TW202344502A - Polymerization initiator, polymerizable composition, cured product and hydroperoxide having thioxanthone skeleton - Google Patents

Abstract

The present invention provides a polymerization initiator (A) which contains a dialkyl peroxide (a-1) that has a thioxanthone skeleton represented by general formula (1) and a hydroperoxide (a-2) that has a thioxanthone skeleton represented by general formula (2), wherein the content of the hydroperoxide (a-2) that has a thioxanthone skeleton is 30 parts by mass or less per 100 parts by mass of the polymerization initiator (A). This polymerization initiator exhibits excellent curability with respect to light having a wavelength of 365 nm or the like, while having excellent long-term storage stability at high temperatures.

Description

Polymerization initiator, polymerizable composition and cured product, and hydroperoxide having thioxanthone skeleton

The present invention relates to a polymerization initiator, a polymerizable composition, a cured product, and a hydroperoxide having a thioxanthone skeleton.

In order to synthesize a polymer compound from a radical polymerizable compound having an unsaturated double bond, a radical polymerization initiator that generates radicals by active energy rays such as light, heat, or oxidation-reduction is widely used. Among them, as a photopolymerization initiator capable of generating free radicals by absorbing active energy rays such as light and through chemical bond cleavage or hydrogen abstraction reaction, for example, α-hydroxyacetophenone derivatives or α-aminoacetophenone derivatives can be used, Cylphosphine oxide derivatives, halomethyltriazine derivatives, benzyl ketal derivatives, thioxanthone derivatives, etc.

The photopolymerizable composition composed of the above-mentioned photopolymerization initiator and a radical polymerizable compound does not necessarily require solvent-based dissolution and drying-based curing of the polymerizable composition, which are widely performed during thermal curing. Therefore, in addition to rapid curing by light irradiation, it is also suitable for coating materials, paints, printing inks, photosensitive printing plates, adhesives or various photoresists from the perspective of low VOC (low volatile organic compounds) (photoresist) and other purposes.

On the other hand, with the photopolymerization initiator, it is difficult for light to be blocked, scattered or absorbed by other substances. However, it is cured in deep or shadowed locations where light is not available, or in locations that contain a large amount of pigment. Therefore, Patent Document 1 discloses a polymerization initiator having a peroxy bond (-O-O-) and a triazine skeleton in the molecule and a polymerizable composition containing the compound. Furthermore, Patent Document 2 discloses a polymerization initiator having a peroxy bond and a thioxanthone skeleton and a polymerizable composition containing the above compound. These radical polymerization initiators can efficiently absorb light of wavelengths such as 365 nm emitted by high-pressure mercury lamps or LEDs, etc., and efficiently generate free radicals. They have excellent curability and have peroxygen bonds in the molecules. It is also thermally polymerizable. Therefore, it has the characteristic of dual curing (Dual Cure) by light and heat, and can cure deep parts that are not exposed to light or positions containing a large amount of pigments.

However, in recent years, in the above-mentioned photopolymerization technical field, there has been a need to further solidify a polymerizable composition containing a large amount of pigments. For example, in applications of printing inks represented by offset printing inks, highly colored inks are required to improve quality. However, as the content of the pigment increases, the transmittance of active energy rays in the polymerizable composition decreases, so it is difficult to cure the ink with the conventional addition amount of the polymerization initiator. For the above problems, curability can be ensured by increasing the amount of polymerization initiator added. The same applies to the curing of coating agents, paints, adhesives or various photoresists, which also have pigments attached. If the amount of the polymerization initiator added to the polymerizable composition is increased, the reactivity will be improved, but the stability of the composition will be deteriorated. However, the polymerizable composition used for the above-mentioned applications has problems in the environment in the shipping container when being transported overseas or detained in port facilities, or in the environment of the printing operation site for printing ink applications. High temperatures may occur at times, requiring stability when stored in an environment without temperature adjustment. Prior art documents Patent documents

Patent Document 1: International Publication No. 2018/221177 Patent Document 2: International Publication No. 2020/067118

Technical problems to be solved by the present invention

The polymerizable composition containing a polymerization initiator described in Patent Document 1 or Patent Document 2 has good curability and can ensure storage stability during transportation and storage. However, since the polymerizable composition contains a large amount of the polymerization initiator, the stability of the polymerizable composition deteriorates. Therefore, there is a need to further improve the storage stability.

Therefore, an object of the present invention is to provide a polymerization initiator that can obtain a polymerizable composition that exhibits excellent curability to light with a wavelength of 365 nm or the like and has excellent long-term storage stability at high temperatures.

Furthermore, an object of the present invention is to provide the above-mentioned polymerizable composition and its cured product.

Furthermore, an object of the present invention is to provide a novel hydroperoxide compound having a thioxanthone skeleton contained in the above-mentioned polymerization initiator. Technical means to solve technical problems

That is, the present invention relates to a polymerization initiator containing a dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) and a polymerization initiator having a thioxanthone skeleton represented by the general formula (2). Polymerization initiator (A) of ketone skeleton hydroperoxide (a-2),

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 with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms or a chlorine atom, n represents an integer from 0 to 2,

In formula (2), R ¹ and R ² independently represent a methyl group or an ethyl group, and R ³ is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Oxygen group or chlorine atom, n represents an integer of 0 to 2, in 100 parts by mass of the polymerization initiator (A), the hydroperoxide (a-2) having a thioxanthone skeleton is 30 parts by mass the following.

Furthermore, the present invention relates to a polymerizable composition containing the polymerization initiator and a radically polymerizable compound (B), and a cured product formed from the polymerizable composition.

Furthermore, the present invention relates to a hydroperoxide (a-2) having a thioxanthone skeleton represented by the above general formula (2). Invention effect

The reason for the excellent storage stability is still unclear, but it is presumed to be due to the following reasons.

In general, thermal decomposition of peroxy bonds proceeds in a temperature-dependent manner, and a trace amount of active radical species can be generated even at low temperatures. Therefore, a polymerizable composition composed of a polymerization initiator having a peroxy bond in the molecule and a radically polymerizable compound can polymerize the radically polymerizable compound through the active radical species generated by the polymerization initiator, and the high molecular weight Become viscous.

The temperature dependence affecting the thermal decomposition of peroxy bonds varies depending on the chemical structure, but among the polymerization initiators having peroxy bonds in the molecule, dialkyl peroxides having a thioxanthone skeleton are thermally stable compounds and can be preserved Good stability. However, depending on transportation conditions or intended use, further improvements in storage stability are required.

In the polymerization initiator of the present invention that contains a dialkyl peroxide having a thioxanthone skeleton and a hydroperoxide having a thioxanthone skeleton at a specific ratio, part of the generated active radical species passes from the dialkyl peroxide having a thioxanthone skeleton to Hydroperoxides with a thioxanthone skeleton are deactivated by abstracting hydrogen atoms, while hydroperoxides with a thioxanthone skeleton on the other side are converted into peroxy radical species by abstracting hydrogen atoms. On the other hand, it is considered that active radical species that have not reacted with the hydroperoxide having a thioxanthone skeleton generate carbon radicals through an addition reaction to a radically polymerizable compound or a hydrogen abstraction reaction from a cured product or the like. species, but forms a thermally stable dialkyl peroxide compound by bonding with the peroxy radical species, thereby suppressing the high molecular weight of the radically polymerizable compound.

It has also been found that photocuring using a polymerization initiator containing a hydroperoxide having a thioxanthone skeleton in a specific amount or more results in poor curing. Therefore, in order to obtain good curability, it is desirable to contain a thioxanthone skeleton in a specific ratio. Dialkyl peroxides with a xanthone skeleton and hydroperoxides with a thioxanthone skeleton. As a result, it was found that the polymerizable composition containing the polymerization initiator of the present invention exhibits good curability and has excellent storage stability.

The polymerization initiator (A) of the present invention contains a dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the following general formula (1) and a thioxanthone skeleton represented by the following general formula (2). Hydroperoxide (a-2) of an anthone skeleton. Dialkyl peroxide (a-1) having a thioxanthone skeleton

The dialkyl peroxide (a-1) having a 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 with 1 to 4 carbon atoms, an alkoxy group with 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. Since the decomposition temperature of the dialkyl peroxide having a thioxanthone skeleton is high, from the viewpoint of improving the storage stability of the polymerizable composition, R ¹ , R ² , R ³ and R ⁴ are preferably methane. base.

In the general formula (1), R ⁵ is an alkyl group or 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 methyl, ethyl, propyl, 2,2-dimethylpropyl or phenyl. Among them, from the viewpoint of easy synthesis of the dialkyl peroxide having a thioxanthone skeleton, a methyl group, an ethyl group or a propyl group is preferred. Since the decomposition temperature of the dialkyl peroxide having a thioxanthone skeleton is high, from the viewpoint of improved storage stability of the polymerizable composition and further high sensitivity to light, methyl and ethyl are more preferred. base or propyl.

In the general formula (1), the substitution position of dialkyl peroxide for thioxanthone is not particularly limited. However, from the viewpoint of high sensitivity to light, it is preferable to substitute positions 2 and 3 of the thioxanthone skeleton. From the viewpoint of ease of synthesis, it is more preferable to substitute the No. 2 or No. 3 position of the thioxanthone skeleton.

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. Relative to the emission wavelength of the lamp used, the light absorption characteristics of the dialkyl peroxide having a thioxanthone skeleton can be adjusted through the push-pull effect of these substituents, thereby efficiently absorbing light.

In the general formula (1), n represents an integer of 0 to 2. From the viewpoint of easy 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. However, from the perspective of high sensitivity to light, it is preferable to substitute 6 of the thioxanthone skeleton. The No. 7 position or the No. 7 position is more preferably substituted for the No. 7 position of the thioxanthone skeleton from the perspective of easy synthesis of the dialkyl peroxide having a thioxanthone skeleton.

Specific examples of R ⁶ include alkyl groups such as methyl, ethyl, isopropyl or n-butyl; methoxy, ethoxy, n-propoxy, sec-butoxy or tert-butyl Oxygen and other alkoxy groups; chlorine atoms, etc. From the viewpoint of high sensitivity to light, a methoxy group or an ethoxy group is more preferred.

Specific examples of the dialkyl peroxide (a-1) having a thioxanthone skeleton of the present invention are shown below, but the present invention is not limited thereto.

Preferred examples of the dialkyl peroxide (a-1) having a thioxanthone skeleton include Compound 1 to Compound 9, and more preferred examples include Compound 1, Compound 2, Compound 3, Compound 7, and Compound 8.

Preparation method of dialkyl peroxide (a-1) having thioxanthone skeleton The preparation method of the dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) is not particularly limited, and for example, refer to International Publication No. 2020/067118.

Hydroperoxide (a-2) having a thioxanthone skeleton The hydroperoxide (a-2) having a thioxanthone skeleton of the present invention can be represented by the following general formula (2). In formula (2), R ¹ and R ² independently represent a methyl group or an ethyl group, and R ³ is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. Oxygen group or chlorine atom, n represents an integer from 0 to 2.

In the general formula (2), R ¹ and R ² independently represent a methyl group or an ethyl group. Since the hydroperoxide having a thioxanthone skeleton has a high decomposition temperature, R ¹ and R ² are preferably methyl groups from the viewpoint of improving the storage stability of the polymerizable composition.

In the general formula (2), R ³ 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 push-pull effect of these substituents relative to the emission wavelength of the lamp used can adjust the light absorption characteristics of the hydroperoxide having a thioxanthone skeleton, thereby efficiently absorbing light.

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

In the general formula (2), when n is an integer of 1 to 2, the substitution position of R ³ is not particularly limited. However, from the perspective of high sensitivity to light, it is preferable to substitute the thioxanthone skeleton. Position 6 or position 7, from the perspective of easy synthesis of the hydroperoxide having a thioxanthone skeleton, is more preferred to replace the position 7 of the thioxanthone skeleton.

Specific examples of R ³ include alkyl groups such as methyl, ethyl, isopropyl or n-butyl; methoxy, ethoxy, n-propoxy, sec-butoxy or tert-butyl Oxygen and other alkoxy groups; chlorine atoms, etc. From the viewpoint of high sensitivity to light, a methoxy group or an ethoxy group is more preferred.

Specific examples of the hydroperoxide (a-2) having a thioxanthone skeleton of the present invention are shown below, but the present invention is not limited thereto.

Preferred examples of the hydroperoxide (a-2) having a thioxanthone skeleton include compounds 10 to 18, and further preferred examples include compound 10 and compound 11. Preparation method of hydroperoxide (a-2) having thioxanthone skeleton

The preparation method of the hydroperoxide (a-2) having a thioxanthone skeleton represented by the general formula (2), for example, as shown in the following reaction formula, includes substituting an isoalkyl group for the thioxanthone A process (hereinafter also referred to as process (A)) in which a derivative reacts with a hydroperoxide in the presence of a metal complex. In addition, after the reaction, a process of removing remaining raw materials and the like by distillation under reduced pressure or a purification process may be included. In the above reaction formula, R ¹ , R ² , R ³ and n are the same as the general formula (2), R ⁴ and R ⁵ independently represent a methyl group or an ethyl group, and R ⁶ represents a carbon number of 1 to 6. alkyl or phenyl.

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

In the process (A), from the perspective of improving the yield of the target product, it is preferable to use 0.8 mol or more of the hydroperoxide relative to 1.0 mol of the isoalkyl-substituted thioxanthone derivative for the reaction. , it is more preferable to use 1.0 mol or more of the hydroperoxide for the reaction, and it is preferable to use the hydroperoxide for the reaction to be 10.0 mol or less, and it is more preferable to use 6.0 mol or less of the hydroperoxide for the reaction. In addition, commercially available hydroperoxides can be used. If there are no commercially available products, they can be synthesized according to a known synthesis method described in Japanese Patent Application Laid-Open No. 58-72557 and the like.

In the process (A), the metal complex may be a metal complex selected from the transition metals of the fourth and fifth periods. Examples of the metal in the metal complex include copper, cobalt, manganese, iron, chromium, or zinc. Examples of the ligand include halogens such as bromine and chlorine; inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, and carbonic acid; Formic acid, acetic acid, acetic acid, naphthenic acid, octenoic acid or gluconic acid and other organic acids; cyanide or acetyl acetone, etc. From the viewpoint of improving the yield of the target product, it is preferable to use 0.0001 mol or more of the metal complex relative to 1.0 mol of hydroperoxide, more preferably 0.001 mol or more of the metal complex, and, The metal complex is preferably 1.0 mol or less, and more preferably 0.1 mol or less.

In the process (A), from the perspective of improving the yield of the target product, the reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and the reaction temperature is preferably 100°C or lower, more preferably 80°C. below ℃. The reaction time differs depending on the raw materials, reaction temperature, etc. and therefore cannot be generalized. Generally, from the viewpoint of improving the yield of the target product, it is preferably 1 hour to 60 hours.

In the process (A), water is preferably used as a medium, and water and an organic solvent can also be used simultaneously. As the organic solvent, for example, benzene, toluene, chlorobenzene, o-dichlorobenzene, nitrobenzene, etc. can be used. Usually, the amount of the organic solvent or water is about 50 to 1000 parts by mass relative to 100 parts by mass of the total amount of raw materials. The hydroperoxide having a thioxanthone skeleton can be extracted by distilling or separating the organic solvent or water after the process (A).

The process (A) can be carried out under any condition of normal pressure, increased pressure or reduced pressure, but is preferably carried out under an inert gas atmosphere such as nitrogen or the air, and is more preferably carried out under the air.

As the purification process, in order to distill away the remaining raw materials or by-products, for example, the use of organic solvents, ion-exchanged water, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide A process in which the target product is purified by cleaning with an alkaline aqueous solution such as sodium sulfate or sodium sulfite aqueous solution, or an acidic aqueous solution such as hydrochloric acid or sulfuric acid. As the organic solvent, for example, benzene, toluene, heptane, methanol, chlorobenzene, o-dichlorobenzene, nitrobenzene, etc. can be used. Among them, it is preferable to use an organic solvent for cleaning, and more preferably to use heptane or methanol for cleaning. The organic solvent may be used alone or in combination of two or more. Usually, the amount of the organic solvent is about 50 to 1000 parts by mass relative to 100 parts by mass of the total amount of raw materials. Polymerization initiator (A)

The polymerization initiator (A) of the present invention contains the dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) and the dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (2). Skeleton hydroperoxide (a-2). The polymerization initiator (A) is decomposed by active energy rays or heat, and the generated radicals have a function of initiating polymerization (curing) of the radically polymerizable compound (B). From the viewpoint of suppressing the high molecular weight of the radically polymerizable compound, the hydroperoxide (a-2) having a thioxanthone skeleton is 30 parts by mass or less in 100 parts by mass of the polymerization initiator (A) , preferably 15 parts by mass or less, and from the perspective of storage stability, the hydroperoxide (a-2) having a thioxanthone skeleton is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more. In addition, from the perspective of curability, the dialkyl peroxide (a-1) having a thioxanthone skeleton is preferably 30 parts by mass or more in 100 parts by mass of the polymerization initiator (A), More preferably, it is 50 parts by mass or more, and from the perspective of storage stability, the dialkyl peroxide (a-1) having a thioxanthone skeleton is preferably 98 parts by mass or less, and more preferably 95 parts by mass. the following.

In addition, the polymerization initiator (A) can contain a polymerization initiator other than a dialkyl peroxide having a thioxanthone skeleton or a hydroperoxide having a thioxanthone skeleton (hereinafter also referred to as other polymerization initiator ). By using two or more types of other polymerization initiators, such as a dialkyl peroxide having a thioxanthone skeleton and a hydroperoxide having a thioxanthone skeleton, and different absorption bands, it is possible to emit various types of radiation with respect to, for example, a high-pressure mercury lamp. A lamp with a wavelength of light is used to achieve high sensitivity of the polymerizable composition. In addition, by using other polymerization methods, the polymerizability of the radically polymerizable compound (B) contained in the polymerizable composition, the type of pigments that absorb or scatter light contained in the polymerizable composition, the film thickness of the cured product, etc. Initiators can improve the surface curability, deep curability, transparency, etc. of the polymerizable composition.

As the other polymerization initiator, a known polymerization initiator can be used, and examples thereof include 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-propiophenone, and 4'-(2-hydroxyethoxy )-2-hydroxy-2-methylpropiophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropyl)benzyl)phenyl)-2-methylpropane -1-Keto and other α-hydroxyacetophenone derivatives; 2-methyl-4'-methylthio-2-morpholinylpropiophenone, 2-benzyl-2-(N,N-dimethyl Amino)-1-(4-morpholinylphenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinylbenzene α-aminoacetophenone derivatives such as methyl)butane-1-one; diphenyl-2,4,6-trimethylbenzylphosphine oxide, phenylbis(2,4,6-trimethyl 1-[4-(Phenylthio)phenyl] Octane-1,2-dione-2-(O-benzoyl oxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxime) Azol-3-yl]ethylene}amino)oxy]ethanone, [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H- Benzo[a]oxazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyl oxime) or 1-[4-[4 -(2-Benzofurancarbonyl)phenyl]thio]phenyl-4-methyl-1-pentanone-1-(O-acetyl oxime) and other oxime ester derivatives; 2-(4-methyl Oxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(tri Chloromethyl) 1,3,5-triazine or 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and other halomethyl groups Triazine derivatives; benzyl ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as isopropylthioxanthone, 4-(4-methylbenzene benzophenone derivatives such as methylthio)benzophenone; 3-benzyl-7-diethylaminocoumarin or 3,3'-carbonylbis(7-diethylaminocoumarin) ) and other coumarin derivatives; 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-oxadiazol-2-yl] -Imidazole derivatives such as 4,5-diphenylimidazole; 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1 Organic peroxides such as methylethyl)-9H-thioxanthene-9-one or diphenyl peroxide; azo compounds such as azobisisobutyronitrile; camphorquinone, etc. Among them, 2-isopropyl-9H-thioxanthene-9-one and 2-(2-hydroxypropan-2-yl)-9H-thioxanthene- are preferred among acylphosphine oxide derivatives and thioxanthone derivatives. More than one type of 9-keto. Other polymerization initiators may be used alone or in combination of two or more.

In addition, when the other polymerization initiator is included in the polymerization initiator (A), the proportion of the other polymerization initiator can be appropriately set according to the wavelength emitted by a lamp, etc., for example, in the polymerization initiator (A) ) is 80 mass% or less or 50 mass% or less. polymeric composition

The polymerizable composition of the present invention contains the polymerization initiator (A) and the radical polymerizable compound (B).

Radically polymerizable compound (B) 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 (B) include (meth)acrylates, styrenes, maleates, fumarates, itanoates, cinnamates, and crotons. Acid esters, vinyl ethers, vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimines, N-vinyl compounds, unsaturated Nitriles or olefins, etc. Among them, highly reactive (meth)acrylates are preferably included. One type of radically polymerizable compound (B) may be used alone or two or more types may be used in combination.

As the (meth)acrylates, monofunctional compounds and polyfunctional compounds can be used. Examples of monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethyl (meth)acrylate. Alkyl (meth)acrylates such as methylhexyl ester, lauryl (meth)acrylate or stearyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate Dicyclopentyl methacrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate or 2-ethyl-2-adamantane (meth)acrylate Ester compounds of (meth)acrylic acid and alicyclic alcohols such as esters; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate Ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, polyethylene glycol mono Monomers with hydroxyl groups such as (meth)acrylate or polypropylene glycol mono(meth)acrylate; methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (meth)acrylate Phenoxypolyethylene glycol methacrylate, 2-phenylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1) ,3-Dioxolane-4-yl)methyl(meth)acrylate, (3-ethyloxetan-3-yl)methyl(meth)acrylate or cyclic trimethylol Monomers with chain or cyclic ether bonds such as propane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl ( Meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide , monomers with nitrogen atoms such as diacetone (meth)acrylamide, (meth)acrylamide or N-(meth)acryloxyethyl hexahydrophthalamide; 2 - Monomers with isocyanate groups such as (meth)acryloxyethyl isocyanate; monomers with epoxy groups such as glycidyl (meth)acrylate 4-hydroxybutyl (meth)acrylate glycidyl ether ; Monomers with phosphorus atoms such as 2-((meth)acryloxy)ethyl phosphate; monomers with silicon atoms such as 3-(meth)acryloxypropyltrimethoxysilane; 2, 2,2-Trifluoroethyl(meth)acrylate, 2,2,3,3,3-pentafluoropropyl(meth)acrylate or 2-(perfluorohexyl)ethyl(meth)acrylic acid Monomers with fluorine atoms such as esters; (meth)acrylic acid, succinic acid mono(2-(meth)acryloxyethyl) ester, phthalic acid mono(2-(meth)acryloxyethyl) Monomers having carboxyl groups, such as ethyl) ester, maleic acid mono(2-(meth)acryloxyethyl) ester, or ω-carboxy-polycaprolactone mono(meth)acrylate, etc.

Examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , glyceryl di(meth)acrylate, glyceryl tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane Tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2,2-bis(4-(meth)acrylate acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9,9-bis(4-(2- (meth)acryloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-(2-(meth)acryloxyethoxy)ethoxy)phenyl) Ester compounds of polyols such as fluorene and (meth)acrylic acid; bis(4-(meth)acryloxyphenyl) sulfide, bis(4-(meth)acrylylthiophenyl) sulfide , tris(2-(meth)acryloxyethyl)isocyanurate, ethylene bis(meth)acrylamide, zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic Urethane acrylate, aromatic urethane acrylate, epoxy acrylate or polyester acrylate, etc.

From the perspective of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, or improving the mechanical strength, hardness, heat resistance, durability or chemical resistance of the cured coating film, the (meth)acrylates are preferably The ester compound of the polyol and (meth)acrylic acid is particularly preferably trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate. or dipentaerythritol hexaacrylate.

From the viewpoint of curability, the content of the polymerization initiator (A) is preferably 0.1 parts by mass or more, and more preferably 1.0 parts by mass or more relative to 100 parts by mass of the radically polymerizable compound (B). In addition, from the viewpoint of storage stability or solubility in a radically polymerizable compound, the content of the polymerization initiator (A) is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less. other ingredients

By using a curing accelerator as the other component, the polymerizable composition can be cured by heating at a low temperature. As a curing accelerator, for example, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole compound, an o-phenyl sulfonimide, or a fourth period transition metal compound can be used. The curing accelerator may be used alone or in combination of two or more types.

The amine compound is preferably a tertiary amine, and examples thereof include N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-bis(2- Hydroxyethyl)-p-toluidine, ethyl 4-(dimethylamino)benzoate or (2-methacryloxy)ethyl 4-dimethylaminobenzoate, etc.

Examples of the thiourea include acetyl thiourea, N,N'-dibutyl thiourea, and the like.

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

The fourth period transition metal compound may be selected from organic acid salts or metal chelate compounds of vanadium, cobalt, copper, etc. Examples include cobalt octoate, cobalt naphthenate, copper naphthenate, and naphthenic acid. Vanadium, copper acetyl acetonate, manganese acetyl acetonate or vanadium acetyl acetonate, etc.

The curing accelerator is preferably blended immediately before use of 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 relative to 100 parts by mass of the radically polymerizable compound (B).

As the other components, various photoresists commonly used in coating agents, paints, printing inks, photosensitive printing plates, adhesives, color resists or black resists can be blended into the polymerizable composition. Additives for use. Examples of additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 9,10-dibutoxy Anthracene, coumarin, coumarinone, acridine orange or camphorquinone, etc.), polymerization inhibitor (p-methoxyphenol, hydroquinone, 2,6-di-tert-butyl-4-methylphenol or phenol Thiazide, etc.), UV absorbers, infrared absorbers, chain transfer agents, light stabilizers, antioxidants, leveling agents, surface conditioners, surfactants, thickeners, defoaming agents, adhesion promoters, plasticizers Agents, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, colored dyes, fluorescent dyes, pigments (organic pigments or inorganic pigments), carbon materials (carbon fiber, carbon black, graphite, graphite Carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoils, carbon nanohorns or carbon aerogels, etc.), metal oxides (titanium oxide, iridium oxide, zinc oxide, aluminum oxide or dioxide) Silicon oxide, etc.), metals (silver or copper, etc.), inorganic compounds (glass powder, layered clay minerals, mica, talc or calcium carbonate, etc.), dispersants or flame retardants, etc. One type of additive may be used alone or two or more types of additives may be used in combination.

The content of the additive can be appropriately selected according to the purpose of use and is not particularly limited. Generally, the content of the additive is preferably 500 parts by mass or less, and more preferably 100 parts by mass relative to 100 parts by mass of the radically polymerizable compound (B). portion or less.

In order to improve the viscosity, coatability or smoothness of the cured film, a solvent may be further added to the polymerizable composition. The solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the polymerization initiator (A), the radically polymerizable compound (B), or the other components, as long as it is volatile at drying temperature.

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

The amount of the solvent is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass relative to 100 parts by mass of the solid content of the polymerizable composition. Preparation method of polymerizable composition

When preparing the polymerizable composition, simply add the polymerization initiator (A) and the radically polymerizable compound (B) to a storage container, add the other components as needed, and use a paint stirrer. shaker), bead mill, sand mill, ball mill, vertical ball mill (attritor mill), two-roller machine, three-roller machine, etc., just dissolve or disperse it according to conventional methods. In addition, it can also be filtered through sieve or membrane screening programs as needed.

In addition, in the preparation of the polymerizable composition, the polymerization initiator (A) may be added to the polymerizable composition initially. When the polymerizable composition is stored for a relatively long period of time, it is preferably added shortly after. The polymerization initiator (A) is dissolved or dispersed in the composition containing the radically polymerizable compound (B) before use.

Preparation method of cured product The cured product of the present invention is formed from the polymerizable composition. The preparation method of the cured product includes any one of a process of applying a polymerizable composition to a substrate and then irradiating the polymerizable composition with active energy rays, a process of heating the polymerizable composition, or both processes. In addition, a process including both the irradiation process with the active energy rays and the heating process is also called a dual curing process.

Examples of the coating method include spin coating, bar coating, spray coating, dip coating, pour coating, slit coating, blade coating, gravure coating, screen printing, and offset printing. , inkjet printing or dispensing printing and other methods. Examples of the substrate include glass, silicon wafers, film-shaped, sheet-shaped, and three-dimensional molded products of metal or plastic, and the shape of the substrate is not limited.

The process of irradiating the above-mentioned polymerizable composition with active energy rays can decompose the polymerization initiator (A) and polymerize the radically polymerizable compound (B) by irradiating active energy rays such as electron beams, ultraviolet rays, visible light, or radiation. Thus, a cured product is obtained.

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

As the light source for the light irradiation, solids such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet electrodeless lamps, LED lamps, xenon arc lamps, carbon arc lamps, sunlight, YAG lasers, etc. can be used. Laser, semiconductor laser or gas laser such as argon laser, etc. In addition, when the polymerization initiator (A) absorbs little visible light to infrared light, curing can be performed by using a sensitizer that absorbs the light as an additive.

The exposure amount of the active energy ray should be appropriately set according to the wavelength or intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure amount in the UV-A region is preferably 10~5,000 mJ/cm ² , more preferably 30~1,000 mJ/cm ² . In addition, as the preparation method of the above-mentioned cured product, when a dual curing process is applied and a heating process is performed after the process of irradiation with the active energy ray, the polymerization initiator (A) should be prevented from being completely decomposed by the active energy ray. to set the exposure appropriately.

The process of heating the polymerizable composition decomposes the polymerization initiator (A) by heat and polymerizes the radically polymerizable compound (B) to obtain a cured product.

In the process of heating the polymerizable composition, examples of the heating method include heating or ventilation heating. The heating method is not particularly limited, and examples include an oven, a hot plate, infrared ray irradiation, or electromagnetic wave irradiation. In addition, as a method of ventilation and heating, an air supply type drying oven can be cited, for example.

In the process of heating the polymerizable composition, the higher the heating temperature, the faster the decomposition rate of the polymerization initiator (A) is accelerated. However, if the decomposition rate is too high, the decomposition residue of the radically polymerizable compound (B) tends to increase. On the other hand, the lower the heating temperature, the slower the decomposition rate of the polymerization initiator (A) is, so that curing takes longer. Therefore, the heating temperature and heating time should be appropriately set according to the composition of the polymerizable composition. As an example, the heating temperature is preferably 50 to 230°C, and more preferably 100 to 200°C. In addition, when blending the curing accelerator into the polymerizable composition, the heating temperature can be arbitrarily adjusted to room temperature to 160°C depending on its type or blending amount. On the other hand, the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.

As the preparation method of the cured product, when the dual curing process is applied, especially the process of heating the polymerizable composition after irradiating it with active energy rays, it is possible to efficiently perform a process containing high concentration It is preferable to cure the deep part of the coating film of the polymerization composition of the colored pigment which absorbs or scatters light, or the position where light is blocked and cannot be irradiated.

In addition, when the solvent is included in the polymerization composition, the preparation method of the cured product may include a drying process. In particular, when applying a process in which the polymerizable composition is applied to a substrate and then irradiated with the active energy rays, it is preferable to provide a drying process before the irradiation with the active energy rays.

In the drying process, methods for drying the solvent include, for example, heating drying, ventilation and heating drying, or reduced pressure drying. The heat drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, or electromagnetic wave irradiation. In addition, as a method of ventilation, heating and drying, an air supply type drying oven can be cited.

In addition, in the drying process, the temperature of the polymerizable composition is lower than the set temperature for drying due to the latent heat of evaporation of the solvent. Therefore, it is possible to ensure that the time for gelation of the polymerizable composition is longer. The time until the above-mentioned gelation occurs is affected by the drying method, film thickness, etc. Therefore, in addition to the selection of the solvent, the drying temperature and time should be appropriately set. As an example, the drying temperature is preferably 20 to 120°C, and more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. In addition, by using the polymerization inhibitor, it is possible to ensure a longer time until gelation occurs. In addition, although the dialkyl peroxide having a thioxanthone skeleton decomposes due to heat, the decomposition rate of the above compound when heated at 90°C for 5 minutes is less than 0.1%, so under such conditions The polymeric composition does not thicken or gel.

The dry film thickness (film thickness of the cured product) of the polymerizable composition can be appropriately set according to the use, but is preferably 0.05 to 500 μm, and more preferably 0.1 to 100 μm.

The polymerizable composition of the present invention can be used as a hard coating agent, a coating agent for optical discs, a coating agent for optical fibers, a coating for mobile terminals, a coating for home appliances, a coating for cosmetic containers, an inner anti-reflective coating for optical elements, and a high refractive index coating. coating agents and low refractive index coating agents, thermal insulation coating agents, heat dissipation coating agents or anti-fogging agents, offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, Printing inks such as insulating inks or light guide plate inks, photosensitive printing plates, nanoimprint materials, resins for 3D printers, holographic recording materials, dental materials, waveguide materials, black stripes for lens sheets , printed circuit boards and electrode materials for capacitors, adhesives for FPD, adhesives for HDD, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch screens , OCR and other adhesives and sealants for touch screens, color resists, black resists, protective films for color filters, photo spacers, black column spacers ), frame resists, photoresists for TFT wiring, resists for FPDs such as interlayer insulating films, resists for printed circuit boards such as liquid solder resists, dry film resists, semiconductor resists, or buffer coatings There are no particular restrictions on its use, including various uses such as materials for semiconductors. Example

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples. Synthesis of dialkyl peroxides with thioxanthone skeleton

Synthesis Example 1: Synthesis of Compound 1. Add 30 mL of benzene, 6.10 g (24.0 mmol) of 2-isopropylthioxanthone, and 0.0238 g (0.24 mmol) of copper chloride (I) into a 200 mL four-necked flask. ), stir at room temperature. Slowly add 15.7 g (0.12 mol) of 69 mass% tert-butyl hydroperoxide aqueous solution. The temperature was raised to 65°C under nitrogen flow and the reaction was carried out for 60 hours. The reaction liquid was cooled, 20 mL of ethyl acetate was added, and the aqueous phase was separated. The oil phase is washed with 5 mass% hydrochloric acid, 5 mass% sodium hydroxide aqueous solution or ion-exchange water, and dried with 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 EI-MS and ¹ H-NMR of the obtained compound 1.

Synthesis Example 2: Synthesis of Compound 2 The same procedure as in Synthesis Example 1 was performed except that the 69 mass% tert-butyl hydroperoxide aqueous solution described in Synthesis Example 1 was changed to 85 mass% tert-amyl hydroperoxide. Compound 2 of the present invention was synthesized according to the described method. Table 1 shows the analysis results of EI-MS and ¹ H-NMR of the obtained compound 2. Synthesis of dialkyl hydroperoxides with thioxanthone skeleton

Synthesis Example 3: Synthesis of Compound 10. Add 300.8 mL of water, 100.3 g (0.39 mol) of 2-isopropylthioxanthone, and 1.0 g of RAPISOL A-80 (manufactured by NOF CORPORATION) into a 2 L four-necked flask. , 0.79 g (0.004 mol) of copper acetate dihydrate and 154.4 g (1.18 mol) of 69 mass% tert-butyl hydroperoxide aqueous solution, and stirred at 70°C for 9 hours. 444.9 g of n-heptane, 444.9 g of methanol and 222.5 g of 10 mass% sodium hydroxide aqueous solution were added to the reaction solution, and then the oil phase and the water phase were separated. The aqueous phase was mixed with 444.9 g of heptane, and the extracted 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 11.5 g (yield 5.4%) of compound 10. Table 1 shows the analysis results of EI-MS and ¹ H-NMR of the obtained compound 10.

Synthesis Example 4: Synthesis of Compound 11 The same procedure as in Synthesis Example 1 was performed except that 2-isopropylthioxanthone described in Synthesis Example 3 was changed to 2-methoxy-7-isopropylthioxanthone. Compound 11 of the present invention was synthesized according to the described method. Table 1 shows the analysis results of EI-MS and ¹ H-NMR of the obtained compound 11.

Synthesis of Other Polymerization Initiators Synthesis Example 5: Synthesis of Compound 19 Mix 64 g of 2-isopropylthioxanthone, 44.5 g of bromosuccinimide and 1.5 L of carbon tetrachloride in a 2 L four-necked flask, and perform a heating and reflux reaction. Cool the reaction solution to room temperature, filter the insoluble matter, dissolve the filtrate in 600 mL of ethyl acetate, and wash it three times with the same volume of water. After extracting the oil phase, dry it with anhydrous sodium sulfate, filter, and remove at reduced temperature. The oil phase was concentrated under pressure to obtain crude product. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate = 5/1) to obtain 30 g of the intermediate 2-(2-bromopropan-2-yl)-9H-thioxanthene-9-one. .

Then, 11 g of the above intermediate 2-(2-bromopropan-2-yl)-9H-thioxanth-9-one was mixed with 150 mL of 1 N sodium hydroxide solution and stirred at room temperature. The reaction solution was adjusted to weak acidity with 1 N hydrochloric acid, and the organic layer was extracted twice with 200 mL of ethyl acetate, and then washed twice with the same volume of water and saturated saline solution. The extracted oil phase was dried with anhydrous sodium sulfate, filtered, and 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 5.7 g (0.021 mol) of compound 19. Table 1 shows the analysis results of EI-MS and ¹ H-NMR of the obtained compound 19.

Table 1 Synthesis example compound EI-MS m/z ¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm) Synthesis example 1 Compound 1 342 1.26(s,9H),1.66(s,6H),7.48-7.52(m,1H),7.57-7.65(m,3H),7.85-7.88(m,1H),8.64-8.67(m,2H) Synthesis example 2 Compound 2 356 1.01(t,3H),1.22(s,6H),1.48(t,2H),1.65(s,6H),7.47-7.51(m,1H),7.57-7.64(m,3H),7.84-7.89( m,1H),8.62-8.65(m,2H) Synthesis example 3 Compound 10 286 1.63(s,6H),7.48-7.53(m,1H),7.62-7.69(m,3H),7.85-7.90(m,1H),8.67-8.71(m,2H) Synthesis example 4 Compound 11 316 1.69(s,6H),3.92(s,3H),7.50-7.53(m,1H),7.59-7.62(m,1H),7.86-7.89(m,1H),7.94-7.97(m,1H), 8.43-8.45(m,1H),8.70(s,1H) Synthesis example 5 Compound 19 270 1.67(s,6H),7.50-7.55(m,1H),7.62-7.70(m,3H),7.87-7.90(m,1H),8.67-8.71(m,2H)

Preparation of polymeric compositions The radically polymerizable compound, pigment, and dispersant in the amounts (parts by mass) shown in Table 2 were mixed and stirred, and a polymerization initiator was added and stirred thoroughly to prepare the polymerizable combinations of Examples 1 to 6 and Comparative Examples 1 to 3. things.

Evaluation of curability: The polymerizable composition prepared above was applied to a PET film (cosmoshine A4300, manufactured by TOYOBO CO., LTD) that had been subjected to an easy-adhesion treatment using a coating rod (#6) to prepare a film with a thickness of approximately 10 μm. Uniform coating film. Then, an LED lamp with a wavelength of 385 nm (UniJet E110III, manufactured by USHIO INC) was used to perform light irradiation under conditions of illumination intensity of 3.5 W/cm ² and line speed of 6 m/min. The surface of the printed matter was touched, and the number of irradiations until the photocurable ink stopped sticking to the hand was evaluated as curability. The results are shown in Table 2.

Long-term storage stability evaluation The polymerizable composition prepared above was put into a brown glass bottle, shielded from light with aluminum foil, and left to stand in a constant-temperature machine at 60°C assuming transportation and storage. The case where gelation was not visually recognized after three months of storage was marked as "O", and the case where gelation was visually recognized after three months of storage was marked as "×". The results are shown in Table 2.

Table 2 Comparative example 2 3.5 3.5 50.0 70 30 2 ○ Comparative example 1 7 0.0 70 30 1 × Example 6 11 4 26.7 70 30 1 ○ Example 5 6 1 14.3 60 40 5 0.5 1 ○ Example 4 4 1 2 14.3 70 30 1 ○ Example 3 5 0.3 0.3 1.4 4.3 70 30 1 ○ Example 2 5 2 28.6 70 30 1 ○ Example 1 6 1 14.3 70 30 1 ○ Compound 1 Compound 2 Compound 10 Compound 11 Compound 9 ITX MAPO (A) (a-2) in 100 parts by mass (parts by mass) ECA TMPTA MA100 BYK-9076 Curability Storage stability (a-1) (a-2) other Polymerization initiator (A) Radically polymerizable compound (B) Pigments dispersant

The compounds listed in Table 2 are as follows. ITX: 2-isopropylthioxanthone MAPO: diphenyl(2,4,6-trimethylbenzyl)phosphine oxide (manufactured by iGM Corporation) ECA: Ethyl carbitol acrylate (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) TMPTA: trimethylolpropane triacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) MA100: Carbon black (manufactured by Mitsubishi Chemical Corporation) BYK-9076: Alkylammonium salt of polymer copolymer (manufactured by BYK JAPAN)

From the results in Table 2, it can be seen that the polymerizable composition of the present invention contains only a dialkyl peroxide having a thioxanthone skeleton and a dialkyl peroxide having a thioxanthone skeleton at a specific ratio. The polymerizable composition of the hydroperoxide having a thioxanthone skeleton has good curability and is excellent in long-term storage stability.

without

without

Claims (4)

A polymerization initiator, which is a dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) and a hydrogen peroxide having a thioxanthone skeleton represented by the general formula (2). a polymerization initiator (A) for oxide (a-2), 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 with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms or a chlorine atom, n represents an integer from 0 to 2; and In formula (2), R ¹ and R ² independently represent a methyl group or an ethyl group, and R ³ is an independent substituent and represents an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms. group or chlorine atom, n represents an integer of 0 to 2, wherein in 100 parts by mass of the polymerization initiator (A), the hydroperoxide (a-2) having a thioxanthone skeleton is 30 parts by mass or less. A polymerizable composition comprising the polymerization initiator as described in claim 1 and a radically polymerizable compound (B). A cured product formed from the polymerizable composition as described in claim 2. A hydroperoxide having a thioxanthone skeleton, which is a hydroperoxide (a-2) having a thioxanthone skeleton represented by the general formula (2), In formula (2), R ¹ and R ² independently represent a methyl group or an ethyl group, and R ³ is an independent substituent and represents an alkyl group with 1 to 4 carbon atoms or an alkoxy group with 1 to 4 carbon atoms. base or chlorine atom, n represents an integer from 0 to 2.