JPH02108660A - Styrene sulfonate compound and composition containing the compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (R is H, halogen or hydrocarbon group; Z is >=2-valent alcohol residue containing a large number of C atoms; n is >=2). EXAMPLE:Triethylene glycol distyrene sulfonate. USE:Useful as a paint, coating agent, lining agent, adhesive, etc. A composition containing a styrene sulfonate compounds has high rate of cure and scratch resistance and is curable by the irradiation of energy radiation (especially light, electron ray, etc.). PREPARATION:The objective compound can be produced by reacting styrene sulfonic acid with sulfonyl chloride and reacting the resultant styrene sulfonyl chloride with a polyhydric alcohol.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a styrene sulfonate compound suitable for use in paints, coating agents, lining agents, adhesives, etc.
The present invention relates to a curable composition, and particularly to a composition curable by irradiation with energy rays such as light and electron beams.

[Prior Art] Curable compositions comprising compounds or oligomers having two or more ethylenically unsaturated bonds in one molecule are known. In particular, photocurable compositions containing a photoreaction initiator generally have a faster curing speed than thermosetting compositions, and the resulting cured product has excellent scratch resistance, solvent resistance, etc. It has such characteristics. Examples of the ethylenically unsaturated bond include allyl groups such as allyl ether groups, allyl urethane groups, and allyl ester groups, acryloyl groups, and methacryloyl groups.

However, in recent years, demands have increased for improving productivity by shortening the coating process and improving the quality of coated products.
There is a growing demand for higher curing speeds and higher hardness, ie, higher scratch resistance.

[Problems to be Solved by the Invention] However, conventional curable compositions are still insufficient in terms of curing speed and hardness of cured products, and in particular, curing is slow in the presence of oxygen, that is, in air. However, there are also problems in that it may not harden sufficiently, and if additives such as pigments that are difficult to transmit light are added, it will not harden sufficiently. Therefore, there is a desire for a composition that has a faster curing rate and provides a cured product with even higher hardness.

Various compounds and curing systems have been proposed to meet these demands, but all of them are compounds that have the above-mentioned allyl group or (meth)acryloyl group as an ethylenically unsaturated bond. The current situation is that it is difficult to make a leap forward.

Therefore, the present invention has a high curing speed and hardness of the cured product (
The object of the present invention is to provide a curable composition with high scratch resistance.

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have determined that the following formula (1 ); [In the formula, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group, Z represents a divalent or higher alcohol residue containing a large number of carbon atoms, and n represents a number of 2 or more. ] It has been discovered that by using the styrene sulfonate compound represented by the formula, it is possible to provide a composition with a high curing speed and high hardness (scratch resistance) of the cured product.

That is, the present invention is based on the following formula (1): [wherein R represents a hydrogen atom, a halogen atom, or a hydrocarbon group, Z represents a divalent or higher alcohol residue containing a large number of carbon atoms, and n represents 2 Indicates the above number. ] and at least one of the styrene sulfonate compounds represented by formula (1).

In the formula, the meaning of R is as above, but examples of halogen atoms include fluorine, chlorine, bromine, etc., and examples of hydrocarbon groups include methyl, ethyl, and their derivatives, such as I.lifluoromethyl and cyano. Examples include groups.

where Z represents a polyhydric alcohol residue containing a large number of carbon atoms, which can be a substituted or unsubstituted alkylene residue, or a substituted or unsubstituted alkylene residue,
Furthermore, hydrogenated or unhydrogenated arylene residues or -CH-2, -C(CH3) 2- -CO
Examples include alcohol residues containing a group such as O--CO--NHCO--802--0-imide or a plurality of arylene residues connected by direct bonds.

Examples include polyhydric aliphatic alcohols and aromatic alcohols.

