JP6265424B2 - (Meth) acrylate compound and resin composition - Google Patents

Description

  The present invention relates to a novel (meth) acrylate compound useful as a polymerizable monomer that can be used particularly for next-generation photoresist applications. Furthermore, the (meth) acrylate compound of the present invention has a low viscosity and excellent curability, and is a particularly useful compound in terms of improving the handling performance while maintaining the cured product hardness of various compositions.

  Photosensitive resin compositions that are cured by irradiating active energy rays such as ultraviolet rays and electron beams have been developed and used practically for various purposes such as printing, paint, and electrical insulation. Advantages include (1) solvent-free and low pollution type, (2) extremely fast curing rate and high product productivity, and (3) very small volume change before and after curing because of solid content. ) Since there is no heat loss due to the material, or heat influence on the material, various paints and adhesives such as plastic, paper and inorganic materials have been developed.

  The (meth) acrylate compounds used in these photosensitive resin compositions are highly reactive and can easily be homopolymerized in the presence of heat, ultraviolet rays, radiation, electron beams, polymerization initiators, or other ethylenically unsaturated groups. Copolymerizes with contained compounds. In particular, polyfunctional (meth) acrylates having two or more (meth) acryl groups in the molecule are used as photosensitive resins, as comonomers for copolymers with crosslinking agents and other ethylenically unsaturated group-containing compounds. It is useful for applications. Monofunctional (meth) acrylates having one (meth) acryl group in the molecule have low viscosity and excellent handling performance, and are useful as reactive diluents and composition modification additives.

  The cured product properties of these (meth) acrylate compounds mainly depend on the base skeleton. For example, Patent Document 1 describes a norbornane ring-containing (meth) acrylate, and it has been found as a feature of skeletal difference to maintain hardness with a lower viscosity than a general bisphenol A type. However, since it is a (meth) acrylate classified as a polyfunctional monomer and has a viscosity of several thousand mPa · s, the requirement for a material having a lower viscosity can be easily estimated.

  Furthermore, various (meth) acrylates having a norbornane skeleton have been developed as photoresist monomers (Patent Documents 2, 3, and 4). There are few types of (meth) acrylates having a norbornane skeleton, and the search for similar skeletons continues as a next-generation resist monomer.

JP 2005-60425 A Japanese Patent No. 4143227 Japanese Patent No. 4924795 Japanese Patent No. 4887710

  Since these (meth) acrylates having a norbornane skeleton have few examples and few production methods suitable for production on an industrial scale, there are few examples of practical use in general photosensitive resin compositions.

  The present invention has found a route for producing a new (meth) acrylate having a norbornane skeleton based on the above requirements, and further provides a (meth) acrylate having a low viscosity and excellent curability and a photosensitive resin composition containing the same. The purpose is to provide.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜６の炭化水素基を、ｍは０〜５の整数を、ｎは０又は１の整数を、点線はメチレン基又は結合が存在しないことをそれぞれ表す）
を、エポキシ化して得られるエポキシ化合物（Ｂ）とエチレン性不飽和基含有モノカルボン酸化合物（Ｃ）を反応させて得られるエチレン性不飽和基含有カルボキシレート化合物（Ｄ）、
（２）エポキシ化合物（Ｂ）が下記式（２）である（１）に記載のエチレン性不飽和基含有カルボキシレート化合物（Ｄ）、

（式（２）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して、水素原子又は炭素数１〜６の炭化水素基を、ｍは０〜５の整数を、ｎは０又は１の整数を、点線はメチレン基又は結合が存在しないことをそれぞれ表す）
（３）エポキシ化合物（Ｂ）が下記式（３）である（１）又は（２）のいずれか一項に記載のエチレン性不飽和基含有カルボキシレート化合物（Ｄ）、

（４）エチレン性不飽和基含有モノカルボン酸化合物（Ｃ）が（メタ）アクリル酸である（１）乃至（３）のいずれか一項記載のエチレン性不飽和基含有カルボキシレート化合物（Ｄ）、
（５）（１）乃至（４）のいずれか一項記載のエチレン性不飽和基含有カルボキシレート化合物（Ｄ）と（Ｄ）以外の重合性化合物（Ｅ）を含有することを特徴とする感光性樹脂組成物、
（６）光重合開始剤（Ｆ）を含有する（５）に記載の感光性樹脂組成物、
（７）（５）又は（６）のいずれか一項に記載の感光性樹脂組成物を硬化して得られる硬化物、
に関する。 That is, the present invention
(1) Cyclic olefin compound (A) having a vinyl group or an allyl group represented by the following formula (1)

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0. Or an integer of 1 and a dotted line represents that no methylene group or bond exists, respectively)
An ethylenically unsaturated group-containing carboxylate compound (D) obtained by reacting an epoxy compound (B) obtained by epoxidation with an ethylenically unsaturated group-containing monocarboxylic acid compound (C),
(2) The ethylenically unsaturated group-containing carboxylate compound (D) according to (1), wherein the epoxy compound (B) is the following formula (2):

(In the formula (2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0. Or an integer of 1 and a dotted line represents that no methylene group or bond exists, respectively)
(3) The ethylenically unsaturated group-containing carboxylate compound (D) according to any one of (1) or (2), wherein the epoxy compound (B) is represented by the following formula (3):

(4) The ethylenically unsaturated group-containing carboxylate compound (D) according to any one of (1) to (3), wherein the ethylenically unsaturated group-containing monocarboxylic acid compound (C) is (meth) acrylic acid. ,
(5) The photosensitive composition comprising the ethylenically unsaturated group-containing carboxylate compound (D) according to any one of (1) to (4) and a polymerizable compound (E) other than (D). Functional resin composition,
(6) The photosensitive resin composition according to (5), which contains a photopolymerization initiator (F),
(7) A cured product obtained by curing the photosensitive resin composition according to any one of (5) or (6),
About.

