JP2022069041A - Polymerization initiator mixture, polymerizable composition, cured object and production method of cured object - Google Patents

Abstract

To provide a radical polymerization initiator mixture comprising photo-polymerizability capable of preferably curing both of a depth to which light hardly reaches, and a surface which is easily subjected to curing inhibition due to oxygen, in photo-curing of a photo-polymerizable composition formed of a polymerization initiator and a radical polymerizable compound.SOLUTION: There is provided a polymerization initiator mixture which contains a triazine peroxide derivative expressed by a following formula (1) and an α-hydroxyketone based photo polymerization initiator, in which the triazine peroxide derivative is included by 60 mass% or greater and 95 mass% or lower, and the α-hydroxyketone based photo polymerization initiator is included by 5 mass% or greater and 40 mass% or lower.SELECTED DRAWING: None

Description

The present invention relates to a polymerization initiator mixture, a polymerizable composition, a cured product, and a method for producing a cured product.

In order to synthesize a polymer or the like, a polymerization initiator capable of generating radicals by heat, light, or oxidation-reduction is widely used. In particular, the photopolymerization initiator can generate radicals by absorbing active energy rays such as light, and is used as a polymerization initiator for radically polymerizable compounds.

Since the photopolymerizable composition composed of the above-mentioned photopolymerization initiator and radically polymerizable compound is rapidly cured by light irradiation, various photoresists such as color resists and black resists, coating agents, paints, printing inks, etc. It is applied to applications such as photosensitive printing plates and adhesives.

Here, in Patent Documents 1 and 2, the selected triazine peroxide derivative can efficiently absorb the light emitted from the high-pressure mercury lamp or the LED lamp, and is superior to the known photopolymerization initiator compound. It is disclosed that it is feasible.

International Publication No. 2018-22177 Japanese Unexamined Patent Publication No. 2020-94196

In recent years, in the above-mentioned photopolymerization technology field, it is required to improve the curability of a deep part where light is hard to reach and the curability of a surface which is easily inhibited by oxygen. For example, a liquid crystal display panel or the like is required to have high color purity, and the content of a pigment is increasing in the production of a color resist, but as the content of the pigment increases, it becomes difficult to cure the color resist. Similarly, printing inks and the like may also contain a large amount of pigment in order to obtain high color development during printing. Therefore, there is a need for a photopolymerization initiator having higher deep curing properties and surface curing properties than conventional photopolymerization initiators.

Therefore, according to the present invention, in photocuring of a photopolymerizable composition composed of a polymerization initiator and a radically polymerizable compound, both the deep part where light is difficult to reach and the surface which is susceptible to curing inhibition by oxygen can be satisfactorily cured. It is intended to provide a radical polymerization initiator mixture having.

Further, the present invention provides a polymerizable composition containing the above-mentioned polymerization initiator mixture and a radically polymerizable compound, a cured product thereof, and a method for producing the cured product.

（式（１）中、Ｒ^１及びＲ^２は独立してメチル基またはエチル基を表す。Ｒ^３は炭素数１～５の脂肪族炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。Ｘは下記一般式（２）：Ａｒ^１、Ａｒ^２、Ａｒ^３またはＡｒ^４で表されるアリール基である。ｎは０から２の整数を表す。）

（式（２）中、ｍは０から３の整数を表す。Ｒ^４は、独立した置換基であって、炭素数１から６のアルキル基、一般式（３）：Ｒ^５－Ｙ－で表される置換基、ニトロ基、またはシアノ基を表す。前記Ｙは、酸素原子または硫黄原子を表す。前記Ｒ^５は、炭素骨格中に、エーテル結合、チオエーテル結合、及び、末端に水酸基のいずれか１つ以上を有していてもよい炭素数１～６の炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。あるいは、Ｒ^４は隣接する２つの前記一般式（３）：Ｒ^５－Ｙ－により５～６員環を形成してもよい。）で表されるトリアジンペルオキシド誘導体と、α－ヒドロキシケトン系光重合開始剤を含有し、前記トリアジンペルオキシド誘導体が６０質量％以上９５質量％以下であり、前記α－ヒドロキシケトン系光重合開始剤が５質量％以上４０質量％以下である重合開始剤混合物に関する。 That is, the present invention has the general formula (1) :.

(In the formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. R ³ has an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a carbon number which may have an alkyl group. Represents an aromatic hydrocarbon group of 6-9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer from 0 to 2. .)

