JP2010006719A - 1,4-naphthalene diether derivative and its production method and photopolymerizable composition containing the 1,4-naphthalene diether derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new photopolymerization sensitizer and a new photopolymerizable composition excellent in sublimation resistance. <P>SOLUTION: There is the 1,4-naphthalene diether derivative of general formula (1) (wherein, one of Z<SP>1</SP>and Z<SP>2</SP>is H, and the other is (meth)acryloyl group; R<SP>1</SP>is an alkyl group which may have a substitutent; X and Y may be each identically or differently H, an alkyl group, or the like). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a 1,4-naphthalenediether derivative and a method for producing the same. Specifically, the present invention relates to a photopolymerization sensitizer and a photopolymerizable composition excellent in sublimation resistance in photopolymerization using active energy rays such as ultraviolet rays or visible rays.

  Photo-curing resins that are polymerized by active energy rays such as ultraviolet rays and visible rays cure quickly and can greatly reduce the amount of organic solvent used compared to thermosetting resins. It is excellent in terms of reduction and is widely used for paints, inks, adhesives, coating agents, and the like. Conventional photocurable resins themselves have a poor polymerization initiating function, and it is usually necessary to use a photopolymerization initiator when curing. However, the onium salt generally used for the photopolymerization initiator has its own light absorption in the vicinity of 225 nm to 350 nm, and does not absorb at 350 nm or more. Therefore, when a medium pressure or high pressure mercury lamp or the like is used as a light source, there is a problem that the photocuring reaction is difficult to proceed, and a photopolymerization sensitizer is generally added as necessary. Examples of the photopolymerization initiator include benzyl ketals, hydroxyacetophenones, aminoacetophenones, benzophenones, benzoin ethers, halogenobisimidazoles, and halogenotriazines. Anthracene, phenothiazine and perylene compounds are known as photopolymerization sensitizers. In particular, 4-alkoxy-1-naphthol, 9,10-dialkoxyanthracene (Patent Document 1), 1,4-diethoxynaphthalene (Patent Document 2) and the like are preferable.

  However, since these photopolymerization initiators and photopolymerization sensitizers have a low molecular weight, the photopolymerization initiators and photopolymerization sensitizers or their decomposition products sublimate or volatilize when irradiated with light. There is a problem. In particular, since the photopolymerization sensitizer remains in the cured product with a low molecular weight after curing, sublimation and scattering from the cured product are problematic. Accordingly, there is a need for photopolymerization sensitizers and photopolymerizable compositions that have low sublimation properties.

  The present inventors have already proposed a 4-alkoxy-1- (2- (meth) acryloyloxyalkoxy) naphthalene compound as a photopolymerization sensitizer that has improved the problem of sublimation (Patent Document 3). However, the compounds of the present invention have further improved sublimation resistance.

JP-A-11-263804 JP 2007-126612 A JP 2008-1640 A

  Accordingly, an object of the present invention is to provide a novel photopolymerization sensitizer and photopolymerizable composition excellent in sublimation resistance.

  As a result of intensive studies to solve the above problems, it was found that the 1,4-naphthalene diether derivative of the present invention was excellent in photopolymerization sensitization performance and excellent in sublimation resistance, and the present invention was completed. It was.

That is, the first gist of the present invention resides in a 1,4-naphthalenediether derivative represented by the following general formula (1).

(In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, and R ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group. An alkyl group which may have one or two or more substituents selected from a group, and X and Y may be the same or different; a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Indicates an aryloxy group or an arylthio group.)

The second gist of the present invention is a 1,4-naphthalenediether derivative in which, in the general formula (1), Z ¹ is a hydrogen atom and Z ² is a (meth) acryloyl group, that is, the following general formula (4) It exists in the 1, 4- naphthalene diether derivative shown by these.

(In the general formula (4), R ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, one or an alkyl group which may have two or more substituents selected from aryl and aryloxy group, R ² Represents a hydrogen atom or a methyl group, and X and Y may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

The third gist of the present invention is a 1,4-naphthalenediether derivative in which, in the general formula (1), Z ¹ is a (meth) acryloyl group and Z ² is a hydrogen atom, that is, the following general formula (5) It exists in the 1, 4- naphthalene diether derivative shown by these.

(In the general formula (5), R ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, one or an alkyl group which may have two or more substituents selected from aryl and aryloxy group, R ² Represents a hydrogen atom or a methyl group, and X and Y may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

According to a fourth aspect of the present invention, the general formula (1) is obtained by reacting a 4-substituted-1-glycidyloxynaphthalene derivative represented by the following general formula (2) with acrylic acid or methacrylic acid. In the production method of a 1,4-naphthalenediether derivative represented by the formula:

In the general formula (2), R ¹ represents an alkyl group which may have one or two or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group and an aryloxy group, and X and Y May be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

The fifth gist of the present invention is represented by the general formula (1), characterized in that a 4-substituted-1-naphthol derivative represented by the following general formula (3) is reacted with glycidyl acrylate or glycidyl methacrylate. In the production method of 1,4-naphthalene diether derivative.

In the general formula (3), R ¹ represents an alkyl group which may have one or two or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group and an aryloxy group, and X and Y May be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

The sixth gist of the present invention resides in a photopolymerization sensitizer containing at least a 1,4-naphthalenediether derivative represented by the general formula (1) as an active ingredient.

The seventh gist of the present invention resides in a photopolymerization initiator composition containing the photopolymerization sensitizer and a photopolymerization initiator.

The eighth gist of the present invention resides in a photopolymerization initiator composition in which the photopolymerization initiator is an onium salt.

The ninth gist of the present invention resides in a photopolymerizable composition containing the photopolymerization initiator composition and a cationic polymerizable compound and / or a radical polymerizable compound.

A tenth aspect of the present invention resides in a photopolymerizable composition containing a 1,4-naphthalenediether derivative represented by the general formula (1) as a photopolymerization initiator and a radical polymerizable compound.

The eleventh aspect of the present invention includes a 1,4-naphthalene diether derivative represented by the general formula (1) as a photopolymerization initiator and a radical polymerizable compound, and further the 1,4-naphthalene diether derivative. It exists in the photopolymerizable composition containing radically polymerizable compounds other than.

The twelfth aspect of the present invention resides in a curing method characterized by curing the photopolymerizable composition according to any one of the ninth to eleventh aspects by irradiation with active energy rays.

The thirteenth aspect of the present invention resides in a cured product obtained by curing the photopolymerizable composition according to any one of the ninth to eleventh aspects by irradiation with active energy rays.

In the description of the present invention, (meth) acryloyl represents acryloyl or methacryloyl.

According to the present invention, a novel 1,4-naphthalenediether derivative and an industrially advantageous production method thereof can be provided. This novel 1,4-naphthalenediether derivative has a sensitizing action for photopolymerization and can be used as a photopolymerization sensitizer and a photopolymerizable composition having excellent sublimation resistance due to its structure.

Hereinafter, the present invention will be described in detail. The 1,4-naphthalenediether derivative of the present invention is represented by the following general formula (1).

In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, and R ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group. Represents an alkyl group which may have one or two or more substituents selected from: X and Y may be the same or different, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl It represents either an oxy group or an arylthio group.

