JP2014198699A - Anthraquinone-based compound and photocurable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition which is highly sensitive to a light beam in the visible range, is advantageous in an electronic material field or a recording display material field using an anthraquinone-based compound having a specific structure and shows an excellent effect as a photopolymerization initiator in the photo-radical polymerization and as a photosensitizer in the photocationic polymerization.SOLUTION: There is provided an anthraquinone-based compound represented by the following general formula (1): (where, X and A each independently represent a divalent organic residue; Y represents a divalent linking group constituted by a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom; n represents an integer of 1 or 2; and provided that when n is 1, A represents a linear or branched alkyl group.)

Description

  The present invention relates to a novel anthraquinone compound and a photocurable resin composition containing it as a photopolymerization initiator, or a photocurable resin composition containing it as a photosensitizer for photocationic polymerization. More specifically, it is cured by a photopolymerization initiator or photocationic photosensitizer that can be used for photoresist materials, printing plate making materials, adhesive materials, sealing materials, coating materials, molding materials, and the like, and a light source of a blue LED lamp. It relates to a photocurable resin composition.

  The photo-curing reaction is a technology that uses a chemical reaction initiated by light and is excellent in practical viewpoints such as resource saving, energy saving, productivity improvement, and working environment. In recent years, in addition to applications such as metal surface processing, it has also been used in a wide range of applications such as photoresist materials for printed wiring boards and liquid crystal panel sealing materials in the fields of electronic materials and recording display materials.

In general, a photocurable resin composition used for a photocuring reaction is composed of a photopolymerization initiator that generates active species by light and monomers and oligomers that can be polymerized by the generated active species. Since it starts from the light absorption of the photopolymerization initiator, it is essential that the photopolymerization initiator is a compound that can generate active species efficiently with respect to the light source.
As described above, the photopolymerization initiator is one of the major factors that determine the characteristics of the photocuring reaction and the final product (photocured product). The photocuring reaction mainly includes radical polymerization or cationic polymerization. Broadly divided.

On the other hand, when it comes to light sources, light sources with a light emission region in a wide wavelength range, such as mercury lamps and metal halide lamps, have been widely used because they have a great merit that they are very easy to use. Because it has the disadvantage that it can bring about factors, recently, in the production of various products utilizing photo-curing reaction technology such as UV-curable paints and coatings, photo-curing adhesives, UV inks, resists, etc., the wavelength range is 400- A 460 nm blue LED lamp has been used as a light source.
However, when this blue LED lamp is used as a light source, it has the advantages of power saving, space saving and long life, but the conventional photopolymerization initiator cannot provide sufficient curing characteristics.

For example, an acetophenone type photoradical polymerization initiator is well known as a photopolymerization initiator used in radical polymerization (Patent Document 1).
In particular, acetophenone-type photopolymerization initiators currently available on the market include benzyl ketals and α-hydroxyacetophenones, but these photopolymerization initiators have a small extinction coefficient at a wavelength of 300 nm or more, so a high-pressure mercury lamp However, there is no problem when photocuring using a light source having light emission in a wide wavelength range, but when photocuring using a light source that uses ultraviolet rays having a relatively long wavelength up to the vicinity of 400 nm, Curing properties are not high, and as a result, unreacted photopolymerization initiators remain and bleed out from the photocured product. This may be a problem in applications where electronic impurities are problematic.

As cationic photopolymerization initiators that generate an acid by light, onium salt compounds such as sulfonium salts and iodonium salts are widely used. For example, iodonium salts have a wavelength of about 250 nm. The photocuring function can be exhibited only by light in the ultraviolet region, and the sulfonium salt can also exhibit the photocuring function only with light having a wavelength of about 360 nm. In addition, a sensitizer such as thioxanthone or dialkoxyanthracene (anthracene diether) must be used in combination.
Therefore, in order to solve such a problem, a photopolymerization initiator suitable for light in the visible region having a wavelength of 400 nm or more is desired, and several compounds have been reported. Has not been reported (Patent Document 2).

Special table 2003-253225 gazette JP 2001-235858 A

The subject of this invention is providing the photocurable resin composition highly sensitive with respect to the light ray of a visible region with a wavelength of 400 nm or more by utilizing the anthraquinone type compound which has a specific structure.

〔式中、Ｘ及びＡは互いに独立に、二価の有機残基を表し、Ｙは炭素原子、水素原子、酸素原子、及び窒素原子から構成される二価の連結基を表し、ｎは１または２の整数を表す。ただし、ｎが１である場合、Ａは直鎖状または分岐状のアルキル基を表す〕
（ii）二価の有機残基が、直鎖状または分岐状アルキレン基、脂環式アルキレン基から選択される基である上記（ｉ）のアントラキノン系化合物
（iii）二価の連結基が、フェニレン基、メチレン基、置換または未置換のイミノ基、エステル基、置換または未置換のアミド基、置換または未置換のウレタン基、エーテル基から選択される基である上記（ｉ）又は（ii）のアントラキノン系化合物
さらに、
（iv）上記（ｉ）〜（iii）のアントラキノン系化合物から選ばれる１種を光重合開始剤として含む、光硬化性樹脂組成物
（ｖ）上記（ｉ）〜（iii）のアントラキノン系化合物から選ばれる１種を光カチオン重合の光増感剤として含む、光硬化性樹脂組成物に関するものである。
As a result of intensive studies on the anthraquinone compound as a photopolymerization initiator, the present inventors have completed the present invention. That is, the present invention
(I) Anthraquinone compounds represented by the following general formula (1)

[Wherein, X and A independently represent a divalent organic residue, Y represents a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, and n represents 1 Or represents the integer of 2. However, when n is 1, A represents a linear or branched alkyl group.
(Ii) The anthraquinone compound (iii) above in which the divalent organic residue is a group selected from a linear or branched alkylene group and an alicyclic alkylene group (iii) a divalent linking group is (I) or (ii) above, which is a group selected from a phenylene group, a methylene group, a substituted or unsubstituted imino group, an ester group, a substituted or unsubstituted amide group, a substituted or unsubstituted urethane group or an ether group Anthraquinone compounds
(Iv) A photocurable resin composition containing one type selected from the above-mentioned anthraquinone compounds (i) to (iii) as a photopolymerization initiator (v) From the anthraquinone compounds (i) to (iii) above The present invention relates to a photocurable resin composition containing one selected as a photosensitizer for photocationic polymerization.

