KR102542689B1 - Triazine peroxide derivative, polymerizable composition containing the compound - Google Patents

Abstract

General Formula (1): (In Formula (1), R ¹ and R ² are independently a methyl group or an ethyl group, and 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 represents a group, n represents an integer of 0 to 2, and X is an aryl group represented by general formula (2): Ar ¹ , Ar ² , Ar ³ , or Ar ⁴ ) (in formula (2), m represents 0 to 2 represents an integer of 3, and R ⁴ represents, as an independent substituent, an alkyl group having 1 to 18 carbon atoms, a substituent represented by General Formula (3): R ⁵ -Y-, a nitro group, or a cyano group, and Y is oxygen represents an atom or a sulfur atom, and R ⁵ is, in the carbon skeleton, an ether bond, a thioether bond, and a hydrocarbon group having 1 to 18 carbon atoms, which may have at least one of a hydroxyl group at the terminal, or a carbon number which may have an alkyl group. Represents an aromatic hydrocarbon group of 6 to 9, or an acyl group of 1 to 8 carbon atoms Alternatively, R ⁴ is a hydrocarbon which forms a 5- to 6-membered ring by two adjacent Formula (3): R ⁵ -Y- A triazine peroxide derivative represented by). The triazine peroxide derivative of the present invention has both photopolymerization property capable of generating radicals by efficiently absorbing light emitted from a lamp having a wavelength of 365 nm or the like, and thermal polymerization property capable of generating radicals by heat, and curing It can reduce the yellowness of water.

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 or light or oxidation-reduction are widely used as polymerization initiators. In particular, a photopolymerization initiator can generate radicals by bond cleavage or hydrogen abstraction reaction by absorbing active energy rays such as light, and is used as a polymerization initiator for radically polymerizable compounds. For example, α-hydroxyacetophenone derivatives, α-aminoacetophenone derivatives, acylphosphine oxide derivatives, halomethyltriazine derivatives, benzylketal derivatives, thioxanthone derivatives and the like are used.

Since the photopolymerizable composition comprising a photopolymerization initiator and a radically polymerizable compound as described above is rapidly cured by light irradiation, from the viewpoints of fast curing properties and low VOC, coating agents, paints, printing inks, photosensitive printing plates, and adhesives , various photoresists, etc. are being applied.

On the other hand, Patent Document 1 discloses a polymerization initiator containing, as an active ingredient, a peroxyester containing a benzophenone group having a peroxidation bond (-O-O-) in a molecule that generates a radical by light or heat. Further, Patent Literature 2 discloses an adhesive composition comprising the polymerization initiator and a radical polymerizable compound, and the adhesive is cured by irradiation of light at room temperature and then cured by heating, thereby forming an adhesive. It exhibits strong adhesive strength and high durability.

Thus, a dual cure type polymerizable composition having both photopolymerization and thermal polymerization properties can be utilized also in improving dark curability. The dual cure type polymerizable composition is, for example, curing of a polymerizable composition in which a pigment or filler that absorbs or scatters light is blended at a high concentration, or a black frame around a protective cover in the manufacturing process of a flat panel display It is also effective for hardening the point where light does not reach, such as the lower part of a touch panel electrode.

Further, 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.

Japanese Unexamined Patent Publication No. 59-197401 Japanese Unexamined Patent Publication No. 2000-96002 Japanese Unexamined Patent Publication No. 54-074887

However, since the benzophenone group-containing peroxyesters described in Patent Document 1 and Patent Document 2 do not sufficiently absorb light with a wavelength of 365 nm or the like emitted from a high-pressure mercury lamp or LED, the most important fundamental of photopolymerization initiators Sensitivity, which is a characteristic, is not sufficient, and improvement in sensitivity is cited as a subject.

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

Therefore, in order to solve the above problems, the present invention, a photopolymerizable property 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 an LED, and generating radicals by heat [PROBLEMS] To provide a triazine peroxide derivative that has thermal polymerizability and can reduce the yellowness of a cured product.

Moreover, this invention provides the polymeric composition containing the polymerization initiator containing the said triazine peroxide derivative, and a radically polymerizable compound, the hardened|cured material and the manufacturing method of this hardened|cured material.

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

[Formula 1]

(In Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, 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, and n is 0 represents an integer of 2 to 2, and X is an aryl group represented by general formula (2): Ar ¹ , Ar ² , Ar ³ , or Ar ⁴ )

[Formula 2]

(In 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, a substituent represented by general formula (3): R ⁵ -Y-, a nitro group, or represents a cyano group, said Y represents an oxygen atom or a sulfur atom, said R ⁵ has 1 to 10 carbon atoms which may have any one or more of ether bond, thioether bond, and hydroxyl group at the terminal in the carbon skeleton; Represents an aromatic hydrocarbon group of 6 to 9 carbon atoms, which may have an 18-member hydrocarbon group, an alkyl group, or an acyl group of 1 to 8 carbon atoms, or R ⁴ represents two adjacent groups of the above general formula (3): R ⁵ -Y- represents a hydrocarbon group forming a 5- to 6-membered ring).

Further, the present invention relates to a polymerizable composition containing (a) a polymerization initiator containing the triazine peroxide derivative and (b) a radically polymerizable compound, a cured product formed from the polymerizable composition, and the cured product It's about manufacturing methods.

The triazine peroxide derivative of the present invention can efficiently generate radicals by efficiently absorbing light with a wavelength of 365 nm emitted from a high-pressure mercury lamp or a lamp such as an LED, and also has a peroxidation bond in the molecule, so that and those useful as thermal polymerization initiators. Therefore, the polymerizable composition containing the triazine peroxide derivative and the radically polymerizable compound can be cured satisfactorily by irradiation with light, and can also be cured satisfactorily by heat even in dark areas where light does not reach.

In addition, halomethyltriazine derivatives release chlor radicals by photolysis, and aromatic chlorides produced by-products are presumed to be the cause of coloration. However, since the triazine peroxide derivatives of the present invention do not contain chlorine atoms, It can reduce the yellowness of water.

