TW201831445A - Peroxycinnamate derivative and polymerizable composition containing said compound - Google Patents

Abstract

The peroxycinnamate derivative according to the present invention is represented by general formula (1) (in formula (1), n represents an integer from 1 to 3; each R1 independently represents a substituent represented by general formula (2): R-X-, a nitro group, or a cyano group; X represents an oxygen atom or sulfur atom; and R represents a hydrocarbon group having 1 to 6 carbons, which may have, in the carbon skeleton, at least any one of an ether bond, thioether bond, and a hydroxyl group at the terminal. Or, R1 represents a hydrocarbon group that forms a 5- or 6-membered ring as provided by two adjacent R-X- substituents represented by general formula (2). R2 represents a hydrogen atom or methyl group; R3 and R4 each independently represent a methyl group or ethyl group; and R5 represents an aliphatic hydrocarbon group having 1 to 5 carbons, or represents an aromatic hydrocarbon group having 6 to 9 carbons, which may have an alkyl group.). This peroxycinnamate derivative exhibits both thermal polymerizability and photopolymerizability whereby radicals can be generated by the efficient absorption of light at a wavelength of, e.g., 365 nm, emitted from a lamp.

Description

Peroxy cinnamate derivative, polymerizable composition containing the compound, its cured product, and preparation method

The present invention relates to a peroxy cinnamate derivative, a polymerizable composition containing a polymerization initiator containing the compound and a radical polymerizable compound, a cured product thereof, and a method for preparing the cured product.

In order to synthesize polymers, radical polymerization initiators that generate radicals by light or heat, and oxidation-reduction are widely used as polymerization initiators. In particular, a photopolymerization initiator can be used as a polymerization initiator of a radical polymerizable compound by absorbing active energy rays such as light and generating radicals through bond cleavage or hydrogen abstraction reactions. For example, an α-hydroxyacetophenone derivative or an α-aminoacetophenone derivative, a fluorenylphosphine oxide derivative, a halomethyltriazine derivative, a benzophenone ketal derivative, or a thioxanthone derivative can be used Wait.

Since the photopolymerizable composition composed of the photopolymerization initiator and the radical polymerizable compound as described above is rapidly cured by light, it is suitable for coating agents, coatings, and printing from the viewpoints of rapid curing and low VOC. Applications include inks, photosensitive printing plates, adhesives, and various photoresists.

On the other hand, Patent Document 1 discloses a polymerization initiator that generates radicals by light or heat. The polymerization initiator contains a benzophenone group-containing radical having a peroxide bond (-OO-) in the molecule. Oxidized ester is an active ingredient. In addition, Patent Document 2 discloses an adhesive composition composed of the polymerization initiator and a radical polymerizable compound. By performing dual curing by light curing at normal temperature and subsequent heat curing, the adhesive exhibits Strong adhesive strength and high durability.

In this manner, a dual-curable polymerizable composition having both photopolymerization and thermal polymerizability can also be used to improve the curability of dark portions. Dual-curable polymerizable composition, for example, curing a polymerizable composition in which a pigment or a 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 to cure the position where the light cannot reach, such as the lower part of the touch panel electrode.

Know-how

Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 59-197401

Patent Document 2: Japanese Patent Laid-Open No. 2000-96002

Technical problem to be solved by the present invention

However, since the benzophenone group-containing peroxide described in Patent Document 1 or Patent Document 2 does not sufficiently absorb long-wavelength light having a wavelength longer than 365 nm emitted by a high-pressure mercury lamp or LED, it is regarded as The sensitivity of the most important basic characteristics of the photopolymerization initiator is insufficient, and as a technical problem, an increase in the sensitivity can be cited.

Therefore, in order to solve the above-mentioned technical problems, the present invention provides a percinnamate derivative having both photopolymerization and thermal polymerizability capable of efficiently absorbing light emitted by a lamp having a wavelength of 365 nm and the like to generate radicals.

Furthermore, this invention provides the polymerizable composition containing the polymerization initiator containing the said peroxy cinnamate derivative and a radically polymerizable compound, its hardened | cured material, and the manufacturing method of this hardened | cured material.

Technical means to solve technical problems

That is, the present invention relates to a percinnamate derivative represented by the general formula (1),

[Chemical Formula 1]

In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, which represents the general formula (2): a substituent represented by RX-, a nitro group or a cyano group, and X represents an oxygen atom Or a sulfur atom, where R represents a hydrocarbon group having 1 to 6 carbon atoms, which may have any one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, or R ¹ represents an Two of said general formula (2): RX—a hydrocarbon group forming a five to six membered ring, R ² represents a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent a methyl group or an ethyl group, and R ⁵ represents the number of carbon atoms An aliphatic hydrocarbon group of 1 to 5 or an aromatic hydrocarbon group of 6 to 9 carbon atoms which may have an alkyl group.

The present invention also relates to a polymerizable composition containing (a) a polymerization initiator and (b) a radical polymerizable compound including the peroxycinnamate derivative, and a cured product formed from the polymerizable composition, And a method for preparing the cured product.

Invention effect

The peroxycinnamate derivative of the present invention can efficiently generate radicals with respect to light having a wavelength of 365 nm or the like emitted from a lamp, and has a peroxide bond in the molecule, and thus is useful as a light and thermal polymerization initiator. Therefore, the polymerizable composition containing the peroxycinnamate derivative and the radically polymerizable compound can be cured well by irradiation with light, and can also be cured well by heat even in a dark part not reachable by light.地 solidify.

<Cinnamon Peroxide Derivatives>

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

[Chemical Formula 2]

In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, which represents the general formula (2): a substituent represented by RX-, a nitro group or a cyano group, and X represents an oxygen atom Or a sulfur atom, where R represents a hydrocarbon group having 1 to 6 carbon atoms, which may have any one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, or R ¹ represents an Two of said general formula (2): RX—a hydrocarbon group forming a five to six membered ring, R ² represents a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent a methyl group or an ethyl group, and R ⁵ represents the number of carbon atoms An aliphatic hydrocarbon group of 1 to 5 or an aromatic hydrocarbon group of 6 to 9 carbon atoms which may have an alkyl group.

