JP7300108B2 - Cured product manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a cured product.

A photopolymerizable composition containing a photopolymerization initiator and a radically polymerizable compound has the advantage that it can be cured in a short time by photocuring and can be patterned by photomask or laser irradiation. However, there is a problem that the hardening is insufficient in the deep part of the molded body with a thick film, which is difficult for light to reach.

As a method for solving this problem, Patent Document 1 proposes a method in which a photocurable composition is formed into a thick film sheet, and then light is irradiated from both sides of the sheet to cure the inside of the thick film. . Further, in Patent Document 2, a photopolymerization initiator and a thermal polymerization initiator are used together, radicals generated from the photopolymerization initiator by light irradiation cause a polymerization reaction, and the heat of the reaction causes the thermal polymerization initiator to generate radicals. , a method of deep curing has been proposed.

JP 2015-163684 A JP-A-2017-8132

However, in the method of Patent Document 1, the curing method is complicated, and the film thickness that can be cured is limited to 10 mm or less. In addition, in the method of Patent Document 2, the photopolymerization initiator that was not photoexcited in the deep part (the part not irradiated with light) remains unreacted in the cured product, and in a high-temperature and high-humidity environment, the initiation There was concern that the agent would bleed out and the cured product would turn white or yellow.

The first object of the present invention has been made in view of the above circumstances, and a cured product having a certain thickness or more can be obtained only by irradiating a composition containing a radically polymerizable compound with an active energy ray. It provides a method for producing a cured product.

In addition, the second object of the present invention has been made in view of the above-mentioned circumstances, and the active energy ray To provide a method for producing a cured product that can sufficiently cure the non-irradiated portions of the rays.

（式（１）中、Ｒ^１およびＲ^２は独立してメチル基またはエチル基を表す。Ｒ^３は炭素数１～５の脂肪族炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。Ｘは下記一般式（２）：Ａｒ^１、Ａｒ^２、Ａｒ^３またはＡｒ^４で表されるアリール基である。ｎは０から２の整数を表す。）

（式（２）中、ｍは０から３の整数を表す。Ｒ^４は、独立した置換基であって、炭素数１から６のアルキル基、一般式（３）：Ｒ^５－Ｙ－で表される置換基、ニトロ基、またはシアノ基を表す。前記Ｙは、酸素原子または硫黄原子を表す。前記Ｒ^５は、炭素骨格中に、エーテル結合、チオエーテル結合、および、末端に水酸基のいずれか１つ以上を有していてもよい炭素数１～６の炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。あるいは、Ｒ^４は隣接する２つの前記一般式（３）：Ｒ^５－Ｙ－により５～６員環を形成してもよい。） The present invention provides a method for producing a cured product, comprising the step (I) of irradiating a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by the following general formula (1) with an active energy ray, The present invention relates to a method for producing a cured product, characterized in that the cured product has a thickness of more than 300 μm.

(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 carbon number which may have an alkyl group. represents an aromatic hydrocarbon group of 6 to 9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer of 0 to 2 .)

(in formula (2), m represents an integer of 0 to 3; R ⁴ is an independent substituent, an alkyl group having 1 to 6 carbon atoms; general formula (3): R ⁵ -Y- represents a substituent, a nitro group, or a cyano group, Y represents an oxygen atom or a sulfur atom, and R ⁵ has an ether bond, a thioether bond, or a hydroxyl group at the end in the carbon skeleton. represents a hydrocarbon group having 1 to 6 carbon atoms which may have ^one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The two general formulas (3): R ⁵ —Y— may form a 5- to 6-membered ring.)

The present invention also provides a method for producing a cured product, wherein the step (I' ), and a step (II) of thermally polymerizing a portion of the composition not irradiated with the active energy ray by the heat of polymerization generated in the step (I′). Regarding.

Although the details of the action mechanism of the effect in the method for producing a cured product of the present invention are partly unknown, it is presumed as follows. However, the present invention need not be construed as being limited to this action mechanism.

The first method for producing a cured product of the present invention includes step (I) of irradiating a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by general formula (1) with an active energy ray, The thickness of the object is over 300 μm. In the second method for producing a cured product of the present invention, a step (I') of irradiating a part of a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by general formula (1) with an active energy ray. and a step (II) of thermally polymerizing a portion of the composition not irradiated with the active energy ray by the heat of polymerization generated in the step (I′). By irradiating the surface of the composition with active energy rays, the triazine peroxide derivative is excited to generate radicals, thereby initiating a polymerization reaction. Furthermore, in the production method, the decomposition of the peroxyester group of the triazine peroxide derivative is promoted by the diffusion of the polymerization heat of the polymerization reaction, so that the curing reaction of the composition can be continued without external heating. Therefore, a cured product having a certain thickness or more can be obtained, and the curing reaction of the composition can be sufficiently cured to deep portions (portions not irradiated with activation energy). Therefore, it can be expected that the unreacted triazine peroxide derivative does not remain in the cured product of the present invention.