Examples of the alkyl group having no substituent represented by R ¹ in the general formula (1) include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s -Butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group and the like.

Examples of the alkyl group having a halogen atom represented by R ¹ in the general formula (1) include a fluoromethyl group, a 1-fluoroethyl group, a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, and a 3-chloropropyl group. 2-chloropropyl group, 4-chlorobutyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 3-bromopropyl group, 2-bromopropyl group, 4-bromobutyl group, iodomethyl group, 1-iodoethyl group, etc. Is mentioned. Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 4-hydroxybutyl group. Examples of the alkyl group having an alkoxy group include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, s-butoxymethyl group, i-butoxymethyl group, methoxyethyl and the like. Ethoxyethyl group, n-propoxyethyl group, i-propoxyethyl group, n-butoxyethyl group, s-butoxyethyl group, i-butoxyethyl group, t-butoxyethyl group and the like. Examples of the alkyl group having an aryl group include phenylmethyl group, tolylmethyl group, naphthylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-tolylethyl group, 2-tolylethyl group, 1-α-naphthylethyl group, Examples include 2-α-naphthylethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, and the like. Examples of the alkyl group having an aryloxy group include phenyloxymethyl group, tolyloxymethyl group, naphthyloxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 1-tolyloxyethyl group, 2-tolyloxy group Examples include an ethyl group, 1-α-naphthyloxyethyl group, 2-α-naphthyloxyethyl group, 1-β-naphthyloxyethyl group, 2-β-naphthyloxyethyl group, and the like.

R ¹ may be an aryl group in addition to the above alkyl group. The aryl group includes a phenyl group, p-chlorophenyl group, p-methylphenyl group, p-methoxyphenyl group, m-chlorophenyl group, m-methylphenyl group, m-methoxyphenyl group, 1-naphthyl group, 2-naphthyl group. Groups and the like.

Examples of the halogen atom represented by X and Y in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the alkyl group includes a methyl group, an ethyl group, an n-propyl group, i. -Propyl group, n-butyl group, i-butyl group, s-butyl group, n-amyl group, i-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl Group, decyl group, dodecyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and a hexyloxy group. Examples of the aryloxy group include a phenoxy group, a p-methylphenoxy group, and a 1-naphthyloxy group. Examples of the arylthio group include a phenylthio group and a 1-naphthylthio group.

In the general formula (1), when Z ¹ is a hydrogen atom and Z ² is a (meth) acryloyl group, a compound of the general formula (4) is obtained.

In the general formula (4), R ¹ represents an alkyl group or an alkyl group containing a halogen atom, a hydroxyl group, an alkoxy group, an aryl group or an aryloxy group, R ² represents a hydrogen atom or a methyl group, and X and Y are They may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

In general formula (4), the alkyl group, halogen atom, alkoxy group, aryl group, aryloxy group, halogen atom represented by X and Y, alkyl group, alkoxy group, aryloxy group, arylthio group represented by R ¹ are: The same as in the general formula (1).

In the general formula (1) is Z ¹ is (meth) acryloyl group, if Z ² is a hydrogen atom, a compound of the general formula (5).

In the general formula (5), R ¹ represents an alkyl group or an alkyl group including a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group, R ² represents a hydrogen atom or a methyl group, and X and Y are They may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an arylthio group.

In general formula (5), the alkyl group, halogen atom, alkoxy group, aryl group, aryloxy group, halogen atom represented by X and Y, alkyl group, alkoxy group, aryloxy group, and arylthio group represented by R ¹ are: The same as in the general formula (1).

Specific examples of the 1,4-naphthalenediether derivative represented by the general formula (4) include the following. That is, 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4-ethoxy-1- (2-hydroxy -3-acryloyloxypropoxy) naphthalene, 4-ethoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4-propoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-propoxy -1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4-butoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-butoxy-1- (2-hydroxy-3-methacryloyloxy) Propoxy) Phthalene, 4-hydroxymethoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-hydroxymethoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4- (2-hydroxyethoxy) -1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4- (2-hydroxyethoxy) -1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4- (3-hydroxypropoxy) -1 -(2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4- (3-hydroxypropoxy) -1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4- (4-hydroxybutoxy) -1- ( 2-hydroxy-3-a Liloyloxypropoxy) naphthalene, 4- (4-hydroxybutoxy) -1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4-methoxymethoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene 4-methoxymethoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene, 4-ethoxymethoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-benzyloxy-1- (2 -Hydroxy-3-acryloyloxypropoxy) naphthalene, 4- (2-methylbenzyloxy) -1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene, 4-naphthylmethyloxy-1- (2-hydroxy-3) -Acryloyl And oxypropoxy) naphthalene.

Specific examples of the 1,4-naphthalenediether derivative represented by the general formula (5) include the following. That is, 4-methoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-methoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4-ethoxy-1- (3-hydroxy 2-acryloyloxypropoxy) naphthalene, 4-ethoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4-propoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-propoxy -1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4-butoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-butoxy-1- (3-hydroxy-2-methacryloyloxy) Propoxy) Phthalene, 4-hydroxymethoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-hydroxymethoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4- (2-hydroxyethoxy) -1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4- (2-hydroxyethoxy) -1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4- (3-hydroxypropoxy) -1 -(3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4- (3-hydroxypropoxy) -1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4- (4-hydroxybutoxy) -1- ( 3-hydroxy-2-a Liloyloxypropoxy) naphthalene, 4- (4-hydroxybutoxy) -1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4-methoxymethoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene 4-methoxymethoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene, 4-ethoxymethoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-benzyloxy-1- (3 -Hydroxy-2-acryloyloxypropoxy) naphthalene, 4- (2-methylbenzyloxy) -1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene, 4-naphthylmethyloxy-1- (3-hydroxy-2 -Acryloyl And oxypropoxy) naphthalene.

In the 1,4-naphthalene diether derivative of the present invention, the 1,4-naphthalene diether skeleton containing the acryloyloxy group is excellent in sublimation resistance, and the bond connecting the naphthalene ring and the acryloyloxy group is a hydroxy group. It has been found that the use of a propyl group having a higher sublimation resistance can be achieved by improving compatibility with peripheral compounds in a photopolymerizable composition and a cured product obtained by curing the photopolymerizable composition. It is a thing.

<Method for producing 1,4-naphthalene diether derivative>
Next, the manufacturing method of the 1, 4- naphthalene diether derivative shown by General formula (1) of this invention is demonstrated. The 1,4-naphthalenediether derivative represented by the general formula (1) of the present invention has two kinds of production methods. That is, the 4-substituted-1-naphthol derivative represented by the general formula (3) is glycidylated to form a 4-substituted-1-glycidyloxynaphthalene derivative represented by the general formula (2), and then acrylated or methacrylated. It is a step production method and a one step production method obtained by reacting a 4-substituted-1-naphthol derivative represented by the general formula (3) with glycidyl acrylate or glycidyl methacrylate.