<Triazine peroxide derivative>

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

[Formula 3]

(In Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, 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, and n is 0 represents an integer of 2 to 2, and X is an aryl group represented by general formula (2): Ar ¹ , Ar ² , Ar ³ , or Ar ⁴ )

[Formula 4]

(In 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, a substituent represented by general formula (3): R ⁵ -Y-, a nitro group, or represents a cyano group, said Y represents an oxygen atom or a sulfur atom, said R ⁵ has 1 to 10 carbon atoms which may have any one or more of ether bond, thioether bond, and hydroxyl group at the terminal in the carbon skeleton; Represents an aromatic hydrocarbon group of 6 to 9 carbon atoms, which may have an 18-member hydrocarbon group, an alkyl group, or an acyl group of 1 to 8 carbon atoms, or R ⁴ represents two adjacent groups of the above general formula (3): R ⁵ -Y- represents a hydrocarbon group forming a 5- to 6-membered ring by

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

In the said general formula (1), R ^<3> is a C1-C5 aliphatic hydrocarbon group, or a C6-C9 aromatic hydrocarbon group which may have an alkyl group. The alkyl group may be a straight chain or a branched chain. Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a phenyl group, and an isopropylphenyl group. Among these, from the viewpoint of easy synthesis of the triazine peroxide derivative, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable. Since the decomposition temperature of the triazine peroxide derivative is high, the storage stability of the polymerizable composition is high, and the sensitivity to light of a lamp is high, so a methyl group or an ethyl group is more preferable.

n in the said General formula (1) is represented by an integer of 0-2. 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, when X is Ar ¹ , the light from the lamp is efficiently absorbed and the yellowness of the cured product is reduced. It is more preferable from the viewpoint of being able to reduce.

m in the said General formula (2) is represented by the integer of 0-3. From the viewpoint of easy synthesis of the triazine peroxide derivative, m is preferably 0 to 2, and from the viewpoint of efficiently absorbing lamp light, m is more preferably 1.

R ⁴ in the general formula (2) represents, as an independent substituent, an alkyl group having 1 to 18 carbon atoms, a substituent represented by general formula (3): R ⁵ -Y-, a nitro group, or a cyano group, and Y is Represents an oxygen atom or a sulfur atom, and the R ⁵ may have a hydrocarbon group having 1 to 18 carbon atoms or an alkyl group which may have at least one of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. A C6-C9 aromatic hydrocarbon group or a C1-C8 acyl group is shown. Alternatively, R ⁴ represents a hydrocarbon group forming a 5- or 6-membered ring by two adjacent formulas (3): R ⁵ -Y-.

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

Specific examples of R ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, octyl group, 2 - Alkyl groups, such as an ethylhexyl group, a dodecyl group, and an 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-hydroxyethoxy)ethoxy group, 2-(2-ethoxyethoxy)ethoxy group, 3-hydroxy-n-propyloxy group, 3-methoxy -n-propyloxy group, 1,2-dihydroxypropyloxy group, methylenedioxy group, dimethylmethylenedioxy group, alkoxy groups such as ethylenedioxy group; aryloxy groups such as a phenyloxy group and a 4-isopropylphenyloxy group; alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, and 2-(2-methoxyethoxy)ethylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group, 2-methylphenylsulfanyl group, and 4-methylphenylsulfanyl group; acyl groups such as acetyl group, n-butanoyl group, 2-ethylhexanoyl group, benzoyl group, and 2-methylbenzoyl group; can The compound represented by the general formula (1) having these functional groups has a high absorbance at a wavelength of 365 nm and efficiently absorbs the light of a lamp, so it is preferable.

Among these, from the viewpoints of high solubility in the polymerizable composition of the triazine derivative, easy synthesis, and high sensitivity to lamp light, the above R ⁴ is a methoxy group, an ethoxy group, or a 2-hydroxy group. A toxyl group is more preferred.

The substitution position of R ⁴ is not particularly limited, but when X is Ar ¹ , at least one of R ⁴ is preferably substituted with the 4-position of the triazine group-substituted benzene ring, and X is Ar ² In this case, it is preferable that at least one of R ⁴ is substituted at position 4 of the benzene ring different from the benzene ring in which the triazine group is substituted, and when X is Ar ³ , at least one of R ⁴ is substituted at position 1. is preferably substituted at the 4-position of the triazine group, and when X is Ar ⁴ , at least one of R ⁴ is substituted at the 4-position of the benzene ring different from the benzene ring in which the triazine group is substituted. It is preferable because it absorbs light efficiently.

Although the specific example of the triazine peroxide derivative of this invention is shown below below, it is not limited to these.

[Formula 5]

The triazine peroxide derivatives of the present invention are 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, and Compound 48, more preferably Compound 25, Compound 26, Compound 31, Compound 32, Compound 35, Compound 37, Compound 38, Compound 41, Compound 44, Compound 47, and Compound 48 are exemplified.

<Method for producing triazine peroxide derivatives>

The method for producing the triazine peroxide derivative represented by the general formula (1) is, for example, a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as a step (A)), followed by the obtained A method including a step of reacting a cyanuric chloride derivative with a hydroperoxide in the presence of an alkali (hereinafter also referred to as a step (B)) is exemplified. Further, after the above steps (A) and/or (B), a step of distilling (removing) excess raw materials under reduced pressure or a purification step may be included.

[Formula 6]

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

In the step (B), a commercial product can be used for 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 synthetic methods, such as a Grignard reaction, a lithiation reaction, a Suzuki coupling reaction, or a Friedel-Crafts reaction.

<Synthesis of cyanuric chloride derivatives by Grignard reaction>

In the step (A), when synthesizing a cyanuric chloride derivative by a Grignard reaction, it can be synthesized according to a known synthesis method described in Japanese Unexamined Patent Publication No. 6-179661 or the like. Z of the aromatic compound in the step (A) can use an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom. 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 preparing the above Grignard reagent, magnesium is preferably used in an amount of 0.8 to 2.0 moles, more preferably 1 to 1.5 moles, based on 1 mole of the aromatic compound. As a reaction initiator, iodine, bromoethane, dibromoethane, etc. may be used, and it is preferable to use 0.0001-0.01 mol with respect to 1 mol of aromatic compounds. 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, and more preferably 1 hour to 10 hours.

In the preparation of the above Grignard reagent, solvents such as ethers such as tetrahydrofuran can be used.

