JPWO2020067118A1 - Dialkyl peroxide having a thioxanthone skeleton, a polymerizable composition containing the compound - Google Patents

Abstract

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は独立してメチル基またはエチル基を表し、Ｒ^５は炭素数１〜６のアルキル基、またはフェニル基を表し、Ｒ^６は独立した置換基であって、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、または塩素原子を表し、ｎは０から２の整数を表す。）で表されることを特徴とするチオキサントン基を有するジアルキルペルオキシド。当該ジアルキルペルオキシドは、高圧水銀ランプやＬＥＤランプ等のランプから放射される波長３６５ｎｍ等の光を効率よく吸収してラジカルを発生できる光重合性と、熱によりラジカルを発生できる熱重合性を有する。General formula (1):

(In formula (1), R ¹ , R ² , R ³ and R ⁴ independently represent a methyl group or an ethyl group, R ⁵ represents an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ⁶ Is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer from 0 to 2). A dialkylperoxide having a characteristic thioxanthone group. The dialkyl peroxide has photopolymerizability capable of efficiently absorbing light having a wavelength of 365 nm or the like emitted from a lamp such as a high-pressure mercury lamp or an LED lamp to generate radicals, and thermopolymerizability capable of generating radicals by heat.

Description

The present invention relates to a dialkyl peroxide having a thioxanthone skeleton, a polymerizable composition containing a polymerization initiator containing the compound and a radically polymerizable compound, a cured product thereof, and a method for producing the cured product.

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

Since the photopolymerizable composition composed of the above-mentioned photopolymerization initiator and radically polymerizable compound is rapidly cured by light irradiation, from the viewpoint of quick curing and low VOC, coating agents, paints, printing inks, etc. 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 containing a peroxy ester having a benzophenone skeleton having a peroxide bond (-O-O-) in a molecule that generates radicals by light or heat as an active ingredient. .. Further, Patent Document 2 discloses an adhesive composition composed of the polymerization initiator and a radically polymerizable compound, which utilizes the characteristics of a dual cure type having both photopolymerizability and thermopolymerizability at room temperature. Due to the dual cure, which cures by irradiating with light and then by heating, the adhesive exhibits strong adhesive strength and high durability.

As described above, the dual cure type polymerizable composition can also be utilized for improving the curability in the dark part. Dual-cure type polymerizable compositions include, for example, curing of polymerizable compositions containing high concentrations of pigments and fillers that absorb or scatter light, and black frames and touch panels around protective covers in the manufacturing process of flat panel displays. It is also effective for curing areas where light does not reach, such as the lower part of the electrode.

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

However, the peroxyester having a benzophenone skeleton described in Patent Document 1 and Patent Document 2 does not sufficiently absorb light having a wavelength longer than 365 nm emitted from a high-pressure mercury lamp or an LED lamp, and thus is a photopolymerization initiator. Sensitivity, which is the most important basic characteristic of LED, is not sufficient, and further improvement of sensitivity is an issue.

Further, the polymerizable composition containing the peroxyester having a benzophenone skeleton described in Patent Document 1 and Patent Document 2 has good storage stability at room temperature, but is stored at a high temperature during transportation and the like. Since it gels at that time, improvement of storage stability at high temperature is an issue.

Therefore, in order to solve the above problems, the present invention has photopolymerizability capable of efficiently absorbing light having a wavelength of 365 nm or the like emitted from a lamp such as a high-pressure mercury lamp or an LED lamp to generate radicals, and radicals by heat. It provides a dialkyl peroxide having a thioxanthone skeleton that also has a thermopolymerizable property that can be generated.

Further, the present invention provides a polymerizable composition having an excellent storage stability and a cured product thereof, which contains a polymerization initiator containing a dialkyl peroxide having a thioxanthone skeleton and a radically polymerizable compound, and a method for producing the cured product. It is to provide.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は独立してメチル基またはエチル基を表し、Ｒ^５は炭素数１〜６のアルキル基、またはフェニル基を表し、Ｒ^６は独立した置換基であって、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、または塩素原子を表し、ｎは０から２の整数を表す。）That is, the present invention has the general formula (1):

(In formula (1), R ¹ , R ² , R ³ and R ⁴ independently represent a methyl group or an ethyl group, R ⁵ represents an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ⁶ Is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer of 0 to 2).

Further, the present invention comprises (a) a polymerization initiator containing a dialkyl peroxide having a thioxanthone skeleton, (b) a polymerizable composition containing a radically polymerizable compound, and a cured product formed from the polymerizable composition. , The method for producing the cured product.

The dialkyl peroxide having a thioxanthone skeleton of the present invention can efficiently absorb light having a wavelength of 365 nm or the like emitted from a lamp such as a high-pressure mercury lamp or an LED lamp, efficiently generate radicals, and form a peroxide bond in the molecule. Since it has, it is useful as a light and thermal polymerization initiator. Therefore, the polymerizable composition containing the dialkyl peroxide having the thioxanthone skeleton and the radically polymerizable compound can be satisfactorily cured by irradiation with light, and can be satisfactorily cured by heat even in a dark part where light does not reach.