According to the present invention, the photocurable resin composition is advantageous in the field of electronic materials and recording display materials because it is highly sensitive to light in the visible region having a wavelength of 400 nm or more as compared with conventional photocurable resin compositions. It became possible to provide.
In addition, the anthraquinone compound of the present invention exhibits excellent effects as a photopolymerization initiator in photoradical polymerization and as a photosensitizer in photocationic polymerization, and has excellent elution from the cured product without elution from a cured product. It was possible to provide a photocurable resin composition.

As a result of intensive studies on the above-mentioned problems, the present inventors have found that a novel anthraquinone compound having a specific structure can be contained in the photocurable resin composition, and have completed the present invention. It was.
Hereinafter, the present invention will be described in detail. First, the anthraquinone compound according to the present invention will be described.

〔式中、Ｘ及びＡは互いに独立に、二価の有機残基を表し、Ｙは炭素原子、水素原子、酸素原子、及び窒素原子から構成される二価の連結基を表し、ｎは１または２の整数を表す。ただし、ｎが１である場合、Ａは直鎖状または分岐状のアルキル基を表す〕 <Anthraquinone compounds>
The anthraquinone compound of the present invention is a compound represented by the general formula (1).

[Wherein, X and A independently represent a divalent organic residue, Y represents a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, and n represents 1 Or represents the integer of 2. However, when n is 1, A represents a linear or branched alkyl group.

In the compound represented by the general formula (1), X and A represent a divalent organic residue. In the present specification, divalent groups generated by removing one each of hydrogen atoms of two different carbon atoms of an aliphatic hydrocarbon compound are collectively referred to as a “divalent organic residue”. Represent.
X and A are preferably a linear or branched alkylene group or an alicyclic alkylene group.
X and A are more preferably a linear or branched alkylene group having 1 to 4 carbon atoms or an alicyclic alkylene group having 4 to 12 carbon atoms.

Specific examples of X and A in the general formula (1) being a linear alkylene group include, for example, a methylene group [—CH 2 —], an ethylene group [—CH 2 —CH 2 —, an n-propylene group. Examples include a linear alkylene group composed of only a carbon atom and a hydrogen atom such as [—CH 2 —CH 2 —CH 2 —] and n-butylene group [—CH 2 —CH 2 —CH 2 —CH 2 —].
Specific examples of those in which X and A are branched alkylene groups include, for example, 1,2-dimethylethylene group [—CH (CH 3) —CH (CH 3) —], ethylidene group [—CH (CH 3) — ], The branched alkylene group by which hydrogen of the linear alkylene group, such as an isopropylidene group [-C (CH3) 2-], was substituted by the alkyl group.
Specific examples of those in which X and A are alicyclic alkylene groups include, for example, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene group, 2,3- Bicyclo [2.2.1] heptylene group, 2.5-bicyclo [2.2.1] heptylene group, 2,6-bicyclo [2.2.1] heptylene group, 2,6-bicyclo [2.2 .2] Monocyclic or bridged cyclic alicyclic alkylene groups such as octylene group and 1,3-adamantylene group.

In the compound represented by the general formula (1), Y represents a divalent linking group composed of a carbon atom, an oxygen atom, and a nitrogen atom.
Y is preferably a phenylene group, a methylene group, a substituted or unsubstituted imino group, an ester group, a substituted or unsubstituted amide group, a substituted or unsubstituted urethane group, or an ether group.
Y is more preferably a phenylene group, a methylene group, an imino group optionally substituted with a linear alkyl group having 1 to 4 carbon atoms, an ester group, or a linear alkyl group having 1 to 4 carbon atoms. An amide group which may be substituted with, a urethane group which may be substituted with a linear alkyl group having 1 to 4 carbon atoms, or an ether group.

As an example of the phenylene group in the general formula (1), -Y- is a linking group formed by removing one hydrogen atom from each of two carbon atoms having different benzene rings. Examples include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.
As an example of a methylene group, -Y- is a linking group consisting of only a carbon atom and a hydrogen atom of [-CH2-].

  As an example of an unsubstituted imino group, -Y- is a linking group consisting of only a nitrogen atom and a hydrogen atom of [-NH-]. As a specific example of an optionally substituted imino group,- Y- is a linear hydrogen atom of an imino group such as, for example, a methylimino group [—N (CH 3) —], an ethylimino group [—N (C 2 H 5) —], a propyl imino group [—N (C 3 H 7) —], etc. An imino group substituted with an alkyl group can be mentioned.

Specific examples of the ester group include an ester bond in which —Y— is composed of only a carbon atom and an oxygen atom, such as [—CO—O—] and [—O—CO—].
As an example of an unsubstituted amide group, -Y- is a linking group consisting of a carbon atom, a nitrogen atom and a hydrogen atom of [-CO-NH-], and a specific example of an optionally substituted amide group As for -Y-, for example, a hydrogen atom of an amide group such as a methylamide group [-CO-N (CH3)-], an ethylamide group [-CO-N (C2H5)-] is substituted with a linear alkyl group Amide group formed.

As an example of an unsubstituted urethane group, -Y- is a linking group consisting of a carbon atom, a nitrogen atom and a hydrogen atom of [—O—CO—NH—], and an optionally substituted urethane group As a specific example, —Y— is, for example, a hydrogen atom of a urethane group such as a methylurethane group [—O—CO—N (CH 3) —] or an ethylurethane group [—O—CO—N (C 2 H 5) —]. As an example of an ether group, —Y— is a linking group consisting of only an oxygen atom of [—O—].
In the compound represented by the general formula (1), when n is 1, A represents a linear or branched alkyl group.
When n is 1, A is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. When n is 1, A is more preferably a linear or branched alkyl group having 1 to 8 carbon atoms.

