CN117177962A

CN117177962A - Triazine peroxide derivative and method for producing same, polymerizable composition, cured product, and method for producing cured product

Info

Publication number: CN117177962A
Application number: CN202280029010.0A
Authority: CN
Inventors: 今井奖; 龙官真琴; 矢野章世
Original assignee: NOF Corp
Current assignee: NOF Corp
Priority date: 2021-09-28
Filing date: 2022-09-26
Publication date: 2023-12-05
Also published as: WO2023054225A1; TW202313576A

Abstract

The present invention provides a triazine peroxide derivative represented by the general formula (1).In the general formula (1), R ¹ R is R ² Independently represent methyl or ethyl, R ³ Represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or the like, R ⁴ Represents an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, etc., and Ar is represented by the following general formula (2): ar (Ar) ¹ 、Ar ² Or Ar ³ An aryl group represented by the formula (I),

Description

Triazine peroxide derivative and method for producing same, polymerizable composition, cured product, and method for producing cured product

Technical Field

The present invention relates to a triazine peroxide derivative, a process for producing the same, a polymerizable composition, and a cured product and a process for producing the same.

Background

As a polymerization initiator, a triazine peroxide derivative which can be used as a photopolymerization initiator and a thermal polymerization initiator is known (patent document 1).

Prior art literature

Patent literature

Patent document 1: international publication No. 2018/221177

Disclosure of Invention

Technical problem to be solved by the invention

The triazine peroxide derivative disclosed in patent document 1 has a specific aryl group and two peroxide bonds in the molecule, and can efficiently absorb light having a wavelength of 365nm or the like emitted from a high-pressure mercury lamp, LED or the like to generate radicals, and thus has excellent sensitivity. However, the polymerizable composition in which the radical polymerizable compound is blended may have insufficient long-term storage stability at high temperature.

In view of the above, an object of the present invention is to provide a novel polymerization initiator which is excellent in sensitivity and has good long-term storage stability even at high temperatures.

Technical means for solving the technical problems

Namely, the present invention relates to a triazine peroxide derivative represented by the general formula (1):

[ chemical formula 1]

In the general formula (1), R ¹ R is R ² Independently represent methyl or ethyl, R ³ Represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms optionally having an alkyl group, R ⁴ Is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', Y represents an oxygen atom or a sulfur atom, R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Ar is represented by the following general formula (2): ar (Ar) ¹ 、Ar ² Or Ar ³ Aryl groups represented.

[ chemical formula 2]

In the general formula (2), m represents an integer of 0 to 3, R ¹¹ Is an independent substituent and is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', Y represents an oxygen atom or a sulfur atom, R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.

The present invention also relates to a polymerizable composition containing (a) a polymerization initiator and (b) a radical polymerizable compound, wherein (a) the polymerization initiator contains the triazine peroxide derivative.

Further, the present invention relates to a cured product formed from the polymerizable composition, and a method for producing a cured product, which includes a step of irradiating the polymerizable composition with active energy rays.

Effects of the invention

The triazine peroxide derivative of the present invention has only one peroxide bond in the molecule, and the number of radicals generated per 1 molecule by the decomposition of the compound is smaller than that of the triazine peroxide derivative having two peroxide bonds in the molecule disclosed in patent document 1, but has an excellent effect of having sensitivity equivalent to that of the compound disclosed in patent document 1. On the other hand, the triazine peroxide derivative of the present invention has a long-term storage stability at high temperature because it has only one peroxide bond in the molecule, which is superior to the triazine peroxide derivative disclosed in the above-mentioned patent document 1.

The triazine peroxide derivative of the present invention is excellent in sensitivity, and is useful as a polymerization initiator for a polymerizable composition such as a black resist containing a light-shielding pigment such as carbon black.

Detailed Description

The triazine peroxide derivative of the present invention is represented by the following general formula (1).

[ chemical formula 3]

In the general formula (1), R ¹ R is R ² Independently represent methyl or ethyl, R ³ Represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms optionally having an alkyl group, R ⁴ Is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', Y represents an oxygen atom or a sulfur atom, R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Ar is represented byThe general formula (2): ar (Ar) ¹ 、Ar ² Or Ar ³ Aryl groups represented.

[ chemical formula 4]

In the general formula (1), R ¹ R is R ² Independently represents methyl or ethyl. Methyl groups are preferred from the viewpoint of increasing the decomposition temperature and the storage stability of the polymerizable composition.

In the general formula (1), R ³ An aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms optionally having an alkyl group. The alkyl group may be linear or branched. As R ³ Specific examples of (a) include methyl, ethyl, propyl, 2-dimethylpropyl, phenyl, isopropylphenyl and the like. Among them, methyl, ethyl, propyl, 2-dimethylpropyl, phenyl are preferable from the viewpoint of easy synthesis of the triazine peroxide derivative. The triazine peroxide derivative is more preferably a methyl group or an ethyl group, since the decomposition temperature of the triazine peroxide derivative is high, and thus the storage stability of the polymerizable composition is improved, and the sensitivity to light is high.

In the general formula (1), R ⁴ Is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 2 to 20 carbon atomsA heterocyclic ring-containing group, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', wherein Y represents an oxygen atom or a sulfur atom, and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Due to R as described above ⁴ The influence on the absorption wavelength of triazine peroxide derivatives is small, even if R ⁴ In the above wide range, good sensitivity can be also exhibited. Further, "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group optionally having an ether bond or a thioether bond in a carbon skeleton, an aromatic hydrocarbon group, a group containing a heterocycle, an acyl group, a cyano group, a nitro group, a carboxyl group, an epoxy group, a hydroxyl group, and the like. From the viewpoint of high stability, R is ⁴ Preferably an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms or-Y-R, more preferably-O-R, from the viewpoint of ease of synthesis, wherein R is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.

In the general formula (2), m represents an integer of 0 to 3, preferably m is 0 to 2 from the viewpoint of easy synthesis, and more preferably m is 1 from the viewpoint of efficient light absorption.

In the general formula (2), R ¹¹ Is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', Y represents an oxygen atom or a sulfur atom, R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atomsHeterocyclic groups. Due to R as described above ¹¹ The influence on the absorption wavelength of triazine peroxide derivatives is small, even if R ¹¹ In the above wide range, good sensitivity can be also exhibited. Further, "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group optionally having an ether bond or a thioether bond in a carbon skeleton, an aromatic hydrocarbon group, a group containing a heterocycle, an acyl group, a cyano group, a nitro group, a carboxyl group, an epoxy group, a hydroxyl group, and the like. R is as described above ¹¹ An alkyl group having 1 to 20 carbon atoms and having an independent substituent is represented by the general formula (3): r is R ¹² -a substituent represented by Y-a nitro group or a cyano group, said Y representing an oxygen atom or a sulfur atom, said R ¹² Optionally a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, optionally an alkyl group, or an acyl group having 1 to 20 carbon atoms, each of which has one or more of an ether bond, a thioether bond and a terminal hydroxyl group in the carbon skeleton, and R ¹¹ Optionally by two of said formulae (3) being contiguous: r is R ¹² Y-forms a 5-to 6-membered ring.

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

[ chemical formula 5]

As the triazine peroxide derivative of the present invention, preferred are compound 19, compound 23, compound 25, compound 26, compound 27, compound 31, compound 32, compound 33, compound 35, compound 37, compound 38, compound 39, compound 43, compound 44, compound 45, compound 46, compound 47, compound 48, compound 49, compound 50, compound 51, compound 52, compound 53, compound 54, compound 55, compound 56, compound 57, compound 60, compound 61, compound 73, compound 77, compound 78, compound 79, and compound 81.

