JP2007099637A - New 9,10-di(meth)acryloxyanthracene compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new compound useful as a photoradical polymerization sensitizer for a photoradically polymerizable composition and a photocurable composition containing the photosensitizer. <P>SOLUTION: The new 9,10-di(meth)acryloxyanthracene compound is obtained. The method for producing the 9,10-di(meth)acryloxyanthracene compound comprises acrylating a 9,10-dihydroxyanthracene compound. The photoradical polymerization sensitizer comprises the 9,10-di(meth)acryloxyanthracene compound. The photocurable composition comprises the photoradical polymerization sensitizer, a radical polymerization initiator and a radically polymerizable monomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel anthracene compound useful as a photoradical polymerization sensitizer, particularly a 9,10-di (meth) acryloxyanthracene compound, a production method thereof, and an application as a photoradical polymerization sensitizer.

Conventionally, acetophenone-type photoradical polymerization initiators are well known as photoradical polymerization initiators. Examples of these include, for example, 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty), 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure manufactured by Ciba Specialty) 651), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty). (See Patent Documents 1 and 2)
However, these acetophenone-type radical polymerization initiators, such as 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty), 2,2-dimethoxy-1,2-diphenylethane-1-one ( Ciba Specialty Irgacure 651) and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Irgacure 907) have the longest UV absorption wavelength It does not exceed 350 nm.
There is no problem when photocuring using a high-pressure mercury lamp, but it cannot cope with longer-wavelength metal halide lamps, and it is disadvantageous in that it does not respond to blue LEDs that use light of 406 nm, which has recently been developed. .

On the other hand, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is known as a polymerization initiator sensitive to a long wavelength and is used under the name of BAPO. However, this BAPO is expensive. Accordingly, an additive (sensitizer) capable of absorbing UV light having a long wavelength exceeding 350 nm and near 400 nm and activating an acetophenone-type photoradical polymerization initiator has been demanded.
JP2003-253225A Patent 3147582

In view of such a situation, the present inventor has completed the present invention as a result of intensive studies to provide a technique that eliminates the above-mentioned drawbacks. That is, the object of the present invention is as follows.
1. 1. To provide a novel sensitizer capable of absorbing a long wavelength UV light and activating an acetophenone-type photoradical polymerization initiator. To provide a photocurable composition that initiates a curing reaction by irradiating with UV light having a long wavelength

As a result of intensive studies on the structure and photoradical generation ability of the aromatic acrylate, the present inventor made the acetophenone type by coexisting the 9,10-di (meth) acryloxyanthracene compound which is an anthracene compound having an acryloxy group. It has been found that even when a photo radical polymerization initiator is used, radicals can be generated by irradiation with light having a long wavelength exceeding 350 nm and close to 400 nm to polymerize a radical polymerizable monomer, and the present invention has been completed. That is, the present invention is based on the following.
(1) A 9,10-di (meth) acryloxyanthracene compound represented by the following formula (1).

(In the formula (1), R is a hydrogen atom or a methyl group, and X and Y may be the same or different, and are a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or a thioalkoxy group. Either.)
(2) The method for producing a 9,10-di (meth) acryloxyanthracene compound according to (1), comprising acrylating a 9,10-dihydroxyanthracene compound.
(3) A photoradical polymerization sensitizer containing the 9,10-di (meth) acryloxyanthracene compound according to (1).
(4) A photocurable composition containing the photoradical polymerization sensitizer described in (3), a photoradical polymerization initiator, and a radical polymerizable monomer.

The present invention is as described in detail below, has the following particularly advantageous effects, and its industrial utility value is extremely great.
1. The 9,10- (meth) acryloxyanthracene compound of the present invention is a novel compound and is useful as a photoradical polymerization sensitizer.
2. The 9,10- (meth) acryloxyanthracene compound of the present invention can be produced using a commercially available 9,10-dihydroxyanthracene compound as a raw material.
3. The photoradical polymerization sensitizer containing the 9,10- (meth) acryloxyanthracene compound of the present invention activates an acetophenone type photoradical polymerization initiator with light having a long wavelength around 400 nm to polymerize a radical polymerizable monomer. Can be made.