First, the two-stage manufacturing method will be described. A first reaction in which a 4-substituted-1-naphthol derivative represented by the general formula (3) is glycidylated to obtain a 4-substituted-1-glycidyloxynaphthalene derivative represented by the general formula (2), and the 4-substituted- A 1,4-naphthalene diether derivative represented by the general formula (4) and a 1,4-naphthalene diether represented by the general formula (5) by reacting a 1-glycidyloxynaphthalene derivative with acrylic acid or methacrylic acid It consists of a second reaction to obtain a derivative. The 1,4-naphthalene diether derivative represented by the general formula (4) and the 1,4-naphthalene diether derivative represented by the general formula (5) are in a structural isomer relationship. In the second reaction, when acrylic acid or methacrylic acid reacts with the epoxy ring of the glycidyl group of the 4-substituted-1-glycidyloxynaphthalene derivative, the general formula (4) or Equation (5) is generated.

First, the first reaction will be described. The 4-substituted-1-glycidyloxynaphthalene derivative can be obtained by glycidylating the 4-substituted-1-naphthol derivative with epihalohydrin in the presence of a basic compound and using a catalyst as necessary.

Specific examples of the 4-substituted-1-naphthol derivative include the following compounds. That is, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hydroxymethoxy-1-naphthol, 4- (2-hydroxyethoxy ) -1-naphthol, 4- (3-hydroxypropoxy) -1-naphthol, 4- (4-hydroxybutoxy) -1-naphthol, 4-methoxymethoxy-1-naphthol, 4-ethoxymethoxy-1-naphthol, 4-Benzyloxy-1-naphthol, 4- (2-methylbenzyloxy) -1-naphthol, 4-naphthylmethyloxy-1-naphthol and the like can be mentioned.

The first reaction is carried out by a known method such as the non-patent document Arch. Pharm. (Weinheim) 314, p432-435 (1981).

Examples of the epihalohydrin compound that can be used include epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferably used because it is easily available. The amount of epihalohydrin used is in the range of 3 to 8 moles per mole of 4-substituted-1-naphthol derivative. When the amount is less than 3 moles, an unreacted 4-substituted-1-naphthol derivative remains. On the other hand, when the amount is more than 8 moles, removal of unreacted epihalohydrin takes time and is inefficient.

In the first reaction, a basic compound is used as a dehydrohalogenating agent. Examples of basic compounds that can be used include organic bases such as trimethylamine, triethylamine, tripropylamine, tributylamine, diethylamine, dibutylamine, piperidine, pyridine, α-picoline, γ-picoline, sodium hydroxide, potassium hydroxide. And inorganic bases such as lithium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate. Among these, it is preferable to use sodium hydroxide or potassium hydroxide because it is easily available.

The amount of these basic compounds used relative to the 4-substituted-1-naphthol derivative is preferably in the range of 2 to 9 mol times. When the amount is less than 2 moles, the 4-substituted-1-naphthol derivative remains unreacted, whereas when the amount of the basic compound is too large, epihalohydrin or epoxy group polymerization or cleavage occurs, resulting in rapid heat generation during the reaction. This is not preferable because it causes a decrease in the purity of the 4-substituted-1-glycidyloxynaphthalene derivative.

In the first reaction, a solvent is usually used. Examples of the solvent that can be used include water, alcohol solvents, ketone solvents, ether solvents, aprotic polar solvents, and halogen solvents. Examples of alcohol solvents include ethanol and 2-propanol, ketone solvents include acetone and methyl isobutyl ketone, ether solvents include dioxane and tetrahydrofuran, and aprotic polar solvents include dimethylformamide, N- Examples of halogen solvents such as methylpyrrolidone include chloroform and dichloromethane. You may use these solvents individually or in combination of 2 or more types. Moreover, the epihalohydrin compound which is a glycidylating agent can also be used as a solvent.

In the first reaction, a catalyst is used as necessary. Catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride and tetrabutylammonium bromide, tertiary amines such as triethylamine and benzyldimethylamine, imidazoles such as 2-phenylimidazole, and phosphines such as triphenylphosphine. Etc.

Next, reaction conditions for the first reaction will be described. The reaction temperature of the first reaction is usually carried out below the boiling point of the solvent or epihalohydrin. For example, when epichlorohydrin is used in the first reaction, the temperature is in the range of 10 to 100 ° C. When an aqueous solution of an inorganic base is added as the dehydrohalogenating agent described above, it is preferable to add epihalohydrin continuously or intermittently in small portions over 1 to 8 hours in order to prevent rapid reaction.

In the first reaction, the inside of the reaction vessel is preferably replaced with an inert gas as necessary. Examples of the inert gas that can be used include nitrogen and argon, and it is preferable to perform the first reaction in the presence of the inert gas. The molecular oxygen concentration inside the reaction vessel is not particularly limited, but is preferably 2% by volume or less.

After completion of the first reaction, the basic compound and by-product salt are removed by washing with water and / or filtered. Subsequently, the 4-substituted-glycidyloxynaphthalene derivative can be obtained by removing the solvent and unreacted epihalohydrin by distilling off under reduced pressure. The obtained 4-substituted-glycidyloxynaphthalene derivative may be separated and purified by silica gel column chromatography, if necessary. The 4-substituted glycidyloxynaphthalene derivative obtained in the first reaction is subjected to the next second reaction.

Next, the second reaction will be described. In the second reaction, the 4-substituted glycidyloxynaphthalene derivative obtained in the first reaction and acrylic acid or methacrylic acid are added in the presence of an esterification catalyst in a solvent. In the second reaction, two types of structural isomers are generated depending on the position where acrylic acid or methacrylic acid is added to the glycidyl group. That is, a 4-substituted-1- {2-hydroxy-3- (meth) acryloyloxypropoxy} naphthalene derivative which is a 1,4-naphthalenediether derivative represented by the following general formula (4), and a general formula (5 Two structural isomers of a 4-substituted-1- {3-hydroxy-2- (meth) acryloyloxypropoxy} naphthalene derivative, which is a 1,4-naphthalenediether derivative shown in FIG.

In the general formula (4), R ¹ represents an alkyl group or an alkyl group containing one or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group, and R ² represents a hydrogen atom Represents an atom or a methyl group, and X and Y may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an arylthio group;

In the general formula (5), R ¹ represents an alkyl group or an alkyl group containing one or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group, and R ² represents hydrogen. Represents an atom or a methyl group, and X and Y may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an arylthio group;

Although it depends on the reaction conditions, in general, two types of 1,4-naphthalene diether derivatives represented by the general formula (4) and 1,4-naphthalene diether derivatives represented by the general formula (5) by the second reaction are used. Structural isomers are obtained as a mixture. These structural isomers can be isolated by separation and purification using silica gel column chromatography or the like. These structural isomers can be used in the photopolymerizable composition of the present invention, which will be described later, in the form of a mixture or separated and purified to be any single compound.

Specific examples of the 4-substituted glycidyloxynaphthalene derivative represented by the general formula (2) include the following compounds. That is, 4-methoxy-1-glycidyloxynaphthalene, 4-ethoxy-1-glycidyloxynaphthalene, 4-propoxy-1-glycidyloxynaphthalene, 4-butoxy-1-glycidyloxynaphthalene, 4-hydroxymethoxy-1-glycidyl Oxynaphthalene, 4- (2-hydroxyethoxy) -1-glycidyloxynaphthalene, 4- (3-hydroxypropoxy) -1-glycidyloxynaphthalene, 4- (4-hydroxybutoxy) -1-glycidyloxynaphthalene, 4- Methoxymethoxy-1-glycidyloxynaphthalene, 4-ethoxymethoxy-1-glycidyloxynaphthalene, 4-benzyloxy-1-glycidyloxynaphthalene, 4- (2-methylbenzyloxy) -1-glycidyloxynaphtha Emissions, 4-naphthylmethyl-1- glycidyloxy naphthalene.