N in the general formula (1) is represented by an integer of 1 to 3, which represents the number of R ¹ side chains on a phenyl ring. From the viewpoint of easily synthesizing the peroxycinnamate derivative, n is preferably 1 or 2.

R ¹ in the general formula (1) is an independent substituent, which represents the general formula (2): a substituent represented by RX-, a nitro group or a cyano group, and X represents an oxygen atom or a sulfur atom. The R represents a hydrocarbon group having 1 to 6 carbon atoms, and may have any one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton. Alternatively, R ¹ represents a hydrocarbon group which forms a five- to six-membered ring by adjacent two of the general formula (2): RX-.

From the viewpoint of high sensitivity to light, it is preferred that R ¹ is an independent substituent, which represents a substituent represented by the general formula (2): RX-, wherein X represents an oxygen atom, and R is a hydrocarbon group having 1 to 6 carbon atoms, and may have any one or more of an ether bond in a carbon skeleton and a terminal hydroxyl group; or R ¹ is two adjacent general formulas (2) : RX- a 5- to 6-membered hydrocarbon group.

Specific examples of the R ¹ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, and n-pentoxy , Cyclopentyloxy, n-hexyloxy, cyclohexyloxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2 -(2-hydroxyethoxy) ethoxy, 2- (2-ethoxyethoxy) ethoxy, 1,2-dihydroxypropoxy, methylenedioxy, ethylenedioxy Alkylthio groups such as methylthio, ethylthio, hexylthio, 2-methoxyethylthio, 2- (2-methoxyethoxy) ethylthio, etc. The compound represented by the general formula (1) having these functional groups is preferable because it has high absorbance at a wavelength of 365 nm and effectively absorbs light.

Furthermore, from the viewpoints that the peroxy cinnamate derivative has high solubility in a polymerizable composition and is easy to synthesize, the R ^{1 is} preferably a methoxy group, an ethoxy group, or a 2-hydroxyethoxy group. And methylenedioxy.

In the general formula (1), R ² represents a hydrogen atom or a methyl group. From the standpoint of increasing the decomposition temperature of the peroxycinnamate derivative and increasing the storage stability of the polymerizable composition, R ^{2 is} preferably a hydrogen atom.

In the general formula (1), R ³ and R ⁴ independently represent a methyl group or an ethyl group. From the viewpoint that the decomposition temperature of the peroxycinnamate derivative is increased and the storage stability of the polymerizable composition is increased, R ³ and R ^{4 are} preferably methyl groups.

In the general formula (1), R ⁵ 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 ⁵ include methyl, ethyl, propyl, 2,2-dimethylpropyl, methylcyclohexyl, phenyl, and isopropylphenyl. Among them, methyl, ethyl, propyl, 2,2-dimethylpropyl, and phenyl are preferred from the viewpoint of easy synthesis of the peroxycinnamate derivative.

Specific examples of the peroxycinnamate derivative of the present invention are shown below.

[Chemical Formula 3]

<Preparation method of peroxycinnamate derivative>

The method for producing the peroxycinnamate derivative represented by the general formula (1) is not particularly limited, and can be synthesized based on a conventional peroxyester synthesis method described in Japanese Patent Application Laid-Open No. 51-115411 and the like. .

The method for producing a peroxycinnamate derivative represented by the general formula (1) includes, for example, a method including the following reaction formula, which includes the following steps: by combining a cinnamic acid derivative with thionyl chloride, A step of reacting a chlorinating agent such as phosphorus trichloride and phosgene to obtain a cinnamyl chloride derivative (hereinafter, also referred to as step (A)); and derivatizing the obtained cinnamyl chloride in the presence of a base A step of reacting a substance with a hydroperoxide (hereinafter, also referred to as step (B)). In addition, after the steps (A) and / or (B), a step of purifying (removing) the remaining chlorinating agent or the like under reduced pressure may be included.

[Chemical Formula 4]

In the above reaction formula, R ¹ , R ² , R ³ , R ^4, and R ⁵ are the same as the general formula (1).

In the step (A), the cinnamic acid derivative may be a commercially available product. When there is no commercially available product, it can be synthesized based on a known synthesis method described in paragraph [0230] of Japanese Patent Application Laid-Open No. 2013-520490 and the like. From the perspective of improving the yield of the target product, the chlorinating agent is preferably reacted at 1 mole or more, and more preferably 1.1 mole at least, compared to 1 mole of cinnamic acid derivative. The chlorinating agent serves also as a solvent to perform the reaction using an excess amount, but it is preferred to perform the reaction at 10 mol or less, and more preferably to perform the reaction at 5 mol or less.

In the step (A), from the viewpoint of improving the yield of the target product, the reaction temperature is preferably 0 ° C or higher, more preferably 20 ° C or higher, and preferably 150 ° C or lower, and more preferably 80 ° C or lower. .

In the step (A), since the reaction time varies depending on the starting materials, the reaction temperature, etc., the reaction time cannot be determined uniformly, but it is usually 30 minutes or more and 20 hours or less from the viewpoint of improving the yield of the target product.

The step (B) of reacting the cinnamyl chloride derivative obtained in the step (A) with a hydroperoxide in the presence of a base can obtain a cinnamate peroxide derivative. From the perspective of improving the yield of the target product, the hydroperoxide is preferably reacted at 0.8 mol or more, more preferably 1.0 mol or more, and more preferably 1 mol of the cinnamyl chloride derivative. The reaction is performed at 3.0 mol or less, and more preferably at 1.5 mol or less. In addition, hydroperoxides can be commercially available products, and when no commercially available products are available, they can be synthesized based on a conventional synthesis method described in Japanese Patent Application Laid-Open No. 58-72557 and the like.

