JP2019044030A - Polymerizable composition containing thioxanthone derivative having peroxyester group, cured product thereof, and method for producing the cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition having both photocurability which can be efficiently cured by light of 365 nm, 385 nm, 395 nm and the like emitted from a lamp such as an LED and thermosetting property which can be efficiently cured by heat. A polymerization initiator containing a thioxanthone derivative having a peroxyester group represented by the formula (1) and a radically polymerizable compound (b) are contained in the above (b) radically polymerizable compound. A polymerizable composition containing a polyfunctional radically polymerizable compound having 3 or more radically polymerizable groups. (R1 and R2 are independently methyl or ethyl groups; R3 is an C1 to 5 alkyl group; R4 is an independently C1 to 4 alkyl group, 1 to 4 carbon number alkoxy group or chlorine; n is Integer from 0 to 3) [Selection diagram] None

Description

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

  In order to synthesize polymers and the like, radical polymerization initiators that generate radicals by heat, light, 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, 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 3,3 ′, 4,4′-tetrakis (tert-butylperoxycarbonyl) benzophenone having a peroxide bond (—O—O—) in a molecule that generates radicals by light or heat. A polymerization initiator containing (BTTB) as an active ingredient is disclosed. Patent Document 2 discloses an adhesive composition composed of BTTB and a radical polymerizable compound, which is a dual that cures by irradiation with light at room temperature and then cures by heating at 150 ° C. for 2 hours. By curing, the adhesive exhibits strong adhesive strength and high heat resistance.

  Thus, the dual cure type polymerizable composition having both photopolymerizability and thermal polymerizability can also be used in improving dark part curability by heating. Such a dual cure type polymerizable composition is, for example, cured of a polymerizable composition containing a pigment or filler that absorbs or scatters light at a high concentration, or around a protective cover in the manufacturing process of a flat panel display. It is effective for curing parts where light does not reach, such as the black frame and the lower part of the touch panel electrode, and carbon fiber reinforced plastic.

JP 59-197401 A JP 2000-96002 A

  However, the benzophenone having a peroxyester group 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 the like. Furthermore, in recent years, LED lamps having a wavelength of 385 nm or a wavelength of 395 nm are being used, but the light absorption characteristics of benzophenone having a peroxyester group for these wavelengths are very poor. For this reason, the polymerizable composition comprising a benzophenone having a peroxyester group and a radically polymerizable compound has insufficient sensitivity to light, which is the most important basic characteristic of the photopolymerizable composition, and there is a problem in improving sensitivity to light. As mentioned.

  Therefore, in order to solve the above problems, the present invention has both photocurability that can be efficiently cured by light of 365 nm, 385 nm, 395 nm, and the like emitted from a lamp such as an LED, and thermosetting that can be efficiently cured by heat. A polymerizable composition is provided. Furthermore, this invention provides the hardened | cured material of polymeric composition, and the manufacturing method of the said hardened | cured material.

（式（１）中、Ｒ^１およびＲ^２は独立してメチル基またはエチル基を表し、Ｒ^３は炭素数１〜５のアルキル基を表し、Ｒ^４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３の整数を表す。）で表されるペルオキシエステル基を有するチオキサントン誘導体を含む（ａ）重合開始剤と、（ｂ）ラジカル重合性化合物を含有し、前記（ｂ）ラジカル重合性化合物は、ラジカル重合性基を３個以上有する多官能ラジカル重合性化合物を含むことを特徴とする重合性組成物、に関する。 That is, the present invention relates to the general formula (1):

(In Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an alkyl group having 1 to 5 carbon atoms, R ⁴ represents an independent substituent, and A thioxanthone derivative having a peroxyester group represented by (a) 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 3. A polymerization initiator, comprising (b) a radical polymerizable compound, wherein the (b) radical polymerizable compound comprises a polyfunctional radical polymerizable compound having three or more radical polymerizable groups Composition.

  Moreover, this invention relates to the hardened | cured material formed from the said polymeric composition, and the manufacturing method of the said hardened | cured material.

