JPWO2018110179A1 - Peroxycinnamate derivative and polymerizable composition containing the compound - Google Patents

Abstract

The peroxycinnamate derivative of the present invention is represented by the general formula (1): (in the formula (1), n represents an integer of 1 to 3, R1 is an independent substituent, and the general formula (2): R -X- represents a substituent, a nitro group, or a cyano group, X represents an oxygen atom or a sulfur atom, and R represents an ether bond, a thioether bond, and a terminal in the carbon skeleton. R 1 represents a hydrocarbon group having 1 to 6 carbon atoms which may have any one or more of hydroxyl groups, or R 1 represents 5 to 6 members depending on two adjacent general formulas (2): R—X—. Represents a hydrocarbon group that forms a ring, R2 represents a hydrogen atom or a methyl group, R3 and R4 independently represent a methyl group or an ethyl group, R5 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an alkyl group. Represents an aromatic hydrocarbon group having 6 to 9 carbon atoms. In represented. The peroxycinnamate derivative has both photopolymerizability capable of efficiently absorbing light having a wavelength of 365 nm and the like emitted from the lamp to generate radicals, and thermal polymerizability.

Description

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

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

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

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

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

JP 59-197401 JP2000-96002

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

  Therefore, in order to solve the above-mentioned problems, the present invention provides a peroxycinnamate derivative having both photopolymerizability capable of efficiently absorbing light having a wavelength of 365 nm or the like emitted from a lamp to generate radicals and thermal polymerizability. Is.

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

（式（１）中、ｎは１から３の整数を表し、Ｒ^１は、独立した置換基であって、一般式（２）：Ｒ−Ｘ−で表される置換基、ニトロ基、またはシアノ基を表し、前記Ｘは、酸素原子または硫黄原子を表し、前記Ｒ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の炭化水素基を表す。あるいは、Ｒ^１は隣接する２つの前記一般式（２）：Ｒ−Ｘ−により５〜６員環を形成する炭化水素基を表す。Ｒ^２は水素原子またはメチル基、Ｒ^３およびＲ^４は独立してメチル基またはエチル基、Ｒ^５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。）で表されるペルオキシシンナメート誘導体、に関する。That is, the present invention relates to the general formula (1):

(In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, and is a substituent represented by the general formula (2): R—X—, a nitro group, or A cyano group, wherein X represents an oxygen atom or a sulfur atom, and R may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. . represents a hydrocarbon group having 1 to 6 carbon atoms or two of the general formula ^{R 1} is adjacent (2): the R-X- represents a hydrocarbon group that forms a 5- or 6-membered ring .R ² is A hydrogen atom or a methyl group, R ³ and R ⁴ are independently a methyl group or an ethyl group, R ⁵ is an aliphatic hydrocarbon group having 1 to ⁵ carbon atoms, or an optionally substituted alkyl group; A peroxycinnamate derivative represented by the following formula:

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

  The peroxycinnamate derivative of the present invention can generate radicals efficiently with respect to light having a wavelength of 365 nm and the like emitted from a lamp, and has a peroxide bond in the molecule, so that it is useful as a light and thermal polymerization initiator. It is. Therefore, the polymerizable composition containing the peroxycinnamate derivative and the radical polymerizable compound can be cured well by light irradiation, and can be cured well by heat even in a dark part where light does not reach.

（式（１）中、ｎは１から３の整数を表し、Ｒ^１は、独立した置換基であって、一般式（２）：Ｒ−Ｘ−で表される置換基、ニトロ基、またはシアノ基を表し、前記Ｘは、酸素原子または硫黄原子を表し、前記Ｒ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の炭化水素基を表す。あるいは、Ｒ^１は隣接する２つの前記一般式（２）：Ｒ−Ｘ−により５〜６員環を形成する炭化水素基を表す。Ｒ^２は水素原子またはメチル基、Ｒ^３およびＲ^４は独立してメチル基またはエチル基、Ｒ^５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。）<Peroxycinnamate derivatives>
The peroxycinnamate derivative of the present invention can be represented by the following general formula (1).