The composition of the present invention contains a radically polymerizable compound and a triazine peroxide derivative represented by general formula (1).

<Radical polymerizable compound>
As the radically polymerizable compound, a compound having an ethylenically unsaturated group can be preferably used. Examples of radically polymerizable compounds include (meth)acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, vinyl ethers, and 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. The radically polymerizable compound may be used alone or in combination of two or more.

Monofunctional compounds and polyfunctional compounds can be used as 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, hydroxyl group-terminated polyethylene glycol mono ( Monomers having a hydroxyl group such as meth)acrylate, hydroxyl-terminated polypropylene glycol mono(meth)acrylate, etc.; methoxyethyl (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (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 ( Monomers having a chain or cyclic ether bond such as meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, etc.; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N -methylol (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, N-(meth)acryloyloxyethylhexahydrophthalimide Monomers having a nitrogen atom such as; monomers having an isocyanate group such as 2-(meth) acryloyloxyethyl isocyanate; monomers having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether; Phosphorus atom-containing monomers such as acid 2-((meth)acryloyloxy)ethyl; Silicon atom-containing monomers such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth) Monomers having a fluorine atom such as acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate; (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. and the like having a carboxyl group.

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, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol di( meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, glycerol propoxy tri(meth)acrylate tricyclodecane dimethanol di(meth)acrylate (Meth)acrylate, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 9,9-bis(4- Polyhydric alcohols such as (2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-(2-(meth)acryloyloxyethoxy)ethoxy)phenyl)fluorene and (meth)acryl Ester compounds with acids; 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 acrylate, epoxy acrylate, polyester acrylate, and the like.

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

（式（１）中、Ｒ^１およびＲ^２は独立してメチル基またはエチル基を表す。Ｒ^３は炭素数１～５の脂肪族炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。Ｘは下記一般式（２）：Ａｒ^１、Ａｒ^２、Ａｒ^３またはＡｒ^４で表されるアリール基である。ｎは０から２の整数を表す。）

（式（２）中、ｍは０から３の整数を表す。Ｒ^４は、独立した置換基であって、炭素数１から６のアルキル基、一般式（３）：Ｒ^５－Ｙ－で表される置換基、ニトロ基、またはシアノ基を表す。前記Ｙは、酸素原子または硫黄原子を表す。前記Ｒ^５は、炭素骨格中に、エーテル結合、チオエーテル結合、および、末端に水酸基のいずれか１つ以上を有していてもよい炭素数１～６の炭化水素基、またはアルキル基を有してもよい炭素数６～９の芳香族炭化水素基を表す。あるいは、Ｒ^４は隣接する２つの前記一般式（３）：Ｒ^５－Ｙ－により５～６員環を形成してもよい。） <Triazine peroxide derivative>
The triazine peroxide derivative is represented by the following 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 carbon number which may have an alkyl group. represents an aromatic hydrocarbon group of 6 to 9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer of 0 to 2 .)

(in formula (2), m represents an integer of 0 to 3; R ⁴ is an independent substituent, an alkyl group having 1 to 6 carbon atoms; general formula (3): R ⁵ -Y- represents a substituent, a nitro group, or a cyano group, Y represents an oxygen atom or a sulfur atom, and R ⁵ has an ether bond, a thioether bond, or a hydroxyl group at the end in the carbon skeleton. represents a hydrocarbon group having 1 to 6 carbon atoms which may have ^one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The two general formulas (3): R ⁵ —Y— may form a 5- to 6-membered ring.)

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

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

n in the general formula (1) is an integer of 0 to 2; n is preferably 0 or 1 from the viewpoint of easy synthesis of the triazine peroxide derivative. X is Ar ² , Ar ³ or Ar ⁴ when n is 0, and X is Ar ¹ when n is 1. It is more preferable from the viewpoint that the yellowness can be reduced.

m in the general formula (2) is an integer of 0 to 3; From the viewpoint of facilitating synthesis of the triazine peroxide derivative, m is preferably 0 to 2, and from the viewpoint of efficient absorption of irradiation light, m is more preferably 1.

In the general formula (2), R ⁴ is an independent substituent, an alkyl group having 1 to 6 carbon atoms, general formula (3): a substituent represented by R ⁵ -Y-, a nitro group , or represents a cyano group. Y represents an oxygen atom or a sulfur atom. R ⁵ has an ether bond, a thioether bond, and a hydrocarbon group having 1 to 6 carbon atoms which may have one or more hydroxyl groups at the end, or an alkyl group in the carbon skeleton; represents an aromatic hydrocarbon group having 6 to 9 carbon atoms which may be substituted. Alternatively, R ⁴ may form a 5- to 6-membered ring with two adjacent general formula (3): R ⁵ -Y-.