In addition, 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 moles, more preferably 0.8 to 1.2 moles, based on 1 mole of the aromatic compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Further, 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, solvents such as ethers such as tetrahydrofuran can be used.

<Synthesis of cyanuric chloride derivatives by lithiation>

In the step (A), when synthesizing a cyanuric chloride derivative by a lithiation reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 or the like. Z of the aromatic compound in the step (A) can use an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom. A cyanuric chloride derivative can be synthesized by preparing a lithium compound by reacting an aromatic compound with a lithiation agent, and then reacting the obtained lithium compound with cyanuric chloride.

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

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

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

In addition, in the above reaction between the lithium compound and cyanuric chloride, cyanuric chloride is preferably used in an amount of 0.7 to 1.5 moles, more preferably 0.8 to 1.2 moles, based on 1 mole of the aromatic compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Further, the cyanuric chloride may be introduced into the prepared lithium compound, or the lithium compound may be introduced into the cyanuric chloride solution.

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

<Synthesis of cyanuric chloride derivatives by Suzuki coupling>

In the step (A), when synthesizing a cyanuric chloride derivative by a Suzuki coupling reaction, it can be synthesized according to a known synthesis method described in WO2012/096263 or the like. For example, a boron compound in which Z of an aromatic compound is converted into a boronyl group or a boronic acid can be synthesized by reacting the above lithium compound with a boron reagent. Subsequently, a cyanuric chloride derivative can be synthesized by reacting the obtained boron compound with cyanuric chloride. In addition, when a 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 moles, more preferably 1.0 to 2.0 moles, based on 1 mole of the lithium compound. The reaction temperature is preferably -100 to 50°C, and more preferably -80 to 20°C. The reaction time is preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

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

In addition, in the above reaction between the boron compound and cyanuric chloride, cyanuric chloride is preferably used in an amount of 0.7 to 1.5 moles, more preferably 0.8 to 1.2 moles, based on 1 mole of the boron compound. The reaction temperature is preferably -30 to 70°C, and more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Further, the cyanuric chloride may be introduced into the boron compound, or the boron compound may be introduced into the solution of the cyanuric chloride.

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

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

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, triphenylphosphine, tricyclohexylphosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, 2-dicyclohexylphosphino-2,6'- Organophosphorus ligands, such as dimethoxy biphenyl, etc. are mentioned.

In the reaction between 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 N,N-dimethylformamide can be used. These organic solvents may be used alone or in combination of two or more. Also, a mixed solvent of the organic solvent and water may be used.

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

In the step (A), when synthesizing a cyanuric chloride derivative by Friedel-Crafts reaction, it can be synthesized according to a known synthesis method described in US5322941 and the like. As for Z of the aromatic compound in the step (A), an aromatic compound represented by a hydrogen atom and 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.

As the Lewis acid, aluminum chloride, aluminum bromide, iron (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, boron trifluoride Ethyl ether complex etc. can be used.

In the above reaction between the aromatic compound and cyanuric chloride, the amount of cyanuric chloride is preferably 0.7 to 1.5 moles, more preferably 0.8 to 1.2 moles, per mole of the aromatic compound. It is preferable to use 1.0-3.0 mol of aluminum chloride, and it is more preferable to use 1.0-2.0 mol with respect to 1 mol of aromatic compounds. The reaction temperature is preferably -50 to 60°C, and more preferably 0 to 40°C. The reaction time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. Further, aluminum chloride may be added to a solution of an aromatic compound and cyanuric chloride, or an aromatic compound may be added to a solution of cyanuric chloride and aluminum chloride.

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

<Synthesis of Triazine Peroxide Derivatives>

In the step (B), the method for producing the triazine peroxide derivative represented by the general formula (1) is not particularly limited, but follows a known method for synthesizing triazine peroxide described in Japanese Patent Publication No. 45-39468 and the like. can be synthesized.

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

In the step (B), the hydroperoxide is preferably reacted in an amount of 1.8 moles or more, more preferably 2.0 moles or more, with respect to 1 mole of the cyanuric chloride derivative, from the viewpoint of increasing the yield of the target product, And it is preferable to make it react 5.0 mol or less, and it is more preferable to make it react 3.8 mol or less. In addition, a commercial item can be used for hydroperoxide, and when there is no commercial item, it can synthesize|combine according to the well-known synthetic method described in Unexamined-Japanese-Patent No. 58-72557 grade|etc.,.

In the step (B), the reaction temperature is preferably -10°C or higher, more preferably 0°C or higher, and preferably 40°C or lower, and more preferably 30°C or lower, from the viewpoint of increasing the yield of the target product. desirable.

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

In the step (B), the alkali used is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, pyridine, α-picoline, γ-picoline, dimethylamino pyridine, triethylamine, tributylamine, N,N-diisopropylethylamine, 1,5-diazabicyclo[4.3.0]-5-nonene and the like. The alkali is preferably used in an amount of 1.8 moles or more, more preferably 2.0 moles or more, and preferably 5.0 moles or less based on 1 mole of the cyanuric chloride derivative, from the viewpoint of increasing the yield of the target product. , It is more preferable to use 3.8 mol or less.

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

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 distilled off after the step (B) to obtain the triazine peroxide derivative, or the triazine peroxide derivative may be used as a dilution of the organic solvent in order to improve handling properties and reduce the risk of thermal decomposition. .

Although the said process (B) can be carried out under normal pressure and under air, you may carry out under a nitrogen stream or nitrogen atmosphere.

In the purification step, in order to remove surplus raw materials and by-products, for example, ion-exchanged water, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, basic aqueous solutions such as potassium hydroxide, sodium sulfite A step of washing with an aqueous solution or the like to purify the target substance is exemplified.

<Polymerizable composition>

The polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radically polymerizable compound. Moreover, a polymeric composition can provide developability by containing (c) alkali-soluble resin. In addition, the polymerizable composition can be contained in an appropriate combination of other components.

<(a) polymerization initiator>

(a) The polymerization initiator of this invention contains the triazine peroxide derivative represented by the said General formula (1). (a) The polymerization initiator is decomposed by active energy rays or heat, and the generated radical has an action of initiating polymerization (curing) of the (b) radically polymerizable compound. Triazine peroxide derivatives may be used independently or may use two or more types together.