  The anthracene compound having a (meth) acryloxy group of the present invention is a compound having a structure described in the following formula (1), in which R is a hydrogen atom or a methyl group, and X and Y are the same. Or may be different and are any one of a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, or a thioalkoxy group.

  In the formula (1), examples of the alkyl group represented by X and Y include methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, i-pentyl group, 4 -Methylpentyl group, n-octyl group, 2-ethylhexyl group, etc. are mentioned. In formula (1), examples of the halogen atom represented by X and Y include a chlorine atom, a bromine atom, and a fluorine atom. In the formula (1), examples of the alkoxy group represented by X and Y include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a phenoxy group, a 4-methylphenoxy group, and a 4-chlorophenoxy group. Can be mentioned. In formula (1), the thioalkoxy groups represented by X and Y include thiomethoxy group, thioethoxy group, thiopropoxy group, thiobutoxy group, thiohexyl group, thioheptyl group, thiooctyl group, thiodecyl group, thiododecyl group, thiophenoxy group , A thio (4-methylphenoxy) group, a thio (4-chlorophenoxy) group, and the like.

  Examples of the anthracene compound having a (meth) acryloxy group represented by the formula (1) include the following. That is, 9,10-diacryloxyanthracene, 9,10-dimethacryloxyanthracene, 2-methyl-9,10-diacryloxyanthracene, 2-methyl-9,10-dimethacryloxyanthracene, 2-ethyl- 9,10-diacryloxyanthracene, 2-ethyl-9,10-dimethacryloxyanthracene, 2-chloro-9,10-diacryloxyanthracene, 2-chloro-9,10-dimethacryloxyanthracene, 2- Methoxy-9,10-diacryloxyanthracene, 2-methoxy-9,10-dimethacryloxyanthracene, 2-ethoxy-9,10-diacryloxyanthracene, 2-ethoxy-9,10-dimethacryloxyanthracene, 2-phenoxy-9,10-diacryl Xyanthracene, 2-phenoxy-9,10-dimethacryloxyanthracene, 2-hydroxy-9,10-diacryloxyanthracene, 2-hydroxy-9,10-dimethacryloxyanthracene, 2-thiomethoxy-9,10- Diacryloxyanthracene, 2-thiomethoxy-9,10-dimethacryloxyanthracene, 2-thiophenoxy-9,10-diacryloxyanthracene, 2-thiophenoxy-9,10-dimethacryloxyanthracene, 1-methyl- 9,10-diacryloxyanthracene, 1-methyl-9,10-dimethacryloxyanthracene, 1-ethyl-9,10-diacryloxyanthracene, 1-ethyl-9,10-dimethacryloxyanthracene, 1- Chloro-9,10- Acrylicoxyanthracene, 1-chloro-9,10-dimethacryloxyanthracene, 1-methoxy-9,10-diacryloxyanthracene, 2-methoxy-9,10-dimethacryloxyanthracene, 1-ethoxy-9,10 -Diacryloxyanthracene, 1-ethoxy-9,10-dimethacryloxyanthracene, 2-phenoxy-9,10-diacryloxyanthracene, 1-phenoxy-9,10-dimethacryloxyanthracene, 1-hydroxy-9 , 10-diacryloxyanthracene, 2-hydroxy-9,10-dimethacryloxyanthracene, 2-thiomethoxy-9,10-diacryloxyanthracene, 1-thiomethoxy-9,10-dimethacryloxyanthracene, 1-thio Phenoxy -9,10-diacryloxyanthracene, 1-thiophenoxy-9,10-dimethacryloxyanthracene, 2,6-dimethyl-9,10-diacryloxyanthracene, 2,6-dimethyl-9,10-di Methacryloxyanthracene, 2,7-dimethyl-9,10-diacryloxyanthracene, 2,76-dimethyl-9,10-dimethacryloxyanthracene, 1,5-dimethyl-9,10-diacryloxyanthracene, , 5-dimethyl-9,10-dimethacryloxyanthracene. A typical structural formula is shown below.

