KR20240068585A - Triazine peroxide derivative and method for producing the same, polymerizable composition, and cured product and method for producing the same - Google Patents

Abstract

(일반식 (1) 중, R¹ 및 R² 는 독립적으로 메틸기 또는 에틸기, R³ 은 탄소수 1 ∼ 5 의 지방족 탄화수소기 등, R⁴ 는 치환되어 있어도 되는 탄소수 1 ∼ 20 의 지방족 탄화수소기 등을 나타내고, Ar 은 하기 일반식 (2) : Ar¹, Ar², 또는 Ar³ 으로 나타내는 아릴기이다)

그 트리아진퍼옥사이드 유도체는, 감도가 우수면서도, 고온 하에서도 양호한 장기 보존 안정성을 갖는 신규의 중합 개시제이다.A triazine peroxide derivative represented by general formula (1).

(In General Formula (1), R ¹ and R ² are independently a methyl group or an ethyl group, R ³ is an aliphatic hydrocarbon group with 1 to 5 carbon atoms, etc., and R ⁴ is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, etc. and Ar is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , or Ar ³ )

The triazine peroxide derivative is a novel polymerization initiator that has excellent sensitivity and good long-term storage stability even at high temperatures.

Description

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

The present invention relates to triazine peroxide derivatives and methods for producing the same, polymerizable compositions, and cured products and methods for producing the same.

As a polymerization initiator, a triazine peroxide derivative that can be used as a light and thermal polymerization initiator is known (Patent Document 1).

International Publication No. 2018/221177

The triazine peroxide derivative disclosed in Patent Document 1 has a specific aryl group and two peroxidation bonds in the molecule, and can generate radicals by efficiently absorbing light with a wavelength of 365 nm emitted from lamps such as high-pressure mercury lamps or LEDs. Because of this, the sensitivity is excellent. However, in polymerizable compositions obtained by mixing this compound with a radically polymerizable compound, long-term storage stability at high temperatures sometimes becomes insufficient.

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

That is, the present invention has general formula (1):

[Formula 1]

((In General Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R ⁴ is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , or Ar ³ . )

[Formula 2]

(In General Formula (2), m represents an integer of 0 to 3, and R ¹¹ is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 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, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) ) relates to a triazine peroxide derivative represented by .

Additionally, the present invention relates to a polymerizable composition containing (a) a polymerization initiator containing the above triazine peroxide derivative, and (b) a radically polymerizable compound.

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

Since the triazine peroxide derivative of the present invention has only one peroxidation bond in the molecule, the number of radicals generated per molecule by decomposition of the compound is that of the triazine peroxide derivative having two peroxidation bonds in the molecule disclosed in Patent Document 1 above. Although it is less than a triazine peroxide derivative, it has the unique effect of having the same level of sensitivity as the compound disclosed in Patent Document 1. On the other hand, since the triazine peroxide derivative of the present invention has only one peroxidation bond in its molecule, it is superior to the triazine peroxide derivative disclosed in Patent Document 1 above in long-term storage stability at high temperatures.

In addition, since the triazine peroxide derivative of the present invention has excellent sensitivity, it is also useful as a polymerization initiator for polymerizable compositions such as black resist containing a light-shielding pigment such as carbon black.

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

[Formula 3]

((In General Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R ⁴ is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , or Ar ³ . )

[Formula 4]

(In General Formula (2), m represents an integer of 0 to 3, and R ¹¹ is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 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, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) )

In General Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, and a methyl group is preferable from the viewpoint of high decomposition temperature and increased storage stability of the polymerizable composition.

In General Formula (1), R ³ represents 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 straight chain or branched chain. Specific examples of R ³ include methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, phenyl group, and isopropylphenyl group. Among these, methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, and phenyl group are preferable from the viewpoint of ease of 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 light is high, it is more preferable that it is a methyl group or an ethyl group.

In 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, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, An acyl group, -YR, or -N-RR' having 1 to 20 carbon atoms which may be substituted, where Y represents an oxygen atom or a sulfur atom, and R and R' are independently hydrogen atoms and 1 to 20 carbon atoms which may be substituted. It represents an aliphatic hydrocarbon group with 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms. Since the above R ⁴ has little influence on the absorption wavelength of the triazine peroxide derivative, good sensitivity is achieved even when R ⁴ is within the above wide range. In addition, the "substituent" in the above "may be substituted" includes a halogen atom, an aliphatic hydrocarbon group that may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic ring-containing group, an acyl group, Cyano group, nitro group, carboxyl group, epoxy group, hydroxyl group, etc. are included. From the viewpoint of high stability, the above R ⁴ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may be substituted, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted, or an optionally substituted aromatic hydrocarbon group having 2 to 20 carbon atoms. is a heterocyclic ring-containing group, an optionally substituted acyl group having 1 to 20 carbon atoms, or -YR. From the viewpoint of ease of synthesis, it is more preferably -OR, where R is an optionally substituted acyl group having 1 to 20 carbon atoms. These include an aliphatic hydrocarbon group, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.

In General Formula (2), m represents an integer of 0 to 3, and from the viewpoint of easy synthesis, m is preferably 0 to 2, and from the viewpoint of efficiently absorbing light, m is more preferably 1. do.

In 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 acyl group, -YR, or -N-RR' having 1 to 20 carbon atoms which may be substituted, where Y represents an oxygen atom or a sulfur atom, and R and R' are independently hydrogen atoms and 1 to 20 carbon atoms which may be substituted. It represents an aliphatic hydrocarbon group of 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms, and an optionally substituted heterocyclic ring-containing group of 2 to 20 carbon atoms. Since the above R ¹¹ has little influence on the absorption wavelength of the triazine peroxide derivative, good sensitivity is achieved even if R ¹¹ is within the above wide range. In addition, the "substituent" in the above "may be substituted" includes a halogen atom, an aliphatic hydrocarbon group that may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, a heterocyclic ring-containing group, an acyl group, Cyano group, nitro group, carboxyl group, epoxy group, hydroxyl group, etc. are included. The above R ¹¹ is an independent substituent and represents an alkyl group having 1 to 20 carbon atoms, a substituent represented by general formula (3): R ¹² -Y-, a nitro group, or a cyano group, and Y is an oxygen atom or a sulfur atom. represents, and R ¹² is a hydrocarbon group having 1 to 20 carbon atoms that may have one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton, or a hydrocarbon group having 6 to 20 carbon atoms that may have an alkyl group. It may be an aromatic hydrocarbon group or an acyl group having 1 to 20 carbon atoms, and R ¹¹ may form a 5- to 6-membered ring by two adjacent general formulas (3): R ¹² -Y-.

