JP2019031471A - Reactive photopolymerization sensitizer - Google Patents

Abstract

To provide a photopolymerization sensitizer providing practically sufficient photosetting rate.SOLUTION: There is provided a 9,10-bis(dihydroxyalkoxy)anthracene compound having a primary hydroxyl group represented by the general formula (1). In the formula (1), n represents the number of 0 to 10, Rand Rmay be same or different and represent hydrogen or an alkyl group having 1 to 20 carbon atoms, the alkyl group may contain oxygen, nitrogen, sulfur, a benzene ring or a naphthalene ring, X and Y may be same or different and represent hydrogen, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.SELECTED DRAWING: None

Description

The present invention relates to a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group, a process for producing the same, and a photopolymerization sensitizer containing the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group. .

Photo-curing resins that are polymerized by active energy rays such as ultraviolet rays and visible rays cure quickly and can significantly reduce the amount of organic solvent used compared to thermosetting resins. It is excellent in that it can be reduced. Conventional photocurable resins themselves have a poor polymerization initiating function, and it is usually necessary to use a photopolymerization initiator for curing. As the photopolymerization initiator, alkylphenone-based polymerization initiators such as hydroxyacetophenone and benzophenone, acylphosphine oxide-based photopolymerization initiators, or onium salts are used (Patent Documents 1, 2, and 3). Among these photopolymerization initiators, when an onium salt-based initiator is used, the light absorption of the onium salt is in the vicinity of 225 nm to 350 nm and does not absorb at 350 nm or more. Therefore, a long wavelength lamp of 350 nm or more is used as a light source. In such a case, there is a problem that the photocuring reaction does not easily proceed, and a photopolymerization sensitizer is generally added. Similarly, many photopolymerization initiators such as alkylphenone polymerization initiators have no absorption at 350 nm or more. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers for these photopolymerization initiators, and anthracene compounds are often used due to color problems (Patent Document 4).

As an anthracene photopolymerization sensitizer, a 9,10-dialkoxyanthracene compound is used. For example, a 9,10-dialkoxyanthracene compound such as 9,10-dibutoxyanthracene or 9,10-diethoxyanthracene is used as a photopolymerization sensitizer for an iodonium salt that is a photopolymerization initiator in photopolymerization. (Patent Documents 5, 6, 7, and 8).

However, this 9,10-dialkoxy anthracene compound is exposed to the photopolymerization sensitizer and the like due to blooming during storage of the photopolymerizable composition before photocuring or the cured product after photocuring. It is known to cause powdering and coloring problems.

As for the photopolymerizable composition, for example, when these photopolymerization sensitizers are used as one component of a photoadhesive for adhering the film to the film, the photopolymerization sensitizer is transferred to a film covered on top ( Migration) and may cause problems with powdering and coloring of the photopolymerization sensitizer on the upper film. Furthermore, there are cases where problems (sublimation) such as contamination of surrounding facilities are caused by powdering of the photopolymerization sensitizer.

Concerning the cured product after photocuring of the photopolymerizable composition, for example, in a flexographic ink for food packaging, there is a concern about contamination of food due to blooming of the photopolymerization sensitizer from the ink printed on the packaging paper to the film. Is done.

Japanese Patent Laid-Open No. 06-345614 Japanese Patent Application Laid-Open No. 07-062010 JP 05-249606 A JP-A-10-195117 JP 2002-302507 A JP 11-279212 A JP 2000-344704 A WO2007 / 126066

Therefore, during storage of the photopolymerizable composition before photocuring and the cured product after photocuring, it has migration resistance and sublimation resistance, causing problems with powdering and coloring of the cured product. Development of a new photopolymerization sensitizer that does not occur is desired.

As a result of further intensive studies on the structure and physical properties of the anthracene compound, the present inventors showed that the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group shown in the present invention was photosensitized in the photopolymerization reaction. The photopolymerization sensitizer migrates both before and after photocuring of the photopolymerizable composition by having a primary hydroxyl group that is both a polar group and a reactive group. Further, it was found that blooming is difficult to occur, and further, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group was found to be a compound excellent in sublimation resistance, and the present invention was completed.

That is, the first gist of the present invention resides in a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

In the general formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group May contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The second gist of the present invention is that, in the general formula (1), R ¹ is a hydrogen atom, and R ² may contain a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group according to claim 1, which is a good alkyl group having 1 to 20 carbon atoms.

The third gist of the present invention resides in a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The fourth gist of the present invention is characterized by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (3) with a glycidol compound represented by the following general formula (4). The present invention resides in a method for producing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the formula (1).

In the general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (4), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group May contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring.

In the general formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group May contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The fifth gist of the present invention is a reaction of a 9,10-dihydroxyanthracene compound represented by the following general formula (3) with a glycidol represented by the following structural formula (5). The present invention resides in a method for producing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by (2).

In the general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The sixth gist of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

In the general formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group May contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

The seventh gist of the present invention resides in a photopolymerization sensitizer containing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

An eighth aspect of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer described in the sixth or seventh aspect and a photopolymerization initiator.

A ninth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition described in the eighth aspect and a photocationically polymerizable compound.

A tenth aspect of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition described in the eighth aspect and a photoradical polymerizable compound.

The eleventh aspect of the present invention is a polymerization method in which the photopolymerizable composition according to the ninth aspect or the tenth aspect is polymerized by irradiating energy rays containing light in a wavelength range of 300 nm to 500 nm. Exist.

A twelfth aspect of the present invention is characterized in that the irradiation source of the energy beam containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm or 405 nm. The present invention resides in the polymerization method described in the 11th gist.

The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention not only has a high effect as a photopolymerization sensitizer in a photopolymerization reaction, but also photopolymerization sensitization of the compound of the present invention. About the photopolymerizable composition contained as an agent, the photopolymerization sensitizer is a useful compound that has a very low degree of migration or blooming both before and after photocuring.

(Compound)
The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is a compound represented by the following general formula (1).

In the general formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group May contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by R ¹ or R ² includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n- Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like can be mentioned. It may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring.

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by X or Y includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , N-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or 2-ethylhexyl group, and the like. As the halogen atom, fluorine atom, chlorine atom, bromine atom or iodine Atom.

