WO2018221177A1

WO2018221177A1 - Triazine peroxide derivative and polymerizable composition containing said compound

Info

Publication number: WO2018221177A1
Application number: PCT/JP2018/018484
Authority: WO
Inventors: 昌樹林; 諒介糸山; 章世矢野
Original assignee: 日油株式会社
Priority date: 2017-06-01
Filing date: 2018-05-14
Publication date: 2018-12-06
Also published as: CN110662738A; KR20200015496A; KR102542689B1; TWI762648B; JPWO2018221177A1; CN110662738B; TW201902881A; JP7021668B2

Abstract

A triazine peroxide derivative represented by general formula (1) (in formula (1), R1 and R2 independently represent a methyl group or ethyl group, R3 represents a C1-5 aliphatic hydrocarbon group or a C6-9 aromatic hydrocarbon group optionally having an alkyl group, n represents an integer of 0-2, and X represents an aryl group represented by Ar1, Ar2, Ar3, or Ar4 in general formula (2)) (in formula (2), m represents an integer of 0-3, R4 is an independent substituent and is a C1-18 alkyl group, a substituent represented by R5-Y- in general formula (3), a nitro group, or a cyano group, Y represents an oxygen atom or sulfur atom, and R5 represents a C1-18 hydrocarbon group optionally having one or more of an ether bond, thioether bond, and end hydroxyl group in the carbon backbone, a C6-9 aromatic hydrocarbon group optionally having an alkyl group, or a C1-8 acyl group. Alternatively, R4 represents a hydrocarbon group that forms a 5- or 6-membered ring with two adjacent R5-Y- in general formula (3).)). This triazine peroxide derivative has both photopolymerizability capable of efficiently absorbing light emitted from a lamp of a wavelength of 365 nm or the like and generating radicals, and thermal polymerizability capable of generating radicals by heat, and can also lower the yellowness of a cured product.

Description

Triazine peroxide derivative, polymerizable composition containing the compound

The present invention relates to a triazine peroxide derivative, a polymerizable composition containing a polymerization initiator containing the compound and a radical polymerizable compound, a cured product thereof, and a method for producing the cured product.

In order to synthesize polymers and the like, radical polymerization initiators that generate radicals by heat, light or oxidation-reduction are widely used as polymerization initiators. In particular, the photopolymerization initiator can generate a radical by bond cleavage or hydrogen abstraction reaction by absorbing active energy rays such as light, and is used as a polymerization initiator for a radical polymerizable compound. For example, α-hydroxyacetophenone derivatives, α-aminoacetophenone derivatives, acylphosphine oxide derivatives, halomethyltriazine derivatives, benzyl ketal derivatives, thioxanthone derivatives, and the like are used.

Since the photopolymerizable composition comprising the photopolymerization initiator and the radical polymerizable compound as described above is quickly cured by light irradiation, from the viewpoint of fast curability and low VOC, a coating agent, paint, printing ink, It is applied to applications such as photosensitive printing plates, adhesives, and various photoresists.

On the other hand, Patent Document 1 discloses a polymerization initiator containing, as an active ingredient, a benzophenone group-containing peroxyester having a peroxide bond (—O—O—) in a molecule that generates radicals by light or heat. Further, Patent Document 2 discloses an adhesive composition comprising the polymerization initiator and a radical polymerizable compound, and by dual cure that performs curing by irradiation with light at room temperature and subsequent curing by heating, The adhesive exhibits strong adhesive strength and high durability.

Thus, the dual cure type polymerizable composition having both photopolymerizability and thermal polymerizability can also be used for improving dark part curability. Dual cure type polymerizable compositions include, for example, curing of polymerizable compositions containing light-absorbing and scattering pigments and fillers at high concentrations, and black frames and touch panels around protective covers in flat panel display manufacturing processes. It is also effective for curing areas where light does not reach, such as the bottom of electrodes.

For example, Patent Document 3 discloses a halomethyltriazine derivative having a specific structure as a photopolymerization initiator having a triazine skeleton, and is known to be effective for photopolymerization.

JP 59-197401 A JP 2000-96002 A Japanese Patent Laid-Open No. 54-074887

However, the benzophenone group-containing peroxyesters described in Patent Document 1 and Patent Document 2 do not sufficiently absorb light having a wavelength of 365 nm or the like emitted from a high-pressure mercury lamp or LED, and are therefore the most important photopolymerization initiator. Sensitivity, which is a basic characteristic, is not sufficient, and improvement of sensitivity is a problem.

On the other hand, halomethyltriazine derivatives described in Patent Document 3 and the like cannot be used for thermal polymerization, and a cured film obtained using the compound as a photopolymerization initiator has high yellowness. Therefore, the said compound cannot be used as a polymerization initiator of the use as which high transparency is requested | required, such as a surface protection sheet of a display, for example, The reduction of yellowness is mentioned as a subject.

Therefore, in order to solve the above problems, the present invention is capable of generating radicals by efficiently absorbing light having a wavelength of 365 nm emitted from a lamp such as a high-pressure mercury lamp or LED, and generating radicals by heat. Further, the present invention provides a triazine peroxide derivative that has both heat-polymerizable properties and that can reduce the yellowness of a cured product.

Furthermore, the present invention provides a polymerizable composition containing a polymerization initiator containing the triazine peroxide derivative and a radical polymerizable compound, a cured product thereof, and a method for producing the cured product.

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

(In the formula (1), R ¹ and R ² are each independently a methyl group or an ethyl group, R ³ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted alkyl group having 6 to 6 carbon atoms. 9 represents an aromatic hydrocarbon group of 9, n represents an integer of 0 to 2, and X is an aryl group represented by the general formula (2): Ar ¹ , Ar ² , Ar ³ , or Ar ⁴ .

(In the formula (2), m represents an integer of 0 to 3, R ⁴ is an independent substituent, an alkyl group having 1 to 18 carbon atoms, represented by the general formula (3): R ⁵ —Y— Represents a substituent, a nitro group, or a cyano group, and Y represents an oxygen atom or a sulfur atom, and R ⁵ represents any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. Or a hydrocarbon group having 1 to 18 carbon atoms which may have one or more, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms Or R ⁴ represents a triazine peroxide derivative represented by two adjacent general formulas (3): a hydrocarbon group that forms a 5- to 6-membered ring by R ⁵ —Y—.

The present invention also includes a polymerizable composition containing (a) a polymerization initiator and (b) a radical polymerizable compound containing the triazine peroxide derivative, a cured product formed from the polymerizable composition, and the curing The present invention relates to a method for manufacturing a product.

The triazine peroxide derivative of the present invention can efficiently generate radicals by efficiently absorbing light having a wavelength of 365 nm or the like emitted from a lamp such as a high-pressure mercury lamp or LED, and has a peroxide bond in the molecule. And useful as a thermal polymerization initiator. Therefore, the polymerizable composition containing the triazine peroxide derivative and the radical polymerizable compound can be cured well by light irradiation and can be cured well by heat even in a dark part where light does not reach.

In addition, halomethyltriazine derivatives release chloro radicals by photolysis, and aromatic chlorides as a by-product are presumed to be the cause of coloration, but the triazine peroxide derivatives of the present invention do not contain chlorine atoms, so The yellowness of the product can be reduced.