From the viewpoint of efficiently absorbing irradiation light, R ⁴ is an independent substituent which is an alkyl group having 1 to 6 carbon atoms, or a substituent represented by general formula (3): R ⁵ -Y- , Y represents an oxygen atom, and R ⁵ is a hydrocarbon group having 1 to 6 carbon atoms which may have one or more of an ether bond and a hydroxyl group at the end in the carbon skeleton. , or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. Alternatively, R ⁴ preferably forms a 5- to 6-membered ring with two adjacent general formulas (3): R ⁵ -X-.

Specific examples of R ⁴ include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group and n-hexyl 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, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxy ethoxy group, 2-butoxyethoxy group, 2-(2-hydroxyethoxy)ethoxy group, 2-(2-ethoxyethoxy)ethoxy group, 1,2-dihydroxypropoxy group, methylenedioxy group, dimethylmethylenedioxy group, alkoxy groups such as ethylenedioxy group; aryloxy groups such as phenyloxy group and 4-isopropylphenyloxy group; methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, 2-(2-methoxy ethoxy)alkylsulfanyl groups such as ethylsulfanyl groups; and arylsulfanyl groups such as phenylsulfanyl groups, 2-methylphenylsulfanyl groups and 4-methylphenylsulfanyl groups. Compounds represented by general formula (1) having these functional groups are preferable because they have high absorbance at 365 nm and efficiently absorb irradiation light.

Furthermore, among these, triazine peroxide derivatives are highly soluble in compositions, easy ^to synthesize, and highly sensitive to irradiation light. is more preferred.

The substitution position of R ⁴ is not particularly limited, but when X is Ar ¹ , at least one R ⁴ is preferably substituted at the 4-position of the benzene ring substituted with a triazine group. Also, when X is Ar ² , at least one R ⁴ is preferably substituted at the 4-position of a benzene ring other than the benzene ring substituted with the triazine group. Also, when X is Ar ³ , at least one R ⁴ is preferably substituted at the 4-position of the triazine group substituted at the 1-position. When X is Ar ⁴ , at least one R ⁴ is preferably substituted at the 4-position of a benzene ring other than the triazine-substituted benzene ring for efficient absorption of irradiation light.

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

As the triazine peroxide derivative, preferably 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 and compound 46, and more preferably compound 25, compound 26, compound 31, compound 32, compound 35, compound 37, compound 38, compound 41 and compound 44.

（上記反応式において、ｎ、Ｒ^１、Ｒ^２、Ｒ^３およびＸは前記一般式（１）と同じである。） <Method for producing triazine peroxide derivative>
The method for producing the triazine peroxide derivative represented by the general formula (1) includes, for example, a step of obtaining a cyanuric chloride derivative (hereinafter also referred to as step (A)) as shown in the following reaction formula, followed by A method comprising a step of reacting a cyanuric chloride derivative with a hydroperoxide in the presence of an alkali (hereinafter also referred to as step (B)). After the step (A) and/or the step (B), 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, n, R ¹ , R ² , R ³ and X are the same as in general formula (1) above.)

In the step (B), a commercially available product can be used as the cyanuric chloride derivative. If there is no commercially available product, it can be synthesized in the step (A) according to known synthesis methods such as Grignard reaction, lithiation reaction, Suzuki coupling reaction, Friedel-Crafts reaction, and the like.

<Synthesis of cyanuric chloride derivative by Grignard reaction>
When synthesizing a cyanuric chloride derivative by a Grignard reaction in the step (A), it can be synthesized according to a known synthesis method described in JP-A-6-179661 and the like. Z of the aromatic compound in step (A) can be an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom. A cyanuric chloride derivative can be synthesized by reacting an aromatic 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 aromatic 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 aromatic compound. The reaction temperature is preferably 0 to 70°C, more preferably 10 to 60°C. The reaction time is preferably 30 minutes to 20 hours, more preferably 1 hour to 10 hours.

Solvents such as ethers such as tetrahydrofuran can be used in the preparation of the Grignard reagent.

In the 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 aromatic compound. more preferred. The reaction temperature is preferably -30 to 70°C, more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Cyanuric chloride may be added to the prepared Grignard reagent, or the Grignard reagent may be added to a solution of cyanuric chloride.

