JP2023119202A - Oxygen inhibition reducing agent, polymerizable composition, cured product, and method of producing cured product - Google Patents

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 The present invention relates to an oxygen inhibition reducing agent, a polymerizable composition, a cured product, and a method for producing a cured product.

Photocuring of the photocurable resin composition is inhibited by diffusion of oxygen from the surface of the coating film into the coating film and dissolved oxygen in the coating film. In particular, the surface of the coating film, which is in direct contact with air, is susceptible to oxygen inhibition, and poor curing of the surface results in abnormal appearance and deterioration of surface physical properties. Therefore, development of a photo-curing system capable of effectively reducing curing inhibition due to oxygen is desired.

Oxygen inhibition is generally known to occur by the following mechanism. When the photocurable resin composition is irradiated with light, active radical species are generated from the photopolymerization initiator, and attack the unsaturated bonds in the monomer to generate growing radical species, and curing progresses. If oxygen is present here, the growing radical species are trapped by oxygen to generate peroxy radical species. Curing is inhibited because the peroxy radical species do not react with the monomer.

As a method of reducing oxygen inhibition, there is a method of increasing the proportion of the number of parts of the photopolymerization initiator added to the entire photocurable resin composition. However, when the number of parts of the photopolymerization initiator added is increased, problems such as deterioration of coating film properties and bleed-out of the photopolymerization initiator onto the coating film surface occur.

Further, Patent Document 1 discloses a method of using an amine compound as an oxygen inhibition reducing agent for reducing oxygen inhibition. The amine compound itself becomes an active radical species by undergoing hydrogen abstraction from the peroxy radical species, and has the effect of reprogressing the curing stopped by oxygen. However, the effect of reducing oxygen inhibition by the amine compound is insufficient, and the cured product yellows, so the applicable conditions are limited. For this reason, further improvement is desired.

Non-Patent Document 1 discloses a method for efficiently sensitizing and decomposing an organic peroxide by irradiating a ketone compound contained in a polymer chain with light. Sensitized decomposition by ketone compounds of organic peroxides produced by recombination or hydrogen abstraction of peroxy radical species is based on the fact that ketone compounds act catalytically and that two active radical species can be regenerated from one peroxide bond. Therefore, it is presumed that the curing inhibition due to oxygen can be efficiently reduced with a small number of parts added.

JP-A-2000-158594

macromolecules, 1978, 11, 937-942.

The present invention provides an oxygen inhibition reducing agent capable of effectively reducing curing inhibition due to oxygen without causing yellowing of the cured product.

Furthermore, the present invention provides a polymerizable composition, a cured product thereof, and a method for producing the cured product.

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

The present invention also relates to a polymerizable composition containing the oxygen inhibition reducing agent and a radically polymerizable compound, a cured product formed from the polymerizable composition, and a method for producing the cured product.

The compound represented by the general formula (1) of the present invention has an aryl ketone structure, so that the compound having a peroxy radical species generated by oxygen inhibition during photocuring is sensitized and decomposed to inhibit curing by oxygen. can be effectively reduced, and yellowing of the cured product is not accompanied. In addition, having a fluoroalkyl group causes segregation on the surface of the coating film, so that poor curing on the surface of the coating film, which is most susceptible to oxygen inhibition, can be improved.

<Oxygen inhibition reducing agent>
The oxygen inhibition reducing agent of the present invention includes a compound represented by the following general formula (1).
(In formula (1), -X- may or may not exist, and when present, X represents an oxygen atom or a sulfur atom. A is an ether bond, a thioether bond, an ester bond, represents an alkylene group which may contain an amide bond.Y represents a fluoroalkyl group having 1 to 18 carbon atoms.)

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.

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.

In the general formula (1), the fluoroalkyl group may be linear or branched. 1 to 18 carbon atoms are preferable, and 2 to 7 carbon atoms are particularly preferable.

The method for producing the compound represented by the general formula (1) includes, for example, a step of reacting a hydroxy group-substituted aryl ketone derivative with a halogenated fluoroalkyl compound in the presence of a base; A wide range of known techniques can be used, such as a method including a step of reacting a hydroxyfluoroalkyl compound under reflux and a step of reacting a carboxy group-substituted aryl ketone derivative with an aminofluoroalkyl compound in the presence of a condensing agent. . After the reaction, a step of distilling off (removing) excess raw materials and the like under reduced pressure and a purification step may be included.

