WO2023054225A1

WO2023054225A1 - Triazine peroxide derivative and production method thereof, polymerizable composition, and cured product and production method thereof

Info

Publication number: WO2023054225A1
Application number: PCT/JP2022/035588
Authority: WO
Inventors: 奨今井; 真琴龍官; 章世矢野
Original assignee: 日油株式会社
Priority date: 2021-09-28
Filing date: 2022-09-26
Publication date: 2023-04-06
Also published as: TW202313576A; CN117177962A

Abstract

A triazine peroxide derivative represented by general formula (1). [In general formula (1), R¹ and R² independently represent a methyl group or an ethyl group, R³ represents a C1-5 aliphatic hydrocarbon group, etc., R⁴ represents an optionally substituted C1-20 aliphatic hydrocarbon group, etc., and Ar represents an aryl group represented by general formula (2): Ar¹, Ar² or Ar³.] This triazine peroxide derivative is a novel polymerization initiator that shows high sensitivity and yet has 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 a triazine peroxide derivative and its production method, a polymerizable composition, a cured product and its production method.

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

WO2018/221177

The triazine peroxide derivative disclosed in Patent Document 1 has a specific aryl group and two peroxide bonds in the molecule, and efficiently absorbs light with a wavelength of 365 nm or the like emitted from lamps such as high-pressure mercury lamps and LEDs. and can generate radicals, so it has excellent sensitivity. However, a polymerizable composition obtained by blending the compound with a radically polymerizable compound may have insufficient long-term storage stability at high temperatures.

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

That is, the present invention provides 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 having 1 to 5 carbon atoms, or the number of carbon atoms that may have an alkyl group represents an aromatic hydrocarbon group of 6 to 9, R ⁴ is an optionally substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms , an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, —Y—R, or —N—RR′, wherein Y is represents an oxygen atom or a sulfur atom, R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic having 6 to 20 carbon atoms represents an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, Ar is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² or Ar ³ .)

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

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

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

Since the triazine peroxide derivative of the present invention has only one peroxide bond in its molecule, the number of radicals generated per molecule due to decomposition of the compound is 2 in the molecule disclosed in Patent Document 1 above. It has the unique effect of having sensitivity similar to that of the compound disclosed in US Pat. On the other hand, since the triazine peroxide derivative of the present invention has only one peroxide 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 resists containing light-shielding pigments such as carbon black.

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

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

In general formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, and a methyl group is preferred from the viewpoint of high decomposition temperature and high 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 linear or branched. Specific examples of R ³ include methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, phenyl group, isopropylphenyl group and the like. Among these, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable from the viewpoint of facilitating the synthesis of the triazine peroxide derivative. A methyl group and an ethyl group are more preferable because the decomposition temperature of the triazine peroxide derivative is high, so that the storage stability of the polymerizable composition is high, and the sensitivity to light is high.

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, a substituted a heterocyclic ring-containing group having 2 to 20 carbon atoms which may be substituted, an optionally substituted acyl group having 1 to 20 carbon atoms, -YR, or -N-RR', wherein Y is an oxygen atom or a sulfur atom represents, R and R ' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, It represents an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. Since R ⁴ has little effect on the absorption wavelength of the triazine peroxide derivative, good sensitivity is exhibited even if R ⁴ is in the above wide range. In addition, the "substituent" in the above "optionally substituted" includes a halogen atom, an aliphatic hydrocarbon group which may have an ether bond or a thioether bond in the carbon skeleton, an aromatic hydrocarbon group, Heterocyclic-containing groups, acyl groups, cyano groups, nitro groups, carboxyl groups, epoxy groups, hydroxyl groups and the like are included. From the viewpoint of high stability, R ⁴ is preferably an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. group, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, or -YR, and from the viewpoint of ease of synthesis, More preferably, -OR, where R is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, It is 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, preferably m is 0 to 2 from the viewpoint of ease of synthesis, and m is 1 from the viewpoint of efficiently absorbing light. It is more preferable to have

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

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

The 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, compound 81 are preferred.

<Method for producing triazine peroxide derivative>
The method for producing the triazine peroxide derivative represented by the general formula (1) includes a step of reacting cyanuric chloride and/or a derivative thereof with hydroperoxide as raw materials. As such a production method, for example, as shown in the following reaction formula, a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as steps (A) and (B)), followed by the obtained cyanuric chloride derivative, A method including a step of reacting a hydroperoxide in the presence of an alkali (hereinafter also referred to as step (C)) may be mentioned. The order of the above steps is not limited. For example, the reaction product of cyanuric chloride and hydroperoxide may be reacted with the following Ar—X or R ⁴ —X, and the steps may be performed simultaneously. you can go Before and after each step, a step of distilling off (removing) excess raw materials or the like under reduced pressure, or a purification step may be included.