(In the formula (2), m represents an integer from 0 to 3. R ⁴ is an independent substituent and is an alkyl group having 1 to 6 carbon atoms. In the general formula (3): R ⁵ -Y-. Represents a substituent, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The ^R5 is any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. It represents a hydrocarbon group having 1 to 6 carbon atoms which may have one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or ^R4 is adjacent. A triazineperoxide derivative represented by the above two general formulas (3): R5-Y- may form a ^5- to 6-membered ring) and an α-hydroxyketone-based photopolymerization initiator. The present invention relates to a polymerization initiator mixture in which the triazine peroxide derivative is 60% by mass or more and 95% by mass or less, and the α-hydroxyketone-based photopolymerization initiator is 5% by mass or more and 40% by mass or less.

The present invention relates to a polymerizable composition containing the above-mentioned polymerization initiator mixture and a radically polymerizable compound.

The present invention relates to a cured product formed from the polymerizable composition.

The present invention relates to a method for producing the cured product, which comprises a step of irradiating the polymerizable composition with an active energy ray.

The details of the mechanism of action of the effect of the polymerization initiator mixture according to the present invention are unknown, but are presumed as follows. However, the present invention is not limited to this mechanism of action.

The polymerization initiator mixture of the present invention contains the above-mentioned triazine peroxide derivative and an α-hydroxyketone-based photopolymerization initiator in a specific amount. The triazine peroxide derivative can efficiently absorb light having a long wavelength such as 365 nm among the light radiated from a lamp such as a high-pressure mercury lamp or an LED lamp, photodecompose it, and generate radicals. Further, in the triazine peroxide derivative, the decomposition of the photosensitive group proceeds by irradiation with light, and the absorption efficiency of light having a wavelength of 365 nm or the like is lowered. Therefore, the light having a wavelength of 365 nm or the like irradiated to the photopolymerizable composition is not hindered by the decomposition residue of the triazine peroxide derivative, and the deep portion where the light is difficult to reach can be satisfactorily cured. On the other hand, the α-hydroxyketone-based photopolymerization initiator efficiently absorbs light having a wavelength shorter than 365 nm to generate radicals, and can satisfactorily cure a surface that is susceptible to curing inhibition by oxygen. Further, since the α-hydroxyketone-based photopolymerization initiator has a low absorption efficiency of light having a long wavelength such as 365 nm, it does not inhibit deep curing by the triazine peroxide derivative. Therefore, by mixing the triazine peroxide derivative with the α-hydroxyketone-based photopolymerization initiator, it is possible to satisfactorily cure both the deep portion where light is difficult to reach and the surface which is susceptible to curing inhibition by oxygen.

The polymerization initiator mixture of the present invention contains a triazine peroxide derivative represented by the following general formula (1) and an α-hydroxyketone-based photopolymerization initiator.

（式（１）中、Ｒ^１及びＲ^２は独立してメチル基またはエチル基を表す。Ｒ^３は炭素数１～５の脂肪族炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。Ｘは下記一般式（２）：Ａｒ^１、Ａｒ^２、Ａｒ^３またはＡｒ^４で表されるアリール基である。ｎは０から２の整数を表す。）

（式（２）中、ｍは０から３の整数を表す。Ｒ^４は、独立した置換基であって、炭素数１から６のアルキル基、一般式（３）：Ｒ^５－Ｙ－で表される置換基、ニトロ基、またはシアノ基を表す。前記Ｙは、酸素原子または硫黄原子を表す。前記Ｒ^５は、炭素骨格中に、エーテル結合、チオエーテル結合、及び、末端に水酸基のいずれか１つ以上を有していてもよい炭素数１～６の炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。あるいは、Ｒ^４は隣接する２つの前記一般式（３）：Ｒ^５－Ｙ－により５～６員環を形成してもよい。） <Triazine peroxide derivative>
The triazine peroxide derivative of the present invention can be represented by the following general formula (1). The triazine peroxide derivative may be used alone or in combination of two or more.

(In the formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. R ³ has an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a carbon number which may have an alkyl group. Represents an aromatic hydrocarbon group of 6-9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer from 0 to 2. .)

(In the formula (2), m represents an integer from 0 to 3. R ⁴ is an independent substituent and is an alkyl group having 1 to 6 carbon atoms, and the general formula (3): R ⁵ -Y-. Represents a substituent, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The ^R5 is any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. It represents a hydrocarbon group having 1 to 6 carbon atoms which may have one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or ^R4 is adjacent. A ^5- to 6-membered ring may be formed by the above two general formulas (3): R5-Y-.)

In the general formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. Methyl groups are preferable for ^R1 and ^R2 from the viewpoint that the higher the cleavage temperature of the peroxide bond contained in the triazine peroxide derivative, the better the storage stability of the polymerizable composition.