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

[Formula 5]

Triazine peroxide derivatives of the present invention include 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 are preferred.

<Method for producing triazine peroxide derivatives>

The method for producing a triazine peroxide derivative represented by the general formula (1) includes a step of reacting cyanuric chloride and/or its derivative with hydroperoxide as a raw material. Such a production method includes, for example, a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as steps (A) and (B)) as shown in the following reaction formula, followed by the obtained cyanuric chloride derivative and A method including a step of reacting roperoxide in the presence of an alkali (hereinafter also referred to as step (C)) is included. In addition, the order of each of the above steps is not limited. For example, the reactants of cyanuric chloride and hydroperoxide may be reacted with Ar-X or R ⁴ -X below, and each step may be performed simultaneously. You can do it. Before and after each process, a process of vacuum distillation (removal) of excess raw materials, etc. or a purification process may be included.

[Formula 6]

(In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ and Ar are the same as the general formula (1))

In the step (C), a commercially available product can be used as the cyanuric chloride derivative. In addition, in the case where there is no commercially available product, in the above steps (A) and (B), known synthetic methods such as Grignard reaction, lithiation reaction, Suzuki coupling reaction, Friedel-Crafts reaction, nucleophilic substitution reaction in the presence of alkali, etc. It can be synthesized according to .

<Synthesis of cyanuric chloride derivatives by Grignard reaction>

In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by Grignard reaction, it can be synthesized according to a known synthesis method described in Japanese Patent Application Laid-Open No. 6-179661, etc. A halogen compound in which X of Ar-X in the step (A) and R ⁴ -X in the step (B) is represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A Grignard reagent can be prepared by reacting a halogen compound with magnesium, and then a cyanuric chloride derivative can be synthesized by reacting the obtained Grignard reagent with cyanuric chloride.

In the preparation of the Grignard reagent, it is preferable to use 0.8 to 2.0 mol of magnesium, and more preferably 1 to 1.5 mol, per 1 mol of the halogen compound. As a reaction initiator, iodine, bromoethane, dibromoethane, etc. may be used, and it is preferably used in an amount of 0.0001 to 0.01 mol per 1 mol of the halogen compound. The reaction temperature is preferably 0 to 70°C, and more preferably 10 to 60°C. The reaction time is preferably 30 minutes to 20 hours, and more preferably 1 hour to 10 hours.

In preparing the Grignard reagent, solvents such as ethers such as tetrahydrofuran can be used.

Additionally, in the reaction between the Grignard reagent and cyanuric chloride, it is preferable to use 0.7 to 1.5 mole of cyanuric chloride, and more preferably 0.8 to 1.2 mole, per 1 mole of the halogen compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 20 hours, and more preferably 30 minutes to 15 hours. Additionally, cyanuric chloride may be added to the prepared Grignard reagent, or Grignard reagent may be added to a solution of cyanuric chloride.

In the reaction between the Grignard reagent and cyanuric chloride, solvents such as ethers such as tetrahydrofuran can be used, for example.

<Synthesis of cyanuric chloride derivatives by lithiation reaction>

In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by lithiation reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 publication, etc. A halogen compound in which X of Ar-X in the step (A) and R ⁴ -X in the step (B) is represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A lithium compound can be prepared by reacting a halogen compound with a lithiating agent, and then a cyanuric chloride derivative can be synthesized by reacting the obtained lithium compound with cyanuric chloride.

Examples of the lithiating agent include alkyl lithium such as methyl lithium, n-butyl lithium, s-butyl lithium, and t-butyl lithium; Aryllithium such as phenyllithium; Examples of lithium amides include lithium diisopropylamide and lithium bis(trimethylsilyl)amide, and n-butyllithium, s-butyllithium, t-butyllithium, and phenyllithium are preferred.

In the preparation of the above lithium compound, the lithiating agent is preferably used in an amount of 0.8 to 3.0 mol, and more preferably in an amount of 1.0 to 2.2 mol, per 1 mol of the halogen compound. The reaction temperature is preferably -100 to 50°C, and more preferably -80 to 0°C. The reaction time is preferably 0.2 to 20 hours, and more preferably 0.5 to 10 hours.

In preparing the above lithium compound, solvents such as ethers such as tetrahydrofuran can be used, for example.

In addition, in the reaction between the above lithium compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mole of cyanuric chloride, and more preferably 0.8 to 1.2 mole per 1 mole of the halogen compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, cyanuric chloride may be added to the prepared lithium compound, or the lithium compound may be added to the solution of cyanuric chloride.

In the reaction between the above lithium compound and cyanuric chloride, solvents such as ethers such as tetrahydrofuran can be used, for example.

<Synthesis of cyanuric chloride derivatives by Suzuki coupling>

In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by Suzuki coupling reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 publication, etc. For example, by reacting the above-mentioned lithium compound with ^a boron reagent, Ar-X in the above step (A) and Boron compounds can be synthesized. Cyanuric chloride derivatives can then be synthesized by reacting the obtained boron compound with cyanuric chloride. Additionally, if a commercial product of a boron compound is available, it can be used as is.

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

In the synthesis of the boron compound described above, it is preferable to use 0.8 to 3.0 mole of the boron reagent, and more preferably 1.0 to 2.0 mole per mole of the lithium compound. The reaction temperature is preferably -100 to 50°C, and more preferably -80 to 20°C. The reaction time is preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

In the synthesis of the above boron compound, solvents such as ethers such as tetrahydrofuran can be used.

In addition, in the reaction between the boron compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mol, and more preferably 0.8 to 1.2 mol, per 1 mol of boron compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, cyanuric chloride may be added to the boron compound, or the boron compound may be added to the solution of cyanuric chloride.

In the reaction between the boron compound and cyanuric chloride, it is preferable to use a palladium catalyst and an alkali, and a ligand may be added as necessary.

Examples of the palladium catalyst include palladium acetate, tetrakistriphenylphosphine palladium, bis(triphenylphosphine)palladium dichloride, (bis(diphenylphosphine)ferrocene)palladium dichloride-methylene chloride complex, etc. .

Examples of the alkali include inorganic bases such as alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium acetate, potassium acetate, and potassium phosphate; Organic bases such as triethylamine can be mentioned.

Examples of the ligand include triphenylphosphine, tricyclohexylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, 2-dicyclohexylphosphino-2,6'- Organophosphorous ligands such as dimethoxybiphenyl, etc. can be mentioned.