(In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, and is a substituent represented by the general formula (2): R—X—, a nitro group, or A cyano group, wherein X represents an oxygen atom or a sulfur atom, and R may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. . represents a hydrocarbon group having 1 to 6 carbon atoms or two of the general formula ^{R 1} is adjacent (2): the R-X- represents a hydrocarbon group that forms a 5- or 6-membered ring .R ² is A hydrogen atom or a methyl group, R ³ and R ⁴ are independently a methyl group or an ethyl group, R ⁵ is an aliphatic hydrocarbon group having 1 to ⁵ carbon atoms, or an optionally substituted alkyl group; Represents an aromatic hydrocarbon group of

In the general formula (1), n is represented by an integer of 1 to 3, and represents the number of R ¹ side chains on the phenyl group ring. n is preferably 1 or 2 from the viewpoint of easy synthesis of the peroxycinnamate derivative.

In the general formula (1), R ¹ is an independent substituent, and represents a substituent represented by the general formula (2): R—X—, a nitro group, or a cyano group. Represents an oxygen atom or a sulfur atom, and R represents a hydrocarbon having 1 to 6 carbon atoms which may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. Represents a group. Alternatively, ^{R 1} is adjacent two of said general formula (2): the R-X- represents a hydrocarbon group that forms a 5- or 6-membered ring.

R ¹ is an independent substituent from the viewpoint of high sensitivity to light of the lamp, and represents a substituent represented by the general formula (2): R—X—, where X represents an oxygen atom. , R is a C 1-6 hydrocarbon group which may have any one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton, or R ¹ is adjacent It is preferably a hydrocarbon group that forms a 5- to 6-membered ring by the two general formulas (2): R—X—.

Specific examples of R ¹ include, for example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, and cyclopentyloxy. Group, n-hexyloxy group, cyclohexyloxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2-hydroxyethoxy) ethoxy group, 2- ( 2-ethoxyethoxy) alkoxy groups such as ethoxy group, 1,2-dihydroxypropoxy group, methylenedioxy group, ethylenedioxy group; methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, 2 -(2-methoxyethoxy) ester Examples thereof include alkylsulfanyl groups such as tilsulfanyl group. The compound represented by the general formula (1) having these functional groups is preferable because it has high absorbance at a wavelength of 365 nm and efficiently absorbs light from the lamp.

Further, among these, from the viewpoint that the peroxycinnamate derivative is highly soluble in the polymerizable composition and easy to synthesize, R ¹ is a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a methylene diene group. An oxy group is preferred.

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

In the general formula (1), R ³ and R ⁴ independently represent a methyl group or an ethyl group. R ³ and R ⁴ are preferably methyl groups from the viewpoint of increasing the decomposition temperature of the peroxycinnamate derivative and increasing the storage stability of the polymerizable composition.

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 a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a methylcyclohexyl group, a phenyl group, and an isopropylphenyl group. Among these, from the viewpoint of easy synthesis of the peroxycinnamate derivative, a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable.

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

<Method for producing peroxycinnamate derivative>
Although the manufacturing method of the peroxycinnamate derivative represented by the general formula (1) is not particularly limited, it can be synthesized according to a known peroxyester synthesis method described in JP-A No. 51-115411. it can.

（上記反応式において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は前記一般式（１）と同じである。）In the method for producing the peroxycinnamate derivative represented by the general formula (1), for example, a cinnamic acid derivative is reacted with a chlorinating agent such as thionyl chloride, phosphorus trichloride, or phosgene as shown in the following reaction formula. The step of obtaining a cinnamic acid chloride derivative (hereinafter also referred to as step (A)), and subsequently the step of reacting the obtained cinnamic acid chloride derivative and hydroperoxide in the presence of an alkali (hereinafter, step) (B) is also included. In addition, after said process (A) and / or (B), the process of distilling off excess chlorinating agent etc. (removal), and the refinement | purification process may be included.