<Triazine peroxide derivative>
The triazine peroxide derivative of the present invention can be represented by the following general formula (1).

(In the formula (2), m represents an integer of 0 to 3, R ⁴ is an independent substituent, an alkyl group having 1 to 18 carbon atoms, represented by the general formula (3): R ⁵ —Y— Represents a substituent, a nitro group, or a cyano group, and Y represents an oxygen atom or a sulfur atom, and R ⁵ represents any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. Or a hydrocarbon group having 1 to 18 carbon atoms which may have one or more, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms Alternatively, R ⁴ represents a hydrocarbon group forming a 5- to 6-membered ring by the two adjacent general formulas (3): R ⁵ —Y—.

In the general formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. R ¹ and R ² are preferably methyl groups from the viewpoint of increasing the storage stability of the polymerizable composition because the decomposition temperature of the triazine peroxide derivative is high.

In the general formula (1), R ³ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The alkyl group may be linear or branched. Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, and an isopropylphenyl group. Among these, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable from the viewpoint of easy 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 increased, and the methyl group and the ethyl group are more preferable from the viewpoint of high sensitivity to light of the lamp.

In the general formula (1), n is represented by an integer of 0 to 2. From the viewpoint of easy synthesis of the triazine peroxide derivative, n is preferably 0 or 1. When n is 0, X is Ar ² , Ar ³ , or Ar ⁴ , and when n is 1, X is Ar ¹ to efficiently absorb the light of the lamp and to obtain a cured product From the viewpoint that the yellowness of can be reduced, it is more preferable.

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

In the general formula (2), R ⁴ is an independent substituent, an alkyl group having 1 to 18 carbon atoms, a general formula (3): a substituent represented by R ⁵ —Y—, a nitro group Or Y represents an oxygen atom or a sulfur atom, and R ⁵ has one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. It represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms. Alternatively, R ⁴ represents a hydrocarbon group that forms a 5- to 6-membered ring by two adjacent general formulas (3): R ⁵ —Y—.

R ⁴ is an independent substituent from the viewpoint of efficiently absorbing the light of the lamp, and is an alkyl group having 1 to 8 carbon atoms, or a substituent represented by the general formula (3): R ⁵ —Y— Y represents an oxygen atom, and R ⁵ has 1 to 8 carbon atoms which may have any one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton. A hydrocarbon group or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R ⁴ is represented by two adjacent general formulas (3): R ⁵ —X— A hydrocarbon group forming a 5- to 6-membered ring is preferable.

Specific examples of R ⁴ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, octyl, 2- Alkyl groups such as ethylhexyl group, dodecyl group, octadecyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, Cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, 2-ethylhexyloxy group, dodecyloxy group, octadecyloxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2-hydroxyethyl) Toxi) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 3-hydroxy-n-propyloxy group, 3-methoxy-n-propyloxy group, 1,2-dihydroxypropyloxy group, methylenedioxy group, Alkoxy groups such as dimethylmethylenedioxy group and ethylenedioxy group; aryloxy groups such as phenyloxy group and 4-isopropylphenyloxy group; methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, Alkylsulfanyl groups such as 2- (2-methoxyethoxy) ethylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group, 2-methylphenylsulfanyl group, 4-methylphenylsulfanyl group, acetyl group, n-butanoyl group, 2- Ethylhe Sanoiru group, a benzoyl group, etc. acyl group such as a 2-methylbenzoyl group. The compound represented by the general formula (1) having these functional groups is preferable because it has high absorbance at a wavelength of 365 nm and efficiently absorbs light from the lamp.

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

The substitution position of R ⁴ is not particularly limited, but when X is Ar ¹ , it is preferable that at least one of R ⁴ is substituted at the 4-position of the benzene ring substituted with the triazine group, and X is Ar. ^In the case of ² , at least one of R ⁴ is preferably substituted at the 4-position of a benzene ring different from the benzene ring substituted with the triazine group. When X is Ar ³ , at least one of R ⁴ is it is preferable substituted in the 4-position of the substituted triazine group in the 1-position when X is Ar ^4, at least one R ⁴ is another benzene ring with the benzene ring to which a triazine group substituted The substitution at the 4-position is preferable in order to efficiently absorb the light of the lamp.

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

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

<Method for producing triazine peroxide derivative>
The method for producing the triazine peroxide derivative represented by the general formula (1) is obtained, for example, by a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as step (A)) as in the following reaction formula. And a method comprising reacting a cyanuric chloride derivative with hydroperoxide in the presence of an alkali (hereinafter also referred to as step (B)). In addition, after said process (A) and / or (B), the process of distilling off excess raw materials etc. (removal), and the refinement | purification process may be included.

(In the above reaction formula, n, R ¹ , R ² , R ³ and X are the same as in the general formula (1).)

In the step (B), a commercially available product can be used as the cyanuric chloride derivative. In addition, when there is no commercial item, in the said process (A), it can synthesize | combine according to well-known synthesis methods, such as a Grignard reaction, a lithiation reaction, a Suzuki coupling reaction, or Friedel-Crafts reaction.

<Synthesis of cyanuric chloride derivatives by Grignard reaction>
In the step (A), when a cyanuric chloride derivative is synthesized by a Grignard reaction, it can be synthesized according to a known synthesis method described in JP-A-6-179661. As the aromatic compound Z in the step (A), an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A cyanuric chloride derivative can be synthesized by preparing a Grignard reagent by reacting an aromatic compound with magnesium and then reacting the obtained Grignard reagent with cyanuric chloride.

In the preparation of the Grignard reagent, magnesium is preferably used in an amount of 0.8 to 2.0 mol, more preferably 1 to 1.5 mol, relative to 1 mol of the aromatic compound. As the reaction initiator, iodine, bromoethane, dibromoethane or the like may be used, and 0.0001 to 0.01 mol is preferably used with respect to 1 mol of the aromatic compound. The reaction temperature is preferably 0 to 70 ° C, more preferably 10 to 60 ° C. The reaction time is preferably 30 minutes to 20 hours, more preferably 1 hour to 10 hours.

In the preparation of the above Grignard reagent, for example, a solvent such as ethers such as tetrahydrofuran can be used.

In the reaction between the Grignard reagent and cyanuric chloride, 0.7 to 1.5 mol of cyanuric chloride is preferably used relative to 1 mol of the aromatic compound, and 0.8 to 1.2 mol is preferably used. More preferred. The reaction temperature is preferably −30 to 70 ° C., more preferably −10 to 40 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. The prepared Grignard reagent may be charged with cyanuric chloride, or the cyanuric chloride solution may be charged with Grignard reagent.

In the reaction of the Grignard reagent and cyanuric chloride, for example, a solvent such as ether such as tetrahydrofuran can be used.

<Synthesis of cyanuric chloride derivatives by lithiation reaction>
In the step (A), when a cyanuric chloride derivative is synthesized by a lithiation reaction, it can be synthesized according to a known synthesis method described in WO2012 / 096263. As the aromatic compound Z in the step (A), an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom can be used. A cyanuric chloride derivative can be synthesized by adjusting a lithio compound by reacting an aromatic compound and a lithiating agent, and then reacting the obtained lithio compound with cyanuric chloride.

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

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

In the preparation of the above-mentioned lithio compound, for example, a solvent such as ethers such as tetrahydrofuran can be used.