  Since the thioxanthone derivative having a peroxyester group of the present invention can efficiently generate radicals with respect to light of 365 nm, 385 nm, 395 nm, etc. emitted from a lamp such as an LED, and has a peroxide bond in the molecule, Since it functions as a light and thermal polymerization initiator, the polymerizable composition containing (a) a polymerization initiator containing the compound and (b) a radical polymerizable compound can be cured well by light irradiation and can reach the light. Even a dark part that is not present can be cured well by heat. In addition, the compound can efficiently initiate polymerization with respect to the radically polymerizable compound (b) including a polyfunctional radically polymerizable compound having three or more radically polymerizable groups, and from a fluid liquid to a solid It is presumed that the oxygen molecule diffusion into the polymerizable composition is suppressed and the oxygen inhibition of the polymerization can be reduced by quickly changing the shape of the polymerizable composition, so that the polymerizable compound can be efficiently cured.

  Moreover, the polymeric composition of this invention can be conveniently used as a negative resist by mix | blending (c) alkali-soluble resin. In addition, since the polymerizable composition of the present invention can efficiently generate radicals with respect to light having the above-mentioned wavelength, for example, it can be efficiently cured even when (d) a colorant having absorption in visible light is blended. can do.

  In addition, the polymerizable composition of the present invention is heated from the outside by initiating a polymerization reaction by light irradiation from the surface of the polymerizable composition, and by promoting the decomposition of the peroxyester group by diffusion of polymerization heat. It is possible to perform frontal polymerization in which the curing reaction of the polymerizable composition is continued to a deep part.

<Polymerizable composition>
The polymerizable composition of the present invention comprises (a) a polymerization initiator containing a thioxanthone derivative having a peroxyester group, and (b) a radical polymerizable compound containing a polyfunctional radical polymerizable compound having three or more radical polymerizable groups Containing. Furthermore, the polymerizable composition may contain (c) an alkali-soluble resin and (d) a colorant as necessary.

<(A) Polymerization initiator>
The polymerization initiator (a) of the present invention contains a thioxanthone derivative having a peroxyester group 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. The thioxanthone derivatives having a peroxyester group may be used alone or in combination of two or more.

（式（１）中、Ｒ^１およびＲ^２は独立してメチル基またはエチル基を表し、Ｒ^３は炭素数１〜５のアルキル基を表し、Ｒ^４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３の整数を表す。） The thioxanthone derivative having the peroxyester group can be represented by the general formula (1).

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

In the general formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group. R ¹ and R ² are preferably methyl groups from the viewpoint of easy synthesis of the thioxanthone derivative having a peroxyester group.

In the general formula (1), R ³ represents an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched. Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, and a 2,2-dimethylpropyl group. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoint of easy synthesis of the thioxanthone derivative. From the viewpoint of high sensitivity of the lamp to light, a methyl group or an ethyl group is more preferable.

  In the general formula (1), the substitution position of the peroxyester group is not particularly limited, but is preferably substituted at the 2-position, 3-position, or 4-position from the viewpoint of high sensitivity to light of the lamp, From the viewpoint of easy synthesis of the thioxanthone derivative, it is more preferable to substitute at the 2-position or the 3-position.

In the general formula (1), R ⁴ 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 peroxyester can be adjusted by the push-pull effect applied to these substituents with respect to the emission wavelength of the lamp used, and the light of the lamp can be absorbed efficiently.

  In the general formula (1), n represents an integer of 0 to 3. From the viewpoint of easy synthesis of the thioxanthone derivative, n is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

In the general formula (1), when n is an integer of 1 to 3, the substitution position of R ⁵ is not particularly limited, but is substituted at the 6-position or the 7-position from the viewpoint of high sensitivity to the light of the lamp. From the viewpoint of easy synthesis of the thioxanthone derivative, substitution at the 7-position is more preferable.

Specific examples of R ⁴ include, for example, alkyl groups such as a methyl group, an ethyl group, an isopropyl group, and an n-butyl group; a methoxy group, an ethoxy group, an n-propyloxy group, a sec-butyloxy group, and a tert-butyloxy group. An alkoxy group such as chlorine atom and the like.