In addition, the polymerization initiator (a) may contain polymerization initiators other than triazine peroxide derivatives (hereinafter, also referred to as other polymerization initiators). By using two or more kinds of triazine peroxide derivatives or other polymerization initiators having different absorption bands, the polymerizable composition can be highly sensitive to a lamp that emits light of a plurality of wavelengths, such as a high-pressure mercury lamp, for example. there is. In consideration of the polymerizability of the (b) radically polymerizable compound contained in the polymerizable composition, the type of pigment that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, and the like, other polymerization initiators are used. By doing so, the surface curability, deep curability, transparency and the like of the polymerizable composition can be improved.

As the other polymerization initiator, known ones can be used, and examples thereof include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, and 4'-(2-hydroxyethoxy )-2-hydroxy-2-methylpropiophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1 α-hydroxyacetophenone derivatives such as -one; 2-methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, α-aminoacetophenone derivatives such as 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; acylphosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl (mesitylcarbonyl)phenylphosphine; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H Oxime ester derivatives, such as -carbazol-3-yl] ethylidene} amino) oxy] ethanone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloro) halomethyltriazine derivatives such as romethyl) 1,3,5-triazine and 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; benzyl ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone; Benzophenone derivatives, such as thioxanthone derivatives, such as isopropyl thioxanthone, and 4-(4-methylphenylthio) benzophenone; coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole, etc. imidazole derivatives of; organic peroxides such as 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; Camphaquinone etc. are mentioned. Other polymerization initiators may be used independently or may use two or more types together.

The content of the polymerization initiator (a) is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to 15 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b). do. (a) Content of a polymerization initiator is unpreferable because a hardening reaction does not advance if it is less than 0.1 mass part with respect to 100 mass parts of (b) radically polymerizable compounds. Further, when the content of the (a) polymerization initiator is greater 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 thus the polymerizable composition During film formation, (a) crystals of the polymerization initiator precipitate and the roughness of the surface of the film becomes a problem, or (a) the strength of the coating film of the cured product is reduced due to the increase of decomposition residues of the polymerization initiator. , which is not desirable.

In the case where the other polymerization initiator is included in the (a) polymerization initiator, the ratio of the other polymerization initiator is preferably 80% by mass or less, and more preferably 50% by mass or less, of the (a) polymerization initiator.

<(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) Examples of the radically polymerizable compound 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 include highly reactive (meth)acrylic acid esters. (b) A radically polymerizable compound may be used independently or may use two or more types together.

As the above (meth)acrylic acid esters, monofunctional compounds and polyfunctional compounds can be used. As monofunctional compounds, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) ) Alkyl (meth)acrylates such as acrylate and stearyl (meth)acrylate; Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2- ester compounds of (meth)acrylic acid and alicyclic alcohol, such as ethyl-2-adamantyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate ) Monomers having a hydroxyl group such as acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; Methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate , (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, cyclic trimethyl monomers having chain-like or cyclic ether bonds, such as all-propaneformyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylamino monomers having nitrogen atoms such as propyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, and N-(meth)acryloyloxyethylhexahydrophthalimide; monomers having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; monomers having epoxy groups such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether; monomers having a phosphorus atom such as 2-((meth)acryloyloxy)ethyl phosphate; monomers having silicon atoms such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate monomers having a fluorine atom, such as; (meth)acrylic acid, monosuccinic acid (2-(meth)acryloyloxyethyl), monophthalic acid (2-(meth)acryloyloxyethyl), monomaleic acid (2-(meth)acryloyloxyethyl) , monomers having carboxyl groups such as ω-carboxy-polycaprolactone mono(meth)acrylate, and the like.

Examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and 1,4-butanediol. Di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin Propoxytri(meth)acrylate, trimethylolethanetri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate Erythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentylglycol di(meth)acrylate, tricyclo Decane dimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9 ,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-(2-(meth)acryloyloxyethoxy) ester compounds of polyhydric alcohols such as oxy)phenyl)fluorene and (meth)acrylic acid; Bis(4-(meth)acryloxyphenyl)sulfide, bis(4-(meth)acryloylthiophenyl)sulfide, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylenebis (meth)acrylamide, zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, polyester acrylate and the like.

From the viewpoint of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, and improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product, the (meth)acrylic acid esters are combined with the polyhydric alcohol (meth) ) Acrylic acid ester compounds are preferred, particularly trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaeryth Litol hexaacrylate is preferred.

In addition, the copolymer obtained from the radically polymerizable compound (b) may 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. (c) As the alkali-soluble resin, those generally used for negative resists can be used, and any resin soluble in aqueous alkali solution is not particularly limited, but a resin containing a carboxyl group is preferable. (c) Alkali-soluble resin may be used independently or may use two 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, or the like is preferably used.

The carboxyl group-containing (meth)acrylic acid ester copolymer is at least one selected from monofunctional compounds of the above-mentioned (meth)acrylic acid esters (except for monomers having the carboxyl group), (meth)acrylic acid, ( Dimer of meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylbenzoic acid, cinnamic acid, succinic acid mono(2-(meth)acryloyloxyethyl), phthalic acid mono(2-(meth)acryloyloxy ethyl), maleate mono(2-(meth)acryloyloxyethyl), ω-carboxy-polycaprolactone mono(meth)acrylate, and ethylenically unsaturated group-containing carboxylic acids such as their acid anhydrides. It is a copolymer containing at least 1 type.

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

As the carboxyl group-containing epoxy acrylate resin, a compound obtained by further reacting an acid anhydride with an epoxy acrylate resin that is a reaction product between 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 resins, phenol novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and trisphenolmethane type epoxy resins. , bisphenyl fluorene type epoxy resin, etc. are mentioned. An epoxy resin may be used independently or may use two 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, chlorendic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, itaconic anhydride, etc. are mentioned.

In the case of synthesis of the carboxyl group-containing epoxy acrylate resin, the carboxyl group can be increased by hydrolyzing the acid anhydride group remaining after the reaction using a tricarboxylic acid anhydride such as trimellitic anhydride as needed. Moreover, the ethylenic double bond can also be further increased using maleic anhydride containing an ethylenically unsaturated group.