Specific examples of the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention include 9,10-bis (2,3-dihydroxypropoxy) anthracene, 9 , 10-bis (2,4-dihydroxybutoxy) anthracene, 9,10-bis (2,5-dihydroxypentyloxy) anthracene, 9,10-bis (2,6-dihydroxyhexyloxy) anthracene, 9,10- Bis (2,8-dihydroxyoctyloxy) anthracene, 9,10-bis (2,10-dihydroxydecyloxy) anthracene, 2-methyl-9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-methyl -9,10-bis (2,4-dihydroxybutoxy) anthracene, 2-methyl -9,10-bis (2,5-dihydroxypentyloxy) anthracene, 2-methyl-9,10-bis (2,6-dihydroxyhexyloxy) anthracene, 2-methyl-9,10-bis (2,8 -Dihydroxyoctyloxy) anthracene, 2-methyl-9,10-bis (2,10-dihydroxydecyloxy) anthracene, 2-ethyl-9,10-bis (2,4-dihydroxybutoxy) anthracene, 2-ethyl- 9,10-bis (2,5-dihydroxypentyloxy) anthracene, 2-ethyl-9,10-bis (2,6-dihydroxyhexyloxy) anthracene, 2-ethyl-9,10-bis (2,8- Dihydroxyoctyloxy) anthracene, 2-ethyl-9,10-bis (2,10-dihydroxydecyl) Xyl) anthracene, 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-t-pentyl-9,10-bis (2,3-dihydroxypropoxy) anthracene, 2,6-dimethyl- 9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-chloro-9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-bromo-9,10-bis (2,3-dihydroxypropoxy) ) Anthracene and the like, and preferred are 9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-methyl-9,10-bis (2,3-dihydroxypropoxy) anthracene, 2-ethyl-9. , 10-bis (2,3-dihydroxypropoxy) anthracene.

Since the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has many hydrophilic groups such as a hydroxyl group in addition to the primary hydroxyl group, the alcohol has an anthracene skeleton. It has the property of being easily soluble in solvents such as, and is also easily soluble in monomers and oligomers having hydrophilic groups such as hydroxyethyl acrylate and oxetane alcohol.

(Production method)
Next, a method for producing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention will be described. The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention is the following reaction of the 9,10-dihydroxyanthracene compound represented by the general formula (3): According to Formula-1, it can be obtained by reacting with the corresponding glycidol compound represented by the general formula (4) in the presence or absence of a basic compound.

In Reaction Formula-1, n represents an integer of 0 to 10, R ¹ and R ² may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group is , An oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.

In Reaction Formula-1, the 9,10-dihydroxyanthracene compound represented by the general formula (3) used as a raw material is obtained by reducing the corresponding 9,10-anthraquinone compound.

Specific examples of the 9,10-dihydroxyanthracene compound used as a raw material in the reaction include 9,10-dihydroxyanthracene, 2-methyl-9,10-dihydroxyanthracene, and 2-ethyl-9,10-dihydroxyanthracene. 2-t-pentyl-9,10-dihydroxyanthracene, 2,6-dimethyl-9,10-dihydroxyanthracene, 2-chloro-9,10-dihydroxyanthracene, 2-bromo-9,10-dihydroxyanthracene, etc. Can be mentioned.

In the case of 9,10-dihydroxyanthracene, as an industrial method, 1,4,4a, 9a-tetrahydroanthraquinone which is a Diels-Alder reaction product of 1,4-naphthoquinone and 1,3-butadiene or By reducing 9,10-anthraquinone using an alkali metal salt of 1,4-dihydro-9,10-dihydroxyanthracene which is the isomer, 9,10-dihydroxyanthracene can be obtained more easily. That is, 1,4,4a, 9a-tetrahydroanthraquinone obtained by reaction of 1,4-naphthoquinone and 1,3-butadiene is prepared in an aqueous medium in the presence of an alkaline compound such as an alkali metal hydroxide. , 10-anthraquinone can be reacted to obtain an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene.

A precipitate of 9,10-dihydroxyanthracene can be obtained by acidifying an aqueous solution of an alkali metal salt of 9,10-dihydroxyanthracene obtained in this reaction in the absence of oxygen. By purifying the precipitate, 9,10-dihydroxyanthracene can be obtained. A 9,10-dihydroxyanthracene compound having a substituent can be obtained in the same manner.

In Reaction Formula-1, as specific examples of the glycidol compound represented by the general formula (4) as a raw material, 2,3-epoxypropanol (glycidol), 3,4-epoxybutanol, 2,3-epoxybutanol, 4,5-epoxypentanol, 5,6-epoxyhexanol, 7,8-epoxyoctanol, 9,10-epoxydecanol and the like. Among these, 2,3-epoxypropanol (glycidol), 3,4-epoxybutanol, 4,5-epoxypentanol, 5,6-epoxyhexanol, 7,8-epoxyoctanol, 9, 10-epoxydecanol is preferred, and 2,3-epoxypropanol (glycidol) is particularly preferred.

As the usage-amount of the glycidol compound represented by General formula (4) in Reaction formula-1, Preferably it is 2.0 mol times or more and less than 20.0 mol times with respect to a 9,10-dihydroxyanthracene compound. Preferably, it is 2.2 mol times or more and less than 15.0 mol times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 20.0 mol times or more, side reactions will occur and the yield and purity will be reduced.

The basic compound used in Reaction Scheme-1 includes sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium hexamethyldisilazide, lithium diisopropylamide, triethylamine, tributylamine, trihexylamine, Examples include dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dimethylaniline, pyridine, piperidine, γ-picoline, and lutidine.

The addition amount of the basic compound is preferably 2.0 mol times or more and less than 5.0 mol times, more preferably 2.2 mol times or more, 3.0 mol times with respect to the 9,10-dihydroxyanthracene compound. It is less than mole times. If it is less than 2.0 mol times, the reaction will not be completed, and if it is 5.0 mol times or more, side reactions will occur and the yield and purity will be reduced.

The reaction is performed in a solvent or without a solvent. The solvent used is not particularly selected as long as it does not react with the glycidol compound used, for example, an aromatic solvent such as toluene, xylene and ethylbenzene, an ether solvent such as tetrahydrofuran and 1,4-dioxane, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, amide solvents such as dimethylacetamide and dimethylformamide, halogenated carbon solvents such as methylene chloride, ethylene dichloride and chlorobenzene, and alcohol solvents such as methanol, ethanol and 1-propanol are used. .