In the reaction of the above-mentioned lithio compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mol, and 0.8 to 1.2 mol of cyanuric chloride to 1 mol of the aromatic compound. More preferred. The reaction temperature is preferably −30 to 70 ° C., more preferably −10 to 40 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. It should be noted that cyanuric chloride may be added to the prepared lithio compound, or the lithium compound may be added to the cyanuric chloride solution.

In the reaction between the above-mentioned lithio compound and cyanuric chloride, for example, a solvent such as ethers such as tetrahydrofuran can be used.

<Synthesis of cyanuric chloride derivatives by Suzuki coupling>
In the step (A), when a cyanuric chloride derivative is synthesized by a Suzuki coupling reaction, it can be synthesized according to a known synthesis method described in WO2012 / 096263. For example, by reacting the above-mentioned lithio compound with a boron reagent, a boron compound in which Z of the aromatic compound is converted into a boronyl group or a boronic acid can be synthesized. Next, a cyanuric chloride derivative can be synthesized by reacting the obtained boron compound with cyanuric chloride. In addition, when the commercial item of a boron compound is sold, it can be used as it 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 above boron compound, the boron reagent is preferably used in an amount of 0.8 to 3.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the lithio compound. The reaction temperature is preferably −100 to 50 ° C., more preferably −80 to 20 ° C. The reaction time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 10 hours.

In the synthesis of the boron compound, for example, a solvent such as ethers such as tetrahydrofuran can be used.

In the reaction between the boron compound and cyanuric chloride, the cyanuric chloride is preferably used in an amount of 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, relative to 1 mol of the boron compound. preferable. The reaction temperature is preferably −30 to 70 ° C., more preferably −10 to 40 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Note that cyanuric chloride may be added to the boron compound, or the boron compound may be added to the cyanuric chloride solution.

In the reaction between the boron compound and cyanuric chloride, a palladium catalyst and an alkali are preferably used, and a ligand may be added as necessary.

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

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.

Examples of the ligand include organic compounds such as triphenylphosphine, tricyclohexylphosphine, 2,2′-bis (diphenylphosphino) -1,1′-binaphthalene, and 2-dicyclohexylphosphino-2,6′-dimethoxybiphenyl. Examples thereof include phosphorus-based ligands.

In the reaction of the above boron compound with cyanuric chloride, ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol and 2-propanol; aromatic hydrocarbons such as toluene and xylene; N, N-dimethyl Organic solvents such as amides such as formamide can be used. The said organic solvent may be used independently and may use 2 or more types together. Furthermore, a mixed solvent of the organic solvent and water can be used.

<Synthesis of cyanuric chloride derivatives by Friedel-Crafts reaction>
In the step (A), when a cyanuric chloride derivative is synthesized by Friedel-Crafts reaction, it can be synthesized according to a known synthesis method described in US Pat. The aromatic compound Z in the step (A) can be a hydrogen atom, and an aromatic compound represented by n = 0 can be used. A 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.

Examples of the Lewis acid include aluminum chloride, aluminum bromide, iron chloride (III), titanium chloride (IV), tin chloride (IV), zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, boron trifluoride. A diethyl ether complex or the like can be used.

In the reaction of the aromatic compound and cyanuric chloride, the cyanuric chloride is preferably used in an amount of 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, per mol of the aromatic compound. preferable. Aluminum chloride is preferably used in an amount of 1.0 to 3.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the aromatic compound. The reaction temperature is preferably −50 to 60 ° C., more preferably 0 to 40 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Aluminum chloride may be added to the solution of the aromatic compound and cyanuric chloride, or the aromatic compound may be added to the solution of cyanuric chloride and aluminum chloride.

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

<Synthesis of triazine peroxide derivative>
In the step (B), the method for producing the triazine peroxide derivative represented by the general formula (1) is not particularly limited, but according to the known method for synthesizing triazine peroxide described in Japanese Patent Publication No. 45-39468. Can be synthesized.

The triazine peroxide derivative is obtained by the step (B) of reacting the cyanuric chloride derivative obtained in the above step (A) with hydroperoxide in the presence of an alkali.

In the step (B), the hydroperoxide is preferably reacted in an amount of 1.8 mol or more, and 2.0 mol or more with respect to 1 mol of the cyanuric chloride derivative from the viewpoint of increasing the yield of the target product. And more preferably 5.0 mol or less, and more preferably 3.8 mol or less. Hydroperoxide is commercially available, and when there is no commercial product, it can be synthesized according to a known synthesis method described in JP-A No. 58-72557.

In the step (B), the reaction temperature is preferably −10 ° C. or higher, more preferably 0 ° C. or higher, and 40 ° C. or lower from the viewpoint of increasing the yield of the target product. Is preferable, and it is more preferable that it is 30 degrees C or less.

In the step (B), the reaction time varies depending on the raw materials, reaction temperature, etc., and thus cannot be determined unconditionally. However, from the viewpoint of increasing the yield of the target product, usually 10 minutes to 6 hours is preferable.

In the step (B), the alkali used is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, α-picoline, γ-picoline, Examples thereof include dimethylaminopyridine, triethylamine, tributylamine, N, N-diisopropylethylamine, 1,5-diazabicyclo [4.3.0] -5-nonene. The alkali is preferably used in an amount of 1.8 mol or more, more preferably 2.0 mol or more, with respect to 1 mol of the cyanuric chloride derivative, from the viewpoint of increasing the yield of the target product. It is preferable to use 0 mol or less, and it is more preferable to use 3.8 mol or less.

In the step (B), when the cyanuric chloride derivative is liquid, the reaction can be performed without using an organic solvent. Moreover, 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. For example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, tetrahydrofuran And ethers such as dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as methylene chloride and chloroform. The said organic solvent may be used independently and may use 2 or more types together.

The amount of the organic solvent used is usually about 30 to 500 parts by mass with respect to 100 parts by mass of the total amount of raw materials. The organic solvent may be removed after the step (B) to take out the triazine peroxide derivative, and the triazine peroxide derivative is used as a diluted product of the organic solvent in order to improve handling and reduce the risk of thermal decomposition. May be used.

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

As the purification step, in order to remove surplus raw materials and by-products, for example, ion-exchanged water or basic such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. A step of purifying the target product by washing with an aqueous solution, an aqueous sodium sulfite solution or the like can be mentioned.

<Polymerizable composition>
The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radical polymerizable compound. Furthermore, the polymerizable composition can impart developability by containing (c) an alkali-soluble resin. Moreover, the polymerizable composition can 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). The (a) polymerization initiator has a function of decomposing by active energy rays or heat, and the generated radicals start polymerization (curing) of the (b) radical polymerizable compound. A triazine peroxide derivative may be used independently and may use 2 or more types together.

The (a) polymerization initiator may contain a polymerization initiator other than the triazine peroxide derivative (hereinafter also referred to as other polymerization initiator). By using two or more types of triazine peroxide derivatives and other polymerization initiators having different absorption bands, the high sensitivity of the polymerizable composition, for example, for a lamp that emits light of multiple wavelengths such as a high-pressure mercury lamp Can be achieved. In addition, in consideration of the polymerizability of the (b) radical polymerizable compound contained in the polymerizable composition, the types of pigments that absorb or scatter light contained in the polymerizable composition, the film thickness of the cured product, etc. By using this polymerization initiator, the surface curability, deep part curability, transparency, etc. of the polymerizable composition can be improved.