In the step (B), from the viewpoint of improving the yield of the target product, 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. the following.

In the step (B), since the reaction time varies depending on the starting materials, the reaction temperature, etc., the reaction temperature cannot be determined uniformly, but it is usually 10 minutes or more and 6 hours or less from the viewpoint of improving the yield of the target product.

The base used in the step (B) is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, α-methylpyridine, and γ -Methylpyridine, dimethylaminopyridine, triethylamine, tributylamine, N , N -diisopropylethylamine, 1,5-diazabicyclo [4.3.0] -5-nonene, and the like. From the viewpoint of improving the yield of the target product, it is preferable to use a base of 0.8 mol or more, more preferably a base of 0.9 mol or more, and preferably 2.0 mol or less, more than 1 mol of hydroperoxide. It is best to use bases less than 1.5 mol.

In the step (B), when the cinnamyl chloride derivative is in a liquid state, the reaction can be performed without using an organic solvent. In addition, when the cinnamyl chloride derivative is a solid, an organic solvent is preferably used. The organic solvent is not particularly limited because its solubility varies depending on the type of cinnamate peroxide derivative. Examples include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Other ketones, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as dichloromethane and chloroform. The organic solvents may be used singly or in combination of two or more kinds.

Generally, the used amount of the organic solvent is about 30 to 500 parts by mass with respect to 100 parts by mass of the total amount of the raw materials. The cinnamate peroxide derivative can be obtained by distilling off the organic solvent after step (B). In order to improve the workability or reduce the risk of thermal decomposition, the cinnamate peroxide derivative can also be used as an organic solvent. Use in the form of a dilution.

The steps (A) and (B) may be performed under air at normal pressure, and may also be performed under a nitrogen gas flow or a nitrogen atmosphere.

As the purification step, in order to remove the remaining raw materials or by-products, for example, ion-exchanged water, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and other alkaline aqueous solutions can be used. The step of washing and purifying the target product.

<Polymerizable composition>

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

＜ (a) Polymerization initiator ＞

The (a) polymerization initiator of the present invention contains a peroxycinnamate derivative represented by the general formula (1). (A) The polymerization initiator is decomposed by active energy rays or heat, and the generated radicals have the effect of initiating the polymerization (curing) of (b) the radical polymerizable compound. The cinnamate peroxide derivative may be used alone or in combination of two or more kinds.

The (a) polymerization initiator may contain a polymerization initiator (hereinafter, also referred to as another polymerization initiator) other than the peroxycinnamate derivative. As another polymerization initiator, for example, by using a polymerization initiator having an absorption band different from that of a peroxy cinnamate derivative, the polymerizable composition can be expected to have a high effect on a lamp that emits light of multiple wavelengths, such as a high-pressure mercury lamp. Sensitization. In addition, in consideration of the polymerizability of the (b) radical polymerizable compound contained in the polymerizable composition, the kind of the light-absorbing or light-scattering pigment contained in the polymerizable composition, and the film thickness of the cured product. The use of other polymerization initiators and the like can improve the surface curability, deep curability, transparency, and the like of the polymerizable composition.

As the other polymerization initiator, conventional ones can be used, and examples thereof include 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-phenylacetone, and 4 '-(2-hydroxyethyl (Oxy) -2-hydroxy-2-methylphenylacetone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanyl) benzyl) phenyl) -2-methyl Α-hydroxyacetophenone derivatives such as propane-1-one; 2-methyl-4'-methylthio-2-morpholine phenylacetone, 2-benzyl-2- ( N , N -dimethyl Amino) -1- (4-morpholinylphenyl) butane-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinyl ) Α-aminoacetophenone derivatives such as butane-1-one; diphenyl-2,4,6-trimethylbenzylidenephosphine oxide, phenylbis (2,4,6-trimethyl Derivatives of fluorenylphosphine oxide, such as benzamidine) phosphine oxide, (2,4,6-trimethylphenylcarbonyl) phenylphosphonic acid ethyl ester; 1- [4- (phenylthio) phenyl] octane -1,2-dione-2- (O-benzimidoxime), 1-[(fluorene 1- [9-ethyl-6- (2-methylbenzylhydrazine) -9H-oxazole- 3-yl] ethylidenefluorenylamino) oxy] acetone and other oxime ester derivatives; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halogen methyltriazine derivatives; 2,2-dimethoxy-2-benzene Benzophenone ketal derivatives such as acetophenone; thioxanthone derivatives such as isopropylthioxanthone; 4- (4-methylphenylthio) benzophenone, 4,4'-bis ( Dibenzophenone derivatives such as diethylamino) benzophenone; 3-benzylidene-7-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin Coumarin derivatives, etc .; 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl ] -4,5-diphenylimidazole and other imidazole derivatives; 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, dibenzofluorene peroxide and other organic peroxides Substances; azo compounds such as azobisisobutyronitrile; camphorquinone. The other polymerization initiators may be used alone or in combination of two or more kinds.

The content of the (a) polymerization initiator is preferably from 0.1 to 40 parts by mass, more preferably from 0.5 to 20 parts by mass, and still more preferably from 1 to 15 with respect to 100 parts by mass of the (b) radical polymerizable compound. Parts by mass. When the content of the (a) polymerization initiator is less than 0.1 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound, the curing reaction does not proceed, which is not preferable. In addition, when the content of the (a) polymerization initiator is more than 40 parts by mass relative to 100 parts by mass of the (b) radical polymerizable compound, the solubility of the (b) radical polymerizable compound is saturated, and in a polymerizable combination (A) Crystallization of the polymerization initiator, roughening of the film surface may be a problem, or (a) the increase in the decomposition residue of the polymerization initiator may reduce the strength of the coating film of the cured product. The situation is not good.