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

<Synthesis of cyanuric chloride derivative by lithiation reaction>
In the step (A), when a cyanuric chloride derivative is synthesized by a lithiation reaction, it can be synthesized according to a known synthesis method described in International Publication No. 2012/096263 and the like. Z of the aromatic compound in step (A) can be an aromatic compound represented by a chlorine atom, a bromine atom, or an iodine atom. A cyanuric chloride derivative can be synthesized by reacting an aromatic 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 lithio compound, the lithiation agent is preferably used in an amount of 0.8 to 3.0 mol, more preferably 1.0 to 2.2 mol, per 1 mol of the aromatic compound. The reaction temperature is preferably -100 to 50°C, more preferably -80 to 0°C. The reaction time is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours.

Solvents such as ethers such as tetrahydrofuran can be used in the preparation of the above lithio compound.

In the reaction between the lithio 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 aromatic compound. more preferred. The reaction temperature is preferably -30 to 70°C, more preferably -10 to 40°C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Cyanuric chloride may be added to the prepared lithio compound, or the lithio compound may be added to a solution of cyanuric chloride.

A solvent such as an ether such as tetrahydrofuran can be used in the reaction between the lithio compound and cyanuric chloride.

<Synthesis of Cyanuric Chloride Derivatives by Suzuki Coupling>
In the step (A), when synthesizing a cyanuric chloride derivative by Suzuki coupling reaction, it can be synthesized according to a known synthesis method described in International Publication No. 2012/096263 and the like. For example, by reacting the aforementioned lithio compound with a boron reagent, it is possible to synthesize a boron compound in which Z in the aromatic compound is converted to a boronyl group or boronic acid. 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, the boron reagent is preferably used in an amount of 0.8 to 3.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of the lithio compound. The reaction temperature is preferably -100 to 50°C, more preferably -80 to 20°C. The reaction time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 10 hours.

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

Further, in the above reaction with 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 of 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 hydrogen carbonate, 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 step (A), 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. Z of the aromatic compound in the step (A) can be a hydrogen atom, and an aromatic compound represented by n=0 can be used. A cyanuric chloride derivative can be synthesized by reacting an aromatic compound with cyanuric chloride in the presence of a Lewis acid such as aluminum chloride.

Examples of Lewis acids include aluminum chloride, aluminum bromide, iron (III) chloride, titanium (IV) chloride, tin (IV) chloride, zinc chloride, bismuth (III) triflate, hafnium (IV) triflate, and boron trifluoride. 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 1.5 mol, more preferably 0.8 to 1.2 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 the solution of the aromatic compound and cyanuric chloride, or the aromatic compound may be added to the solution of cyanuric chloride and aluminum chloride.

Solvents such as dichloromethane, 1,2-dichloroethane, and xylene can be used in the above reaction of the aromatic compound and cyanuric chloride.

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

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

In the step (B), 1.8 mol or more, preferably 2.0 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 5.0 mol or less is preferable, and 3.8 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 (B), the reaction temperature is preferably −10° C. or higher, more preferably 0° C. or higher, and 40° C. or lower, from the viewpoint of increasing the yield of the target product. is preferred, and 30°C or lower is more preferred.

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

The alkali used in the step (B) 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. 5. The alkali is preferably used in an amount of 1.8 mol or more, more preferably 2.0 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 3.8 mol or less.

In the step (B), 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 500 parts by mass per 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 step (B). may be used.

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

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

The blending amount of the composition of the present invention and the like will be described below.

The content of the triazine peroxide derivative is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, and more preferably 0.05 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. to 5 parts by mass is more preferable. If the content of the triazine peroxide derivative is less than 0.01 parts by mass with respect to 100 parts by mass of the radically polymerizable compound, the curing reaction does not proceed, which is not preferable. When the content of the triazine peroxide derivative is more than 20 parts by mass with respect to 100 parts by mass of the radically polymerizable compound, the solubility in the radically polymerizable compound reaches saturation, and the triazine peroxide is Derivative crystals may be precipitated, causing a problem of roughening of the coating surface, and an increase in decomposition residue of the triazine peroxide derivative may reduce the strength of the coating film of the cured product, which is not preferable.

In addition to the triazine peroxide derivative, other polymerization initiators may be used in the composition to improve the surface curability, depth curability, transparency, and the like of the composition. In selecting other polymerization initiators, the radically polymerizable compound, the type of other additives, the film thickness of the cured product, and the like are taken into consideration.

<Other ingredients>
Additives commonly used in applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, and various photoresists such as color resists and black resists can be added to the composition. Examples of additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4′-bis(diethylamino)benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibition agents (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers, infrared absorbers, light stabilizers, antioxidants, leveling agents, surface conditioners , surfactants, thickeners, defoamers, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, colored dyes, fluorescent dyes, pigments (yellow pigments, blue pigments, red pigments, white pigments, black pigments, etc.), carbon-based materials (carbon fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerenes, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.) , metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, etc.), metals (silver, copper, etc.), inorganic compounds (silica, glass powder, lamellar clay minerals, mica, talc, calcium carbonate, etc.), inorganic fillers (aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium sulfate, barium titanate, magnesium oxide, zinc oxide, zirconium oxide, zirconium silicate, etc.), dispersants, flame retardants, and the like. Additives may be used alone or in combination of two or more.