  The ethylenically unsaturated group-containing carboxylate compound of the present invention is low in viscosity and excellent in curability and has a high cured product hardness, and can be applied as, for example, a monomer for semiconductor resist and a dilution monomer for various polymerizable resin compositions. . Furthermore, the cured film of the photosensitive resin composition of the present invention has excellent curability and high hardness, and various coating fields such as ink, plastic paint, paper printing, metal coating, furniture painting, lining, adhesives, and electronics field. Can be applied to many fields such as insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants.

  The cyclic olefin compound having a vinyl group or an allyl group in the present invention is a compound represented by the following formula (1).

In formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0 or An integer of 1 and a dotted line respectively represent that a methylene group or a bond does not exist.

Specific examples of the hydrocarbon group having 1 to 6 carbon atoms among R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, phenyl group and the like. All of R ¹ , R ² , R ³ and R ⁴ are preferably a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a methyl group.
m is preferably 1.
Further, the purity of the compound represented by the formula (1) is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more.

  Among the compounds represented by the formula (1), vinyl norbornene represented by the following formula (4) is preferable. Moreover, the existing method is known for the reaction. Org. Chem. It can be obtained by using the method described in 1988, 53, 3587-3593.

  The epoxy compound (B) used in the present invention may be a commercially available one, and any epoxy compound represented by the following formula (2) can be used. For example, Celoxide 2000 manufactured by Daicel Corporation Etc.

  Among the compounds represented by the formula (2), a norbornane skeleton-containing epoxy compound represented by the following formula (3) is preferable.

  Here, the example of the specific manufacturing method of the compound of Formula (2) thru | or Formula (3) is explained in full detail.

  The method for epoxidizing a cyclic olefin compound having a vinyl group or an allyl group is obtained by mixing and stirring (a) a heteropolyacid, (b) a quaternary ammonium salt, a cyclic olefin compound having a vinyl group or an allyl group, and hydrogen peroxide. be able to.

First, (a) heteropolyacid will be described.
The heteropolyacid in the present invention is a polyacid in which a hetero atom belonging to Group 13-18 of the periodic table, such as silicon, phosphorus, and arsenic, is inserted into the metal oxyacid skeleton.
Specific examples include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, etc. Among them, monoepoxidation of a cyclic olefin compound having a vinyl group or an allyl group can be completed in a short time. Is particularly preferred.

  The above heteropolyacids may be used alone or in combination.

  The amount of the heteropoly acid used is equivalent to a metal element (tungstenic acid for tungsten atom, molybdic acid for molybdenum) with respect to 1 mol (functional group equivalent) of the olefin in the cyclic olefin compound having a vinyl group or allyl group represented by the formula (1). The number of moles of atoms is 1.0 to 20 mmol, preferably 1.5 to 15 mmol, and more preferably 2.0 to 10 mmol.

Next, (b) the quaternary ammonium salt will be described.
Specific examples of the quaternary ammonium salt include tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixture of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a group). Type) ammonium salt, trihexadecylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, di-cured tallow alkyldimethylammonium Examples thereof include but are not limited to salts.
Moreover, a carboxylate ion can be used for the anionic species of these salts. As the carboxylate ion, acetate ion, carbonate ion and formate ion are preferable. In particular, acetate ion is preferred.
In addition, it will not specifically limit if it is a well-known quaternary ammonium salt, A cetyl pyridinium chloride etc. can also be used.

  A commercially available product may be used as the quaternary ammonium salt having a carboxylate ion as an anion. For example, the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be used.

  The quaternary ammonium salts described above may be used alone or in combination.

  The amount of the quaternary ammonium salt used is preferably 0.2 to 10 parts by mass, particularly 0.4 to 3 parts by mass with respect to 100 parts by mass of the cyclic olefin compound having a vinyl group or an allyl group represented by the formula (1). Part is preferred. If the amount is less than 0.2 parts by mass, the reaction becomes extremely slow, and the reaction time is too long. If the amount is more than 10 parts by mass, a problem causing coloring occurs without being removed by purification after the reaction.

In the mixing and stirring, tungstate may be further added.
Tungstate is a tungsten compound in the form of a hydrate of tungsten trioxide, H ₂ WO ₄ , H ₄ WO _5, and H ₆ [H ₂ W ₁₂ O ₄₀ ] or H produced by condensation thereof. _It is an alkali metal salt or ammonium salt of tungstic acid represented by ₁₀ [H ₁₀ W ₁₂ O ₄₆ ].
Specific examples include sodium tungstate, potassium tungstate, ammonium tungstate and hydrates thereof, and sodium tungstate (and / or hydrate thereof) is particularly preferable.
The tungstate described above may be used alone or in combination.