In the second reaction, the amount of acrylic acid or methacrylic acid to be used with respect to the 4-substituted-glycidyloxynaphthalene derivative is 1 to 5 mol times, preferably 1.5 to 3.0 mol times. If the amount of acrylic acid or methacrylic acid used is less than 1 mol, unreacted 4-substituted-glycidyloxynaphthalene derivative remains, whereas if it exceeds 5 mol, a copolymer of acrylic acid or methacrylic acid is produced. However, the purity of the target product is undesirably lowered.

The solvent to be used may be any one that does not react with a 4-substituted glycidyloxynaphthalene derivative and acrylic acid or methacrylic acid, such as benzene, toluene, o-xylene, m-xylene, ethylbenzene, i-propylbenzene, chlorobenzene. , Aromatic solvents such as o-chlorobenzene, methylnaphthalene, chloronaphthalene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, methylpyrrolidone, dimethylformamide, dimethylacetamide Amide solvents such as tetrahydrofuran, ether solvents such as 1,4-dioxane, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. The amount of the solvent used may be an amount that can dissolve the 4-substituted-glycidyloxynaphthalene derivative.

Although it does not specifically limit in a 2nd reaction, It is preferable to use an esterification catalyst normally. Specific examples of the esterification catalyst include triethylamine, N, N-dimethylaniline, benzyldimethylamine, triethanolamine, tributylamine, dimethyllaurylamine, tripropylamine, hexamethylenediamine, dimethylaminomethylphenol, α-methylbenzyl. Tertiary amines such as dimethylamine, quaternary amines such as tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, trimethyldodecylammonium chloride, trimethylammonium chloride, triethylammonium chloride, formamide, N-methylformamide, N-ethylformamide, acetamide, benzamide, N, N-dimethylformamide, N, N-dimethylacrylic Amides such as amides, imidazoles such as 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-5-methylimidazole Pyridines such as pyridine, pyridine hydrochloride, vinylpyridine, p-dimethylaminopyridine, γ-picoline, triphenylphosphine, tri (2-methylphenyl) phosphine, tri (3-methylphenyl) phosphine, tri (4 -Phosphines such as methylphenyl) phosphine, triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, trimethylphenylphosphonium bromide, trimethylbenzylphosphonium bromide, tributylphosphonium bromide Phosphonium salts such as de, triphenylsulfonium chloride, trimethylsulfonium chloride, sulfonium salt such as dimethyl phenyl sulfonium chloride. Of these, quaternary ammonium salts or quaternary phosphonium salts are preferable, and specifically, tetrabutylammonium bromide or tetrabutylphosphonium bromide is preferable. Such esterification catalysts may be used alone or in combination of two or more.

The usage-amount of an esterification catalyst is 0.005-0.5 mol with respect to 1 mol of 4-substituted- glycidyl oxynaphthalene derivatives, Preferably it is 0.01-0.3 mol. If the amount is less than 0.005 mol, the esterification reaction is insufficient and an unreacted 4-substituted-glycidyloxynaphthalene derivative remains. On the other hand, if the amount exceeds 0.5 mol, the cost is undesirable.

The reaction temperature of the second reaction is in the range of 50 to 150 ° C, preferably in the range of 70 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction takes too much time. On the other hand, if the reaction temperature is higher than 150 ° C., acrylic acid or methacrylic acid is polymerized to lower the purity and yield of the desired product, which is not preferable.

In the second reaction, a polymerization inhibitor may be present to prevent polymerization of acrylic acid or methacrylic acid or the reaction product. As the polymerization inhibitor, 4-methoxyphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like are used. The addition amount of the polymerization inhibitor is preferably 0.05 to 5% by weight based on acrylic acid or methacrylic acid.

Although 2nd reaction is not specifically limited, It is preferable to carry out in the range of atmospheric pressure-3 atmospheres. Usually reacts under atmospheric pressure.

Next, the one-stage manufacturing method will be described. The one-step production method is a method for producing a 1,4-naphthalenediether derivative by reacting the 4-substituted-1-naphthol derivative represented by the general formula (3) with glycidyl acrylate or glycidyl methacrylate. The 4-substituted-1-naphthol derivative used as a raw material is the same as the 4-substituted-1-naphthol derivative used in the first reaction in the two-stage production method described above.

Glycidyl acrylate or glycidyl methacrylate is used in an amount of 1 to 5 moles, preferably 1.5 to 3 moles per mole of the 4-substituted-1-naphthol derivative. If the amount of glycidyl acrylate or glycidyl methacrylate used is less than 1 mole, unreacted 4-substituted naphthol derivative remains, whereas if it exceeds 5 moles, a copolymer of glycidyl acrylate or glycidyl methacrylate is formed. The purity of the target product is lowered, which is not preferable.

In the method for producing a 1,4-naphthalenediether derivative by reacting a 4-substituted-1-naphthol derivative with glycidyl acrylate or glycidyl methacrylate, an etherification catalyst is used as necessary. Catalysts that can be used are tertiary amines, quaternary amines, amides, imidazoles, phosphines, phosphonium salts, sulfonium salts, etc., and 4-substituted-1-glycidyloxynaphthalene derivatives and acrylic acid or methacrylic acid. The same compounds as the esterification catalyst exemplified in the reaction with can be used.

The amount of the etherification catalyst used is 0.005 to 0.5 mol, preferably 0.01 to 0.3 mol, per 1 mol of the 4-substituted-1-naphthol derivative. When the amount is less than 0.005 mol, the etherification reaction is insufficient and an unreacted 4-substituted naphthol derivative remains. On the other hand, when the amount exceeds 0.5 mol, the cost is undesirable.

Solvent to be used in the method for producing the 1,4-naphthalenediether derivative represented by the general formula (4) or the general formula (5) by reacting a 4-substituted-1-naphthol derivative with glycidyl acrylate or glycidyl methacrylate. As long as it does not react with glycidyl acrylate or glycidyl methacrylate, for example, benzene, toluene, o-xylene, m-xylene, ethylbenzene, i-propylbenzene, chlorobenzene, o-chlorobenzene, methylnaphthalene, chloronaphthalene, etc. Aromatic solvents, halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, amide solvents such as methylpyrrolidone, dimethylformamide, dimethylacetamide, tetra Dorofuran, ether solvents 1,4-dioxane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. The amount of the solvent used may be an amount that can dissolve the 4-substituted naphthol derivative.

The reaction temperature in the reaction between the 4-substituted-1-naphthol derivative and glycidyl acrylate or glycidyl methacrylate is in the range of 50 to 150 ° C, preferably in the range of 70 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction takes too much time. On the other hand, if the reaction temperature is higher than 150 ° C., glycidyl acrylate or glycidyl methacrylate is polymerized to lower the purity and yield of the desired product, which is not preferable.