The acid value of the alkali-soluble resin (c) is preferably 20 to 300 mgKOH/g, more preferably 40 to 180 mgKOH/g. When the acid value is less than 20 mgKOH/g, since the solubility in aqueous alkali solution is insufficient, developing of the unexposed portion becomes difficult, so it is not preferable. Further, when the acid value is higher than 300 mgKOH/g, the exposed portion tends to be easily separated from the substrate during development, which is not preferable.

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

Moreover, it is preferable that it is 10-70 mass % in the total solid content of polymeric composition, and, as for the ratio of (c) alkali-soluble resin, it is more preferable that it is 15-60 mass %. When the ratio is less than 10% by mass, developability is poor, so it is not preferable. When the ratio is more than 70% by mass, reproducibility of the pattern shape and heat resistance are lowered, which is not preferable.

In addition, as the alkali-soluble resin (c), a reaction solution obtained by the synthesis reaction, a dried product thereof, or the like can be used as is, in addition to being able to use an alkali-soluble resin obtained by isolating and refining the alkali-soluble resin as an active ingredient after the synthesis reaction.

<Other ingredients>

Curing by heating of a polymeric composition can also be performed at low temperature by using a hardening accelerator as said other component. As the curing accelerator, for example, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole-based compound, an orthobenzoxulfimide, a fourth period transition metal compound, or the like can be used. A hardening accelerator may be used independently or may use two or more types together.

As said amine compound, a tertiary amine is preferable, For example, N,N- dimethylaniline, N,N- dimethyltoluidine, N,N- diethylaniline, N,N-bis (2-hydroxy Ethyl)-p-toluidine, 4-(dimethylamino) ethyl benzoate, 4-dimethylamino benzoate (2-methacryloyloxy) ethyl, etc. are mentioned.

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

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

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

It is preferable to mix|blend the said hardening accelerator immediately before using a polymeric composition. The content of the curing accelerator is preferably from 0.1 to 20 parts by mass, more preferably from 0.2 to 10 parts by mass, based on 100 parts by mass of the radically polymerizable compound (b).

As the other components, additives 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 can be incorporated into the polymerizable composition. As an additive, for example, a sensitizer (isopropylthioxanthone, diethylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin , acridine orange, camphaquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers, infrared absorbers , light stabilizer, antioxidant, leveling agent, surface conditioner, surfactant, thickener, antifoaming agent, adhesion promoter, plasticizer, epoxy compound, thiol compound, resin having ethylenically unsaturated bonds, saturated resin, colored dye, fluorescent dye, pigment ( organic pigments, inorganic pigments), carbon-based materials (carbon fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerenes, graphene, carbon micro coils, carbon nano horns, carbon aerogels, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, lamellar viscosity minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants, etc. there is. An additive may be used independently or may use two or more types together.

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

A solvent may be further added to the polymerizable composition to improve the viscosity, paintability, and smoothness of the cured film. The solvent is a solvent capable of dissolving or dispersing the (a) polymerization initiator, (b) radically polymerizable compound, (c) alkali-soluble resin, and other components, and volatilizes at a drying temperature. It is not particularly limited.

Examples of the solvent include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, and carbitol acetate. system solvents, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like are exemplified. A solvent may be used independently or may use two or more types together.

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>

In the case of preparing the polymerizable composition, the (a) polymerization initiator, the (b) radical polymerizable compound, and, if necessary, the (c) alkali-soluble resin or other components are put into a storage container, and the paint It may be dissolved or dispersed in a conventional manner using a shaker, bead mill, sand grind mill, ball mill, attritor mill, two roll mill, three roll mill or the like. Moreover, you may filter through a mesh or membrane filter etc. as needed.

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

<Method for producing cured product>

The hardened|cured material of this invention is formed from the said polymeric composition. A method for producing a cured product is a production method including either a step of applying the polymerizable composition onto a substrate, then a step of irradiating the polymerizable composition with active energy rays, or a step of heating the polymerizable composition. Moreover, a 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, and offset printing. , inkjet printing method, and various methods such as dispenser printing method. In addition, the substrate may be, for example, a film or sheet of glass, silicon wafer, metal, plastic, or the like, and a three-dimensional molded article, and the shape of the substrate is not limited.

In the step of irradiating the polymerizable composition with active energy rays, (a) the polymerization initiator is decomposed, and (b) the radical polymerizable compound is polymerized by irradiation with active energy rays such as electron beams, ultraviolet rays, visible rays, and radiation. By doing so, a cured product can be obtained.

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

As a light source for irradiation of the light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a light emitting diode (LED), a xenon arc lamp, a carbon arc lamp, sunlight, a YAG laser, or the like Gas lasers, such as a solid-state laser, a semiconductor laser, and an argon laser, etc. can be used. Further, (a) In the case of 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 dose of the active energy ray must be appropriately set depending on the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably 10 to 5,000 mJ/cm 2 , and more preferably 30 to 1,000 mJ/cm 2 . Further, in the method for producing the cured product described above, when a dual cure process is applied and a heating process is performed after the irradiation process with the active energy ray, (a) the polymerization initiator is completely decomposed by the active energy ray, It is necessary to properly set the exposure amount so as not to be discarded.

In the step of heating the above polymerizable composition, a cured product can be obtained by decomposing (a) the polymerization initiator with heat and polymerizing the (b) radically 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, and electromagnetic wave irradiation. Moreover, as a system 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 the (a) polymerization initiator. However, when the decomposition rate is too fast, there is a case where the decomposition residue of the (b) radically polymerizable compound increases. On the other hand, since the decomposition rate of (a) polymerization initiator is so slow that a heating temperature is low, hardening requires a long time. Therefore, the heating temperature and heating time must be appropriately set depending on the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230°C, and more preferably 100 to 160°C. Moreover, when mix|blending the said hardening accelerator with the said polymeric composition, the heating temperature can be arbitrarily adjusted from room temperature to 160 degreeC with the kind and compounding quantity. On the other hand, the heating time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.

As a method for producing the cured product, in the case of applying the dual cure step, in particular, after the step of irradiating the polymerizable composition with active energy rays, the step of heating is performed so that the color pigment that absorbs or scatters light is produced at a high concentration. It is preferable because it is possible to efficiently cure the deep part of the coating film of the polymeric composition to be contained or the point where light is blocked and does not reach light.