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

<(B) Radical polymerizable compound>

As the (b) radical polymerizable compound of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of the (b) radical polymerizable compound include (meth) acrylates, styrenes, maleates, fumarates, itaconic acid esters, cinnamate esters, and crotons. Acid esters, vinyl ethers, vinyl esters, vinyl ketones, allyl ethers, allyl esters, N -substituted maleimines, N -vinyl compounds, unsaturated Nitriles, olefins, etc. Among these, it is preferable to contain a highly reactive (meth) acrylate. (B) The radical polymerizable compound may be used alone or in combination of two or more kinds.

As the (meth) acrylates, monofunctional compounds and polyfunctional compounds can be used. Examples of the monofunctional compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethyl (meth) acrylate Alkyl (meth) acrylates, such as methylhexyl ester, lauryl (meth) acrylate, and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (formyl) (Diyl) dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate Ester compounds such as (meth) acrylic acid and alicyclic alcohols; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol Monomers having a hydroxyl group, such as alcohol mono (meth) acrylate; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (methyl Acrylate, phenoxy polyethylene glycol (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2 -Ethyl-1,3-dioxolane-4-yl) meth (meth) acrylate, (3-ethyloxetane-3-yl) meth (meth) acrylate, Monomers having chain or cyclic ether bonds, such as cyclic trimethylolpropane formal (meth) acrylate; N , N -dimethylaminoethyl (meth) acrylate, N , N -Dimethyl (meth) acrylamide, N -hydroxymethyl (meth) acrylamide, N -isopropyl (meth) acrylamide, N , N -dimethylaminopropyl (methyl N- (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylamide, morpholine, N- (meth) acryloxyethylhexahydrophthalimide, etc. have nitrogen atoms Monomers; monomers having isocyanate groups such as 2- (meth) acryloxyethyl isocyanate; glycidyl (meth) acrylate, glycidyl ether 4-hydroxybutyl (meth) acrylate, etc. Epoxy-based monomer Monomers having a phosphorus atom, such as 2-((meth) acryloxy) ethyl acid; monomers having a silicon atom, 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 esters; (meth) acrylic acid, mono (2- (meth) acryloxyethyl) succinate, mono (2- (meth) acryloxyethyl) phthalate Monomers having a carboxyl group such as ethyl) ester, maleic acid mono (2- (meth) acryloxyethyl) ester, 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, and polypropylene glycol di (methyl) Base) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, three Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hydroxypivalic acid neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol propoxy tri (meth) acrylate, tricyclodecane dimethanol dimethyl (methyl) Base) acrylate, bisphenol A ethylene oxide addition di (meth) acrylate, bisphenol A propylene oxide addition di (meth) acrylate, 9,9-bis (4- (2 -(Meth) acryloxyethoxy) phenyl) fluorene, 9,9-bis (4- (2- (2- (meth) acryloxyethoxyethyl) Esters of polyhydric alcohols such as oxy) ethoxy) phenyl) fluorene and (meth) acrylic acid; bis (4- (meth) acryloxyphenyl) sulfide, bis (4- (methyl) Acrylic thiothiophenyl) sulfide, tris (2- (meth) acryloxyethyl) isocyanurate, ethylene bis (meth) acrylamide, zinc (meth) acrylate, (formaldehyde) Based) Zirconium 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, or improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product, the (meth) acrylates The ester compound of the polyhydric alcohol and (meth) acrylic acid is preferred, and particularly preferred are trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and Pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.

The polymerizable composition may contain a copolymer obtained from the (b) radical polymerizable compound.

＜ (c) Alkali soluble resin ＞

The polymerizable composition can be suitably used as a negative resist by further blending (c) an alkali-soluble resin. As the (c) alkali-soluble resin, those generally used in negative resists can be used. The resin is not particularly limited as long as it is a resin soluble in an alkaline aqueous solution, and a resin containing a carboxyl group is preferred. (C) The alkali-soluble resin may be used alone or in combination of two or more kinds.

The (c) alkali-soluble resin of the present invention is preferably a carboxyl group-containing (meth) acrylate copolymer, a carboxyl group-containing epoxy acrylate resin, or the like.

The carboxyl group-containing (meth) acrylate copolymer contains at least one selected from the above-mentioned (meth) acrylate-based monofunctional compounds (except for the monomer having the carboxyl group), and (Meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl benzoic acid, cinnamic acid, succinic acid mono (2- (meth) acrylic acid Ethoxyethyl) ester, phthalic acid mono (2- (meth) acrylic acid ethoxyethyl) ester, maleic acid mono (2- (meth) acrylic acid ethoxyethyl) ester, ω -Carboxy-polycaprolactone mono (meth) acrylate and at least one of ethylenically unsaturated group-containing carboxylic acids such as acid anhydrides of these materials.

Examples of the carboxyl group-containing (meth) acrylate copolymer include a copolymer of methyl methacrylate, cyclohexyl methacrylate, and methacrylic acid, or a copolymer of benzyl methacrylate and methacrylic acid. Copolymers, etc. Further, it may be styrene, alpha] -methylstyrene, N - vinyl-2-pyrrolidone, N - acyl methyl maleic imide, N - phenylmaleimide (PEI), N - cyclohexylmaleimide Copolymers of arsenimide, diethyl fumarate, diethyl itaconic acid, etc.

In addition, the carboxyl group-containing (meth) acrylate copolymer is more preferably used in a side chain from the viewpoint of balancing the developability of a negative resist with coating characteristics such as heat resistance, hardness, and chemical resistance. A carboxyl group-containing (meth) acrylate copolymer into which a reactive group such as an ethylenically unsaturated group is introduced. Examples of the method for introducing an ethylenically unsaturated group into the side chain include, for example, adding glycidyl (meth) acrylate to a part of the carboxyl group of a carboxyl group-containing (meth) acrylate copolymer. Method for compound having an epoxy group and an ethylenically unsaturated group in a molecule; or adding a monocarboxylic group containing an ethylenically unsaturated group such as methacrylic acid to a (meth) acrylate copolymer containing an epoxy group and a carboxyl group Acid method; or a compound containing an isocyanate group and an ethylenically unsaturated group in the molecule, such as 2- (meth) acryloxyethyl isocyanate, on a (meth) acrylate copolymer containing a hydroxyl group and a carboxyl group Methods etc.