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

A commercially available product can be used as the cyanuric chloride derivative in the step (C). If there is no commercially available product, in the steps (A) and (B), known reactions 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 the synthesis method of.

<Synthesis of cyanuric chloride derivative by Grignard reaction>
When synthesizing a cyanuric chloride derivative by a Grignard reaction in steps (A) and (B), it can be synthesized according to a known synthetic method described in JP-A-6-179661 and the like. A halogen compound in which X of Ar—X in the step (A) and R ⁴ —X in the step (B) is a chlorine atom, a bromine atom, or an iodine atom can be used. A cyanuric chloride derivative can be synthesized by reacting a halogen compound with magnesium to prepare a Grignard reagent and then reacting the obtained Grignard reagent with cyanuric chloride.

In the preparation of the above Grignard reagent, magnesium is preferably used in an amount of 0.8 to 2.0 mol, more preferably 1 to 1.5 mol, per 1 mol of the halogen compound. As a reaction initiator, iodine, bromoethane, dibromoethane, or the like may be used, and it is preferable to use 0.0001 to 0.01 mol per 1 mol of the halogen 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, solvents such as ethers such as tetrahydrofuran can be used.

In the above reaction between the Grignard reagent and cyanuric chloride, cyanuric chloride is preferably used in an amount of 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of the halogen 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 20 hours, more preferably 30 minutes to 15 hours. Cyanuric chloride may be added to the prepared Grignard reagent, or the Grignard reagent may be added to a solution of cyanuric chloride.

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

<Synthesis of cyanuric chloride derivative by lithiation reaction>
When synthesizing a cyanuric chloride derivative by a lithiation reaction in steps (A) and (B), it can be synthesized according to a known synthesis method described in WO2012/096263 and the like. A halogen compound in which X of Ar—X in the step (A) and R ⁴ —X in the step (B) is a chlorine atom, a bromine atom, or an iodine atom can be used. A cyanuric chloride derivative can be synthesized by reacting a halogen compound with a lithiating agent to prepare a lithio compound, and then reacting the obtained lithio compound with cyanuric chloride.

Examples of the lithiation agent include alkyllithiums such as methyllithium, n-butyllithium, s-butyllithium and t-butyllithium; aryllithiums such as phenyllithium; lithium diisopropylamide and lithium bis(trimethylsilyl)amide. Examples include lithium amides, and n-butyllithium, s-butyllithium, t-butyllithium and phenyllithium are preferred.

In the preparation of the above lithiation compound, it is preferable to use 0.8 to 3.0 mol, more preferably 1.0 to 2.2 mol, of the lithiation agent per 1 mol of the halogen 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 lithio compounds, for example, solvents such as ethers such as tetrahydrofuran can be used.

In the above reaction of the lithio compound and cyanuric chloride, it is preferable to use 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, of cyanuric chloride with respect to 1 mol of the halogen 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. Cyanuric chloride may be added to the prepared lithio compound, or the lithio compound may be added to a solution of cyanuric chloride.

In the above reaction between the 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>
When synthesizing a cyanuric chloride derivative by Suzuki coupling reaction in steps (A) and (B), it can be synthesized according to a known synthesis method described in WO2012/096263 and the like. For example, a boron compound in which X of Ar—X in the step (A) and R ⁴ —X in the step (B) is converted to a boronyl group or boronic acid is obtained by reacting the aforementioned lithio compound with a boron reagent. Can be synthesized. Then, 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 above synthesis of the boron compound, it is preferable to use 0.8 to 3.0 mol, more preferably 1.0 to 2.0 mol, of the boron reagent 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 above boron compounds, for example, solvents such as ethers such as tetrahydrofuran can be used.

In the above reaction of the boron compound and cyanuric chloride, cyanuric chloride is preferably used in an amount of 0.7 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 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. Cyanuric chloride may be added to the boron compound, or the boron compound may be added to a solution of cyanuric chloride.

A palladium catalyst and an alkali are preferably used in the above reaction between the boron compound and cyanuric chloride, 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 hydrogencarbonate, sodium acetate, potassium acetate and potassium phosphate; and organic bases such as triethylamine.

As the ligand, organic Phosphorus-based ligands and the like can be mentioned.

In the reaction of the above 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 formamide can be used. The organic solvent may be used alone or in combination of two or more. Furthermore, a mixed solvent of the organic solvent and water can be used.

<Synthesis of Cyanuric Chloride Derivatives by Friedel-Crafts Reaction>
In the steps (A) and (B), when the cyanuric chloride derivative is synthesized by the Friedel-Crafts reaction, it can be synthesized according to the known synthetic method described in US Pat. No. 5,322,941 and the like. An aromatic compound in which X of Ar—X in the step (A) and R ⁴ —X in the step (B) is a hydrogen atom 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 (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, and boron trifluoride. A diethyl ether complex or the like can be used.