  The 9,10-diacryloxyanthracene compound or 9,10-dimethacryloxyanthracene compound of the present invention is obtained by adding acryloyl chloride or methacryloyl chloride to the corresponding 9,10-dihydroxyanthracene compound in the presence or absence of a base. It is obtained by making it act.

  Examples of the 9,10-dihydroxyanthracene compound include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, 2-ethyl-9,10-dihydroxyanthracene, and 2-chloro-9,10-dihydroxy. Anthracene, 2-methoxy-9,10-dihydroxyanthracene, 2-ethoxy-9,10-dihydroxyanthracene, 2-phenoxy-9,10-dihydroxyanthracene, 2-hydroxy-9,10-dihydroxyanthracene, 2-thiomethoxy- 9,10-dihydroxyanthracene, 2-thiododecyloxy-9,10-dihydroxyanthracene, 2-thiophenoxy-9,10-dihydroxyanthracene, 1-methyl-9,10-dihydroxyanthracene, 2-d Ru-9,10-dihydroxyanthracene, 1-chloro-9,10-dihydroxyanthracene, 1-methoxy-9,10-dihydroxyanthracene, 1-ethoxy-9,10-dihydroxyanthracene, 1-phenoxy-9,10- Dihydroxyanthracene, 1-hydroxy-9,10-dihydroxyanthracene, 1-thiomethoxy-9,10-dihydroxyanthracene, 1-thiododecyloxy-9,10-dihydroxyanthracene, 1-thiophenoxy-9,10-dihydroxyanthracene, etc. Is mentioned.

  Examples of the base include trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, piperidine and the like.

  Solvents used in the reaction include aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane, and dichloroethylene, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. An amide solvent such as N-methylpyrrolidone and dimethylformamide, and an ether solvent such as tetrahydrofuran and 1,4-dioxane are preferably used.

  The amount of acryloyl chloride or methacryloyl chloride added to the 9,10-dihydroxyanthracene compound is 2 to 3 mole times, preferably 2.2 to 2.4 mole times. The reaction temperature is 0 ° C to 80 ° C, preferably 0 ° C to 20 ° C. This reaction is exothermic and requires cooling. The reaction time is about 15 to 60 minutes. After completion of the reaction, water or methanol is added to hydrate the unreacted acryloyl chloride or methacryloyl chloride, and then the hydrochloride is removed by filtration. Then, water is added to the filtrate for crystallization, and the precipitated crystals are filtered. As a result, a yellowish white powder is obtained. Furthermore, for example, recrystallization from methylene chloride / methanol can yield white yellow crystals.

The obtained compound was identified using a ¹ H NMR spectrum, an IR spectrum, and a Mass spectrum, and confirmed to be a 9,10-diacryloxyanthracene compound or a 9,10-dimethacryloxyanthracene compound.

  The 9,10-di (meth) acryloxyanthracene of the present invention acts as a photoradical polymerization sensitizer, and in combination with an acetophenone type photoradical polymerization initiator, generates radicals with light having a wavelength around 400 nm, A radical polymerizable monomer can be polymerized. In addition to 9,10-di (meth) acryloxyanthracene, a known sensitizer, a solvent, a diluent and the like may be further contained to form a photoradical polymerization sensitizer.

  Examples of the acetophenone type photo radical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty), 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Special Irgacure 651), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty). When these photopolymerization initiators are used alone, radically polymerizable monomers cannot be polymerized using light having a wavelength of around 400 nm, but they are easy to coexist with a 9,10-di (meth) acryloxyanthracene compound. It becomes sensitive to a wavelength around 400 nm, and a radically polymerizable monomer can be polymerized.