  Specific examples of the thioxanthone derivative having a peroxyester group of the present invention are shown below, but the present invention is not limited thereto.

  The thioxanthone derivative having a peroxyester group is preferably Compound 1 to Compound 9, and more preferably Compound 1, Compound 2, Compound 4, Compound 5, Compound 7, and Compound 8.

（上記反応式において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、およびｎは前記一般式（１）と同じである。） The method for producing a thioxanthone derivative having a peroxyester group represented by the general formula (1) includes, for example, a carboxylic acid form and a chlorinating agent such as thionyl chloride, phosphorus trichloride, phosgene as shown in the following reaction formula. A step of obtaining an acid chloride by reaction (hereinafter also referred to as step (A)), and subsequently a step of reacting the obtained acid chloride derivative and hydroperoxide in the presence of an alkali (hereinafter referred to as “step (A)”). And a method including a step (B)). 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 addition, the said process (B) and the process after it can also synthesize | combine according to the synthesis method of the well-known peroxy ester as described in Unexamined-Japanese-Patent No. 51-115411.

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

  In the step (A), a commercially available product can be used as the carboxylic acid form. In addition, when there is no commercial item, it can synthesize | combine according to the well-known synthesis method as described in Japanese translations of PCT publication No. 2012-512819. 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 the carboxylic acid compound, from the viewpoint of increasing the yield of the target product, and a solvent. It is also possible to carry out the reaction using a large excess amount, but it is preferred to react 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, etc., and thus cannot be determined unconditionally, but is usually from 30 minutes to 20 hours from the viewpoint of improving the yield of the target product.

  A thioxanthone derivative having a peroxyester group is obtained by the step (B) in which the acid chloride obtained in the step (A) is reacted 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 acid chloride, from the viewpoint of increasing the yield of the target product. It is preferable to react at 0.0 mol or less, and it is preferable to react at 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, but is usually from 10 minutes to 6 hours from the viewpoint of increasing the yield of the target product.

  In the step (B), the alkali used is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium 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 acid chloride derivative is liquid, the reaction can be performed without using an organic solvent. When the 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 thioxanthone derivative having a peroxyester group, but for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Examples include ketones, 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 the step (B) to take out the peroxycinnamate derivative, and the thioxanthone derivative having a peroxyester group is organically added in order to improve handling and reduce the risk of thermal decomposition. It may be used as a diluted product of a solvent.

  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.

  The (a) polymerization initiator may contain a polymerization initiator other than the thioxanthone derivative having the peroxyester group (hereinafter also referred to as other polymerization initiator). By using other polymerization initiators having different absorption bands, for example, it is possible to increase the sensitivity of the polymerizable composition for a lamp that emits light of a plurality of wavelengths, such as an LED or a high-pressure mercury lamp. . Further, in consideration of (b) the polymerizability of the radically polymerizable compound described later contained in the polymerizable composition, the type of (d) the colorant described later contained in the polymerizable composition, the film thickness of the cured product, etc. By using other polymerization initiators, the surface curability, deep curability, transparency, etc. of the polymerizable composition can be improved.

  As said other polymerization initiator, a well-known thing can be used, for example, alpha-hydroxy acetophenone derivatives, such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl- propiophenone; 2-methyl-4 ' Α-aminoacetophenone derivatives such as methylthio-2-morpholinopropiophenone and 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one; Acylphosphine oxide derivatives such as 4,6-trimethylbenzoylphosphine oxide and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide; 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyloxime), 1-[({1- [9-ethyl-6 Oxime ester derivatives such as-(2-methylbenzoyl) -9H-carbazol-3-yl] ethylidene} amino) oxy] ethanone; 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1, Halomethyltriazine derivatives such as 3,5-triazine; thioxanthone derivatives such as isopropylthioxanthone; benzophenone derivatives such as 4- (4-methylphenylthio) benzophenone; 3-benzoyl-7-diethylaminocoumarin, 3,3′-carbonylbis ( Coumarin derivatives such as 7-diethylaminocoumarin); 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl] -4,5- Imidazole derivatives such as diphenylimidazole; dibenzoyl peroxy Organic peroxides such as side; azo compounds such as azobisisobutyronitrile; camphorquinone 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 described later. More preferred 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 70 mass% or less in (a) polymerization initiator, and 40 masses More preferably, it is% or less.