  The amount of tungstate used is 0.5 to 20 mmol in terms of tungsten element, preferably 1 to 20 mol of olefin in the cyclic olefin compound having a vinyl group or an allyl group represented by formula (1), preferably It is 1.0-15 mmol, More preferably, it is 1.2-10 mmol.

The mixing and stirring may be performed by adding a phosphate.
Phosphate is added for the purpose of adjusting the pH of the reaction system. Phosphate is an alkali metal salt or alkaline earth metal salt of phosphoric acid.
Specifically, potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, primary magnesium phosphate, magnesium monohydrogen phosphate, primary calcium phosphate, calcium monohydrogen phosphate And hydrates thereof. Among them, potassium dihydrogen phosphate (and / or its hydrate), sodium dihydrogen phosphate (and / or its hydrate) are preferable because pH adjustment of the catalyst is easy. Particularly preferred.
The aforementioned phosphates may be used alone or in combination.

  The usage-amount of a phosphate is 0.005-5 molar equivalent normally with respect to hydrogen peroxide, Preferably it is 0.01-4 molar equivalent, More preferably, it is 0.012-3 molar equivalent. At this time, pH adjustment is required when it exceeds 5 molar equivalents with respect to hydrogen peroxide, and when it is less than 0.005 molar equivalents, the hydrolyzate of the generated epoxy group is likely to proceed or the reaction is slowed. The harmful effects of The amount of phosphate used is preferably adjusted so that the pH of the reaction system is 2.0 to 10.0, more preferably pH 3.0 to 6.0. When the pH is less than 2.0, the epoxy group hydrolysis reaction and polymerization reaction easily proceed. Moreover, when pH 10.0 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise.

  The epoxidation method of the cyclic olefin compound which has a vinyl group or an allyl group of this invention performs epoxidation using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by mass is preferable because of easy handling. When the concentration exceeds 40% by mass, it is not preferable because handling becomes difficult and the decomposition reaction of the produced epoxy resin also easily proceeds.

  The amount of hydrogen peroxide used is 0.1 to 0.7 molar equivalents relative to the carbon-carbon double bond in the cyclic olefin compound having a vinyl group or an allyl group. Among these, 0.15-0.5 equivalent is preferable, More preferably, it is 0.2-0.4 equivalent. If the ratio is less than 0.1, the yield of the monoepoxy compound is remarkably lowered and the efficiency is poor. If the ratio is greater than 0.7, a large amount of diepoxy compound and / or hydrolyzate of the diepoxy compound is formed. Is remarkably lowered and the efficiency is unfavorable.

  Although the monoepoxidation method of the cyclic olefin compound having a vinyl group or an allyl group of the present invention can be carried out in an organic solvent, it is 0 to 5% by mass relative to the mass of the cyclic olefin compound having a vinyl group or an allyl group. It is preferable from the viewpoint of reducing waste, and more preferably 0 to 1% by mass. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, nitrile compounds such as acetonitrile, Chloroform and the like can also be used.

  Although reaction temperature is not specifically limited, 30-90 degreeC is preferable and 50-90 degreeC is more preferable. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. The preferred range is 0.5 to 48 hours, preferably 1 to 36 hours, and more preferably 2 to 30 hours.

  After completion of the reaction, an excess of hydrogen peroxide can be quenched. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferred treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 12 with a basic compound. If the pH is less than 6, the heat generated during the reduction of excess hydrogen peroxide is large, which may cause decomposition products.

  Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. The amount of the reducing agent used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol with respect to the number of moles of excess hydrogen peroxide. is there.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mol, more preferably 0.05 to 3 times mol. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times in terms of mass ratio with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

  After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product can be extracted from the layer. The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times in terms of mass ratio with respect to the cyclic olefin compound having a vinyl group or an allyl group. This operation is repeated several times as necessary, and then the organic layer is separated. If necessary, the organic layer is washed with water and purified.

The obtained organic layer may be an ion exchange resin or a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially a chemical activated carbon is particularly preferred), or a composite metal salt (especially a basic composite metal salt). Are preferably removed), clay minerals (especially lamellar clay minerals such as montmorillonite are preferred), impurities are removed, water washing and filtration are performed, the solvent is distilled off, and the target vinyl group or allyl group is removed. A monoepoxidized product of a cyclic olefin compound is obtained. In some cases, it may be further purified by column chromatography, distillation or vacuum distillation.
By performing a purification treatment such as vacuum distillation after the quench treatment described above, a monoepoxidized product with high purity can be obtained.

  Furthermore, as described above, it is possible to obtain a high-purity epoxy resin having a high area% by gas chromatography (GC) analysis of a monoepoxy compound by performing a purification treatment such as vacuum distillation. Here, the purity of the monoepoxy body finally obtained is preferably 80 area% or more, more preferably 90 area% or more, and 95 area% or more in area% by GC analysis. It is particularly preferred.