Moreover, when the said solvent is included in the said polymerization composition, the manufacturing method of the said hardened|cured material may include a drying process. In particular, when applying the step of irradiating with the active energy ray continuously 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 above drying step, the method for drying the solvent includes, for example, heating drying, ventilation heating drying, reduced pressure drying, and the like. The heat drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, and electromagnetic wave irradiation. Moreover, as a system of ventilation heating drying, a ventilation type drying oven etc. are mentioned, for example.

In the drying step, the temperature of the polymerizable composition is lowered than the set temperature for drying due to the latent heat of evaporation of the solvent, so that a long time can be secured until the polymerizable composition gels. Since the time until gelation affects the drying method, film thickness, etc., the drying temperature and time must 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. It is preferable that it is 1 to 60 minutes, and, as for drying time, it is more preferable that it is 1 to 30 minutes. Moreover, the time to gelation can also be ensured long by using the said polymerization inhibitor. In addition, although the triazine peroxide derivative is decomposed by heat, since the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%, the polymerizable composition is hardly thickened or gelled under these conditions. .

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

<Pattern formation method>

When the polymerizable composition 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 the substrate and, if necessary, dried to form a dry film. And it becomes a cured film by irradiating an active energy ray to a dried film through a mask, and (b) radically polymerizable compound polymerizes in an exposure part. On the other hand, by direct drawing using a laser, a highly precise pattern shape can also be manufactured without using a mask.

After said exposure, an unexposed part is developed and removed with alkali developing solutions, such as a 0.3-3 mass % sodium carbonate aqueous solution, for example, and a patterned cured film is obtained. Further, post-baking at 180 to 250°C for 20 to 90 minutes is performed as post-drying for the purpose of enhancing 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 is a hard coat agent, a coating agent for optical disks, a coating agent for optical fibers, a coating agent for mobile terminals, a coating agent for home appliances, a coating agent for cosmetic containers, an internal antireflection coating agent for optical elements, and a high/low refractive index. paints and coating agents such as coating agents, heat-resistant coating agents, heat-resistant coating agents, and antifogging agents; printing inks such as offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, conductive ink, insulating ink, and light guide plate ink; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; dental materials; materials for waveguides; Black stripe for lens sheet; green sheets and electrode materials for capacitors; adhesives and sealing agents such as adhesives for FPDs, adhesives for HDDs, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch panels, and OCR for touch panels; resists for FPDs such as color resists, black resists, protective films for color filters, photo spacers, black column spacers, frame resists, photoresists for TFT wiring, and interlayer insulating films; resists for printed circuit boards, such as liquid soldering resists and dry film resists; It can be used for various applications such as materials for semiconductors such as semiconductor resists and buffer coat films, and there are no particular limitations on the applications.

Example

The present invention will be described in more detail by way of examples below, but the present invention is not limited only to these examples.

<Examples 1 to 5>

(1) Synthesis of triazine peroxide derivatives

[Synthesis Example 1: Synthesis of Compound 1]

1.66 g of ion-exchanged water and 0.553 g (6.64 mmol) of a 48 mass% sodium hydroxide aqueous solution were added to a 20 ml eggplant flask, and 0.698 g (5.31 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution was added at 30°C or less. was added slowly. Here, a mixed solution of 0.500 g of 2,4-dichloro-6-phenyl-1,3,5-triazine (2.21 mmol, purchased from Namiki Corporation) and 1 ml of tetrahydrofuran was stirred at 10°C for 10 minutes. It was dripped over and it was made to react at 20 degreeC for 3.5 hours. After completion of the reaction, after adding 10 ml of dichloromethane, the aqueous phase was separated. The oil phase was washed with ion-exchanged water and dried over anhydrous magnesium sulfate at 0°C. After filtration, the oil phase was concentrated under reduced pressure to obtain 0.683 g (92% yield) of Compound 1 of the present invention. Table 1 and Table 2 show the properties of Compound 1 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 2: Synthesis of Compound 23]

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

0.815 g of ion-exchanged water and 0.272 g (3.26 mmol) of a 48 mass% sodium hydroxide aqueous solution were added to a 30 ml eggplant flask, and 0.343 g (2.61 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution was added at 30°C or less. was added slowly. Here, 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 stirred at 10°C for 10 minutes. It was dripped over and it was made to react at 20 degreeC 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 0.216 g (52% yield) of the compound 23 of the present invention. Table 1 and Table 2 show the properties of the obtained compound 23 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 3: Synthesis of Compound 25]

5.01 g (31.7 mmol) of 1-methoxynaphthalene, 100 mL of dehydrated dichloromethane, and 6.12 g (33.2 mmol) of cyanuric chloride were placed in a 300 mL eggplant flask, and the mixture was 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-cooled 1 M hydrochloric acid, and the aqueous phase was separated. The oil phase was washed with 100 ml of saturated brine and dried over anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure to obtain a yellow solid of 9.59 g of the crude product. The crude product was purified by silica gel column chromatography (n-hexane/toluene = 4/1 to 1.5/1) to obtain 8.05 g (83% yield) of 2,4-dichloro-6-(4-methoxy-1- naphthalenyl)-1,3,5-triazine was obtained.

0.245 g of ion-exchanged water and 0.0817 g (0.98 mmol) of a 48 mass% sodium hydroxide aqueous solution were added to a 30 ml eggplant flask, and 0.103 g (0.78 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution was added at 30°C or less. was added slowly. Here, 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, It was dripped at 10 degreeC over 10 minutes, and it was made to react at 20 degreeC for 4 hours. After completion of the reaction, 50 ml of ethyl acetate and 50 ml of ion-exchanged 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 (93% yield) of the compound 25 of the present invention. Table 1 and Table 2 show the properties of Compound 25 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 4: Synthesis of Compound 26]

Compound 26 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 Compound 26 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 5: Synthesis of Compound 31]

Compound 31 of the present invention is 2,4-dichloro-6-phenyl-1,3,5-triazine described in Synthesis Example 1, 2,4-dichloro-6- (4-ethoxy-1-naphthal Renyl) -1,3,5-triazine (Sigma Aldrich reagent) was synthesized according to the method described in Synthesis Example 1 except for changing. Table 1 and Table 2 show the properties of the obtained compound 31 and the results of analysis by EI-MS and ¹ H-NMR.