In the general formula ( ¹ ), R3 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be a straight chain or a branched chain. Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group and an isopropylphenyl group. Among these, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group and a phenyl group are preferable from the viewpoint of facilitating the synthesis of the triazine peroxide derivative. Since the decomposition temperature of the triazine peroxide derivative is high, the storage stability of the polymerizable composition is high, and the sensitivity to irradiation light is high, so that a methyl group or an ethyl group is more preferable.

In the general formula (1), n is represented by an integer from 0 to 2. From the viewpoint of facilitating the synthesis of the triazine peroxide derivative, n is preferably 0 or 1. When n is 0, X is Ar ² , Ar ³ , or Ar ⁴ , and when n is 1, X is Ar ^1. It efficiently absorbs the irradiation light and the cured product. It is more preferable from the viewpoint that the yellowness can be reduced.

In the general formula (2), m is represented by an integer from 0 to 3. From the viewpoint of easy synthesis of the triazine peroxide derivative, m is preferably 0 to 2, and from the viewpoint of efficiently absorbing irradiation light, m is more preferably 1.

In the general formula (2), R ⁴ is an independent substituent, which is an alkyl group having 1 to 6 carbon atoms, a general formula (3): a substituent represented by R5 ^- Y-, and a nitro group. , Or a cyano group. Y represents an oxygen atom or a sulfur atom. The R ⁵ has an ether bond, a thioether bond, and a hydrocarbon group having 1 to 6 carbon atoms, which may have one or more hydroxyl groups at the terminal, or an alkyl group in the carbon skeleton. It represents an aromatic hydrocarbon group having 6 to 9 carbon atoms which may be used. Alternatively, R ⁴ may form a 5- to 6-membered ring by the two adjacent general formulas (3): R ⁵ -Y-.

The ^R4 is an independent substituent from the viewpoint of efficiently absorbing the irradiation light, and is an alkyl group having 1 to 6 carbon atoms or a substituent represented by the general formula (3): R5 ^- Y-. , Y represents an oxygen atom, and R5 is a hydrocarbon group having 1 to ⁶ carbon atoms which may have one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton. , Or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. Alternatively, it is preferable that R ⁴ forms a 5- to 6-membered ring by the two adjacent general formulas (3): R ⁵ -X-.

Specific examples of the ^R4 include, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-hexyl group; a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and the like. n-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxy Ethoxy group, 2-butoxyethoxy group, 2- (2-hydroxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 1,2-dihydroxypropoxy group, methylenedioxy group, dimethylmethylenedioxy group, Aalkoxy group such as ethylenedioxy group; aryloxy group such as phenyloxy group and 4-isopropylphenyloxy group; methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, 2- (2-methoxy) Ethoxy) Alkyl sulfanyl group such as ethyl sulfanyl group; aryl sulfanyl group such as phenylsulfanyl group, 2-methylphenylsulfanyl group, 4-methylphenylsulfanyl group and the like can be mentioned. The compound represented by the general formula (1) having these functional groups is preferable because it has a high absorbance at 365 nm and efficiently absorbs irradiation light.

Further, among these, from the viewpoint of high solubility of the triazine derivative in the polymerizable composition, easy synthesis, and high sensitivity to irradiation light, the R ¹ has a methoxy group, an ethoxy group, and a 2-hydroxyl group. The ethoxy group is more preferred.

The substitution position of R ⁴ is not particularly limited, but when X is Ar ¹ , it is preferable that at least one of R ⁴ is substituted with the 4-position of the benzene ring substituted with the triazine group. When X is Ar ² , it is preferable that at least one of R ⁴ is substituted at the 4-position of a benzene ring different from the benzene ring substituted with the triazine group. When X is Ar ³ , it is preferable that at least one of R ⁴ is substituted with the 4-position of the triazine group substituted with the 1-position. When X is Ar ⁴ , it is preferable that at least one of R ⁴ is substituted at the 4-position of a benzene ring different from the benzene ring substituted with the triazine group because it efficiently absorbs irradiation light.

Specific examples of the triazine peroxide derivative of the present invention are shown below, but the present invention is not limited thereto.

The triazine peroxide derivative of the present invention is preferably compound 19, compound 23, compound 25, compound 26, compound 27, compound 28, compound 31, compound 32, compound 33, compound 35, compound 37, compound 38, compound 39, Examples thereof include compound 40, compound 41, compound 42, compound 43, compound 44, compound 46, compound 47, and compound 48, and more preferably compound 25, compound 26, compound 31, compound 32, compound 35, compound 37, and compound 38. , Compound 41, compound 44, compound 47, compound 48 and the like.