  Examples of the ethylenically unsaturated group-containing monocarboxylic acid compound (C) used in the present invention include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and saturated or unsaturated dibasic acid and unsaturated compounds. A reaction product with a saturated group-containing monoglycidyl compound is exemplified. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. Is mentioned.

  Among these, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is preferable in terms of sensitivity when a photosensitive resin composition is used.

  The ethylenically unsaturated group-containing carboxylate compound (D) of the present invention can be obtained by reacting an epoxy compound (B) with an ethylenically unsaturated group-containing monocarboxylic acid compound (C).

The reaction can be carried out without solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the reaction.
The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and use of the resulting resin, but preferably 90 to 30% by weight, more preferably 80 to 50% by weight as the solid content. Use.

Specific examples of what can be used as the above solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and Examples thereof include petroleum ether, white gasoline, and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, it can carry out in single or mixed organic solvents, such as the reaction polymerizable compound (E) mentioned later other than (D). In this case, when used as a curable composition, it can be used directly as a composition.

  During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is the reaction product, that is, the epoxy compound (B), the ethylenically unsaturated group-containing monocarboxylic acid compound (C), and In some cases, the content is 0.1 to 10% by weight based on the total amount of the reaction product to which a solvent or the like is added. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include, for example, triethylamine, benzyldimethylamine, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate, tetra Examples include known general basic catalysts such as methylammonium chloride, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, and quaternary salts.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

The usage-amount of the ethylenically unsaturated group containing monocarboxylic acid compound (C) in this reaction is 90-200 mol% with respect to an epoxy compound (B), Preferably it is 95-180 mol%. At that time, the reaction is carried out by appropriately measuring the acid value while sampling, and the target value is set from the number calculated from the excess amount of the ethylenically unsaturated group-containing monocarboxylic acid compound (C) used by the acid value of the sample. The time when the target is below the target is the end point.
After completion of the reaction, the purity can be increased by diluting with the solvent and removing the acrylic acid component by neutralization washing. Here, in order to further increase the purity, it is possible to go through a concentration step with an evaporator or the like after removing the acrylic acid component.

The ethylenically unsaturated group-containing carboxylate compound (D) thus obtained has a structure represented by the following formula (5) as a main component.

In formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0 or An integer of 1 and a dotted line respectively represent that a methylene group or a bond does not exist.

Among them, those having a structure represented by the following formula (6) as a main component are preferable.

  The photosensitive resin composition of the present invention can contain an ethylenically unsaturated group-containing carboxylate compound (D) of the present invention and a polymerizable compound (E) other than the component (D) as optional components. Specific examples of the polymerizable compound (E) that can be used include a compound having a (meth) acryloyloxy group, a maleimide compound, a (meth) acrylamide compound, and an unsaturated polyester.

Specific examples of the compound having a (meth) acryloyloxy group that can be used in combination with the photosensitive resin composition of the present invention include (poly) ester (meth) acrylate (E-1); urethane (meth) acrylate (E-2). ); Epoxy (meth) acrylate (E-3); (poly) ether (meth) acrylate (E-4); alkyl (meth) acrylate or alkylene (meth) acrylate (E-5); having an aromatic ring (meta) ) Acrylate (E-6); (meth) acrylate (E-7) having an alicyclic structure, maleimide group-containing compound (E-8), (meth) acrylamide compound (E-9), unsaturated polyester (E-) 10) and the like, but are not limited thereto.
In addition, about a reaction material, it can obtain on well-known reaction conditions.

  The (poly) ester (meth) acrylate (E-1) that can be used in combination with the photosensitive resin composition of the present invention is a general term for (meth) acrylate having one or more ester bonds in the main chain, and urethane (meth). Acrylate (E-2) is a general term for (meth) acrylates having one or more urethane bonds in the main chain. Epoxy (meth) acrylate (E-3) is a monofunctional or higher functional epoxy compound and (meth). As a generic name of (meth) acrylate obtained by reacting acrylic acid, (poly) ether (meth) acrylate (E-4) is a generic name of (meth) acrylate having one or more ether bonds in the main chain, Alkyl (meth) acrylate or alkylene (meth) acrylate (E-5) means that the main chain is straight chain alkyl, branched alkyl, straight chain or halogen at the terminal. As a general term for (meth) acrylate which may have a child and / or a hydroxyl group, (meth) acrylate (E-6) having an aromatic ring is a (meth) acrylate having an aromatic ring in the main chain or side chain. As a general term, (meth) acrylate (E-7) having an alicyclic structure has an alicyclic structure that may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain (meth). These are used as a general term for acrylates.

  Examples of the (poly) ester (meth) acrylate (E-1) that can be used in combination with the photosensitive resin composition of the present invention include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalate. Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalate ester neopentyl glycol di (meth) Acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; trimethylolpropane or glycerol 1 1 mole or more ε- caprolactone, .gamma.-butyrolactone, .delta.-valerolactone of triol obtained by adding a cyclic lactone compound of mono-, di- or tri (meth) acrylate;

  Mono, di, tri or tetra (meth) acrylate of tetraol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane Mono- or poly (meth) acrylate of hexaol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of dipentaerythritol;

  Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, maleic acid, fumaric acid, succinic acid Acids, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, polybasic acids such as 5-sodium sulfoisophthalic acid, and their reactants (Meth) acrylates of polyester polyols, such as (meth) acrylates of cyclic lactone-modified polyester diols composed of the diol component and polybasic acids and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. Multifunctional (poly) ester ( Can be mentioned data) acrylate, and the like, but is not limited thereto.