  As the radical polymerizable monomer, for example, styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, methacrylic acid ester, and the like can be used. (Meth) acrylic acid esters include methyl acrylate, acrylic acid-n-butyl, cyclohexyl acrylate, acrylic acid-2-ethylhexyl, acrylic acid-2-hydroxyethyl, methyl methacrylate, methacrylate-n-butyl, Examples include cyclohexyl methacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide acrylate. These polymerizable monomers may be one kind or a mixture of two or more kinds.

  The amount of the 9,10-di (meth) acryloxyanthracene compound added as a sensitizer is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the monomer. . If the concentration of the sensitizer is too low, the curing speed becomes slow, and if the concentration of the sensitizer is too high, the physical properties of the cured product deteriorate. The amount of radical photopolymerization initiator added to the monomer is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight. The addition ratio (weight ratio) of 9,10-di (meth) acryloxyanthracene to the acetophenone type polymerization initiator is preferably 0.1 to 5 times, and more preferably 0.3 to 1 times. As the photocurable composition of the present invention, in addition to the above-mentioned photoradical polymerization sensitizer, photoradical polymerization initiator, and radical polymerizable monomer, a diluent, coloring, and the like within a range not impairing the effects of the present invention. Various resin additives such as additives, organic or inorganic fillers, leveling agents, surfactants, antifoaming agents, thickeners, flame retardants, antioxidants, stabilizers, lubricants, and plasticizers can be incorporated. .

  The photocurable composition can be cured in the form of a film or in the form of a lump. When curing in the form of a film, for example, a photocurable composition is applied to a polyester film substrate using a bar coater and then irradiated with light. Examples of the lamp to be used include a metal halide lamp, a xenon lamp, an ultraviolet LED, a blue LED, a white LED, a Fusion-made D lamp, and a V lamp. The use of sunlight is also possible. The light irradiation is desirably performed in the absence of oxygen. In the presence of oxygen, the surface of the film is hardly sticky due to oxygen inhibition, and a large amount of polymerization initiator must be added. Examples of the curing method in the absence of oxygen include performing in an atmosphere such as nitrogen gas or helium gas. A method of photocuring with an oxygen-impermeable film is also effective.

  Determination of photocuring was performed based on a tack-free test (finger touch test). That is, because the photocurable composition on the film surface can be tacked by light irradiation, the time when the film surface is touched with a finger and no tack (stickiness on the surface) disappears is called “tack-free time” (curing time). did.

  A similar curing test was performed using 9- (meth) acryloxyanthracene compound instead of 9,10-di (meth) acryloxyanthracene compound, and the curing rate was 9,10-di (meth) acrylic. Compared to the case of using an oxyanthracene compound, the curing time is required to be nearly 6 times, which is not effective.

  The following examples illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise noted, all parts and percentages are by weight.

“Synthesis Example 1”
Under a nitrogen atmosphere, 11.6 g (0.115 mol) of triethylamine was added to a solution of 10.0 g (0.048 mol) of 9,10-dihydroxyanthracene and 120 mL of N-methylpyrrolidone, and the mixture was cooled to 10 ° C. or lower. 9.5 g (0.105 mol) of acryloyl chloride was added dropwise over 15 minutes. 30 minutes after the start of dropping, 5 mL of methanol was added to hydrate acryloyl chloride, and the precipitated triethylamine hydrochloride was removed by filtration. After cooling the filtrate to 10 ° C. or less, 120 mL of water was added to precipitate crystals, which were filtered, washed with water, and dried to give 12.1 g (0) of 9,10-diacryloxyanthracene as pale yellow crystals. 0.038 mol, yield: 79 mol%).

The analysis results of the obtained compound are as shown below. From ¹ H-NMR, IR, and mass spectrum, it was confirmed that this was 9,10-diacryloxyanthracene.