<Α-Hydroxyketone-based photopolymerization initiator>
The α-hydroxyketone-based photopolymerization initiator of the present invention can be used without limitation as long as it generates radicals by light having a wavelength shorter than 365 nm emitted from a lamp such as a high-pressure mercury lamp or an LED lamp. For example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2F-hydroxyethoxy) -2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- (4). -(4- (2-Hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one and other α-hydroxyketone derivatives can be used, among which 1-hydroxycyclohexylphenylketone. Is more preferable.

In the polymerization initiator mixture, the triazine peroxide derivative is 60% by mass or more and 95% by mass or less. From the viewpoint of achieving both deep curability and surface curability in the polymerization initiator mixture, the triazine peroxide derivative is preferably 60% by mass or more and 85% by mass or less, and 65% by mass or more and 80% by mass or less. It is preferable to have. In the polymerization initiator mixture, the α-hydroxyketone-based photopolymerization initiator is 5% by mass or more and 40% by mass or less. From the viewpoint of achieving both deep curability and surface curability in the polymerization initiator mixture, the α-hydroxyketone-based photopolymerization initiator is preferably 15% by mass or more and 40% by mass or less, preferably 20% by mass. It is more preferably 35% by mass or less.

The polymerization initiator mixture of the present invention may be a composition containing a sensitizer. The sensitizer may be used alone or in combination of two or more.

<Sensitizer>
The sensitizer of the present invention can be used without limitation as long as it transfers the absorbed light energy to the polymerization initiator by irradiation with active energy rays, and can be used without limitation, for example, 4,4'-bis (diethylamino) benzophenone and the like. Benzophenone derivatives; Thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone; Anthracene derivatives such as 9,10-dibutoxyanthracene; Cumarin derivatives such as coumarin and ketocoumarin; Examples thereof include benzoic acid ester derivatives such as ethyl acid, isoamyl 4-dimethylaminobenzoate, and ethyl benzoate (2-dimethylamino); alkylamine derivatives such as triethanolamine and methyldiethanolamine; camphorquinone and the like.

With respect to 100 parts by mass of the triazine peroxide derivative, the sensitizer efficiently absorbs light emitted from a lamp such as a high-pressure mercury lamp or an LED lamp and efficiently generates a radical, and is 1 part by mass or more. It is preferably 10 parts by mass or more, and from the viewpoint of preventing coloring of the cured product, it is preferably 500 parts by mass or less, and more preferably 100 parts by mass or less.

<Polymerizable composition>
The polymerizable composition of the present invention contains the above-mentioned polymerization initiator mixture and a radically polymerizable compound.

The radically polymerizable compound can be used without particular limitation as long as it is a compound having curability by radicals.

<Radical polymerizable compound>
As the radically polymerizable compound, a compound having an ethylenically unsaturated group can be preferably used. Examples of the radically polymerizable compound include (meth) acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamon acid esters, crotonic acid esters, vinyl ethers, and vinyl. Examples thereof include esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins and the like. Among these, it is preferable to contain highly reactive (meth) acrylic acid esters. The radically polymerizable compound may be used alone or in combination of two or more.

As the (meth) acrylic acid esters, monofunctional compounds and polyfunctional compounds can be used. Examples of the monofunctional compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl. Alkyl (meth) acrylates such as (meth) acrylates; cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylicates, dicyclopentenyl (meth) acrylicates, dicyclopentenyloxyethyl Ester compounds of (meth) acrylic acid and alicyclic alcohol such as (meth) acrylicate, 2-ethyl-2-adamantyl (meth) acrylate; aryl such as phenyl (meth) acrylate and benzyl (meth) acrylate (meth) Meta) acrylate; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono Monomer having a hydroxy group such as (meth) acrylate, polypropylene glycol mono (meth) acrylate; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-phenylphenoxyethyl (meth). ) Acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) Monomer having a chain or cyclic ether bond such as acrylate, cyclic trimethylolpropaneformal (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol. (Meta) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acryloylmorpholine, N- (meth) acryloyloxyethyl hexahydrophthalimide, etc. A monomer having a nitrogen atom; a monomer having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; a glycidyl (meth) acrylic Monomer having an epoxy group such as relate, 4-hydroxybutyl (meth) acrylate glycidyl ether; Monomer having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; 3- (meth) acryloxypropyltrimethoxy Monomers with silicon atoms such as silane; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl ( Monomer having a fluorine atom such as (meth) acrylate; (meth) acrylic acid, mono succinate (2- (meth) acryloyloxyethyl), mono phthalate (2- (meth) acryloyloxyethyl), mono (2) maleic acid. Examples thereof include monomers having a carboxyl group such as- (meth) acryloyloxyethyl) and ω-carboxy-polycaprolactone mono (meth) acrylate.