Further, since the dialkyl peroxide having the thioxanthone skeleton of the present invention has a dialkyl peroxide structure having high thermal stability as a peroxide, the polymerizable composition containing the compound and the radically polymerizable compound is excellent in storage stability.

（式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は独立してメチル基またはエチル基を表し、Ｒ^５は炭素数１〜６のアルキル基、またはフェニル基を表し、Ｒ^６は独立した置換基であって、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、または塩素原子を表し、ｎは０から２の整数を表す。）<Dialkyl peroxide with thioxanthone skeleton>
The dialkyl peroxide having the thioxanthone skeleton of the present invention can be represented by the following general formula (1).

(In formula (1), R ¹ , R ² , R ³ and R ⁴ independently represent a methyl group or an ethyl group, R ⁵ represents an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ⁶ Is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer of 0 to 2).

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ independently represent a methyl group or an ethyl group. R ¹ , R ² , R ³ and R ⁴ are preferably methyl groups from the viewpoint of increasing the storage stability of the polymerizable composition because the decomposition temperature of the dialkyl peroxide having the thioxanthone skeleton is high.

In the general formula (1), ^{R 5} is an alkyl group or a phenyl group, having 1 to 6 carbon atoms. The alkyl group may be a straight chain or a branched chain. Specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group and a phenyl group. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of facilitating the synthesis of the dialkyl peroxide having the thioxanthone skeleton. Since the decomposition temperature of the dialkyl peroxide having a thioxanthone skeleton is high, the storage stability of the polymerizable composition is high, and the sensitivity to the light of the lamp is high, so that the methyl group and the ethyl group are more preferable.

In the general formula (1), the substitution position of the dialkyl peroxide with respect to thioxanthone is not particularly limited, but it is substituted with the 2-position, 3-position, or 4-position of the thioxanthone skeleton from the viewpoint of high sensitivity to the light of the lamp. Is preferable, and from the viewpoint of easy synthesis, it is more preferable that the thioxanthone skeleton is substituted at the 2- or 3-position.

In the general formula (1), R ⁶ is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom. The light absorption characteristics of the dialkyl peroxide having the thioxanthone skeleton can be adjusted by the push-pull effect applied to these substituents with respect to the emission wavelength of the lamp to be used, and the light of the lamp can be efficiently absorbed. can.

In the general formula (1), n represents an integer from 0 to 2. From the viewpoint of facilitating the synthesis of the dialkyl peroxide having a thioxanthone skeleton, n is preferably an integer of 0 to 1, and more preferably 0.

In the general formula (1), when n is an integer of 1 to 2, ^{the substitution position of R 6} is not particularly limited, but is set to the 6th or 7th position of the thioxanthone skeleton from the viewpoint of high sensitivity to the light of the lamp. It is preferably substituted, and it is more preferable that it is substituted at the 7-position of the thioxanthone skeleton from the viewpoint of facilitating the synthesis of the dialkyl peroxide having the thioxanthone skeleton.

Specific examples of the R ⁶ include alkyl groups such as methyl group, ethyl group, isopropyl group and n-butyl group; methoxy group, ethoxy group, n-propyloxy group, sec-butyloxy group and tert-butyloxy group. Alkyl groups such as; chlorine atoms and the like. A methoxy group or an ethoxy group is more preferable because the lamp has high sensitivity to light.

Specific examples of the dialkyl peroxide having the thioxanthone skeleton of the present invention are shown below, but the present invention is not limited thereto.

Examples of the dialkyl peroxide having a thioxanthone skeleton include compounds 1 to 9, and more preferably compounds 1, compound 2, compound 3, compound 7, and compound 8.

（上記反応式において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびｎは前記一般式（１）と同じである。）<Method for producing dialkyl peroxide having a thioxanthone skeleton>
The method for producing a dialkyl peroxide having a thioxanthone skeleton represented by the general formula (1) is, for example, a step of reacting an isoalkyl group-substituted thioxanthone derivative with a hydroperoxide in the presence of a metal complex, as shown in the following reaction formula. Hereinafter, a method including the step (A)) can be mentioned. After the reaction, a step of distilling off (removing) excess raw materials under reduced pressure and a purification step may be included.

(In the above reaction formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n are the same as the general formula (1).)

In the step (A), a commercially available product can be used as the isoalkyl group-substituted thioxanthone derivative. If there is no commercially available product, for example, J.A. Chem. Soc. As described in 99,645 (1911), it can be synthesized by reacting 2,2'-dithiodibenzoic acid with an aromatic compound in sulfuric acid.