In the above reaction between the aromatic compound and cyanuric chloride, cyanuric chloride is preferably used in an amount of 0.7 to 2.5 mol, more preferably 0.8 to 1.5 mol, per 1 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 a solution of an aromatic compound and cyanuric chloride, an aromatic compound may be added to a solution of cyanuric chloride and aluminum chloride, or cyanuric chloride may be added to a solution of an aromatic compound and aluminum chloride. good too.

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

<Synthesis of triazine peroxide derivative>
In the step (C), the method for producing the triazine peroxide derivative represented by the general formula (1) is not particularly limited. Can be synthesized.

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

In the step (C), 0.9 mol or more, preferably 1.0 mol or more of hydroperoxide is reacted with respect to 1 mol of the cyanuric chloride derivative from the viewpoint of increasing the yield of the target product. is more preferable, and 3.0 mol or less is preferable, and 2.0 mol or less is more preferable. The hydroperoxide can be used as a commercially available product, and if there is no commercially available product, it can be synthesized according to the known synthetic method described in JP-A-58-72557.

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

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

The alkali used in the step (C) is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, pyridine, α-picoline, γ-picoline, dimethylaminopyridine, triethylamine, tributylamine, N,N-diisopropylethylamine, 1,5-diazabicyclo[4.3.0]-5-nonene and the like. 3. The alkali is preferably used in an amount of 0.8 mol or more, more preferably 1.0 mol or more, relative 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, more preferably 2.0 mol or less.

In the step (C), when the cyanuric chloride derivative is liquid, the reaction can be carried out 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. Examples include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; , ethers such as dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as methylene chloride and chloroform. The organic solvent may be used alone or in combination of two or more.

The amount of the organic solvent used is usually about 30 to 1000 parts by mass with respect to 100 parts by mass of the total amount of raw materials. The triazine peroxide derivative may be taken out by distilling off the organic solvent after the step (C). may be used.

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

In the purification step, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium sulfite, hydrogen chloride, sulfuric acid, A step of purifying the target product by washing with an electrolyte aqueous solution such as sodium chloride or ion-exchanged water can be mentioned.

<Polymerizable composition>
The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radically polymerizable compound. Furthermore, the polymerizable composition can be imparted with developability by containing (c) an alkali-soluble resin. In addition, the polymerizable composition can contain other components in appropriate combination.

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

In addition, the (a) polymerization initiator can contain a polymerization initiator other than the triazine peroxide derivative (hereinafter also referred to as another polymerization initiator). By using two or more types of triazine peroxide derivatives with different absorption bands and other polymerization initiators, the polymerizable composition has high sensitivity to lamps that emit light of multiple wavelengths, such as high-pressure mercury lamps. can be improved. In addition, considering the polymerizability of the (b) radical polymerizable compound contained in the polymerizable composition, the type of pigments that absorb or scatter light contained in the polymerizable composition, the film thickness of the cured product, etc. By using the polymerization initiator, the surface curability, deep part curability, transparency, etc. of the polymerizable composition can be improved.

As the other polymerization initiator, known ones can be used. -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-aminoacetophenone derivatives such as amino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2 ,4,6-trimethylbenzoyl)phosphine oxide, ethyl(mesitylcarbonyl)phenylphosphinate and other acylphosphine oxide derivatives; 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]carbazolyl]][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O -acetyloxime), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl-4-methyl-1-pentanone-1-(O-acetyloxime) and other oxime ester derivatives;2 -(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)1,3, Halomethyltriazine derivatives such as 5-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 2,2-dimethoxy-2-phenylacetophenone benzyl ketal derivatives such as; thioxanthone derivatives such as isopropylthioxanthone; benzophenone derivatives such as 4-(4-methylphenylthio)benzophenone; 3-benzoyl-7-diethylaminocoumarin, 3,3′-carbonylbis(7-diethylaminocoumarin) coumarin derivatives of; imidazole derivatives such as 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1-methylethyl)-9H-thioxanthen-9-one, dibenzoyl peroxide organic peroxides such as; azo compounds such as azobisisobutyronitrile; and camphorquinone. Other polymerization initiators may be used alone or in combination of two or more.

The content of the (a) polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the radically polymerizable compound (b). More preferably, it is 1 to 15 parts by mass. If the content of the polymerization initiator (a) is less than 0.1 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (b), 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 the (b) radically polymerizable compound, the solubility in the (b) radically polymerizable compound reaches saturation and polymerization (a) When the polymerization initiator crystals are precipitated during the film formation of the composition, causing a problem of roughening of the film surface, or (a) the increase in the decomposition residue of the polymerization initiator may reduce the strength of the cured product coating film. is not preferred because it may decrease

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

<(b) radically 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 and the like. Among these, it is preferable to contain highly reactive (meth)acrylic acid esters. (b) Radically polymerizable compounds may be used alone or in combination of two or more.