<(B) Radical polymerizable compound>
The radically polymerizable compound (b) of the present invention contains a polyfunctional radically polymerizable compound having 3 or more radically polymerizable groups. The radical polymerizable group is preferably a carbon-carbon double bond, and more preferably a carbon-carbon double bond conjugated and activated by an adjacent functional group.

  Examples of the conjugated activated carbon-carbon double bond include a carbon-carbon double bond in which a carbon-carbon double bond such as a 1,3-butadiene structure is adjacently conjugated, and a carbonyl group is adjacently conjugated. A carbon-carbon double bond in which a cyano group is adjacently conjugated, a carbon-carbon double bond in which an aromatic ring is adjacently conjugated, and the like. Among these conjugated activated carbon-carbon double bonds, from the viewpoint of increasing polymerization activity, a carbon-carbon double bond in which a carbonyl group is adjacently conjugated, and a carbon-carbon in which a cyano group is adjacently conjugated. A carbon-carbon double bond in which a double bond and an aromatic ring are adjacently conjugated is preferable, a carbon-carbon double bond in which a carbonyl group is adjacently conjugated is more preferable, and a (meth) acryloyl group and a maleimide group are more preferable. , (Meth) acryloyl groups are more preferred, and acryloyl groups are even more preferred.

  Examples of the polyfunctional radical polymerizable compound having three or more (meth) acryloyl groups include trimethylol ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, and pentaerythritol tris. Polyhydric alcohols such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate; An ester compound with (meth) acrylic acid, a compound having two or more isocyanate groups, one or more hydroxyl groups in the molecule, and three, four or five (meth) acryloyloxy groups; Have Multifunctional urethane acrylate compound obtained by the compound is reacted, and the like.

  Moreover, the said (b) radically polymerizable compound can contain a monofunctional compound and / or a bifunctional compound. Examples of the monofunctional compound and / or bifunctional compound include (meth) acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, and crotonic acid esters. , 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. A monofunctional compound and / or a bifunctional compound may be used independently and may use 2 or more types together.

  Examples of the monofunctional compound include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate; (meth) acrylic acids such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate and alicyclic rings. Ester compounds with aliphatic alcohols; aryl (meth) acrylates such as benzyl (meth) acrylate; 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyl-terminated polyethylene glycol mono (meth) Monomers having a linear or cyclic ether bond, such as monomers having a hydroxy group such as acrylate; methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. Monomers having a nitrogen atom such as (meth) acryloylmorpholine, N- (meth) acryloyloxyethyl hexahydrophthalimide; Monomers having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; Glycidyl (meth) acrylate A monomer having an epoxy group such as: a monomer having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; a monomer having a silicon atom such as 3- (meth) acryloxypropyltrimethoxysilane; Monomers having a fluorine atom such as perfluorohexyl) ethyl (meth) acrylate; monomers having a carboxyl group such as (meth) acrylic acid and mono (2- (meth) acryloyloxyethyl) succinate.

  Examples of the bifunctional compound include diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide addition di (meth) acrylate, and bisphenol A. Propylene oxide-added di (meth) acrylate, glycerin di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 9,9-bis (4- (2- (meth) acryloyl) And oxyethoxy) phenyl) fluorene, ethylenebis (meth) acrylamide, and the like. Also, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, etc. having two unsaturated double bonds such as (meth) acryloyl group and vinyl group in the skeleton of polyester, epoxy, urethane, etc. are used. be able to.