In the step (A), the hydroperoxide is preferably reacted with 1.0 mol of the isoalkyl group-substituted thioxanthone derivative in an amount of 0.8 mol or more, preferably 1.0 mol, from the viewpoint of increasing the yield of the target product. The above reaction is more preferable, the reaction is preferably 10.0 mol or less, and the reaction is more preferably 6.0 mol or less. As the hydroperoxide, a commercially available product can be used, and if there is no commercially available product, the hydroperoxide can be synthesized according to a known synthesis method described in JP-A-58-72557 and the like.

In the step (A), as the metal complex, a metal complex of a metal selected from the transition metals of the 4th and 5th periods can be used. Examples of the metal of the metal complex include copper, cobalt, manganese, iron, chromium and zinc, and examples of the ligand include halogens such as bromine and chlorine, and ores such as sulfuric acid, phosphoric acid, nitrate and carbon dioxide. Examples thereof include organic acids such as acid, formic acid, acetic acid, naphthenic acid, octenoic acid and gluconic acid, cyanide and acetylacetonate. The metal complex is preferably used in an amount of 0.0001 mol or more, more preferably 0.001 mol or more, and more preferably 0.001 mol or more, based on 1.0 mol of hydroperoxide, from the viewpoint of increasing the yield of the target product. It is preferable to use 1.0 mol or less, and more preferably 0.1 mol or less.

In the step (A), the reaction temperature is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and 100 ° C. or lower from the viewpoint of increasing the yield of the target product. It is preferably 80 ° C. or lower, more preferably 80 ° C. or lower. The reaction time cannot be unconditionally determined because it varies depending on the raw material, the reaction temperature, and the like, but is usually preferably 1 hour to 60 hours from the viewpoint of increasing the yield of the target product.

In the step (A), it is preferable to use an organic solvent, and as the organic solvent, for example, benzene, toluene, chlorobenzene, o-dichlorobenzene, nitrobenzene and the like can be used. The organic solvent may be used alone or in combination of two or more. The amount of the organic solvent used is usually about 50 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the raw materials. The organic solvent may be distilled off after the step (A) to take out the dialkyl peroxide having a thioxanthone skeleton, and in order to improve the handleability and reduce the risk at the time of thermal decomposition, the triazine peroxide derivative is used as the organic solvent. It may be used as a diluted product.

The step (A) can be carried out under any of the conditions of normal pressure, pressurization and reduced pressure, but it is preferably carried out in an atmosphere of an inert gas such as nitrogen.

In the purification step, in order to remove excess raw materials and by-products, for example, ion-exchanged water or basicity such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like Examples thereof include a step of purifying the target product by washing with a basic aqueous solution such as an aqueous solution or an aqueous solution of sodium carbonate, or an acidic aqueous solution such as hydrochloric acid or sulfuric acid.

<Polymerizable composition>
The polymerizable composition of the present invention contains (a) a polymerization initiator containing a dialkyl peroxide having a thioxanthone skeleton represented by the general formula (1), and (b) a radically polymerizable compound. Further, the polymerizable composition can be imparted with developability by containing (c) an alkali-soluble resin. In addition, the polymerizable composition can contain other components in an appropriate combination.

<(A) Polymerization initiator>
The (a) polymerization initiator of the present invention contains a dialkyl peroxide having a thioxanthone skeleton represented by the general formula (1). The (a) polymerization initiator has a function of being decomposed by active energy rays or heat, and the generated radicals (b) initiating the polymerization (curing) of the radically polymerizable compound. The dialkyl peroxide having a thioxanthone skeleton may be used alone or in combination of two or more.

In addition, the (a) polymerization initiator may contain a polymerization initiator (hereinafter, also referred to as another polymerization initiator) other than the dialkyl peroxide having a thioxanthone skeleton. By using a dialkyl peroxide having two or more types of thioxanthone skeletons having different absorption bands or another polymerization initiator, a polymerizable composition is used for a lamp that emits light of multiple wavelengths, for example, a high-pressure mercury lamp. It is possible to increase the sensitivity of the. In addition, in consideration of (b) the polymerizable property of the radically polymerizable compound contained in the polymerizable composition, the type of pigment or the like that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, etc. By using the above-mentioned polymerization initiator, the surface curability, deep curability, transparency and the like of the polymerizable composition can be improved.