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

  In the step (A), a commercially available product can be used as the cinnamic acid derivative. In addition, when there is no commercial item, it can synthesize | combine according to the well-known synthesis method as described in Paragraph [0230] etc. of Unexamined-Japanese-Patent No. 2013-520490. The chlorinating agent is preferably reacted in an amount of 1 mol or more, more preferably 1.1 mol or more, with respect to 1 mol of cinnamic acid derivative, from the viewpoint of increasing the yield of the target product, and the solvent is added. It can also be reacted using a large excess amount, but it is preferably 10 mol or less, and preferably 5 mol or less.

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

  In the step (A), the reaction time varies depending on the raw materials, reaction temperature, and the like, and thus cannot be determined unconditionally.

  A peroxycinnamate derivative is obtained by the step (B) of reacting the cinnamic acid chloride derivative obtained in the above step (A) with hydroperoxide in the presence of an alkali. Hydroperoxide is preferably reacted in an amount of 0.8 mol or more, more preferably 1.0 mol or more, with respect to 1 mol of cinnamic acid chloride derivative, from the viewpoint of increasing the yield of the target product, and It is preferable to make it react 3.0 mol or less, and it is preferable to react 1.5 mol or less. Hydroperoxide is commercially available, and when there is no commercially available product, it can be synthesized according to a known synthesis method described in JP-A No. 58-72557.

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

  In the step (B), the reaction time varies depending on the raw materials, reaction temperature, etc., and thus cannot be determined unconditionally.

  In the step (B), the alkali used is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, α-picoline, γ-picoline, Examples include dimethylaminopyridine, triethylamine, tributylamine, N, N-diisopropylethylamine, 1,5-diazabicyclo [4.3.0] -5-nonene. The alkali is preferably used in an amount of 0.8 mol or more, more preferably 0.9 mol or more, from the viewpoint of increasing the yield of the target product per mol of hydroperoxide, and 2.0 It is preferable to use less than or equal to mol, and more preferably less than or equal to 1.5 mol.

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

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

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

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

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

<(A) Polymerization initiator>
The polymerization initiator (a) of the present invention contains a peroxycinnamate derivative represented by the general formula (1). The (a) polymerization initiator has a function of decomposing by active energy rays or heat, and the generated radicals start polymerization (curing) of the (b) radical polymerizable compound. Peroxycinnamate derivatives may be used alone or in combination of two or more.

  The (a) polymerization initiator may contain a polymerization initiator other than the peroxycinnamate derivative (hereinafter also referred to as other polymerization initiator). As another polymerization initiator, for example, by using a polymerization initiator having an absorption band different from that of the peroxycinnamate derivative, a polymerizable composition for a lamp that emits light of a plurality of wavelengths such as a high-pressure mercury lamp. High sensitivity of objects can be achieved. In addition, in consideration of the polymerizability of the (b) radical polymerizable compound contained in the polymerizable composition, the types of pigments that absorb or scatter light contained in the polymerizable composition, the film thickness of the cured product, etc. By using this polymerization initiator, the surface curability, deep part curability, transparency, etc. of the polymerizable composition can be improved.

  As said other polymerization initiator, a well-known thing can be used, for example, 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl- propiophenone, 4 '-(2-hydroxyethoxy) -2-hydroxy. Α-Hydroxyacetophenone derivatives such as 2-methylpropiophenone and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one 2-methyl-4′-methylthio-2-morpholinopropiophenone, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethyl Α-aminoacetophene such as amino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one Non-derivatives; Acylphosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (mesitylcarbonyl) phenylphosphinate; [4- (Phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyloxime), 1-[({1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester derivatives such as 3-yl] ethylidene} amino) oxy] ethanone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3 4-dimethoxystyryl) -4,6-bis (trichloromethyl) 1,3,5-triazine, 2- ( -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyltriazine derivatives; 2,2-dimethoxy-2-phenylacetophenone and other benzyl ketal derivatives; isopropylthioxanthone Benzoxanthone derivatives such as 4- (4-methylphenylthio) benzophenone, 4,4′-bis (diethylamino) benzophenone; 3-benzoyl-7-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylamino) Coumarin derivatives such as coumarin); 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole, etc. Imidazole derivatives; 3,3 ′, 4,4′-tetra Scan (tert- butylperoxy carbonyl) benzophenone, organic peroxides such as dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; camphor quinone and the like. Another polymerization initiator may be used independently and may use 2 or more types together.