As the other polymerization initiators, known ones can be used, such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4 ′-(2-hydroxyethoxy) -2-hydroxy. Α-Hydroxyacetophenone derivatives such as -2-methylpropiophenone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one 2-methyl-4′-methylthio-2-morpholinopropiophenone, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethyl Α-aminoacetoph such as amino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one Enone derivatives; acyl phosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (mesitylcarbonyl) phenylphosphinate; [4- (Phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyloxime), 1-[({1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester derivatives such as 3-yl] ethylidene} amino) oxy] ethanone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3 4-dimethoxystyryl) -4,6-bis (trichloromethyl) 1,3,5-triazine, 2- Halomethyltriazine derivatives such as 4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine; benzyl ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone; isopropyl Thioxanthone derivatives such as thioxanthone, benzophenone derivatives such as 4- (4-methylphenylthio) benzophenone; coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin); 2- ( Imidazole derivatives such as 2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole; , 4'-Tetrakis (tert-butylperoxycarbonyl) Zofenon, organic peroxides such as dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; camphor quinone and the like. Another polymerization initiator may be used independently and may use 2 or more types together.

The content of the (a) polymerization initiator is preferably 0.1 to 40 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound. More preferably, it is 1 to 15 parts by mass. If the content of the (a) polymerization initiator is less than 0.1 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound, the curing reaction does not proceed, which is not preferable. Further, when the content of (a) the polymerization initiator is more than 40 parts by mass with respect to 100 parts by mass of (b) radical polymerizable compound, the solubility in (b) radical polymerizable compound reaches saturation, and When (a) the crystal of the polymerization initiator is precipitated during film formation of the adhesive composition and the surface of the film becomes rough, or (a) the strength of the coating film of the cured product increases due to an increase in the decomposition residue of the polymerization initiator. Is not preferred because it may decrease.

In addition, when the said (a) polymerization initiator contains the said other polymerization initiator, it is preferable that the ratio of another polymerization initiator is 80 mass% or less in (a) polymerization initiator, and is 50 masses. More preferably, it is% or less.

<(B) Radical polymerizable compound>
As the radically polymerizable compound (b) of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of (b) radical polymerizable compounds include (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 and the like. Among these, it is preferable to contain (meth) acrylic acid esters having high reactivity. (B) A radically polymerizable compound may be used independently and may use 2 or more types together.

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, lauryl (meth) acrylate, stearyl (meth) Alkyl (meth) acrylates such as acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth) acrylic acid and alicyclic alcohols such as acrylate, 2-ethyl-2-adamantyl (meth) acrylate; aryl (meth) such as phenyl (meth) acrylate and benzyl (meth) acrylate Chryrate; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono (meth) ) Monomers having a hydroxy group such as 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-dioxolan-4-yl) methyl (meth) acrylate, (3 Monomers having a chain or cyclic ether bond such as ethyl oxetane-3-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, etc .; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acryloylmorpholine, N- Monomers having a nitrogen atom such as (meth) acryloyloxyethyl hexahydrophthalimide; monomers having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; glycidyl (meth) acrylate, 4- Monomers having an epoxy group such as droxybutyl (meth) acrylate glycidyl ether; Monomers having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; Silicon atoms such as 3- (meth) acryloxypropyltrimethoxysilane Monomers having 2,5,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, etc. Monomers having fluorine atoms; (meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono (2- (meth) acryloyloxyethyl), maleic acid mono (2- (meth) acryloyl) Oxyethyl), ω-carboxy-polycaprolactone mono (me A) Monomers having a carboxyl group such as 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, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin propoxytri (meth) acrylate, trimethylol ethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol Di (meth) acrylate monostearate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 9,9-bis (4- (2- (meta Esters of polyhydric alcohols such as) acryloyloxyethoxy) phenyl) fluorene, 9,9-bis (4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) fluorene, and (meth) acrylic acid Compound; Bis (4- (meth) acryloxy Phenyl) sulfide, bis (4- (meth) acryloylthiophenyl) sulfide, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene bis (meth) acrylamide, zinc (meth) acrylate, (meth) acrylic acid Zirconium, aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, polyester acrylate and the like can be mentioned.

The (meth) acrylic acid esters are used to improve the sensitivity of the polymerizable composition, reduce oxygen inhibition, and improve the mechanical strength and hardness, heat resistance, durability, and chemical resistance of the cured coating film. From the above, an ester compound of the polyhydric alcohol and (meth) acrylic acid is preferable, and in particular, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate is preferred.

In addition, the copolymer obtained from the said (b) radically polymerizable compound can be added to the said polymeric composition.

<(C) Alkali-soluble resin>
The polymerizable composition can be suitably used as a negative resist by further blending (c) an alkali-soluble resin. (C) As alkali-soluble resin, what is generally used for a negative resist can be used, and it will not be specifically limited if it is resin soluble in alkaline aqueous solution, However, It should be resin containing a carboxyl group. preferable. (C) Alkali-soluble resin may be used independently and may use 2 or more types together.

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

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

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

In addition, the carboxyl group-containing (meth) acrylic acid ester copolymer is a reaction of ethylenically unsaturated groups, etc., from the viewpoint of achieving both the developability of the negative resist and the film properties such as heat resistance, hardness, and chemical resistance. A carboxyl group-containing (meth) acrylic acid ester copolymer in which a functional group is introduced into the side chain is also preferably used. As a method for introducing an ethylenically unsaturated group into the above side chain, for example, a part of the carboxyl group of the carboxyl group-containing (meth) acrylic ester copolymer, an epoxy group in the molecule such as glycidyl (meth) acrylate And a method of adding a compound having an ethylenically unsaturated group, a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to an epoxy group- and carboxyl group-containing (meth) acrylic acid ester copolymer, And a method of adding a compound having an isocyanate group and an ethylenically unsaturated group in a molecule such as 2- (meth) acryloyloxyethyl isocyanate to a hydroxyl group- and carboxyl group-containing (meth) acrylic acid ester copolymer. .

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

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, trisphenol methane type epoxy resin, and bisphenyl fluorene. Type epoxy resin and the like. An epoxy resin may be used independently and may use 2 or more types together.

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

Furthermore, when synthesizing the carboxyl group-containing epoxy acrylate resin, if necessary, by using a tricarboxylic acid anhydride such as trimellitic anhydride, the acid anhydride group remaining after the reaction is hydrolyzed to obtain a carboxyl group. Can be increased. In addition, ethylenic double bonds can be increased by using maleic anhydride containing an ethylenically unsaturated group.

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

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

In addition, the ratio of (c) alkali-soluble resin is preferably 10 to 70% by mass, and more preferably 15 to 60% by mass in the total solid content of the polymerizable composition. When the ratio is less than 10% by mass, the developability is poor, which is not preferable. When the ratio is more than 70% by mass, the pattern shape reproducibility and heat resistance are lowered, which is not preferable.

The (c) alkali-soluble resin may be a product obtained by isolating and purifying an alkali-soluble resin which is an active ingredient after the synthesis reaction, or a reaction solution obtained by the synthesis reaction, a dried product thereof, or the like. You can also.