As the other polymerization initiator, known ones can be used, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy) -2-hydroxy. Α-Hydroxyacetophenone derivatives such as -2-methylpropiophenone, 2-hirodoxy-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) butane-1-one, 2- (dimethyl) Α-Aminoacetophenone derivatives such as amino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1-one; diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis (2) , 4,6-trimethylbenzoyl) phosphine oxide, acylphosphine oxide derivatives such as ethyl (mesitylcarbonyl) phenylphosphinate; 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- (O) -Oxime ester derivatives such as-benzoyloxime), 1-[({1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etylidene} amino) oxy] etanone; 2- (4-Methenylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) 1,3,5 -Halomethyltriazine derivatives such as -triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 2,2-dimethoxy-2-phenylacetophenylone and the like. Benzyl ketal derivatives; thioxanthone derivatives such as isopropylthioxanthone, benzophenone derivatives such as 4- (4-methylphenylthio) benzophenone; Kumarin derivative; imidazole derivative such as 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole; 3,3', 4,4'-tetrakis (tert-butylperoxycarbonyl) Organic peroxides such as nzophenone and dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; camphorquinone and the like can be mentioned. The other polymerization initiators may be used alone or in combination of two or more.

The content of the (a) polymerization initiator is preferably 0.1 to 40 parts by mass and 0.5 to 20 parts by mass with respect to 100 parts by mass of the (b) radically polymerizable compound. More preferably, it is 1 to 15 parts by mass. The content of the (a) polymerization initiator is not preferable if it is less than 0.1 parts by mass with respect to 100 parts by mass of the (b) radically polymerizable compound because the curing reaction does not proceed. 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) the radically polymerizable compound, (b) the solubility in the radically polymerizable compound reaches saturation and polymerization is achieved. Strength of the coating film of the cured product due to (a) precipitation of crystals of the polymerization initiator during film formation of the sex composition and roughening of the film surface, or (a) increase in decomposition residue of the polymerization initiator. Is not preferable because it may decrease.

When the (a) polymerization initiator contains the other polymerization initiator, the proportion of the other polymerization initiator can be appropriately set according to the wavelength emitted from the lamp or the like, and for example, (a). ) 80% by mass or less and 50% by mass or less can be exemplified in the polymerization initiator.

<(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 the radically polymerizable compound include (meth) acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, and vinyl ethers. , Vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins and the like. Among these, it is preferable to contain highly reactive (meth) acrylic acid esters. (B) The radically polymerizable compound may be used alone or in combination of two or more.

As the (meth) acrylic acid esters, 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, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth). Alkyl (meth) acrylates such as acrylates; cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylicates, dicyclopentenyl (meth) acrylicates, dicyclopentenyloxyethyl (meth) Acrylate, ester compound of (meth) acrylic acid such as 2-ethyl-2-adamantyl (meth) acrylate and alicyclic alcohol; aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate 2-Hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono (meth) Monomer having a hydroxy group such as acrylate, polypropylene glycol mono (meth) acrylate; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, cyclic Monomer having a chain or cyclic ether bond such as trimethylolpropaneformal (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) Nitrogen atoms such as acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acryloylmorpholine, N- (meth) acryloyloxyethyl hexahydrophthalimide, etc. Monomer having: Monomer having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; Glysidyl (meth) acrylate, 4 − Monomers having an epoxy group such as hydroxybutyl (meth) acrylate glycidyl ether; Monomers having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; Monomer with silicon atom; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate Monomers having fluorine atoms such as (meth) acrylic acid, mono succinate (2- (meth) acryloyloxyethyl), mono phthalate (2- (meth) acryloyloxyethyl), mono (2- (meth) maleate). ) Acryloyloxyethyl), ω-carboxy-polycaprolactone Mono (meth) acrylate and other monomers having a carboxyl group can be mentioned.

Examples of the polyfunctional compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. 1,6-Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin propoxytri (meth) acrylate, trimethyl ethanetri (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate Monostearate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, tricyclodecanedimethanol di (meth) acrylate, 2,2-bis (4- (meth) acryloxiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) phenyl) fluorene, 9,9-bis (4-( An ester compound of a polyhydric alcohol such as 2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) fluorene and (meth) acrylic acid; bis (4- (meth) acryloyloxyphenyl) sulfide, bis (4-) (Meta) acryloylthiophenyl) sulfide, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylenebis (meth) acrylamide, zinc (meth) acrylate, zirconium (meth) acrylate, aliphatic urethane acrylate, aromatic Group urethane acrylate, epoxy acrylate, polyester acrylate and the like can be mentioned.

The (meth) acrylic acid esters are used from the viewpoints of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, and improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product. Therefore, the ester compound of the polyhydric alcohol and (meth) acrylic acid is preferable, and in particular, trimethylol ethane triacrylate, trimethylol propantriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. Pentaerythritol hexaacrylate is preferred.

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

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

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

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

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

Further, the carboxyl group-containing (meth) acrylic acid ester copolymer is a reaction of an ethylenically unsaturated group or the like from the viewpoint of achieving both the developability of a negative resist and the coating properties such as heat resistance, hardness and chemical resistance. A carboxyl group-containing (meth) acrylic acid ester copolymer in which a sex group is introduced into a 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 acid ester copolymer has an epoxy group in the molecule such as glycidyl (meth) acrylate. And a method of adding a compound having an ethylenically unsaturated group, or a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to an epoxy group and a carboxyl group-containing (meth) acrylic acid ester copolymer. , A method of adding a compound having an isocyanate group and an ethylenically unsaturated group in a molecule such as 2- (meth) acryloyloxyethyl isocyanate to a (meth) acrylic acid ester copolymer containing a hydroxyl group and a carboxyl group can be mentioned. ..