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

<Radical polymerizable compound>
A compound having an ethylenically unsaturated group can be preferably used as the radically polymerizable compound of the present invention. Examples of radically polymerizable compounds include (meth)acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, vinyl ethers, and vinyl esters. , vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins and the like. Among these, it is preferable to contain highly reactive (meth)acrylic acid esters. The radically polymerizable compound may be used alone or in combination of two or more.

Monofunctional compounds and polyfunctional compounds can be used as the (meth)acrylic acid esters. Monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Alkyl (meth)acrylates such as acrylates; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth)acrylic acid and alicyclic alcohol such as acrylate and 2-ethyl-2-adamantyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate ; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, polyethylene glycol mono (meth) Monomers having a hydroxy group such as acrylates and polypropylene glycol mono(meth)acrylates; Tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, cyclic Monomers having a chain or cyclic ether bond such as trimethylolpropane formal (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-methylol (meth) Nitrogen atoms such as acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acryloylmorpholine, N-(meth)acryloyloxyethylhexahydrophthalimide Monomers having; 2-(meth) acryloyloxyethyl isocyanate and other isocyanate group-containing monomers; glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and other epoxy group-containing monomers; phosphoric acid 2-(( Phosphorus atom-containing monomers such as meth)acryloyloxy)ethyl; Silicon atom-containing monomers such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2,2 , 3,3,3-Pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate and other fluorine atom-containing monomers; (meth)acrylic acid, monosuccinic acid (2-(meth) acryloyloxyethyl), phthalate mono(2-(meth)acryloyloxyethyl), maleate mono(2-(meth)acryloyloxyethyl), ω-carboxy-polycaprolactone mono(meth)acrylate, etc. A monomer etc. are mentioned.

Examples of the polyfunctional compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 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, neopentylglycol hydroxypivalate di(meth)acrylate, tricyclodecanedimethanol 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, 9,9-bis(4-( 2-(2-(meth)acryloyloxyethoxy)ethoxy)phenyl) ester compounds of polyhydric alcohols such as fluorene and (meth)acrylic acid; bis(4-(meth)acryloxyphenyl)sulfide, bis(4- (Meth)acryloylthiophenyl)sulfide, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene bis(meth)acrylamide, zinc (meth)acrylate, zirconium (meth)acrylate, aliphatic urethane acrylate, aromatic group urethane acrylates, epoxy acrylates, polyester acrylates, and the like.

The (meth) acrylic esters improve the sensitivity of the polymerizable composition, reduce oxygen inhibition, and improve the mechanical strength and hardness of the coating film of the cured product, heat resistance, durability, and chemical resistance. Therefore, ester compounds of the polyhydric alcohol and (meth)acrylic acid are preferable, and in particular, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate is preferred.

The content of the compound represented by the general formula (1) 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 radically polymerizable compound. is more preferable, and 1 to 15 parts by mass is even more preferable.

<Alkali-soluble resin>
The polymerizable composition can be suitably used as a negative resist by further blending an alkali-soluble resin. As the alkali-soluble resin, those commonly used for negative resists can be used, and there is no particular limitation as long as the resin is soluble in an alkaline aqueous solution, but a resin containing a carboxyl group is preferred. Alkali-soluble resins may be used alone or in combination of two or more.

A polymerization initiator can be added to the polymerizable composition for the purpose of accelerating curing and improving physical properties of the cured product. The polymerization initiator is decomposed by active energy rays, and the generated active species act to initiate polymerization (curing) of the radically polymerizable compound. A polymerization initiator may be used alone or in combination of two or more.

As the polymerization initiator, known ones can be used. -α-hydroxyacetophenone derivatives such as methylpropiophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one;2 -methyl-4'-methylthio-2-morpholinopropiophenone, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino) α-aminoacetophenone derivatives such as -2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenylbis(2,4 ,6-trimethylbenzoyl)phosphine oxide, ethyl(mesitylcarbonyl)phenylphosphinate and other acylphosphine oxide derivatives; 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl oxime), 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethylidene}amino)oxy]ethanone; -Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)1,3,5-triazine , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and the like; halomethyltriazine derivatives such as 2,2-dimethoxy-2-phenylacetophenone and the like; ketal derivatives; 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;3, Organic peroxides such as 3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone and dibenzoyl peroxide; azo compounds such as azobisisobutyronitrile; and camphorquinone.

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 1 to 15 parts by mass with respect to 100 parts by mass of the radically polymerizable compound. Parts by mass are more preferred.

A solvent may be further added to the polymerizable composition in order 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 radically polymerizable compound and the like and is volatilized 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, diethylene glycol dimethyl ether, and the like. The solvent may be used alone or in combination of two or more.