Examples of the polyfunctional compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 1,4-butanediol di (meth). Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin propoxytri (meth) acrylate, trimethylol Etantri (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene, 9,9-bis (4) -Ester compound of polyhydric alcohol such as 2- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) fluorene and (meth) acrylic acid; bis (4- (meth) acryloyloxyphenyl) sulfide, bis ( 4- (meth) acryloylthiophenyl) sulfide, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylenebis (meth) acrylamide, zinc (meth) acrylate, zirconium (meth) acrylate, aliphatic urethane acrylate , Aromatic urethane acrylate, epoxy acrylate, polyester acrylate and the like.

The (meth) acrylic acid esters are used from the viewpoints of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, and improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product. Therefore, the ester compound of the polyhydric alcohol and (meth) acrylic acid is preferable, and in particular, dipropylene glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and di Pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable.

A copolymer obtained from the radically polymerizable compound can be added to the polymerizable composition.

The content of the polymerization initiator mixture is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and 0 by mass with respect to 100 parts by mass of the radically polymerizable compound. It is more preferably .8 to 10 parts by mass. The content of the polymerization initiator mixture is not preferable if it is less than 0.1 part by mass with respect to 100 parts by mass of the radically polymerizable compound because the curing reaction does not proceed. When the content of the polymerization initiator mixture is more than 20 parts by mass with respect to 100 parts by mass of the radically polymerizable compound, the solubility in the radically polymerizable compound reaches saturation and the polymerizable composition is formed. This is because crystals of the polymerization initiator mixture may precipitate during the film and the surface of the film may be roughened, or the strength of the coating film of the cured product may decrease due to an increase in the decomposition residue of the polymerization initiator mixture. , Not preferable.

<Pigment>
By blending the pigment, the polymerizable composition can be suitably used as various photoresists such as color resists and black resists, coating agents, paints, printing inks, photosensitive printing plates, adhesives and the like. The pigments include yellow pigments, blue pigments, and red pigments that are generally used in various photoresistes such as color resists and black resists, coating agents, paints, printing inks, photosensitive printing plates, adhesives, and the like. , White pigment, black pigment, carbon black and the like can be used, and the present invention is not particularly limited. The pigment may be used alone or in combination of two or more.

When the pigment is used, the proportion of the pigment is preferably about 10 to 90% by mass, more preferably about 20 to 50% by mass, based on the total solid content of the polymerizable composition. If the content of the pigment is too small, sufficient coloring property may not be obtained, and conversely, if the content of the pigment is too large, the strength of the cured film and the image forming property may be deteriorated.

<Alkali-soluble resin>
The polymerizable composition can be suitably used as a negative resist by blending an alkali-soluble resin. As the alkali-soluble resin, those generally used for negative resists can be used, and the resin is not particularly limited as long as it is soluble in an alkaline aqueous solution, but a resin containing a carboxyl group is preferable. The alkali-soluble resin may be used alone or in combination of two or more.

As the alkali-soluble resin, for example, a carboxyl group-containing (meth) acrylic acid ester copolymer, a carboxyl group-containing epoxy acrylate resin, or the like is preferably used.

The carboxyl group-containing (meth) acrylic acid ester copolymer is at least one selected from the monofunctional compounds of the (meth) acrylic acid esters described above (excluding the monomer having the carboxyl group) and (meth). ) Acrylic acid, (meth) acrylic acid dimer, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl benzoic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono Ethylene unsaturated groups such as (2- (meth) acryloyloxyethyl), mono (2- (meth) acryloyloxyethyl), ω-carboxy-polycaprolactone mono (meth) acrylate, and their acid anhydrides. It is a copolymer containing at least one selected from the contained carboxylic acids.

Examples of the carboxyl group-containing (meth) acrylic acid ester copolymer include a copolymer of methyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Further, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diethyl fumarate, diethyl itaconic acid and the like may be copolymerized.

Further, the carboxyl group-containing (meth) acrylic acid ester copolymer is a reaction of an ethylenically unsaturated group or the like from the viewpoint of achieving both the developability of the negative resist and the film characteristics such as heat resistance, hardness and chemical resistance. Carboxyl group-containing (meth) acrylic acid ester copolymers having a sex group introduced into the side chain are also preferably used. As a method for introducing an ethylenically unsaturated group into the above side chain, for example, an epoxy group in a molecule such as glycidyl (meth) acrylate is added to a part of the carboxyl group of the carboxyl group-containing (meth) acrylic acid ester copolymer. And a method of adding a compound having an ethylenically unsaturated group, or a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to an epoxy group and a carboxyl group-containing (meth) acrylic acid ester copolymer. , A method of adding a compound having an isocyanate group and an ethylenically unsaturated group in a molecule such as 2- (meth) acryloyloxyethyl isocyanate to a (meth) acrylic acid ester copolymer containing a hydroxyl group and a carboxyl group can be mentioned. ..