In the reaction between the boron compound and cyanuric chloride, ethers such as tetrahydrofuran and 1,4-dioxane; Alcohols such as methanol and 2-propanol; Aromatic hydrocarbons such as toluene and xylene; Organic solvents such as amides such as N,N-dimethylformamide can be used. The organic solvent may be used individually or two or more types may be used in combination. Additionally, a mixed solvent of the organic solvent and water may be used.

<Synthesis of cyanuric chloride derivatives by Friedel-Crafts reaction>

In the above steps (A) and (B), when synthesizing a cyanuric chloride derivative by the Friedel-Crafts reaction, it can be synthesized according to a known synthesis method described in US5322941 publication, etc. An aromatic compound in which X of Ar-X in the step (A) and R ⁴ -X in the step (B) is represented by a hydrogen atom can be used. Cyanuric chloride derivatives can be synthesized by reacting an aromatic compound with cyanuric chloride in the presence of a Lewis acid such as aluminum chloride.

The Lewis acids include aluminum chloride, aluminum bromide, iron (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, and boron trifluoride. Ethyl ether complexes, etc. can be used.

In the reaction between the above aromatic compound and cyanuric chloride, it is preferable to use 0.7 to 2.5 mole of cyanuric chloride, and more preferably 0.8 to 1.5 mole per 1 mole of the aromatic compound. It is preferable to use 1.0 to 3.0 mol of aluminum chloride, and more preferably 1.0 to 2.0 mol per 1 mol of the aromatic compound. The reaction temperature is preferably -50 to 60°C, and more preferably 0 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Additionally, aluminum chloride may be added to a solution of an aromatic compound and cyanuric chloride, an aromatic compound may be added to a solution of cyanuric chloride and aluminum chloride, and cyanuric chloride may be added to a solution of an aromatic compound and aluminum chloride.

In the reaction between the aromatic compound and cyanuric chloride, solvents such as dichloromethane, 1,2-dichloroethane, and xylene can be used, for example.

<Synthesis of triazine peroxide derivatives>

In the above step (C), the method for producing the triazine peroxide derivative represented by general formula (1) is not particularly limited, but is performed according to the known synthesis method of triazine peroxide described in Japanese Patent Publication No. 45-39468, etc. It can be synthesized.

A triazine peroxide derivative is obtained through step (C) of reacting the cyanuric chloride derivative obtained in the above steps (A) and (B) with hydroperoxide in the presence of an alkali.

In the above step (C), it is preferable to react 0.9 mol or more, and more preferably 1.0 mol or more of hydroperoxide per 1 mol of cyanuric chloride derivative, from the viewpoint of increasing the yield of the target product, And, it is preferable to react at 3.0 mol or less, and it is more preferable to react at 2.0 mol or less. In addition, hydroperoxide can be used as a commercial product, and if a commercial product is not available, it can be synthesized according to a known synthesis method described in Japanese Patent Application Laid-Open No. 58-72557, etc.

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

In the above step (C), the reaction time cannot be uniformly determined because it varies depending on the raw materials, reaction temperature, etc., but is usually preferably 10 minutes to 6 hours from the viewpoint of increasing the yield of the target product.

In the above step (C), the alkali used is not particularly limited, but is sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, α-picolin, γ-picolin, dimethylamino. Examples include pyridine, triethylamine, tributylamine, N,N-diisopropylethylamine, and 1,5-diazabicyclo[4.3.0]-5-nonene. From the viewpoint of increasing the yield of the target product, the alkali is preferably used at 0.8 mol or more, more preferably at least 1.0 mol, and preferably at most 3.0 mol per 1 mol of cyanuric chloride derivative. , it is more preferable to use 2.0 mol or less.

In the above step (C), when the cyanuric chloride derivative is in a liquid state, the reaction can be carried out without using an organic solvent. Additionally, when the cyanuric chloride derivative is solid, it is preferable to use an organic solvent. The organic solvent is not particularly limited because the solubility varies depending on the type of cyanuric chloride derivative, but examples include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, acetone, methyl ethyl ketone, and methyl isobutyl. Examples include ketones such as ketones, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as methylene chloride and chloroform. The organic solvent may be used individually or two or more types may be used in combination.

The amount of the organic solvent used is usually about 30 to 1000 parts by mass based on 100 parts by mass of the total amount of raw materials. The organic solvent may be distilled off after step (C) to extract the triazine peroxide derivative, or in order to improve handling and reduce the risk of thermal decomposition, the triazine peroxide derivative may be used as a dilution of the organic solvent. .

The above step (C) can be performed under normal pressure and air, but may also be performed under a nitrogen stream or nitrogen atmosphere.

In the above purification process, in order to remove excess raw materials and by-products, for example, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfite, hydrogen chloride, sulfuric acid, sodium chloride, etc. A step of washing using an aqueous electrolyte solution or ion-exchanged water and purifying the target product may be included.

<Polymerizable composition>

The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radically polymerizable compound. Additionally, the polymerizable composition can impart developability by containing (c) alkali-soluble resin. Additionally, the polymerizable composition may contain other components in appropriate combination.

<(a) Polymerization initiator>

The polymerization initiator (a) of the present invention contains a triazine peroxide derivative represented by the general formula (1). (a) The polymerization initiator is decomposed by active energy rays or heat, and the generated radicals have the function of initiating polymerization (curing) of the (b) radically polymerizable compound. Triazine peroxide derivatives may be used individually or two or more types may be used in combination.

In addition, the polymerization initiator (a) may contain polymerization initiators other than triazine peroxide derivatives (hereinafter also referred to as other polymerization initiators). By using two or more triazine peroxide derivatives or other polymerization initiators with different absorption bands, it is possible to achieve higher sensitivity of the polymerizable composition to, for example, a lamp that emits light of multiple wavelengths, such as a high-pressure mercury lamp. there is. In addition, taking into account the polymerizability of (b) radically polymerizable compound contained in the polymerizable composition, the type of pigment etc. that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, etc., a different polymerization initiator may be used. By doing so, the surface hardenability, deep hardenability, transparency, etc. of the polymerizable composition can be improved.