When a 9,10-dihydroxyanthracene compound is dissolved in an aqueous solution of an inorganic base and reacted with glycidol, use of a phase transfer catalyst is effective. Examples of the phase transfer catalyst include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, trioctylmethylammonium bromide, trioctylethylammonium bromide, trioctylpropylammonium bromide, trioctylbutylammonium bromide. , Benzyldimethyloctadecylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, trioctylmethylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride Id, trioctyl butyl ammonium chloride, benzyl dimethyl ammonium chloride or the like.

The addition amount of the phase transfer catalyst is preferably 0.01 mol times or more and less than 1.0 mol times, more preferably 0.05 mol times or more, 0.5 mol times, with respect to the 9,10-dihydroxyanthracene compound. It is less than mole times. If it is less than 0.01 mol times, the reaction rate is slow, and if it is 1.0 mol times or more, the purity of the product decreases, which is not preferable.

The reaction temperature of the reaction is usually 20 ° C. or higher and 200 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower. If it is less than 20 ° C., it takes too much reaction time, and if it is heated above 200 ° C., impurities increase and the purity of the target compound decreases, both of which are not preferable.

The reaction time in the reaction varies depending on the reaction temperature, but is usually about 0.5 to 20 hours. More preferably, it is 1 hour to 10 hours.

After completion of the reaction, if necessary, the unreacted raw material, solvent and catalyst are removed by a method such as washing, distillation under reduced pressure, and filtration alone or in combination. When the product is a solid, crystals are precipitated during the concentration, and can be recrystallized from a poor solvent such as alcohol or hexane, or dried up as it is to obtain crystals. When the product is a liquid, it can be dried up as it is and purified as necessary by distillation or the like to obtain a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group.

(Photopolymerization sensitizer)
The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention acts as a photopolymerization sensitizer. A photopolymerization initiator composition can be obtained by mixing the photopolymerization sensitizer and a photopolymerization initiator, and a photopolymerizable composition can be obtained by further mixing a photopolymerizable compound. it can. The photopolymerizable composition can be easily photocured by irradiation with light having a long wavelength such as ultraviolet LED light having a central wavelength of 395 nm.

As the photopolymerization initiator used in the present invention, an onium salt, a benzylmethyl ketal-based, an α-hydroxyalkylphenone-based polymerization initiator and the like are preferable. As the onium salt, an iodonium salt or a sulfonium salt is usually used. Examples of the iodonium salt include 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexamethoxyantimonate, 4-isopropylphenyl-4′-methylphenyliodonium tetrakispentamethoxyphenylborate, 4 -Isopropylphenyl-4'-methylphenyliodonium tetrakispentafluorophenylborate and the like, for example, Irgacure 250 manufactured by BSF (Irgacure is a registered trademark of BSF), Rhodia RODSIL 2074 (RODSIL is a registered trademark of Rhodia), IK-1 manufactured by San Apro, etc. can be used. On the other hand, examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexamethoxyphosphate, diphenyl-4-phenylthiophenylsulfonium hexanium. Examples thereof include methoxyphosphate, triphenylsulfonium hexamethoxyphosphate, etc., for example, Daicel CPI-100P, CPI101P, CPI-200K, BASF Irgacure 270, Dow Chemical's UVI6992, etc. Can be used. These photopolymerization initiators may be used alone or in combination of two or more.

The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention is a radical polymerization such as a benzylmethyl ketal-based or α-hydroxyalkylphenone-based polymerization initiator. It also has an excellent photopolymerization sensitization effect for the initiator.

Examples of the benzylmethyl ketal-based radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BAS Corporation), and the like. -Hydroxyalkylphenone-based radical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), 1-hydroxycyclohexylphenyl Ketone (trade name “Irgacure 184” manufactured by BSF Corporation), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one ( Trade name “Irgacure 2959” manufactured by BSF Corporation), 2-hydroxy-1- {4- [4- (2-hydroxy 2-methyl-propionyl) - benzyl] phenyl} -2-methyl-1-one (trade name "Irgacure 127" BAS-F Inc.).

In particular, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure 651” manufactured by BAS Corporation), which is a benzylmethyl ketal radical polymerization initiator, α-hydroxyalkyl 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name “Darocur 1173” manufactured by BASF), which is a phenone radical polymerization initiator, 1-hydroxycyclohexyl phenyl ketone (product) The name “Irgacure 184” manufactured by BSF Corporation) is preferred.

Further, acetophenone radical polymerization initiators such as acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2 -Isobutoxy-2-phenylacetophenone, benzyl radical polymerization initiator benzyl, 4,4'-dimethoxybenzyl, anthraquinone radical polymerization initiator 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-phenoxyanthraquinone 2- (phenylthio) anthraquinone, 2- (hydroxyethylthio) anthraquinone, and the like can also be used.

Of the illustrated photopolymerization initiators, onium salts are particularly preferable. As a onium salt, not only an iodonium salt but also a sulfonium salt, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has a photopolymerization sensitizing effect. One.

Although the usage-amount with respect to the photoinitiator of the photoinitiator of the photopolymerization sensitizer containing the 9, 10-bis (dihydroxyalkoxy) anthracene compound which has the primary hydroxyl group represented by General formula (1) of this invention is not specifically limited. The range is usually from 5% by weight to 100% by weight, preferably from 10% by weight to 50% by weight, based on the photopolymerization initiator. If the amount of the photopolymerization sensitizer used is less than 5% by weight, it takes too much time to photopolymerize the photopolymerizable compound. On the other hand, even if it exceeds 100% by weight, an effect commensurate with the addition is obtained. Absent.

(Photopolymerization initiator composition)
The photopolymerization sensitizer containing the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention can be directly added to the photopolymerizable compound. However, after preparing a photopolymerization initiator composition by blending with a photopolymerization initiator in advance, it can also be added to the photopolymerizable compound. That is, the photopolymerization initiator composition of the present invention includes a photopolymerization sensitizer containing at least a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) and a photopolymerization agent. It is a composition containing a polymerization initiator.