Monofunctional compounds and polyfunctional compounds can be used for the (meth)acrylic acid esters. 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 acrylates; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth)acrylic acid and alicyclic alcohol such as acrylate and 2-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) acrylate, polyethylene glycol mono (meth) Monomers having a hydroxy group such as acrylates and polypropylene glycol mono(meth)acrylates; Tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic Monomers having a chain or cyclic ether bond such as trimethylolpropane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-methylol (meth) Nitrogen atoms such as acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, N-(meth)acryloyloxyethylhexahydrophthalimide Monomers having; 2-(meth) acryloyloxyethyl isocyanate and other isocyanate group-containing monomers; glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and other epoxy group-containing monomers; phosphoric acid 2-(( Phosphorus atom-containing monomers such as meth)acryloyloxy)ethyl; Silicon atom-containing monomers such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2 , 3,3,3-Pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate and other fluorine atom-containing monomers; (meth)acrylic acid, monosuccinic acid (2-(meth) acryloyloxyethyl), phthalate mono(2-(meth)acryloyloxyethyl), maleate mono(2-(meth)acryloyloxyethyl), ω-carboxy-polycaprolactone mono(meth)acrylate, etc. A monomer etc. are mentioned.

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 propoxy tri(meth)acrylate, trimethylolethane tri (meth)acrylates, 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, neopentylglycol hydroxypivalate di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-( 2-(2-(meth)acryloyloxyethoxy)ethoxy)phenyl)fluorene, ester compound of polyhydric alcohol and (meth)acrylic acid; bis(4-(meth)acryloxyphenyl)sulfide, bis(4 - (meth) acryloylthiophenyl) sulfide, tris (2-(meth) acryloyloxyethyl) isocyanurate, ethylene bis (meth) acrylamide, zinc (meth) acrylate, zirconium (meth) acrylate, aliphatic urethane acrylate, Aromatic urethane acrylates, epoxy acrylates, polyester acrylates and the like can be mentioned.

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

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

<(c) Alkali-soluble resin>
The polymerizable composition can be suitably used as a negative resist by further blending (c) an alkali-soluble resin. As the alkali-soluble resin (c), those commonly used in negative resists can be used, and there are no particular limitations as long as the resin is soluble in an alkaline aqueous solution, but a resin containing a carboxyl group is preferred. preferable. (c) The alkali-soluble resin may be used alone or in combination of two or more.

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, etc. are preferably used.

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

Examples of the carboxyl group-containing (meth)acrylic acid ester copolymer include copolymers of methyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Furthermore, 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 reacts with an ethylenically unsaturated group, etc., from the viewpoint of achieving both developability of a negative resist and film properties such as heat resistance, hardness, and chemical resistance. A carboxyl group-containing (meth)acrylic acid ester copolymer having a side chain introduced with a functional group is also preferably used. As a method for introducing an ethylenically unsaturated group to the side chain, for example, a part of the carboxyl group of the carboxyl group-containing (meth)acrylic acid 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 a 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 the molecule such as 2-(meth)acryloyloxyethyl isocyanate to a hydroxyl group- and carboxyl group-containing (meth)acrylic acid ester copolymer, and the like. .

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

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, trisphenolmethane type epoxy resin, bisphenylfluorene. type epoxy resin and the like. Epoxy resins may be used alone or in combination of two or more.

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

Furthermore, when synthesizing the carboxyl group-containing epoxy acrylate resin, if necessary, using a tricarboxylic acid anhydride such as trimellitic anhydride, by hydrolyzing the acid anhydride group remaining after the reaction, the carboxyl group can be increased. Also, ethylenically unsaturated group-containing maleic anhydride can be used to further increase the number of ethylenic double bonds.

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

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

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

As the alkali-soluble resin (c), the alkali-soluble resin, which is an active ingredient, can be isolated and purified after the synthesis reaction. 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. Examples of curing accelerators that can be used include amine compounds, thiourea compounds, 2-mercaptobenzimidazole compounds, orthobenzoic sulphimides, and fourth period transition metal compound compounds. The curing accelerator may be used alone or in combination of two or more.

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

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

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

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

The curing accelerator is preferably added 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, the polymerizable composition is 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 can be added. 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, chain transfer agents, light stabilizers, antioxidants, leveling agents , surface modifiers, surfactants, thickeners, defoamers, 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 fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerenes, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.), metal oxides (oxidation titanium, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, lamellar clay minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants, etc. . Additives may be used alone or in combination of two or more.