As the other polymerization initiators, known ones can be used, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy )-2-Hydroxy-2-methylpropiophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1 α-hydroxyacetophenone derivatives such as -one; 2-methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, α-aminoacetophenone derivatives such as 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; Acylphosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl(mesitylcarbonyl)phenylphosphinate; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]ethylidene}amino)oxy]ethanone,], [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[ a]carbazoyl]][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime), 1-[4-[4-(2-benzofura oxime ester derivatives such as nylcarbonyl)phenyl]thio]phenyl-4-methyl-1-pentanone-1-(O-acetyloxime); 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Halomethyltriazine derivatives such as romethyl)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 isopropylthioxanthone, and benzophenone derivatives such as 4-(4-methylphenylthio)benzophenone; Coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole, etc. imidazole derivatives of; 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1-methylethyl)-9H-thioxanthen-9-one , organic peroxides such as dibenzoyl peroxide; Azo compounds such as azobisisobutyronitrile; Camphorquinone, etc. can be mentioned. Other polymerization initiators may be used individually or may be used in combination of two or more types.

The content of the polymerization initiator (a) is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b). do. The content of the polymerization initiator (a) is not preferable because the curing reaction does not proceed if it is less than 0.1 parts by mass based on 100 parts by mass of the radically polymerizable compound (b). Moreover, when the content of (a) the polymerization initiator is more than 40 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (b), the solubility of the radically polymerizable compound in (b) reaches saturation, and the polymerizable composition During film formation, (a) crystals of the polymerization initiator may precipitate, causing roughness of the film surface, or (a) the strength of the cured film may decrease due to an increase in the decomposition residue of the polymerization initiator. , is not desirable.

In addition, when the other polymerization initiator is included in the polymerization initiator (a), the proportion of the other polymerization initiator is preferably 80% by mass or less, and more preferably 50% by mass or less, based on the polymerization initiator (a).

<(b) Radical polymerizable compound>

As the (b) radically polymerizable compound of the present invention, a compound having an ethylenically unsaturated group can be preferably used. (b) Radically polymerizable compounds include, for example, (meth)acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, and vinyl ethers. , vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins, etc. Among these, those containing highly reactive (meth)acrylic acid esters are preferable. (b) The radically polymerizable compound may be used individually or may be used in combination of two or more types.

As the (meth)acrylic acid esters, monofunctional compounds and polyfunctional compounds can be used. Monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. ) Alkyl (meth)acrylates such as acrylate and stearyl (meth)acrylate; Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2- Ester compounds of (meth)acrylic acid and alicyclic alcohol, such as ethyl-2-adamantyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth) ) Monomers having a hydroxyl group such as acrylate, polyethylene glycol mono(meth)acrylate, and 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-dioxoran-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic trimethyl Monomers having chain-like or cyclic ether bonds, such as all-propane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylamino Monomers having a nitrogen atom such as propyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, and N-(meth)acryloyloxyethylhexahydrophthalimide; Monomers having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; Monomers having an epoxy group such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether; Monomers having a phosphorus atom such as 2-((meth)acryloyloxy)ethyl phosphoric acid; Monomers having silicon atoms such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate monomers having fluorine atoms, such as; (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, mono(2-(meth)acryloyloxyethyl) phthalate, mono(2-(meth)acryloyloxyethyl) maleate and monomers having a carboxyl group such as ω-carboxy-polycaprolactone mono(meth)acrylate.

Examples of the multifunctional compounds 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 Propoxy tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate Erythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tricyclo Decane dimethanol 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-(2-(2-(meth)acryloyloxyethoxy) Ester compounds of polyhydric alcohols such as toxy)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, etc.

The (meth)acrylic acid esters are a combination of the polyhydric alcohol and (meth)acrylic acid esters from the viewpoint 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. ) Ester compounds of acrylic acid are preferable, especially trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythate. Litolhexaacrylate is preferred.

Additionally, the polymerizable composition may contain a copolymer obtained from the radically polymerizable compound (b).

<(c) Alkali soluble resin>

The polymerizable composition can be suitably used as a negative resist by further adding (c) an alkali-soluble resin. (c) The alkali-soluble resin can be one that is generally used in negative resists, and is not particularly limited as long as it is a resin that is soluble in aqueous alkali solution, but it is preferable that it is a resin containing a carboxyl group. (c) Alkali-soluble resin may be used individually or two or more types may be used in combination.

For the (c) alkali-soluble resin of the present invention, for example, carboxyl group-containing (meth)acrylic acid ester copolymer, carboxyl group-containing epoxy acrylate resin, etc. are preferably used.

The carboxyl group-containing (meth)acrylic acid ester copolymer includes at least one selected from the monofunctional compounds of the above-mentioned (meth)acrylic acid esters (however, excluding the monomer having the carboxyl group), (meth)acrylic acid, ( Dimer of meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylbenzoic acid, cinnamic acid, mono(2-(meth)acryloyloxyethyl) succinic acid, mono(2-(meth)acryloyloxy phthalate) ethyl), maleic acid mono(2-(meth)acryloyloxyethyl), ω-carboxy-polycaprolactone mono(meth)acrylate, and their acid anhydrides, etc. carboxylic acids containing ethylenically unsaturated groups. It is a copolymer containing at least one type.

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

In addition, the carboxyl group-containing (meth)acrylic acid ester copolymer has a carboxyl group in which a reactive group such as an ethylenically unsaturated group is introduced into the side chain from the viewpoint of achieving both the developability of negative resist and film properties such as heat resistance, hardness, and chemical resistance. Containing (meth)acrylic acid ester copolymers are also preferably used. As a method of introducing an ethylenically unsaturated group into the above side chain, for example, a carboxyl group-containing (meth)acrylic acid ester copolymer having an epoxy group and an ethylenically unsaturated group in a molecule such as glycidyl (meth)acrylate is part of the carboxyl group. A method of adding a compound, a method of adding a monocarboxylic acid containing an ethylenically unsaturated group such as methacrylic acid to a (meth)acrylic acid ester copolymer containing an epoxy group and a carboxyl group, or a copolymerization of a (meth)acrylic acid ester containing a hydroxyl group and a carboxyl group. and 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 water.

The carboxyl group-containing epoxy acrylate resin is preferably a compound obtained by 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 (o, m, p-) cresol novolak-type epoxy resin, phenol novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and trisphenolmethane-type epoxy resin. , bisphenyl fluorene type epoxy resin, etc. Epoxy resins may be used individually or two or more types may be used in combination.

Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and itaconic anhydride can be mentioned.

Additionally, when synthesizing a carboxyl group-containing epoxy acrylate resin, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride can be used and the acid anhydride group remaining after the reaction can be hydrolyzed to increase the carboxyl group. Additionally, the ethylenic double bond can be further increased by using maleic anhydride containing an ethylenically unsaturated group.