[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 aqueous solution of 69 mass% tert-butyl hydroperoxide described in Synthesis Example 3 was changed to 85 mass% tert-amyl hydroperoxide. Table 1 and Table 2 show the properties of the obtained compound 32 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 7: Synthesis of Compound 33]

Compound 33 of the present invention is 2,4-dichloro-6-phenyl-1,3,5-triazine described in Synthesis Example 1, 2-(4-biphenylyl)-4,6-dichloro-1, It was synthesized according to the method described in Synthesis Example 1 except for changing to 3,5-triazine (Tokyo Chemical Industry Reagent). Table 1 and Table 2 show the properties of the obtained compound 33 and the results of analysis by EI-MS and ¹ H-NMR.

[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 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, 1-bromonaphthalene described in Synthesis Example 2, 4-bromo-4'-methoxybiphenyl, and 69 mass% tert-butyl hydroperoxide aqueous solution were mixed with 85 mass% tert-amyl Except for changing to hydroperoxide, it was synthesized according to the method described in Synthesis Example 2. Table 1 and Table 2 show the properties of 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, 1-bromonaphthalene described in Synthesis Example 2, 4-bromo-4'-methoxybiphenyl, and 69 mass% tert-butyl hydroperoxide aqueous solution were mixed with 90 mass% tert-hexylhydride. It was synthesized according to the method described in Synthesis Example 2 except for changing to loperoxide. Table 1 and Table 2 show the properties of Compound 38 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 11: Synthesis of Compound 40]

Compound 40 of the present invention, 1-bromonaphthalene described in Synthesis Example 2, 4-bromo-4'-methoxybiphenyl, and 69 mass% tert-butyl hydroperoxide aqueous solution were mixed with 80 mass% cumene hydroper Except for changing to oxide, 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 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, cyanuric chloride 5.70 g (10 mmol), trans-phenylvinylboronic acid 1.56 g (30 mmol, Sigma Aldrich reagent), bis(triphenylphosphine)dichloride 0.31 g (0.4 m mol) and 40 ml of toluene were added, and the mixture was 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 dropwise addition, reaction was performed at room temperature for 1 hour. After completion of the reaction, the aqueous phase was separated. After the oil phase was washed once with saturated brine, it was 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 (78% yield) of 2,4-dichloro-6-(2-phenylethenyl)-1,3,5-triazine.

0.893 g of ion-exchanged water and 0.298 g (3.57 mmol) of a 48 mass% sodium hydroxide aqueous solution were added to a 20 ml eggplant flask, and 0.376 g (2.86 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution was added at 30°C or less. was added slowly. Here, 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 stirred at 10°C for 10 minutes. It was dripped over and it was made to react at 20 degreeC for 2 hours. After completion of the reaction, 50 ml of dichloromethane and 50 ml of ion-exchanged 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 (71% yield) of Compound 43 of the present invention. Table 1 and Table 2 show the properties of Compound 43 and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 14: Synthesis of Compound 44]

Compound 44 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 Compound 44 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 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 Compound 48 and the results of analysis by EI-MS and ¹ H-NMR.

(2) Evaluation of UV absorption characteristics

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

<Comparative Examples 1 to 2>

Moreover, as a comparative example, the results of compound R1 and compound R2 are shown in Table 3. In addition, compound R1 was synthesized according to the manufacturing method described in Unexamined-Japanese-Patent No. 59-197401, and was identified by EI-MS and ¹ H-NMR. As compound R2, Irgacure 184 (manufactured by BASF) was used.

[Formula 7]

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 absorption at the wavelength 313 nm The coefficient (L·mol ^-1 ·cm ^-1 ) and ε ₃₆₅ represent the molar extinction coefficient (L·mol ^-1 ·cm ^-1 ) at a wavelength of 365 nm.

In general, the larger the molar extinction coefficient of the photopolymerization initiator at the exposure wavelength is, the easier light is absorbed and the easier it is to generate radicals. That is, a compound having a large molar extinction coefficient at an exposure wavelength is preferable for high sensitivity of the photopolymerization initiator. Ultra-high pressure mercury lamps and high-pressure mercury lamps used for UV curing use a wavelength of 365 nm (i-line) as a dominant wavelength and emit light with a wavelength of 313 nm (j-line) or the like efficiently. From the results in Table 3, it can be seen that the triazine peroxide derivative of the present invention has large molar extinction coefficients at wavelengths of 365 nm and 313 nm emitted from a high-pressure mercury lamp or the like with respect to compound R1 of the benzophenone skeleton. In addition, although single light with a wavelength of 365 nm or the like is emitted from the LED, 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 It turns out that silver has a large molar extinction coefficient at a wavelength of 365 nm.

<Examples 18 to 34, Comparative Examples 3 to 5>

<Preparation of polymerizable compositions (A) to (C)>

(b) radical polymerizable compound in the amount shown in Table 4, (c) alkali-soluble resin and other components were mixed and stirred, (a) polymerization initiator was added and stirred well, Examples 18 to 34 and Comparative Example 3 The polymerizable compositions (A) to (C) of 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 Toa Synthetic Industries Co., Ltd.);

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

EMK: 4,4'-bis(diethylamino)benzophenone (Tokyo Chemical Industry Reagent)

F-477 is a fluorine-based leveling agent (trade name: Megafac F-477, manufactured by DIC Corporation);

PGMEA is propylene glycol monomethyl ether acetate (Wako Pure Chemical Industries, Ltd.); indicates

(3) Evaluation of sensitivity

The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After the application, the solvent was dried by drying the aluminum substrate for 2.5 minutes in a 90°C clean oven to prepare a uniform coating film having a thickness of 1.5 μm. Next, step exposure was performed in the range of 10 to 1000 mJ/cm 2 through a mask pattern using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source. The aluminum substrate after exposure was immersed in 1.0 mass % sodium carbonate aqueous solution at 23 degreeC for 60 second, and the unexposed part was removed by image development. Subsequently, it was washed with pure water for 30 seconds to obtain a patterned shape. The lowest exposure amount at which a pattern shape was formed was evaluated as "sensitivity". Table 5 shows the evaluation results of each (a) polymerization initiator.