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

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

<(B) Radical polymerizable compound>
As the radically polymerizable compound (b) of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of (b) radical polymerizable compounds include (meth) acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, and vinyl ethers. , Vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins and the like. Among these, it is preferable to contain (meth) acrylic acid esters having high reactivity. (B) A radically polymerizable compound may be used independently and may use 2 or more types together.

  As the (meth) acrylic acid esters, monofunctional compounds and polyfunctional compounds can be used. Monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Alkyl (meth) acrylates such as acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth) acrylic acid such as acrylate, 2-ethyl-2-adamantyl (meth) acrylate and alicyclic alcohol; aryl (meth) such as phenyl (meth) acrylate and benzyl (meth) acrylate Acrylate; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono (meth) ) Monomers having a hydroxy group such as acrylate; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate And monomers having a chain or cyclic ether bond such as cyclic trimethylolpropane formal (meth) acrylate; 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) acryloyloxyethyl hexahydrophthalimide, etc. A monomer having a nitrogen atom; a monomer having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether A monomer having an epoxy group such as ruthenium; a monomer having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; a monomer having a silicon atom such as 3- (meth) acryloxypropyltrimethoxysilane; A monomer having a fluorine atom such as 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate; (Meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono (2- (meth) acryloyloxyethyl), maleic acid mono (2- (meth) acryloyloxyethyl), ω- Monomers having a carboxyl group such as carboxy-polycaprolactone mono (meth) acrylate Etc.

  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, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, glycerin di (Meth) acrylate, glycerin propoxy tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene oxide addition di (meth) acrylate of bisphenol A, propylene oxide addition di (meth) acrylate of bisphenol A, 9,9- Polyhydric alcohols such as bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene and 9,9-bis (4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) fluorene; Ester compound with (meth) acrylic acid; bis (4- (meth) acryloxyphenyl) sulfide, bis (4- (meth) acryloylthiophenyl) sulfide, tris (2- (meth) acryloyloxyethyl) isocyanurate, Ethylene bis Meth) acrylamide, (meth) zinc acrylate, (meth) zirconium acrylate, aliphatic urethane acrylates, aromatic urethane acrylates, epoxy acrylates, polyester acrylates, and the like.

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

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

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

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

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

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

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

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

  Examples of the epoxy resin include (o, m, p-) cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, and bisphenyl fluorene. Type epoxy resin and the like. An epoxy resin may be used independently and may use 2 or more types together.

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

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

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

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

  Moreover, it is preferable that the ratio of (c) alkali-soluble resin is 10 to 70 mass% in the total solid of a polymeric composition, and it is more preferable that it is 15 to 60 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 pattern shape reproducibility and heat resistance are lowered, which is not preferable.

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

<Other ingredients>
By using a curing accelerator as the other component, the polymerizable composition can be cured by heating at a low temperature. As the curing accelerator, for example, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole compound, an orthobenzoixsulfimide, a fourth-period transition metal compound compound, or the like can be used. A hardening accelerator may be used independently and may use 2 or more types together.

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

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

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

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

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

  As the other components, the polymerizable composition is generally used in applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, various photoresists such as color resists and black resists. Additives can be blended. Examples of the additives include sensitizers (isopropylthioxanthone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-dithiol). -T-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorber, infrared absorber, light stabilizer, antioxidant, leveling agent, surface conditioner, surfactant, thickener, antifoaming agent, adhesion Accelerator, plasticizer, epoxy compound, thiol compound, resin having ethylenically unsaturated bond, saturated resin, colored dye, fluorescent dye, pigment (organic pigment, inorganic pigment), carbonaceous material (carbon fiber, carbon black, graphite) , Graphitized carbon black, activated carbon, carbon nanotube, fullerene, graphene, carbon microco , Carbon nanohorn, carbon aerogel, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, lamellar clay minerals, mica, talc, etc.) , Calcium carbonate, etc.), dispersants, flame retardants and the like. An additive may be used independently and may use 2 or more types together.