  The urethane (meth) acrylate (E-2) that can be used in combination with the photosensitive resin composition of the present invention comprises at least one (meth) acryloyloxy group-containing hydroxy compound (E-2-i) and an isocyanate compound (E- It is a general term for (meth) acrylates obtained by reaction with 2-ro).

  Specific examples of the hydroxy compound (E-2-i) having at least one (meth) acryloyloxy group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy Ring-opening reaction product of (meth) acrylate compound having various hydroxyl groups such as -3-phenoxypropyl (meth) acrylate, and (meth) acrylate compound having the above hydroxyl group and ε-caprolactone Etc. can be mentioned.

  Specific examples of the isocyanate compound (E-2-ro) include, for example, P-phenylene diisocyanate, m-phenylene diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-triene. Aromatic diisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Or diisocyanates having an alicyclic structure; one or more burettes of isocyanate monomers or the above diisocyanates Things a trimer polyisocyanates of the isocyanate and the like; the and the isocyanate compound include polyisocyanates obtained by urethane reaction of the polyol compound.

In the reaction of the hydroxy compound (E-2-i) having a (meth) acryloyloxy group and the isocyanate compound (E-2-ro) when obtaining urethane (meth) acrylate, a polyol is optionally reacted. It doesn't matter.
Examples of the polyol that can be used include 1 to 10 carbon atoms such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Triols such as alkylene glycol, trimethylolpropane, pentaerythritol, alcohols having a cyclic skeleton such as tricyclodecane dimethylol, bis- [hydroxymethyl] -cyclohexane, and the like; and these polyhydric alcohols and polybasic acids (for example, succinic acid) , Phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.) polyester polyol obtained by reaction with polyhydric alcohol and ε-caprolactone Lactone alcohol, polycarbonate polyol (for example, polycarbonate diol obtained by reaction of 1,6-hexanediol and diphenyl carbonate) or polyether polyol (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.) Etc.

  The epoxy (meth) acrylate (E-3) that can be used in combination with the photosensitive resin composition of the present invention is obtained by reacting an epoxy resin containing an epoxy group having one or more functionalities with (meth) acrylic acid (meta). ) A general term for acrylate. Specific examples of epoxy resins used as raw materials for epoxy (meth) acrylates include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy Resin, bisphenol-S type epoxy resin, bisphenol type epoxy compound such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound; hydrogenated bisphenol- A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane Epoxy Hydrogenated bisphenol type epoxy compounds such as compounds; Halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resins and brominated bisphenol-F type epoxy resins; Alicyclic diglycidyl such as cyclohexanedimethanol diglycidyl ether compounds Ether compounds; Aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and diethylene glycol diglycidyl ether; Polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether; Phenol Novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadienephenol Epoxy resins, biphenol type epoxy resin, bisphenol -A novolac epoxy resins, naphthalene skeleton-containing epoxy resin, a heterocyclic epoxy resin or the like.

  Examples of the (poly) ether (meth) acrylate (E-4) that can be used in combination with the photosensitive resin composition of the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl ( (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, etc. Functional (poly) ether (meth) acrylates;

  Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymer, copolymer of propylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, polyhydric hydroxyl compounds such as hydrogenated polybutadiene glycol and other polyhydric hydroxyl compounds and (meth) acrylic Polyfunctional (meth) acrylates derived from acids; 1 mole or more of ethylene oxide, propylene oxide, butylene oxide, etc. per 1 mole of neopentyl glycol Di (meth) acrylate of a diol obtained by adding Jo ether;

  Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; Hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S (Meth) acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of trimethylolpropane or glycerin;

  Mono-, di-, tri-, or tetra (meth) acrylates of triols obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of pentaerythritol or ditrimethylolpropane; 1 mol of dipentaerythritol Examples thereof include polyfunctional (poly) ether (meth) acrylates such as hexaol tri- to hexafunctional (meth) acrylates to which cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide and the like are added in a molar amount or more.

  Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (E-5) that can be used in combination with the photosensitive resin composition of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , N-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate , Isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, etc. Monofunctional (meth) acrylates of

  Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2 -Di (meth) acrylates of hydrocarbon diols of methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate;

  Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Triols such as acrylate or poly (meth) acrylate, mono- or poly (meth) acrylate of pentaerythritol, mono- or poly (meth) acrylate of ditrimethylolpropane, mono- or poly (meth) acrylate of dipentaerythritol, tetraol, hexa Mono- or poly (meth) acrylates of polyhydric alcohols such as oar;

  And hydroxyl group-containing (meth) acrylic compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

  Examples of the (meth) acrylate (E-6) having an aromatic ring that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate. And di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate, but are not limited thereto.