  The ratio of the polyfunctional radical polymerizable compound having 3 or more radical polymerizable groups is 15% by mass or more from the viewpoint of efficiently curing the polymerizable composition in the (b) radical polymerizable compound. Preferably, it is 30% by mass or more, more preferably 60% by mass or more, and 10% by mass from the viewpoint of efficiently curing the polymerizable composition in the total solid content of the polymerizable composition. % Or more, preferably 20% by mass or more, and more preferably 40% by mass or more.

  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 a GPC apparatus, three TSKgelHZM-M (manufactured by Tosoh Corporation) are used as columns, tetrahydrofuran is used as a developing solvent, column temperature is 40 ° C., flow rate is 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.

  The proportion of the alkali-soluble resin (c) is preferably 10 to 70% by mass and more preferably 15 to 60% by mass in the total solid content of the polymerizable composition. 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 mass ratio ((b) / (c)) of the (b) radical polymerizable compound and the (c) alkali-soluble resin is from the viewpoint of reproducibility of the pattern shape and compatibility between heat resistance and alkali developability. It is preferably 20/80 or more, more preferably 30/70 or more, further preferably 40/60 or more, and preferably 80/20 or less, and 70/30 or less. It is more preferable that the ratio is 60/40 or less.

  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.

<(D) Colorant>
The colorant of the present invention is not particularly limited in color tone, and may be appropriately selected according to the use such as printing ink and color filter, and may be a pigment, a dye, or a natural pigment. The colorant is preferably a colorant having high color developability and high heat resistance, and organic pigments and inorganic pigments are usually used. (D) A coloring agent may be used independently and may use 2 or more types together.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the color index (C .. I.) numbers can be mentioned, for example, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment violet 23, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment black 7 and the like. Examples of the inorganic pigment include carbon black and titanium black.

  (D) The proportion of the colorant is preferably 0.1 to 60% by mass, more preferably 1 to 40% by mass, and 2 to 20% by mass in the total solid content of the polymerizable composition. More preferably it is. When the ratio is less than 0.1% by mass, the colorability is poor, which is not preferable. When the ratio is more than 60% by mass, the curability is lowered, which is not preferable.

<Other ingredients>
The polymerizable composition of the present invention can contain other components in appropriate combination. 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 additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4′-bis (diethylamino) benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibition Agents (p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.), ultraviolet absorbers, infrared absorbers, light stabilizers, antioxidants, leveling agents, surface conditioners , Surfactant, thickener, antifoaming agent, adhesion promoter, plasticizer, epoxy compound, thiol compound, resin having ethylenically unsaturated bond, saturated resin, fluorescent dye, metal oxide (titanium oxide, iridium oxide , Zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass) End, the layered clay mineral, mica, talc, calcium carbonate, etc.), dispersing agents, 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 50 parts by mass or less with respect to 100 parts by mass of the (b) radical polymerizable compound. The amount is preferably 20 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, the (d) colorant, and the other components. There is no particular limitation as long as the solvent is volatile at the drying temperature.

  Examples of the solvent include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, carbitol acetate solvents. Examples include solvents, propylene glycol monomethyl ether acetate, 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 preparing the polymerizable composition, in the storage container, the (a) polymerization initiator, the (b) radical polymerizable compound, if necessary, the (c) alkali-soluble resin, the (d) The colorant and other components may be added and dissolved or dispersed in accordance with a conventional method using a paint shaker, bead mill, sand grind mill, ball mill, attritor mill, two roll mill, three roll mill or the like. Moreover, you may filter through a mesh or 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 the (b) radical polymerizable compound 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. In particular, the polymerizable composition can be rapidly cured by an LED lamp having a center wavelength in the range of 380 to 405 nm.

  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 amount in the UV-A region is preferably 10 to 5,000 mJ / cm ² , and more preferably 30 to 1,500 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, if the decomposition rate is too high, (a) the decomposition residue of the polymerization initiator 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 0.5 to 60 minutes, more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to ensure a long time until gelation. The thioxanthone derivative having a peroxyester group is decomposed by heat, but the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%. 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 application, but is preferably 0.05 to 300 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. 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 internal antireflection coating material for optical elements,・ 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.