The additive is appropriately selected depending on the purpose of use and is not particularly limited, but pigments, carbonaceous materials, metal oxides, inorganic compounds, inorganic fillers are preferable, and black pigments, carbon black, alumina, silica. is more preferred.

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

A solvent may be further added to the composition in order to improve viscosity, coatability, and smoothness of the cured film. The solvent is not particularly limited as long as it is capable of dissolving or dispersing the radically polymerizable compound, the triazine peroxide derivative, and the other components, and is volatile at the drying temperature.

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

When the solvent is used, the amount of the solvent used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the solid content of the composition.

<Method for preparing composition>
When preparing the composition, the radically polymerizable compound, the triazine peroxide derivative, and, if necessary, the other components are put into a storage container, and the paint shaker, bead mill, sand grind mill, ball mill, atto A lighter mill, two-roll mill, three-roll mill, or the like may be used for dissolution or dispersion according to a conventional method. In addition, if necessary, it may be filtered through a mesh or membrane filter or the like.

In addition, in the preparation of the composition, the triazine peroxide derivative may be added to the composition from the beginning. , preferably dissolved or dispersed in a composition containing a radically polymerizable compound.

<Method for producing cured product>
The first method for producing a cured product of the present invention includes step (I) of irradiating a composition containing the radically polymerizable compound and the triazine peroxide derivative represented by the general formula (1) with an active energy ray, The thickness of the cured product is more than 300 µm. In the second method for producing a cured product of the present invention, a step (I') of irradiating a part of a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by general formula (1) with an active energy ray. and a step (II) of thermally polymerizing a portion of the composition not irradiated with the active energy ray by the heat of polymerization generated in the step (I′).

Since the composition contains the triazine peroxide derivative, a solid cured product can be formed by irradiation with active energy rays. Therefore, the shape of the composition and its cured product is not limited at all, and examples thereof include sheet-like, plate-like and bulk-like (massive) shapes. The composition can be applied, for example, by spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, inkjet printing. It may be coated on a substrate by various coating methods such as a method, a dispenser printing method, etc., or may be cast into a container having a depth. Examples of the substrate and container include films and sheets of glass, silicon wafers, metals, plastics, etc., and three-dimensional molded products, and the shape of the substrate and container is not limited.

Examples of the active energy rays include active energy rays such as electron beams, ultraviolet rays, visible rays, and radiation.

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

The light source for irradiation of the active energy ray includes 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, and YAG. Solid lasers such as lasers, semiconductor lasers, gas lasers such as argon lasers, and the like can be used. When visible light to infrared light, which is less absorbed by the triazine peroxide derivative, is used, curing can be performed by using a sensitizer that absorbs the light as the additive.

The amount of exposure to the active energy ray is such that the composition cures by facilitating the decomposition of the peroxyester group of the triazine peroxide derivative due to the diffusion of the polymerization heat of the polymerization reaction initiated by irradiation with the active energy ray. The amount of exposure should be set appropriately according to the wavelength and intensity of the active energy ray and the components of the 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 . Further, when the composition contains a light-shielding component, the exposure dose in the UV-A region is preferably 100 to 500,000 mJ/cm ² , more preferably 1,000 to 200,000 mJ/cm ² . is more preferable.

In the method for producing the first cured product of the present invention, the thickness of the cured product is more than 300 μm. The thickness indicates the thickness and length depending on the shape of the cured product. For example, when the shape of the cured product is a sheet, it indicates the film thickness. Indicates thickness or length. The thickness of the cured product is a range in which the composition can be cured by facilitating the decomposition of the peroxyester group of the triazine peroxide derivative by diffusion of the polymerization heat of the polymerization reaction initiated by irradiation with an active energy ray. If so, the upper limit is not limited at all, but for example, 500 mm or less and 300 mm or less can be exemplified as the upper limit. Moreover, from the viewpoint of making the most of the advantage of being able to cure the portion of the composition that is not reached by active energy rays, the lower limit of the thickness of the cured product can be, for example, 400 μm or more and 500 μm or more.

In addition, the manufacturing method of the 1st and 2nd hardened|cured material of this invention can include the process of heating if needed.