  Examples of the (meth) acrylate (E-7) having an alicyclic structure that can be used in combination with the photosensitive resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, and di Monofunctional (meth) acrylates having an alicyclic structure such as cyclopentenyl (meth) acrylate; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecane dimethylol di ( Examples thereof include polyfunctional (meth) acrylates having a cyclic structure such as (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom or the like in the structure such as tetrafurfuryl (meth) acrylate. However, it is not limited to these.

  Examples of the compound having a (meth) acryloyl group that can be used in combination with the photosensitive resin composition of the present invention include, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate, in addition to the above-described compounds. Or a poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid; a (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanuric (meth) acrylates such as (meth) acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates, melamine (meth) acrylates, and the like can also be used.

  Examples of the maleimide group-containing compound (E-8) that can be used in combination with the photosensitive resin composition of the present invention include Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2- Monofunctional aliphatic maleimides such as maleimidoethyl-propyl carbonate and N-ethyl- (2-maleimidoethyl) carbamate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene Aliphatic bismaleimides such as glycol-bis (3-maleimidopropyl) ether and bis (2-maleimidoethyl) carbonate; cycloaliphatic such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide) Bismaleimide; maleimidoacetic acid and poly Obtained by esterification of carboxymaleimide derivatives such as maleimide compounds obtained by esterification with tetramethylene glycol, maleimide compounds by maleification of maleimidocaproic acid and pentaerythritol tetraethylene oxide adducts, and various (poly) ols. (Poly) ester (poly) maleimide compounds, aromatic maleimide compounds and the like that can be used can be exemplified, but the invention is not limited thereto.

  Examples of the (meth) acrylamide compound (E-9) that can be used in combination with the photosensitive resin composition of the present invention include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; Examples thereof include polyfunctional (meth) acrylamides such as (meth) acrylamide.

  Examples of the unsaturated polyester (E-10) that can be used in combination with the photosensitive resin composition of the present invention include fumaric acid esters such as dimethyl malate and diethyl malate; polyunsaturated such as maleic acid and fumaric acid. The esterification reaction product of carboxylic acid and a polyhydric alcohol can be mentioned.

  As the polymerizable compound (E) that can be used in combination with the photosensitive resin composition of the present invention, a preferable material can be appropriately selected according to the use. However, in order to improve the cured film strength, alkyl (meth) acrylate or alkylene (meta) ) Acrylate (E-5) is preferably used in combination.

  In the photosensitive resin composition of the present invention, the ratio of the components (D) and (E) is not particularly limited, but the component (E) is 10 to 2000 wt. %, Preferably 20 to 1000% by weight.

  Specific examples of the photopolymerization initiator (F) used in the photosensitive resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4 Acetophenones such as-(methylthio) phenyl] -2-morpholinopropan-1-one; anthraquino such as 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide . The addition ratio of these is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  These can be used singly or as a mixture of two or more, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester Can be used in combination with an accelerator such as a benzoic acid derivative. As an addition amount of these accelerators, an amount of 100% by weight or less is added to the photopolymerization initiator (F) as necessary.

  Furthermore, the photosensitive resin composition of the present invention is a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, an oxidation, depending on the application. Inhibitors, ultraviolet absorbers, flame retardants, pigments, dyes, and the like can be used as appropriate.

  Specific examples of the non-reactive compound include a liquid or solid oligomer or resin having low reactivity or non-reactivity, and includes an alkyl (meth) acrylate copolymer, an epoxy resin, liquid polybutadiene, Cyclopentagen derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, phthalate esters, phosphate esters, Glycol esters, citric acid esters, aliphatic dibasic acid esters, fatty acid esters, epoxy plasticizers, castor oils, terpene hydrogenated resin polyisoprene skeletons, oligomers or polymers having polybutadiene skeletons or xylene skeletons, and That S Le product, homopolymer, epoxy-modified polybutadiene, butadiene - styrene random copolymer, polybutene, and the like can be mentioned softening agents etc., but is not limited thereto. The weight ratio of such components in the ultraviolet curable resin composition is usually 10 to 80% by weight, preferably 10 to 70% by weight.

  Examples of the inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, and glass. , Mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon, and the like. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen group, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group.

  Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, Nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like can be mentioned.

  Examples of the silane coupling agent include silane coupling agents such as γ-glycidoxypropyl tremethoxysilane and γ-chloropropyltrimethoxysilane, and tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl). ) Titanate coupling agents such as phosphite titanate and bis (dioctylpyrophosphate) ethylene titanate; Aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; Zirconium coupling agents such as acetylacetone / zirconium complex, etc. be able to.

  Any tackifier, antifoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant, pigment, and dye that can be used in the photosensitive resin composition of the present invention can be used. In the range which does not impair the sclerosis | hardenability and resin characteristic, a thing can be especially used without a restriction | limiting.

In order to obtain the photosensitive resin composition of the present invention, the above-described components may be mixed, and the order and method of mixing are not particularly limited.
When present in the composition of various additives, the weight ratio of the various additives in the photocurable transparent adhesive composition is 0.01 to 3% by weight, preferably 0.01 to 1% by weight, and more preferably. Is 0.02 to 0.5% by weight.

