to the system, and after stirring, water-DMSO was removed, and an oily substance was extracted with benzene.
The benzene layer was repeatedly washed with water until the pH of the aqueous layer reached 7, and benzene was removed under reduced pressure to obtain 4,4'-diaminodiphenylsulfone (1.0 equivalent) and chloromethylstyrene (1.0 equivalent) as oils. Reaction product (hereinafter, N-
TVBDDS) yield 90%, viscosity 22 poise /
Obtained at 25 ° C.

The content of divinylbenzyl ether in the obtained N-TVBDDS was determined by GPC.
% By weight. This N-TV BDDS is benzene,
It was soluble in various organic solvents such as toluene, acetone and MEK.

Synthesis Example 2 4,4'-diaminodiphenyl sulfone (1.0 equivalent)
Synthesis of a mixture by the reaction of chloromethylstyrene (1.5 equivalents) In Synthesis Example 1, 228.8 parts (1.5 equivalents) of chloromethylstyrene and 84.2 parts (1.5 equivalents) of potassium hydroxide were added. The reaction was performed in the same manner as in Synthesis Example 1 except that an aqueous potassium hydroxide solution consisting of 45 parts of water was used, and the reaction product (hereinafter referred to as CMS1.5N-TVBDDS) was obtained in a yield of 95% and a viscosity of 4.5 poise. Obtained at / 25 ° C.

The content of divinylbenzyl ether in the obtained CMS1.5N-TVBDDS was determined by GPC and found to be 30% by weight. This CMS 1.5N
-TVBDDS is benzene, toluene, acetone, M
It was soluble in organic solvents such as EK.

Synthesis Example 3 Synthesis of bisphenol type epoxy acrylate Bisphenol type epoxy resin having an epoxy equivalent of 185 (Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 185
110 parts (1.0 equiv.) In a flask equipped with a condenser.
The mixture was heated and stirred at 0 ° C., and 110 parts of methyl hydroquinone (0.1 parts) and tris (diaminomethyl) phenol (1.0 parts) dissolved in 72 parts (1.0 equivalent) of acrylic acid were added to the solution.
It was added dropwise at 30 ° C. for about 30 minutes. After that, 120-130
The reaction was continued at 0 ° C., and when the acid value reached 8 to 9, it was cooled and the reaction was terminated to synthesize a bisphenol type epoxy acrylate (hereinafter abbreviated as 828 diacrylate).

Examples 1 to 10 828 diacrylate and N-TVBDDS were 828 diacrylate / N-TVBDDS = 95/5, 90/1
Mixture in the weight ratio of 0, 70/30, 50/50, 0/100, 828 diacrylate and CMS 1.5N
-TVBDDS is 828 diacrylate / N-TVBD
DS = 95/5, 90/10, 70/30, 50/5
The mixture having a weight ratio of 0.00 / 100 was applied to a glass plate to a thickness of 50 μm, and the time until the surface tack disappeared by irradiation with sunlight was measured as the curing time.
The results are shown in Table 1.

Comparative Example 1 828 diacrylate was applied to a glass plate to a thickness of 50 μm, and the same test as in Examples 1 to 10 was carried out by irradiating with sunlight. The results are shown in Table 1.

[0038]

[Table 1]

The cured coatings of Examples 1 to 10 showed almost no change when brought into contact with a solvent such as acetone.

Examples 11 to 13 50 parts of N-TVBDDS / 50 parts of neopentyl glycol diacrylate (NPGDA), N-TVBDDS5
0 parts / trimethylolpropane triacrylate (TM
PTA) 50 parts and N-TVBDDM 50 parts / dipentaerythritol hexaacrylate (DPHA) 5
0 part of each of the three types of mixtures was applied to a glass plate to a thickness of 50 μm, and the same test as in Examples 1 to 10 was performed by irradiating sunlight. The results are shown in Table 2.

Comparative Examples 2 to 4 Each of NPGDA, TMPTA and DPHA was applied on a glass plate to a thickness of 50 μm and irradiated with sunlight to give Examples 1 to 4.
The same test as 10 was conducted. The results are shown in Table 2.

[0042]

[Table 2]

The cured coatings of Examples 11 to 13 showed almost no change even when contacted with a solvent such as acetone.

Examples 14 to 21 Using 828 diacrylate and N-TVBDDS as 828 diacrylate / N-TVBDDS = 95/5, 90/1
A mixture of N70, 30, 50, 50, 0/100 in a weight ratio of NPGDA 50 parts / N-TVBDDS5
0 copy, TMPTA 50 copy / N-TV BDDS 50 copy, D
50 parts of PHA / 50 parts of N-TVBDDS were coated on a glass plate to a thickness of 50 μm, respectively, under a high pressure mercury lamp (2 kw) as a photocuring light source for 4 seconds, 8 seconds, 12
Second, 30 seconds, 40 seconds each time exposure,
The cured film was checked for tack. The results are shown in Table 3.

Comparative Examples 5-8 828 diacrylate, NPGDA, TMPTA, DP
Each of HA was applied on a glass plate to a thickness of 50 μm, and the same test as in Examples 14 to 21 was performed. The results are shown in Table 3.
It was shown to.

[0046]

[Table 3]

Examples 22 to 23 N-TVBDDS alone and 2 parts of a mixture of 50 parts of 828 diacrylate / 50 parts of N-TVBDDS were each mixed in 3 parts.
Pour into a mold made of two 5 mm thick glass plates with a 5 mm thick rubber plate as a spacer and irradiate with sunlight for 12 hours while measuring the Barcol hardness (BH) every 4 hours, and after photo-curing, 250 ° C After 5 hours of curing, two types of cast cured products were obtained. The obtained cast cured product was cut into a size of 80 × 23 × 3 mm to obtain a Barcol hardness, J
Flexural strength and flexural modulus were measured at room temperature and during hot according to IS K6911. The results are shown in Table 4.

Comparative Example 9 To 100 parts of 828 diacrylate, 1.5 phr of a peroxide catalyst 328E manufactured by Kayaku Akzo Co., Ltd. and 0.5 phr of cobalt naphthenate (metal content 6%) were added, and a 3 mm rubber plate was added thereto. It was poured into a mold made of two glass plates as spacers, cured at room temperature and then post-cured at 120 ° C. for 2 hours to obtain a cast cured product. The cast-cured products obtained were tested in the same manner as in Examples 22-23. The results are shown in Table 4.

[0049]

[Table 4]

[0050]

The curable composition of the present invention has high photosensitivity to active energy rays, especially sunlight, and its cured product exhibits excellent mechanical properties, thermal stability and chemical resistance. It can be widely used in industry as an adhesive, a casting material, and a prepreg material.

Claims (2)

[Claims] 1. A compound of the general formula (I), obtained by reacting diaminodiphenyl sulfone with chloromethylstyrene in the presence of an alkali. (In the formula, X represents a residue obtained by removing y hydrogen atoms from the amino group of diaminodiphenyl sulfone, and y is a number of 2 to 4.) and a vinylbenzyl compound represented by the general formula (I
I) [Chemical 2] A curable composition comprising a mixture of divinylbenzyl ether represented by 2. A curable composition comprising a mixture of a vinylbenzyl compound represented by the general formula (I) according to claim 1 and a divinylbenzyl ether represented by the general formula (II) and a vinyl group-containing compound. ..