The first and second cured product manufacturing methods of the present invention and the resulting cured product include hard coating agents, optical disk coating agents, optical fiber coating agents, mobile terminal coatings, home appliance coatings, cosmetic container coatings, Paints and coating agents such as inner anti-reflection coatings for optical elements, high/low refractive index coating agents, heat shield coating agents, heat radiation coating agents, anti-fogging agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks , conductive ink, insulating ink, printing ink such as ink for light guide plate; photosensitive printing plate; nanoimprint material; resin for 3D printer; holographic recording material; Green sheets and electrode materials for capacitors; FPD adhesives, HDD adhesives, optical pickup adhesives, image sensor adhesives, organic EL sealants, OCA for touch panels, OCR for touch panels, and other adhesives and sealants Color resist, black resist, protective film for color filter, photo spacer, black column spacer, frame resist, photoresist for TFT wiring, FPD resist such as interlayer insulating film; liquid solder resist, dry film resist for printed circuit board Resists: can be used for various applications such as semiconductor resists and materials for semiconductors such as buffer coat films, and there are no particular restrictions on the applications.

The present invention will be described in more detail with reference to examples below.

<Synthesis of triazine peroxide derivative>
[Synthesis Example 1: 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 that had been heat-dried and stirred at room temperature. A mixed solution of 7.07 g (50.7 mmol) of 1-bromonaphthalene and 57 mL of dehydrated tetrahydrofuran was added dropwise thereto, followed by refluxing and stirring. After 1 hour, the internal temperature was cooled to -60°C or below. A mixed solution of 8.92 g (48.4 mmol) of cyanuric chloride prepared separately and dehydrated tetrahydrofuran was added dropwise over 15 minutes. After that, the temperature was raised to room temperature over 30 minutes, and the mixture was stirred in a water bath. After 62 hours, the reaction solution was cooled in an ice bath, 1M hydrochloric acid was added, and the pH was adjusted to 8 with a saturated sodium bicarbonate aqueous solution. Then, 160 mL of ion-exchanged water was added, and the mixture was extracted with ethyl acetate. The oil phase was washed once with saturated saline and then dehydrated with magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 14.6 g of crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 1/1 to 1/3) to give 5.14 g (yield 38%) 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 48% by mass sodium hydroxide aqueous solution were added to a 30 mL eggplant flask, and 0.343 g (2.61 mmol) of 69% by mass tert-butyl hydroperoxide aqueous solution was added at 30° C. or lower. was added gradually. A mixed solution of 0.300 g (1.09 mmol) of 2,4-dichloro-6-(1-naphthalenyl)-1,3,5-triazine and 3 mL of tetrahydrofuran was added dropwise thereto at 10° C. over 10 minutes, The reaction was carried out at 20°C for 2 hours. After completion of the reaction, the reaction solution was poured into 50 mL of ice water. Precipitated crystals were filtered, washed with ion-exchanged water, and dried under reduced pressure to obtain 0.216 g (yield 52%) of Compound 23 of the present invention. Tables 1 and 2 show the properties of Compound 23 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 2: 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 stirred in an ice bath. After 15 minutes, 4.43 g (33.2 mmol) of aluminum chloride was added and the temperature was raised to room temperature. After 1 hour, the reaction solution was poured into 75 mL of ice-cold 1 M hydrochloric acid, and the aqueous phase was separated. The oil phase was washed with 100 mL of saturated saline and dehydrated with anhydrous sodium sulfate. After filtration, the mixture was concentrated under reduced pressure to obtain 9.59 g of a crude yellow solid. The crude product was purified by silica gel column chromatography (n-hexane/toluene = 4/1 to 1.5/1) to give 8.05 g (yield 83%) 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 48% by mass sodium hydroxide aqueous solution were added to a 30 mL eggplant flask, and 0.103 g (0.78 mmol) of 69% by mass tert-butyl hydroperoxide aqueous solution was added at 30°C or lower. was added gradually. 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 was added at 10° C. over 10 minutes. and reacted at 20° C. 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 a 5% aqueous sodium hydroxide solution and deionized water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to give 0.125 g (93% yield) of compound 25 of the present invention. Tables 1 and 2 show the properties of Compound 25 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 3: Synthesis of compound 26]
Compound 26 of the present invention was synthesized according to the method described in Synthesis Example 1, except that 1-bromonaphthalene described in Synthesis Example 1 was changed to 2-bromo-6-methoxynaphthalene. Tables 1 and 2 show the properties of Compound 26 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 4: Synthesis of compound 31]
Compound 31 of the present invention was synthesized according to the method described in Synthesis Example 2, except that 1-methoxynaphthalene described in Synthesis Example 2 was changed to 1-ethoxynaphthalene. Tables 1 and 2 show the properties of Compound 31 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 5: Synthesis of compound 32]
Compound 32 of the present invention was synthesized according to the method described in Synthesis Example 2, except that the 69% by mass tert-butyl hydroperoxide aqueous solution described in Synthesis Example 2 was changed to 85% by mass tert-amyl hydroperoxide. bottom. Tables 1 and 2 show the properties of Compound 32 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 6: Synthesis of Compound 35]
Compound 35 of the present invention was synthesized according to the method described in Synthesis Example 1, except that 1-bromonaphthalene described in Synthesis Example 1 was changed to 4-bromo-4'-methoxybiphenyl. Tables 1 and 2 show the properties of Compound 35 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 7: Synthesis of compound 37]
Compound 37 of the present invention was prepared by converting 1-bromonaphthalene described in Synthesis Example 1 into 4-bromo-4'-methoxybiphenyl and 69% by mass of tert-butyl hydroperoxide aqueous solution into 85% by mass of tert-amyl hydroperoxide. Synthesis was carried out according to the method described in Synthesis Example 1, except for the changes. Tables 1 and 2 show the properties of Compound 37 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 8: Synthesis of Compound 38]
In Compound 38 of the present invention, 1-bromonaphthalene described in Synthesis Example 1 was replaced with 4-bromo-4'-methoxybiphenyl, and 69% by mass of tert-butyl hydroperoxide aqueous solution was changed to 90% by mass of tert-hexyl hydroperoxide. Synthesis was carried out according to the method described in Synthesis Example 1, except that Tables 1 and 2 show the properties of Compound 38 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 9: Synthesis of compound 40]
In Compound 40 of the present invention, 1-bromonaphthalene described in Synthesis Example 1 was changed to 4-bromo-4'-methoxybiphenyl, and 69% by mass of tert-butyl hydroperoxide aqueous solution was changed to 80% by mass of cumene hydroperoxide. Synthesis was carried out according to the method described in Synthesis Example 1 except for the above. Tables 1 and 2 show the properties of Compound 40 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 10: Synthesis of Compound 41]
Compound 41 of the present invention was synthesized according to the method described in Synthesis Example 1, except that 1-bromonaphthalene described in Synthesis Example 1 was changed to 4-bromostilbene. Tables 1 and 2 show the properties of Compound 41 obtained and the results of analysis by EI-MS and ¹ H-NMR.