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

A 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) radically polymerizable compound, the (c) alkali-soluble resin, and the other components, and volatilizes at the drying temperature. There are no particular restrictions as long as it is a solvent.

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. The solvent may be used alone or in combination of two or more.

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

<Method for preparing polymerizable composition>
When preparing the polymerizable composition, the (a) polymerization initiator, the (b) radically polymerizable compound, and, if necessary, the (c) alkali-soluble resin and other components are placed in a storage container. and dissolved or dispersed according to a conventional method using a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, or the like. In addition, if necessary, it may be filtered through a mesh or membrane filter or the like.

In the preparation of the polymerizable composition, the (a) polymerization initiator may be added to the polymerizable composition from the beginning. It is preferable to dissolve or disperse (a) the polymerization initiator in (b) the radically polymerizable composition immediately before use.

<Method for producing cured product>
The cured product of the present invention is formed from the polymerizable composition. The method for producing a cured product comprises any one of a step of applying a polymerizable composition on a substrate, irradiating the polymerizable composition with an active energy ray, and a step of heating the polymerizable composition. The method. A process including both the step of irradiating with active energy rays and the step of heating is also referred to as a dual cure step.

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

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

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

Light sources for the light irradiation 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, and the like. solid-state lasers, semiconductor lasers, gas lasers such as argon lasers, and the like can be used. In addition, (a) in the case of using light from visible light to infrared light that 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 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, when a dual curing step is applied as the method for producing the cured product, and a step of heating is performed after the step of irradiating with the active energy ray, (a) the polymerization initiator is completely cured by the active energy ray. The amount of exposure should be appropriately set so as not to decompose into two.

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

In the step of heating the polymerizable composition, examples of heating methods 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 ventilation heating method, for example, a ventilation drying oven or the like can be used.

In the step 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 (b) decomposition residue of the radically polymerizable compound may increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of (a) the polymerization initiator, and the longer the curing time is required. Therefore, the heating temperature and the heating time should be appropriately set according to the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230°C, more preferably 100 to 160°C. When the curing accelerator is added to the polymerizable composition, the heating temperature can be arbitrarily adjusted from room temperature to 160° C. depending on the type and amount of the curing accelerator. On the other hand, the heating time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.

When the dual curing step is applied as the method for producing the cured product, in particular, after the step of irradiating the polymerizable composition with an active energy ray, a heating step may be performed to absorb or scatter light. It is preferable because it is possible to efficiently cure the deep part of the coating film of the polymer composition containing at a high concentration and the part where the light is blocked and the light does not reach.

Further, when the solvent is included in the polymerization composition, the method for producing the cured product can include a drying step. In particular, when applying the step of irradiating with the active energy ray after coating 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, methods for drying the solvent include, for example, drying by heating, drying by ventilation by heating, and drying under reduced pressure. The method of drying by heating 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 heat-drying, a ventilation-type drying oven etc. are mentioned, for example.

In addition, in the drying step, the temperature of the polymerizable composition becomes lower than the set temperature for drying due to the latent heat of evaporation of the solvent, so it is possible to ensure a long time until the polymerizable composition gels. Since the time until this gelation is affected by the drying method, the film thickness, etc., the drying temperature and time including the selection of the solvent should be appropriately set. As an example, the drying temperature is preferably 20 to 120°C, more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. In addition, by using the polymerization inhibitor, it is possible to secure a long time until gelation. Although the triazine peroxide derivative decomposes by heat, the decomposition rate of the compound when heated at 80° C. for 5 minutes is about 0.1%. Not much thickening or gelling.

The dry film thickness (film thickness of the cured product) of the polymerizable composition is appropriately set according to 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 photolithography. The polymerizable composition is applied to the substrate in the same manner as described above, and if necessary, dried to form a dry film. By irradiating the dry film with an active energy ray through a mask, the radically polymerizable compound (b) is polymerized in the exposed portion to form a cured film. On the other hand, it is also possible to produce a pattern shape with high precision without using a mask by direct drawing using a laser.

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

The polymerizable composition of the present invention includes hard coating agents, optical disc coating agents, optical fiber coating agents, mobile terminal coatings, home appliance coatings, cosmetic container coatings, internal antireflection coatings for optical elements, and high/low refractive index coatings. Coating agents, heat-shielding coating agents, heat-dissipating coating agents, anti-fogging agents, etc.; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, inks for light guide plates Photosensitive printing plates; nanoimprint materials; resins for 3D printers; holography recording materials; dental materials; waveguide materials; black stripes for lens sheets; HDD adhesives, optical pickup adhesives, image sensor adhesives, organic EL sealants, touch panel OCA, touch panel OCR adhesives and sealants; color resists, black resists, protective films for color filters, FPD resists such as photo spacers, black column spacers, frame resists, photoresists for TFT wiring, and interlayer insulating films; printed circuit board resists such as liquid solder resists and dry film resists; semiconductor materials such as semiconductor resists and buffer coat films It can be used for various purposes such as, and there is no particular limitation on its use.