(Photopolymerizable composition)
Furthermore, a photopolymerizable composition can also be prepared by blending the photopolymerization initiator composition and a photopolymerizable compound. The photopolymerizable composition of the present invention comprises a photopolymerization sensitizer containing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention and a photopolymerization initiator composition containing a photopolymerization initiator. And a radically polymerizable compound or a cationic photopolymerizable compound. The photopolymerization sensitizer and the photopolymerization initiator containing the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention are separately added to the photoradical polymerizable compound or the photocationic polymerizable compound. As a result, a photopolymerization initiator composition may be formed in the photo radical polymerizable compound or the photo cationic polymerizable compound. Furthermore, it is good also as a hybrid composition containing both a radical photopolymerizable compound and a photocationic polymerizable compound.

As the photoradical polymerizable compound, for example, an organic compound having a double bond such as styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester can be used. . Of these radical polymerizable compounds, acrylic acid esters and methacrylic acid esters (hereinafter, both are referred to as (meth) acrylic acid esters) are preferable from the viewpoint of film forming ability and the like. (Meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid Cyclohexyl, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclo [5,2,1,02,6] decandimethanol diacrylate, isobornyl methacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, Polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, imide acrylate, etc. It is. These radical photopolymerizable compounds may be one kind or a mixture of two or more kinds.

In particular, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is also highly compatible with a monomer having a hydroxyl group.

Examples of the photocationically polymerizable compound include an epoxy compound, an oxetane compound, and vinyl ether. Examples of general epoxy compounds include alicyclic epoxy compounds, epoxy-modified silicones, and aromatic glycidyl ethers. As the alicyclic epoxy compound, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation), bis (3 4-epoxycyclohexyl) adipate and the like. Examples of the epoxy-modified silicone include UV-9300 manufactured by Toshiba GE Silicone. Examples of the aromatic glycidyl compound include 2,2'-bis (4-glycidyloxyphenyl) propane. As the oxetane compound, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (manufactured by Toa Gosei Co., Ltd., trade name: OXT-101), 2-ethylhexyloxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-212), Xylylenebisoxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-121), 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl} oxetane (manufactured by Toagosei Co., Ltd., trade name: OXT) -221). Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and the like. These photocationically polymerizable compounds may be one kind or a mixture of two or more kinds.

In the photopolymerizable composition of the present invention, the amount of the photopolymerization initiator composition used is in the range of 0.005 wt% or more and 10 wt% or less, preferably 0.025 wt% with respect to the photopolymerizable composition. The content is 5% by weight or less. If it is less than 0.005% by weight, it takes time to photopolymerize the photopolymerizable composition. On the other hand, if it exceeds 10% by weight, the hardness of the photocured product obtained by photopolymerization decreases. This is not preferable because the physical properties of the cured product are deteriorated.

In addition, the photopolymerizable composition of the present invention has a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, within a range not impairing the effects of the present invention. Various resin additives such as flame retardants, antioxidants, stabilizers, lubricants, and plasticizers may be blended.

(Photocured product)
A photocured product can be obtained by polymerizing the photopolymerizable composition of the present invention by irradiating light. When the photopolymerizable composition is irradiated with light to be polymerized and photocured, the photopolymerizable composition can be formed into a film and photocured, or can be formed into a lump and photocured. When forming into a film shape and photocuring, the liquid photopolymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using a bar coater or the like. On the other hand, it can also be applied with a thinner or thicker film by spin coating or screen printing.

A photocured product is obtained by irradiating a coating film made of the photopolymerizable composition thus prepared with ultraviolet light having a wavelength range of 300 nm to 500 nm at an intensity of about 1 to 1000 mW / cm ^2. Can do. As a light source to be used, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, xenon lamp, gallium doped lamp, black light, 405 nm ultraviolet LED, 395 nm ultraviolet LED, 385 nm ultraviolet LED, 365 nm ultraviolet LED, blue LED, white LED, fusion A D valve, a V valve, etc. manufactured by the company are listed. Natural light such as sunlight can also be used. In particular, it has a sensitizing action even in light having a long wavelength range of 365 nm to 405 nm such as 405 nm UV LED, 395 nm UV LED, 385 nm UV LED, 375 nm UV LED, 365 nm UV LED. It is preferable.

(Optical DSC measurement)
In the present invention, the optical DSC measurement method can be used as a method for quantitatively evaluating the photopolymerization rate of the photopolymerizable composition under light irradiation. According to this method, the calorific value accompanying curing can be continuously and simply measured while directly irradiating the sample with light. When a sample set in the optical DSC measuring apparatus is irradiated with light, a light curing reaction starts and heat generation is observed. The baseline of the DSC curve, which was horizontal before photocuring, is shifted to the exothermic side and returns to the original baseline position when the reaction is completed. The calorific value can be obtained from the peak size of the DSC curve. That is, the progress of polymerization can be evaluated by irradiating the photopolymerizable composition with light and measuring and comparing the calorific value per 1 mg.

(Determination of migration resistance of the composition)
As a method for determining whether or not the photopolymerization sensitizer contained in the photopolymerizable composition of the present invention migrates to a film or the like, the photopolymerizable composition containing the photopolymerization sensitizer is a thin film. Create a product applied to the object, cover it with a polyethylene film, store it at a constant temperature (26 ° C) for a certain period of time, then peel off the polyethylene film, and examine whether the photopolymerization sensitizer has transferred to the polyethylene film The migration resistance was determined. The peeled polyethylene film was washed after washing the surface composition with acetone, measured for UV resistance of the polyethylene film, and measured for migration resistance by examining the increase in absorption intensity caused by the photopolymerization sensitizer. did. For the measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used. In order to quantitatively compare with 9,10-dibutoxyanthracene, which is the compound of the comparative example, the obtained absorbance was converted to the absorbance value of 9,10-dibutoxyanthracene. In conversion, the absorbance at 260 nm of the compound of the present invention and 9,10-dibutoxyanthracene was measured with an ultraviolet / visible spectrophotometer, the respective molar extinction coefficients were calculated from the absorbance value and molar concentration, and the ratio And converted.

