JPH01123805A - Photocurable resin composition - Google Patents

Abstract

PURPOSE:To obtain the above composition excellent in rapid curability, curing characteristics and useful for a coating, an adhesive or the like, by using a reaction product of 1,2,3,4-butanetetracarboxylic acid or its anhydride with a specified compound as a curable component. CONSTITUTION:A curable component is obtained by reacting 1,2,3,4- butanecarboxylic acid or its anhydride with a compound having at least one ethylenically unsaturated group and an OH or glycidyl group (e.g., 2- hydroxyethyl acrylate or glycidyl acrylate) in the presence of, optionally, 0.01-10wt.% catalyst (e.g., triethylamine), 0.005-0.1wt.% polymerization inhibitor (e.g., p-methoxyphenol) and a solvent (e.g., toluene). 100pts.wt. curable component is mixed with, optionally, 100pts.wt. or below reactive diluent (e.g., 2- ethylhexyl acrylate), 0.01-20pts.wt. polymerization initiator (e.g., benzoin ethyl ether), and 0.01-20pts.wt. sensitizer (e.g., triethylamine) to obtain the title composition.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel photocurable resin composition.

[Prior Art] In recent years, photocurable resins have been widely studied in various fields, and many have been put into practical use. This is because photocurable resins have many advantages over conventional thermosetting and solvent-soluble resins in terms of productivity, energy saving, non-polluting properties, and the like.

In general, photocurable resins are classified into photodimerizable types such as cinnamic acid esters, photopolymerizable types such as acrylic esters, and photodegradable types such as azide compounds, depending on the type of photosensitive group. The acrylic ester type is the most widely used because it has excellent performance in both curability and film properties.

The main component of acrylic ester-based photocurable resin is a high-molecular-weight acrylic oligomer with acrylic monomer added as a reactive diluent, and optionally a photopolymerization initiator, sensitizer, and other various substances. It is used with addition clause 1 added.

Here, examples of known acrylic oligomers include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, acrylic acrylate, alkyd acrylate, etc.
Among them, polyester acrylate is the most widely used because it is inexpensive and exhibits well-balanced performance.

[Problems to be Solved by the Invention] However, conventional photocurable resin compositions containing polyester acrylate as a main component have a slow curing speed, especially in the presence of air, and do not have a sufficiently satisfactory photocuring speed. has not yet been discovered.

The present inventors have conducted extensive research to develop a resin composition that can be cured by short-term light irradiation without reducing storage stability or physical properties of the cured product. It was discovered that an acrylic compound obtained using an anhydride as a raw material has the desired effect, and based on this knowledge, the present invention was completed.

That is, an object of the present invention is to provide a novel photocurable resin composition that cures faster than ever before.

[Means for solving the problems] The photocurable resin composition according to the present invention has a temperature of 1,2°3.4-
Butanetetracarboxylic acid (hereinafter abbreviated as rBTCJ).

) or its acid anhydride and a compound having at least one ethylenically unsaturated group and a hydroxyl group or a glycidyl group as a curable component.

Such a reaction product comprises BTC or its acid anhydride and a compound having at least one ethylenically unsaturated group and a hydroxyl group or a glycidyl group, preferably in the presence of a catalyst and a thermal polymerization inhibitor. It can be synthesized by stirring under heating in the presence of a solvent or without using a solvent at about 50 to 150'C for about 5 to 20 hours.

Examples of compounds having at least one ethylenically unsaturated group and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, and trimethylolpropane. (meth)acrylate, pentaerythritol (meth)acrylate, bisphenol type epoxy (meth)acrylate, 2-
Examples include hydroxyethyl cinnamate.

In addition, examples of compounds having at least 1 ethylenically unsaturated group and a glycidyl group include glycidyl (meth)acrylate, glycidyl cinnamate, epoxy stearyl (meth)acrylate, bisphenol A type or bisphenol F type epoxy. Examples include compounds in which one of two glycidyl groups is (meth)acrylated.

These compounds may be used alone or in combination of two or more, and the excess remaining unreacted can be used as is as a reactive diluent in the photocurable resin composition.

This reaction can be carried out without a catalyst, but from an industrial perspective it is more preferable to add a suitable catalyst. Suitable catalysts include acid catalysts such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid, tertiary amines such as triethylamine, triethanolamine, N,N-dimethylaniline, dimethylamine hydrochloride,
Examples include amine salts such as diethylamine acetate and dimethylamine sulfur rIi salt, and the amount used is O, O'l~1
It is about 0% by weight, preferably about 0.1 to 5% by weight.

Examples of thermal polymerization inhibitors include quinones such as benzoquinone and naphthoquinone, phenols such as hydroquinone and hydroquinone monomethyl ether tecol, and metal salts such as copper naphthenate. .1% by weight, preferably about 0.01 to 0.03% by weight.

In order to suppress polymerization, it is also effective to carry out the reaction while supplying a gas containing oxygen, such as air, little by little to the reaction system.