Specific examples when A in the general formula (1) is a linear or branched alkyl group include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl Group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2, 6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n Dodecyl group.
In the compound represented by the general formula (1), preferred specific examples in the case where n is 1 include, for example, the following compounds, but the present invention is not limited thereto.

In the compound represented by the general formula (1), preferred specific examples when n is 2 include, for example, the following compounds, but the present invention is not limited thereto.

〔式中、Ｚはハロゲン原子を表し、Ｘ、Ｙ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕
なお、上記一般式（２）において、Ｚは塩素原子であることが好ましい。 <Method for producing anthraquinone compound>
The anthraquinone compound represented by the general formula (1) according to the present invention can be produced by various organic chemical methods.
That is, for example, the compound represented by the general formula (1) reacts the halogenated anthraquinone compound represented by the general formula (2) with the mercapto compound represented by the general formula (3) in the presence of a base. Can be manufactured in one step.

[Wherein Z represents a halogen atom, and X, Y, A, and n represent the same meaning as in the general formula (1)].
In the general formula (2), Z is preferably a chlorine atom.

  The mercapto compound represented by the general formula (3) can be produced by referring to a method known per se. For example, thioglycol in the case where X is a methylene group and -Y- is an ester group. Methyl acid, butyl thioglycolate, 1,4-butanediol bis (thioglycolate), for example, 3,6-dioxa-1,8-octanedithiol when X is an ethylene group and -Y- is an ether group Some are available as commercial products, and can be easily obtained from, for example, Tokyo Chemical Industry and Wako Pure Chemical Industries.

〔式中、Ｘ、Ｙ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕 For example, it can be produced by reacting a halogenated derivative represented by the general formula (4) with hydrogen sulfide or thiosulfuric acid [for example, US Pat. No. 2,342,142, US Pat. No. 4,355,185, Journal of the American Chemical Society, 1930, vol,
52, can be produced according to the method described in P655].

[Wherein, X, Y, A and n represent the same meaning as in the general formula (1)]

〔式中、Ｘ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕 Furthermore, a production example of the compound represented by the general formula (3) will be described with reference to a chemical reaction formula.
For example, as a production example in the case where -Y- is an ester group represented by the general formula (3a), for example, a carboxylic acid derivative represented by the following general formula (5) and the following general formula (6) It can manufacture by dehydrating condensation with the alcohol derivative represented [For example, it can manufacture in accordance with the method of US Pat. No. 2,832,750].

[Wherein, X, A and n represent the same meaning as in the general formula (1)]

〔式中、Ｘ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕
一般式（３）で表されるメルカプト化合物の使用量は特に制限されるものではなく、一般式（２）で表されるハロゲン化アントラキノン化合物に対して、一般に、０．５〜２．５モル程度使用することが好ましく、０．５〜１．５モル程度使用することがより好ましい。 Next, for example, when -Y- is an unsubstituted amide group represented by the general formula (3b), the carboxylic acid derivative represented by the following general formula (7) and the following general formula (8) are represented. It can be produced by dehydration condensation with an amine derivative [for example, it can be produced according to the method described in US Pat. No. 2,832,750].

[Wherein, X, A and n represent the same meaning as in the general formula (1)]
The amount of the mercapto compound represented by the general formula (3) is not particularly limited, and is generally 0.5 to 2.5 mol with respect to the halogenated anthraquinone compound represented by the general formula (2). It is preferable to use about 0.5 to 1.5 moles.

  The amount of the base used is not particularly limited, and is generally preferably about 1.0 to 3.0 mol based on the halogenated anthraquinone compound represented by the general formula (2). It is more preferable to use about ~ 2.0 mol.

The solvent is not particularly limited as long as it does not inhibit this reaction, but 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, 2-methyl-2-butanol, and the like. Alcohols, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and dimethyl sulfoxide.
These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more.
In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times, preferably 5 to 50 times that of the whole compound by weight ratio.

Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, potassium phosphate, sodium hydrogen carbonate, potassium hydrogen carbonate, such as sodium tert-butoxide, potassium- Metal alkoxides such as tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, for example, potassium acetate, sodium acetate, triethylamine, triisopropylamine, tri-n-butylamine, tetra-n-butylammonium Bromide, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), N, N, N ′, N '-Tetramethylethylenediamine , And the like of an organic base.
The amount of the base used is not particularly limited, and is generally preferably about 0.01 to 10.0 mol based on the halogenated anthraquinone compound represented by the general formula (2). It is more preferable to use about ~ 2.0 mol.

The reaction temperature may be appropriately selected in the range of 0 to 200 ° C., but is preferably in the range of room temperature to solvent reflux temperature.
The reaction time is not constant depending on the reaction scale and reaction temperature, but may be appropriately selected within the range of 1 to 48 hours.

  When a solvent that dissolves in water is used after completion of the reaction, the reaction solution is discharged into water, and the precipitate is filtered off and washed with methanol. When a solvent insoluble in water is used, the solvent is distilled off under reduced pressure, water is added, the precipitate is filtered off and washed with methanol. If necessary, the precipitate can be purified by a method such as recrystallization.

〔式中、Ｚはハロゲン原子を表し、Ｘ、Ｙ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕 In addition, in the compound represented by the general formula (1), as a production method in the case where -Y- is an ester group shown as the general formula (1a), other than the above production method, for example, the general formula ( The intermediate represented by the general formula (10) synthesized by reacting the halogenated anthraquinone compound represented by 2) with the mercapto compound represented by the general formula (9) in the presence of a base, It can also be produced in two steps by reacting an acid halide represented by the general formula (11).

[Wherein Z represents a halogen atom, and X, Y, A, and n represent the same meaning as in the general formula (1)].