(Determination of migration resistance of photocured product)
(Elution test of photopolymerization sensitizer)
Light from the photocured product as a method for determining whether the photopolymerization sensitizer present in the photocured product obtained by photocuring the photopolymerizable composition of the present invention migrates to a film or the like. A dissolution test of the polymerization sensitizer was conducted. The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention has not only an effect as a photopolymerization sensitizer in a photopolymerization reaction, but also the compound. By polymerizing a photopolymerizable composition contained as a photopolymerization sensitizer, it is presumed that the photopolymerization sensitizer itself causes a photopolymerization reaction and is taken into the photocured product. The self-polymerization property of the photopolymerization sensitizer was evaluated by the following method. That is, after photocuring a photopolymerizable composition containing a photopolymerization sensitizer, the photocured product is extracted with acetone in which the photopolymerization sensitizer of the present invention is dissolved, and photopolymerized in an organic solvent. This was confirmed by measuring the elution rate of the sensitizer. The amount of the photopolymerization sensitizer contained in the photocured product before and after the extraction treatment with acetone was measured by UV spectrum. For the UV spectrum measurement, an ultraviolet / visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV2600) was used.

(Determination of sublimation resistance)
The sublimation resistance of the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the general formula (1) of the present invention is determined by heating the compound at a constant temperature for a certain period of time in a nitrogen atmosphere. The weight loss was measured with a differential calorimeter (TG / DTA 7200 manufactured by Hitachi High-Tech Science Co., Ltd.).

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise specified, all parts are parts by weight. The product was confirmed based on the measurement by the following equipment.

The compound of the present invention was identified using the following equipment.
Infrared (IR) spectrophotometer: manufactured by Thermo, model is50 FT-IR
Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model ECS-400
Melting point: Melting point measuring device manufactured by Guerencamp, model MFB-595 (conforms to JIS K0064)

(Synthesis Example 1) 9,10-bis (2,3-dihydroxypropoxy) anthracene 99.1 g of sodium salt of 9,10-dihydroxyanthracene 29.1 g (24 mmol as anthraquinone) was stirred in a nitrogen box. In a 100 ml four-necked flask. After adding 12.5 g of ethanol as a reaction solvent, the temperature was raised to 55 ° C., and a solution of 17.8 g (240 mmol) of glycidol in ethanol (12.5 g) was added dropwise over 1 hour. After stirring for 2 hours and cooling, the anthraquinone impurity was filtered off, and the filtrate was concentrated and cooled to precipitate crystals. Crystals were separated by filtration, washed with ion-exchanged water, and dried to obtain 4.3 g (light yellow crystals) of 9,10-bis (2,3-dihydroxypropoxy) anthracene. The yield was 50 mol% and the purity was 97%.

(1) Melting point: 164-166 ° C
(2) IR (KBr, cm ⁻¹ ): 3271, 2930, 2879, 1620, 1400, 1355, 1319, 1168, 1122, 1040, 1002, 812, 683
(3) ¹ H-MNR (DMSO-D ₆ , 400 MHz): δ = 3.59-3.61 (m, 4H), 4.02-4.09 (m, 4H), 4.12-4. 19 (m, 2H), 4.77 (t, 2H), 5.29 (d, 2H), 7.52-7.55 (m, 4H), 8.37-8.41 (m, 4H)

(Synthesis Example 2) 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene In a nitrogen atmosphere, 5.0 g (21 mmol) of 2-ethyl-9,10-anthraquinone in a 200 ml four-necked flask, 9.2 g (85 mmol) of thiourea dioxide, 8.5 g (213 mmol) of sodium hydroxide and 50 g of ion-exchanged water were charged and stirred at 60 ° C. for 1 hour. After adding 12.5 g of ethanol as a reaction solvent to the obtained sodium salt aqueous solution of 2-ethyl-9,10-dihydroxyanthracene, the internal temperature was adjusted to 55 ° C., and 15.7 g (212 mmol) of glycidol in ethanol (12. 5 g) The solution was added dropwise over 3 hours. The mixture was stirred for 3 hours, cooled, neutralized with 35% hydrochloric acid, extracted with methyl isobutyl ketone (MIBK), and washed with water. The obtained MIBK solution was concentrated and dried to obtain 4.2 g (orange oil) of 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene. The yield was 52 mol% and the purity was 94%.

(1) IR (Nujol, cm ⁻¹ ) 3326, 2928, 2872, 1348, 1320, 1040, 995, 767, 622.
(2) ¹ H-MNR (DMSO-D ₆ , 400 MHz): δ = 1.32 (t, 3H, J1 = 7.3 Hz, J2 = 7.8 Hz), 2.82 (q, 2H, J1 = 7) 3 Hz, J2 = 7.8 Hz), 3.57-3.64 (m, 4H), 4.03-4.18 (m, 6H), 4.72-4.75 (m, 2H), 5 .24-5.26 (m, 2H), 7.41-7.44 (m, 1H), 7.47-7.51 (m, 2H), 8.12-8.39 (m, 4H)

(Optical DSC measurement in a system using an iodonium salt as a photopolymerizable composition and a photopolymerization initiator)
In this example, optical DSC measurement was performed as follows. That is, the DSC measurement apparatus used was XDSC-7200 manufactured by Hitachi High-Tech Co., Ltd., and a DSC measurement unit was mounted on the DSC measurement apparatus so that DSC measurement could be performed while irradiating light. As a light source for light irradiation, LA-410UV manufactured by Hayashi Watch Industry Co., Ltd. was used, and the sample was irradiated with 405 nm light by a band pass filter. The illuminance of light was 50 mW / cm ² . The light from the light source can be guided to the top of the sample using a glass fiber, and the shutter of the light source can be trigger controlled so that DSC measurement can be performed simultaneously with the start of light irradiation. For optical DSC measurement, a sample was precisely weighed in an aluminum pan for measurement of about 1 mg, placed in a DSC measurement unit, and then an optical DSC unit was mounted. Thereafter, the inside of the measurement part was kept in a nitrogen atmosphere and allowed to stand for 10 minutes, and measurement was started. The measurement was continued for 6 minutes with normal light irradiation. After the first measurement, the sample was again measured under the same conditions, and the value obtained by subtracting the second measurement result from the first measurement result was taken as the measurement result of the sample. The results were compared by the total calorific value per 1 mg of sample in 1 minute after light irradiation unless otherwise specified. Depending on the measurement conditions, the photoreaction may not be completed in 1 minute, but in order to compare the reaction behavior at the initial stage of light irradiation, the total calorific value for 1 minute was compared. When polymerization of a sample (photopolymerizable composition) occurs with light irradiation, reaction heat is generated along with the polymerization, but the reaction heat can be measured by optical DSC. Therefore, the progress of polymerization by light irradiation can be measured by optical DSC. In this example, the total calorific value for 1 minute after light irradiation is measured, but as long as the same polymerizable compound is used, when the value is compared, the larger the value, the more efficiently the polymerization proceeds. Can be considered.