Process for the preparation of triazine peroxide derivatives

The preparation method of the triazine peroxide derivative represented by the general formula (1) comprises the step of reacting cyanuric chloride and/or a derivative thereof with a hydroperoxide as a raw material. Examples of such a production method include a method including steps represented by the following reaction formula: a step of obtaining a cyanuric chloride derivative (hereinafter, also referred to as steps (A) and (B)); and then reacting the obtained cyanuric chloride derivative with a hydroperoxide in the presence of a base (hereinafter, also referred to as step (C)). The order of the above steps is not limited, and for example, the reactant of cyanuric chloride and hydroperoxide may be reacted with Ar-X or R as described below ⁴ X may be reacted, or the steps may be performed simultaneously. The steps may include a step of removing (removing) the remaining raw materials or the like by distillation under reduced pressure, or a purification step, before and after each step.

[ chemical formula 6]

< procedure (A) >)

< procedure (B) >)

< procedure (C) >)

In the above reaction formula, R ¹ 、R ² 、R ³ 、R ⁴ Ar is the same as that of the general formula (1).

In the step (C), a commercially available product can be used as the cyanuric chloride derivative. In the case of no commercial products, the synthesis in the steps (A) and (B) may be performed according to a known synthesis method such as a Grignard reaction, a lithiation reaction, a Suzuki coupling reaction, a Fu Lie Deltaz (Friedel-Crafts) reaction, a nucleophilic substitution reaction in the presence of a base, or the like.

< Synthesis of cyanuric chloride derivative reacted with group Yu Geshi >

In the above steps (A) and (B), when the cyanuric chloride derivative is synthesized by the Grignard reaction, the synthesis can be performed according to a known synthesis method described in Japanese unexamined patent publication No. 6-179661. Ar-X in the step (A) and R in the step (B) can be used ⁴ -a halogen compound wherein X is represented by a chlorine atom, a bromine atom or an iodine atom. The cyanuric chloride derivative can be synthesized by preparing a grignard reagent by reacting a halogen compound with magnesium, and then reacting the obtained grignard reagent with cyanuric chloride.

In the preparation of the grignard reagent described above, 0.8 to 2.0 mol of magnesium is preferably used, and 1 to 1.5 mol of magnesium is more preferably used, relative to 1 mol of the halogen compound. As the reaction initiator, iodine, bromoethane, dibromoethane, etc., may be used, and 0.0001 to 0.01 mol is preferably used with respect to 1 mol of the halogen compound. The reaction temperature is preferably 0 to 70 ℃, more preferably 10 to 60 ℃. The reaction time is preferably 30 minutes to 20 hours, more preferably 1 hour to 10 hours.

In the preparation of the grignard reagent, for example, a solvent such as an ether such as tetrahydrofuran is used.

In addition, in the reaction of the grignard reagent with cyanuric chloride, 0.7 to 1.5 mol of cyanuric chloride is preferably used, and 0.8 to 1.2 mol of cyanuric chloride is more preferably used, relative to 1 mol of halogen compound. The reaction temperature is preferably-30 to 70 ℃, more preferably-10 to 40 ℃. The reaction time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 15 hours. Alternatively, cyanuric chloride may be added to the prepared grignard reagent, or the grignard reagent may be added to a solution of cyanuric chloride.

In the reaction between the grignard reagent and cyanuric chloride, for example, a solvent such as an ether such as tetrahydrofuran may be used.

< Synthesis of cyanuric chloride derivative based on lithiation reaction >

In the above steps (a) and (B), when the cyanuric chloride derivative is synthesized by a lithiation reaction, the synthesis can be performed according to a known synthesis method described in, for example, WO 2012/096263. Ar-X in the step (A) and R in the step (B) can be used ⁴ -a halogen compound wherein X is represented by a chlorine atom, a bromine atom or an iodine atom. The cyanuric chloride derivative can be synthesized by reacting a halogen compound with a lithiating agent to prepare a lithium compound, and then reacting the resulting lithium compound with cyanuric chloride.

Examples of the lithiating agent include alkyllithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium; aryl lithium such as phenyl lithium; lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide are preferably n-butyllithium, sec-butyllithium, tert-butyllithium and phenyllithium.

In the preparation of the above lithium compound, it is preferable to use 0.8 to 3.0 mol of the lithiating agent, more preferably 1.0 to 2.2 mol of the lithiating agent, relative to 1 mol of the halogen compound. The reaction temperature is preferably-100 to 50 ℃, more preferably-80 to 0 ℃. The reaction time is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours.

In the preparation of the lithium compound, for example, an ether solvent such as tetrahydrofuran may be used.

In addition, in the reaction of the above lithium compound with cyanuric chloride, 0.7 to 1.5 mol of cyanuric chloride is preferably used, and 0.8 to 1.2 mol of cyanuric chloride is more preferably used, relative to 1 mol of halogen compound. The reaction temperature is preferably-30 to 70 ℃, more preferably-10 to 40 ℃. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Alternatively, cyanuric chloride may be added to the prepared lithium compound, or the lithium compound may be added to a solution of cyanuric chloride.

In the reaction of the lithium compound and cyanuric chloride, for example, a solvent such as ethers, e.g., tetrahydrofuran, may be used.

< Synthesis of Cyanuric chloride derivative based on Suzuki coupling >

In the above steps (a) and (B), when the cyanuric chloride derivative is synthesized by the suzuki coupling reaction, the synthesis can be performed according to a known synthesis method described in WO 2012/096263. For example, ar-X in the step (A) and R in the step (B) are synthesized by reacting the above lithium compound with a boron reagent ⁴ -a boron compound in which X is a boric acid group (boronyl group) or boric acid (boronic acid). Then, the obtained boron compound is reacted with cyanuric chloride, whereby cyanuric chloride derivatives can be synthesized. In addition, the boron compound may be used as it is in the case of a commercial product in which a boron compound is sold.

Examples of the boron reagent include trimethyl borate, triisopropyl borate, and 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborane.

In the synthesis of the above-mentioned boron compound, it is preferable to use 0.8 to 3.0 mol of the boron reagent, and it is more preferable to use 1.0 to 2.0 mol of the boron reagent, relative to 1 mol of the lithium compound. The reaction temperature is preferably-100 to 50 ℃, more preferably-80 to 20 ℃. The reaction time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 10 hours.

For the synthesis of the boron compound, for example, an ether solvent such as tetrahydrofuran may be used.

In addition, in the reaction of the above-mentioned boron compound with cyanuric chloride, 0.7 to 1.5 mol of cyanuric chloride is preferably used, and 0.8 to 1.2 mol of cyanuric chloride is more preferably used, relative to 1 mol of boron compound. The reaction temperature is preferably-30 to 70 ℃, more preferably-10 to 40 ℃. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. In addition, cyanuric chloride may be added to the boron compound, or the boron compound may be added to a solution of cyanuric chloride.

In the reaction of the boron compound and cyanuric chloride, a palladium catalyst and a base are preferably used, and a ligand may be added as needed.

Examples of the palladium catalyst include palladium acetate, tetraphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride, (bis (diphenylphosphino) ferrocene) palladium dichloride-dichloromethane complex, and the like.

Examples of the base include inorganic bases such as alkali metal salts of sodium carbonate, sodium hydrogencarbonate, sodium acetate, potassium phosphate and the like; organic bases such as triethylamine.

Examples of the ligand include organic phosphine ligands such as triphenylphosphine, tricyclohexylphosphine, 2' -bis (diphenylphosphine) -1,1' -binaphthyl, and 2-dicyclohexylphosphino-2, 6' -dimethoxybiphenyl.

In the reaction of the boron compound and cyanuric chloride, ethers such as tetrahydrofuran and 1, 4-dioxane can be used; alcohols such as methanol and 2-propanol; aromatic hydrocarbons such as toluene and xylene; organic solvents such as amides such as N, N-dimethylformamide. The organic solvents may be used alone or in combination of two or more. Further, a mixed solvent of the organic solvent and water can also be used.