As the carboxyl group-containing epoxy acrylate resin, a compound obtained by further reacting an acid anhydride with an epoxy acrylate resin which is a reaction product of an epoxy compound and the ethylenically unsaturated group-containing carboxylic acid is suitable.

Examples of the epoxy resin include (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, and bisphenylfluorene. Examples include type epoxy resins. The epoxy resin may be used alone or in combination of two or more.

Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornendicarboxylic acid anhydride, and trimellitic anhydride. , Pyromytz anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, itaconic anhydride and the like.

Further, when synthesizing a carboxyl group-containing epoxy acrylate resin, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride is used to hydrolyze the acid anhydride group remaining after the reaction to obtain a carboxyl group. Can be increased. In addition, maleic anhydride containing an ethylenically unsaturated group can be used to further increase the ethylenically double bond.

The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g, more preferably 40 to 180 mg / KOH. When the acid value is less than 20 mgKOH / g, the solubility in an alkaline aqueous solution is poor, which makes it difficult to develop the unexposed portion, which is not preferable. Further, when the acid value is more than 300 mgKOH / g, the exposed portion tends to be easily detached from the substrate during development, which is not preferable.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, preferably 1,500 to 30,000. When the weight average molecular weight is smaller than 1,000, the heat resistance and hardness of the exposed portion are poor, which is not preferable. If the weight average molecular weight is larger than 100,000, it may be difficult to develop the unexposed portion, which is not preferable. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. As an example, using HLC-8220GPC (manufactured by Tosoh Corporation) as a GPC device and three TSKgelHZM-M (manufactured by Tosoh Corporation) as a column, tetrahydrofuran is used as a developing solvent, the column temperature is 40 ° C., and the flow velocity is 0.3 ml / min. Chromatography can be performed under the conditions of an RI detector, a sample injection concentration of 0.5% by mass, and an injection amount of 10 microliters, and can be obtained as a weight average molecular weight in terms of polystyrene.

The proportion of the alkali-soluble resin is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, based on the total solid content of the polymerizable composition. If the ratio is less than 10% by mass, the developability is poor, which is not preferable. If the ratio is more than 70% by mass, the reproducibility of the pattern shape and the heat resistance are lowered, which is not preferable.

As the alkali-soluble resin, an alkali-soluble resin which is an active ingredient after the synthesis reaction can be isolated and purified, or a reaction solution obtained by the synthesis reaction, a dried product thereof, or the like can be used as it is. ..

<Other ingredients>
As the other components, the polymerizable composition is generally used in various photoresists such as color resists and black resists, coating agents, paints, printing inks, photosensitive printing plates, adhesives and the like. Additives can be added. Examples of the additive include a polymerization inhibitor (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), an ultraviolet absorber, an infrared absorber, a chain transfer agent, and light. It has stabilizers, antioxidants, leveling agents, surface conditioners, surfactants, thickeners, defoaming agents, adhesion promoters, curing accelerators, plasticizers, epoxy compounds, thiol compounds, and ethylenically unsaturated bonds. Resins, saturated resins, colored dyes, fluorescent dyes, carbon-based materials (carbon fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.), metals Oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, layered viscosity minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants And so on. The additive may be used alone or in combination of two or more.

The content of the additive is appropriately selected according to the purpose of use and is not particularly limited, but is usually preferably 500 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound. It is more preferable that the amount is 100 parts by mass or less.

A solvent may be further added to the polymerizable composition in order to improve the viscosity, coatability, and smoothness of the cured film. The solvent can dissolve or disperse components such as the polymerization initiator mixture and the radically polymerizable compound, and is not particularly limited as long as it is a solvent that volatilizes at a drying temperature.

Examples of the solvent include water, alcohol-based solvent, carbitol-based solvent, ester-based solvent, ketone-based solvent, ether-based solvent, lactone-based solvent, unsaturated hydrocarbon-based solvent, cellosolve acetate-based solvent, and carbitol acetate-based solvent. Examples thereof include a solvent, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and the like. The solvent may be used alone or in combination of two or more.

The amount of the solvent used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable composition.

<Method for preparing a polymerizable composition>
When preparing the polymerizable composition, components such as the polymerization initiator mixture, the radically polymerizable compound, and if necessary, the pigment are put into a storage container, and a paint shaker, a bead mill, and a sand grind mill are added. , A ball mill, an attritor mill, a two-roll mill, a three-roll mill, or the like, and may be dissolved or dispersed according to a conventional method. Further, if necessary, filtration may be performed through a mesh or a membrane filter or the like.