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

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

  Examples of the solvent include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, carbitol acetate solvents. Examples include solvents, propylene glycol monomethyl ether acetate, and diethylene glycol dimethyl ether. A solvent may be used independently and may use 2 or more types together.

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

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

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

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

  Examples of the coating method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, and inkjet. Various methods, such as a printing method and a dispenser printing method, are mentioned. Examples of the substrate include glass, silicon wafer, metal and plastic films and sheets, and three-dimensional molded products, and the shape of the substrate is not limited.

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

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

  As the light source for the light irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a light emitting diode (LED), a xenon arc lamp, a carbon arc lamp, sunlight, a YAG laser, etc. A gas laser such as a solid-state laser, a semiconductor laser, or an argon laser can be used. In addition, (a) When using visible light to infrared light with little absorption of the polymerization initiator, curing can be performed by using a sensitizer that absorbs the light as the additive. .

The exposure amount of the active energy ray should be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure dose in the UV-A region is preferably 10 to 5,000 mJ / cm ² , and more preferably 30 to 1,000 mJ / cm ² . In addition, as a manufacturing method of said hardened | cured material, when applying a dual cure process and performing the process of heating after the process of irradiating with the said active energy ray, (a) polymerization initiator is completely by an active energy ray. The exposure amount should be set as appropriate so that it is not decomposed.

  The process of heating said polymeric composition can obtain hardened | cured material by decomposing | disassembling a (a) polymerization initiator with a heat | fever and polymerizing a (b) radically polymerizable compound.

  In the step of heating the polymerizable composition, examples of the heating method include heating and ventilation heating. The heating method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like. Moreover, as a method of ventilation heating, a ventilation drying oven etc. are mentioned, for example.

  In the step of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of (a) the polymerization initiator. However, when the decomposition rate is too high, the decomposition residue of the (b) radical polymerizable compound tends to increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of (a) the polymerization initiator, and thus a longer time is required for curing. Therefore, the heating temperature and the heating time should be appropriately set depending on the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230 ° C, and more preferably 100 to 160 ° C. Moreover, when mix | blending the said hardening accelerator with the said polymeric composition, heating temperature can be arbitrarily adjusted at 160 degreeC from room temperature with the kind and compounding quantity. On the other hand, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.

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

  Moreover, when the said polymerization composition contains the said solvent, the manufacturing method of the said hardened | cured material can include a drying process. In particular, when applying the step of irradiating with the active energy ray after applying the polymerizable composition on the substrate, it is preferable to provide a drying step before the step of irradiating with the active energy ray.

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

  Further, in the drying step, the temperature of the polymerizable composition is lower than the preset drying temperature due to the latent heat of vaporization of the solvent, and therefore it is possible to ensure a long time until the polymerizable composition is gelled. Since the time until gelation is affected by the drying method, film thickness, and the like, the drying temperature and time should be appropriately set including the selection of the solvent. As an example, the drying temperature is preferably 20 to 120 ° C., and more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to ensure a long time until gelation. Although the peroxycinnamate derivative is decomposed by heat, the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%. There is not much thickening or gelation.

  Although the dry film thickness (film thickness of hardened | cured material) of a polymeric composition is set suitably according to a use, it is preferable that it is 0.05 to 300 micrometers, and it is more preferable that it is 0.1 to 100 micrometers.

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

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

  The polymerizable composition of the present invention includes a hard coating agent, a coating agent for optical disks, a coating agent for optical fibers, a coating material for mobile terminals, a coating material for home appliances, a coating material for woodwork, a coating material for cosmetic containers, an inner surface antireflection coating material for optical elements, a high coating material.・ Paints and coating agents such as low refractive index coating agent, thermal barrier coating agent, heat radiation coating agent, anti-fogging agent; offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, 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; dental material; waveguide material; black stripe for lens sheet; green sheet and electrode material for capacitor; Adhesive, HDD adhesive, optical pickup adhesive, image sensor contact Adhesive, sealant for organic EL, OCA for touch panel, OCR for touch panel, etc .; Color resist, black resist, protective film for color filter, photo spacer, black column spacer, frame resist, photoresist for TFT wiring Resist for FPD such as interlayer insulation film; Resist for printed circuit board such as liquid solder resist and dry film resist; Can be used in various applications such as semiconductor materials such as semiconductor resist, buffer coat film, etc. .