The reaction pressure in the reaction between the 4-substituted-1-naphthol derivative and glycidyl acrylate or glycidyl methacrylate is not particularly limited, but it is preferably performed in the range of atmospheric pressure to 3 atmospheric pressure. Usually reacts under atmospheric pressure.

In the reaction, a polymerization inhibitor may be present to prevent the polymerization of glycidyl acrylate or glycidyl methacrylate or the reaction product. As the polymerization inhibitor, 4-methoxyphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like are used. As the addition amount of the polymerization inhibitor, it is preferable to add 0.1 to 5% by weight with respect to glycidyl acrylate or glycidyl methacrylate.

Although it depends on the reaction conditions, in general, a 1,4-naphthalenediether derivative represented by the general formula (4) and a general formula (5) obtained by reacting a 4-substituted-1-naphthol derivative with glycidyl acrylate or glycidyl methacrylate. Two structural isomers of the 1,4-naphthalenediether derivative shown in the above are obtained as a mixture. These structural isomers can be isolated by separation and purification using silica gel column chromatography or the like. These structural isomers can be used in the photopolymerizable composition of the present invention, which will be described later, in the form of a mixture or separated and purified to be any single compound.

The 1,4-naphthalenediether derivative represented by the general formula (1) of the present invention that can be produced by the two-stage production method and the one-step production method, specifically, the general formula of the present invention. The 1,4-naphthalenediether derivative represented by (4) and general formula (5) can be used as a photopolymerization sensitizer as a single compound as a mixture or separated and purified as a radically polymerizable compound. It can also be used.

A photopolymerization initiator composition can be prepared by blending the 1,4-naphthalene diether derivative with a photopolymerization initiator as a photopolymerization sensitizer. And a photopolymerizable composition can be adjusted by mix | blending the said photoinitiator composition, a cationically polymerizable compound, and / or a radically polymerizable compound.

On the other hand, a photopolymerizable composition can also be prepared by blending the 1,4-naphthalene diether derivative as a radical polymerizable compound with a photopolymerization initiator. Moreover, a photopolymerizable composition can be prepared by mix | blending radical polymerizable compounds other than the said 1, 4- naphthalene diether derivative with this photopolymerizable composition.

In a photopolymerizable composition prepared by using a 1,4-naphthalene diether derivative as a radical polymerizable compound, the 1,4-naphthalene diether derivative undergoes a radical polymerization reaction to produce a cured product. Depending on the conditions, the compound itself acts as a sensitizer and also transmits the irradiated light energy to the photopolymerization initiator.

<Photopolymerization initiator composition using 1,4-naphthalene diether derivative as a photopolymerization sensitizer>
The photopolymerization initiator composition of the present invention comprises a 1,4-naphthalenediether derivative represented by the general formula (1) and a photopolymerization initiator as a photopolymerization sensitizer. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Acetophenones; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropyl Thioxanthones such as oxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2- (4-methoxyphenyl) -4,6-bis- (trichloro Halogenated hydrocarbon derivatives such as methyl) -1,3,5-triazine, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole Hexaarylbi Imidazole compounds, and the like. Photopolymerization initiators introduced in publicly known documents such as Journal of Organic Synthetic Chemistry 66,458 (2008) can also be used. Specifically, from the market, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals, Irgacure is a registered trademark of Ciba Specialty Chemicals), (2-methyl-1- (4- (methylthio)) Phenyl) -2- (4-morpholinyl) -1-propanone) (Irgacure 907), acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide (Irgacure 819); η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784), 2,4,6-trimethylbenzoyl -Diphenylphosphine oxide (BASF Titanocene compounds such as lucillin TPO, lucillin is a registered trademark of BASF), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (DAROCUR TRO manufactured by Ciba Specialty Chemicals); 6,12-bis (trimethylsilyloxy)- A naphthacene quinone compound such as 1,11-naphthacene quinone can be easily obtained.

An onium salt can also be used. Examples of onium salts include iodonium salts, sulfonium salts, ammonium salts, phosphonium salts, and the like.

Examples of the iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodoniumtetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium Hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4- Methylphenyl-4- (1-methylethyl) phenyliodonium Hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, 4-methyl Phenyl-4-isobutylphenyliodonium hexafluorophosphate, 4-methylphenyl-4-isobutylphenyliodonium hexafluoroantimonate, 4-methylphenyl-4-isobutylphenyliodonium tetrafluoroborate, 4-methylphenyl-4-isobutylphenyliodonium Examples include tetrakis (pentafluorophenyl) borate.

Examples of the sulfonium salt include S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium, bishexafluorophosphate, diphenyl-4-phenylthiophenylsulfonium hexa Examples thereof include fluorophosphate and triphenylsulfonium hexafluorophosphate.

Examples of ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, 1-naphthylmethyl-2-cyanopyridinium hexafluorophosphate, 1-naphthylmethyl-2-cyanopyridinium hexafluoroantimonate, 1-naphthylmethyl-2-cyanopyridinium tetrafluoroborate, 1- And naphthylmethyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate.

Examples of phosphonium salts include tetraphenylphosphonium hexafluorophosphate, tetraphenylphosphonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzyltriphenylphosphonium hexafluoroantimonate, p-methylbenzyl-triphenylphosphonium hexafluorophosphate, p -Methylbenzyl-triphenylphosphonium hexafluoroantimonate, p-methoxybenzyl-triphenylphosphonium hexafluorophosphate, p-methoxybenzyl-triphenylphosphonium hexafluoroantimonate and the like.

These photopolymerization initiators may be used alone or in admixture of two or more.

Among these initiators, halogenated hydrocarbon derivatives, hexaarylbiimidazoles and onium salts are preferable because the sensitizing effect of the 1,4-naphthalenediether derivative of the present invention is large, and among them, onium salts are particularly preferable. . Among the onium salts, the iodonium salt is preferable because it is easily available, and 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (Irgacure 250 manufactured by Ciba Specialty Chemicals) is particularly preferable.

Although the sensitization mechanism of the photopolymerization sensitizer of the present invention is not clear, the photopolymerizable composition containing the photopolymerization sensitizer and the photopolymerization initiator is irradiated with active energy rays such as ultraviolet rays or visible rays. Thus, it is considered that the photopolymerization sensitizer is excited and the excited photopolymerization sensitizer forms a complex with the ground-state photopolymerization initiator. By this complex formation, electron transfer occurs from the photopolymerization sensitizer to the photopolymerization initiator, the photopolymerization initiator is decomposed to generate an acid or a radical species, and polymerization is considered to be initiated by this acid or radical species.

The amount used when the 1,4-naphthalenediether derivative represented by the general formula (1) is used as a photopolymerization sensitizer is not particularly limited, but is usually 0.01 to 2 with respect to the photopolymerization initiator. The range is 0.0% by weight, preferably 0.1 to 1.0% by weight. If the amount of the photopolymerization sensitizer used is too small, it takes too much time to photopolymerize the photopolymerizable compound, which is not preferable.