<Synthesis Example 1-8>
(1) Synthesis of Triazine Peroxide Derivative [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 3.00 g (16.3 mmol) of cyanuric chloride was added thereto, 2.39 g (17.9 mmol) of aluminum chloride 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-cold 1 M hydrochloric acid and stirred to separate the aqueous phase. The oil phase was washed with 50 mL of saturated saline and dehydrated with anhydrous sodium sulfate. After filtration, it 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 give 5.03 g (yield 92.6%) of 2,4-dichloro-6-(4- Phenylthio-1-phenyl)-1,3,5-triazine was obtained.

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 were added to a 100 mL eggplant flask and heated to 40°C. After adding 4.67 g of ion-exchanged water and 4.31 g (26.9 mmol) of a 25% by mass sodium hydroxide aqueous solution, 0.32 g (9.87 mmol) of methanol was added dropwise over 10 minutes, and the mixture was reacted at 40° C. for 2 hours. let me At 40° C. or lower, 1.29 g (9.87 mmol) of a 69% by mass tert-butyl hydroperoxide aqueous solution was added dropwise over 10 minutes, and reacted at 40° C. for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was poured into 50 mL of ice water. Precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 2.60 g of compound 19 of the present invention (yield: 75.5%). Table 1 shows the analysis results of the obtained compound 19 by EI-MS and ¹ H-NMR.

[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 diphenyl sulfide described in Synthesis Example 1 was changed to 1-methoxynaphthalene. Table 1 shows the analysis results of the obtained compound 25 by EI-MS and ¹ H-NMR.

[Synthesis Example 3: Synthesis of compound 35]
0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were placed in a heat-dried 100 mL three-necked flask 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 another 100 mL three-necked flask and cooled to 0°C. The previously prepared mixed solution was added dropwise thereto over 30 minutes, the temperature was raised to room temperature, and the mixture was stirred for 15 hours. The reaction solution was cooled in an ice bath, 1M hydrochloric acid was added, the mixture was stirred, and the pH was adjusted to 8 with a saturated sodium bicarbonate aqueous solution. It was then 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 a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1) to give 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4- (4′-Methoxybiphenyl)]-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 and heat to 40°C. bottom. After adding 1.88 g of ion-exchanged water and 1.74 g (10.9 mmol) of a 25% by mass sodium hydroxide aqueous solution, 0.13 g (3.98 mmol) of methanol was added dropwise over 5 minutes, and the mixture was reacted at 40° C. for 2 hours. let me At 40° C. or lower, 0.52 g (3.98 mmol) of a 69 mass % aqueous tert-butyl hydroperoxide solution was added dropwise over 5 minutes, and reacted at 40° C. for 1 hour. After completion of the reaction, the aqueous phase was separated, and the oil phase was poured into 50 mL of ice water. Precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 1.04 g of Compound 35 of the present invention (yield: 75.0%). Table 1 shows the analysis results of the obtained compound 35 by EI-MS and ¹ H-NMR.

[Synthesis Example 4: Synthesis of Compound 48]
Compound 48 of the present invention is described in Synthesis Example 3, except that the methanol described in Synthesis Example 3 is replaced with ethanol, and the 69% by mass tert-butyl hydroperoxide aqueous solution is replaced with an 85% by mass tert-amyl hydroperoxide solution. Synthesized according to the method of Table 1 shows the analysis results of the obtained compound 48 by EI-MS and ¹ H-NMR.

[Synthesis Example 5: Synthesis of compound 53]
Compound 53 of the present invention is the same as in Synthesis Example 3, except that the methanol described in Synthesis Example 3 is changed to isopropyl alcohol, and the 69% by mass tert-butyl hydroperoxide aqueous solution is changed to a 90% by mass tert-hexyl hydroperoxide solution. Synthesized according to the described method. Table 1 shows the analysis results of the obtained compound 53 by EI-MS and ¹ H-NMR.

[Synthesis Example 6: Synthesis of compound 56]
Compound 6 of the present invention is the same as in Synthesis Example 3, except that the methanol described in Synthesis Example 3 is changed to tert-butyl alcohol, and the 69% by mass tert-butyl hydroperoxide aqueous solution is changed to an 80% by mass cumene hydroperoxide solution. Synthesized according to the described method. Table 1 shows the analysis results of the obtained compound 56 by EI-MS and ¹ H-NMR.