〔式中、Ｘ、Ｙ、Ａ及びｎは一般式（１）の場合と同じ意味を表す〕 Furthermore, in the compound represented by the general formula (1), an anthraquinone compound represented by the above general formula (10) may be used as a production method in the case where -Y- is an ether group represented by the general formula (1b). Further, it can also be produced by reacting a halide represented by the general formula (12).

[Wherein, X, Y, A and n represent the same meaning as in the general formula (1)]

  The amount of the mercapto compound represented by the general formula (9) is not particularly limited, but since this reaction is an equimolar reaction, the halogenated anthraquinone compound represented by the general formula (2) The mercapto compound represented by the formula (9) may be reacted by 1.0 times mole, but the amount of the compound represented by the general formula (9) is 1.0 to 1.5 times mole. What is necessary is just to select suitably by the range, Preferably it is the range of 1.0-1.3 times mole.

  The reaction for obtaining the intermediate represented by the general formula (10) is carried out in an organic solvent, and the solvent that can be used is not particularly limited. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene and chlorobenzene, and ether solvents such as tetrahydrofuran and 1,4-dioxane. In particular, the halogenated anthraquinone compound represented by the general formula (2) A solvent having a high solubility of pyridine, such as pyridine, N, N-dimethylformamide, N-methylpyrrolidone and the like is preferable.

Examples of the base include alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkalis such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate and cesium carbonate. Mention may be made of organic bases such as metal carbonates, pyridine, triethylamine and ammonia.
Such bases may be used alone or in combination. The amount of the base used is not particularly limited, but is generally 0.5 to 3.0 mol, preferably 0 to 1 mol of the halogenated anthraquinone compound represented by the general formula (2). .8 to 2.5 moles are used.

The reaction temperature is selected in the range of 20 ° C to 180 ° C, preferably in the range of 50 ° C to 100 ° C. When the temperature is low, the reaction rate is low and the time until the reaction is completed is long. When the temperature is high, a side reaction occurs and the reaction product becomes dirty.
The reaction time is selected in the range of 1 hour to 10 hours depending on the reaction temperature, and preferably in the range of 3 hours to 5 hours. After completion of the reaction, the reaction mixture is cooled, water is added to the reaction mixture to precipitate crystals, and the filtered crystals are dried to obtain an intermediate represented by the general formula (10).

Next, by reacting the intermediate represented by the general formula (10) with the compound represented by the general formula (11) or the general formula (12) in an organic solvent in the presence of a base, the general formula ( The compound represented by 1a) or general formula (1b) can be produced.
The amount of the compound represented by the general formula (11) or the general formula (12) is not particularly limited, but when n is 1, since this reaction is an equimolar reaction, the general formula (10 The intermediate compound represented by the general formula (11) or the general formula (12) may be reacted in a 1.0-fold molar reaction with the intermediate represented by the general formula (11) or the general formula (12). The amount of the compound represented by the above formula may be appropriately selected within the range of 1.0 to 1.5 times mol, and preferably within the range of 1.0 to 1.3 times mol.
When n is 2, since this reaction is a 0.5-fold molar reaction, the compound represented by the general formula (11) or the general formula (12) is added to the intermediate represented by the general formula (10). The amount of the compound represented by the general formula (11) or the general formula (12) may be appropriately selected within the range of 0.5 to 0.7 times mole. What is necessary is just to be 0.5-0.6 times mole range.

The solvent is not particularly limited as long as it does not inhibit this reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, Alcohols such as 2-methoxyethanol and 2-ethoxyethanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as methyl acetate and ethyl acetate; -Ethers such as dimethoxyethane, tetrahydrofuran, dioxane and the like can be mentioned, and ketones are particularly preferable.
These solvents are appropriately selected according to the ease of reaction, and can be used singly or in combination of two or more. In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times, preferably 5 to 50 times that of the whole compound by weight ratio.

Such a base is not particularly limited as long as it can accelerate the reaction, and examples thereof include pyridine, triethylamine, potassium carbonate, and sodium carbonate.
Of these, pyridine is preferable, and the amount of pyridine used may be appropriately selected within a range of 0.5 to 6.0 times the molar ratio of the general formula (11) or the general formula (12), preferably The range is 1.5 to 4.0 moles.

The reaction temperature may be appropriately selected in the range of −30 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., and the reaction time is not constant depending on the reaction scale and reaction temperature, but is 1 to 12 hours. It suffices to select appropriately within the range.
After completion of the reaction, the reaction mixture is cooled, the reaction mixture is discharged into water, methanol, or a mixed solution of water and methanol to precipitate crystals, and the filtered crystals are dried to obtain a general formula (1a) or general formula (1b). The compound represented is obtained.
In addition, the anthraquinone type compound represented by General formula (1) based on this invention synthesize | combined in this way has the maximum absorption wavelength in the range of 370-450 nm.
Next, the photocurable resin composition containing the anthraquinone compound of the present invention will be described.

<Photocurable resin composition>
The photocurable resin composition of the present invention contains a polymerizable compound and a photopolymerization initiator as active ingredients.
Below, a polymerizable compound is demonstrated first and then a photoinitiator is demonstrated.

<Polymerizable compound>
There is no restriction | limiting in particular as a polymeric compound, Any of low molecular weight (monomer property)-high molecular weight (oligomer property) which has the site | part which can superpose | polymerize in a structure may be sufficient. Further, depending on the use of the photocurable resin composition, it may be a compound having a site that expresses another function in the structure. For example, when the photocurable resin composition is used as a recording material, It may have a site that promotes the color reaction of the color forming component constituting the part, or a site that suppresses color development.
Specific examples include compounds having at least one ethylenically unsaturated double bond in the molecule, epoxy compounds, cyclic ether compounds, oxetane compounds, cyclic thioether compounds, spiro ortho ester compounds, spiro ortho carbonate compounds, and the like. It is done.