The carboxyl group-containing epoxy acrylate resin is preferably a compound obtained by further reacting an acid anhydride with an epoxy acrylate resin that is a reaction product of an epoxy compound and the ethylenically unsaturated group-containing carboxylic acid.

Examples of the epoxy resin include (ortho, meta, and para) cresol novolac epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and Phenol methane type epoxy resin, diphenyl fluorene type epoxy resin and the like. The epoxy resin may be used alone or in combination of two or more kinds.

Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and Methylene tetrahydrophthalic anhydride, chloric anhydride, trimellitic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, itaconic anhydride Wait.

Further, when synthesizing a carboxyl group-containing epoxy acrylate resin, a tricarboxylic anhydride such as trimellitic anhydride may be used as needed, and the acid anhydride group remaining after the hydrolysis reaction may be added to increase the carboxyl group. In addition, an ethylenically unsaturated group-containing maleic anhydride may be used to further increase the ethylenic double bond.

The acid value of the (c) alkali-soluble resin is preferably 20 to 300 mgKOH / g, and more preferably 40 to 180 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in an alkaline aqueous solution is lacking, and development of the unexposed portion becomes difficult, which is not preferable. In addition, when the acid value is more than 300 mgKOH / g, the exposed portion tends to be easily detached from the substrate during development, which is not preferable.

The weight average molecular weight of the (c) alkali-soluble resin is preferably 1,000 to 100,000, and more preferably 1,500 to 30,000. When the weight average molecular weight is less than 1,000, it is not preferable because the heat resistance and hardness of the exposed portion are poor. When the weight average molecular weight is more than 100,000, it is not preferable because development of the unexposed portion may be difficult. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. As an example, HLC-8220GPC (manufactured by TOSOH CORPORATION) can be used as a GPC device, three TSKgelHZM-M (manufactured by TOSOH CORPORATION) can be used as a chromatography column, and tetrahydrofuran can be used as an eluent. Chromatographic analysis was performed under conditions of 0.3 ml / min, RI detector, sample injection concentration of 0.5% by mass, and injection amount of 10 microliters, and it was calculated | required as the weight molecular weight of polystyrene conversion.

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

In addition, as the (c) alkali-soluble resin, an alkali-soluble resin that is separated and purified as an active ingredient after the synthesis reaction can be used. In addition, the reaction solution obtained by the synthesis reaction, a dried substance thereof, or the like can also be directly used.

＜ Other ingredients ＞

As the other component, the polymerizable composition can be cured by heating at a low temperature by using a curing accelerator. As the curing accelerator, for example, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole-based compound, o-sulfobenzimidazine, a fourth-cycle transition metal compound, and the like can be used. The curing accelerator may be used alone or in combination of two or more kinds.

The amine compound is preferably a tertiary amine, and examples thereof include N , N -dimethylaniline, N , N -dimethyltoluidine, N , N -diethylaniline, N , N -bis ( 2-hydroxyethyl) -p-toluidine, ethyl 4- (dimethylamino) benzoate, 4-dimethylaminobenzoic acid (2-methacryloxy) ethyl, and the like.

Examples of the thiourea compound include acetothiourea, N , N' -dibutylthiourea, and the like.

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

The fourth-cycle transition metal compound may be selected from organic acid salts or metal chelate compounds such as vanadium, cobalt, and copper. Examples include cobalt octoate, cobalt naphthenate, copper naphthenate, and naphthenic acid. Vanadium, copper acetoacetone, manganese acetoacetone, vanadyl acetoacetate, etc.

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

As the other component, various photoresists commonly used in coating agents, coatings, printing inks, photosensitive printing plates, adhesives, color resists, and black resists can be blended into the polymerizable composition. Additives in other applications. Examples of the additives include sensitizers (isopropylthioxanthone, 9,10-dibutoxyanthracene, coumarin, coumarinone, acridine orange, camphorquinone, etc.), and polymerization inhibitors ( P-methoxyphenol, hydroquinone, 2,6-di-tert-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorber, infrared absorber, light stabilizer, antioxidant, leveling agent , Surface modifier, surfactant, thickener, defoamer, tackifier, plasticizer, epoxy compound, thiol compound, resin with ethylenic unsaturated bond, saturated resin, coloring dye, fluorescent Dyes, pigments (organic pigments, inorganic pigments), carbon materials (carbon fiber, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerenes, graphene, carbon microcoils, carbon nanometers, Carbon aerogels, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silicon dioxide, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, layered clay minerals, mica, Talc, calcium carbonate, etc.), dispersant, flame retardant, etc. The additives may be used singly or in combination of two or more kinds.

The content of the additive can be appropriately selected according to the purpose of use, and is not particularly limited, but generally, it is preferably 500 parts by mass or less, more preferably 100 parts by mass or less, based on 100 parts by mass of the (b) radical polymerizable compound. .

In order to improve viscosity, paintability, and smoothness of the cured film, a solvent may be further added to the polymerizable composition. The solvent is a solvent capable of dissolving or dispersing the (a) polymerization initiator, the (b) radical polymerizable compound, the (c) alkali-soluble resin, and the other components, as long as it is at a drying temperature The volatile solvent 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, acetic acid cellosolve solvents, Diethylene glycol monoethyl ether acetate solvents, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like. The solvents may be used singly or in combination of two or more kinds.

The use amount of the solvent is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass based on 100 parts by mass of the solid content of the polymerizable composition.