[Synthesis Example 7: Synthesis of compound 77]
0.44 g (17.1 mmol) of magnesium, 15 mL of dehydrated tetrahydrofuran, and a catalytic amount of iodine were placed in a heat-dried 100 mL three-necked flask 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 another 100 mL three-necked flask and cooled to 0°C. The previously prepared mixed solution was added dropwise thereto over 30 minutes, the temperature was raised to room temperature, and the mixture was stirred for 15 hours. The reaction solution was cooled in an ice bath, 1M hydrochloric acid was added, the mixture was stirred, and the pH was adjusted to 8 with a saturated sodium bicarbonate aqueous solution. It was then 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 a crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 3/1 to 1/1) to give 2.07 g (yield 38.2%) of 2,4-dichloro-6-[4- (4′-Methoxybiphenyl)]-1,3,5-triazine was obtained.

3.03 g (16.3 mmol) of anisole 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 2,4-dichloro-6-[4-(4′-methoxybiphenyl)]-1,3,5-triazine, 2.39 g (17 .9 mmol) 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-cold 1 M hydrochloric acid and stirred to separate the aqueous phase. The oil phase was washed with 50 mL of saturated saline and dehydrated with anhydrous sodium sulfate. After filtration, it 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 give 5.03 g (yield 92.6%) of 2-chloro-4-(4-methoxyphenyl )-6-[4-(4′-methoxybiphenyl)]-1,3,5-triazine.

1.88 g of ion-exchanged water and 1.74 g (10.9 mmol) of 25% by mass sodium hydroxide aqueous solution were added to a 50 mL eggplant flask, and 0.52 g (3.98 mmol) of 69% by mass tert-butyl hydroperoxide aqueous solution was added at 30° C. or lower. was added gradually. Here, 1.20 g (3.62 mmol) of 2-chloro-4-(4-methoxyphenyl)-6-[4-(4'-methoxybiphenyl)]-1,3,5-triazine and 10 mL of tetrahydrofuran were mixed. The 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 deionized water and dried over anhydrous magnesium sulfate at 0°C. After filtration, the oil phase was concentrated under reduced pressure to give 1.04 g (75.0% yield) of compound 77 of the present invention. Table 1 shows the analysis results of the obtained compound 77 by EI-MS and ¹ H-NMR.

[Synthesis Example 8: Synthesis of Compound 81]
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 to a 100 mL eggplant flask and cooled to 20°C. 5.16 g (32.6 mmol) of 1-methoxynaphthalene was added thereto over 15 minutes and reacted at 20° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to 0° C., 50 mL of ice-cold 1 M hydrochloric acid was added, and the mixture was stirred to separate the aqueous phase. The oil phase was washed with 50 mL of saturated saline and dehydrated with anhydrous sodium sulfate. After filtration, it 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. rice field.

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 were added to a 100 mL eggplant flask, and the mixture was heated to 40°C. warmed up. A mixed liquid of 2.18 g (10.9 mmol) of 20% by mass sodium hydroxide aqueous solution and 1.42 g (10.9 mmol) of 69% by mass tert-butyl hydroperoxide aqueous solution was added dropwise thereto over 10 minutes, and the temperature was maintained at 40°C. It was reacted 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 deionized 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. Table 1 shows the analysis results of the obtained compound 81 by EI-MS and ¹ H-NMR.

<Examples 1 to 8, Comparative Example 1>
<Preparation of polymerizable composition (A)>
Radical polymerizable compound in the amount shown in Table 2, alkali-soluble resin, and other components were mixed and stirred, a polymerization initiator was added and well stirred, and polymerizable compositions of Examples 1 to 8 and Comparative Example 1 (A ) was prepared. In addition, in Comparative Example 1, a compound R1 represented by the following formula was used as a polymerization initiator.

In Table 2 above and Tables 4 and 6 below, 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/cyclohexylmaleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid value: 90 (synthetic product);
F-477 is a fluorine-based leveling agent (trade name: Megafac F-477, manufactured by DIC Corporation);
PGMEA indicates propylene glycol monomethyl ether acetate;

(1) Evaluation of Sensitivity The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After coating, the solvent was dried by drying the aluminum substrate in a clean oven at 90° C. for 2.5 minutes to form a uniform coating film with a thickness of 1.5 μm. Then, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, stepwise exposure was performed through a mask pattern in the range of 10 to 1000 mJ/cm ² . The exposed aluminum substrate was immersed in a 1.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds to remove the unexposed portion by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The minimum exposure dose at which a resist pattern was formed was evaluated as "sensitivity". A smaller value of the minimum exposure amount indicates that a pattern can be formed with a smaller amount of light, and a value of 200 mJ/cm ² or less indicates high sensitivity. Table 3 shows the results.