[Synthesis Example 11: Synthesis of Compound 44]
Compound 44 of the present invention was synthesized according to the method described in Synthesis Example 1, except that 1-bromonaphthalene described in Synthesis Example 1 was changed to p-(2-bromo)vinylanisole. Tables 1 and 2 show the properties of Compound 44 obtained and the results of analysis by EI-MS and ¹ H-NMR.

<Example 1>
<Adjustment of composition>
100 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.2 parts by mass of compound 23 as a photopolymerization initiator were mixed and stirred to obtain a composition.

<Examples 2 to 11 and Comparative Example 1>
A composition was prepared in the same manner as in Example 1, except that the photopolymerization initiator shown in Table 3 was used. In Comparative Example 1, compound R1 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM)) was used as a known photopolymerization initiator.

<Production of cured product>
A test tube (diameter 10 mm, height 90 mm) was filled with the composition prepared by the above method to a height of 50 mm. The test tube was shielded from light with aluminum foil except for the upper part, and irradiated from the upper part of the test tube with a 365 nm LED light source at 10 mW/cm ² for 5 seconds (=50 mJ/cm ² ) to produce a cured product. Formation of the cured product (cured layer) was confirmed by removing the cured product from the test tube, and the thickness (mm) of the cured product (cured layer) was measured.

<Example 12>
<Adjustment of composition>
100 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 3,7-bis(2-oxo-1H-indole-3(2H)-ylidene)benzo[1,2-b:4 as a black pigment ,5-b′]difuran-2,6-(3H,7H)-dione and 0.2 parts by mass of Compound 25 as a photopolymerization initiator were mixed and stirred to obtain a composition.

<Examples 13 to 15 and Comparative Example 2>
A composition was prepared in the same manner as in Example 12, except that the photopolymerization initiator shown in Table 4 was used. In Comparative Example 2, compound R1 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM)) was used as a known photopolymerization initiator.

<Production of black cured product>
A test tube (diameter 10 mm, height 90 mm) was filled with the composition prepared by the above method to a height of 50 mm. The test tube was shielded from light with aluminum foil except for the upper part, and irradiated from the upper part of the test tube with a 365 nm LED light source at 350 mW/cm ² for 5 seconds (=1750 mJ/cm ² ) to produce a cured product. Formation of the cured product (cured layer) was confirmed by removing the cured product from the test tube, and the thickness (mm) of the cured product (cured layer) was measured.

<Example 16>
<Adjustment of composition>
100 parts by mass of trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Industry), 60 parts by mass of colloidal silica (manufactured by Fuso Chemical Industry), and 1 part by mass of compound 25 as a photopolymerization initiator are mixed and stirred to obtain a composition. rice field.