More specifically, examples of polyhydric aliphatic alcohols include HO(CR) such as ethylene glycol, propylene glycol, butanediol, and neopentyl glycol.
2) A compound represented by nOH [n is a number of 1 or more, R is a hydrogen atom or a hydrocarbon group such as a methyl group,
HO (CH2CHRO) such as polyethylene glycol and polypropylene glycol. H[n is a number greater than or equal to 2, R
represents a hydrogen atom or a hydrocarbon group such as a methyl group]
Examples include compounds represented by the above, trivalent or higher aliphatic alcohols such as glycerin, and the like. Examples of polyhydric aromatic alcohols include aromatic diols such as HO-
[+CH2CH(OH) l A r (X
A r ) m+0-CH(OH)-CH2). −
〇] p-H (n is 0 or 1, m is 0 or a number of 1 or more, p is 1 or a number of 2 or more, X is -CH
-2, C(CH) --C(CF3) 2COO
-CO-N HCOS O-, ,5O2NH--0-imide, etc., Ar is a phenyl group, a biphenyl group,
terphenyl group, etc.), for example,
Examples include bisphenol A1 bisphenol F1 bisphenol S1 and suphenol AF, biphenyl diol, terphenyl diol, hydroquinone, resorcinol, bisphenol A diglycidyl ether, bisphenol A diglycidyl ether condensate, and the like.

The compound represented by formula (1) of the present invention can be produced, for example, by the following method. First, methynone sulfonic acid or its salt is reacted with sulfonyl chloride to synthesize styrene sulfonyl chloride, and then this intermediate is
The styrene sulfonate compound of the present invention can be obtained by reaction with a polyhydric alcohol as described above.

Among these, compounds in which a styrene sulfonate group is directly bonded to an aromatic ring are particularly preferred in terms of hydrolysis resistance.

The composition of the present invention may be composed only of the styrene sulfonate compound represented by formula (1), or
It may also be a mixture of the styrene sulfonate compound and other compounds that can be copolymerized. Such other compounds include compounds or oligomers having ethylenically unsaturated bonds. For example, (di)ethylene glycol di(meth) which is an ester or partial ester of polyhydric alcohol and (meth)acrylic acid.
Acrylate, brobylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc.; Epoxy resin and (meth)acrylate Epoxy (meth)acrylate, etc., which is a reaction product with acrylic acid, or polyester (meth) having one or more (meth)acryloyloxy groups in one molecule
Examples include acrylate, polyurethane (meth)acrylate, and the like. Other examples include unsaturated polyesters, which are esters of ethylenically unsaturated polycarboxylic acids or mixtures of ethylenically unsaturated polycarboxylic acids and saturated polycarboxylic acids, and polyfd[i alcohols. Also, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (
Diluting compounds with one ethylenically unsaturated bond such as meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, and styrene. It may also be used as an agent.

In addition, the composition of the present invention may contain various polymers, inorganic compounds, etc., in addition to coloring agents such as viscosity moderators, surface tension reducers, slip aids, reinforcing agents, dyes, and pigments, as necessary. Fillers can also be blended. Additionally, a solvent may be used for dilution.

To cure the composition of the present invention, a method of simply heating may be used, but a method of irradiating with active energy rays can be effectively used. Examples of active energy rays include ultraviolet rays, electron beams, gamma rays, and X-rays, among which ultraviolet rays and electron beams are preferred.

When ultraviolet rays are used as active energy rays, it is usually preferable to include a photocatalytic system such as a photosensitizer or a photoreaction accelerator having an IPI or higher as a photoreaction initiator in the composition. Examples of the photosensitizer include benzophenone, benzyl acetophenone, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, dimethoxyacetophenone, jetoxyacetophenone, dimethoxyphenylacetophenone, diphenyl sulfide, α-alkylbenzoin, and the like. . Examples of the photoreaction accelerator include tertiary amines and the like. The amount of these initiators added is 0.
0.01% by weight or more, preferably 0.5 to 10% by weight26. When the composition of the present invention is cured by electron beam irradiation, it is not necessarily necessary to add a sensitizer.