<Preparation method of polymerizable composition>

When preparing the polymerizable composition, the (a) polymerization initiator and the (b) radical polymerizable compound are charged into a storage container, and the (c) alkali-soluble resin and the other are charged as needed. The ingredients can be dissolved or dispersed according to a general method using a paint shaker, a bead mill, a sand mill, a ball mill, a vertical ball mill, a double roll mill, a three roll mill, and the like. In addition, if necessary, filtration may be performed by a screen, a membrane filter, or the like.

In addition, in the preparation of the polymerizable composition, the (a) polymerization initiator may be initially added to the polymerizable composition, but when the polymerizable composition is stored for a long time, it is preferably (A) A polymerization initiator is dissolved or dispersed in a composition containing (b) a radical polymerizable compound before use.

＜ Method for preparing cured product ＞

The cured product of the present invention is formed from the polymerizable composition. The method for preparing a cured product includes any of the following steps: a step of applying a polymerizable composition on a substrate, and irradiating the polymerizable composition with active energy rays, and a step of heating the polymerizable composition. In addition, a step containing both the step of irradiating with active energy rays and the heating step is also referred to as a double curing step.

Examples of the coating method include a spin coating method, a bar coating method, a spray coating method, a dip coating method, a flow coating method, a slit coating method, a doctor blade coating method, and a gravure coating method. Methods, screen printing method, offset printing method, inkjet printing method, dispenser coating method and other methods. In addition, examples of the substrate include films or sheets such as glass, silicon wafers, metals, and plastics, and three-dimensional shaped products, and the shape of the substrate is not limited.

In the step of irradiating the polymerizable composition with active energy rays, the irradiation of active energy rays such as electron beams, ultraviolet rays, visible rays, and radiation decomposes (a) the polymerization initiator and polymerizes (b) the radical polymerizable compound. Thus, a cured product can be obtained.

The active energy ray is preferably light having a wavelength of 250 to 450 nm, and is more preferably light having a wavelength of 350 to 410 nm from the viewpoint that curing can be rapidly performed.

As the light irradiation source, 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, YAG can be used Solid lasers such as lasers, semiconductor lasers, and gas lasers such as argon lasers. Moreover, when using the light of the infrared light of visible light with little absorption from (a) a polymerization initiator, as said additive, it can be hardened by using the sensitizer which absorbs this light.

The exposure amount of the active energy ray should be appropriately set according to the wavelength or intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably 10 to 5,000 mJ / cm ² , and more preferably 30 to 1,000 mJ / cm ² . In addition, as the above-mentioned method for producing a cured product, when a dual curing step is applied and the heating step is performed after the step of irradiating with active energy rays, the polymerization initiator should not be completely caused by the active energy rays. The decomposition method appropriately sets the exposure amount.

In the step of heating the polymerizable composition, (a) a polymerization initiator is decomposed by heat, and (b) a radical polymerizable compound is polymerized to obtain a cured product.

Examples of the heating method in the step of heating the polymerizable composition include heating, ventilation heating, and the like. 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 method of ventilation heating, a ventilation drying oven etc. are mentioned, for example.

In the step of heating the polymerizable composition, the higher the heating temperature, the faster the (a) decomposition rate of the polymerization initiator. However, if the decomposition rate is too fast, (b) there is a tendency that the decomposition residues of the radical polymerizable compound increase. On the other hand, since the lower the heating temperature, the slower the decomposition rate of (a) the polymerization initiator, the longer it takes to cure. Therefore, the heating temperature and the heating time should be appropriately set according to the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230 ° C, and more preferably 100 to 160 ° C. In addition, when the curing accelerator is blended into the polymerizable composition, the heating temperature can be arbitrarily adjusted from room temperature to 160 ° C. according to the type and amount of the curing accelerator. On the other hand, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.

As the method for preparing the cured product, when the dual curing step is applied, in particular, the heating step is performed after the step of irradiating the polymerizable composition with an active energy ray, and it is possible to efficiently perform absorption or light absorption at a high concentration. It is preferable to cure the deep part of the coating film of the polymerizable composition of the scattering colored pigment or the position where the light is blocked and cannot be reached.

When the solvent is contained in the polymerizable composition, the method for producing the cured product may include a drying step. In particular, when the step of irradiating with an active energy ray is applied after the polymerizable composition is applied to a substrate, it is preferable to provide a drying step before the step of irradiating with an active energy ray.

Examples of the method for drying the solvent in the drying step include heat drying, air heating drying, and drying under reduced pressure. The method of heating and drying is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, and electromagnetic wave irradiation. In addition, as a method of ventilation heating drying, a ventilation drying oven etc. are mentioned, for example.

In addition, in the drying step, since the temperature of the polymerizable composition becomes lower than the set temperature for drying due to the latent heat of evaporation of the solvent, it is possible to ensure a long time until the polymerizable composition is gelled. Since the time until gelation is also affected by the drying method, film thickness, etc., the drying temperature and time should be appropriately set and the solvent should be selected. As an example, the drying temperature is preferably 20 to 120 ° C, and more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. In addition, by using the polymerization inhibitor, it is possible to ensure a long time until gelation. In addition, the peroxy cinnamate derivative is decomposed by heat, but the decomposition rate of the compound is about 0.1% when heated at 80 ° C for 5 minutes. Therefore, under this condition, the polymerizable combination It hardly thickens or gels.

The dry film thickness (film thickness of the cured product) of the polymerizable composition can be appropriately set according to the application, and 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. The polymerizable composition is applied to a substrate in the same manner as described above, and dried as necessary to form a dry film. Then, the dried film is irradiated with active energy rays through a photomask, and (b) a radical polymerizable compound is polymerized in the exposed portion to form a cured film. On the other hand, by using direct drawing using a laser, it is possible to produce a highly accurate pattern shape without a mask.