The acid value of the alkali-soluble resin (c) is preferably 20 to 300 mgKOH/g, and more preferably 40 to 180 mgKOH/g. When the acid value is less than 20 mgKOH/g, it is not preferable because the solubility in aqueous alkaline solution is insufficient and development of unexposed areas becomes difficult. Additionally, if 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 (c) is preferably 1,000 to 100,000, and preferably 1,500 to 30,000. If the weight average molecular weight is less than 1,000, it is not preferable because the heat resistance and hardness of the exposed area are insufficient. When the weight average molecular weight is greater than 100,000, it is not preferable because development of unexposed areas may become difficult. Additionally, the weight average molecular weight can be measured by gel permeation chromatography (GPC). As an example, HLC-8220GPC (manufactured by Tosoh Corporation) was used as a GPC device, three TSKgelHZM-M (manufactured by Tosoh Corporation) were used as columns, tetrahydrofuran was used as a developing solvent, column temperature was 40°C, flow rate was 0.3 milliliter/min, RI Chromatography can be performed under the conditions of a detector, a sample injection concentration of 0.5% by mass, and an injection amount of 10 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.

Moreover, the proportion of (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 above ratio is less than 10% by mass, developability is insufficient, so it is not preferable. When the above ratio is more than 70% by mass, the reproducibility of the pattern shape and heat resistance decrease, so it is not preferable.

In addition, the alkali-soluble resin (c) above can be obtained by isolating and purifying the alkali-soluble resin, which is an active ingredient, after the synthesis reaction. In addition, the reaction solution obtained through the synthesis reaction, its dried product, etc. can also be used as is.

＜Other ingredients＞

By using a curing accelerator as the other component, the polymerizable composition can be cured by heating at a low temperature. As the curing accelerator, for example, amine compounds, thiourea compounds, 2-mercaptobenzimidazole-based compounds, orthobenzoixulfimide, fourth-period transition metal compounds, etc. can be used. A hardening accelerator may be used individually, or two or more types may be used together.

The amine compound is preferably a tertiary amine, for example, N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-bis(2-hydroxy Ethyl)-p-toluidine, 4-(dimethylamino)ethyl benzoate, 4-dimethylaminobenzoate (2-methacryloyloxy)ethyl, etc. are mentioned.

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

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

The fourth period transition metal compound may be selected from organic acid salts or metal chelate compounds such as vanadium, cobalt, and copper, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, and copper acetyl. Acetonate, manganese acetylacetonate, vanadyl acetylacetonate, etc. can be mentioned.

The curing accelerator is preferably mixed immediately before using the polymerizable composition. The content of the curing accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b).

As the other components mentioned above, the polymerizable composition can be blended with additives that are generally used for applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, and various photoresists such as color resists and black resists. Additives include, for example, sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin) , acridine orange, camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorber, infrared absorber , chain transfer agents, light stabilizers, antioxidants, leveling agents, surface conditioners, surfactants, thickeners, anti-foaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, colored dyes, fluorescent dyes. , pigments (organic pigments, inorganic pigments), carbon-based materials (carbon fiber, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoil, carbon nanohorn, carbon airgel, etc.) , metal 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, etc. can be mentioned. Additives may be used individually or two or more types may be used in combination.

The content of the additive is appropriately selected depending on the purpose of use and is not particularly limited, but is usually preferably 500 parts by mass or less, and more preferably 100 parts by mass or less, with respect to 100 parts by mass of the radically polymerizable compound (b). do.

A solvent may be further added to the polymerizable composition to improve viscosity, paintability, and smoothness of the cured film. The solvent is capable of dissolving or dispersing the (a) polymerization initiator, (b) the radically polymerizable compound, (c) the alkali-soluble resin, and the other components, and is a solvent that volatilizes at a drying temperature, There is no particular limitation.

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. Examples include solvents such as propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether. Solvents may be used individually or two or more types may be used in combination.

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

<Method for preparing polymerizable composition>

When preparing the polymerizable composition, the polymerization initiator (a), the radical polymerizable compound (b), and, if necessary, the alkali-soluble resin (c) and the other components are added into a storage container, and then painted. It may be dissolved or dispersed according to a conventional method using a shaker, bead mill, sand grind mill, ball mill, attritor mill, two-bone roll mill, three-bone roll mill, etc. Additionally, if necessary, filtration may be performed through a mesh or membrane filter, etc.

In addition, in the preparation of the polymerizable composition, the polymerization initiator (a) may be added to the polymerizable composition from the beginning, but when the polymerizable composition is stored for a relatively long time, the polymerization initiator (a) is added immediately before use. (b) It is preferable to dissolve or disperse in a composition containing a radically polymerizable compound.

<Method for producing hardened 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 that includes any of the steps of applying the polymerizable composition to a substrate and then irradiating the polymerizable composition with active energy rays and heating the polymerizable composition. Additionally, a process including both the step of irradiating with the active energy ray and the step of heating is also called a dual cure process.

Examples of the application method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, and offset printing. , inkjet printing, and dispenser printing. Additionally, the substrate may be, for example, a film or sheet made of glass, silicon wafer, metal, or plastic, or a three-dimensional molded product, and the shape of the substrate is not limited.

The step of irradiating the polymerizable composition with active energy rays includes (a) decomposing the polymerization initiator and (b) polymerizing the radically polymerizable compound by irradiating the polymerizable composition with active energy rays such as electron beams, ultraviolet rays, visible rays, and radiation. By doing so, a cured product can be obtained.

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

Light sources for the irradiation of the light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet electrodeless lamps, light-emitting diodes (LEDs), xenon arc lamps, carbon arc lamps, sunlight, YAG lasers, etc. Solid-state lasers, semiconductor lasers, gas lasers such as argon lasers, etc. can be used. In addition, (a) when using light from visible light to infrared light, which is less absorbed by the polymerization initiator, curing can be performed by using a sensitizer that absorbs the light as the additive.

The exposure amount of the active energy ray must 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 . In addition, as a method for producing the cured product described above, when a dual cure process is applied and a heating process is performed after the process of irradiating with active energy rays, (a) the polymerization initiator is completely decomposed by the active energy rays, To avoid wasting it, the exposure amount must be set appropriately.

In the step of heating the polymerizable composition described above, a cured product can be obtained by (a) decomposing the polymerization initiator and (b) polymerizing the radically polymerizable compound by heat.