Synthesis of cyanuric chloride derivatives based on Fu Lie DeltaLaves reaction

In the above steps (a) and (B), when the cyanuric chloride derivative is synthesized by the Fu Lie delta-clafuz reaction, the synthesis can be performed according to a known synthesis method described in US 5322941. Ar-X in the step (A) and R in the step (B) can be used ⁴ -an aromatic compound in which X is represented by a hydrogen atom. The cyanuric chloride derivative can be synthesized by reacting an aromatic compound with cyanuric chloride in the presence of a lewis acid such as aluminum chloride.

As the lewis acid, aluminum chloride, aluminum bromide, iron (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) trifluoromethane sulfonate, hafnium (IV) trifluoromethane sulfonate, boron trifluoride diethyl ether complex, and the like can be used.

In the reaction of the above aromatic compound with cyanuric chloride, it is preferable to use 0.7 to 2.5 moles of cyanuric chloride, more preferably 0.8 to 1.5 moles of cyanuric chloride, relative to 1 mole of the aromatic compound. It is preferable to use 1.0 to 3.0 moles of aluminum chloride, and more preferably 1.0 to 2.0 moles of aluminum chloride, relative to 1 mole of aromatic compound. The reaction temperature is preferably-50 to 60 ℃, more preferably 0 to 40 ℃. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. In addition, aluminum chloride may be added to the solution of the aromatic compound and cyanuric chloride, the aromatic compound may be added to the solution of cyanuric chloride and aluminum chloride, and cyanuric chloride may be added to the solution of the aromatic compound and aluminum chloride.

In the reaction of the aromatic compound with cyanuric chloride, for example, a solvent such as methylene chloride, 1, 2-dichloroethane, xylene or the like can be used.

< Synthesis of triazine peroxide derivatives >

In the step (C), the method for producing the triazine peroxide derivative represented by the general formula (1) is not particularly limited, and the triazine peroxide derivative can be synthesized according to the known synthesis method of triazine peroxide described in Japanese patent publication No. 45-39468.

The triazine peroxide derivative can be obtained by the step (C) of reacting the cyanuric chloride derivative obtained in the steps (A) and (B) with a hydroperoxide in the presence of a base.

In the step (C), from the viewpoint of improving the yield of the target product, it is preferable to react 0.9 mol or more of the hydroperoxide, more preferably 1.0 mol or more of the hydroperoxide, and it is preferable to react 3.0 mol or less of the hydroperoxide, more preferably 2.0 mol or less of the hydroperoxide, with respect to 1 mol of the cyanuric chloride derivative. The hydroperoxide may be synthesized by a known synthesis method described in Japanese patent application laid-open No. 58-72557, etc., when no commercial product is available.

In the step (C), the reaction temperature is preferably-10℃or higher, more preferably 0℃or higher, and preferably 50℃or lower, more preferably 40℃or lower, from the viewpoint of improving the yield of the target product.

In the step (C), the reaction time is not generally determined because it varies depending on the raw material, the reaction temperature, etc., but is usually preferably 10 minutes to 6 hours from the viewpoint of improving the yield of the target product.

The base used in the step (C) is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium hydrogencarbonate, pyridine, α -methylpyridine, γ -methylpyridine, dimethylaminopyridine, triethylamine, tributylamine, N-diisopropylethylamine, 1, 5-diazabicyclo [4.3.0] non-5-ene, and the like. From the viewpoint of improving the yield of the target product, it is preferable to use 0.8 mole or more of a base, more preferably 1.0 mole or more of a base, and it is preferable to use 3.0 mole or less of a base, more preferably 2.0 mole or less of a base, relative to 1 mole of the cyanuric chloride derivative.

In the step (C), when the cyanuric chloride derivative is in a liquid state, the reaction can be performed without using an organic solvent. In addition, when the cyanuric chloride derivative is a solid, an organic solvent is preferably used. The organic solvent is not particularly limited as the solubility varies depending on the type of cyanuric chloride derivative, and examples thereof include aromatic hydrocarbons such as toluene, xylene and ethylbenzene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as methylene chloride and chloroform, and the like. The organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent is usually about 30 to 1000 parts by mass based on 100 parts by mass of the total amount of the raw materials. The triazine peroxide derivative may be extracted by removing the organic solvent by distillation after the step (C), or the triazine peroxide derivative may be used as a diluted product of the organic solvent in order to improve the handleability or reduce the risk of decomposition by heating.

The step (C) may be carried out under atmospheric pressure under air, but may be carried out under a nitrogen stream or a nitrogen atmosphere.

Examples of the purification step include a step of washing with an aqueous electrolyte solution such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfite, hydrogen chloride, sulfuric acid, sodium chloride or ion-exchanged water to remove the residual raw material or by-product, and purifying the target product.

Polymerizable composition

The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radical polymerizable compound. Further, the polymerizable composition may be imparted with developability by containing (c) an alkali-soluble resin. The polymerizable composition may contain other components in an appropriate combination.

(a) polymerization initiator

The polymerization initiator (a) of the present invention contains the triazine peroxide derivative represented by the general formula (1). (a) The polymerization initiator is decomposed by active energy rays or heat, and the radical generated by the polymerization initiator initiates polymerization (curing) of the radical polymerizable compound (b). The triazine peroxide derivatives may be used singly or in combination of two or more.

The (a) polymerization initiator may contain a polymerization initiator other than the triazine peroxide derivative (hereinafter, also referred to as another polymerization initiator). By using two or more triazine peroxide derivatives having different absorption bands or other polymerization initiators, for example, the polymerizable composition can be made highly sensitive to a lamp such as a high-pressure mercury lamp that emits light of a plurality of wavelengths. Further, by using other polymerization initiators in consideration of the polymerizability of the radical polymerizable compound (b) contained in the polymerizable composition, the kind of light absorbing or scattering pigment or the like contained in the polymerizable composition, the film thickness of the cured product or the like, the surface curability, deep curability, transparency or the like of the polymerizable composition can be improved.

Examples of the other polymerization initiator that can be used include known polymerization initiators include α -hydroxyacetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4' - (2-hydroxyethoxy) -2-hydroxy-2-methylbenzophenone, 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one, and the like; α -aminoacetophenone derivatives such as 2-methyl-4' -methylthio-2-morpholinophenone, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, and the like; acyl phosphine oxide derivatives such as diphenyl-2, 4, 6-trimethylbenzoyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (lecarbonyl) phenyl phosphinate (ethyl (mesitylcarbonyl) phenylphosphinate); oxime ester derivatives such as 1- [4- (phenylthio) phenyl ] octane-1, 2-dione-2- (O-benzoyloxime), 1- [ ({ 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethylene } amino) oxy ] ethanone, ], 8- [5- (2, 4, 6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [ a ] carbazole ] ] [2- (2, 3-tetrafluoropropoxy) phenyl ] methanone- (O-acetoxime), and 1- [4- [4- (2-benzofuranylcarbonyl) phenyl ] thio ] phenyl-4-methyl-1-pentanone-1- (O-acetoxime); halomethyltriazine derivatives such as 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-dimethoxystyryl) -4, 6-bis (trichloromethyl) 1,3, 5-triazine, and 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; benzyl ketal derivatives such as 2, 2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as isopropyl thioxanthone, and benzophenone derivatives such as 4- (4-methylphenyl thio) benzophenone; coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin and 3,3' -carbonylbis (7-diethylaminocoumarin); imidazole derivatives such as 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4, 5-diphenyl-1, 3-oxadiazol-2-yl ] -4, 5-diphenylimidazole; organic peroxides such as 3,3', 4' -tetra (t-butylperoxycarbonyl) benzophenone, 2- (1-t-butylperoxy-1-methylethyl) -9H-thioxanth-9-one, dibenzoyl peroxide, and the like; azo compounds such as azobisisobutyronitrile; camphorquinone, and the like. The other polymerization initiators may be used alone or in combination of two or more.