Melting point: 209-211 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 6.24 (d, 2H, vinyl group), 6.65 (dd, 2H, vinyl group), 6.87 (d, 2H, vinyl group), 7 .46-7.55 (m, 4H, anthracene ring), 7.89-7.99 (m, 4H, anthracene ring).
IR (KBr, cm ^-1 ): 687, 764, 804, 984, 1039, 1143, 1177, 1363, 1410, 1631, 1736.
Mass spectrum: (EI-MS) m / z = 318 (M ⁺ )

“Synthesis Example 2”
Under a nitrogen atmosphere, 11.6 g (0.115 mol) of triethylamine was added to a solution of 10.0 g (0.048 mol) of 9,10-dihydroxyanthracene and 120 mL of N-methylpyrrolidone, and the mixture was cooled to 10 ° C. or lower. 11.0 g (0.105 mol) of methacryloyl chloride was added dropwise over 15 minutes. 30 minutes after the start of dropping, 5 mL of methanol was added to hydrate methacryloyl chloride, and the precipitated triethylamine hydrochloride was removed by filtration. After cooling the filtrate to 10 ° C. or lower, 120 mL of water was added to precipitate crystals, which were filtered, washed with water, and then dried to give 15.3 g (0) of 9,10-dimethacryloxyanthracene as pale yellow crystals. 0.044 mol, yield: 92 mol%).

The analysis results of the obtained compound are as shown below. From ¹ H-NMR, IR, and mass spectrum, it was confirmed that this was 9,10-dimethacryloxyanthracene.

Melting point: 226-227 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 2.24 (s, 6H, methyl group), 5.98 (dd, 2H, vinyl group), 6.70 (s, 2H, vinyl group), 7 .47-7.56 (m, 4H, anthracene ring), 7.80-8.02 (m, 4H, anthracene ring).
IR (KBr, cm ⁻¹ ): 755, 970, 1039, 1119, 1290, 1367, 1439, 1632, 1734.
Mass spectrum: (EI-MS) m / z = 346 (M ⁺ )

“Synthesis Example 3”
Under a nitrogen atmosphere, 10.8 g (0.107 mol) of triethylamine was added to a solution of 10.0 g (0.045 mol) of 2-methyl-9,10-dihydroxyanthracene and 120 mL of N-methylpyrrolidone, and the temperature was lowered to 10 ° C or lower. After cooling, 10.2 g (0.098 mol) of methacryloyl chloride was added dropwise over 15 minutes. 30 minutes after the start of dropping, 5 mL of methanol was added to hydrate methacryloyl chloride, and the precipitated triethylamine hydrochloride was removed by filtration. After cooling the filtrate to 10 ° C. or lower, 120 mL of water was added to precipitate crystals, which were filtered, washed with water, and then dried to give pale yellow crystals of 2-methyl-9,10-dimethacryloxyanthracene 12 0.9 g (0.036 mol, yield: 80 mol%) was obtained.

The analysis results of the obtained compound are as shown below. From ¹ H-NMR, IR, and mass spectrum, it was confirmed that this was 2-methyl-9,10-dimethacryloxyanthracene.

Melting point: 223-224 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 2.24 (s, 3H, methyl group), 2.25 (s, 3H, methyl group), 2.53 (s, 3H, methyl group), 5 .99 (dd, 2H, vinyl group), 6.70 (d, 2H, vinyl group), 7.32-7.35 (m, 1H, anthracene ring), 7.44-7.49 (m, 2H) , Anthracene ring), 7.66 (s, 1H, anthracene ring), 7.83-7.94 (m, 3H, anthracene ring).
IR (KBr, cm ^-1 ): 752,800,955,1039,1122,1309,1371,1446,1635,1730.
Mass spectrum: (EI-MS) m / z = 360 (M ⁺ )

"Example 1"
10 mg of acetophenone-type photoradical polymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651, manufactured by Ciba Specialty Co., Ltd.), 2 g of trimethylolpropane triacrylate as a monomer, synthesized in Synthesis Example 1 10 mg of 9,10-diacryloxyanthracene was added to obtain a uniform composition. This composition was applied on a polyester film (trade name: Lumirror, manufactured by Toray Industries, Inc., thickness of 100 microns) to a thickness of 12 microns using a bar coater. Then, an ultraviolet LED was irradiated in a nitrogen atmosphere. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until stickiness disappears was 10 seconds.