In the step of heating the polymerizable composition, examples of heating methods include heating, ventilation heating, and the like. The heating method is not particularly limited, and examples include oven, hot plate, infrared irradiation, and electromagnetic wave irradiation. In addition, examples of ventilation heating methods include a blowing drying oven and the like.

In the process of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of (a) the polymerization initiator. However, if the decomposition rate is too fast, the decomposition residue of the (b) radically polymerizable compound may increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of the polymerization initiator (a), so curing requires a longer time. Therefore, the heating temperature and heating time must be appropriately set depending on the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230°C, and more preferably 100 to 160°C. In addition, when blending the curing accelerator in the polymerizable composition, the heating temperature can be arbitrarily adjusted from room temperature to 160°C depending on the type or blending amount. Meanwhile, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.

As a method for producing the cured product, when applying the dual cure process, in particular, a heating process is performed after the process of irradiating the polymerizable composition with active energy rays to increase the coloring pigment that absorbs or scatters light at a high concentration. This is preferable because curing can be carried out efficiently in the deep part of the coating film of the polymer composition containing it or in points where light does not reach due to shading.

In addition, when the polymer composition includes the solvent, the method for producing the cured product may include a drying process. In particular, when applying the step of applying the polymerizable composition to a substrate and subsequently irradiating it with the active energy ray, it is preferable to provide a drying step before the step of irradiating the polymerizable composition with the active energy ray.

In the drying process, examples of methods 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 include oven, hot plate, infrared irradiation, and electromagnetic wave irradiation. Moreover, as a method of ventilation heating drying, a ventilation type drying oven etc. are mentioned, for example.

In addition, in the drying process, the temperature of the polymerizable composition is lowered than the set temperature for drying due to the latent heat of evaporation of the solvent, so a long time until the polymerizable composition gels can be ensured. Since the time until gelation also affects the drying method and film thickness, the drying temperature and time, including the selection of solvent, must be set appropriately. As an example, the drying temperature is preferably 20 to 120°C, and more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. Additionally, by using the polymerization inhibitor, a longer time until gelation can be ensured. In addition, the triazine peroxide derivative is decomposed by heat, but the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%, so under these conditions, the polymerizable composition is unlikely to thicken or gel. .

The dry film thickness (film thickness of the cured product) of the polymerizable composition is appropriately set depending on the application, but is preferably 0.05 to 300 μm, and more preferably 0.1 to 100 μm.

＜Pattern formation method＞

When the polymerizable composition includes (c) an alkali-soluble resin, a pattern can be formed by photolithography. In the same manner as above, the polymerizable composition is applied to the substrate and, if necessary, dried to form a dry film. Then, by irradiating the dried film with active energy rays through a mask, the radically polymerizable compound (b) polymerizes in the exposed area to form a cured film. On the other hand, a high-precision pattern shape can also be manufactured without a mask through direct drawing using a laser.

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

The polymerizable composition of the present invention is a hard coat agent, a coating agent for optical disks, a coating agent for optical fibers, a paint for mobile terminals, a paint for home appliances, a paint for cosmetic containers, an inner anti-reflection paint for optical elements, and a high/low refractive index. Paints and coating agents such as coating agents, heat-insulating coating agents, heat-dissipating coating agents, and anti-fog agents; Printing inks such as offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, conductive ink, insulating ink, and light guide plate ink; photosensitive printing plate; nano imprint material; Resin for 3D printers; Holographic recording material; Dental materials; Materials for waveguides; Black stripe for lens seat; Green sheets and electrode materials for condensers; Adhesives and sealants such as adhesives for FPDs, adhesives for HDDs, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch panels, and OCR for touch panels; Resists for FPD, such as color resist, black resist, protective film for color filters, photo spacer, black column spacer, frame resist, photoresist for TFT wiring, and interlayer insulation film; Resists for printed circuit boards, such as liquid solder resist and dry film resist; It can be used for various purposes such as semiconductor materials such as semiconductor resists and buffer coat films, and there are no particular restrictions on its use.

Example

<Synthesis Example 1-8>

(1) Synthesis of triazine peroxide derivatives

[Synthesis Example 1: Synthesis of Compound 19]

3.03 g (16.3 mmol) of diphenyl sulfide and 30 mL of dehydrated dichloromethane were added to a 100 mL eggplant flask, and cooled to 0°C. After adding 3.00 g (16.3 mmol) of cyanuric chloride, 2.39 g (17.9 mmol) of aluminum chloride was added over 10 minutes, and reaction was performed at 0°C for 3 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure to obtain a crude body. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 4/1 to 2/1) to obtain 5.03 g (yield 92.6%) of 2,4-dichloro-6-(4-phenylthio-1- Phenyl)-1,3,5-triazine was obtained.

Add 3.00 g (8.98 mmol) of 2,4-dichloro-6-(4-phenylthio-1-phenyl)-1,3,5-triazine and 30 mL of methyl ethyl ketone to a 100 mL eggplant flask, and add 40 mL of methyl ethyl ketone. Warmed to ℃. After adding 4.67 g of ion-exchanged water and 4.31 g (26.9 mmol) of 25% by mass aqueous sodium hydroxide solution, 0.32 g (9.87 mmol) of methanol was added dropwise over 10 minutes, and reaction was performed at 40°C for 2 hours. 1.29 g (9.87 mmol) of a 69% by mass tert-butylhydroperoxide aqueous solution was added dropwise over 10 minutes at 40°C or lower, and reacted at 40°C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 2.60 g (yield 75.5%) of Compound 19 of the present invention. The results of analysis of the obtained compound 19 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 2: Synthesis of Compound 25]

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. The results of analysis of the obtained compound 25 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 3: Synthesis of Compound 35]

In a heat-dried 100 mL three-necked flask, 0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and stirred at room temperature. A mixed solution of 4.29 g (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and 15 mL of dehydrated tetrahydrofuran was added dropwise, followed by refluxing and stirring for 1 hour. 3.00 g (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added to a separate 100 mL three-necked flask, and cooled to 0°C. The mixed solution prepared previously was added dropwise over 30 minutes, raised to room temperature, and stirred for 15 hours. The reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added, stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. The oil phase was washed once with saturated saline solution and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1), and 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxy) was obtained. Cibiphenyl)]-1,3,5-triazine was obtained.