The content of the (a) polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the (b) radical polymerizable compound. The content of the polymerization initiator (a) is not preferable because the curing reaction is not performed when the content is less than 0.1 part by mass per 100 parts by mass of the radical polymerizable compound (b). Further, when the content of the (a) polymerization initiator is more than 40 parts by mass per 100 parts by mass of the (b) radical polymerizable compound, the solubility of the (b) radical polymerizable compound becomes saturated, and there are cases where the problem of crystal precipitation of the (a) polymerization initiator occurs at the time of film formation of the polymerizable composition, and the film surface is cracked, or there are cases where the strength of the cured coating film is lowered due to an increase in the decomposition residue of the (a) polymerization initiator, which is not preferable.

When the other polymerization initiator is contained in the (a) polymerization initiator, the proportion of the other polymerization initiator in the (a) polymerization initiator is preferably 80 mass% or less, more preferably 50 mass% or less.

(b) radical polymerizable Compound

As the radical polymerizable compound (b) of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of the radical polymerizable compound (b) include (meth) acrylates, styrenes, maleates, fumarates, itaconates, cinnamates, crotonates, vinyl ethers, vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins, and the like. Among them, highly reactive (meth) acrylates are preferably contained. (b) The radical polymerizable compounds may be used alone or in combination of two or more.

The (meth) acrylic acid esters may use monofunctional compounds and polyfunctional compounds. Examples of the monofunctional compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearic (meth) acrylate; esters of (meth) acrylic acid with alicyclic alcohols, such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate; monomers having a chain or cyclic ether bond such as methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl-2-ethyl-1, 3-dioxan-4-yl) methyl (meth) acrylate, 3-ethyloxetan-3-yl) methyl (meth) acrylate, and cyclic trimethylolpropane formal (meth) acrylate; monomers having a nitrogen atom such as N, N-dimethylaminoethyl (meth) acrylate, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acryloylmorpholine, N- (meth) acryloyloxyethyl hexahydrophthalimide; monomers having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; monomers having an epoxy group such as glycidyl (meth) acrylate and glycidyl 4-hydroxybutyl (meth) acrylate; monomers having a phosphorus atom such as 2- ((meth) acryloyloxy) ethyl phosphate; monomers having a silicon atom such as 3- (meth) acryloxypropyl trimethoxysilane; monomers having fluorine atoms such as 2, 2-trifluoroethyl (meth) acrylate, 2, 3-pentafluoropropyl (meth) acrylate, and 2- (perfluorohexyl) ethyl (meth) acrylate; monomers having a carboxyl group such as (meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl ester), phthalic acid mono (2- (meth) acryloyloxyethyl ester), maleic acid mono (2- (meth) acryloyloxyethyl ester), and ω -carboxyl-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, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propoxytri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 9-bis (2- (meth) acryloxyfluorenyl) ethoxy) propane, an esterified product of a polyhydric alcohol such as 9, 9-bis (4- (2- (2- (meth) acryloyloxyethoxy) 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 preferably esters of the polyhydric alcohol and (meth) acrylic acid, and particularly preferably trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, from the viewpoints of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, or improving the mechanical strength or hardness, heat resistance, durability, and chemical resistance of the cured product coating film.

The polymerizable composition may further contain a copolymer obtained from the radical polymerizable compound (b).

Alkali-soluble resin (c)

By further adding (c) an alkali-soluble resin, the polymerizable composition can be suitably used as a negative resist. As the alkali-soluble resin (c), an alkali-soluble resin commonly used for negative resists can be used, and the resin is not particularly limited as long as it is a resin soluble in an aqueous alkali solution, but a resin containing a carboxyl group is preferable. (c) The alkali-soluble resin may be used alone or in combination of two or more.

For the alkali-soluble resin (c) of the present invention, for example, a carboxyl group-containing (meth) acrylate copolymer, a carboxyl group-containing epoxy acrylate resin, or the like is preferably used.

The carboxyl group-containing (meth) acrylate copolymer is a copolymer containing: at least one kind of monofunctional compound selected from the (meth) acrylic esters (excluding the monomer having a carboxyl group) and at least one kind of carboxylic acid having an ethylenically unsaturated group selected from (meth) acrylic acid, a dimer of (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylbenzoic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl ester), phthalic acid mono (2- (meth) acryloyloxyethyl ester), maleic acid mono (2- (meth) acryloyloxyethyl ester), ω -carboxyl-polycaprolactone mono (meth) acrylate and anhydrides thereof.

Examples of the carboxyl group-containing (meth) acrylate 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 itaconate and the like may be copolymerized.

Further, from the viewpoint of satisfying both the developability of the negative resist and the coating properties such as heat resistance, hardness, and chemical resistance, it is preferable to use a carboxyl group-containing (meth) acrylate copolymer having a reactive group such as an ethylenically unsaturated group introduced into a side chain. Examples of the method for introducing an ethylenically unsaturated group into the side chain include the following methods: a method of adding a compound having an epoxy group and an ethylenically unsaturated group in the molecule, such as glycidyl (meth) acrylate, to a part of the carboxyl group-containing (meth) acrylate copolymer; or a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to a (meth) acrylate copolymer containing an epoxy group and a carboxyl group; or a method of adding a compound having an isocyanate group and an ethylenically unsaturated group in the molecule, such as 2- (meth) acryloyloxyethyl isocyanate, to a (meth) acrylate copolymer having a hydroxyl group and a carboxyl group.

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

Examples of the epoxy resin include (ortho-, meta-, and para) -cresol novolak type epoxy resins, phenol novolak type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, triphenol methane type epoxy resins, and biphenyl fluorene 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, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, itaconic anhydride, and the like.

Further, when synthesizing the carboxyl group-containing epoxy acrylate resin, a tricarboxylic acid anhydride such as trimellitic anhydride may be used as needed, and an acid anhydride group remaining after the hydrolysis reaction may be used to increase the carboxyl group. In addition, maleic anhydride containing an ethylenically unsaturated group may be used to further increase the olefinic double bond.

The acid value of the alkali-soluble resin (c) is preferably 20 to 300mgKOH/g, more preferably 40 to 180 mgKOH/g. When the acid value is less than 20mgKOH/g, the solubility in an aqueous alkali solution is insufficient, and development of an unexposed portion becomes difficult, which is not preferable. In addition, when the acid value is more than 300mgKOH/g, the exposed portion tends to be easily detached from the substrate even during development, which is not preferable.

The weight average molecular weight of the alkali-soluble resin (c) is preferably 1,000 to 100,000, more preferably 1,500 to 30,000. When the weight average molecular weight is less than 1,000, the heat resistance, hardness, and the like of the exposed portion are insufficient, which is not preferable. When the weight average molecular weight is more than 100,000, development of the unexposed portion may be difficult, which is not preferable. In addition, the weight average molecular weight may be determined by Gel Permeation Chromatography (GPC). As an example, it was determined by performing a chromatographic analysis using HLC-8220GPC (manufactured by TOSOH CORPORATION) as a GPC apparatus, 3 TSKgelHZM-M (manufactured by TOSOH CORPORATION) as a column, tetrahydrofuran as an eluent, and a weight average molecular weight in terms of polystyrene under the conditions of a column temperature of 40℃and a flow rate of 0.3 ml/min, an RI detector, a sample injection concentration of 0.5 mass%, and an injection amount of 10. Mu.l.

The proportion of the (c) 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. When the proportion is less than 10% by mass, the developability is insufficient, which is not preferable. If the ratio is more than 70 mass%, the reproducibility of the pattern shape and the heat resistance are deteriorated, which is not preferable.