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

<Examples 1-6>
(1) Synthesis of peroxycinnamate derivative [Synthesis Example 1: Synthesis of Compound 1]
To 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. The mixture was heated to 80 ° C. and allowed to react for 2 hours. After cooling to room temperature, thionyl chloride was distilled off under reduced pressure to obtain 4-methoxycinnamic acid chloride. Subsequently, 5 mL of toluene was added to the obtained 4-methoxycinnamic acid chloride and stirred, and then cooled to 5 ° C. in an ice bath. To a 10 mL beaker, 0.945 g of ion-exchanged water and 1.26 g (7.86 mmol) of 35% by weight potassium hydroxide aqueous solution were added, and 1.03 g (7.86 mmol) of 69% by weight tert-butyl hydroperoxide aqueous solution was added at 30 ° C. or lower. The added mixed solution was prepared separately, and this mixed solution was added dropwise over 10 minutes, and reacted at 10 ° C. for 5 hours. After completion of the reaction, 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 5% aqueous sodium hydroxide solution and ion-exchanged water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to give 1.29 g of compound 1 of the invention. Table 1 and Table 2 show the properties, EI-MS and ¹ H-NMR analysis results of the obtained Compound 1.

[Synthesis Examples 2 to 6: Synthesis of Compounds 6, 10, 14, 16, and 19]
Compound 6, Compound 10, and Compound 19 of the present invention were prepared by converting 4-methoxycinnamic acid described in Synthesis Example 1 to 3,4-dimethoxy cinnamic acid, 3,4,5-trimethoxy cinnamic acid, and 4- The compound was synthesized according to the method described in Synthesis Example 1 except that it was changed to nitrocinnamic acid. Compound 14 and Compound 16 of the present invention were obtained by changing 4-methoxycinnamic acid described in Synthesis Example 1 to 3,4-dimethoxycinnamic acid, respectively, and further 69% by mass tert-butyl described in Synthesis Example 1 The aqueous hydroperoxide solution was synthesized according to the method described in Synthesis Example 1 except that the aqueous hydroperoxide solution was changed to 90% by mass tert-hexyl hydroperoxide and 80% by mass cumene hydroperoxide, respectively. Tables 1 and 2 show properties of the obtained Compound 6, Compound 10, Compound 14, Compound 16, and Compound 19, and analysis results by EI-MS and ¹ H-NMR.

(2) Evaluation of UV absorption characteristics About the acetonitrile solutions of Compound 1, Compound 6, Compound 10, Compound 14, Compound 16, and Compound 19 obtained above, a UV-VIS spectrum measuring apparatus (1.0 cm quartz cell, Shimadzu) UV-VIS spectrum at a wavelength of 200 to 600 nm was measured using UV-2450) manufactured by Seisakusho. The results are shown in Table 3.

<Comparative Examples 1-3>
As Comparative Examples, Table 3 shows the results of Compound R1, Compound R2, and Compound R3. Compound R1 was synthesized according to 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. did. Compound R2 was synthesized according to the production method described in JP-A-59-197401. Compound 3 was Irgacure 184 (manufactured by BASF).

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

  In general, as the molar extinction coefficient is larger, light is more easily absorbed and radicals are more likely to occur. That is, a compound having a large molar extinction coefficient at the exposure wavelength is suitable for increasing the sensitivity of the polymerization initiator. From the results of Table 3, the absorption band of Compound 1, Compound 6, Compound 10, Compound 14, Compound 16, and Compound 19 of the present invention is shifted to the long wavelength region with respect to Compound R1 having no substituent on the benzene ring. It can be seen that the molar extinction coefficient at a wavelength of 365 nm, which is one of the emission wavelengths of the high-pressure mercury lamp, is large.

<Examples 7 to 12 and Comparative Examples 4 to 6>
<Preparation of polymerizable composition (A)>
The amounts shown in Table 4 (b) radical polymerizable compound, (c) alkali-soluble resin, and other components were mixed and stirred, (a) a polymerization initiator was added and stirred well, and Examples 7 to 12 and Comparative Example The polymerizable compositions (A) of Examples 4 to 6 were prepared.