Add 1.20 g (3.62 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine and 10 mL of methyl ethyl ketone to a 50 mL eggplant flask. , warmed to 40°C. After adding 1.88 g of ion-exchanged water and 1.74 g (10.9 mmol) of a 25% by mass aqueous sodium hydroxide solution, 0.13 g (3.98 mmol) of methanol was added dropwise over 5 minutes, and the mixture was allowed to react at 40°C for 2 hours. 0.52 g (3.98 mmol) of a 69% by mass tert-butylhydroperoxide aqueous solution was added dropwise over 5 minutes at 40°C or lower, and reaction was performed at 40°C for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was added to 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 1.04 g (yield 75.0%) of compound 35 of the present invention. The results of analysis of the obtained compound 35 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 4: Synthesis of Compound 48]

Compound 48 of the present invention is the same as described in Synthesis Example 3, except that methanol as described in Synthesis Example 3 is changed to ethanol, and the 69 mass% tert-butylhydroperoxide aqueous solution is changed to an 85 mass% tert-amylhydroperoxide solution. It was synthesized according to the method. The results of analysis of the obtained compound 48 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 5: Synthesis of Compound 53]

Compound 53 of the present invention was prepared according to Synthesis Example 3, except that methanol as described in Synthesis Example 3 was changed to isopropyl alcohol, and the 69 mass% tert-butylhydroperoxide aqueous solution was changed to a 90 mass% tert-hexylhydroperoxide solution. It was synthesized according to the method described in . The results of analysis of the obtained compound 53 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 6: Synthesis of Compound 56]

Compound 6 of the present invention was prepared in Synthesis Example 3, except that the methanol described in Synthesis Example 3 was changed to tert-butyl alcohol, and the 69 mass% tert-butylhydroperoxide aqueous solution was changed to 80 mass% cumene hydroperoxide solution. It was synthesized according to the described method. The results of analysis of the obtained compound 56 by EI-MS and ¹ H-NMR are shown in Table 1.

[Synthesis Example 7: Synthesis of Compound 77]

In a heat-dried 100 mL three-necked flask, 0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were added, and stirred at room temperature. A mixed solution of 4.29 g (16.3 mmol) of 4-bromo-4'-methoxybiphenyl and 15 mL of dehydrated tetrahydrofuran was added dropwise, followed by refluxing and stirring for 1 hour. 3.00 g (16.3 mmol) of cyanuric chloride and 15 mL of dehydrated tetrahydrofuran were added to a separate 100 mL three-necked flask, and cooled to 0°C. The mixed solution prepared previously was added dropwise over 30 minutes, raised to room temperature, and stirred for 15 hours. The reaction solution was cooled in an ice bath, 1 M hydrochloric acid was added, stirred, and the pH was adjusted to 8 with saturated aqueous sodium bicarbonate solution. Then, extraction was performed with ethyl acetate. The oil phase was washed once with saturated saline solution and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1), and 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4-(4'-methoxy) was obtained. Cibiphenyl)]-1,3,5-triazine was obtained.

In a 100 mL eggplant flask, 3.03 g (16.3 mmol) of anisole and 30 mL of dehydrated dichloromethane were added, and the mixture was cooled to 0°C. Here, 3.00 g (16.3 mmol) of 2,4-dichloro-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine was added, and then 2.39 g (17.9 mmol) of aluminum chloride was added. ) was added over 10 minutes and reacted at 0°C for 3 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice-cooled 1 M hydrochloric acid, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, the product was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 4/1 to 2/1) to obtain 5.03 g (yield 92.6%) of 2-chloro-4-(4-methoxyphenyl)-6-. [4-(4'-methoxybiphenyl)]-1,3,5-triazine was obtained.

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

[Synthesis Example 8: Synthesis of Compound 81]

In a 100 mL eggplant flask, 3.00 g (16.3 mmol) of cyanuric chloride, 30 mL of dehydrated dichloromethane, and 4.35 g (32.6 mmol) of aluminum chloride were added and cooled to 20°C. Here, 5.16 g (32.6 mmol) of 1-methoxynaphthalene was added over 15 minutes, and reaction was performed at 20°C for 3 hours. After completion of the reaction, the reaction solution was cooled to 0°C, 50 mL of ice-cooled 1 M hydrochloric acid was added, stirred, and the aqueous phase was separated. The oil phase was washed with 50 mL of saturated saline solution and dehydrated with anhydrous sodium sulfate. After filtration, the product was concentrated under reduced pressure to obtain 5.48 g (78.6% yield) of crude 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine.

3.00 g (5.45 mmol) of crude 2-chloro-4,6-bis(4-methoxy-1-naphthalenyl)-1,3,5-triazine and 30 mL of tetrahydrofuran in a 100 mL eggplant flask. was added and warmed to 40°C. A mixture of 2.18 g (10.9 mmol) of 20 mass% sodium hydroxide aqueous solution and 1.42 g (10.9 mmol) of 69 mass% tert-butylhydroperoxide aqueous solution was added dropwise over 10 minutes and allowed to react at 40°C for 4 hours. After completion of the reaction, 50 mL of dichloromethane was added, and the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0°C. After filtration, it was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (using dichloromethane) to obtain 1.63 g (yield 62.3%) of compound 81 of the present invention. The results of analysis of the obtained compound 81 by EI-MS and ¹ H-NMR are shown in Table 1.

<Examples 1 to 8, Comparative Example 1>

<Preparation of polymerizable composition (A)>

The amounts of the radically polymerizable compound, alkali-soluble resin, and other components shown in Table 2 were mixed and stirred, a polymerization initiator was added, and the mixture was stirred well to prepare the polymerizable composition (A) of Examples 1 to 8 and Comparative Example 1. did. In addition, in Comparative Example 1, compound R1 represented by the following formula was used as a polymerization initiator.

[Formula 7]

In Table 2 above and Table 4 and Table 6 below, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (brand name: Aronix M-402, manufactured by Toa Synthetic Company);

RD200 is a copolymer of methyl methacrylate/methacrylic acid/cyclohexylmaleimide (mass%: 61/14/25), weight average molecular weight: 17,000, acid value: 90 (synthetic product);

F-477 silver, fluorine-based leveling agent (brand name: Megapak F-477, manufactured by DIC);

PGMEA is propylene glycol monomethyl ether acetate; represents.