The alkali-soluble resin (c) may be a solution obtained by a synthesis reaction, a dried product thereof, or the like, in addition to a substance obtained by separating and purifying an alkali-soluble resin as an active ingredient after the synthesis reaction.

< other Components >)

The heat-based curing of the polymerizable composition may also be performed at a low temperature by using a curing accelerator as the other ingredient. Examples of the curing accelerator include amine compounds, thiourea compounds, 2-mercaptobenzimidazole compounds, o-sulfonylbenzoyl imides, and fourth-period transition metal compounds. The curing accelerator may be used alone or in combination of two or more.

The amine compound is preferably a tertiary amine, and examples thereof include N, N-dimethylaniline, N-dimethyltoluidine, N-diethylaniline, N-bis (2-hydroxyethyl) -p-toluidine, ethyl 4- (dimethylamino) benzoate, and (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate.

Examples of the thiourea include acetylthiourea and N, N' -dibutylthiourea.

Examples of the 2-mercaptobenzimidazole compound include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and 2-mercaptomethoxybenzimidazole.

The fourth-period transition metal compound may be selected from organic acid salts such as vanadium, cobalt, and copper, and metal chelate compounds, and examples thereof include cobalt octoate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, copper acetylacetonate, manganese acetylacetonate, and vanadium acetylacetonate.

The curing accelerator is preferably added immediately before the polymerizable composition is used. The content of the curing accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (b).

As the other component, additives commonly used for various photoresists and the like such as coating agents or paints, printing inks, photosensitive printing plates, adhesives, color resists, black resists and the like can be blended into the polymerizable composition. Examples of the additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4' -bis (diethylamino) benzophenone, 9, 10-dibutoxyanthracene, coumarin ketone, acridine orange, camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2, 6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers, infrared absorbers, chain transfer agents, light stabilizers, antioxidants, leveling agents, surface regulators, surfactants, thickeners, antifoaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins having an ethylenically unsaturated bond, saturated resins, coloring dyes, fluorescent dyes, pigments (organic pigments, inorganic pigments), carbon-based materials (carbon fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerenes, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, aluminum oxide, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass, mica, layered minerals, talc, dispersing agents, talc, etc.), flame retardants, etc. The additives may be used alone or in combination of two or more.

The content of the additive is not particularly limited, and is usually preferably 500 parts by mass or less, more preferably 100 parts by mass or less, per 100 parts by mass of the radical polymerizable compound (b), as appropriate, depending on the purpose of use.

In order to improve the viscosity, coatability, and smoothness of the cured film, a solvent may be further added to the polymerizable composition. The solvent is not particularly limited as long as it can dissolve or disperse the (a) polymerization initiator, the (b) radical polymerizable compound, the (c) alkali-soluble resin, and the other components, and is a solvent that volatilizes at a drying temperature.

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

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

Process for producing polymerizable composition

In preparing the polymerizable composition, the (a) polymerization initiator, the (b) radical polymerizable compound, the (c) alkali-soluble resin and the other components, which are added as needed, may be added to a container, and dissolved or dispersed by a conventional method using a paint shaker (paint shaker), a bead mill, a sand mill, a ball mill, an attritor, a twin-roll mill, a three-roll mill, or the like. In addition, filtration may be performed by a screen, a membrane filter, or the like, as necessary.

In addition, in the preparation of the polymerizable composition, the (a) polymerization initiator may be initially added to the polymerizable composition, but when the polymerizable composition is stored for a long period of time, it is preferable that the (a) polymerization initiator is dissolved or dispersed in the composition containing the (b) radical polymerizability immediately before use

Preparation method of cured product

The cured product of the present invention is formed from the polymerizable composition. The preparation method of the cured product comprises the following steps: a step of applying a polymerizable composition on a substrate, and then irradiating the polymerizable composition with active energy rays, and a step of heating the polymerizable composition. The step including the step of irradiating with active energy rays and the step of heating is also referred to as a dual curing step.

Examples of the coating method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, inkjet printing, and dispenser printing. Examples of the substrate include films and sheets of glass, silicon wafers, metals, plastics, and the like, and molded articles of three-dimensional shape, and the shape of the substrate is not limited.

The step of irradiating the polymerizable composition with active energy rays may be performed by irradiating the composition with active energy rays such as electron beams, ultraviolet rays, visible light, and radioactive rays to decompose the polymerization initiator (a) and polymerize the radical polymerizable compound (b) to obtain a cured product.

The active energy ray is preferably light having a wavelength of 250 to 450nm, and more preferably light having a wavelength of 350 to 410nm, from the viewpoint of enabling rapid curing.

As a light source for irradiating the light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a Light Emitting Diode (LED), a solid laser such as a xenon arc lamp, a carbon arc lamp, sunlight, YAG laser, a semiconductor laser, a gas laser such as an argon laser, or the like can be used. In addition, when (a) light of the polymerization initiator that absorbs little visible light to infrared light 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 or intensity of the active energy ray and the composition of the polymerizable composition. As an example, the UV-A region is preferably exposed to an amount of 10 to 5,000mJ/cm ² More preferably 30 to 1,000mJ/cm ² . In the method for producing the cured product, when a dual curing step is applied and a heating step is performed after the step of irradiation with the active energy rays, the exposure amount should be appropriately set so that (a) the polymerization initiator is not completely decomposed by the active energy rays.

The step of heating the polymerizable composition can be carried out by thermally decomposing the (a) polymerization initiator and polymerizing the (b) radical polymerizable compound to obtain a cured product.

In the step of heating the polymerizable composition, examples of the heating method include heating and ventilation heating. The heating method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like. Examples of the ventilation heating method include a blower type drying oven.

In the step of heating the polymerizable composition, the higher the heating temperature is, (a) the faster the decomposition rate of the polymerization initiator is. However, if the decomposition rate is too high, the decomposition residue of the radical polymerizable compound (b) may increase. On the other hand, the lower the heating temperature is, (a) the slower the decomposition rate of the polymerization initiator is, and thus a long time is required for curing. Therefore, the heating temperature and the heating time should be appropriately set according to the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230℃and more preferably 100 to 160 ℃. In addition, when the curing accelerator is added to the polymerizable composition, the heating temperature may be arbitrarily adjusted in the room temperature to 160 ℃ depending on the kind or the addition amount thereof. On the other hand, the heating time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.

When the dual curing step is applied as a method for producing the cured product, it is preferable to perform the heating step after the step of irradiating the polymerizable composition with active energy rays, because the deep part of the coating film of the polymerizable composition containing the coloring pigment absorbing or scattering light at a high concentration or the part where light is not irradiated due to light shielding can be effectively cured.

In addition, when the solvent is contained in the polymeric composition, the method of preparing the cured product may include a drying process. In particular, when the step of irradiating the substrate with active energy rays is applied after the polymerizable composition is coated on the substrate, a drying step is preferably provided before the step of irradiating the substrate with active energy rays.

In the drying step, examples of the method for drying the solvent include heat drying, ventilation heat drying, and reduced pressure drying. The method of heat drying is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like. Examples of the method of the ventilation heating drying include a blower drying oven.

In the drying step, since the temperature of the polymerizable composition is lower than the set temperature for drying due to the latent heat of vaporization of the solvent, the time required for the polymerizable composition to gel can be ensured to be long. Since the time until gelation is affected by the drying method, the film thickness, and the like, the drying temperature and time should be appropriately set in addition to the selection of the solvent. As an example, the drying temperature is preferably 20 to 120℃and more preferably 40 to 100 ℃. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. In addition, by using the polymerization inhibitor, the time until gelation can be ensured to be long. Further, although the triazine peroxide derivative is decomposed by heat, the decomposition rate of the compound is about 0.1% when heated at 80℃for 5 minutes, and the polymerizable composition hardly thickens or gels as long as the decomposition rate is about that.