The amount of the solvent used is preferably 10 to 1,000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the solid content of the polymerizable composition.

<Method for preparing polymerizable composition>
When preparing the polymerizable composition, the oxygen inhibition reducing agent, the radically polymerizable compound, and, if necessary, the alkali-soluble resin and the other components are put into a storage container, and a paint shaker and a bead mill are used. , a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, or the like may be used for dissolution or dispersion according to a conventional method. In addition, if necessary, it may be filtered through a mesh or membrane filter or the like.

In the preparation of the polymerizable composition, the oxygen inhibition reducing agent and the polymerization initiator may be added to the polymerizable composition from the beginning. It is preferable to dissolve or disperse the oxygen inhibition reducing agent and the polymerization initiator in the composition containing the radically polymerizable compound immediately before use.

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

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 can be used. 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.

In the step of irradiating the polymerizable composition with an active energy ray, a cured product can be obtained by polymerizing the radically polymerizable compound by irradiating with an active energy ray such as an electron beam, ultraviolet light, visible light, or radiation. It is possible.

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

The light source for the light irradiation includes 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, and solid-state lasers such as YAG lasers. , a semiconductor laser, a gas laser such as an argon laser, or the like can be used. If necessary, curing can be performed by using a sensitizer that absorbs the light as the additive.

The exposure amount of the active energy ray should be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition. As an example, the exposure dose in the UV-A region is preferably 10 to 5,000 mJ/cm ² and more preferably 30 to 1,000 mJ/cm ² .

Moreover, when the solvent is included in the polymerization composition, the method for producing the cured product may include a drying step.

In the drying step, methods for drying the solvent include, for example, drying by heating, drying by ventilation by heating, and drying under reduced pressure. The method of drying by heating 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 heat-drying, a ventilation-type drying oven etc. are mentioned, for example.

In addition, in the drying step, the temperature of the polymerizable composition becomes lower than the set temperature for drying due to the latent heat of evaporation of the solvent, so it is possible to ensure a long time until the polymerizable composition gels. Since the time until this gelation is affected by the drying method, the film thickness, etc., the drying temperature and time including the selection of the solvent should be appropriately set. As an example, the drying temperature is preferably 20 to 120°C, more preferably 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

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

<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 the substrate in the same manner as described above, and if necessary, dried to form a dry film. By irradiating the dry film with active energy rays through a mask, the radically polymerizable compound is polymerized in the exposed portion to form a cured film. On the other hand, it is also possible to produce a pattern shape with high precision without using a mask by direct drawing using a laser.

After the above exposure, the unexposed areas are removed by development with an alkali developer such as a 0.3 to 3% by mass sodium carbonate aqueous solution, for example, to obtain a patterned cured film. Further, post-baking at 180 to 250° C. for 20 to 90 minutes is performed as post-drying for the purpose of enhancing adhesion between the cured film and the substrate. Thus, a desired pattern based on the cured film is formed.

The polymerizable composition of the present invention includes hard coating agents, optical disc coating agents, optical fiber coating agents, mobile terminal coatings, home appliance coatings, cosmetic container coatings, wood coatings, internal antireflection coatings for optical elements, high・Paints and coating agents such as low refractive index coating agents, heat shield coating agents, heat dissipation coating agents, anti-fogging agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, Printing inks such as inks for light guide plates; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; Adhesives/sealants for optical pickups, HDD adhesives, optical pickup adhesives, image sensor adhesives, organic EL sealants, OCA for touch panels, OCR for touch panels; color resists, black resists, color filters protective film, photo spacer, black column spacer, frame resist, photoresist for TFT wiring, FPD resist such as interlayer insulating film; printed circuit board resist such as liquid solder resist, dry film resist; semiconductor resist, buffer coat film, etc. It can be used for various applications such as materials for semiconductors, and there are no particular restrictions on the applications.

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

<Example 1>
[Synthesis of compound 1]
[Synthesis Example 1: Synthesis of Compound 1]
In a 200 mL two-necked flask, 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 were added. and stirred at room temperature for 7 hours. 0.67 g (4.5 mmol) of 2,2,3,3,3-pentafluoropropylamine was gradually added and stirred at 80° C. for 6 hours. After adding 30 mL of ethyl acetate and 30 mL of water, the aqueous phase was separated off. Further, the aqueous phase was 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 of compound 1 (yield 12%). Table 1 shows the results of ¹ H-NMR and ¹⁹ F-NMR analysis of Compound 1 obtained.