(1) Evaluation of sensitivity

The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After application, the aluminum substrate was dried in a clean oven at 90°C for 2.5 minutes to dry the solvent, thereby producing a uniform coating film with a thickness of 1.5 μm. Next, step exposure was performed in the range of 10 to 1000 mJ/cm ² through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The aluminum substrate after exposure was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The lowest exposure amount at which a resist pattern is formed was evaluated as “sensitivity.” The smaller the value of the minimum exposure amount, the more it is possible to form a pattern with a small amount of light, and 200 mJ/cm ² or less indicates 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, shielded from light with aluminum foil, and left to stand in a constant temperature thermostat set at 50°C. The number of days required for gelation was designated as ○ if it was 60 days or more, and × if it was less than 60 days. The results are shown in Table 3.

<Examples 9 to 16, Comparative Example 2>

<Preparation of polymerizable composition (B)>

The amounts of the radically polymerizable compound, alkali-soluble resin, black pigment, and other components shown in Table 4 were mixed and stirred, a polymerization initiator was added, and the polymerizable compositions of Examples 9 to 16 and Comparative Example 2 (B) were stirred well. ) was prepared. Additionally, in Comparative Example 2, compound R1 represented by the above formula was used as a polymerization initiator.

In Table 4 above, TSG-BK133 represents a carbon black dispersion (manufactured by Taisei Chemical Co., Ltd.).

(3) Evaluation of resolution

The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After application, the solvent was dried by drying the glass substrate in a clean oven at 90°C for 2.5 minutes to produce a uniform coating film with a thickness of 1.5 μm. Next, 200 mJ/cm ² exposure was performed through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The glass substrate after exposure was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The obtained pattern was observed under a microscope, and those with a minimum pattern dimension of 10 ㎛ or less were designated ◎, those with a minimum pattern dimension of more than 10 ㎛ and 20 ㎛ or less as ○, those with a minimum pattern dimension of more than 20 ㎛ and 30 ㎛ or less as △, and those with a minimum pattern dimension of more than 30 ㎛ as ×. The results are shown in Table 5.

<Examples 17 to 24, Comparative Example 3>

<Preparation of polymerizable composition (C)>

The radically polymerizable compound, alkali-soluble resin, green pigment, and other components in the amounts shown in Table 6 were mixed and stirred, a polymerization initiator was added, and the polymerizable composition (C) of Examples 17 to 24 and Comparative Example 3 was stirred well. ) was prepared. Additionally, in Comparative Example 3, compound R1 represented by the above formula was used as a polymerization initiator.

In Table 6 above, SG036 represents a green pigment dispersion (manufactured by Taisei Chemical Co., Ltd.).

(4) Evaluation of undercut

The polymerizable composition (C) prepared above was applied onto a glass substrate using a spin coater. After application, the solvent was dried by drying the glass substrate in a clean oven at 90°C for 2.5 minutes to produce a uniform coating film with a thickness of 1.5 μm. Next, 150 mJ/cm ² exposure was performed through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The glass substrate after exposure was immersed in a 1.0% by mass aqueous solution of sodium carbonate at 23°C for 60 seconds, and the unexposed portion was removed by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. Among the obtained patterns, the cross section of the pattern corresponding to the line-shaped opening with an opening width of 15 μm was observed under a microscope, and the undercut of the line-shaped pattern was evaluated by the difference between the maximum and minimum widths among the pattern widths parallel to the substrate surface. . The smaller the difference between the maximum width and the minimum width, the more suppressed the undercut is. 1.5 ㎛ or less was designated as ○, greater than 1.5 ㎛ and 2.5 ㎛ or less was designated as △, and greater than 2.5 ㎛ was designated as ×. The results are shown in Table 7.

<Examples 25 to 32, Comparative Example 4>

<Preparation of polymerizable composition (D)>

The amounts of the radically polymerizable compound, polymerization initiator, curing accelerator, and solvent shown in Table 8 were added and stirred well to prepare the polymerizable composition (D) of Examples 25 to 32 and Comparative Example 4. Additionally, in Comparative Example 4, compound R1 represented by the above formula was used as a polymerization initiator.

(5) Evaluation of hardenability

The polymerizable composition (D) prepared above was applied to a thickness of 100 μm on a glass substrate using a bar coater. After application, it was dried in an oven at 90°C for 2.5 minutes, and then irradiated at 30 mJ/cm ² using a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp. Next, it was heated in a 150 degreeC oven for 30 minutes, and the cured film was obtained. The polymerization conversion rate of the obtained cured film was measured, and curability was evaluated based on the following standards. In addition, the polymerization conversion rate was measured by attenuated total reflection infrared spectroscopy (ATR-IR), and the peak area A of the absorption spectrum (810 cm ^-1 ) derived from the double bond group and the absorption spectrum derived from the carbonyl group that did not change before and after exposure were measured. Using the peak area B of (1740 cm ^-1 ), the polymerization conversion rate was calculated based on the following formula. The results are shown in Table 9.

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

○: Polymerization conversion rate is 80% or more

△: Polymerization conversion ratio is 60% or more and less than 80%

×: Polymerization conversion rate is less than 60%

In Table 8 above, TMPTA is trimethylolpropane triacrylate (manufactured by Shinnakamura Chemical Industry);

PE4A is pentaerythritol tetraacrylate (Fujifilm Wako Pure Chemical Reagent); represents.

Claims (6)

General formula (1):

((In General Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an aliphatic hydrocarbon group with 1 to 5 carbon atoms or an aromatic hydrocarbon group with 6 to 9 carbon atoms which may have an alkyl group, and R ⁴ is an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms, and an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms. As an acyl group, -YR, or -N-RR', Y represents an oxygen atom or a sulfur atom, and R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a substituted Ar represents an aromatic hydrocarbon group of optionally 6 to 20 carbon atoms or a heterocyclic ring-containing group of optionally substituted carbon atoms of 2 to 20. Ar is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , or Ar ³ . )

(In General Formula (2), m represents an integer of 0 to 3, and R ¹¹ is an independent substituent, which may be an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group with 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, -YR, or -N-RR', where Y represents an oxygen atom or a sulfur atom, R and R' independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group with 2 to 20 carbon atoms.) ) A triazine peroxide derivative characterized by being represented by . A polymerizable composition comprising (a) a polymerization initiator containing the triazine peroxide derivative according to claim 1, and (b) a radically polymerizable compound. According to claim 2,
A polymerizable composition further comprising (c) an alkali-soluble resin. A cured product formed from the polymerizable composition according to claim 2 or 3. A method for producing a cured product according to claim 4, comprising the step of irradiating the polymerizable composition with active energy rays. A method for producing the triazine peroxide derivative according to claim 1, comprising:
A method for producing a triazine peroxide derivative, comprising the step of reacting cyanuric chloride and/or its derivatives with hydroperoxide as a raw material.