The dry film thickness (film thickness of the cured product) of the polymerizable composition may be appropriately set according to the application, and is preferably 0.05 to 300. Mu.m, more preferably 0.1 to 100. Mu.m.

Pattern forming method

When the polymerizable composition contains (c) an alkali-soluble resin, a pattern can be formed by photolithography. In the same manner as described above, the polymerizable composition is applied to the substrate, and if necessary, dried to form a dried film. Then, the dry film is irradiated with an active energy ray through a mask, whereby the radical polymerizable compound is polymerized in the exposed portion (b) to form a cured film. On the other hand, a pattern shape with high accuracy can be produced by direct drawing using a laser without a mask.

After the exposure, the unexposed portion can be developed and removed, for example, with an alkali developer such as a sodium carbonate aqueous solution of 0.3 to 3 mass%, to obtain a patterned cured film. Further, in order to improve the adhesion between the cured film and the substrate, post baking at 180 to 250℃for 20 to 90 minutes may be performed as post drying. In the above manner, a desired pattern based on the cured film can be formed.

The polymerizable composition of the present invention can be used for paints and paints such as hard paint, optical disk paint, optical fiber paint, mobile terminal paint, household appliance paint, cosmetic container paint, inner surface reflection preventing paint for optical element, high refractive index paint, low refractive index paint, heat insulating paint, heat dissipating paint, antifogging paint and the like; printing inks such as offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, and inks for light guide plates; photosensitive printing plate; a nanoimprint material; resin for 3D printer; a holographic recording material; a dental material; a waveguide material; black bars for lens sheets; a printed circuit board for a capacitor and an electrode material; an adhesive for FPD, an adhesive for HDD, an adhesive for optical pickup, an adhesive for image sensor, a sealant for organic EL, OCA for touch screen, an adhesive for OCR for touch screen, and a sealant; FPD resists such as color resists, black resists, protective films for color filters, photo spacers (black column spacer), frame resists, photoresists for TFT wiring, and interlayer insulating films; a resist for a printed board such as a liquid solder resist and a dry film resist; the use of the material for semiconductors such as a semiconductor resist and a buffer coating is not particularly limited.

Examples

Synthesis examples 1 to 8

(1) Synthesis of triazine peroxide derivatives

Synthesis example 1: synthesis of Compound 19

To a 100mL eggplant-shaped flask, 3.03g (16.3 mmol) of diphenyl sulfide, 30mL of dehydrated dichloromethane were added, and cooled to 0 ℃. At this time, 3.00g (16.3 mmol) of cyanuric chloride was added, and then 2.39g (17.9 mmol) of aluminum chloride was added over 10 minutes, and reacted at 0℃for 3 hours. After completion of the reaction, the reaction mixture was poured into 50mL of ice-cold 1M hydrochloric acid and stirred, and the aqueous phase was separated. The oil phase was washed with 50mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, concentration under reduced pressure was performed to obtain a crude product. The crude product was purified by silica gel chromatography (n-hexane/ethyl acetate=4/1 to 2/1) to give 5.03g (yield 92.6%) of 2, 4-dichloro-6- (4-phenylthio-1-phenyl) -1,3, 5-triazine.

To a 100mL eggplant-shaped flask was added 3.00g (8.98 mmol) of 2, 4-dichloro-6- (4-phenylthio-1-phenyl) -1,3, 5-triazine, 30mL of methyl ethyl ketone, and the temperature was raised to 40 ℃. After adding 4.67g of ion-exchanged water and 4.31g (26.9 mmol) of a 25 mass% aqueous sodium hydroxide solution, 0.32g (9.87 mmol) of methanol was added dropwise over 10 minutes, and the reaction was carried out at 40℃for 2 hours. 1.29g (9.87 mmol) of 69 mass% aqueous t-butyl hydroperoxide was added dropwise at 40℃or below over 10 minutes, and the mixture was reacted at 40℃for 1 hour. After the reaction, the aqueous phase was separated out and the oil phase was poured into 50mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 2.60g (yield 75.5%) of compound 19 according to the present invention. EI-MS based on Compound 19 thus obtained ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 2: synthesis of Compound 25

The compound 25 of the present invention was synthesized according to the method described in synthesis example 1, except that the diphenyl sulfide described in synthesis example 1 was changed to 1-methoxynaphthalene. EI-MS based on Compound 25 thus obtained ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 3: synthesis of Compound 35

Into a 100mL three-necked flask dried by dry heat, 0.44g (17.1 mmol) of magnesium, 15mL of dehydrated tetrahydrofuran and a catalytic amount of iodine were added, and the mixture was stirred at room temperature. After a mixed solution of 4.29g (16.3 mmol) of 4-bromo-4' -methoxybiphenyl and 15mL of dehydrated tetrahydrofuran was added dropwise, the mixture was stirred under reflux for 1 hour. A100 mL three-necked flask was additionally taken and 3.00g (16.3 mmol) of cyanuric chloride, 15mL of dehydrated tetrahydrofuran were added thereto, and cooled to 0 ℃. At this time, the previously prepared mixed solution was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 15 hours. The reaction solution was cooled by ice bath, 1M hydrochloric acid was added thereto and stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. After washing the oil phase with saturated brine 1 time, dehydration was performed using magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to give a crude product. The crude product was purified by silica gel chromatography (n-hexane/ethyl acetate=3/1 to 1/1) to give 2.07g (yield 38.2%) of 2, 4-dichloro-6- [4- (4' -methoxybiphenyl) ] -1,3, 5-triazine.

To a 50mL eggplant-shaped flask was added 1.20g (3.62 mmol) of 2, 4-dichloro-6- [4- (4' -methoxybiphenyl)]-1,3, 5-triazine, 10mL methyl ethyl ketone and heating to 40 ℃. 1.88g of ion exchange water and 1.74g (10.9 mmol) of a 25% by mass aqueous sodium hydroxide solution were added, and then 0.13g (3.98 mmol) of methanol was added dropwise over 5 minutes to react at 40℃for 2 hours. 0.52g (3.98 mmol) of 69 mass% aqueous t-butyl hydroperoxide was added dropwise at 40℃or below over 5 minutes and reacted at 40℃for 1 hour. After the reaction, the aqueous phase was separated out and the oil phase was poured into 50mL of ice water. Filtering to separate outAnd washed with ion-exchanged water, and dried under reduced pressure to give 1.04g (yield 75.0%) of compound 35 of the present invention. EI-MS based on the obtained compound 35 ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 4: synthesis of Compound 48

The compound 48 of the present invention was synthesized by the method described in synthesis example 3, except that methanol described in synthesis example 3 was changed to ethanol, and 69 mass% of the aqueous t-butyl hydroperoxide solution was changed to 85 mass% of the aqueous t-amyl hydroperoxide solution. EI-MS based on the obtained compound 48 ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 5: synthesis of Compound 53

The compound 53 of the present invention was synthesized by the method described in synthesis example 3, except that methanol described in synthesis example 3 was changed to isopropanol, and 69 mass% of the aqueous t-butyl hydroperoxide solution was changed to 90 mass% of the aqueous t-hexyl hydroperoxide solution. EI-MS based on the obtained compound 53 ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 6: synthesis of Compound 56

The compound 6 of the present invention was synthesized by the method described in synthesis example 3, except that the methanol described in synthesis example 3 was changed to t-butanol and 69 mass% of the aqueous t-butyl hydroperoxide solution was changed to 80 mass% of the cumene hydroperoxide solution. EI-MS based on the obtained Compound 56 ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 7: synthesis of Compound 77

To a 100mL three-necked flask dried by dry heat, 0.44g (17.1 mmol) of magnesium, 15mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and stirring was performed at room temperature. A mixed solution of 4.29g (16.3 mmol) of 4-bromo-4' -methoxybiphenyl and 15mL of dehydrated tetrahydrofuran was added dropwise, followed by stirring under reflux for 1 hour. A100 mL three-necked flask was additionally taken and 3.00g (16.3 mmol) of cyanuric chloride, 15mL of dehydrated tetrahydrofuran were added thereto, and cooled to 0 ℃. At this time, the previously prepared mixed solution was added dropwise over 30 minutes, and the temperature was raised to room temperature and stirred for 15 hours. The reaction solution was cooled by ice bath, 1M hydrochloric acid was added thereto and stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. After washing the oil phase with saturated brine 1 time, dehydration was performed using magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to give a crude product. The crude product was purified by silica gel chromatography (n-hexane/ethyl acetate=3/1 to 1/1) to give 2.07g (yield 38.2%) of 2, 4-dichloro-6- [4- (4' -methoxybiphenyl) ] -1,3, 5-triazine.