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

The polymerizable composition of the present invention can be used for hard coating agents, coating agents for optical disks, coating agents for optical fibers, coatings for mobile terminals, coatings for home appliances, coatings for woodworking, coatings for cosmetic containers, and anti-reflection coatings for optical elements. Coatings and coating agents such as high and low refractive index coating agents, heat insulation coating agents, heat dissipation coating agents, and anti-fog agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulation Printing inks such as flexible inks, inks for light guide plates; photosensitive printing plates; nano-imprint materials; resins for 3D printing; holographic recording materials; dental materials; waveguide materials; black stripe for lens sheets ; Capacitor blank and electrode material; FPD adhesive, HDD adhesive, optical pickup adhesive, image sensor adhesive, organic EL sealant, touch panel OCA, touch panel OCR And other adhesives and sealants; color resists, black resists, protective films for color filters, photo spacers, black column spacers (black column sp acer), frame resists, photoresists for TFT wiring, interlayer insulation films and other FPD resists; liquid solder resists, dry film resists and other printed circuit board resists; semiconductor resistance Various uses of semiconductor materials such as an etchant and a buffer coating film are not particularly limited.

Examples

The following examples illustrate the present invention in further detail, but the present invention is not limited only by these examples.

<Examples 1 to 6>

(1) Synthesis of peroxycinnamate derivatives

[Synthesis Example 1: Synthesis of Compound 1]

In a 50 mL three-necked flask, 1.00 g (5.61 mmol) of 4-methoxycinnamic acid and 3.0 mL of thionyl chloride were added and stirred. It heated to 80 degreeC, and reacted for 2 hours in this state. After cooling to room temperature, the thionyl chloride was distilled off under reduced pressure to obtain 4-methoxycinnamonyl chloride. Then, 5 mL of toluene was added to the obtained 4-methoxycinnamonyl chloride, and the mixture was stirred and cooled to 5 ° C with an ice bath. 0.945 g of ion-exchanged water and 1.26 g of a 35 mass% potassium hydroxide aqueous solution (7.86 mmol) were added to a 10 mL beaker, and 1.03 g of a 69 mass% tert-butyl hydroperoxide aqueous solution was additionally prepared at 30 ° C or lower. (7.86 mmol) of the mixed solution, the mixed solution was added dropwise over 10 minutes, and reacted at 10 ° C for 5 hours. After the reaction was completed, ion-exchanged water was added until the precipitated inorganic salt was dissolved, and then the aqueous phase was separated. The oil phase was washed with a 5% sodium hydroxide aqueous solution and ion-exchanged water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain 1.29 g of Compound 1 of the present invention. Table 1 and Table 2 show the properties of the obtained compound 1 and the analysis results of EI-MS and ¹ H-NMR.

[Synthesis Examples 2 to 6: Synthesis of Compounds 6, 10, 14, 16, 19]

Compound 6, Compound 10, and Compound 19 of the present invention were changed from 4-methoxycinnamic acid described in Synthesis Example 1 to 3,4-dimethoxycinnamic acid and 3,4,5-trimethoxycinnamic acid, respectively. Other than acids and 4-nitrocinnamic acid, they were synthesized based on the method described in Synthesis Example 1. Compound 14 and Compound 16 of the present invention were changed from 4-methoxycinnamic acid described in Synthesis Example 1 to 3,4-dimethoxycinnamic acid, respectively, and further 69% by mass of tert-butyl described in Synthesis Example 1. Based on the method described in Synthesis Example 1, the hydroperoxide aqueous solution was changed to 90% by mass of tert-hexyl hydroperoxide and 80% by mass of cumene hydroperoxide, respectively. The properties of the obtained compound 6, compound 10, compound 14, compound 16 and compound 19, and EI-MS and ¹ H-NMR analysis results are shown in Tables 1 and 2.

[Chemical Formula 5]

[Table 1]

[Table 2]

(2) Evaluation of UV absorption characteristics

The acetonitrile solutions of Compound 1, Compound 6, Compound 10, Compound 14, Compound 16 and Compound 19 obtained above were measured using a UV-VIS spectrometer (1.0 cm quartz chamber, manufactured by Shimadzu Corporation, UV-2450). UV-VIS spectrum with a wavelength of 200 to 600 nm. The results are shown in Table 3.

<Comparative Examples 1 to 3>

In addition, as a comparative example, Table 3 shows the results of Compound R1, Compound R2, and Compound R3. Compound R1 was synthesized based on the method described in Synthesis Example 1, except that 4-methoxycinnamic acid described in Synthesis Example 1 was changed to cinnamic acid, and identified by EI-MS and ¹ H-NMR. Compound R2 was synthesized based on the production method described in Japanese Patent Application Laid-Open No. 59-197401. Compound 3 used IRGACURE 184 (manufactured by BASF).

[Chemical Formula 6]

[table 3]

In Table 3, λ _max represents the maximum absorption wavelength (nm), ε _max represents the Moire absorption coefficient (L · mol ^-1 · cm ^-1 ) of the maximum absorption wavelength, and ε ₃₆₅ represents the Moire absorption coefficient at a wavelength of 365 nm ( L · mol ^-1 · cm ^-1 ).

Generally, the larger the molar absorption coefficient, the easier it is to absorb light, and the easier it is to cause the generation of free radicals. That is, in order to increase the sensitivity of the polymerization initiator, a compound having a large Moire absorption coefficient at an exposure wavelength is preferable. From the results in Table 3, it can be seen that the absorption bands of Compound 1, Compound 6, Compound 10, Compound 14, Compound 16 and Compound 19 of the present invention are shifted to the long wavelength region with respect to the compound R1 having no substituent on the benzene ring. One of the light-emitting wavelengths of the high-pressure mercury lamp has a large Moire absorption coefficient at a wavelength of 365 nm.

<Examples 7 to 12, Comparative Examples 4 to 6>

<Preparation of polymerizable composition (A)>

(B) a radical polymerizable compound, (c) an alkali-soluble resin, and other components were mixed and stirred in the amounts shown in Table 4, and (a) a polymerization initiator was added and stirred sufficiently to prepare Examples 7 to 12 and Comparative Examples. 4 to 6 polymerizable composition (A).