In the preparation of the polymerizable composition, the polymerization initiator mixture may be added to the polymerizable composition from the beginning, but it is used when the polymerizable composition is stored for a relatively long time. Immediately before, the polymerization initiator mixture is preferably dissolved or dispersed in the composition containing the radically polymerizable compound.

<Manufacturing method of cured product>
The cured product of the present invention is formed from the polymerizable composition. The method for producing a cured product is a production method including a step of applying a polymerizable composition on a substrate and then irradiating the polymerizable composition with an active energy ray.

Examples of the coating method include spin coating method, bar coating method, spray coating method, dip coating method, flow coating method, slit coating method, doctor blade coating method, gravure coating method, screen printing method, offset printing method, and inkjet. Various methods such as a printing method and a dispenser printing method can be mentioned. Further, examples of the substrate include films and sheets such as glass, silicon wafers, metals and plastics, and three-dimensional molded products, and the shape of the substrate is not limited.

In the step of irradiating the above polymerizable composition with active energy rays, the polymerization initiator mixture is decomposed by irradiation with active energy rays such as electron beam, ultraviolet rays, visible light, and radiation to polymerize the radically polymerizable compound. As a result, a cured product can be obtained.

The active energy ray is preferably light having a wavelength of 250 to 450 nm. Further, from the viewpoint of achieving both deep curability and surface curability, it is more preferable to use a combination of light having a long wavelength such as 365 nm and light having a wavelength shorter than 365 nm.

The light source for irradiating the light is a solid-state laser such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet non-electrode lamp, an LED lamp, a xenon arc lamp, a carbon arc lamp, sunlight, and a YAG laser. , A gas laser such as a semiconductor laser or an argon laser can be used. When light from visible light to infrared light, which absorbs less of the polymerization initiator mixture, is used, curing can be performed by using a sensitizer that absorbs the light as the additive.

The exposure amount of the active energy ray should be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably 10 to 5,000 mJ / cm ² , and more preferably 30 to 1,000 mJ / cm ² .

When the polymerization composition contains the solvent, the method for producing the cured product can include a drying step.

Examples of the method for drying the solvent in the drying step include heat drying, ventilation heating drying, vacuum drying and the like. The heat-drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, and electromagnetic wave irradiation. Further, as a method of ventilation heating and drying, for example, a ventilation type drying oven and the like can be mentioned.

Further, in the drying step, the temperature of the polymerizable composition becomes lower than the set temperature for drying due to the latent heat of vaporization of the solvent, so that it is possible to secure a long time until the polymerizable composition gels. Since the time until gelation is affected by the drying method, film thickness, etc., the drying temperature and time should be appropriately set including the selection of the solvent. As an example, the drying temperature is preferably 20 to 120 ° C, more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to secure a long time until gelation.

The dry film thickness (film thickness of the cured product) of the polymerizable composition is appropriately set depending on the intended use, but is preferably 0.05 to 500 μm, more preferably 0.1 to 100 μm. ..

<Pattern formation method>
When the polymerizable composition contains the alkali-soluble resin, a pattern can be formed by a photolithography method. The polymerizable composition is applied to the substrate in the same manner as described above, and if necessary, dried to form a dry film. Then, by irradiating the dry film with active energy rays via a mask, the radically polymerizable compound is polymerized in the exposed portion to form a cured film. On the other hand, it is also possible to produce a highly accurate pattern shape without using a mask by direct drawing using a laser.

After the above exposure, the unexposed portion is developed and removed with an alkaline developer such as, for example, 0.3 to 3% by mass of an aqueous sodium carbonate solution to obtain a patterned cured film. Further, for the purpose of improving the adhesion between the cured film and the substrate, post-baking is performed at 180 to 250 ° C. and 20 to 90 minutes as post-drying. In this way, a desired pattern based on the cured film is formed.