<Examples 17 to 19 and Comparative Example 3>
A composition was prepared in the same manner as in Example 16, except that the photopolymerization initiator shown in Table 5 was used. In Comparative Example 3, compound R1 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM)) was used as a known photopolymerization initiator.

<Production of hardened product containing inorganic filler>
A test tube (diameter 10 mm, height 90 mm) was filled with the composition prepared by the above method to a height of 50 mm. Light was shielded with aluminum foil except for the top of the test tube, and a 365 nm LED light source was used from the top of the test tube to irradiate at 650 mW/cm ² for 90 seconds (=58500 mJ/cm ² ) to produce a cured product. Formation of the cured product (cured layer) was confirmed by removing the cured product from the test tube, and the thickness (mm) of the cured product (cured layer) was measured.

In the composition of each example, the formation of a cured product (cured layer) on the upper portion of the composition was confirmed by visual observation by irradiation with an active energy ray, and even after irradiation with an active energy ray, the cured layer was formed. It was confirmed that the interface gradually descended. Moreover, the cured product was taken out from the test tube and the thickness (mm) of the cured product (cured layer) was measured, and it was confirmed that the thickness was 50 mm. Therefore, it is clear that the composition of each example can be cured into a cured product having a certain thickness or more only by the step of irradiating with an active energy ray.

Further, in the composition of the comparative example, the interface of the cured layer did not change after irradiation with active energy rays. Therefore, it is clear that the composition of each example can sufficiently cure the portion of the composition that is not irradiated with the active energy ray by irradiating a portion of the composition containing the radically polymerizable compound with the active energy ray. be.

Claims (4)

A method for producing a cured product,
A step (I) of irradiating a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by the following general formula (1) with an active energy ray,
A method for producing a cured product, wherein the cured product has a thickness of more than 300 µm.

(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 carbon number which may have an alkyl group. represents an aromatic hydrocarbon group of 6 to 9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer of 0 to 2 .)

(in formula (2), m represents an integer of 0 to 3; R ⁴ is an independent substituent, an alkyl group having 1 to 6 carbon atoms; general formula (3): R ⁵ -Y- represents a substituent, a nitro group, or a cyano group, Y represents an oxygen atom or a sulfur atom, and R ⁵ has an ether bond, a thioether bond, or a hydroxyl group at the end in the carbon skeleton. represents a hydrocarbon group having 1 to 6 carbon atoms which may have ^one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The two general formulas (3): R ⁵ —Y— may form a 5- to 6-membered ring.) In general formula (2), m represents an integer of 0 to 3, R ⁴ is an independent substituent and an alkyl group having 1 to 6 carbon atoms, or general formula (3): R ⁵ -Y represents a substituent represented by -, the Y represents an oxygen atom, and the R ⁵ may have one or more of an ether bond in the carbon skeleton and a hydroxyl group at the end. represents a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R ⁴ represents two adjacent general formulas (3): R 2. The method for producing a cured product according to claim 1, wherein ⁵ -Y- may form a 5- to 6-membered ring. A method for producing a cured product,
A step (I') of irradiating a portion of a composition containing a radically polymerizable compound and a triazine peroxide derivative represented by the following general formula (1) with an active energy ray, and polymerization heat generated in the step (I') and a step (II) of thermally polymerizing a portion of the composition not irradiated with the active energy ray.

(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 carbon number which may have an alkyl group. represents an aromatic hydrocarbon group of 6 to 9. X is an aryl group represented by the following general formula (2): Ar ¹ , Ar ² , Ar ³ or Ar ^4. n represents an integer of 0 to 2 .)

(in formula (2), m represents an integer of 0 to 3; R ⁴ is an independent substituent, an alkyl group having 1 to 6 carbon atoms; general formula (3): R ⁵ -Y- represents a substituent, a nitro group, or a cyano group, Y represents an oxygen atom or a sulfur atom, and R ⁵ has an ether bond, a thioether bond, or a hydroxyl group at the end in the carbon skeleton. represents a hydrocarbon group having 1 to 6 carbon atoms which may have ^one or more, or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group. The two general formulas (3): R ⁵ —Y— may form a 5- to 6-membered ring.) In general formula (2), m represents an integer of 0 to 3, R ⁴ is an independent substituent and an alkyl group having 1 to 6 carbon atoms, or general formula (3): R ⁵ -Y represents a substituent represented by -, the Y represents an oxygen atom, and the R ⁵ may have one or more of an ether bond in the carbon skeleton and a hydroxyl group at the end. represents a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group, or R ⁴ represents two adjacent general formulas (3): R 4. The method for producing a cured product according to claim 3, wherein ⁵ -Y- may form a 5- to 6-membered ring.