<Example 2>
[Synthesis of compound 2]
[Synthesis Example 2: Synthesis of compound 2]
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 were placed in a 200 mL two-necked flask and stirred at room temperature for 6 hours. . 2.2 g (15 mmol) of 2,2,3,3,3-pentafluoropropylamine was gradually added and stirred at room temperature for 4 hours. After adding 50 mL of ethyl acetate and 50 mL of water, the aqueous phase was separated off. Further, the aqueous phase was 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 of compound 2 (yield 74%). Table 2 shows the results of ¹ H-NMR and ¹⁹ F-NMR analysis of Compound 2 obtained.

<Example 3>
[Synthesis of compound 3]
[Synthesis Example 3: Synthesis of Compound 3]
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 were placed in a 200 mL two-necked flask and stirred at room temperature for 7 hours. . 2.0 g (4.5 mmol) of 1H,1H-heptafluorobutylamine was gradually added and stirred at 80° C. for 6 hours. After adding 30 mL of ethyl acetate and 30 mL of water, the aqueous phase was separated off. Further, the aqueous phase was 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 of compound 3 (yield 57%). Table 3 shows the results of ¹ H-NMR and ¹⁹ F-NMR analysis of Compound 3 obtained.

<Preparation of polymerizable composition (A)>
The amounts of the radically polymerizable compound and the solvent shown in Table 4 were mixed and stirred, and the oxygen inhibition reducing agent and polymerization initiator were added and thoroughly stirred to prepare the polymerizable compositions (A) of Example 4 and Comparative Example 1. did.

In Table 4 above, BAPO is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM);
TMPTA is trimethylolpropane triacrylate (Tokyo Kasei Kogyo Reagent);
THF represents tetrahydrofuran (Tokyo Kasei Kogyo Reagent);

<Evaluation of curing inhibition by oxygen>
The polymerizable composition (A) prepared above was applied onto a glass substrate using a spin coater. After coating, the solvent was dried by drying the glass substrate in a clean oven at 60° C. for 3 minutes to prepare a coating film. Then, using an exposure machine using a UV-LED lamp as a light source, light with a wavelength of 365 nm was irradiated at an exposure amount of 150000 mJ/cm ² . The cured film portion was subjected to attenuated total reflection infrared spectroscopy (ATR-IR) to measure the residual rate (%) of acrylate. At that time, using the peak areas of the absorption spectrum (809 cm ^-1 ) of the out-of-plane bending vibration of the double bond group and the absorption spectrum (1728 cm ^-1 ) of the carbonyl group which does not change before and after exposure, to calculate the residual rate of acrylate. In addition, the presence or absence of yellowing of the cured film was visually confirmed. Table 5 shows the results.

<Preparation of polymerizable composition (B)>
The amounts of the radically polymerizable compound and the solvent shown in Table 6 were mixed and stirred, the oxygen inhibition reducing agent and the polymerization initiator were added, and the mixture was stirred well to prepare the polymerizable compositions (B) of Example 5 and Comparative Example 2. did.

<Evaluation of curing inhibition by oxygen>
The polymerizable composition (B) prepared above was applied onto a glass substrate using a spin coater. After coating, the solvent was dried by drying the glass substrate in a clean oven at 60° C. for 3 minutes to prepare a coating film. Next, using a proximity exposure machine using a low-pressure mercury lamp as a light source, light with a wavelength of 254 nm was irradiated at an exposure amount of 6000 mJ/cm ² . The cured film portion was subjected to attenuated total reflection infrared spectroscopy (ATR-IR) to measure the residual rate (%) of acrylate. At that time, using the absorption spectrum of the out-of-plane bending vibration of the double bond group (1634 cm ^-1 ) and the peak area of the standard peak (2970 cm ^-1 ) which does not change before and after exposure, the acrylate The survival rate was calculated. In addition, the presence or absence of yellowing of the cured film was visually confirmed. Table 7 shows the results.

Claims (4)

An oxygen inhibition reducing agent comprising a compound represented by the following general formula (1).
(In formula (1), -X- may or may not exist, and when present, X represents an oxygen atom or a sulfur atom. A is an ether bond, a thioether bond, an ester bond, represents an alkylene group which may contain an amide bond.Y represents a fluoroalkyl group having 1 to 18 carbon atoms.) A polymerizable composition comprising the oxygen inhibition reducing agent according to claim 1 and a radically polymerizable compound. A cured product formed from the polymerizable composition according to claim 2 . A method for producing a cured product, comprising the step of irradiating the polymerizable composition according to claim 2 with an active energy ray.