“Comparative Example 1”
A photocuring composition was prepared in the same manner as in Example 1 except that 9,10-diacryloxyanthracene was not added, and a curing time was determined by irradiating an ultraviolet LED (395 nm, irradiation intensity 3 mw / cm ² ). The tack free time was 50 seconds.

"Comparative Example 2"
A photocuring composition was prepared in the same manner as in Example 1 except that 9,10-diacryloxyanthracene was changed to 9-acryloxyanthracene and irradiated with an ultraviolet LED (395 nm, irradiation intensity 3 mw / cm ² ). The cure time was determined. The tack free time was 60 seconds.

“Comparative Example 3”
A photocuring composition was prepared in the same manner as in Example 1 except that 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 manufactured by Ciba Specialty) was not added. It was prepared and irradiated with an ultraviolet LED (395 nm, irradiation intensity 3 mw / cm ² ) to determine the curing time. The tack free time was 60 seconds.

"Example 2"
2 g of trimethylolpropane triacrylate as monomer and acetophenone type photo radical polymerization initiator 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by Ciba Specialty) 10 mg and 9,10-diacryloxyanthracene synthesized in Synthesis Example 1 were added to obtain a uniform composition. This composition was applied on a polyester film (trade name: Lumirror, 100 μm thick, manufactured by Toray Industries, Inc.) using a bar coater so as to have a film thickness of 12 μm. Then, an ultraviolet LED was irradiated from the surface in a nitrogen atmosphere. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until stickiness disappears was 16 seconds.

“Comparative Example 4”
A photocuring composition was prepared in the same manner as in Example 1 except that 9,10-diacryloxyanthracene was not added, and a curing time was determined by irradiating an ultraviolet LED (395 nm, irradiation intensity 3 mw / cm ² ). The tack free time was 70 seconds.

"Example 3"
10 mg of acetophenone-type photoradical polymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by Ciba Specialty) as a monomer and 9,10-diacryl synthesized in Synthesis Example 1 10 mg of oxyanthracene was added to obtain a uniform composition. This composition was applied onto a polyester film (trade name: Lumirror, 100 μm thick, manufactured by Toray Industries, Inc.) using a bar coater so as to have a film thickness of 12 μm, and then UV LED was irradiated from the surface in a nitrogen atmosphere. . The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 3 mW / cm ² . The light irradiation time “tack free time” until tackiness disappears was 30 seconds.

“Comparative Example 5”
A photocuring composition was prepared in the same manner as in Example 3 except that 9,10-diacryloxyanthracene was not added, and when it was ultraviolet LED (395 nm, irradiation intensity 3 mw / cm ² ), it was not cured at all even after 10 minutes. It was.

Claims (4)

A 9,10-di (meth) acryloxyanthracene compound represented by the following formula (1).

(In the formula (1), R is a hydrogen atom or a methyl group, and X and Y may be the same or different, and are a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group or a thioalkoxy group. Either.)   The method for producing a 9,10-di (meth) acryloxyanthracene compound according to claim 1, comprising acrylating the 9,10-dihydroxyanthracene compound.   A photoradical polymerization sensitizer containing the 9,10-di (meth) acryloxyanthracene compound according to claim 1. The photocurable composition containing the photoradical polymerization sensitizer of Claim 3, a radical polymerization initiator, and a radically polymerizable monomer.