(1) Synthesis of thioxanthone derivative having a peroxyester group [Synthesis Example 1: Synthesis of Compound 1]
To a 50 mL eggplant flask, 565 mg (2.06 mmol) of 9-oxo-9H-thioxanthene-2-carboxylic acid and 6 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 9-oxo-9H-thioxanthene-2-carboxylic acid chloride. Next, 20 mL of dichloromethane was added to the obtained 9-oxo-9H-thioxanthene-2-carboxylic acid chloride, and the mixture was stirred and cooled to 15 ° C. in an ice bath. A mixed solution in which 371 mg of ion-exchanged water and 495 mg (3.09 mmol) of a 35% by weight aqueous solution of potassium hydroxide were added to a 10 mL beaker and 403 mg (3.09 mmol) of a 69% by weight aqueous solution of tert-butyl hydroperoxide was added at 30 ° C. or lower. Was prepared separately, and this mixed solution was added dropwise over 10 minutes, followed by reaction at 15 ° C. for 1 hour. After completion of the reaction, 20 mL of dichloromethane was added, 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 ion exchange water and dried over anhydrous magnesium sulfate. After filtration, the oil phase was concentrated under reduced pressure to give 372 mg of compound 1 of the present invention. The analysis results are shown below.
Appearance: Pale yellow crystals Melting point (° C): 136
EI-MS (m / z): 328
^{· 1 H-NMR (400MHz,} CDCl 3) δ (ppm): 1.46 (s, 9H, -C (CH 3) 3), 7.52-7.57 (m, 1H, Ar-H), 7.61-7.62 (dd, J = 8.1 Hz, 0.8 Hz, 1H, Ar—H), 7.65-7.70 (m, 2H, Ar—H), 8.16-8. 19 (dd, J = 8.5 Hz, 2.0 Hz, 1H, Ar-H), 8.62-8.64 (dd, J = 8.1 Hz, 1.1 Hz, 1H, Ar-H), 9. 14-9.15 (d, J = 1.7 Hz, 1H, Ar-H)

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

<Comparative Example 1>
As a comparative example, Table 1 shows the results of Compound R1. 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 1, 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 ₃₆₅ nm (L · mol ^{− 1} · cm ⁻¹ ), ε ₃₈₅ represents a molar extinction coefficient at ₃₈₅ nm (L · mol ⁻¹ · cm ⁻¹ ), and ε ₃₉₅ represents a molar extinction coefficient at ₃₉₅ nm (L · mol ⁻¹ · cm ⁻¹ ).

  In general, the larger the molar extinction coefficient of the photopolymerization initiator at the exposure wavelength, the easier the light is absorbed and the more easily radicals are generated. That is, a compound having a large molar extinction coefficient at the exposure wavelength is suitable for increasing the sensitivity of the photopolymerization initiator. When used for UV curing, an ultra-high pressure mercury lamp or a high-pressure mercury lamp efficiently emits light having a wavelength of 365 nm (i-line) as a main wavelength. In the printing ink field or the like, LED lamps having a wavelength of 385 nm or a wavelength of 395 nm are used. From the results of Table 3, it can be seen that the compound 1 of the thioxanthone derivative having a peroxyester group of the present invention has a larger molar extinction coefficient at 365 nm, 385 nm, and 395 nm, compared to the compound R1 of a benzophenone derivative having a peroxyester group.

(3) Sensitivity evaluation using an ultra high pressure mercury lamp <Example 2 and Comparative Example 2>
<Preparation of polymerizable composition (A)>
The amount of (b) radical polymerizable compound, (c) alkali-soluble resin and other components shown in Table 2 were mixed and stirred, (a) a polymerization initiator was added and stirred well, and Example 2 and Comparative Example 2 A polymerizable composition (A) was prepared.

In Table 2 above, DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
Acrylic 1 is 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.

The polymerizable composition (A) prepared 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”. The evaluation results of each polymerizable composition (A) are shown in Table 3.