<Photopolymerizable composition containing a photopolymerization initiator composition using a 1,4-naphthalene diether derivative as a photopolymerization sensitizer>
The photopolymerizable composition of the present invention contains the above-mentioned photopolymerization initiator composition, a cationic polymerizable compound and / or a radical polymerizable compound.

Examples of the cationic polymerizable compound include alicyclic epoxy compounds, epoxy-modified silicones, epoxy compounds such as aromatic glycidyl ether, vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and 2-ethylhexyl vinyl ether. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) adipate, and the like. Examples of commercially available products include trade names: UVR6105, UVR6110, manufactured by The Dow Chemical Company. Examples of the epoxy-modified silicone include a product name: UV-9300 manufactured by GE Toshiba Silicone Co., Ltd. These cationically polymerizable compounds may be used singly or as a mixture of two or more kinds, and may be oligomers thereof.

Examples of the radical polymerizable compound include styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic acid ester, and methacrylic acid ester. Specific examples of (meth) acrylic acid esters include methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate. , Tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate, 1,6-hexanediol diacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate , Polyether acrylate, silicone resin acrylate, imide acrylate, etc., or oligomers thereof. It is. These radically polymerizable compounds or these oligomers may be used alone or as a mixture of two or more.

The usage-amount of the photoinitiator with respect to these cationically polymerizable compounds and / or radically polymerizable compounds is the range of 0.01 to 5.0 weight%, Preferably it is 0.05 to 2.0 weight%. . If it is less than 0.01% by weight, it takes time to photopolymerize the photopolymerizable composition, while if it exceeds 5.0% by weight, the hardness of the cured product obtained by photopolymerization may decrease. This is not preferable because the physical properties of the cured product are deteriorated.

<Photopolymerizable composition using 1,4-naphthalenediether derivative as radical polymerizable compound>
On the other hand, when a 1,4-naphthalene diether derivative is used as a radical polymerizable compound, a radical other than the 1,4-naphthalene diether derivative, a photopolymerization initiator, and, if necessary, a 1,4-naphthalene diether derivative. A photopolymerizable composition can be adjusted with a polymerizable compound. By using a 1,4-naphthalenediether derivative as a radically polymerizable compound, depending on conditions, the compound itself acts as a sensitizer, and serves to transmit irradiated light energy to the photopolymerization initiator.

When the 1,4-naphthalene diether derivative is used as a radically polymerizable compound, not only the sublimation resistance is improved, but also a cured product obtained by curing the photopolymerizable composition is used with a substrate such as a polyester film. It was found that adhesion was improved. The theoretical background is not clear, but it is presumed to be due to the relationship between the generated coating film and the surface free energy of the substrate.

A 1,4-naphthalene diether derivative can be used alone as a radical polymerizable compound, but since the average molecular weight of the photocured product is reduced, it is a mixture with a radical polymerizable compound other than the 1,4-naphthalene diether derivative. It is preferable to use as. The mixing ratio of the radically polymerizable compound other than the 1,4-naphthalene diether derivative and the 1,4-naphthalene diether derivative can be arbitrarily selected, but the ratio of the 1,4-naphthalene diether derivative is 1,4-naphthalene diene. If it exceeds 80% by weight based on the total amount of radically polymerizable compounds other than the ether derivative and 1,4-naphthalenediether derivative, the average molecular weight of the photocured product is decreased, which is not preferable. .

Moreover, in order to acquire the effect which improves adhesiveness with base materials, such as this film, although based also on a base material, the usage-amount of the said 1, 4- naphthalene diether derivative is 1,4- naphthalene diether derivative and It is preferable to use 30% by weight or more, more preferably 50% by weight or more, based on the total amount of radically polymerizable compounds other than 1,4-naphthalene diether derivatives.

As the radical polymerizable compound other than the 1,4-naphthalene diether derivative, a photopolymerizable composition containing a photopolymerization initiator composition using the above-mentioned 1,4-naphthalene diether derivative as a photopolymerization sensitizer. The radically polymerizable compounds mentioned in the adjustment can be used.

In particular, a compound having two or more radical polymerizable groups (polyfunctional radical polymerizable compound) is preferable. That is, a compound that can crosslink radical polymerization with two or more radically polymerizable groups is preferred.

Examples of such polyfunctional radical polymerizable compounds include 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Examples include propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Furthermore, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Monohydroxypenta (meth) acrylate, glycerol di (meth) acrylate, triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl di (meth) acrylate, etc. Also mentioned.

Examples of the photopolymerization initiator that can be used include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 -Dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenones such as 1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxan , Thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone Benzophenones such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2- (4-methoxyphenyl) -4,6 -Halogenated hydrocarbon derivatives such as bis- (trichloromethyl) -1,3,5-triazine, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1, 2'-Bimida Hexaarylbiimidazoles and the like, such Lumpur. Photopolymerization initiators introduced in publicly known documents such as Journal of Organic Synthetic Chemistry 66,458 (2008) can also be used. Specifically, from the market, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals), (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) -1 -Propanone) (Irgacure 907) and acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide (Irgacure 819); bis (η5-2,4-cyclopentadien-1-yl ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO manufactured by BASF), 2 , 4,6-Trimethylbenzoyl-diphenyl Titanocene compounds such as ruphosphine oxide (DAROCUR TRO manufactured by Ciba Specialty Chemicals); naphthacene quinone compounds such as 6,12-bis (trimethylsilyloxy) -1,11-naphthacenequinone and the like can be easily obtained. An onium salt can also be used. Examples of onium salts include iodonium salts, sulfonium salts, ammonium salts, phosphonium salts, and the like. You may use these individually or in mixture of 2 or more types.

The amount of the photopolymerization initiator used is 0.1 to 5.0% by weight based on the total amount of radically polymerizable compounds other than the 1,4-naphthalene diether derivative and 1,4-naphthalene diether derivative of the present invention. The range is preferably 0.2 to 3.0% by weight, more preferably 0.3 to 1.0% by weight. If the amount is less than 0.1% by weight, the polymerization rate is slow and the efficiency is poor.

Photopolymerizable composition containing photopolymerization initiator composition using 1,4-naphthalene diether derivative as photopolymerization sensitizer and photopolymerizable composition using 1,4-naphthalene diether derivative as radical polymerizable compound As long as the effects of the present invention are not impaired, diluents, colorants, organic or inorganic fillers, leveling agents, surfactants, antifoaming agents, thickeners, flame retardants, antioxidants, stabilizers Various resin additives such as lubricants and plasticizers may be blended.

<Method for curing photopolymerizable composition and cured product thereof>
The photopolymerizable composition of the present invention can be formed into a film or sheet and cured, or can be cured in a lump. For example, in the case of curing in the form of a film, the photopolymerizable composition is applied onto a polyester substrate using a bar coater and then cured by irradiation with active energy rays. The active energy ray is preferably ultraviolet rays or visible rays. As the light source, any light source capable of irradiating ultraviolet rays in a wavelength range of 300 to 400 nm may be used. For example, a metal halide lamp, a xenon lamp, an ultraviolet LED, a blue LED, a white LED, a D lamp, a V lamp manufactured by Fusion, etc. be able to. Sunlight can also be used. In particular, a high-pressure mercury lamp that can irradiate ultraviolet rays in a wavelength range of 300 to 400 nm with high output is preferable.