For compound R1 of the benzophenone skeleton, from the results of Table 5, compound 23, compound 25, compound 26, compound 31, compound 32, compound 33, compound 35, compound 37, compound 38, compound 40, compound 41, compound 43 , it became clear that the sensitivity of compound 44, compound 5, compound 19, and compound 48 was high. Since these compounds have high molar extinction coefficients at a wavelength of 365 nm and a wavelength of 313 nm, it is estimated that the sensitivity is high. Moreover, it became clear that the sensitivity improved by using a sensitizer together with the compound 1. Since the efficiency of energy transfer from the sensitizer of compound 1 is excellent, it is estimated that sensitivity is high.

<Example 35, Comparative Example 6>

<Preparation of polymerizable composition (D)>

The amounts shown in Table 6 (b) radically polymerizable compound and curing accelerator were mixed and stirred, (a) polymerization initiator was added and stirred well to prepare polymerizable compositions (B) of Example 29 and Comparative Example 6. .

In Table 6, UV-3700B is urethane acrylate (trade name: Jakwang UV-3700B, manufactured by Nippon Synthetic Chemical Industries, Ltd.);

IBOA is isobornyl acrylate (Tokyo Chemical Industry Co., Ltd.);

THFA is tetrahydrofurfuryl acrylate (Tokyo Chemical Industry Co., Ltd.);

TMPTA is trimethylolpropane triacrylate (Tokyo Chemical Industry Co., Ltd.);

DMT is N,N-dimethyltoluidine (Tokyo Chemical Industry Co., Ltd.); indicates

(4) Evaluation of dual cure curing characteristics

The polymerizable composition (D) prepared above was applied to a PET film (trade name: Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 µm and treated for easy adhesion with an applicator to a thickness of 50 µm, and the surface was coated with black PET. A film (the transmittance at a wavelength of 365 nm is less than 0.1%) was installed in the half area of the film. And irradiation of 100 mJ/cm<2> was performed using the conveyor-type UV irradiation apparatus equipped with the high-pressure mercury lamp. Next, it was made to stand still in the blowing constant temperature thermostat, and the heating for 90 minutes was performed at 90 degreeC.

After the above heating, the black coated PET film was removed to expose the cured film, and the cured film portion was measured for curing degree (%) by attenuated total reflection infrared spectroscopy (ATR-IR). At that time, using the peak area of the absorption spectrum of the in-plane angular vibration of the double bond group (1410 cm ^-1 ) and the absorption spectrum of the carbonyl group without change before and after exposure (1740 cm ^-1 ), the curing rate is based on the following formula (degree of cure) was calculated. The results are shown in Table 7.

From the results of Table 7, it is clear that the triazine peroxide derivative of the present invention and the polymerizable composition containing the compound have excellent sensitivity to light and have photocurability and heat curability as features. .

<Examples 36 to 39, Comparative Examples 7 to 8>

<Preparation of polymerizable composition (E)>

(b) radically polymerizable compound in the amount shown in Table 8, (c) alkali-soluble resin and other components were mixed and stirred, (a) polymerization initiator was added and stirred well, Examples 36 to 39 and Comparative Example 7 The polymerizable composition (E) of -8 was prepared. In addition, as compounds R3 and R4, which are halomethyltriazine derivatives of comparative examples, Tokyo Chemical Industry Co., Ltd. was used.

[Formula 8]

(5) evaluation of color (b ^* value)

The polymerizable composition (E) prepared above was applied onto a glass substrate using a spin coater. After the coating, the solvent was dried by drying the glass substrate for 2.5 minutes in a clean oven at 90°C to prepare a uniform coating film having a thickness of 1.5 µm. And irradiation of 300 mJ/cm<2> was performed using the conveyor-type UV irradiation apparatus equipped with the high-pressure mercury lamp, and the test piece was manufactured. As a result of measuring the curing degree of the obtained test pieces, the curing degree was 90% or more in all the test pieces. For the obtained test piece, the L ^* , a ^* , and b ^* colorimetric values were measured by the transmission method according to JIS-Z-8722 using a spectrophotometer (CM-3500d, manufactured by Minolta Cameras). The value of b ^* is evaluated as an index of yellowness, and yellowness is so low that b ^* is small. The results are shown in Table 9.

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

Claims (7)

General formula (1):

(In formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a phenyl group with or without an alkyl group, and n represents an integer of 0 to 2 and X is an aryl group represented by General Formula (2): Ar ¹ , Ar ² , Ar ³ , or Ar ⁴ )

(In 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, a substituent represented by general formula (3): R ⁵ -Y-, a nitro group, or a cyano group, wherein Y represents an oxygen atom or a sulfur atom, and R ⁵ has any one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon backbone, or has none. represents a hydrocarbon group having 1 to 18 carbon atoms, a phenyl group with or without an alkyl group, or an acyl group having 1 to 8 carbon atoms, or R ⁴ is 5 by two adjacent formula (3): R ⁵ -Y- represents a hydrocarbon group forming a six-membered ring). According to claim 1,
In the general formula (2), R ⁴ represents, as an independent substituent, an alkyl group having 1 to 8 carbon atoms or a substituent represented by the general formula (3): R ⁵ -Y-, wherein Y represents an oxygen atom; Said R ⁵ is, in the carbon skeleton, an ether bond; and a terminal hydroxyl group; Represents a phenyl group having or not having any one or more of the above, or having no C1-C8 hydrocarbon group or an alkyl group, or R ⁴ is adjacent to two of the above general formula (3): R ⁵ - A triazine peroxide derivative characterized by representing a hydrocarbon group forming a 5- to 6-membered ring by Y-. A polymerizable composition characterized by containing (a) a polymerization initiator containing the triazine peroxide derivative according to claim 1, and (b) a radically polymerizable compound. According to claim 3,
A polymerizable composition characterized by further containing (c) an alkali-soluble resin. A cured product characterized by being formed from the polymerizable composition according to claim 3 or 4. A method for producing a cured product according to claim 5, comprising a step of irradiating the polymerizable composition with an active energy ray. According to claim 6,
A method for producing a cured product characterized by further including a step of heating after the step of irradiating with the active energy ray.