As the carboxyl group-containing epoxy acrylate resin, a compound obtained by further reacting an acid anhydride with an epoxy acrylate resin which 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 novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, and bisphenyl fluorene. Examples include type epoxy resins. The epoxy resin may be used alone or in combination of two or more.

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

Further, in the synthesis of the carboxyl group-containing epoxy acrylate resin, if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride is used to hydrolyze the acid anhydride group remaining after the reaction to obtain a carboxyl group. Can be increased. Further, the ethylenically double bond can be further 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, 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, which makes it difficult to develop the unexposed portion, which is not preferable. Further, when the acid value is more than 300 mgKOH / g, the exposed portion tends to be easily separated from the substrate during development, which is not preferable.

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

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

As the alkali-soluble resin (c), an alkali-soluble resin which is an active ingredient after the synthesis reaction can be isolated and purified, or a reaction solution obtained by the synthesis reaction, a dried product thereof, or the like can be used as it is. You can also do it.

<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 orthobenzoixulfimide, a fourth period transition metal compound and the like can be used. The curing accelerator may be used alone or in combination of two or more.

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 thereof include toluidine, ethyl 4- (dimethylamino) benzoate, ethyl 4-dimethylaminobenzoate (2-methacryloyloxy) and the like.

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

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

The fourth cycle transition metal compound can be selected from organic acid salts such as vanadium, cobalt and copper or metal chelate compounds, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate and copper. Examples thereof include acetylacetonate, manganese acetylacetonate, vanadylacetylacetonate 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) radically 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, and various photoresists such as color resists and black resists. Additives can be added. Examples of the additive include a sensitizer (4,4'-bis (diethylamino) benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acrydin orange, camphorquinone, etc.) and a polymerization inhibitor (p-methoxyphenol). , Hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), UV absorber, infrared absorber, chain transfer agent, light stabilizer, antioxidant, leveling agent, surface conditioner, interface Activators, thickeners, defoaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, coloring dyes, fluorescent dyes, pigments (organic pigments, inorganic pigments) , Carbon-based materials (carbon fibers, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.), metal oxides (titanium oxide, iridium oxide, oxidation Examples include zinc, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder, layered viscosity minerals, mica, talc, calcium carbonate, etc.), dispersants, flame retardants, and the like. The additive may be used alone or in combination of two or more.

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

A solvent may be further added to the polymerizable composition in order to improve the viscosity, coatability, and smoothness of the cured film. The solvent can dissolve or disperse the (a) polymerization initiator, the (b) radically polymerizable compound, the (c) alkali-soluble resin, and the other components, and volatilizes at a drying temperature. As long as it is a solvent, it is not particularly limited.

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

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

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

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

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

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

In the step of irradiating the above-mentioned polymerizable composition with active energy rays, (a) the polymerization initiator is decomposed by irradiation with active energy rays such as electron beam, ultraviolet rays, visible light, and radiation, and (b) radical polymerization. A cured product can be obtained by polymerizing the sex compound.

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

The light source for irradiating the light is a solid-state laser such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless electrode lamp, an LED lamp, a xenon arclamp, a carbon arclamp, sunlight, and a YAG laser. , A gas laser such as a semiconductor laser or an argon laser can be used. When (a) light from visible light to infrared light, which absorbs little of the polymerization initiator, is used, 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 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 . When the dual cure step is applied as the method for producing the cured product and the step of heating is performed after the step of irradiating with the active energy ray, (a) the polymerization initiator is completely removed by the active energy ray. The exposure amount should be set appropriately so that it does not decompose into.

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

In the step of heating the polymerizable composition, examples of the heating method 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. Further, as a method of ventilation heating, for example, a ventilation type drying oven or the like can be mentioned.

In the step of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of (a) the polymerization initiator. However, if the decomposition rate is too fast, (b) the decomposition residue of the radically polymerizable compound tends to increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of (a) the polymerization initiator, so that it takes a long time 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, more preferably 100 to 200 ° C. When the curing accelerator is added to the polymerizable composition, the heating temperature can be arbitrarily adjusted from room temperature to 160 ° C. depending on the type and amount of the curing accelerator. On the other hand, the heating time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.

When the dual cure step is applied as a method for producing the cured product, in particular, a step of heating the polymerizable composition after the step of irradiating the polymerizable composition with an active energy ray is a coloring pigment that absorbs or scatters light. It is preferable because it is possible to efficiently cure the deep part of the coating film of the polymerization composition containing a high concentration of light and the portion where the light is blocked and the light does not reach.