When a radical polymerizable compound is contained in the photopolymerizable composition, it is preferably photocured in the absence of molecular oxygen. That is, in the presence of molecular oxygen, radicals generated by the photopolymerization initiator are trapped by oxygen, and a large amount of photopolymerization initiator must be added to generate further radicals.

As a method for confirming that the photopolymerizable composition is cured when irradiated with light, a method for determining the presence or absence of stickiness on the surface of the cured product with an index finger or the like is generally used. Specifically, the time from the irradiation of the photopolymerizable composition on the surface of the film coated with the photopolymerizable composition until tackiness (stickiness) is taken is measured as the curing time (tack free time).

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the following description examples, unless the meaning is exceeded.

The product was confirmed by measurement using the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer
(4) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000

(Example 1) Glycidylation reaction of 4-methoxy-1-naphthol (first reaction in a two-stage production method)
Under a nitrogen atmosphere, 30.0 g (172 mmol) of 4-methoxy-1-naphthol was added to a reactor equipped with a dropping funnel, a condenser, and a thermometer, and then 63.7 g (688 mmol) of epichlorohydrin, methanol. 24.3 g was added and stirred. At room temperature (20 ° C.), 25.8 g of a 40 wt% aqueous solution of sodium hydroxide was added dropwise over 1 hour. At this time, the temperature in the reactor was controlled so as not to exceed 60 ° C. After further stirring for 1 hour, the mixture was cooled to 20 ° C., 50 g of methyl isobutyl ketone and 30 g of water were added to separate into two layers, the aqueous layer was extracted, and the organic layer was washed with 30 g of water. Methyl isobutyl ketone and unreacted epichlorohydrin in the organic layer were distilled off under reduced pressure to obtain 38.1 g of a brown liquid. 120 g of methanol was added to the brown liquid and stirred, and the mixture was refluxed for 2 hours, and then cooled to 20 ° C. Then, crystals were precipitated, which were filtered and dried to obtain 30.6 g (133 mmol) of silver gray 4-methoxy-1-glycidyloxynaphthalene. The isolation yield was 77.3 mol%.

The obtained silver gray crystal was identified by melting point measurement, ¹ H-NMR, IR spectrum, and Mass spectrum, and confirmed to be 4-methoxy-1-glycidyloxynaphthalene.

Melting point: 119-120 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 0.30 (s, 9H), 7.36-7.43 (m, 4H) 8.14-8.21 (m, 4H).
IR (KBr, cm ⁻¹ ): 3076, 2960, 1384, 1260, 1180, 1080, 880, 840, 762, 703, 652, 515.
Mass spectrum: (EI-MS) m / z = 436 (M ^<+> ).

(Example 2) Methacrylation reaction of 4-methoxy-1-glycidyloxynaphthalene (second reaction of the two-stage production method)
Under a nitrogen stream, 10 g (43.5 mmol) of 4-methoxy-1-glycidyloxynaphthalene synthesized in Example 1 and 7.5 g (87.2 mmol) of methacrylic acid were synthesized in a 300 ml three-necked flask equipped with a stirrer and a thermometer. ), 700 mg of tetrabutylammonium bromide as a catalyst, 7 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter abbreviated as TEMPO) as a polymerization inhibitor, and 50 ml of methyl isobutyl ketone as a solvent Was added. The mixture was heated to 100 ° C. and stirred at 100 ° C. for 3 hours. Thereafter, the reaction solution was cooled to 20 ° C., the reaction solution was extracted with 30 ml of ethyl acetate, and the organic layer (ethyl acetate layer) was washed 3 times with 30 g of a saturated aqueous sodium hydrogen carbonate solution to remove excess methacrylic acid. Next, after the organic layer was washed once with 30 g of water, the organic layer was distilled off with a rotary evaporator to obtain 11.5 g of a brown liquid. As a result of analyzing the purity of this liquid by high performance liquid chromatography, it was found that it had two main peaks and was a mixture of two kinds of compounds. The two kinds of compounds are temporarily called A1 and B1. From the peak area ratio on the chromatogram, Compound A1 was 21.8% by weight, and Compound B1 was 74.7% by weight.

To separate and purify Compound A1 and Compound B1 and identify them, 10 g of toluene and 10 g of n-hexane were added to 11.5 g of the brown liquid obtained in the above reaction to obtain a homogeneous solution, which was cooled to −10 ° C. Left for hours. Then, since crystals were precipitated, the crystals were filtered, washed with 10 g of n-hexane, and dried to obtain 6.7 g of white crystals. This was compound B1 as analyzed by high performance liquid chromatography.

The obtained white crystal was identified by melting point measurement, ¹ H-NMR, IR spectrum, and Mass spectrum. The white crystal as Compound B1 was 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene. It was confirmed.

Melting point: 64-65 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 1.97 (s, 3H), 2.71 (bs, 1H), 3.96 (s, 3H), 4.18 (d, 2H), 4 .37-4.52 (m, 3H), 5.61 (s, 1H), 6.17 (s, 1H), 6.70 (dd, 2H), 7.48-7.55 (m, 2H) ), 8.12-8.27 (m, 2H).
IR (KBr, cm ⁻¹ ): 3500, 2960, 1698, 1638, 1605, 1470, 1400, 1280, 1245, 1170, 1105, 1025, 960, 770.
Mass spectrum: (EI-MS) m / z = 316 (M ^<+> ).

On the other hand, in separation and purification of Compound A1 and Compound B1, the filtrate obtained by filtering the crystals is distilled off with a rotary evaporator, and 100 mg of the remaining viscous liquid is taken and dissolved in 0.5 g of chloroform. This was applied to a silica gel plate and developed with an eluent having a volume ratio of ethyl acetate: n-hexane = 1: 2. As a result, the color development of the two components by UV was confirmed.

The eluent of the fraction corresponding to the A1 component is collected, the solvent is distilled off with a rotary evaporator, and the resulting colorless transparent liquid is identified by ¹ H-NMR, IR spectrum, and Mass spectrum. A certain compound A1 was confirmed to be 4-methoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene.

¹ H-NMR (CDCl ₃ , ppm): δ = 1.97 (s, 3H), 2.17 (t, 1H), 3.95 (s, 3H), 4.03 (t, 2H), 4 .32 (d, 2H), 5.37-5.48 (m, 1H), 5.60 (s, 1H), 6.18 (s, 1H), 6.70 (dd, 2H), 7. 44-7.53 (m, 2H), 8.10-8.23 (m, 2H).
IR (KBr, cm ⁻¹ ): 3450, 2960, 2940, 1720, 1630, 1598, 1465, 1390, 1275, 1160, 1100, 808, 763.
Mass spectrum: (EI-MS) m / z = 316 (M ^<+> ).