<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, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole compound, an orthobenzoixsulfimide, a fourth-period transition metal compound compound, or the like can be used. A hardening accelerator may be used independently and may use 2 or more types together.

The amine compound is preferably a tertiary amine, for example, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-bis (2-hydroxyethyl) -p- Toluidine, ethyl 4- (dimethylamino) benzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate and the like.

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

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

The compound of the fourth period transition metal compound can be selected from organic acid salts such as vanadium, cobalt, copper, or metal chelate compounds, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate. , Copper acetylacetonate, manganese acetylacetonate, vanadyl acetylacetonate and the like.

The curing accelerator is preferably blended immediately before using the polymerizable composition. The content of the curing accelerator is preferably 0.1 to 20 parts by mass and more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound.

As the other components, the polymerizable composition is generally used in applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, various photoresists such as color resists and black resists. Additives can be blended. Examples of additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4′-bis (diethylamino) benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibition Agents (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers, infrared absorbers, light stabilizers, antioxidants, leveling agents, surface conditioners , Surfactant, thickener, antifoaming agent, adhesion promoter, plasticizer, epoxy compound, thiol compound, resin with ethylenically unsaturated bond, saturated resin, colored dye, fluorescent dye, pigment (organic pigment, inorganic Pigments), carbon-based materials (carbon fiber, carbon black, graphite, graphitized carbon black, Charcoal, carbon nanotube, fullerene, graphene, carbon microcoil, carbon nanohorn, carbon aerogel, etc.), metal oxide (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metal (silver, copper, etc.), inorganic Examples include compounds (glass powder, lamellar viscosity minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants, and the like. An additive may be used independently and may use 2 or more types together.

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

The solvent may be further added to the polymerizable composition in order to improve the viscosity, paintability, and smoothness of the cured film. The solvent is capable of dissolving or dispersing the (a) polymerization initiator, the (b) radical polymerizable compound, the (c) alkali-soluble resin, and the other components, and is volatilized at a drying temperature. If it is a solvent, it will not restrict | limit in particular.

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. Examples include solvents, propylene glycol monomethyl ether acetate, and diethylene glycol dimethyl ether. A solvent may be used independently and may use 2 or more types together.

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

<Method for Preparing Polymerizable Composition>
When adjusting the polymerizable composition, the (a) polymerization initiator, the (b) radical polymerizable compound, and, if necessary, the (c) alkali-soluble resin and the other components in a storage container. And then dissolved or dispersed in accordance with a conventional method using a paint shaker, bead mill, sand grind mill, ball mill, attritor mill, 2-roll mill, 3-roll mill or the like. Moreover, you may filter through a mesh or a membrane filter etc. as needed.

In the preparation of the polymerizable composition, the (a) polymerization initiator may be added to the polymerizable composition from the beginning, but when the polymerizable composition is stored for a relatively long time. The (a) polymerization initiator is preferably dissolved or dispersed in the composition containing (b) radical polymerizability immediately before use.

<Method for producing cured product>
The cured product of the present invention is formed from the polymerizable composition. The manufacturing method of hardened | cured material is a manufacturing which includes any process of the process of irradiating the said polymeric composition with an active energy ray, and heating the said polymeric composition after apply | coating a polymeric composition on a board | substrate. Is the method. Moreover, the process including both the process of irradiating with the active energy ray and the process of heating is also referred to as a dual cure process.

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, and inkjet. Various methods, such as a printing method and a dispenser printing method, are mentioned. Examples of the substrate include glass, silicon wafer, metal and plastic films and sheets, and three-dimensional molded products, and the shape of the substrate is not limited.

The step of irradiating the polymerizable composition with active energy rays comprises (a) decomposing a polymerization initiator by irradiating active energy rays such as electron beam, ultraviolet ray, visible light, and radiation, and (b) radical polymerization. A cured product can be obtained by polymerizing the active compound.

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

As the light source for the light irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a light emitting diode (LED), a xenon arc lamp, a carbon arc lamp, sunlight, a YAG laser, etc. A gas laser such as a solid-state laser, a semiconductor laser, or an argon laser can be used. In addition, (a) When using visible light to infrared light with little absorption of 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 should be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure dose 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 manufacturing method of said hardened | cured material, when applying a dual cure process and performing the process of heating after the process of irradiating with the said active energy ray, (a) polymerization initiator is completely by an active energy ray. The exposure amount should be set as appropriate so that it is not decomposed.

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

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. Moreover, as a method of ventilation heating, a ventilation drying oven etc. are mentioned, for example.

In the step of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of (a) the polymerization initiator. However, when the decomposition rate is too high, there are cases where the decomposition residue of (b) radical polymerizable compound increases. On the other hand, the lower the heating temperature, the slower the decomposition rate of (a) the polymerization initiator, and thus a longer time is required for curing. Therefore, the heating temperature and the heating time should 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. Moreover, when mix | blending the said hardening accelerator with the said polymeric composition, heating temperature can be arbitrarily adjusted at 160 degreeC from room temperature with the kind and compounding quantity. On the other hand, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.

When applying the dual cure process as a method for producing the cured product, in particular, a colored pigment that absorbs or scatters light by performing a heating process after a process of irradiating the polymerizable composition with active energy rays. This is preferable because it can efficiently cure the deep part of the coating film of the polymerization composition containing a high concentration of light and a portion where light is blocked and light does not reach.

Further, when the polymerization composition contains the solvent, the method for producing the cured product may include a drying step. In particular, when applying the step of irradiating with the active energy ray after applying the polymerizable composition on the substrate, it is preferable to provide a drying step before the step of irradiating with the active energy ray.

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. Moreover, as a system of ventilation heating drying, a ventilation drying oven etc. are mentioned, for example.

In the drying step, the temperature of the polymerizable composition is lower than the preset drying temperature due to the latent heat of vaporization of the solvent, so that it is possible to ensure a long time until the polymerizable composition is gelled. Since the time until gelation is affected by the drying method, film thickness, and the like, the drying temperature and time should be appropriately set including the selection of the solvent. As an example, the drying temperature is preferably 20 to 120 ° C., and more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to ensure a long time until gelation. 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%. There is not much thickening or gelation.

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, more preferably 0.1 to 100 μm. .

<Pattern formation method>
When the polymerizable composition contains (c) an alkali-soluble resin, a pattern can be formed by a photolithography method. In the same manner as described above, the polymerizable composition is applied to a substrate and dried as necessary to form a dry film. Then, by irradiating the dry film with active energy rays through a mask, the radical polymerizable compound (b) is polymerized in the exposed portion to form a cured film. On the other hand, a highly accurate pattern shape can be produced without using a mask by direct writing using a laser.

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

The polymerizable composition of the present invention includes a hard coating agent, a coating agent for optical disks, a coating agent for optical fibers, a coating material for mobile terminals, a coating material for home appliances, a coating material for cosmetic containers, an inner surface antireflection coating material for optical elements, and a high / low refractive index. Coating agents, thermal barrier coating agents, heat dissipation coating agents, anti-fogging agents, and other paints and coating agents; offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, conductive ink, insulating ink, light guide plate ink Photosensitive printing plates; nanoimprint materials; 3D printer resins; holographic recording materials; dental materials; waveguide materials; black stripes for lens sheets; green sheets and electrode materials for capacitors; adhesives for FPDs; HDD adhesive, optical pickup adhesive, image sensor adhesive, organic Adhesives and sealants such as L sealant, OCA for touch panel, OCR for touch panel; color resist, black resist, color filter protective film, photo spacer, black column spacer, frame resist, TFT wiring photoresist, interlayer insulation Resist for FPD such as film; Resist for printed circuit board such as liquid solder resist, dry film resist; Semiconductor materials such as semiconductor resist, buffer coat film, etc.