  The compound having at least one ethylenically unsaturated double bond in the molecule is not particularly limited, and examples thereof include acrylic acid and its salts such as acrylic esters and acrylamides, methacrylic esters and methacrylamides. Methacrylic acid and salts thereof, maleic anhydride, maleic esters, itaconic acid, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, aryl ethers, allyl esters, And maleimides.

  The epoxy compound is not particularly limited. Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, novolak glycidyl ether, hexahydrophthalic acid Glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, resorcinol diglycidyl ether, hexahydrobisphenol glycidyl ether, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene Oxide, phenyl glycidyl ether, cresyl glycidyl ether, -sec- butyl phenyl glycidyl ether, glycidyl methacrylate, tertiary carboxylic acid glycidyl esters, diglycidyl ether, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether

  The cyclic ether compound is not particularly limited, and specific examples thereof include dioxanes such as dioxane and 4-phenyl-1,3-dioxane, trioxane, 1,3-dioxepane, tetrahydrofuran, 2-methyl-tetrahydrofuran, tetrahydro Compounds such as pyran, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and alkyl ethers of furfuryl alcohol can be used.

  The oxetane compound is not particularly limited, and specifically, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, alkyloxetane such as 3,3-dimethyloxetane, 3-methyl- Examples include 3-methoxymethyloxetane, 3,3-di (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, and 3,3-bis (chloromethyl) oxetane.

  Although there is no restriction | limiting in particular as a cyclic thioether compound, Specifically, the compound whose oxygen of said epoxy compound, a cyclic ether compound, and an oxetane compound becomes sulfur is mentioned.

  The spiro orthoester compound is not particularly limited, and specifically, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4- Examples thereof include hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

  The spiro orthocarbonate compound is not particularly limited, and specifically, 1,5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,7,11- Tetraoxaspiro [5,5] undecane, 1,4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane, 1,4 Examples thereof include compounds such as 6-trioxaspiro [4,5] decane.

Among these, the polymerizable compound used in the present invention is preferably a compound having at least one ethylenically unsaturated double bond in the molecule.
The content of the polymerizable compound in the present invention is usually 10 to 99.9% by mass, preferably 20 to 99% by mass, and preferably 30 to 95% by mass based on the total mass of the photocurable resin composition. % Is more preferable.

<Photopolymerization initiator>
The photopolymerization initiator includes a case where the anthraquinone compound according to the present invention is used as an active ingredient and a case where a combination with an onium salt is used as an active ingredient.
In the former case, the anthraquinone compound according to the present invention functions as a photopolymerization initiator for initiating radical polymerization, and in the latter case, the anthraquinone compound according to the present invention acts as a photosensitizer, In combination with an onium salt having a function of generating an acid, it functions as a photopolymerization initiator for initiating cationic polymerization.

As the onium salt, a sulfonium salt or an iodonium salt is usually used.
Examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate. Fate and triphenylsulfonium hexafluorophosphate.
Examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentafluorophenylborate, and the like. Can be mentioned.

The amount of the anthraquinone compound according to the present invention to be added to the onium salt is preferably selected in the range of 10 to 50% by mass, more preferably in the range of 20 to 40% by mass. If the amount of the anthraquinone compound according to the present invention is less than 10% by mass, the polymerization may not proceed sufficiently. If it exceeds 50% by mass, the hardness and weather resistance of the cured product may decrease. is there.
The addition amount of the photopolymerization initiator according to the present invention is preferably selected in the range of 0.01 to 10% by mass, more preferably in the range of 0.1 to 3% by mass with respect to the polymerizable compound. When the addition amount of the photopolymerization initiator is less than 0.01% by mass, the polymerization rate is slow, and when it exceeds 10% by mass, the physical properties of the cured product are deteriorated.

<Other ingredients>
If necessary, the photocurable resin composition of the present invention is a photopolymerization initiator other than the photopolymerization initiator according to the present invention, a silane coupling agent, a solvent, a dye, a colorant, a surfactant, and a polymerization inhibitor. , May contain components such as various anti-foaming agents, antioxidants, organic or inorganic fillers, leveling agents, thickeners, flame retardants, stabilizers, lubricants, plasticizers and various resin additives, Used according to purpose.
In addition, a conventionally well-known thing can be used for any component. These components are preferably added in an amount of 0.01 to 20% by mass, more preferably 0.2 to 15% by mass based on the total mass of the photocurable resin composition, and 0.5 to 10%. It is particularly preferable to add mass%.

As the photopolymerization initiator other than the photopolymerization initiator according to the present invention, those having photosensitivity to visible light are preferable, and active agents that generate active radicals or initiators that initiate cationic polymerization are preferable. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1- Propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, 1- [9-ethyl-6 (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4- Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid , Benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2- Chlorothioxanthone, 2,4-dimethyl Oxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o -Chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethyl Minobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether , Acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone P-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, Oxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9 -Acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methyl) Enyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrene Butylphenyl -s- triazine, 2,4-bis - trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl -s- triazine.
Silane coupling agents are used to improve adhesion and minimize outgassing during curing. For example, vinyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ-glycol are used. Sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane . These silane coupling agents may be used alone or in combination of two or more. These silane coupling agents may be subjected to oligomerization treatment by dehydration condensation with other silane compounds such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane.

The solvent is used for improving coatability and adjusting the viscosity, and examples thereof include alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, alkyl lactate esters, and alkylene glycol monoalkyl ether acetates. These solvents may be used alone or in combination of two or more.
The dye is used as a sensitizing dye and may be any dye used in conventional photocurable resin compositions, and examples thereof include a cationic dye, a neutral dye, and an anionic dye. Examples of the colorant include a blue pigment, a yellow pigment, a red pigment, a white pigment, and a black pigment. Examples of the surfactant include anionic, cationic, and nonionic compounds.
Examples of the polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine compounds.

<Method for preparing photocurable resin composition>
The photocurable resin composition of the present invention can be obtained by mixing at least the polymerizable compound and a photopolymerization initiator. The mixing method is not particularly limited as long as it is a known method capable of dispersion mixing or kneading, and can be performed by a roll mill method, a ball mill method, a sand mill method, or the like.