[Table 4]

In the above Table 4, DPHA represents a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: ARONIX M-402, manufactured by TOAGOSEI CO., LTD.);

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

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

PGMEA stands for propylene glycol monomethyl ether acetate.

(3) Evaluation of sensitivity

The polymerizable composition (A) obtained above was applied onto an aluminum substrate using a spin coater. After coating, the aluminum substrate was dried in a dustless oven at 90 ° C. for 2.5 minutes, and the solvent was dried to produce a uniform coating film having a thickness of 1.5 μm. Then, a proximity exposure machine using an ultra-high pressure mercury lamp as a light source was used to perform segmented exposure in the range of 10 to 1000 mJ / cm ² through a mask pattern. The exposed aluminum substrate was immersed in a 1.0% by mass sodium carbonate aqueous solution at 23 ° C. for 60 seconds to remove unexposed portions by development. Then, it washed with pure water for 30 second, and obtained the pattern shape. The minimum exposure amount for forming a pattern shape was evaluated as "sensitivity". Table 5 shows the evaluation results of each (a) polymerization initiator.

[table 5]

From the results in Table 5, it can be seen that the compound 1, compound 6, compound 10, compound 14, compound 16, and compound 19 of the present invention are highly sensitive to the compound R1 having no substituent on the benzene ring. In addition, although compound 1 has a smaller Mohr absorption coefficient at a wavelength of 365 nm than compound R2 of benzophenone skeleton, its sensitivity is high. Generally, even if a polymerization initiator absorbs light and is excited, if the proportion of excitation energy used due to fluorescent light emission or thermal deactivation is large, the efficiency of generating radicals is reduced. That is, it is presumed that the percinnamate peroxide derivative of the present invention has high generation efficiency of light-based radicals.

<Examples 13 to 14, Comparative Example 6>

<Preparation of polymerizable composition (B)>

The amount of (b) the radical polymerizable compound and the curing accelerator shown in Table 6 were mixed and stirred, and (a) the polymerization initiator was added and stirred sufficiently to prepare polymerizable compositions of Examples 13, 14 and Comparative Example 6 ( B).

[TABLE 6]

In Table 6, UV-3700B represents a polyurethane acrylate (trade name: Violet UV-3700B, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.); IBOA represents isobornyl acrylate; THA represents tetrahydrofurfuryl acrylate; TMPTA represents Trimethylolpropane triacrylate; DMT stands for N , N -dimethyltoluidine.

(4) Evaluation of dual-cure curing characteristics

Using an applicator, the polymerizable composition prepared as described above was applied on a 100 μm-thick, easily-adhesive-treated PET film (trade name: Cosmo Shine A4300, manufactured by TOYOBO CO., LTD.) So as to have a thickness of 50 μm ( B) A PET film with a black coating on the surface (with a transmittance of less than 0.1% at a wavelength of 365 nm) is provided on a half of the film. Then, a belt-type UV irradiation device provided with a high-pressure mercury lamp was used to irradiate 100 mJ / cm ² . Then, it was left still in a constant-temperature air supply constant temperature machine, and was heated at 90 degreeC for 90 minutes.

After the above heating, the PET film to which the black coating was applied was removed to expose the cured film, and the degree of curing (%) of the cured film portion was measured by the ATR-IR method. At this time, using the peak area of the absorption spectrum (1410 cm ^-1 ) of in-plane deformation vibration of the double bond group and the absorption spectrum (1740 cm ^-1 ) of the carbonyl group that did not change before and after exposure, the curing rate was calculated according to the following formula. The results are shown in Table 7.

[Mathematical formula 1]

[TABLE 7]

From the results in Table 7, it is understood that the percinnamate peroxide derivative of the present invention and the polymerizable composition containing the compound are characterized by having excellent sensitivity to light and having photo-curability and thermo-curability.

no

no

Claims (7)

A cinnamate peroxide derivative, which is represented by the general formula (1): [Chemical Formula 1] In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, which represents the general formula (2): a substituent represented by RX-, a nitro group or a cyano group, and X represents an oxygen atom or A sulfur atom, where R represents a hydrocarbon group having 1 to 6 carbon atoms, and may have any one or more of an ether bond, a thioether bond, and a terminal hydroxyl group in the carbon skeleton, or R ¹ represents an Each of the general formula (2): RX—a hydrocarbon group forming a five- to six-membered ring, R ² represents a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent a methyl group or an ethyl group, and R ⁵ represents the number of carbon atoms as The aliphatic hydrocarbon group of 1 to 5 or the aromatic hydrocarbon group of 6 to 9 carbon atoms which may have an alkyl group. The cinnamate peroxide derivative according to item 1 of the scope of patent application, wherein in the general formula (1), R ¹ is an independent substituent, which represents the substituent represented by general formula (2): RX- , X represents an oxygen atom, and R represents a hydrocarbon group having 1 to 6 carbon atoms, which may have any one or more of an ether bond in a carbon skeleton and a terminal hydroxyl group, or R ¹ represents an adjacent two The general formula (2): RX—a hydrocarbon group forming a five- to six-membered ring. A polymerizable composition comprising (a) a polymerization initiator and (b) a radical polymerizable compound including a peroxy cinnamate derivative according to item 1 or 2 of the scope of patent application. The polymerizable composition according to item 3 of the patent application scope, further comprising (c) an alkali-soluble resin. A cured product formed from the polymerizable composition according to item 3 or 4 of the scope of patent application. A method for preparing a cured product is the method for preparing a cured product according to item 5 of the scope of patent application, which includes a step of irradiating the polymerizable composition with active energy rays. The method for preparing a cured product according to item 6 of the scope of application for a patent, further comprising a step of heating after the step of irradiating with an active energy ray.