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

<Examples 1 to 5>
(1) Synthesis of triazine peroxide derivative [Synthesis Example 1: Synthesis of Compound 1]
To a 20 mL eggplant flask, 1.66 g of ion-exchanged water and 0.553 g (6.64 mmol) of a 48% by mass sodium hydroxide aqueous solution were added, and 0.698 g (5.31 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution at 30 ° C. or lower. Was gradually added. To this, a mixed solution of 0.500 g of 2,4-dichloro-6-phenyl-1,3,5-triazine (2.21 mmol, purchased from Namiki Shoji) and 1 mL of tetrahydrofuran was added dropwise at 10 ° C. over 10 minutes. And reacted at 20 ° C. for 3.5 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 exchange water and dried over anhydrous magnesium sulfate at 0 ° C. After filtration, the oil phase was concentrated under reduced pressure to obtain 0.683 g (yield 92%) of Compound 1 of the present invention. Table 1 and Table 2 show the properties, EI-MS and ¹ H-NMR analysis results of the obtained Compound 1.

[Synthesis Example 2: Synthesis of Compound 23]
In a 500 mL three-necked flask dried by heat drying, 1.69 g (69.5 mmol) of magnesium, 57 mL of dehydrated tetrahydrofuran and a catalytic amount of iodine were added and stirred at room temperature. To this was added dropwise a mixed solution of 7.07 g (50.7 mmol) of 1-bromonaphthalene and 57 mL of dehydrated tetrahydrofuran, followed by stirring under reflux. After 1 hour, the internal temperature was cooled to −60 ° C. or lower. A separately prepared mixed solution of cyanuric chloride 8.92 g (48.4 mmol) and dehydrated tetrahydrofuran was added dropwise over 15 minutes. Thereafter, the mixture was raised to room temperature over 30 minutes and stirred in a water bath. After 62 hours, the reaction solution was cooled in an ice bath, 1M hydrochloric acid was added, and the pH was adjusted to 8 with a saturated aqueous sodium hydrogen carbonate solution. Next, 160 mL of ion-exchanged water was added and extracted with ethyl acetate. The oil phase was washed once with saturated saline and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 14.6 g of a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 1/1 to 1/3) and 5.14 g (yield 38%) of 2,4-dichloro-6- (1-naphthalenyl). -1,3,5-triazine was obtained.

To a 30 mL eggplant flask, 0.815 g of ion-exchanged water and 0.272 g (3.26 mmol) of a 48% by mass aqueous sodium hydroxide solution were added, and 0.343 g (2.61 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution at 30 ° C. or lower. Was gradually added. A mixed solution of 0.300 g (1.09 mmol) of 2,4-dichloro-6- (1-naphthalenyl) -1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10 ° C. over 10 minutes. The reaction was carried out at 20 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice water. The precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain Compound 2 of the present invention at 0.216 g (yield 52%). Table 1 and Table 2 show the properties, EI-MS and ¹ H-NMR analysis results of the obtained Compound 1.

[Synthesis Example 3: Synthesis of Compound 25]
A 300 mL eggplant flask was charged with 5.01 g (31.7 mmol) of 1-methoxynaphthalene, 100 mL of dehydrated dichloromethane and 6.12 g (33.2 mmol) of cyanuric chloride, and stirred in an ice bath. After 15 minutes, 4.43 g (33.2 mmol) of aluminum chloride was added, and the temperature was raised to room temperature. After 1 hour, the reaction solution was poured into 75 mL of ice-cold 1M hydrochloric acid, and the aqueous phase was separated. The oil phase was washed with 100 mL of saturated brine and dehydrated with anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to obtain 9.59 g of a yellow solid as a crude product. The crude product was purified by silica gel column chromatography (n-hexane / toluene = 4/1 to 1.5 / 1), and 8.05 g (yield 83%) of 2,4-dichloro-6- (4-methoxy). -1-Naphthalenyl) -1,3,5-triazine was obtained.

To a 30 mL eggplant flask, 0.245 g of ion-exchanged water and 0.0817 g (0.98 mmol) of a 48 mass% sodium hydroxide aqueous solution were added, and 0.103 g (0.78 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution at 30 ° C. or lower. Was gradually added. A mixed solution of 0.100 g (0.33 mmol) of 2,4-dichloro-6- (4-methoxy-1-naphthalenyl) -1,3,5-triazine and 2 mL of tetrahydrofuran was added at 10 ° C. over 10 minutes. The solution was added dropwise and reacted at 20 ° C. for 4 hours. After completion of the reaction, 50 mL of ethyl acetate and 50 mL of ion exchange water were added, and then the aqueous phase was separated. The oil phase was washed with 5% aqueous sodium hydroxide solution and ion-exchanged water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 0.125 g (yield 93%) of Compound 3 of the present invention. Table 1 and Table 2 show the properties of the obtained compound 3, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 4: Synthesis of Compound 26]
Compound 4 of the present invention was synthesized according to the method described in Synthesis Example 2, except that 1-bromonaphthalene described in Synthesis Example 2 was changed to 2-bromo-6-methoxynaphthalene. Table 1 and Table 2 show the properties of the obtained Compound 26 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 5: Synthesis of Compound 31]
Compound 4 of the present invention is obtained by reacting 2,4-dichloro-6-phenyl-1,3,5-triazine described in Synthesis Example 1 with 2,4-dichloro-6- (4-ethoxy-1-naphthalenyl)- The compound was synthesized according to the method described in Synthesis Example 1, except that it was changed to 1,3,5-triazine (Sigma-Aldrich reagent). Properties and EI-MS and ¹ H-NMR analysis results of the resulting compound 31 are shown in Tables 1 and 2.

[Synthesis Example 6: Synthesis of Compound 32]
Compound 32 of the present invention was synthesized according to the method described in Synthesis Example 3 except that the 69% by mass tert-butyl hydroperoxide aqueous solution described in Synthesis Example 3 was changed to 85% by mass tert-amyl hydroperoxide. did. Properties and EI-MS and ¹ H-NMR analysis results of the resulting compound 32 are shown in Tables 1 and 2.

[Synthesis Example 7: Synthesis of Compound 33]
Compound 33 of the present invention is obtained by reacting 2,4-dichloro-6-phenyl-1,3,5-triazine described in Synthesis Example 1 with 2- (4-biphenylyl) -4,6-dichloro-1,3, The compound was synthesized according to the method described in Synthesis Example 1 except that 5-triazine (Tokyo Chemical Industry Reagent) was used. Properties and EI-MS and ¹ H-NMR analysis results of the resulting compound 33 are shown in Tables 1 and 2.