When the polymerization composition contains the solvent, the method for producing the cured product can include a drying step. In particular, when the step of irradiating the polymerizable composition on the substrate and then irradiating with the active energy ray is applied, 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 heating drying, and vacuum drying. The heat-drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, and electromagnetic wave irradiation. Further, as a method of ventilation heating and drying, for example, a ventilation type drying oven and the like can be mentioned.

Further, in the drying step, the temperature of the polymerizable composition becomes lower than the set temperature of drying due to the latent heat of vaporization of the solvent, so that a long time until the polymerizable composition gels can be secured. Since the time until gelation is affected by the drying method, film thickness, etc., 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, more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to secure a long time until gelation. The dialkyl peroxide having the thioxanthone skeleton is decomposed by heat, but the decomposition rate of the compound when heated at 90 ° C. for 5 minutes is less than 0.1%, so that the compound is polymerizable under such conditions. The composition does not thicken or gel.

The dry film thickness (film thickness of the cured product) of the polymerizable composition is appropriately set depending on the intended use, but is preferably 0.05 to 500 μm, more preferably 0.1 to 100 μm. ..

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

After the above exposure, the unexposed portion is developed and removed with an alkaline developer such as 0.3 to 3% by mass of sodium carbonate aqueous solution to obtain a patterned cured film. Further, for the purpose of improving the adhesion between the cured film and the base material, post-baking is performed at 180 to 250 ° C. and 20 to 90 minutes as post-drying. 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 paint for mobile terminals, a paint for home appliances, a paint for cosmetic containers, a paint for woodwork, an internal antireflection paint for optical elements, and a high coating agent. -Paints / coating agents such as low refractive index coating agents, heat shielding coating agents, heat dissipation coating agents, antifogging agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, Printing inks such as light guide plate inks; Photosensitive printing plates; Nanoimprint materials; Resins for 3D printers; Holography recording materials; Dental materials; Waveguide materials; Black stripes for lens sheets; Green sheets and electrode materials for capacitors; FPD Adhesives for, HDD adhesives, optical pickup adhesives, image sensor adhesives, organic EL sealants, touch panel OCA, touch panel OCR adhesives / sealants; color resists, black resists, color filters Protective film, photo spacer, black column spacer, frame resist, photoresist for TFT wiring, resist for FPD such as interlayer insulating film; resist for printed substrate such as liquid solder resist, dry film resist; semiconductor resist, buffer coat film, etc. It can be used for various purposes such as materials for semiconductors, and there is no particular limitation on the application.

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

(1) Synthesis of dialkyl peroxide having a thioxanthone skeleton [Synthesis Example 1: Synthesis of Compound 1]
30 mL of benzene, 6.10 g (24.0 mmol) of 2-isopropylthioxanthone, and 0.0238 g (0.24 mmol) of copper (I) chloride were placed in a 200 mL four-necked flask and stirred at room temperature. 15.7 g (120 mmol) of a 69 mass% tert-butyl hydroperoxide aqueous solution was gradually added. The mixture was heated to 65 ° C. under a nitrogen stream and reacted for 60 hours. The reaction mixture was cooled, 20 mL of ethyl acetate was added, and then the aqueous phase was separated. The oil phase was washed with 5% by mass hydrochloric acid, 5% by mass aqueous sodium hydroxide solution and ion-exchanged water, and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 5/1) to obtain 2.55 g (yield 31%) of Compound 1. Table 1 shows the analysis results of the obtained compound 1 by EI-MS and ^{1 1 H-NMR.}

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

[Synthesis Example 3: Synthesis of Compound 3]
Compound 3 of the present invention was synthesized according to the method described in Synthesis Example 1 except that the 69% by mass tert-butyl hydroperoxide aqueous solution described in Synthesis Example 1 was changed to 90% by mass tert-hexyl hydroperoxide. bottom. Table 1 shows the analysis results of the obtained compound 3 by EI-MS and ^{1 1 H-NMR.}

[Synthesis Example 4: Synthesis of Compound 7]
Compound 7 of the present invention was synthesized according to the method described in Synthesis Example 1 except that 2-isopropylthioxanthone described in Synthesis Example 1 was changed to 2-methoxy-7-isopropylthioxanthone. Table 1 shows the analysis results of the obtained compound 7 by EI-MS and ^{1 1 H-NMR.}

[Synthesis Example 5: Synthesis of Compound 8]
Compound 8 of the present invention was synthesized according to the method described in Synthesis Example 1 except that 2-isopropylthioxanthone described in Synthesis Example 1 was changed to 3-methoxy-7-isopropylthioxanthone. Table 1 shows the analysis results of the obtained compound 8 by EI-MS and ^{1 1 H-NMR.}

[Synthesis Example 6: Synthesis of Compound 9]
Compound 2 of the present invention was synthesized according to the method described in Synthesis Example 1 except that 2-isopropylthioxanthone described in Synthesis Example 1 was changed to 2-chloro-7-isopropylthioxanthone. Table 1 shows the analysis results of the obtained compound 9 by EI-MS and ^{1 1 H-NMR.}

(2) Evaluation of UV absorption characteristics <Examples 1 to 6, Comparative Example 1>
The UV-VIS spectrum of the acetonitrile solution of the compound shown in Table 1 was measured at a wavelength of 200 to 600 nm using a UV-VIS spectrum measuring device (1.0 cm quartz cell, manufactured by Shimadzu Corporation, UV-2450). The results are shown in Table 2.