To a 100mL eggplant-shaped flask, 3.03g (16.3 mmol) of anisole and 30mL of dehydrated dichloromethane were added, and cooled to 0 ℃. At this time, 2, 4-dichloro-6- [4- (4' -methoxybiphenyl) ] -1,3, 5-triazine was added, and then 2.39g (17.9 mmol) of aluminum chloride was added over 10 minutes and reacted at 0℃for 3 hours. After completion of the reaction, the reaction mixture was poured into 50mL of ice-cold 1M hydrochloric acid and stirred, and the aqueous phase was separated. The oil phase was washed with 50mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, concentration under reduced pressure was performed to obtain a crude product. The crude product was purified by silica gel chromatography (n-hexane/ethyl acetate=4/1 to 2/1) to give 5.03g (yield 92.6%) of 2-chloro-4- (4-methoxyphenyl) -6- [4- (4' -methoxybiphenyl) ] -1,3, 5-triazine.

To a 50mL eggplant-shaped flask, 1.88g of ion exchange water, 1.74g (10.9 mmol) of a 25 mass% aqueous sodium hydroxide solution, and 0.52g (3.98 mmol) of a 69 mass% aqueous tert-butyl hydroperoxide solution were slowly added at 30℃or lower. At this time, 1.20g (3.62 mmol) of 2-chloro-4- (4-methoxyphenyl) -6- [4- (4' -methoxybiphenyl) were added dropwise at 10℃over 10 minutes]A mixed solution of 1,3, 5-triazine and 10mL of tetrahydrofuran was reacted at 20℃for 3 hours. After the completion of the reaction, 10mL of methylene chloride was added, and the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried at 0 ℃ with anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 1.04g (yield 75.0%) of the compound 77 of the present invention. EI-MS based on the obtained compound 77 ¹ The results of the H-NMR analysis are shown in Table 1.

Synthesis example 8: synthesis of Compound 81

To a 100mL eggplant-shaped flask was added 3.00g (16.3 mmol) of cyanuric chloride, 30mL of dehydrated dichloromethane, 4.35g (32.6 mmol) of aluminum chloride, and cooled to 20 ℃. At this time, 5.16g (32.6 mmol) of 1-methoxynaphthalene was added over 15 minutes, and the reaction was carried out at 20℃for 3 hours. After the completion of the reaction, the reaction mixture was cooled to 0℃and 50mL of ice-cooled 1M hydrochloric acid was added thereto, followed by stirring, and the aqueous phase was separated. The oil phase was washed with 50mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, concentration under reduced pressure gave 5.48g (yield 78.6%) of a crude product of 2-chloro-4, 6-bis (4-methoxy-1-naphthyl) -1,3, 5-triazine.

To a 100mL eggplant-shaped flask was added 3.00g (5.45 mmol) of the crude product of 2-chloro-4, 6-bis (4-methoxy-1-naphthyl) -1,3, 5-triazine, 30mL of tetrahydrofuran, and the temperature was raised to 40 ℃. At this time, a mixture of 2.18g (10.9 mmol) of a 20 mass% aqueous sodium hydroxide solution and 1.42g (10.9 mmol) of a 69 mass% aqueous t-butyl hydroperoxide solution was added dropwise over 10 minutes, and reacted at 40℃for 4 hours. After completion of the reaction, 50mL of methylene chloride was added, and the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried at 0 ℃ with anhydrous magnesium sulfate. After filtration, concentration was performed under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography (using methylene chloride) to give 1.63g (yield 62.3%) of compound 81 of the present invention. EI-MS based on Compound 81 thus obtained ¹ The results of the H-NMR analysis are shown in Table 1.

TABLE 1

Examples 1 to 8 and comparative example 1 >, respectively

Preparation of polymerizable composition (A)

The polymerizable compositions (a) of examples 1 to 8 and comparative example 1 were prepared by mixing and stirring the amounts of the radical polymerizable compound, the alkali-soluble resin, and other components shown in table 2, adding the polymerization initiator, and carefully stirring them. In addition, for comparative example 1, a compound R1 represented by the following formula was used as a polymerization initiator.

[ chemical formula 7]

TABLE 2

Composition of the components	Details of the ingredients	Blending amount (parts by mass)
			Polymerization initiator	TABLE 1	3
Radical polymerizable compound	DPHA	50
			Alkali-soluble resin	RD200	50
Leveling agent	F-477	0.5
			Solvent(s)	PGMEA	400

In the above Table 2 and tables 4 and 6 below, DPHA represents a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: ARONIX M-402, manufactured by TOAGOSEICO., LTD.);

RD200 represents a methyl methacrylate/methacrylic acid/cyclohexylmaleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid number: 90 (composite article);

f-477 represents a fluorine-based leveling agent (trade name: manufactured by MEGAFACE F-477,DIC Corporation);

PGMEA represents propylene glycol monomethyl ether acetate.

(1) Evaluation of sensitivity

The polymerizable composition (a) prepared above was coated on an aluminum substrate using a spin coater. After the coating, the aluminum substrate was subjected to a drying treatment in a dust-free oven at 90℃for 2.5 minutes, whereby the solvent was dried to prepare a uniform coating film having a thickness of 1.5. Mu.m. Then, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, passing through a mask pattern at a speed of 10 to 1000mJ/cm ² Is subjected to the step exposure. The exposed aluminum substrate was immersed in a 1.0 mass% sodium carbonate aqueous solution at 23 ℃ for 60 seconds, and the unexposed portion was removed by development. Then, the resist pattern was obtained by washing with pure water for 30 seconds. The lowest exposure amount at which a resist pattern can be formed was evaluated as "sensitivity". The smaller the value of the minimum exposure amount, the pattern can be formed with a small amount of light, the exposure amount is 200mJ/cm ² Hereinafter, the high sensitivity will be referred to as "high sensitivity". The results are shown in Table 3.

(2) Evaluation of Long-term storage stability

The polymerizable composition (a) prepared above was placed in a brown glass bottle, and after light shielding with aluminum foil, it was allowed to stand in a constant temperature machine set at 50 ℃. The number of days required for gelation was evaluated as good for 60 days or more, and the number of days less than 60 days was evaluated as X. The results are shown in Table 3.

TABLE 3

Examples 9 to 16 and comparative example 2 >, respectively

Preparation of polymerizable composition (B)

The polymerizable compositions (B) of examples 9 to 16 and comparative example 2 were prepared by mixing and stirring the amounts of the radical polymerizable compound, the alkali-soluble resin, the black pigment, and other components shown in table 4, and adding the polymerization initiator thereto and carefully stirring them. In addition, for comparative example 2, the table compound R1 represented by the above formula was used as a polymerization initiator.