  From the results in Table 3, it was revealed that the sensitivity of the polymerizable composition containing Compound 1 was higher than that of the polymerizable composition containing Compound R1 of the benzophenone derivative having a peroxyester group.

(4) Sensitivity evaluation using an LED lamp having a wavelength of 385 nm
<Preparation of polymerizable composition (B) to (D)>
The amounts of (b) radical polymerizable compound and solvent shown in Table 4 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and the polymerizable compositions of Examples 3 to 4 and Comparative Examples 3 to 8 (B) was prepared.

In Table 4 above, TMPTA is trimethylolpropane triacrylate (Tokyo Chemical Industry Reagent);
HDDA indicates 1,6-hexanediol diacrylate (trade name: Light acrylate 1,6HX-A, manufactured by Kyoeisha Chemical Co., Ltd.).

The polymerizable compositions (B) to (D) prepared above were 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 solvent was dried on the glass substrate in a dryer at 90 ° C. for 2 minutes to produce a uniform coating film having a thickness of 3 μm. Subsequently, irradiation was performed at 1300 mJ / cm ² using an LED lamp (UniJet E110III, manufactured by Ushio Inc.) having a wavelength of 385 nm. The degree of cure (%) of the cured film portion was measured by attenuated total reflection infrared spectroscopy (ATR-IR). At that time, using the peak area of the double bond absorption spectrum of plane deformation vibration of (810 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 curing rate (curing degree) was calculated. The results are shown in Table 5.

  In addition, Table 5 shows the results of the compounds R2 to R5 as comparative examples. Compound R2 was Irgacure 184 (manufactured by BASF), Compound R3 was Irgacure 819 (manufactured by BASF), Compound R4 was Irgacure 369 (manufactured by BASF), and Compound R5 was Irgacure OXE02 (manufactured by BASF).

  From the results of Table 5, it is clear that the polymerizable composition containing Compound 1 has higher sensitivity than the polymerizable composition containing the compound R1 of the benzophenone derivative having a peroxyester group and other photopolymerization initiators. It became. Moreover, it became clear that the polymeric composition (D) which does not contain the polyfunctional radically polymerizable compound which has 3 or more of radically polymerizable groups as (b) radically polymerizable monomer has low sensitivity.

(5) Evaluation of sensitivity of coloring composition using high-pressure mercury lamp <Example 5, Comparative Examples 9 to 13>
<Preparation of polymerizable composition (E)>
The amounts of (b) radical polymerizable compound, (d) colorant dispersion and solvent shown in Table 6 were mixed and stirred, (a) the polymerization initiator was added and stirred well, and Example 5 and Comparative Example 9 ˜13 polymerizable compositions (B) were prepared.

  In Table 6 above, blue pigment 1 is C.I. I. Pigment Blue 15: 6 dispersion (pigment concentration: 10%, SB156, manufactured by Taisei Kako Co., Ltd.) is shown.

Using the polymerizable composition (E) prepared above and a bar coater (# 18), it was applied onto a PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) that had been subjected to an easy adhesion treatment. After the application, the PET film was dried in a dryer at 90 ° C. for 2 minutes to dry the solvent, thereby preparing a uniform coating film having a thickness of 3 μm. Subsequently, 80 mJ / cm < ² > irradiation was performed using the UV conveyor apparatus (ECS-4011GX, the eye graphics company make) in which the high pressure mercury lamp was installed. The degree of cure (%) of the cured film portion was measured by ATR-IR. The results are shown in Table 7.

  From the results of Table 7, it is clear that the polymerizable composition containing Compound 1 has higher sensitivity than the polymerizable composition containing the compound R1 of the benzophenone derivative having a peroxyester group and other photopolymerization initiators. It became.

(5) Evaluation of dual cure curing characteristics <Example 6, Comparative Example 14>
<Preparation of polymerizable composition (F)>
The polymerization composition (F) of Example 6 and Comparative Example 14 was prepared by adding (a) a polymerization initiator to the amount of (b) radical polymerizable compound shown in Table 8 and stirring well.