[Effects of the Invention] The styrene sulfonate compound composition of the present invention has a higher curing speed than a curable composition consisting of a compound or oligomer having two or more ethylenically unsaturated bonds in one molecule, and the resulting curing is faster. It is characterized by its high hardness. In particular, when curing with active energy rays, the composition of the present invention has a high polymerization rate even in the presence of oxygen. Therefore, it is useful as a composition that can be photocured in air. Furthermore, since the composition of the present invention has a high curing speed, it also has the characteristic that sufficient curing can be achieved even if additives such as pigments that are difficult to transmit light are added.

The composition according to the present invention can be used in various coating materials such as ink, plastic paint, paper printing, film coating, metal coating, furniture painting, FRP, lining, and even insulation panels in the electronics field.
Insulating sheets, laminates, printed circuit boards, resist inks,
It can be applied to many fields such as semiconductor encapsulation materials.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited in any way by the description of these Examples.

Example 1 In a 3000 ml container, 500 g of dry sodium styrene sulfonate, 350 g of dimethylformamide, and t-
Butylcatechol 0.05g and chloroform 1000g
ml of thionyl chloride was added, and while stirring under a nitrogen atmosphere, 569.7 g of thionyl chloride was started dropwise at 0°C, and was added little by little so as to keep the humidity in the system below 5°C. After the completion of the dropwise addition, the internal temperature was raised to 30° C. and maintained for 3 hours with stirring. After the reaction was completed, the reaction solution was added to 2000 ml of cold water with stirring. At this time, the internal temperature was maintained at 10°C or less.

Thirty minutes after the completion of the dropwise addition, the organic layer was separated. Subsequently, the separated organic layer was washed three times with cold water at 10,100 O and then dehydrated with zeolum. Then, 0.05 g of t-butylcatechol was added and chloroform was distilled under reduced pressure to obtain 403 g of styrene sulfonic acid chloride.

Next, 153 g of the obtained styrene sulfonic acid chloride, 300 g of chloroform, and 380 pyridine 1. and t-butylcatechol 0.02
45.4 g of triethylene glycol and 230 g of chloroform at 0°C while stirring under a nitrogen atmosphere.
A solution of g was added dropwise little by little. After the reaction for 2 hours, 950 ml of a 5N sulfuric acid aqueous solution was added dropwise to keep the internal temperature below 10°C, and after the addition was completed, the organic layer was separated. After washing the separated organic layer three times with 10,100 O of water and dehydrating it with Zeolum, 0.02 g of hydroquinone methyl ether was added and chloroform was distilled under reduced pressure to obtain 110 g of triethylene glycol e-distyrene sulfonate.

Example 2 Bisphenol A69, og
and 300 g of chloroform, and then styrene sulfonic acid chloride 15 obtained in the same manner as in Example 1.
After charging 3 g of chloroform, 300 g of chloroform, and 0.02 g of t-butylcatechol, 153 g of triethylamine was added dropwise little by little at room temperature while stirring under a nitrogen atmosphere. After 2 hours of reaction, 950 m of 5N sulfuric acid aqueous solution
1 was added dropwise to keep the internal temperature below 10°C, and after the addition was completed, the organic layer was separated. Pour the separated organic layer into 10,100 ml of water.
After washing with O three times, pouring into ethanol and filtering, washing and drying the resulting precipitate, bisphenol A-
158 g of 4,4-distyrene sulfonate were obtained.

Example 3 Example 2 was carried out in the same manner as Synthesis Example 2, except that 103 g of bisphenol A diglycidyl ether was used instead of bisphenol A and the reaction temperature was raised to 50°C. As a result, 160 g of styrene sulfonic acid diester of bisphenol A diglycidyl ether was obtained.

Example 4 To the triethylene glycol distyrene sulfonate obtained in Example 1, 2% by weight of benzoin methyl ether was added as a sensitizer, and the mixture was coated on a polyester film using a bar coater and heated using a high-pressure mercury lamp (output 33 W).
/cm) for 10 minutes, a cured film was obtained.