When using a solvent, use an inert solvent such as benzene, toluene, chlorobenzene, 1,4-dioxane, etc. and distill it off after the reaction, or use trimethylolpropane tri(meth)acrylate under the above reaction conditions. Examples include a method in which an inert curable compound is used as a reactive diluent in the curable resin composition without being removed after the reaction.

The photocurable resin composition according to the present invention can be obtained by blending a reactive diluent, a polymerization initiator, a sensitizer, etc. as necessary with the curable compound obtained as described above.

Examples of reactive diluents include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and cyclohexyl (meth)acrylate.
Acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, 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, polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (meth)acrylate,
Neopentyl glycol di(meth)acrylate, hydroxypivalic acid ester neopentyl glycol di(meth)acrylate,
meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)
Acrylate, dipentaerythritol hexa(meth)
Examples include acrylate, diallyl phthalate, triallyl cyanurate, N-vinylpyrrolidone, vinyl acetate, styrene, vinyltoluene, etc., and the amount thereof is 100 parts by weight or less, preferably 50 parts by weight, based on 100 parts by weight of the curable compound. Parts by weight or less.

Examples of the polymerization initiator include benzoin ethyl ether (hereinafter abbreviated as rBEEJ), benzophenone, 2
, 2-jethoxyacetophenone, benzyl dimethyl ketal, 2-ethyl anthraquinone, Michler's ketone and the like.

In addition, as sensitizers, amines such as triethylamine and triethylenetetramine, ureas such as allylthiourea,
Examples include sulfur compounds such as sodium diethyldithiophosphate, nitriles such as N,N-dimethyl-p-aminobenzonitrile, and phosphorus compounds such as tri-n-butylphosphine.

The blending amount of each of the above components is approximately 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the curable component.

The curable resin composition according to the present invention can be not only photocured but also thermocured or room temperature cured in the presence of a polymerization initiator or a curing accelerator. Such polymerization initiators include benzoyl peroxide, dicumyl peroxide, te
Various peroxides such as rt-butyl perbenzoate, azobisisobutyronitrile, phenylacetaldehyde, etc. are exemplified, and as curing accelerators, metal salts such as cobalt naphthenate and manganese naphthenate, N,N-dimethyl Examples include compounds that form a redox catalyst system with the above various peroxides, such as aromatic tertiary amines such as aniline and N,N-dimethyl-p-toluidine. The amount of this compound relative to the curable component is the same as in the case of photocuring.

Various additives such as other reactive oligomers, fillers, colorants, leveling agents, and plasticizers can be appropriately added to the curable resin composition according to the present invention, if necessary.

The cured products thus obtained can be used as paints, varnishes, coating agents, adhesives, pressure-sensitive adhesives, binders, sealants, printing inks, plate-making materials, photoresists, sealants for electrical parts, potting agents, lenses, optical disk substrates, etc. It is suitable for various uses such as molding materials.

Furthermore, when the curable compound according to the present invention has a carboxyl group, it is very useful as a curable compound soluble in alkaline water for plate-making materials, resists, adhesives, etc. It can also be used as a curing agent for epoxy resins, and in that case, unlike conventional epoxy resin curing agents, it can be pre-cured by light and then completely cured by heat treatment, which can improve productivity. Very effective.

[Example code] The present invention will be described in detail below with reference to Examples.

Example 1 BTC dianhydride 999.2-hydroxyethyl acrylate (hereinafter abbreviated as rHEAJ) 139.9!?
, triethylamine (hereinafter abbreviated as rTEAJ) 0.21 as a catalyst, and hydroquinone monomethyl ether (hereinafter abbreviated as rMEHQJ) as a polymerization inhibitor.
0.0449 were charged into a reaction vessel and reacted at 80'C for 10 hours to form 1.2.3.4-butanetetracarboxylic acid diacryloyloxyethyl ester (rBT
It is abbreviated as c-2HEAJ. ) and HEA were obtained as a colorless and transparent liquid reaction product.

3 parts by weight of BEE as a polymerization initiator was blended with 100 parts by weight of the obtained reaction product to prepare photocurable resin compositions listed in Table 1.

The rotational viscosity and curing time of the photocurable resin composition obtained by 1q,
The pencil hardness, adhesion, and bending resistance of the cured product were measured. The results obtained are shown in Table 1.

The method for measuring each physical property value is as follows.

, rotational viscosity It was measured at 30'C using an E-type rotational viscometer.

A curable resin composition was applied onto a length ± Kasaoka tin plate using a B-type film applicator, and ultraviolet rays were irradiated from a distance of 10 cm using a 100 W high-pressure mercury lamp in the air to dry the coating surface to the touch. The time was measured.

A curable resin composition coated on a pencil hardness steel plate was heated to 10100W-1.
It was photocured for a predetermined time using a high-pressure mercury lamp at 0°C. The resulting cured film (thickness: approximately 50 μm) was measured in accordance with JIS-5400 “Pencil Scratch Test”.

The cured film obtained in the same manner as in the case of adhesion pencil hardness measurement was cut at intervals of 1# vertically and horizontally to create 100 base marks, and then peeled off with cellophane tape to remove the base remaining on the steel plate. The number of eyes was measured.