In Table 4, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
RD200 is a methyl methacrylate / methacrylic acid / cyclohexyl maleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid value: 90 (synthetic product);
F-477 is a fluorine-based leveling agent (trade name: Megafac F-477, manufactured by DIC Corporation);
PGMEA indicates 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 application, the aluminum substrate was dried in a clean oven at 90 ° C. for 2.5 minutes to dry the solvent, thereby producing a uniform coating film having a thickness of 1.5 μm. Subsequently, stepwise exposure was performed in a range of 10 to 1000 mJ / cm ² through a mask pattern using a proximity exposure machine using an ultrahigh pressure mercury lamp as a light source. The exposed aluminum substrate was immersed in a 1.0% by mass aqueous sodium carbonate solution at 23 ° C. for 60 seconds to remove unexposed portions by development. Subsequently, washing was performed with pure water for 30 seconds to obtain a pattern shape. The minimum exposure amount at which a pattern shape was formed was evaluated as “sensitivity”. Table 5 shows the evaluation results of each (a) polymerization initiator.

  From the results of Table 5, it is clear that the sensitivity of the compound 1, compound 6, compound 10, compound 14, compound 16, and compound 19 of the present invention is high with respect to the compound R1 having no substituent on the benzene ring. It was. Compound 1 is more sensitive than Compound R2 having a benzophenone skeleton, although the molar extinction coefficient at a wavelength of 365 nm is smaller. In general, even if the polymerization initiator is excited by absorbing light, if a large proportion of the excitation energy is used due to fluorescence emission or thermal deactivation, the radical generation efficiency decreases. That is, it is estimated that the peroxycinnamate derivative of the present invention has high radical generation efficiency by light.

<Examples 13 to 14, Comparative Example 6>
<Adjustment of polymerizable composition (B)>
The amounts of (b) radical polymerizable compound and curing accelerator shown in Table 6 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and the polymerizable compositions of Examples 13 and 14 and Comparative Example 6 (B) was adjusted.

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

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

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

  From the results in Table 7, the peroxycinnamate derivative of the present invention and the polymerizable composition containing the compound have excellent sensitivity to light, and are characterized by having photocurability and thermosetting properties. Is clear.

Claims (7)

General formula (1):

(In the formula (1), n represents an integer of 1 to 3, R ¹ is an independent substituent, and is a substituent represented by the general formula (2): R—X—, a nitro group, or A cyano group, wherein X represents an oxygen atom or a sulfur atom, and R may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. . represents a hydrocarbon group having 1 to 6 carbon atoms or two of the general formula ^{R 1} is adjacent (2): the R-X- represents a hydrocarbon group that forms a 5- or 6-membered ring .R ² is A hydrogen atom or a methyl group, R ³ and R ⁴ are independently a methyl group or an ethyl group, R ⁵ is an aliphatic hydrocarbon group having 1 to ⁵ carbon atoms, or an optionally substituted alkyl group; Peroxycinnamate, characterized in that it represents an aromatic hydrocarbon group of Conductor. In the general formula (1), R ¹ is an independent substituent, and represents a substituent represented by the general formula (2): R—X—, where 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 and a hydroxyl group at the terminal in the carbon skeleton, or R ¹ represents the two adjacent ones. The peroxycinnamate derivative according to claim 1, wherein the peroxycinnamate derivative represents a hydrocarbon group forming a 5- to 6-membered ring by the general formula (2): R-X-.   A polymerizable composition comprising (a) a polymerization initiator comprising the peroxycinnamate derivative according to claim 1 or 2, and (b) a radical polymerizable compound.   The polymerizable composition according to claim 3, further comprising (c) an alkali-soluble resin.   A cured product formed from the polymerizable composition according to claim 3.   The method for producing a cured product according to claim 5, comprising a step of irradiating the polymerizable composition with active energy rays.   The method for producing a cured product according to claim 6, further comprising a step of heating after the step of irradiating with the active energy ray.