<Uses of photocurable resin composition>
The photocurable resin composition obtained by the above method can be cured by irradiating the coating film with light in the visible region after coating on the substrate.
The substrate is not particularly limited to the material, shape, surface state, etc., such as those exhibiting a dimensionally stable plate shape, those exhibiting a curved surface, and those exhibiting a three-dimensional shape.
For example, as dimensionally stable plates, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and metals such as aluminum (including aluminum alloys), zinc, copper, etc. Of plastic, such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include films, paper or plastic films on which the above metals are laminated or deposited.

The application method is not particularly limited as long as the photocurable resin composition can be applied to the surface of the substrate, and may be a bar coating method, a spray coating method, or the like.
Moreover, on the layer of the photocurable resin composition provided on the base material, for the purpose of preventing the polymerization inhibiting action due to oxygen in the air, for example, an oxygen barrier property such as polyvinyl alcohol, acidic celluloses, etc. It is optional to provide a protective layer made of an excellent polymer.
The photocurable resin composition applied to the substrate surface can be cured by light irradiation from a light source having a wavelength of 300 nm to 1000 nm.

The photocurable resin composition of the present invention has a thickness of 300 to 500 nm.
By irradiating with an active energy ray having a wavelength of 1, it can be cured rapidly. Examples of the light source capable of irradiating active energy rays in this wavelength range include light sources such as a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, a metal halide lamp, a UV-LED lamp, a blue LED lamp, and a white LED lamp. Sunlight can also be used.
In particular, since the anthraquinone compound according to the present invention has a maximum absorption wavelength in the range of 370 to 450 nm, the photocurable resin composition is 400 to 400 nm.
It becomes highly sensitive to an active energy ray having a wavelength of 460 nm, can be polymerized using a blue LED lamp, and is very useful industrially.
For example, the photocurable resin composition of the present invention is applied in the form of a film and cured, by the following procedure. That is, the photocurable resin composition is applied to the surface of a substrate such as a polyester film so as to have a film thickness of 5 to 300 μm using, for example, a bar coater.

Confirmation of the completion of curing of the photocurable resin composition of the present invention is performed based on a tack-free test (finger touch test). That is, it is common to measure the time until the tack (stickiness) of the photocurable resin composition on the film surface is removed by light irradiation as the curing time. The shorter this time, the faster the curing reaction. To do.
As described above, the photocurable resin composition of the present invention is similar to the ordinary photocurable resin composition, and is a photocurable paint, coating, photocurable sealant, photocurable adhesive, and photocurable type. It can be used for surface treatment of adhesives, photocurable inks, color filters, hologram recording media, lithographic printing, resin relief printing, photoresists, solder resists, various metals and resins, glass, paper, wood, etc. .

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
In all Examples, the method for evaluating an anthraquinone compound of the present invention measured an absorption spectrum and TG-DTA. For the measurement of the absorption spectrum, about 10 mg of the sample is weighed, put into a 100 mL volumetric flask, dissolved in toluene or N-methylpyrrolidone and made up. Remove 5 mL of the solution with a whole pipette and place in a new 100 mL volumetric flask. This solution was put into a 1 cm quartz cell, and an absorption spectrum was measured using a U-3500 type spectrophotometer manufactured by Hitachi High-Tech Fielding Co., Ltd. to obtain a maximum absorption wavelength (λmax).
The maximum absorption wavelength can be used as an index indicating sensitivity.
In addition, the Gram extinction coefficient calculated | required the light absorbency (Abs) in the maximum absorption wavelength of an absorption spectrum, and calculated | required the Gram extinction coefficient ((epsilon) g) from the following formula.
C (concentration) = (10/100) × (5/100) (g / mL)
εg = Abs / (C × B) (mL / gcm) B = cell length (1 cm)
TG-DTA is measured by putting about 5 mg of each material in a quartz pan, using a differential thermobalance TG8120 manufactured by Rigaku Corporation, using alumina as a reference for the pan, and 800 ° C. for a heating rate of 10 ° C./min. Measurements were made up to.

[Example 1] Synthesis of exemplified compound (1-5) 20 g of 2-chloroanthraquinone was added to 115 g of DMF, and the mixture was heated to 95 ° C while stirring. 14.78 g of butyl thioglycolate and 3.36 g of sodium hydroxide were also added dropwise at the same temperature, and the mixture was stirred for 9 hours. After cooling to room temperature and discharging the reaction product to 400 g of 5% aqueous hydrochloric acid, the precipitate was filtered, washed with water and dried to give Exemplified Compound (1-5) as yellow crystals. The yield of the obtained crystal relative to the raw material 2-chloroanthraquinone was 37.1 mol%, and the absorption spectrum and TG-DTA were measured.
Maximum absorption wavelength: 385.5 nm εg = 11460 mL / gcm
DTA (melting point): 74.4 ° C

[Example 2] Synthesis of exemplary compound (1-31) 19.9 g of 2-chloroanthraquinone was added to 100 g of DMF, and 7.47 g of 3,6-dioxa-1,8-octanedithiol and potassium tert-butoxide were stirred. 9.2 g and 2-methyl-2-butanol 52 g were added, heated to 100 ° C. with stirring, and stirred for 1 hour. After cooling to room temperature and discharging the reaction product into 400 g of water, the precipitate was filtered, washed with water and methanol and then dried to obtain Exemplified Compound (1-31) as yellow crystals. The yield of the obtained crystal relative to the raw material 2-chloroanthraquinone was 92.7 mol%, and the absorption spectrum and TG-DTA were measured.
Maximum absorption wavelength: 401.5 nm εg = 15550 mL / gcm
DTA (melting point): 212.5 ° C