  The photosensitive resin composition of the present invention does not substantially require a solvent. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, benzene, toluene, xylene and the like It is also possible to dilute and use the photosensitive resin composition of the present invention with other generally used organic solvents such as aromatic hydrocarbons.

  The photosensitive resin composition of the present invention can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm. Further, it can be cured by irradiation with energy rays other than ultraviolet rays or by heat.

  Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short. Examples include arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, and sunlight.

  The photosensitive resin composition of the present invention is excellent in flexibility, weather resistance, light resistance, and optical applications that need to maintain transparency, as well as ink, plastic paint, paper printing, metal coating, furniture It is useful in many fields such as various coating fields such as painting, linings, adhesives, and insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants in the electronics field. More specific applications include planographic relief inks, flexographic inks, gravure inks, screen inks and other ink fields, glossy fields, paper coating materials fields, wood coating materials fields, beverage can coating materials or printing ink fields, Soft packaging film coating agent, printing ink or adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, adhesive or optical fiber coating agent, liquid crystal display device, organic EL display device, touch panel type image display device It is useful for applications such as air gap fillers for display devices (fillers for gaps between display devices and face plates).

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example. Gas chromatography was performed under the following conditions.
<Gas chromatography (GC)>
Manufacturer: Shimadzu Corporation Model: GC2010
Column: HP-5MS 15m manufactured by Agilent Technologies
Carrier gas: Helium 1.0 ml / min.
Detector: FID
Split ratio: 30: 1
Temperature condition injection: 300 ° C
Column: held at 50 ° C. for 2 minutes, 10 ° C./min. Temperature rise to 300 ° C, hold at 300 ° C for 20 minutes Detector: 300 ° C

Synthesis example 1
In a glass four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 17.8 g (5.2 mmol) of phosphotungstic acid n-hydrate (n≈30) and 5.4 g of cetylpyridinium chloride (15. 6 mmol), 2220 g of chloroform, and 190.4 g (1.96 mol) of 35 mass% hydrogen peroxide were added, and 156.2 (1.30 mol) of vinyl norbornene was added dropwise over 30 minutes while stirring at room temperature (23 ° C.). Thereafter, the flask was heated in a water bath equipped with a heating device, and chloroform was refluxed, followed by stirring for 3 hours while confirming the progress of the reaction by gas chromatography. The obtained reaction solution was washed with water, treated, distilled off with an evaporator, and purified by distillation, whereby 75 g of an epoxy compound (B-1) whose main component is represented by the following formula (3) (purity: GC) 98 area% in the analysis).

Example 1
In a glass four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 41.7 g (0.30 mol) of the epoxy compound (B-1) obtained in Synthesis Example 1 and an ethylenically unsaturated group-containing mono Acrylic acid 28.4 g (0.39 mol) as carboxylic acid compound (C), toluene 30.0 g as reaction solvent, triphenylphosphine 0.7 g as reaction catalyst, 3,5-di-tert-butyl-as polymerization inhibitor 0.2 g of 4-hydroxytoluene was added and the reaction was carried out with stirring under reflux for 32 hours. The reaction was tracked by acid value, and the point where the acid value became 60 or less in 32 hours was defined as the reaction end point. To the resulting reaction solution, 250 g of toluene was further diluted and neutralized and washed with an aqueous sodium carbonate solution to remove excess acrylic acid component. Next, it concentrated with the evaporator and 50g of ethylenically unsaturated group containing carboxylate compounds (D-1) were obtained. It was 120 mPa * s (E type viscometer) when the viscosity of the obtained compound (D-1) was measured. The NMR spectrum of the obtained compound was as shown below.

Example 2
As a photopolymerization initiator, the compound (D-1) obtained in Example 1 was used as an Irg. 184 (manufactured by Ciba Specialty Chemicals: 1-hydroxycyclohexyl phenyl ketone) was added and blended, and the resulting photosensitive resin composition was formed on a stainless steel plate with a wall made of gum tape (thickness: 200 μm). The film was applied using a bar coater, and irradiated with ultraviolet rays at a conveying speed of 5 m / min from a distance of 10 cm in lamp height under a nitrogen atmosphere to obtain a cured film having a thickness of about 200 μm. It was F when the pencil hardness (750 g load) of this cured film was measured.

Ｒ−１２８Ｈ：日本化薬（株）製；フェニルグリシジルエーテルエポキシアクリレート
ＥＰＡ：日本化薬（株）製；４−ジメチルアミノ安息香酸エステル Examples 3-4, Comparative Examples 1-2 (curability test)
The composition shown in Table 1 was applied, and the resulting photosensitive resin composition was applied to a stainless steel plate with a wall made of gum tape (thickness: 200 μm) using a bar coater, and the lamp height was 10 cm under a nitrogen atmosphere. The curability was compared by irradiating ultraviolet rays at a conveying speed of 5 m / min from the above distance and changing the amount of ultraviolet rays to be exposed. In addition, the determination result of sclerosis | hardenability was as follows.
○ ・ ・ ・ No tack (completely cured)
Δ: Adhesive (polymerization proceeds)
× ・ ・ ・ No change

R-128H: Nippon Kayaku Co., Ltd .; phenyl glycidyl ether epoxy acrylate EPA: Nippon Kayaku Co., Ltd .; 4-dimethylaminobenzoic acid ester

Examples 5-7, Comparative Examples 3-5
The photosensitive resin composition blended with the composition shown in Table 2 was applied to an easy-adhesion treated polyester film (manufactured by Toyobo Co., Ltd .: A-4300, film thickness 188 μm) using a bar coater (No. 20), and 80 ° C. After being left in a drying furnace for 1 minute, using a 120 W / cm high-pressure mercury lamp in an air atmosphere, irradiating with ultraviolet rays at a conveying speed of 5 m / min from a distance of 10 cm from the lamp height to form a cured film (10 to 15 μm) A film having was obtained.