(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 then placed in a constant temperature thermostat set at 50 ° C. It was allowed to stand. When the number of days required for gelation was 60 days or more, it was evaluated as O, and when it was less than 60 days, it was evaluated as X. Table 3 shows the results.

<Examples 9 to 16, Comparative Example 2>
<Preparation of polymerizable composition (B)>
Radical polymerizable compound in the amount shown in Table 4, alkali-soluble resin, black pigment, and other components were mixed and stirred, a polymerization initiator was added and well stirred, and polymerizable compositions of Examples 9 to 16 and Comparative Example 2. Item (B) was prepared. In Comparative Example 2, the compound R1 represented by the above formula was used as the polymerization initiator.

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

(3) Evaluation of Resolution The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After coating, the solvent was dried by drying the glass substrate in a clean oven at 90° C. for 2.5 minutes to form a uniform coating film with a thickness of 1.5 μm. Then, exposure was performed at 200 mJ/cm ² through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The exposed glass substrate was immersed in a 1.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds to remove the unexposed portion by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a resist pattern. The obtained patterns were observed with a microscope, and the minimum pattern size was evaluated as ⊚ when the minimum pattern size was 10 μm or less, ∘ when over 10 μm and 20 μm or less, Δ when over 20 μm and 30 μm or less, and x when over 30 μm. Table 5 shows the results.

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

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

(4) Evaluation of Undercut The polymerizable composition (C) prepared above was applied onto a glass substrate using a spin coater. After coating, the solvent was dried by drying the glass substrate in a clean oven at 90° C. for 2.5 minutes to form a uniform coating film with a thickness of 1.5 μm. Then, exposure was performed at 150 mJ/cm ² through a mask pattern using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source. The exposed glass substrate was immersed in a 1.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds to remove the unexposed portion 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 with a microscope, and the underlining of the line-shaped pattern was determined by the difference between the maximum width and the minimum width of the pattern width parallel to the substrate surface. Evaluate the cut. The smaller the difference between the maximum width and the minimum width, the more the undercut is suppressed. x. Table 7 shows the results.

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

(5) Curability Evaluation The polymerizable composition (D) prepared above was applied to a glass substrate to a thickness of 100 μm using a bar coater. After the coating was dried in an oven at 90° C. for 2.5 minutes, it was irradiated with 30 mJ/cm ² using a conveyor-type UV irradiation device equipped with a high-pressure mercury lamp. Then, it was heated in an oven at 150° C. for 30 minutes to obtain a cured film. The polymerization conversion rate of the resulting cured film was measured, and the curability was evaluated according to the following criteria. The polymerization conversion rate was measured by attenuated total reflection infrared spectroscopy (ATR ^- IR). Using the peak area B of the absorption spectrum (1740 cm ⁻¹ ) derived from the carbonyl group that does not exist, the polymerization conversion was calculated based on the following formula. Table 9 shows the results.
Polymerization conversion = (1-(A/B after curing)/(A/B before curing)) x 100
○: Polymerization conversion rate is 80% or more △: Polymerization conversion rate 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 Shin-Nakamura Chemical Industry);
PE4A indicates pentaerythritol tetraacrylate (Fuji Film Wako Pure Chemical Reagent);

Claims

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 having 1 to 5 carbon atoms, or the number of carbon atoms that may have an alkyl group represents an aromatic hydrocarbon group of 6 to 9, R 4 is an optionally substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms , an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, —Y—R, or —N—RR′, wherein Y is represents an oxygen atom or a sulfur atom, R and R' are independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic having 6 to 20 carbon atoms represents an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, Ar is an aryl group represented by the following general formula (2): Ar 1 , Ar 2 or Ar 3 .)

(In the general formula (2), m represents an integer of 0 to 3, R 11 is an independent substituent, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, an optionally substituted acyl group having 1 to 20 carbon atoms, -Y- R or -N-RR', Y represents an oxygen atom or a sulfur atom, R and R' are independently a hydrogen atom, and an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms , an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.))). Peroxide derivative.
A polymerizable composition comprising (a) a polymerization initiator containing the triazine peroxide derivative according to claim 1, and (b) a radically polymerizable compound.
The polymerizable composition according to claim 2, further comprising (c) an alkali-soluble resin.
A cured product characterized by being formed from the polymerizable composition according to claim 2 or claim 3.
The method for producing a cured product according to claim 4, comprising a step of irradiating the polymerizable composition with an active energy ray.
A method for producing the triazine peroxide derivative according to claim 1,
A method for producing a triazine peroxide derivative, comprising a step of reacting cyanuric chloride and/or a derivative thereof with a hydroperoxide as raw materials.