[Example 3] Synthesis of exemplary compound (1-9) 60 g of 2-chloroanthraquinone was added to 360 g of DMF, and the mixture was heated to 90 ° C while stirring. 2-Mercaptoethanol (20.85 g) and sodium hydroxide (10.0 g) were also added dropwise at the same temperature, and the mixture was stirred for 8 hours. After cooling to room temperature and discharging the reaction product into 400 g of water, the precipitate was filtered, washed with water and dried to obtain 64.0 g of 2-hydroxyethylthioanthraquinone.
Next, 25.59 g of 2-hydroxyethylthioanthraquinone and 9.49 g of pyridine were added to 170 g of methyl ethyl ketone, and the temperature was raised to 50 ° C. while stirring. Furthermore, 8.48 g of acetyl chloride was added dropwise at the same temperature over 1 hour, and then heated to 80 ° C. and stirred at the same temperature for 1 hour. After cooling to room temperature and discharging the reaction product into a mixed solution of 100 g of water and 100 g of methanol, the precipitate was filtered, washed with methanol and then dried to obtain Exemplified Compound (1-9) as yellow crystals. The yield of the obtained crystal relative to the raw material 2-chloroanthraquinone was 75.3 mol%, and the absorption spectrum and TG-DTA were measured.
Maximum absorption wavelength: 388.5 nm εg = 12970 mL / gcm
DTA (melting point): 131.2 ° C

[Example 4] Synthesis of exemplary compound (1-6) To 100 g of methyl ethyl ketone, 14.22 g of 2-hydroxyethylthioanthraquinone synthesized in Example 3 and 4.75 g of pyridine were added and heated to 60 ° C while stirring. I let you. Further, 5.09 g of propionic acid chloride was added dropwise at the same temperature over 30 minutes, and then the temperature was raised to 80 ° C. and stirred at the same temperature for 1 hour. After cooling to room temperature and discharging the reaction product into 200 g of methanol, the precipitate was filtered, washed with methanol, and dried to give Exemplified Compound (1-6) as yellow crystals. The yield of the obtained crystals relative to the raw material 2-chloroanthraquinone was 80.6 mol%, and the absorption spectrum and TG-DTA were measured.
Maximum absorption wavelength: 389.0 nm εg = 12730 mL / gcm
DTA (melting point): 106.5 ° C

[Example 5] Synthesis of exemplary compound (1-25) To 160 g of methyl isobutyl ketone, 25.59 g of 2-hydroxyethylthioanthraquinone synthesized in Example 3 and 7.11 g of pyridine were added and heated to 60 ° C while stirring. The temperature was raised. Furthermore, 5.09 g of propionic acid chloride was added dropwise at the same temperature over 2 hours, and then heated to 80 ° C. and stirred at the same temperature for 1 hour. After cooling to room temperature and discharging the reaction product into a mixed solution of 100 g of water and 100 g of methanol, the precipitate was filtered, washed with methanol and then dried to obtain Exemplified Compound (1-25) as yellow crystals. The yield of the obtained crystal relative to the raw material 2-chloroanthraquinone was 87.9 mol%, and the absorption spectrum and TG-DTA were measured.
Maximum absorption wavelength: 389.0 nm εg = 112210 mL / gcm
DTA (melting point): 134.3 ° C

[Example 6] Evaluation test To 5 g of trimethylolpropane triacrylate as a polymerizable compound, 10 mg of the exemplified compound (1-5) synthesized in Example 1 as a photopolymerization initiator was added and mixed uniformly at room temperature to produce a photocurable resin. A composition was obtained. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed under a nitrogen atmosphere, and the light-curing resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 3 mw / cm 2. A tack-free test was performed while irradiating the blue LED lamp. Tack (stickiness) is eliminated by irradiating the coated surface with a blue LED lamp, so the time until the cured film on the film surface is touched with a fingertip and the cured film is free of tack is defined as tack-free time. The tack free time in this example was 12 seconds.

[Example 7] Evaluation test 10 mg of the exemplified compound (1-31) synthesized in Example 2 as a photopolymerization initiator was added to 5 g of trimethylolpropane triacrylate as a polymerizable compound, and the photocurable resin was uniformly mixed at room temperature. A composition was obtained. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a thickness of 12 microns by a bar coater method. Next, this polyester film was placed under a nitrogen atmosphere, and the light-curing resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 3 mw / cm 2. It was 14 seconds when the tack free time was measured by the same method as in Example 6.

[Example 8] Evaluation test 10 mg of the exemplified compound (1-9) synthesized in Example 3 as a photopolymerization initiator was added to 5 g of trimethylolpropane triacrylate as a polymerizable compound, and the photocurable resin was uniformly mixed at room temperature. A composition was obtained. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed under a nitrogen atmosphere, and the light-curing resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 3 mw / cm 2. It was 20 seconds when the tack free time was measured by the same method as in Example 6.

[Example 9] Evaluation test To 5 g of trimethylolpropane triacrylate as a polymerizable compound, 10 mg of the exemplified compound (1-6) synthesized in Example 4 as a photopolymerization initiator was added and mixed uniformly at room temperature to produce a photocurable resin. A composition was obtained. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed under a nitrogen atmosphere, and the light-curing resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 3 mw / cm 2. When tack-free time was measured by the same method as in Example 6, it was 24 seconds.

[Example 10] Evaluation test 10 mg of the exemplified compound (1-25) synthesized in Example 5 as a photopolymerization initiator was added to 5 g of trimethylolpropane triacrylate as a polymerizable compound, and the photocurable resin was uniformly mixed at room temperature. A composition was obtained. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed under a nitrogen atmosphere, and the light-curing resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 3 mw / cm 2. The tack free time was measured by the same method as in Example 6 and found to be 36 seconds.