The polymerization initiator mixture of the present invention is a resist for FPD such as a color resist, a black resist, a protective film for a color filter, a photo spacer, a black column spacer, a frame resist, a photoresist for TFT wiring, and an interlayer insulating film; a liquid solder resist, Resists for printed substrates such as dry film resists; Semiconductor resists, materials for semiconductors such as buffer coat films; Offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, light guide plate inks. Printing inks such as; Photosensitive printing plates; Nanoimprint materials; Resins for 3D printers; Hard coating agents, coating agents for optical disks, coating agents for optical fibers, paints for mobile terminals, paints for home appliances, paints for cosmetic containers, paints for woodwork, etc. Paints / coating agents such as internal antireflection paints for optical elements, high / low refractive index coating agents, heat shielding coating agents, heat dissipation coating agents, antifogging agents; holography recording materials; dental materials; waveguide materials; lens sheets Black stripes; Green sheets and electrode materials for capacitors; FPD adhesives, HDD adhesives, optical pickup adhesives, image sensor adhesives, organic EL sealants, touch panel OCA, touch panel OCR adhesives, etc. It can be used for various purposes such as agents and sealants, and there are no particular restrictions on the application.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(1) Preparation of polymerizable composition <Preparation of polymerizable composition (A)>
The amounts of (b) radically polymerizable compound, (c) alkali-soluble resin, and other components shown in Table 1 are mixed and stirred, and (a) the polymerization initiator mixture is added and stirred well, and Examples 1 to 4 and The polymerizable composition (A) of Comparative Examples 1 to 3 was prepared.

In Table 1 above, TMPTA is trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.);
RD210 is a copolymer of methyl methacrylate / methacrylic acid / cyclohexylmaleimide (mass%: 52/23/25), weight average molecular weight: 17,800, acid value: 49 (synthetic product);
F-477 is a fluorine-based leveling agent (trade name: Megafuck F-477, manufactured by DIC Corporation);
PGMEA indicates propylene glycol monomethyl ether acetate;

<Preparation of Polymerizable Composition (B)>
The amount of the radically polymerizable compound (b) shown in Table 2 and the mixture of (a) the polymerization initiator were added and stirred well, and the polymerizable compositions (B) of Examples 1 to 4 and Comparative Examples 1 to 3 were added. Was prepared.

(2) Evaluation of Deep Curability The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After coating, the aluminum substrate was dried in a clean oven at 90 ° C. for 2.5 minutes to dry the solvent to prepare a uniform coating film having a thickness of 1.5 μm. Then, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, stepwise exposure was performed in the range of 10 to 1000 mJ / cm ² via a mask pattern. The exposed aluminum substrate was immersed in a 1.0 mass% sodium carbonate aqueous solution at 23 ° C. for 60 seconds to remove the unexposed portion by development. Then, it was washed with pure water for 30 seconds to obtain a pattern shape. The minimum exposure amount at which the pattern shape was formed was evaluated as deep curability. The results are shown in Table 3.

(3) Evaluation of surface curability The polymerizable composition (B) prepared above is applied to a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) that has been easily adhered using a bar coater (# 6). To prepare a uniform coating film having a thickness of 10 μm. Next, light irradiation of 100 mJ / cm ² was performed using a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp (manufactured by Eye Graphic). Light irradiation was repeated until the coating film did not adhere to the finger when the cured surface was touched with a finger, and the number of times of repeated light irradiation was evaluated as surface curability. The results are shown in Table 3.

In Table 3 above, HK represents 1-hydroxycyclohexylphenylketone.

From the results in Table 3, the triazine peroxide derivative of the present invention, the polymerization initiator mixture containing the α-hydroxyketone-based photopolymerization initiator, and the polymerizable composition containing the compound have excellent deep curability with respect to light. It is clear that it is characterized by having both surface curability and surface curability. Further, the polymerization initiator composition of the present invention is obtained by combining two or more different light sources, that is, a light source that emits light having a long wavelength such as a wavelength of 365 nm and a light source that emits light having a wavelength shorter than 365 nm. It has excellent deep curability and surface curability in the process of light irradiation.

Claims (4)

General formula (1):

(In the formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. R ³ has an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a carbon number which may have an alkyl group. Represents an aromatic hydrocarbon group of 6-9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer from 0 to 2. .)

(In the formula (2), m represents an integer from 0 to 3. R ⁴ is an independent substituent and is an alkyl group having 1 to 6 carbon atoms, and the general formula (3): R ⁵ -Y-. Represents a substituent, a nitro group, or a cyano group. The Y represents an oxygen atom or a sulfur atom. The ^R5 is any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. It represents a hydrocarbon group having 1 to 6 carbon atoms which may have one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or ^R4 is adjacent. The triazineperoxide derivative represented by the above general formula (3): R5-Y— may form a ^5- to 6-membered ring.
Contains α-hydroxyketone-based photopolymerization initiator,
A polymerization initiator mixture, wherein the triazine peroxide derivative is 60% by mass or more and 95% by mass or less, and the α-hydroxyketone-based photopolymerization initiator is 5% by mass or more and 40% by mass or less. A polymerizable composition comprising the polymerization initiator mixture according to claim 1 and a radically polymerizable compound. A cured product, which is formed from the polymerizable composition according to claim 2. A method for producing a cured product, which comprises a step of irradiating the polymerizable composition according to claim 2 with an active energy ray.