Thus, the photopolymerization performance evaluation test of the photopolymerizable composition using the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention as a photopolymerization sensitizer will be described below.

(Evaluation Example 1 for Photocuring Rate)
As a photocationically polymerizable compound, 100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation) , 2 parts by weight of 4-isobutylphenyl-4′-methylphenyliodonium hexafluorophosphate (manufactured by BASF, trade name Irgacure 250) as a photopolymerization initiator, synthesized as a photopolymerization sensitizer A photopolymerizable composition was prepared by mixing 0.5 parts by weight of 9,10-bis (2,3-dihydroxypropoxy) anthracene obtained by the same method as in Example 1 at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement by the above-described method, the total calorific value per minute from the start of light irradiation was 153 mJ / mg.

(Example 2 of photocuring rate evaluation)
Photocuring Rate Evaluation 2-Ethyl-9,10-bis (2,3) obtained in the same manner as in Synthesis Example 2 instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene in Example 1 Except for using -dihydroxypropoxy) anthracene, the optical DSC measurement was carried out in the same manner as in Photocuring Rate Evaluation Example 1, and the total calorific value per minute from the start of light irradiation was 123 mJ / mg.

(Photocuring rate evaluation comparative example 1)
As a photocationically polymerizable compound, 100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: Celoxide 2021P, Celoxide is a registered trademark of Daicel Corporation) As a photopolymerization initiator, 2 parts by weight of (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BASF Corporation) Were mixed at room temperature to prepare a photopolymerizable composition. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value per minute from the start of light irradiation was 0.3 mJ / mg.

(Photocuring rate evaluation comparative example 2)
Photocuring rate evaluation Photocuring rate except that 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer is used in place of 9,10-bis (2,3-dihydroxypropoxy) anthracene in Example 1. When optical DSC measurement was performed in the same manner as in Evaluation Example 1, the total calorific value per minute from the start of light irradiation was 147 mJ / mg.

(Evaluation Example 3 for Photocuring Rate)
As a photoradical polymerizable compound, (4-methylphenyl) [4- (2-methylpropyl) phenyl as a photopolymerization initiator for 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) ] 9 and 10 obtained in the same manner as in Synthesis Example 1 using 2 parts by weight of iodonium-hexafluorophosphine candy (trade name Irgacure 250, manufactured by BASF Corporation) and a photopolymerization sensitizer. 1 part by weight of bis (2,3-dihydroxypropoxy) anthracene was mixed at room temperature to prepare a photopolymerizable composition. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value per minute from the start of light irradiation was 493 mJ / mg.

(Photocuring rate evaluation example 4)
Photocuring Rate Evaluation 2-Ethyl-9,10-bis (2,3) obtained in the same manner as in Synthesis Example 2 instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene in Example 3 Except for using -dihydroxypropoxy) anthracene, the optical DSC measurement was carried out in the same manner as in Photocuring Rate Evaluation Example 3, and the total calorific value per minute from the start of light irradiation was 644 mJ / mg.

(Photocuring rate evaluation comparative example 3)
As a photoradical polymerizable compound, (4-methylphenyl) [4- (2-methylpropyl) phenyl as a photopolymerization initiator for 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) A photopolymerizable composition was prepared by mixing 2 parts by weight of iodonium-hexafluorophosphate (trade name Irgacure 250, manufactured by BSF Corporation) at room temperature. When this photopolymerizable composition was subjected to optical DSC measurement, the total calorific value per minute from the start of light irradiation was 14 mJ / mg.

(Photocuring rate evaluation comparative example 4)
Photocuring rate evaluation Photocuring rate except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used in place of 9,10-bis (2,3-dihydroxypropoxy) anthracene in Comparative Example 3. When optical DSC measurement was performed in the same manner as in Evaluation Example 3, the total calorific value per minute from the start of light irradiation was 430 mJ / mg.

As is clear by comparing the results of Photocuring Rate Evaluation Examples 1 and 2 and Photocuring Rate Evaluation Comparative Example 1, 9,10-bis (dihydroxyalkoxy) having the primary hydroxyl group of the present invention in photocationic polymerization. It can be seen that by adding the anthracene compound as a photopolymerization sensitizer, the total calorific value is increased and the polymerization reaction is remarkably accelerated. In addition, as is clear by comparing the results of Photocuring Rate Evaluation Examples 3 and 4 and Photocuring Rate Evaluation Comparative Example 3, 9,10-bis having the primary hydroxyl group of the present invention in photoradical polymerization ( It can be seen that by adding the dihydroxyalkoxy) anthracene compound, the total calorific value similarly increases, and the polymerization reaction is remarkably accelerated. That is, it can be seen that the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention has a photopolymerization sensitizing effect in both photocationic polymerization and photoradical polymerization.

Furthermore, as is clear by comparing the results of Photocuring Rate Evaluation Examples 1 and 2 and Photocuring Rate Evaluation Comparative Example 2, 9,10-bis (dihydroxy) having the primary hydroxyl group of the present invention in photocationic polymerization. It can be seen that the alkoxy) anthracene compound has a photopolymerization sensitizing effect equivalent to or higher than 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer. Further, as is clear by comparing the results of the photocuring rate evaluation examples 3 and 4 and the photocuring rate evaluation comparative example 4, 9,10-bis having the primary hydroxyl group of the present invention ( It can be seen that the dihydroxyalkoxy) anthracene compound has a photopolymerization sensitizing effect equivalent to or higher than that of 9,10-dibutoxyanthracene, which is also a known photopolymerization sensitizer. That is, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is a 9,10-dibutoxyanthracene which is a known photopolymerization sensitizer in both photocationic polymerization and photoradical polymerization. It can be seen that it has a photopolymerization sensitizing effect equivalent to or higher than.