[Comparative Example 1] Evaluation Test In Example 6, the same procedure as described in Example 6 was used except that the exemplified compound (1-5) was changed to 1-hydroxycyclohexyl phenyl ketone as the photopolymerization initiator. The composition was prepared, applied to the polyester film surface, and irradiated with a blue LED lamp in the same procedure. The tack free time was measured by the same method and found to be 59 seconds.
From the above Examples 6 to 10 and Comparative Example 1, the anthraquinone compound of the present invention has an effect as a photopolymerization initiator in photo radical polymerization, and the photocurable resin composition according to the present invention has an excellent effect rate. You can see that

Example 11 Evaluation Test 100 g of UVR6105 (alicyclic epoxy compound) manufactured by Dow Chemical Co. as a polymerizable compound and 2.5 g of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate as a photopolymerization initiator Then, 1.0 g of the exemplary compound (1-5) synthesized in Example 1 was added as a photosensitizer and mixed uniformly at room temperature to obtain a photocurable resin composition. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed in a nitrogen atmosphere, and the light-cured resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 10 mw / cm 2. When tack-free time was measured by the same method as in Example 6, it was 15 seconds.

[Example 12] Evaluation test 100 g of UVR6105 (alicyclic epoxy compound) manufactured by Dow Chemical Company as a polymerizable compound and 2.5 g of 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate as a photopolymerization initiator Then, 1.0 g of the exemplary compound (1-31) synthesized in Example 2 was added as a photosensitizer and mixed uniformly at room temperature to obtain a photocurable resin composition. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed in a nitrogen atmosphere, and the light-cured resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 10 mw / cm 2. When tack-free time was measured by the same method as in Example 6, it was 18 seconds.
It can be seen that the resin composition has an excellent effect rate.

Example 13 Evaluation Test 100 g of UVR6105 (alicyclic epoxy compound) manufactured by Dow Chemical Co. as a polymerizable compound and 2.5 g of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate as a photopolymerization initiator Then, 1.0 g of the exemplary compound (1-9) synthesized in Example 3 was added as a photosensitizer and mixed uniformly at room temperature to obtain a photocurable resin composition. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed in a nitrogen atmosphere, and the light-cured resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 10 mw / cm 2. The tack free time was measured by the same method as in Example 6 and found to be 23 seconds.

[Example 14] Evaluation test 100 g UVR6105 (alicyclic epoxy compound) manufactured by Dow Chemical Co. as a polymerizable compound and 2.5 g 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate as a photopolymerization initiator Then, 1.0 g of the exemplary compound (1-6) synthesized in Example 4 was added as a photosensitizer and mixed uniformly at room temperature to obtain a photocurable resin composition. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed in a nitrogen atmosphere, and the light-cured resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 10 mw / cm 2. The tack free time was measured by the same method as in Example 6 and found to be 31 seconds.

[Example 15] Evaluation test 100 g of UVR6105 (alicyclic epoxy compound) manufactured by Dow Chemical Co. as a polymerizable compound and 2.5 g of 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate as a photopolymerization initiator Then, 1.0 g of the exemplary compound (1-25) synthesized in Example 5 was added as a photosensitizer and mixed uniformly at room temperature to obtain a photocurable resin composition. This photocurable resin composition was applied to the surface of a polyester film (trade name: Lumirror, thickness 100 microns) so as to have a film thickness of 12 microns by a bar coater method. Next, this polyester film was placed in a nitrogen atmosphere, and the light-cured resin composition application surface was irradiated with a blue LED lamp at an irradiation intensity of 10 mw / cm 2. The tack free time was measured by the same method as in Example 6 and found to be 35 seconds.

[Comparative Example 2] Evaluation test In Example 11, a composition was prepared by the same procedure as described in Example 11 except that the exemplified compound (1-5) was not added as a photopolymerization initiator. It apply | coated to the film surface and the blue LED lamp was irradiated in the same procedure. The tack free time was measured by the same method, but it did not cure even after 30 minutes of irradiation.
From the above Examples 11 to 15 and Comparative Example 2, the anthraquinone compound of the present invention has an effect as a photopolymerization initiator in photo radical polymerization, and the photocurable resin composition according to the present invention has an excellent effect rate. You can see that

[Example 16] Dissolution test In Example 6, the polyester film coated with the photocurable resin composition was cut into a size of 2 cm x 2 cm, and the irradiation intensity was 3 mw / cm2 with a blue LED lamp on the coated surface in a nitrogen atmosphere. And cured with irradiation. Subsequently, after leaving at 20 degreeC for 15 hours in 20 mL of methyl ethyl ketone, it took out and dried and measured the UV spectrum. In addition, when the UV absorption intensity at 385.5 nm which is the maximum absorption wavelength of the exemplary compound (1-5) synthesized in Example 1 used as the photopolymerization initiator in Example 6 was compared, no change was observed. This shows that the anthraquinone compound of the present invention is not eluted.

  The photocurable resin composition containing the anthraquinone compound of the present invention is highly sensitive to visible light having a wavelength of 400 nm or more as compared with conventional photocurable resin compositions, and is used in the field of electronic materials and recording displays. It is advantageous in the material field. In addition, the anthraquinone compound of the present invention is used as a photopolymerization initiator in photoradical polymerization, and exhibits an excellent effect as a photosensitizer in photocationic polymerization, has no elution from a cured product, and is environmentally friendly. However, an excellent photo-curable resin composition is provided.

Claims (5)

Anthraquinone compounds represented by the following general formula (1)

[Wherein, X and A independently represent a divalent organic residue, Y represents a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, and n represents 1 Or represents the integer of 2. However, when n is 1, A represents a linear or branched alkyl group. The anthraquinone compound according to claim 1, wherein the divalent organic residue is a group selected from a linear or branched alkylene group and an alicyclic alkylene group. The divalent linking group is a group selected from a phenylene group, a methylene group, a substituted or unsubstituted imino group, an ester group, a substituted or unsubstituted amide group, a substituted or unsubstituted urethane group, and an ether group. Item 1 or 2 anthraquinone compound The photocurable resin composition containing 1 type chosen from the anthraquinone type compound of Claims 1-3 as a photoinitiator. The photocurable resin composition which contains 1 type chosen from the anthraquinone type compound of Claims 1-3 as a photosensitizer of photocationic polymerization.