As a comparative example, the results of compound R1 are shown in Table 2. Compound R1 was synthesized according to the production method described in JP-A-59-197401 and ^{identified by EI-MS and 1} H-NMR.

In Table 2, 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 (L · mol) at a wavelength of 365 nm. ^-1 · cm ^-1 ) and ε ₃₈₅ indicate the molar extinction coefficient (L · mol ^-1 · cm ^-1 ) at a wavelength of 385 nm.

In general, the larger the molar extinction coefficient of the photopolymerization initiator at the exposure wavelength, the easier it is for light to be absorbed and for the generation of radicals to occur. That is, a compound having a large molar extinction coefficient at the exposure wavelength is suitable for increasing the sensitivity of the photopolymerization initiator. Ultra-high pressure mercury lamps and high pressure mercury lamps widely used in UV curing efficiently emit light having a wavelength of 365 nm (i-line) as the main wavelength. Further, LED lamps used in the field of printing ink and the like efficiently emit light of a single wavelength having a wavelength of 385 nm. From the results in Table 2, the compounds 1, compound 2, compound 3, compound 7, compound 8 and compound 9 of the present invention have a wavelength of 365 nm and a wavelength of 385 nm with respect to compound R1 which is a peroxyester having a benzophenone skeleton. It can be seen that the molar absorption coefficient is large.

(3) Preparation of polymerizable composition <Preparation of polymerizable composition (A)>
The amounts of (b) radically polymerizable compound, (c) alkali-soluble resin, and other components shown in Table 3 were mixed and stirred, and (a) a polymerization initiator was added and stirred well. Example 19 The polymerizable composition (A) of Comparative Example 2 and Comparative Example 8 was prepared.

In Table 3 above, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
RD200 is a copolymer of methyl methacrylate / methacrylic acid / cyclohexyl maleimide (mass%: 61/14/25), weight average molecular weight: 17,000, acid value: 90 (synthetic product);
F-477 is a fluorine-based leveling agent (trade name: Megafuck F-477, manufactured by DIC Corporation);
PGMEA represents propylene glycol monomethyl ether acetate (Wako Pure Chemical Industries, Ltd. reagent);

<Preparation of polymerizable composition (B)>
The amounts of (b) radically polymerizable compound and solvent shown in Table 4 were mixed and stirred, and (a) a polymerization initiator was added and stirred well, and Examples 13 to 18, Examples 26 to 31, and Comparative Examples 5 and 5 were added. The polymerizable composition (B) of 6 and Comparative Example 10 was prepared.

In Table 4 above, TMPTA represents trimethylolpropane triacrylate (trade name: NK ester A-TMPT, containing 98 ppm of a polymerization inhibitor (hydroquinone monomethyl ether)).

(4) Evaluation of Sensitivity by Ultra High Pressure Mercury Lamp <Examples 7 to 12, Comparative Example 2>
The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After coating, the aluminum substrate was dried in a clean oven at 90 ° C. for 2.5 minutes to dry the solvent to prepare a uniform coating film having a thickness of 1.5 μm. Next, using a proximity exposure machine using an ultra-high pressure mercury lamp as a light source, stepwise exposure was performed in the range of ^{10 to 1000 mJ / cm 2 via a mask pattern.} The exposed aluminum substrate was immersed in a 1.0 mass% sodium carbonate aqueous solution at 23 ° C. for 60 seconds to remove the unexposed portion by development. Subsequently, it was washed with pure water for 30 seconds to obtain a pattern shape. The minimum exposure amount at which the pattern shape was formed was evaluated as "sensitivity". The evaluation results of each (a) polymerization initiator are shown in Table 5.

From the results in Table 5, it is clear that the sensitivities of Compound 1, Compound 2, Compound 3, Compound 7, Compound 8, and Compound 9 of the present invention are high with respect to Compound R1, which is a peroxyester having a benzophenone skeleton. became. Since these compounds have a high molar extinction coefficient at a wavelength of 365 nm, they are presumed to have high sensitivity.