TABLE 4

Composition of the components	Details of the ingredients	Blending amount (parts by mass)
			Polymerization initiator	TABLE 1	2.5
Radical polymerizable compound	DPHA	25
			Alkali-soluble resin	RD200	25
Black pigment	TSG-BK133	50
			Leveling agent	F-477	0.5
Solvent(s)	PGMEA	400

In table 4, TSG-BK133 represents a carbon black dispersion (manufactured by Taisei Kako co., ltd.).

(3) Evaluation of resolution

The polymerizable composition (B) prepared above was coated on a glass substrate using a spin coater. After the coating, the glass substrate was subjected to a drying treatment in a dust-free oven at 90℃for 2.5 minutes, whereby the solvent was dried to prepare a uniform coating film having a thickness of 1.5. Mu.m. Then, using a proximity type exposure machine using an ultra-high pressure mercury lamp as a light source, the exposure machine was used to perform exposure at 200mJ/cm via a mask pattern ² Exposure is performed. The exposed glass substrate was immersed in a 1.0 mass% aqueous sodium carbonate solution at 23 ℃ for 60 seconds, and the unexposed portion was removed by development. Then, the resist pattern was obtained by washing with pure water for 30 seconds. The obtained pattern was observed by a microscope, and the minimum pattern size was evaluated as excellent at 10 μm or less, the minimum pattern size was evaluated as good at 10 μm or more and 20 μm or less, the minimum pattern size was evaluated as delta at 20 μm or more and 30 μm or less, and the minimum pattern size was evaluated as x at 30 μm or more. The results are shown in Table 5.

TABLE 5

Examples	Polymerization initiator	Resolution ratio
			Example 9	Compound 19	◎
Example 10	Compound 25	◎
			Example 11	Compound 35	◎
Example 12	Compound 48	◎
			Example 13	Compound 53	◎
Example 14	Compound 56	◎
			Example 15	Compound 77	〇
Example 16	Compound 81	◎
			Comparative example 2	Compound R1	△

Examples 17 to 24 and comparative example 3 >, respectively

Preparation of polymerizable composition (C)

The polymerizable compositions (C) of examples 17 to 24 and comparative example 3 were prepared by mixing and stirring the amounts of the radical polymerizable compound, the alkali-soluble resin, the green pigment, and other components shown in table 6, and adding the polymerization initiator thereto and carefully stirring them. In addition, for comparative example 3, the compound R1 represented by the above formula was used as a polymerization initiator.

TABLE 6

Composition of the components	Details of the ingredients	Blending amount (parts by mass)
			Polymerization initiator	TABLE 7	2.5
Radical polymerizable compound	DPHA	25
			Alkali-soluble resin	RD200	25
Green pigment	SG036	25
			Leveling agent	F-477	0.5
Solvent(s)	PGMEA	400

In table 6, SG036 represents a green pigment dispersion (manufactured by Taisei Kako co., ltd.).

(4) Evaluation of under etch (unrercut)

The polymerizable composition (C) prepared above was coated on a glass substrate using a spin coater. After the coating, the glass substrate was subjected to a drying treatment in a dust-free oven at 90℃for 2.5 minutes, whereby the solvent was dried to prepare a uniform coating film having a thickness of 1.5. Mu.m. Then, using a proximity type exposure machine using an ultra-high pressure mercury lamp as a light source, 150mJ/cm was used via a mask pattern ² Exposure is performed. The exposed glass substrate was immersed in a 1.0 mass% aqueous sodium carbonate solution at 23 ℃ for 60 seconds, and the unexposed portion was removed by development. Then, the resist pattern was obtained by washing with pure water for 30 seconds. The cross section of the pattern corresponding to the linear opening portion having an opening width of 15 μm was observed by a microscope, and the undercut of the linear pattern was evaluated by the difference between the maximum width and the minimum width among the pattern widths parallel to the substrate surface. The smaller the difference between the maximum width and the minimum width, the less the undercut was suppressed, the better the difference was evaluated as 1.5 μm or less, the better the difference was evaluated as delta greater than 1.5 μm and 2.5 μm or less, and the better the difference was evaluated as x greater than 2.5 μm.

The results are shown in Table 7.

TABLE 7

Examples	Polymerization initiator	Difference between maximum width and minimum width of pattern
			Example 17	Compound 19	〇
Example 18	Compound 25	〇
			Example 19	Compound 35	〇
Example 20	Compound 48	〇
			Example 21	Compound 53	〇
Example 22	Compound 56	〇
			Example 23	Compound 77	〇
Example 24	Compound 81	〇
			Comparative example 3	Compound R1	△

Examples 25 to 32 and comparative example 4 >, respectively

Preparation of polymerizable composition (D)

The polymerizable compositions (D) of examples 25 to 32 and comparative example 4 were prepared by adding the radically polymerizable compound, the polymerization initiator, the curing accelerator, and the solvent in the amounts shown in table 8 and carefully stirring them. In addition, for comparative example 4, the compound R1 represented by the above formula was used as a polymerization initiator.

TABLE 8

(5) Evaluation of curability

The polymerizable composition (D) prepared above was applied to a glass substrate at a thickness of 100. Mu.m, using a bar coater. After coating, it was dried in an oven at 90℃for 2.5 minutes, and then, a conveyor type UV irradiation apparatus provided with a high-pressure mercury lamp was used at 30mJ/cm ² Irradiation is performed. Then, the resultant film was heated in an oven at 150℃for 30 minutes to obtain a cured film. The polymerization conversion of the obtained cured film was measured, and the curability was evaluated according to the following criteria. The polymerization conversion was measured by Fourier transform attenuated total reflection infrared spectroscopy (ATR-IR), and at this time, an absorption spectrum (810 cm) from a double bond group was used ^-1 ) The peak area A of (2) and the absorption spectrum from carbonyl group (1740 cm) ^-1 ) The polymerization conversion was calculated based on the following formula.

The results are shown in Table 9.

Polymerization conversion = (1- (a/B after curing)/(a/B before curing)) ×100

And (2) the following steps: the polymerization conversion rate is more than 80 percent

Delta: the polymerization conversion rate is more than 60% and less than 80%

X: the polymerization conversion rate is less than 60 percent

TABLE 9

Examples	Polymerization initiator	Cobalt octoate	Polymerization conversion
				Example 25	Compound 19	-	〇
Example 26	Compound 25	-	〇
				Example 27	Compound 35	-	〇
Example 28	Compound 48	-	〇
				Example 29	Compound 53	-	〇
Example 30	Compound 56	-	〇
				Example 31	Compound 77	1	〇
Example 32	Compound 81	-	〇
				Comparative example 4	Compound R1	-	△

In Table 8 above, TMPTA represents trimethylolpropane triacrylate (SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD.);

PE4A represents pentaerythritol tetraacrylate (agent FUJIFILM Wako Pure Chemical Corporation).

Claims

1. A triazine peroxide derivative characterized by being represented by the general formula (1):

[ chemical formula 1]

In the general formula (1), R ¹ R is R ² Independently represent methyl or ethyl, R ³ Represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms optionally having an alkyl group, R ⁴ Is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y-R or-N-RR ', Y represents an oxygen atom or a sulfur atom, R and R' independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, ar is a group represented by the following general formula (2): ar (Ar) ¹ 、Ar ² Or Ar ³ An aryl group represented by the formula (I),

[ chemical formula 2]

2. A polymerizable composition comprising (a) a polymerization initiator and (b) a radical polymerizable compound, wherein the (a) polymerization initiator comprises the triazine peroxide derivative according to claim 1.

3. The polymerizable composition according to claim 2, further comprising (c) an alkali-soluble resin.

4. A cured product comprising the polymerizable composition according to claim 2 or 3.

5. A method for producing a cured product according to claim 4, comprising the step of irradiating the polymerizable composition with active energy rays.

6. A process for producing a triazine peroxide derivative according to claim 1, comprising the step of reacting cyanuric chloride and/or a derivative thereof with a hydroperoxide as a raw material.