In Table 8, UV-3700B is urethane acrylate (trade name: Purple light UV-3700B, manufactured by Nippon Synthetic Chemical Industry);
IBOA is isobornyl acrylate;
THFA is tetrahydrofurfuryl acrylate;
TMPTA indicates trimethylolpropane triacrylate.

The polymerizable composition (F) prepared above was applied to a PEN film subjected to an easy adhesion treatment with an applicator to a thickness of 50 μm, and a PEN film with a black coating (the transmittance at 365 nm was less than 0.1%) ) Was placed in half the area 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 60 minutes at 120 degreeC.

  After the above heating, the black film-coated PEN film was removed to expose the cured film, and the degree of cure (%) of the cured film portion was measured by ATR-IR. The results are shown in Table 9.

  From the results shown in Table 9, it is clear that the polymerizable composition containing the compound 1 of the present invention is characterized by excellent photocurability and thermosetting.

(6) Evaluation of frontal polymerization characteristics <Example 7>
6.75 g of TMPTA was added to 5.0 g of carbon black dispersion (trade name: TSBK-403, manufactured by Taisei Kako Co., Ltd., pigment concentration: 15%, solvent: PGMEA and ethyl acetate), and stirred under reduced pressure. A TMPTA dispersion of carbon black was prepared by distilling off PGMEA and ethyl acetate.
Polymeric composition of Example 7 by adding 0.3 g of 4-acryloylmorpholine (Tokyo Chemical Industry Reagent) and 0.070 g of Compound 1 to 1.5 g of the TMPTA dispersion of carbon black prepared above, and stirring well. A product (G1) was prepared.
The polymerizable composition (G1) was poured into a glass tube having a diameter of 5 mm and a length of 40 mm to a height of about 3 cm, and the glass tube was fixed. Then, the glass tube was preheated for 2 minutes in a dryer at 60 ° C., and a 385 nm LED was exposed only from the upper part of the test tube at room temperature, and the polymerizable composition (G1) was observed visually. The exposure was stopped when the formation of a cured layer was confirmed on the top.
As a result, the interface of the cured layer gradually dropped downward thereafter, and reached the bottom of the glass tube after about 8 minutes, confirming the progress of frontal polymerization of about 3 cm.

<Comparative Example 15>
The method described in Example 7 was followed except that Compound 1 described in Example 7 was changed to Compound R1, TMPTA was changed to HDDA, and a polymerizable composition (G2) was prepared. When formation of a cured layer was confirmed on the upper part of the polymerizable composition (G2), the exposure was stopped.
As a result, the interface of the cured layer did not drop downward, and the progress of frontal polymerization could not be confirmed.

From the results of Example 7 and Comparative Example 15, the polymerizable composition containing a thioxanthone derivative having a peroxyester group according to the present invention is excellent in photocurability and thermosetting, and thus it is possible to construct a frontal polymerization system. It is clear that

Claims (7)

General formula (1):

(In Formula (1), R ¹ and R ² independently represent a methyl group or an ethyl group, R ³ represents an alkyl group having 1 to 5 carbon atoms, R ⁴ represents an independent substituent, and A thioxanthone derivative having a peroxyester group represented by (a) 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 3. A polymerization initiator and (b) a radical polymerizable compound,
Said (b) radically polymerizable compound contains the polyfunctional radically polymerizable compound which has 3 or more of radically polymerizable groups, Polymerizable composition characterized by the above-mentioned.   (C) The polymerizable composition according to claim 1, comprising an alkali-soluble resin.   (D) The polymerizable composition according to claim 1 or 2, further comprising a colorant.   Hardened | cured material formed from the polymeric composition in any one of Claims 1-3.   The method for producing a cured product according to claim 4, comprising a step of irradiating the polymerizable composition with active energy rays.   6. The method for producing a cured product according to claim 5, wherein the light source of the active energy ray is an LED lamp having a center wavelength in a range of 380 nm to 405 nm.   The method for producing a cured product according to claim 5 or 6, further comprising a heating step after the irradiation with the active energy rays.