(5) Evaluation of Sensitivity by LED Lamp with Wavelength 385 nm <Examples 13 to 18, Comparative Examples 3 to 7>
The polymerizable composition (B) prepared above was applied onto a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) that had been subjected to an easy-adhesion treatment using a bar coater (# 18). After coating, the PET film was dried in a dryer at 90 ° C. for 2 minutes to dry the solvent to prepare a uniform coating film having a thickness of 3 μm. Next, an LED lamp having a wavelength of 385 nm (UniJet E110III, manufactured by Ushio, Inc.) was used to irradiate light at ^{1000 mJ / cm 2.} The degree of curing (%) of the cured film portion was measured by attenuated total reflection infrared spectroscopy (ATR-IR). At that time, using the peak areas of the absorption spectrum of the out-of-plane variable angle vibration of the double bond group (810 cm ^-1 ) and the absorption spectrum of the carbonyl group that does not change before and after exposure (1740 cm ^-1 ), based on the following equation. The curing rate (curing degree) was calculated. The results are shown in Table 6.

As a comparative example, the results of compounds R1 to R5 are shown in Table 6. The compound R2 used was Irgacure 184 (manufactured by BASF), the compound R3 used Irgacure 819 (manufactured by BASF), the compound R4 used Irgacure 369 (manufactured by BASF), and the compound R5 used Irgacure OXE02 (manufactured by BASF).

From the results in Table 6, the compounds 1, compound 2, compound 3, compound 7, and compound 8 were compared with respect to compound R1 which is a peroxy ester having a benzophenone group as a skeleton and other photopolymerization initiators (compounds R2 to R5). , And compound 9 were found to be highly sensitive. Since these compounds have a high molar extinction coefficient at a wavelength of 385 nm, they are presumed to have high sensitivity.

(6) Evaluation of Dual Cure Curing Characteristics <Example 19, Comparative Example 8>
The polymerizable composition (A) prepared above was applied onto an aluminum substrate using a spin coater. After coating, the aluminum substrate was dried in a constant temperature and constant temperature machine at 90 ° C. for 2.5 minutes to dry the solvent to prepare a uniform coating film having a thickness of 1.5 μm. Then, a conveyor type UV irradiation device (ECS-4011GX, manufactured by Eye Graphics Co., Ltd.) equipped with a high-pressure mercury lamp was used to ^{irradiate light at 100 mJ / cm 2} , and the degree of curing was measured. Further, the aluminum substrate after the light irradiation was heat-treated for 30 minutes in a blower constant temperature incubator at 170 ° C., and the degree of curing was measured. The results are shown in Table 7.

From the results in Table 7, it is clear that the compound of the present invention is characterized by having photocurability and thermosetting property.

(7) Evaluation of thermal decomposition of dialkyl peroxide having a thioxanthone skeleton <Examples 20 to 25, Comparative Example 9>
A sample of 1 to 2 mg was placed in a stainless steel sealed cell, set in a differential scanning calorimeter (DSC, manufactured by Seiko Instruments Inc., EXSTAR6200), heated at a heating rate of 10 ° C./min, and measured. In the heat generation curve due to heat of decomposition, the intersection of the tangent line and the baseline at the inflection point was defined as the decomposition start temperature (° C.). The evaluation results of each (a) polymerization initiator are shown in Table 8.

From the results in Table 8, compound 1, compound 2, compound 3, compound 7, compound 8 and compound 9 of the present invention can be decomposed at a higher temperature with respect to compound R1 which is a peroxy ester having a benzophenone skeleton. It became clear.

(8) Evaluation of dark storage stability of the polymerizable composition <Examples 26 to 31, Comparative Example 10>
The polymerizable composition (B) prepared above was placed in a brown glass bottle, shielded from light with aluminum foil, and then allowed to stand in a constant temperature incubator set at 60 ° C. Table 9 shows the number of days when gelation occurred visually.

From the results in Table 9, the polymerizable composition containing the compound R1 which is a peroxyester having a benzophenone skeleton contains the compound 1, the compound 2, the compound 3, the compound 7, the compound 8 and the compound 9 of the present invention. It has been clarified that the polymerizable composition is excellent in storage stability in a dark place.

Claims (6)

General formula (1):

(In formula (1), R ¹ , R ² , R ³ and R ⁴ independently represent a methyl group or an ethyl group, R ⁵ represents an alkyl group or a phenyl group having 1 to 6 carbon atoms, and R ⁶ Is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer from 0 to 2). A dialkylperoxide having a characteristic thioxanthone group. The polymerizable composition according to claim 1, which contains (a) a polymerization initiator containing a dialkyl peroxide having a thioxanthone group, and (b) a radically polymerizable compound. The polymerizable composition according to claim 2, further comprising (c) an alkali-soluble resin. A cured product, which is formed from the polymerizable composition according to claim 2 or 3. The method for producing a cured product according to claim 4, further comprising a step of irradiating the polymerizable composition with an active energy ray. The method for producing a cured product according to claim 5, further comprising a step of heating after the step of irradiating with the active energy ray.