[Synthesis Example 8: Synthesis of Compound 35]
Compound 35 of the present invention was synthesized according to the method described in Synthesis Example 2, except that 1-bromonaphthalene described in Synthesis Example 2 was changed to 4-bromo-4′-methoxybiphenyl. Table 1 and Table 2 show the properties of the obtained Compound 35, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 9: Synthesis of Compound 37]
Compound 37 of the present invention was prepared by converting 1-bromonaphthalene described in Synthesis Example 2 into 4-bromo-4′-methoxybiphenyl and 69% by mass tert-butyl hydroperoxide aqueous solution into 85% by mass tert-amyl hydroperoxide. The compound was synthesized according to the method described in Synthesis Example 2 except for the change. Table 1 and Table 2 show the properties of the obtained Compound 37, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 10: Synthesis of Compound 38]
Compound 38 of the present invention was prepared by changing 1-bromonaphthalene described in Synthesis Example 2 to 4-bromo-4′-methoxybiphenyl and a 69% by mass tert-butyl hydroperoxide aqueous solution to 90% by mass tert-hexyl hydroperoxide. Except for the above, it was synthesized according to the method described in Synthesis Example 2. Table 1 and Table 2 show the properties of the obtained Compound 38, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 11: Synthesis of Compound 40]
In Compound 40 of the present invention, 1-bromonaphthalene described in Synthesis Example 2 was changed to 4-bromo-4′-methoxybiphenyl, and 69% by mass aqueous tert-butyl hydroperoxide solution was changed to 80% by mass cumene hydroperoxide. Except for the above, it was synthesized according to the method described in Synthesis Example 2. Table 1 and Table 2 show the properties of the obtained compound 40, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 12: Synthesis of Compound 41]
Compound 41 of the present invention was synthesized according to the method described in Synthesis Example 2, except that 1-bromonaphthalene described in Synthesis Example 2 was changed to 4-bromostilbene. Table 1 and Table 2 show the properties of the obtained Compound 41 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 13: Synthesis of Compound 43]
In a 100 mL eggplant flask, 5.70 g (10 mmol) of cyanuric chloride, 1.56 g of trans-phenylvinylboronic acid (30 mmol, Sigma-Aldrich reagent), 0.31 g (0.4 mmol) of bis (triphenylphosphine) dichloride, and 40 mL of toluene were added. And stirred at room temperature. 10 mL of an aqueous solution of 8.68 g (40 mmol) of tripotassium phosphate was added dropwise at 0 ° C. After completion of the dropping, the reaction was performed at room temperature for 1 hour. After completion of the reaction, the aqueous phase was separated. The oil phase was washed once with saturated saline 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 to obtain 2.08 g (yield 78%) of 2,4-dichloro-6- (2-phenylethenyl) -1,3,5-triazine.

To a 20 mL eggplant flask, 0.893 g of ion-exchanged water and 0.298 g (3.57 mmol) of 48 mass% sodium hydroxide aqueous solution were added, and 0.376 g (2.86 mmol) of 69 mass% tert-butyl hydroperoxide aqueous solution at 30 ° C. or lower. Was gradually added. A mixed solution of 0.300 g (1.19 mmol) of 2,4-dichloro-6- (2-phenylethenyl) -1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise at 10 ° C. over 10 minutes. And reacted at 20 ° C. for 2 hours. After completion of the reaction, 50 mL of dichloromethane and 50 mL of ion exchange water were added, and then the aqueous phase was separated. The oil phase was washed with 5% aqueous sodium hydroxide solution and ion-exchanged water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 0.308 g (yield 71%) of Compound 43 of the present invention. Properties and EI-MS and ¹ H-NMR analysis results of the resulting compound 43 are shown in Tables 1 and 2.

[Synthesis Example 14: Synthesis of Compound 44]
Compound 35 of the present invention was synthesized according to the method described in Synthesis Example 2, except that 1-bromonaphthalene described in Synthesis Example 2 was changed to p- (2-bromo) vinylanisole. Table 1 and Table 2 show the properties of the obtained Compound 41 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 15: Synthesis of Compound 5]
Compound 5 of the present invention was synthesized according to the method described in Synthesis Example 3 except that 1-methoxynaphthalene described in Synthesis Example 3 was changed to anisole. Table 1 and Table 2 show the properties of the obtained compound 5, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 16: Synthesis of Compound 19]
Compound 19 of the present invention was synthesized according to the method described in Synthesis Example 3, except that 1-methoxynaphthalene described in Synthesis Example 3 was changed to diphenyl sulfide. Table 1 and Table 2 show the properties of the obtained Compound 19, and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 17: Synthesis of Compound 48]
Compound 48 of the present invention was synthesized according to the method described in Synthesis Example 3, except that 1-methoxynaphthalene described in Synthesis Example 3 was changed to 1- (2-ethylhexyloxy) naphthalene. Table 1 and Table 2 show the properties of the obtained Compound 19, and the results of analysis by EI-MS and ¹ H-NMR.

(2) Evaluation of UV absorption characteristics About acetonitrile solutions of the compounds described in Table 1, using a UV-VIS spectrum measurement device (1.0 cm quartz cell, manufactured by Shimadzu Corporation, UV-2450) at a wavelength of 200 to 600 nm UV-VIS spectrum was measured. The results are shown in Table 3.

<Comparative Examples 1 and 2>
In addition, as a comparative example, Table 3 shows the results of Compound R1 and Compound R2. Compound R1 was synthesized according to the production method described in JP-A-59-197401 and identified by EI-MS and ¹ H-NMR. As compound R2, Irgacure 184 (manufactured by BASF) was used.

In Table 3, λ _max is the maximum absorption wavelength (nm), ε _max is the molar extinction coefficient at the maximum absorption wavelength (L · mol ⁻¹ · cm ⁻¹ ), and ε ₃₁₃ is the molar extinction coefficient at the wavelength of ₃₁₃ nm (L · mol). ⁻¹ · cm ⁻¹ ) and ε ₃₆₅ indicate the molar extinction coefficient (L · mol ⁻¹ · cm ⁻¹ ) at a wavelength of 365 nm.

Generally, the larger the molar extinction coefficient of the photopolymerization initiator at the exposure wavelength, the easier the light is absorbed and the more easily radicals are generated. That is, a compound having a large molar extinction coefficient at the exposure wavelength is suitable for increasing the sensitivity of the photopolymerization initiator. When used for UV curing, an ultra-high pressure mercury lamp or a high-pressure mercury lamp has a wavelength of 365 nm (i-line) as a main wavelength and efficiently emits light having a wavelength of 313 nm (j-line). From the results in Table 3, it can be seen that the triazine peroxide derivative of the present invention has a large molar extinction coefficient at a wavelength of 365 nm and a wavelength of 313 nm emitted from a high-pressure mercury lamp or the like with respect to the compound R1 having a benzophenone skeleton. Furthermore, a single light having a wavelength of 365 nm or the like is emitted from the LED, but compound 25, compound 26, compound 31, compound 32, compound 35, compound 37, compound 38, compound 40, compound 41, compound 44, compound 19 and Compound 48 are found to have a large molar extinction coefficient at a wavelength of 365 nm.

<Examples 18 to 34, Comparative Examples 3 to 5>
<Adjustment of polymerizable composition (A) to (C)>
The amounts of (b) radical polymerizable compound, (c) alkali-soluble resin and other components shown in Table 4 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and Examples 18 to 34 and Comparative Example The polymerizable compositions (A) to (C) of Examples 3 to 5 were prepared.