Test Example The following items were evaluated for the films obtained in Examples or Comparative Examples, and the results are shown in Table 2. In addition, Example 5 shall be read as Reference Example 1.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film was measured using pencil scratching. That is, on a polyester film having a cured film to be measured, a pencil was applied at a 45 degree angle and a 1 kg load was applied from above to scratch about 5 mm to confirm the degree of scratching. Take 5 measurements and count the number of scratches.
Evaluation 5/5: No damage in 5 out of 5 times 0/5: All scratches occurred in 5 times

(Abrasion resistance test)
A load of 200 g / cm <2> was applied on steel wool # 0000 for 10 reciprocations, and the condition of the scratch was judged visually.
Evaluation ○: No scratch ×: Scratch occurrence

ＤＰＨＡ：日本化薬（株）製；ジペンタエリスリトールヘキサアクリレートとペンタアクリレートの混合物
ＤＰＨＡ−４０Ｈ：日本化薬（株）製；多官能ウレタンアクリレート
ＵＸ−５０００：日本化薬（株）製；多官能ウレタンアクリレート
ＭＥＫ：２−ブタノン (Adhesion)
In accordance with JIS K 5400, 100 vertical grids are made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the film. When cellophane tape (registered trademark) was brought into close contact with the surface and peeled off at once, the number of cells remaining without peeling was displayed.
Evaluation ○: 80 or more ×: 79 or less

DPHA: manufactured by Nippon Kayaku Co., Ltd .; mixture of dipentaerythritol hexaacrylate and pentaacrylate DPHA-40H: manufactured by Nippon Kayaku Co., Ltd .; multifunctional urethane acrylate UX-5000: manufactured by Nippon Kayaku Co., Ltd .; multifunctional Urethane acrylate MEK: 2-butanone

  From the results shown in Table 2, the film coated with the photosensitive resin composition containing the ethylenically unsaturated group-containing carboxylate compound (D-1) of the present invention maintains the adhesion, and also has pencil hardness and resistance. Excellent in terms of scratch resistance.

  The ethylenically unsaturated group-containing carboxylate compound of the present invention is low in viscosity and excellent in curability and has a high cured product hardness, and can be applied as, for example, a monomer for semiconductor resist and a dilution monomer for various polymerizable resin compositions. . Furthermore, the cured film of the photosensitive resin composition of the present invention has excellent curability and high hardness, and various coating fields such as ink, plastic paint, paper printing, metal coating, furniture painting, lining, adhesives, and electronics field. Can be applied to many fields such as insulating varnishes, insulating sheets, laminates, printed boards, resist inks, and semiconductor encapsulants.

Claims (7)

Cyclic olefin compound (A) having a vinyl group or an allyl group represented by the following formula (1)

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0. Or an integer of 1 and a dotted line represents that no methylene group or bond exists, respectively)
, An ethylenically unsaturated group-containing carboxylate compound (D) obtained by reacting an epoxy compound (B) obtained by epoxidation with an ethylenically unsaturated group-containing monocarboxylic acid compound (C), and urethane (meth) Photosensitive resin composition for insulating varnish containing acrylate (E-2). The epoxy compound (B) is represented by the following formula (2): The photosensitive resin for insulating varnish containing the ethylenically unsaturated group-containing carboxylate compound (D) according to claim 1 and a urethane (meth) acrylate (E-2). Resin composition.

(In the formula (2), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m is an integer of 0 to 5, and n is 0. Or an integer of 1 and a dotted line represents that no methylene group or bond exists, respectively) The epoxy compound (B) is represented by the following formula (3): The ethylenically unsaturated group-containing carboxylate compound (D) according to any one of claims 1 and 2, wherein the epoxy compound (B) is any one of claims 1 and 2. The photosensitive resin composition for insulating varnishes described in 1.

The ethylenically unsaturated group-containing carboxylate compound (D) according to any one of claims 1 to 3, wherein the ethylenically unsaturated group-containing monocarboxylic acid compound (C) is (meth) acrylic acid. The photosensitive resin composition for insulating varnishes as described in any one of 2 or 2. 5. The photosensitive resin for insulating varnish comprising the ethylenically unsaturated group-containing carboxylate compound (D) according to claim 1 and a polymerizable compound (E) other than (D). Composition. The photosensitive resin composition for insulating varnishes of Claim 5 containing a photoinitiator (F). Hardened | cured material of the photosensitive resin composition for insulating varnishes as described in any one of Claims 1 thru | or 6.