(Example 1 for evaluating migration resistance of composition)
Synthesis Example 1 as a photopolymerization sensitizer with respect to 100 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel) as a photocationically polymerizable compound A composition was prepared by mixing 0.5 parts by weight of 9,10-bis (2,3-dihydroxypropoxy) anthracene synthesized in the same manner at room temperature. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coated material and stored for one day in a dark place, and stored for five days. After storage, the polyethylene film was peeled off, and the polyethylene film was removed. After washing with acetone and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 260 nm was measured. The absorbance due to the resulting 9,10-bis (2,3-dihydroxypropoxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.001 after 1 day storage and 0.006 after 5 days storage.

(Evaluation Example 2 for Migration Resistance of Composition)
As a photopolymerization sensitizer, 2-ethyl-9,10-bis (2,3-dihydroxy) synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene A composition was prepared by the same method as in Example 1 except that propoxy) anthracene was used. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coating and stored for one day in a dark place and those stored for five days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance due to the obtained 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene was converted to 9,10-dibutoxyanthracene. Absorbance was 0.001 after 1 day storage and 0.005 after 5 days storage.

(Comparative Example 1 for evaluating migration resistance of composition)
Evaluation of migration resistance other than using 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene as the photopolymerization sensitizer A composition was prepared in the same manner as in Example 1. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coating and stored for one day in a dark place and those stored for five days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance of the polyethylene film at 260 nm was measured. The absorbance of 9,10-dibutoxyanthracene was 0.400 after 1-day storage and 0.464 after 5-day storage.

(Evaluation Example 3 for Migration Resistance of Composition)
9,10-bis (2,3-dihydroxypropoxy) synthesized in the same manner as in Synthesis Example 1 as a photopolymerization sensitizer as a photopolymerizable sensitizer as a photoradical polymerizable compound with respect to 100 parts by weight of 2-hydroxyethyl acrylate. ) 1 part by weight of anthracene was mixed at room temperature to prepare a composition. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness of 30 microns) is placed on the obtained coated material, and one that is stored for one day in the dark and one that is stored for five days are prepared. After peeling off, washing the polyethylene film with acetone and drying, the UV spectrum of the polyethylene film was measured and the absorbance at 260 nm was measured. However, absorption due to the obtained 9,10-bis (2,3-dihydroxypropoxy) anthracene was not observed after storage for one day and after storage for five days.

(Evaluation Example 4 for Migration Resistance of Composition)
As a photopolymerization sensitizer, 2-ethyl-9,10-bis (2,3-dihydroxy) synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene A composition was prepared in the same manner as in Example 3 except that propoxy) anthracene was used. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coating and stored for one day in a dark place and those stored for five days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 260 nm was measured. However, absorption resulting from the obtained 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene was not observed after storage for one day and after storage for five days.

(Comparative Example 2 for evaluating migration resistance of composition)
Evaluation of migration resistance other than using 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene as the photopolymerization sensitizer A composition was prepared in the same manner as in Example 3. The composition was applied on a polyester film using a bar coater so that the film thickness was 12 microns. Next, a low-density polyethylene film (film thickness: 30 microns) was put on the obtained coating and stored for one day in a dark place and those stored for five days. After storage, the polyethylene film was peeled off, and acetone was removed. After washing and drying, the UV spectrum of the polyethylene film was measured, and the absorbance at 260 nm was measured. The absorbance of the obtained 9,10-dibutoxyanthracene was 0.700 after storage for 1 day and 0.802 after 5 days.

Evaluation of Migration Resistance of Compositions As is clear by comparing Examples 1 and 2 with Comparative Example 1 of migration resistance of the composition, 9,10-dibutoxy which is a known photopolymerization sensitizer in the composition. Anthracene is transferred to a polyethylene film covered on the composition by 0.400 after storage for one day and 0.464 after storage for five days, whereas the primary hydroxyl group that is the photopolymerization sensitizer of the present invention is used. The 9,10-bis (dihydroxyalkoxy) anthracene compound having a transition to a polyethylene film placed on the composition is 0.01 or less even after storage for 5 days, and it can be said that the migration resistance is extremely excellent. .

Further, as is apparent from comparing Examples 3 and 4 of the composition with respect to migration resistance and Comparative Example 2 with respect to migration resistance of the composition, it is also a known photopolymerization sensitizer in the composition. , 10-dibutoxyanthracene is 0.700 after storage for 1 day and 0.802 after storage for 5 days on the polyethylene film placed on the composition, whereas the photopolymerization sensitizer of the present invention In the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group, migration to a polyethylene film placed on the composition is not observed even after storage for 5 days, and migration resistance is extremely excellent. It can be said.

That is, it can be said that the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is excellent in migration resistance of the composition in both photocationic polymerization and photoradical polymerization.

(Example 1 for evaluating migration resistance of photocured product)
As a cationic photopolymerizable compound, 85 parts by weight of 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P manufactured by Daicel), 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd.) (OXT-101: oxetane alcohol) 15 parts by weight, (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium-hexafluorophosphate (BAS Corporation) as a photopolymerization initiator Manufactured, trade name Irgacure 250) 3.0 parts by weight, and 1 part by weight of 9,10-bis (2,3-dihydroxypropoxy) anthracene synthesized by the same method as in Synthesis Example 1 as a photopolymerization sensitizer Then, a photopolymerizable composition was prepared. The composition thus prepared was applied on a polyester film using a bar coater so that the film thickness was 30 microns. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² .

Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 15 hours, dried, and the UV spectrum of the cured product was measured. The UV absorption intensity at 405 nm due to 9,10-bis (2,3-dihydroxypropoxy) anthracene used as a photopolymerization sensitizer was measured, and 9,10-bis (2,3-dihydroxypropoxy before and after immersion in the solvent. ) The content of anthracene was calculated. As a result, the UV absorption intensity of 9,10-bis (2,3-dihydroxypropoxy) anthracene added as a photopolymerization sensitizer after immersion in the solvent is the same as the UV absorption intensity before immersion in the solvent, and there is no change. It was. That is, it was found that 9,10-bis (2,3-dihydroxypropoxy) anthracene was not eluted after the solvent immersion.