In Table 4 above, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
RD200 is a methyl methacrylate / methacrylic acid / cyclohexyl maleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid value: 90 (synthetic product);
EMK: 4,4'-bis (diethylamino) benzophenone (Tokyo Chemical Industry Reagent)
F-477 is a fluorine-based leveling agent (trade name: Megafax F-477, manufactured by DIC Corporation);
PGMEA indicates propylene glycol monomethyl ether acetate (Wako Pure Chemical Industries, Ltd.).

(3) Evaluation of sensitivity The polymerizable composition (A) prepared as described above was applied on 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 having a thickness of 1.5 μm. Subsequently, stepwise exposure was performed in a range of 10 to 1000 mJ / cm ² through a mask pattern using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source. The exposed aluminum substrate was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23 ° C. for 60 seconds to remove unexposed portions by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a pattern shape. The minimum exposure amount at which a pattern shape was formed was evaluated as “sensitivity”. Table 5 shows the evaluation results of each (a) polymerization initiator.

Based on the results in Table 5, for compound R1 having a benzophenone skeleton, compound 23, compound 25, compound 26, compound 31, compound 32, compound 33, compound 35, compound 37, compound 38, compound 40, compound 41, and compound 43 are obtained. Compound 44, Compound 5, Compound 19, and Compound 48 were found to have high sensitivity. Since these compounds have high molar extinction coefficients at a wavelength of 365 nm and a wavelength of 313 nm, it is assumed that the sensitivity is high. Moreover, it became clear that a sensitivity improves by using a sensitizer together with the compound 1. Since the energy transfer efficiency from the sensitizer of Compound 1 is excellent, it is presumed that the sensitivity is high.

<Example 35, Comparative Example 6>
<Adjustment of polymerizable composition (D)>
The amount of (b) radical polymerizable compound and curing accelerator shown in Table 6 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and the polymerizable compositions of Example 29 and Comparative Example 6 (B ) Was adjusted.

In Table 6, UV-3700B is urethane acrylate (trade name: Purple light UV-3700B, manufactured by Nippon Synthetic Chemical Industry);
IBOA is isobornyl acrylate (Tokyo Chemical Industry Reagent);
THFA is tetrahydrofurfuryl acrylate (Tokyo Chemical Industry Reagent);
TMPTA is trimethylolpropane triacrylate (Tokyo Chemical Industry Reagent);
DMT indicates N, N-dimethyltoluidine (Tokyo Chemical Industry Reagent).

(4) Evaluation of dual cure curing characteristics The polymerizable composition (D) prepared as described above was applied to a PET film (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm by an applicator. A PET film (having a wavelength of 365 nm having a transmittance of less than 0.1%) applied to 50 μm and having a black coating on the surface was placed in a half region of the coating. And irradiation of 100 mJ / cm < ² > was performed using the conveyor type | mold UV irradiation apparatus in which the high pressure mercury lamp was installed. Then, it left still in a ventilation constant temperature thermostat, and heated for 90 minutes at 90 degreeC.

After the above heating, the black film-coated PET film was removed to expose the cured film, and the cured film portion was measured for degree of cure (%) by attenuated total reflection infrared spectroscopy (ATR-IR). . At that time, using the peak area of the double bond plane absorption spectrum of bending vibration of the (1410 cm ^-1) and absorption spectra of the free carbonyl group of changes before and after exposure (1740 cm ^-1), based on the following equation The curing rate (curing degree) was calculated. The results are shown in Table 7.

From the results shown in Table 7, the triazine peroxide derivative of the present invention and the polymerizable composition containing the compound have excellent sensitivity to light, and are characterized by having photocurability and thermosetting properties. it is obvious.

<Examples 36 to 39, Comparative Examples 7 to 8>
<Adjustment of polymerizable composition (E)>
The amounts of (b) radical polymerizable compound, (c) alkali-soluble resin and other components shown in Table 8 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and Examples 36 to 39 and Comparative Examples The polymerizable compositions (E) of Examples 7 to 8 were prepared. In addition, as a compound R3 and a compound R4, which are halomethyltriazine derivatives of comparative examples, Tokyo Kasei Reagent was used.

(5) Evaluation of hue (b ^* value) The polymerizable composition (E) prepared above was applied onto a glass substrate using a spin coater. After coating, the glass substrate was dried in a clean oven at 90 ° C. for 2.5 minutes to dry the solvent, thereby preparing a uniform coating film having a thickness of 1.5 μm. And 300 mJ / cm < ² > was irradiated using the conveyor type UV irradiation apparatus in which the high pressure mercury lamp was installed, and the test piece was produced. As a result of measuring the degree of cure of the obtained test pieces, the degree of cure of all the test pieces was 90% or more. About the obtained test piece, the value of L ^* , a ^* , b ^* color system was measured by the transmission method according to JIS-Z-8722 using a spectrocolorimeter (CM-3500d, manufactured by Minolta Camera). . b ^* of the value evaluated as an indicator of yellowness, low yellowness index as b ^* is small. The results are shown in Table 9.

From the results in Table 9, it is clear that the cured film formed from the polymerizable composition containing the triazine peroxide derivative of the present invention is characterized by low yellowness.

Claims

General formula (1):

(In the formula (1), R 1 and R 2 are each independently a methyl group or an ethyl group, R 3 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted alkyl group having 6 to 6 carbon atoms. 9 represents an aromatic hydrocarbon group of 9, n represents an integer of 0 to 2, and X is an aryl group represented by the general formula (2): Ar 1 , Ar 2 , Ar 3 , or Ar 4 .

(In the formula (2), m represents an integer of 0 to 3, R 4 is an independent substituent, an alkyl group having 1 to 18 carbon atoms, represented by the general formula (3): R 5 —Y— Represents a substituent, a nitro group, or a cyano group, and Y represents an oxygen atom or a sulfur atom, and R 5 represents any of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. Or a hydrocarbon group having 1 to 18 carbon atoms which may have one or more, an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or an acyl group having 1 to 8 carbon atoms Or R 4 is a triazine represented by the above-mentioned two general formulas (3): a hydrocarbon group which forms a 5- to 6-membered ring by R 5 —Y—. Peroxide derivatives.
In the general formula (2), R 4 is an independent substituent and represents an alkyl group having 1 to 8 carbon atoms, or a substituent represented by the general formula (3): R 5 —Y—, Y represents an oxygen atom, and R 5 represents a hydrocarbon group having 1 to 8 carbon atoms which may have any one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton, Or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R 4 is a 5- to 6-membered ring by two adjacent general formulas (3): R 5 —Y— The triazine peroxide derivative according to claim 1, which represents a hydrocarbon group which forms
A polymerizable composition comprising (a) a polymerization initiator containing the triazine peroxide derivative according to claim 1 or 2, and (b) a radical polymerizable compound.
The polymerizable composition according to claim 3, further comprising (c) an alkali-soluble resin.
A cured product formed from the polymerizable composition according to claim 3 or 4.
The method for producing a cured product according to claim 5, comprising a step of irradiating the polymerizable composition with active energy rays.
The method for producing a cured product according to claim 6, further comprising a heating step after the step of irradiating with the active energy ray.