10100 of the photocurable resin composition coated on the tin plate.
It was photocured for a predetermined time using a W-10 high pressure mercury lamp. The bending resistance of the obtained cured film was measured in accordance with JIS-5400.

Example 2 A photocurable resin composition was prepared in the same manner as in Example 1, except that the amount of BEE added was replaced with 1 part by weight, and its physical properties were measured. The results obtained are shown in Table 1.

Example 3 BTC-21- with the amount of HEA added as 169.8g
Example 1 except that the content ratio of IEA and HEA was changed.
A photocurable resin composition was prepared in the same manner as above, and its physical properties were measured. The results obtained are shown in Table 1.

Example 4 B -r C dianhydride 999.2-human [1-xypropyl acrylate (hereinafter abbreviated as rHPAJ) 187
．． 39, TEAo, 29g and M, EHQO, 048g
1 and 2 in accordance with Example 1.
, 3,4-butanetetracarboxylic acid diacryloyloxypropyl ester (hereinafter abbreviated as rBTc-2HPAJ) and H1]A, a colorless and transparent liquid reaction product was obtained. A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured.

The results obtained are shown in Table 1.

Example 5 BTC dianhydride 99g, HEA121.8y, 1.6-
48 g of hexanediol diacrylate (hereinafter abbreviated as rHDDAJ), TEAo, 279 and MEHQo
, 051g of each were placed in a reaction vessel and heated at 80°C for 1
The reaction was carried out for 5 hours to obtain a colorless and transparent liquid reaction product consisting of BTC-2HEA and HDDA. A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured. The results obtained are shown in Table 1.

Example 6 99 g of BTC dianhydride, 121.8 g of HEA, trimethylolpropane triacrylate (hereinafter referred to as rTMPTAJ)
It is abbreviated as. >65.99, TEAo as catalyst, 29
9 and 055 g of MEHQo as a polymerization inhibitor were charged into a reaction vessel, and BTC-2HE was prepared according to Example 5.
A colorless and transparent liquid reaction product consisting of A and TMPTA was obtained.

A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured. The results obtained are shown in Table 1.

Example 7 99 g of BTC dianhydride, 121 g of HEA. EEF, 2-ethylhexyl acrylate (hereinafter abbreviated as rEHAJ.>32.1g, TEAo, 25!7 and MEHQo,
045! ? were charged into a reaction vessel, and a colorless and transparent liquid reaction product consisting of BTC-2HEA and EHA was obtained according to Example 5. Example 1 from such reaction products
A photocurable resin composition was prepared in the same manner as above, and its physical properties were measured.

The results obtained are shown in Table 2.

Example 8 BTC dianhydride 99g, HEA 187.5! ? , T.E.A.
36 g of MEHQo and 056 g of MEHQo were charged into a reaction vessel, and the reaction was carried out at 80° C. for 10 hours. After cooling, add glycidyl methacrylate 719 and further 95
The reaction was carried out at ℃ for 7 hours, and a colorless and transparent liquid of 1.2,
3.4-Butanetetracarboxylic acid cyacroyloxyethyl 7-hydroxy-3-methacryloyloxyethyl ester (rBTC-2HEA-1GMA)
It is abbreviated as. ) and HEA were obtained. A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured. The results obtained are shown in Table 2.

Comparative Example 1 Phthalic anhydride 148g, HEA 121.8! ? , T.E.A.
o, 279 and MEHQo, 056 g were charged into a reaction vessel, and the reaction was carried out at 80'C for 7 hours to form phthalic acid monoacryloyloxyethyl ester (hereinafter referred to as rPA-1).
It is abbreviated as HEA. ) and HEA, a slightly cloudy liquid reaction product was obtained. A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured. The results obtained are shown in Table 2.

Comparative Example 2 Anhydrous Pyromellit 1109g, HEA 266g, TEA
o, 38g, MEHQo, 06! ? were charged into a reaction vessel and reacted at 80'C for 7 hours to form pyromellitic acid diacryloyloxyethyl ester (hereinafter referred to as rPM).
It is abbreviated as DA-2HEAJ. ) and HEA were obtained as a yellow transparent liquid reaction product. A photocurable resin composition was prepared from the reaction product in the same manner as in Example 1, and its physical properties were measured. The results obtained are shown in Table 2.

Comparative Example 3 The physical properties of a photocurable resin composition prepared by blending 3 parts by weight of BFE with 100 parts by weight of polyester acrylate (phthalic anhydride-neopedyl glycol system) were measured in the same manner as in Example 1. The results obtained are shown in Table 2.

[Effects of the Invention] The photocurable resin composition containing as a curable component a polyester acrylate obtained using BTC as a raw material according to the present invention maintains excellent cured physical properties and is completely cured extremely quickly.

Patent applicant: Shin Nippon Rika Co., Ltd.

Claims (1)

[Claims] 1 A reaction product of 1,2,3,4-butanetetracarboxylic acid or its acid anhydride and a compound having at least one ethylenically unsaturated group and a hydroxyl group or a glycidyl group as a curable component A photocurable resin composition comprising: