Oxygen inhibition reducer, polymerizable composition, cured product, and method for producing the cured product

Abstract

To provide an oxygen inhibition reducing agent that can effectively reduce inhibition of curing by oxygen without yellowing a cured product.SOLUTION: An oxygen inhibition reducing agent contains a compound represented by the general formula (1) in the figure. (In the formula (1), -X- may be present or absent, and if present then X represents an oxygen or sulfur atom; A represents an alkylene group which may comprise an ether bond, thioether bond, ester bond or amide bond; and Y represents a C1-18 fluoroalkyl group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an oxygen inhibition reducer, a polymerizable composition, a cured product, and a method for producing the cured product. [Background technology]

[0002] During photocuring of photocurable resin compositions, curing is inhibited by oxygen diffusing from the coating surface into the coating and by oxygen dissolved in the coating. The coating surface, which is in direct contact with air, is particularly susceptible to oxygen inhibition, resulting in poor curing of the surface, resulting in abnormal appearance and deterioration of surface properties. Therefore, there is a need for a photocuring system that can effectively reduce curing inhibition caused by oxygen.

[0003] Oxygen inhibition is generally known to occur through the following mechanism: When a photocurable resin composition is irradiated with light, active radical species are generated from the photopolymerization initiator, which attacks the unsaturated bonds in the monomer, generating growing radical species and causing curing to proceed. If oxygen is present, the growing radical species are trapped by the oxygen, generating peroxy radical species. Since the peroxy radical species do not react with the monomer, curing is inhibited.

[0004] One method for reducing oxygen inhibition is to increase the proportion of the photopolymerization initiator added to the entire photocurable resin composition, but increasing the number of parts of the photopolymerization initiator added can cause problems such as a decrease in the physical properties of the coating film and bleeding of the photopolymerization initiator onto the coating film surface.

[0005] Patent Document 1 also discloses a method of using an amine compound as an oxygen inhibition reducer for reducing oxygen inhibition. Amine compounds undergo hydrogen abstraction from peroxy radical species, thereby becoming active radical species and reactivating curing that has been stopped by oxygen. However, the effect of amine compounds in reducing oxygen inhibition is insufficient, and the cured product turns yellow, limiting the conditions under which they can be used. For these reasons, further improvements are desired.

[0006] Furthermore, Non-Patent Document 1 discloses a method for efficiently sensitized decomposition of organic peroxides by irradiating light to a ketone compound contained in a polymer chain. The sensitized decomposition by a ketone compound of organic peroxides generated by recombination or hydrogen abstraction of peroxy radical species is presumed to be able to efficiently reduce curing inhibition by oxygen with a small amount of addition, because the ketone compound acts catalytically and can regenerate two active radical species from one peroxide bond. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-158594

[0008] [Non-Patent Document 1] macromolecules,1978,11,937-942. Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention provides an oxygen inhibition reducer that can effectively reduce curing inhibition caused by oxygen without causing yellowing of the cured product.

[0010] Furthermore, the present invention provides a polymerizable composition, a cured product thereof, and a method for producing the cured product. [Means for solving the problem]

[0011] That is, the present invention relates to an oxygen inhibition reducer containing a compound represented by the following general formula (1). [ka] (In formula (1), -X- may or may not be present. When present, X represents an oxygen atom or a sulfur atom. A represents an alkylene group which may contain an ether bond, a thioether bond, an ester bond, or an amide bond. Y represents a fluoroalkyl group having 1 to 18 carbon atoms.)

[0012] The present invention also relates to a polymerizable composition containing the oxygen inhibition reducer and a radically polymerizable compound, a cured product formed from the polymerizable composition, and a method for producing the cured product. [Effects of the Invention]

[0013] The compound of the present invention represented by the above general formula (1) has an aryl ketone structure, and by sensitizing the decomposition of compounds having peroxy radical species generated by oxygen inhibition during photocuring, it can effectively reduce curing inhibition caused by oxygen and does not cause yellowing of the cured product. Furthermore, by having a fluoroalkyl group, it segregates on the coating film surface, thereby improving curing defects on the coating film surface, which is most susceptible to oxygen inhibition. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Oxygen inhibition reducer> The oxygen inhibition reducer of the present invention contains a compound represented by the following general formula (1). [ka] (In formula (1), -X- may or may not be present. When present, X represents an oxygen atom or a sulfur atom. A represents an alkylene group which may contain an ether bond, a thioether bond, an ester bond, or an amide bond. Y represents a fluoroalkyl group having 1 to 18 carbon atoms.)

[0015] In the general formula (1), X is preferably an oxygen atom or a sulfur atom, from the viewpoint of increasing the sensitivity to lamp light and increasing the efficiency of sensitized decomposition.

[0016] In the general formula (1), A is preferably an alkylene group having 0 to 6 carbon atoms. The alkylene group may be linear or branched. Among these, from the viewpoint of ease of synthesis, A preferably contains an ether bond, an ester bond, or an amide bond, and particularly preferably contains an ether bond or an amide bond.

[0017] In the general formula (1), the fluoroalkyl group may be either a straight chain or a branched chain, and preferably has 1 to 18 carbon atoms, particularly preferably 2 to 7 carbon atoms.

[0018] The method for producing the compound represented by the general formula (1) can be widely based on known techniques, such as a method including a step of reacting a hydroxy-substituted aryl ketone derivative with a halogenated fluoroalkyl compound in the presence of a base, a step of reacting a carboxy-substituted aryl ketone derivative with a hydroxyfluoroalkyl compound under reflux, or a step of reacting a carboxy-substituted aryl ketone derivative with an aminofluoroalkyl compound in the presence of a condensing agent. After the reaction, the method may include a step of distilling off (removing) excess raw materials under reduced pressure, or a purification step.

[0019] <Polymerizable composition> The polymerizable composition of the present invention contains a compound represented by the general formula (1) and a radically polymerizable compound. Furthermore, the polymerizable composition can be provided with developability by containing an alkali-soluble resin. The polymerizable composition can also contain other components in appropriate combination.

[0020] <Radical polymerizable compound> As the radical polymerizable compound of the present invention, a compound having an ethylenically unsaturated group can be preferably used. Examples of the radical polymerizable compound include (meth)acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, vinyl ethers, vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, and olefins. Among these, it is preferable to use (meth)acrylic acid esters, which have high reactivity. The radical polymerizable compound may be used alone or in combination of two or more kinds.

[0021] The (meth)acrylic acid esters may be monofunctional or polyfunctional compounds. Examples of the monofunctional compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Acrylate, 2-ethyl-2-adamantyl (meth)acrylate and other (meth)acrylic acid ester compounds with alicyclic alcohols; phenyl (meth)acrylate, benzyl (meth)acrylate and other aryl (meth)acrylates; 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene Monomers having a hydroxy group, such as polyethylene glycol mono(meth)acrylate; methoxyethyl(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, 2-phenylphenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, (3-ethyloxetan-3-yl)methyl(meth)acrylate, cyclic trimethylol Monomers having a chain or cyclic ether bond, such as dipropylpropaneformal (meth)acrylate; monomers having a nitrogen atom, such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, diacetone(meth)acrylamide, (meth)acryloylmorpholine, and N-(meth)acryloyloxyethylhexahydrophthalimide;Monomers having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; monomers having an epoxy group such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether; monomers having a phosphorus atom such as 2-((meth)acryloyloxy)ethyl phosphate; monomers having a silicon atom such as 3-(meth)acryloxypropyltrimethoxysilane; monomers having a fluorine atom such as 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, and 2-(perfluorohexyl)ethyl (meth)acrylate; and monomers having a carboxyl group such as (meth)acrylic acid, mono(2-(meth)acryloyloxyethyl) succinate, mono(2-(meth)acryloyloxyethyl) phthalate, mono(2-(meth)acryloyloxyethyl) maleate, and ω-carboxy-polycaprolactone mono(meth)acrylate.

[0022] Examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin 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, and hydroxypivalic acid neopentyl. Polyhydric alcohols such as diglycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, and 9,9-bis(4-(2-(2-(meth)acryloyloxyethoxy)ethoxy)phenyl)fluorene. and (meth)acrylic acid; bis(4-(meth)acryloxyphenyl)sulfide, bis(4-(meth)acryloylthiophenyl)sulfide, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylenebis(meth)acrylamide, zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, polyester acrylate, etc.

[0023] From the viewpoints of improving the sensitivity of the polymerizable composition, reducing oxygen inhibition, and improving the mechanical strength, hardness, heat resistance, durability, and chemical resistance of the coating film of the cured product, the (meth)acrylic acid esters are preferably ester compounds of the polyhydric alcohols and (meth)acrylic acid, and particularly preferred are trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0024] The content of the compound represented by the general formula (1) is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the radical polymerizable compound.

[0025] <Alkali-soluble resin> The polymerizable composition can be suitably used as a negative resist by further blending an alkali-soluble resin. The alkali-soluble resin can be any resin commonly used in negative resists, and is not particularly limited as long as it is soluble in an alkaline aqueous solution, but is preferably a resin containing a carboxyl group. The alkali-soluble resin may be used alone or in combination of two or more types.

[0026] A polymerization initiator can be added to the polymerizable composition for the purpose of accelerating curing or improving the physical properties of the cured product. The polymerization initiator is decomposed by active energy rays, and the generated active species have the function of initiating polymerization (curing) of the radical polymerizable compound. The polymerization initiator may be used alone or in combination of two or more types.

[0027] As the polymerization initiator, known ones can be used, for example, α-hydroxyacetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy)-2-hydroxy-2-methylpropiophenone, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; 2-methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylphenyl)propiophenone, and the like. α-Aminoacetophenone derivatives such as 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; acylphosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (mesitylcarbonyl)phenylphosphinate; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2- (O-benzoyloxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethylidene}amino)oxy]ethanone, and other oxime ester derivatives; halomethyltriazine derivatives, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; Benzil ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as isopropylthioxanthone, benzophenone derivatives such as 4-(4-methylphenylthio)benzophenone; coumarin derivatives such as 3-benzoyl-7-diethylaminocoumarin and 3,3'-carbonylbis(7-diethylaminocoumarin); imidazole derivatives such as 2-(2-chlorophenyl)-1-[2-(2-chlorophenyl)-4,5-diphenyl-1,3-diazol-2-yl]-4,5-diphenylimidazole;Examples include organic peroxides such as 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; and camphorquinone.

[0028] The content of the polymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the radical polymerizable compound.

[0029] A solvent may be further added to the polymerizable composition to improve viscosity, coatability, and smoothness of the cured film. The solvent is not particularly limited as long as it can dissolve or disperse the radical polymerizable compound and the like and is volatilized at a drying temperature.

[0030] 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, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, etc. The solvents may be used alone or in combination of two or more.

[0031] The amount of the solvent used is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass, per 100 parts by mass of the solid content of the polymerizable composition.

[0032] <Method for preparing polymerizable composition> When preparing the polymerizable composition, the oxygen inhibition reducer, the radical polymerizable compound, and, if necessary, the alkali-soluble resin and other components are placed in a container, and dissolved or dispersed according to a conventional method using a paint shaker, a bead mill, a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, etc. Furthermore, if necessary, the mixture may be filtered through a mesh or membrane filter, etc.

[0033] In preparing the polymerizable composition, the oxygen inhibition reducer and the polymerization initiator may be added to the polymerizable composition from the beginning. However, when the polymerizable composition is to be stored for a relatively long period of time, it is preferable to dissolve or disperse the oxygen inhibition reducer and the polymerization initiator in a composition containing a radical polymerizable compound immediately before use.

[0034] <Method of manufacturing the cured product> The cured product of the present invention is formed from the polymerizable composition. Examples of a method for producing the cured product include a production method including a step of applying the polymerizable composition onto a substrate and then irradiating the polymerizable composition with active energy rays.

[0035] 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, inkjet printing, dispenser printing, etc. Examples of the substrate include films and sheets of glass, silicon wafers, metals, plastics, etc., and three-dimensional molded products, and the shape of the substrate is not limited.

[0036] The step of irradiating the polymerizable composition with active energy rays is a step of polymerizing the radical polymerizable compound by irradiation with active energy rays such as electron beams, ultraviolet rays, visible light, and radiation, thereby obtaining a cured product.

[0037] The active energy rays are preferably light having a wavelength of 250 to 450 nm, and more preferably light having a wavelength of 350 to 410 nm from the viewpoint of rapid curing.

[0038] The light source for the light irradiation can be a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, an LED lamp, a xenon arc lamp, a carbon arc lamp, sunlight, a solid-state laser such as a YAG laser, a semiconductor laser, a gas laser such as an argon laser, etc. If necessary, curing can be carried out by using a sensitizer that absorbs the light as the additive.

[0039] The exposure dose of the active energy ray should be appropriately set depending on the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. For example, the exposure dose in the UV-A region is 10 to 5,000 mJ / cm. 2 Preferably, the concentration is 30 to 1,000 mJ / cm 2 It is more preferable that:

[0040] In addition, when the polymerizable composition contains the solvent, the method for producing the cured product may include a drying step.

[0041] In the drying step, examples of the method for drying the solvent include heat drying, ventilation heating drying, reduced pressure drying, etc. The method for heating drying is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, etc. Furthermore, examples of the method for ventilation heating drying include a blower drying oven, etc.

[0042] Furthermore, in the drying step, the temperature of the polymerizable composition is lower than the set drying temperature due to the latent heat of evaporation of the solvent, thereby ensuring a long time until the polymerizable composition gels. Since the time until gelation is affected by the drying method, film thickness, etc., the drying temperature and time should be appropriately set, including the selection of the solvent. For example, the drying temperature is preferably 20 to 120°C, more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

[0043] The dry film thickness of the polymerizable composition (film thickness of the cured product) is appropriately set depending on the application, but is preferably 0.05 to 500 μm, and more preferably 0.1 to 100 μm.

[0044] <Pattern formation method> When the polymerizable composition contains an alkali-soluble resin, a pattern can be formed by photolithography. The polymerizable composition is applied to a substrate in the same manner as described above, and, if necessary, dried to form a dry film. The dried film is then irradiated with active energy rays through a mask, whereby the radically polymerizable compound in the exposed areas polymerizes to form a cured film. Alternatively, a highly accurate pattern shape can also be produced by direct drawing using a laser without using a mask.

[0045] After the exposure, the unexposed areas are removed by development using an alkaline developer such as a 0.3 to 3% by weight aqueous solution of sodium carbonate, to obtain a patterned cured film. Furthermore, to enhance adhesion between the cured film and the substrate, post-baking is performed at 180 to 250°C for 20 to 90 minutes as post-drying. In this way, a desired pattern is formed based on the cured film.

[0046] The polymerizable composition of the present invention can be used in a wide variety of applications, including paints and coatings such as hard coating agents, coating agents for optical disks, coating agents for optical fibers, paints for mobile terminals, paints for home appliances, paints for cosmetic containers, paints for woodworking, internal anti-reflection coatings for optical elements, high and low refractive index coating agents, heat-shielding coating agents, heat-dissipating coating agents, and anti-fogging agents; printing inks such as offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, and inks for light guide plates; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; dental materials; waveguide materials; black stripes for lens sheets; and coatings for optical elements. These materials can be used for a variety of purposes, including green sheets and electrode materials for capacitors; adhesives and sealants such as adhesives for FPDs, adhesives for HDDs, adhesives for optical pickups, adhesives for image sensors, sealants for organic EL, OCA for touch panels, OCR for touch panels; resists for FPDs such as color resists, black resists, protective films for color filters, photospacers, black column spacers, frame resists, photoresists for TFT wiring, and interlayer insulating films; resists for printed circuit boards such as liquid solder resists and dry film resists; and semiconductor materials such as semiconductor resists and buffer coat films, with no particular restrictions on their uses. [Example]

[0047] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0048] Example 1 [Synthesis of Compound 1] [ka] [Synthesis Example 1: Synthesis of Compound 1] A 200 mL two-neck flask was charged with 0.40 g (1.5 mmol) of 2-(9-oxoxanthen-2-yl)propionic acid, 0.32 g (2.0 mmol) of 1,1'-carbonyldiimidazole, and 30 mL of dehydrated acetone, and the mixture was stirred at room temperature for 7 hours. 0.67 g (4.5 mmol) of 2,2,3,3,3-pentafluoropropylamine was gradually added, and the mixture was stirred at 80°C for 6 hours. 30 mL of ethyl acetate and 30 mL of water were added, and the aqueous phase was removed by separation. The aqueous phase was further extracted twice with 30 mL of ethyl acetate. The oil phases were combined and concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized in toluene to obtain 0.07 g (12% yield) of compound 1. 1 H-NMR and 19 The results of the F-NMR analysis are shown in Table 1.

[0049] [Table 1]

[0050] <Example 2> [Synthesis of Compound 2] [ka] [Synthesis Example 2: Synthesis of Compound 2] A 200 mL two-neck flask was charged with 1.1 g (5.0 mmol) of 4-benzoylbenzoic acid, 0.9 g (5.5 mmol) of 1,1'-carbonyldiimidazole, and 30 mL of dehydrated tetrahydrofuran, and the mixture was stirred at room temperature for 6 hours. 2.2 g (15 mmol) of 2,2,3,3,3-pentafluoropropylamine was gradually added, and the mixture was stirred at room temperature for 4 hours. 50 mL of ethyl acetate and 50 mL of water were added, and the aqueous phase was removed by separation. The aqueous phase was further extracted twice with 50 mL of ethyl acetate. The oil phases were combined and concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 3 / 1) to obtain 1.3 g (74% yield) of compound 2. The obtained compound 2 1 H-NMR and 19 The results of the F-NMR analysis are shown in Table 2.

[0051] [Table 2]

[0052] Example 3 [Synthesis of Compound 3] [ka] [Synthesis Example 3: Synthesis of Compound 3] A 200 mL two-neck flask was charged with 0.40 g (1.5 mmol) of 4-benzoylbenzoic acid, 0.34 g (2.0 mmol) of 1,1'-carbonyldiimidazole, and 30 mL of dehydrated tetrahydrofuran, and the mixture was stirred at room temperature for 7 hours. 2.0 g (4.5 mmol) of 1H,1H-heptafluorobutylamine was gradually added, and the mixture was stirred at 80°C for 6 hours. 30 mL of ethyl acetate and 30 mL of water were added, and the aqueous phase was removed by separation. The aqueous phase was further extracted twice with 30 mL of ethyl acetate. The oil phases were combined and concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 2 / 1) to obtain 1.2 g (yield 57%) of compound 3. The obtained compound 3 1 H-NMR and 19 The results of the F-NMR analysis are shown in Table 3.

[0053] [Table 3]

[0054] <Preparation of Polymerizable Composition (A)> The radical polymerizable compound and solvent in the amounts shown in Table 4 were mixed and stirred, and then an oxygen inhibition reducer and a polymerization initiator were added and stirred thoroughly to prepare polymerizable compositions (A) of Example 4 and Comparative Example 1.

[0055] [Table 4]

[0056] In Table 4 above, BAPO represents phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM); TMPTA, trimethylolpropane triacrylate (Tokyo Chemical Industry Reagents); THF refers to tetrahydrofuran (Tokyo Chemical Industry Reagents);

[0057] <Evaluation of cure inhibition by oxygen> The polymerizable composition (A) prepared above was applied onto a glass substrate using a spin coater. After application, the glass substrate was dried in a clean oven at 60°C for 3 minutes to remove the solvent, producing a coating film. Next, using an exposure machine with a UV-LED lamp as the light source, the substrate was exposed to light with a wavelength of 365 nm at an exposure dose of 150,000 mJ / cm. 2 The cured film was irradiated with light. The residual rate (%) of acrylate was measured by attenuated total reflection infrared spectroscopy (ATR-IR). At that time, the absorption spectrum of the out-of-plane bending vibration of the double bond group (809 cm -1 ) and the absorption spectrum of the carbonyl group (1728 cm -1 The residual rate of acrylate was calculated based on the following formula using the peak area of ​​2.0g of acrylate. The cured film was also visually inspected for yellowing. The results are shown in Table 5.

number

[0058] [Table 5]

[0059] <Preparation of Polymerizable Composition (B)> The radical polymerizable compound and solvent in the amounts shown in Table 6 were mixed and stirred, and the oxygen inhibition reducer and polymerization initiator were added and stirred thoroughly to prepare polymerizable compositions (B) of Example 5 and Comparative Example 2.

[0060] [Table 6]

[0061] <Evaluation of cure inhibition by oxygen> The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After application, the glass substrate was dried in a clean oven at 60°C for 3 minutes to remove the solvent, producing a coating film. Next, using a proximity exposure machine with a low-pressure mercury lamp as the light source, light with a wavelength of 254 nm was applied at an exposure dose of 6000 mJ / cm. 2 The cured film was irradiated with light. The residual rate (%) of acrylate was measured by attenuated total reflection infrared spectroscopy (ATR-IR). At that time, the absorption spectrum of the out-of-plane bending vibration of the double bond group (1634 cm -1 ) and a standard peak (2970 cm ) that remains unchanged before and after exposure -1 The residual rate of acrylate was calculated based on the following formula using the peak area of ​​2.0g of acrylate. The cured film was also visually inspected for yellowing. The results are shown in Table 7.

number

[0062] [Table 7]

Claims

1. An oxygen inhibition reducer comprising a compound represented by the following general formula (1): 【Chemistry 1】 (In formula (1), X represents an oxygen atom. A represents an alkylene group which may contain an ether bond, a thioether bond, an ester bond, or an amide bond. Y represents a fluoroalkyl group having 1 to 18 carbon atoms.)

2. A polymerizable composition comprising the oxygen inhibition reducer according to claim 1 and a radical polymerizable compound.

3. A cured product formed from the polymerizable composition according to claim 2.

4. A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to claim 2 with active energy rays.

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