The hardness of the cured product was H. In addition, if a polyester film is placed on top of the applied liquid to cut off contact with air,
Hardened in seconds.

Comparative Example 1 Example 4 was added to triethylene glycol dimethacrylate.
In the same manner as above, 2 parts by weight of benzoin methyl ether (96%) were added, and the mixture was coated on a polyester film using a bar coater, and was irradiated with a high-pressure mercury lamp (output 33 W/Cm) for 20 minutes, but it did not harden. Further, a polyester film was placed on top of the solution applied in the same manner as in Example 4, and when contact with air was cut off, the film was cured in 10 seconds. The hardness of this cured product is
It was B.

Example 5 50% by weight of methyl ethyl ketone was added to the bisphenol A-4,4-distyrene sulfonate obtained in Example 2, and 2% by weight of benzoin methyl ether was added as a sensitizer in the same manner as in Example 4 to form a polyester film. using a bar coater and applying it using a high-pressure mercury lamp (output 33).
When irradiated with W/Cm) for 10 minutes, a cured film was obtained. The hardness of the cured product was 3H. Furthermore, when a polyester film was placed on top of the applied solution and contact with air was cut off, the solution cured in 10 seconds.

Even if the cured film is immersed in boiling water for 1 hour, it will not react with a 10% by weight aqueous solution of sodium hydroxide or 10% by weight of hydrochloric acid.
Even after being immersed in an aqueous solution for 3 days, no hydrolysis of the cured product occurred. On the other hand, in the film obtained in Example 4, hydrolysis occurred.

Example 6 50% by weight of methyl ethyl ketone was added to the bisphenol A-4,4 distyrene sulfonate obtained in Example 2, and 4% by weight of benzoin methyl ether was added in the same manner as in Example 5.
and 10% by weight of yellow pigment were added, coated on a polyester film using a bar coater, and heated using a high-pressure mercury lamp (
When irradiated with an output of 33 W/cm for 10 minutes,
A cured film was obtained. The hardness of the cured product was 3H. Furthermore, when a polyester film was placed on top of the applied solution and contact with air was cut off, the solution cured in 10 seconds.

Comparative Example 2 Example 6 was added to triethylene glycol dimethacrylate.
Similarly, 4% by weight of benzoin methyl ether and 10% of yellow pigment and 96% of yellow pigment were added, coated on a polyester film using a bar coater, and heated with a high-pressure mercury lamp (output 33).
W/cm) was irradiated for 20 minutes, but no curing occurred. Therefore, even if a polyester film was placed on top of the applied solution to cut off contact with air, a sufficiently cured film could not be obtained.

Example 7 50% by weight of methyl ethyl ketone was added to the styrene sulfonic acid diester of bisphenol A diglycidyl ether obtained in Example 3, and 2% by weight of benzoin methyl ether was added as a sensitizer in the same manner as in Example 4 to form a polyester film. A hardened film was obtained by coating the film using a bar coater and irradiating it with a high-pressure mercury lamp (output 33 W/cm) for 10 minutes. The hardness of the cured product was H. Furthermore, when a polyester film was placed on top of the applied solution and contact with air was cut off, the solution cured in 10 seconds.

Claims (3)

[Claims] (1) The following formula (1); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group, and Z represents a divalent group containing many carbon atoms. represents the above alcohol residue, and n represents a number of 2 or more. ] A composition comprising at least one of the styrene sulfonate compound represented by formula (1) and the styrene sulfonate compound represented by formula (1). (2) R shown in formula (1) is a hydrogen atom, and Z is 2
The styrene sulfonate compound according to claim 1, which is a polyhydric aliphatic alcohol having a higher valence or higher, and a curable composition. (3) R shown in formula (1) is a hydrogen atom, and Z is 2
The styrene sulfonate compound according to claim 1, which is a polyhydric aromatic alcohol having a higher valence or higher, and a curable composition.