(Example 2 for evaluating migration resistance of photocured product)
As a photopolymerization sensitizer, 2-ethyl-9,10-bis (2,3-dihydroxy) synthesized in the same manner as in Synthesis Example 2 instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene Evaluation of migration resistance of photocured material except that propoxy) anthracene is used, a photopolymerizable composition is prepared in the same manner as in Example 1, and the composition is formed on a polyester film using a bar coater. It applied so that it might become a micron. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 15 hours, dried, and the UV spectrum of the cured product was measured. The UV absorption intensity at 405 nm due to 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene used as a photopolymerization sensitizer was measured, and 2-ethyl-9,10- before and after immersion in the solvent. The content of bis (2,3-dihydroxypropoxy) anthracene was calculated. As a result, the UV absorption intensity of 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene added as a photopolymerization sensitizer after solvent immersion is the same as the UV absorption intensity before solvent immersion, There was no change. That is, it was found that 2-ethyl-9,10-bis (2,3-dihydroxypropoxy) anthracene was not eluted after immersion in the solvent.

(Comparative example 1 for evaluating migration resistance of photocured product)
As a photopolymerization sensitizer, a photocured product is used except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, is used instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene. Migration Resistance Evaluation A photopolymerizable composition was prepared in the same manner as in Example 1, and the composition was applied on a polyester film using a bar coater so that the film thickness was 30 microns. Next, the surface of the polyester film coated with the composition was irradiated with light for 6 minutes using a UV LED manufactured by Foseon. The central wavelength of the irradiation light is 395 nm and the irradiation intensity is 50 mW / cm ² . Next, the photocured product was cut into 2 cm square, dipped in acetone as a solvent at 25 ° C. for 15 hours, dried, and the UV spectrum of the cured product was measured. The UV absorption intensity at 405 nm due to 9,10-dibutoxyanthracene used as the photopolymerization sensitizer was measured, and the content of 9,10-dibutoxyanthracene before and after immersion in the solvent was calculated. As a result, the UV absorption intensity of 9,10-dibutoxyanthracene added as a photopolymerization sensitizer after immersion in the solvent was reduced to 7% before immersion in the solvent. That is, it was found that 93% of 9,10-dibutoxyanthracene was eluted after immersion in the solvent.

As is apparent by comparing Examples 1 and 2 of the photocured product with respect to migration resistance and Comparative Example 1 with respect to the photocured product in terms of migration resistance, the photocured product obtained by polymerizing the photopolymerizable composition is known. When 9,10-dibutoxyanthracene, which is a photopolymerization sensitizer, is eluted in acetone, 9,10-bis (dihydroxyalkoxy) anthracene having a primary hydroxyl group of the present invention is used. When the compound is used as a photopolymerization sensitizer, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group does not elute even when the photocured product is immersed in a solvent for a long time. A 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group, which is an agent, also undergoes a photopolymerization reaction and is produced by the polymerization reaction That is estimated to be incorporated into the polymer resin backbone.

(Sublimation resistance evaluation example 1)
The 9,10-bis (2,3-dihydroxypropoxy) anthracene synthesized in Synthesis Example 1 was heated in a nitrogen atmosphere (flow rate 100 ml / min), and the weight loss was measured by a differential calorimeter (TG / manufactured by Hitachi High-Tech Science Co., Ltd.). DTA7200). As heating conditions, the temperature was raised from room temperature to 180 ° C. (10 ° C./min) and then held for 60 minutes. The weight loss before and after heating was 0.4%.

(Sublimation resistance evaluation comparative example 1)
Evaluation of sublimation resistance was performed in the same manner as in Example 1 except that 9,10-dibutoxyanthracene, which is a known photopolymerization sensitizer, was used instead of 9,10-bis (2,3-dihydroxypropoxy) anthracene. Tested. As a result, the weight loss before and after heating was 12.5%.

As is clear by comparing sublimation resistance evaluation example 1 and sublimation resistance evaluation comparative example 1, 9,10-bis (2,3-dihydroxypropoxy) anthracene of the present invention is a known photopolymerization sensitization. Compared with 9,10-dibutoxyanthracene, which is an agent, the weight loss upon heating is small, indicating that the compound has low sublimation properties, that is, excellent sublimation resistance.

From the above results, the 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group of the present invention is a known photopolymerization sensitizer in 10, 10-dibutoxy in photocationic polymerization and photoradical polymerization. Compared to anthracene compounds, it not only has the same photopolymerization sensitizing ability, but also has a primary hydroxyl group, so it is an excellent compound with high migration resistance and sublimation resistance, and is extremely useful as a photopolymerization sensitizer. It turns out to be a useful compound.

Claims (12)

A 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

(In General Formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring, X and Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or Represents a halogen atom.) In the general formula (1), R ¹ is a hydrogen atom, and R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring. The 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group according to claim 1. A 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

(In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.) A primary hydroxyl group represented by the general formula (1), wherein a 9,10-dihydroxyanthracene compound represented by the following general formula (3) is reacted with a glycidol compound represented by the general formula (4): Of a 9,10-bis (dihydroxyalkoxy) anthracene compound having:

(In general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)

(In General Formula (4), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; The group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring.)

(In General Formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring, X and Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or Represents a halogen atom.) A primary hydroxyl group represented by the general formula (2) is produced by reacting a 9,10-dihydroxyanthracene compound represented by the following general formula (3) with a glycidol represented by the structural formula (5). A process for producing a 9,10-bis (dihydroxyalkoxy) anthracene compound.

(In general formula (3), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.)


(In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.) A photopolymerization sensitizer containing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (1).

(In General Formula (1), n represents an integer of 0 to 10, R ¹ and R ² may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a benzene ring or a naphthalene ring, X and Y may be the same or different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or Represents a halogen atom.) A photopolymerization sensitizer containing a 9,10-bis (dihydroxyalkoxy) anthracene compound having a primary hydroxyl group represented by the following general formula (2).

(In the general formula (2), X and Y may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom.) A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 6 or 7 and a photopolymerization initiator. A photopolymerizable composition comprising the photopolymerization initiator composition according to claim 8 and a photocationically polymerizable compound. The photopolymerization composition containing the photoinitiator composition of Claim 8, and a radical photopolymerizable compound. The polymerization method which superposes | polymerizes the photopolymerizable composition of Claim 9 or Claim 10 by irradiating the energy ray containing the light of the wavelength range of 300 nm to 500 nm. 12. The polymerization method according to claim 11, wherein the irradiation source of the energy ray containing light in the wavelength range of 300 nm to 500 nm is an ultraviolet LED having a center wavelength of 365 nm, 375 nm, 385 nm, 395 nm, or 405 nm.