(Example 3) Glycidyl methacrylate reaction of 4-methoxy-1-naphthol (one-step production method)
Under a nitrogen stream, in a 300 ml three-necked flask equipped with a stirrer and a thermometer, 5.0 g (28.7 mmol) of 4-methoxy-1-naphthol, 12.2 g (85.9 mmol) of glycidyl methacrylate, tetrabutyl as a catalyst 150 mg of phosphonium bromide and 20 ml of methyl isobutyl ketone as a solvent were added. The mixture was heated to 100 ° C. and stirred at 100 ° C. for 3 hours. Thereafter, the reaction solution was cooled to 20 ° C., the reaction solution was extracted with 15 ml of ethyl acetate, the organic layer (ethyl acetate layer) was washed once with 20 g of water, and then the organic layer was distilled off with a rotary evaporator. 15.2 g of oil was obtained. Thereafter, 50 g of hexane was added to the oil to remove excess glycidyl methacrylate, thereby obtaining 8.4 g (26.6 mmol) of a blackish brown oil. When the purity was analyzed by high performance liquid chromatography, it was found that there were two main peaks, and it was a mixture of two kinds of compounds. The two kinds of compounds are temporarily referred to as A2 and B2. From the peak area ratio on the chromatogram, Compound A2 was 12.6% by weight and Compound B2 was 66.2% by weight.

In order to separate, purify, and identify the compound A2 and the compound B2, 25 ml of methanol and 5 ml of water were added to the black brown oily substance and dissolved, and crystallized at -10 ° C. Then, since white crystals were precipitated, the white crystals were filtered and dried to obtain 4.2 g (13.3 mmol) of white crystals. The yield of this white crystal was 46.3 mol%. This was compound B2 as analyzed by high performance liquid chromatography.

The obtained white crystal was identified by melting point measurement, ¹ H-NMR, IR spectrum, and Mass spectrum. The white crystal as compound B2 was 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene. It was confirmed.

Melting point: 64-65 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 1.97 (s, 3H), 2.71 (bs, 1H), 3.96 (s, 3H), 4.18 (d, 2H), 4 .37-4.52 (m, 3H), 5.61 (s, 1H), 6.17 (s, 1H), 6.70 (dd, 2H), 7.48-7.55 (m, 2H) ), 8.12-8.27 (m, 2H).
IR (KBr, cm ⁻¹ ): 3500, 2960, 1698, 1638, 1605, 1470, 1400, 1280, 1245, 1170, 1105, 1025, 960, 770.
Mass spectrum: (EI-MS) m / z = 316 (M ^<+> ).

On the other hand, in separation and purification of compound A2 and compound B2, the solvent was distilled off from the filtrate obtained by filtering the crystals with a rotary evaporator, and the remaining viscous liquid was 3.9 g. This viscous liquid was separated and purified using a silica gel plate in the same manner as in Example 2.

The eluent of the fraction corresponding to the A2 component is collected, the solvent is distilled off with a rotary evaporator, and the resulting colorless transparent liquid is identified by ¹ H-NMR, IR spectrum, and Mass spectrum. A certain compound A2 was confirmed to be 4-methoxy-1- (3-hydroxy-2-methacryloyloxypropoxy) naphthalene.

¹ H-NMR (CDCl ₃ , ppm): δ = 1.97 (s, 3H), 2.17 (t, 1H), 3.95 (s, 3H), 4.03 (t, 2H), 4 .32 (d, 2H), 5.37-5.48 (m, 1H), 5.60 (s, 1H), 6.18 (s, 1H), 6.70 (dd, 2H), 7. 44-7.53 (m, 2H), 8.10-8.23 (m, 2H).
IR (KBr, cm ⁻¹ ): 3450, 2960, 2940, 1720, 1630, 1598, 1465, 1390, 1275, 1160, 1100, 808, 763.
Mass spectrum: (EI-MS) m / z = 316 (M ^<+> ).

Example 4
Acrylation reaction of 4-methoxy-1-glycidyloxynaphthalene (second reaction of the two-stage production method)
In a 300 ml three-necked flask equipped with a stirrer and a thermometer under a nitrogen stream, 10 g (43.5 mmol) of 4-methoxy-1-glycidyloxynaphthalene synthesized in Example 1 and 6.3 g (87.5 mmol) of acrylic acid were synthesized. ), 980 mg of tetrabutylammonium bromide as a catalyst, 10 mg of TEMPO as a polymerization inhibitor, and 50 ml of methyl isobutyl ketone as a solvent were added. The mixture was heated to 100 ° C. and stirred at 100 ° C. for 3.5 hours. Thereafter, the reaction solution was cooled to 20 ° C., the reaction solution was extracted with 30 ml of ethyl acetate, and the organic layer (ethyl acetate layer) was washed 3 times with 30 g of a saturated aqueous sodium hydrogen carbonate solution to remove excess methacrylic acid. Next, after the organic layer was washed once with 30 g of water, the organic layer was distilled off with a rotary evaporator to obtain 12.3 g of a brown liquid. As a result of analyzing the purity of this liquid by high performance liquid chromatography, it was found that it had two main peaks and was a mixture of two kinds of compounds. The two kinds of compounds are temporarily referred to as A3 and B3. From the peak area ratio on the chromatogram, Compound A3 was 20.6% by weight and Compound B3 was 74.6% by weight.

In order to separate and purify and identify Compound A3 and Compound B3, 35 g of toluene and 10 g of hexane were added to this brown liquid, and the mixture was cooled to −10 ° C. and crystallized. Then, crystals were precipitated, and the crystals were filtered and dried to obtain 6.4 g (21.2 mmol) of pale yellow crystals. The yield was 48.7 mol%. This was compound B3 as analyzed by high performance liquid chromatography.

The obtained pale yellow crystal was identified by melting point measurement, ¹ H-NMR, IR spectrum, and Mass spectrum. The pale yellow crystal as Compound B3 was 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene. It was confirmed that.

Melting point: 81-82 ° C
¹ H-NMR (CDCl ₃ , ppm): δ = 2.66 (d, 1H), 3.95 (s, 3H), 4.18 (d, 2H), 4.37-4.56 (m, 3H), 5.89 (d, 1H), 6.18 (dd, 1H), 6.47 (d, 1H), 6.72 (dd, 2H), 7.48-7.57 (m, 2H) ), 8.11-8.26 (m, 2H).
IR (KBr, cm ⁻¹ ): 3420, 2930, 2500, 1703, 1640, 1600, 1462, 1420, 1280, 1220, 1110, 1096, 1080, 800, 760.
Mass spectrum: (EI-MS) m / z = 302 (M ^<+> ).

On the other hand, in the separation and purification of Compound A3 and Compound B3, the filtrate obtained by filtering the crystals was evaporated using a rotary evaporator, and the remaining viscous liquid was 5.8 g. This viscous liquid was separated and purified using a silica gel plate in the same manner as in Example 2.

The eluent of the fraction corresponding to the A3 component is collected, the solvent is distilled off with a rotary evaporator, and the resulting colorless transparent liquid is identified by ¹ H-NMR, IR spectrum, and Mass spectrum. It was confirmed that a certain compound A3 was 4-methoxy-1- (3-hydroxy-2-acryloyloxypropoxy) naphthalene.

¹ H-NMR (CDCl ₃ , ppm): δ = 2.04 (t, 1H), 3.94 (s, 1H), 4.04 (t, 2H), 4.30 (d, 2H), 5 40-50.50 (m, 1H), 5.88 (d, 1H), 6.20 (dd, 1H), 6.47 (d, 1H), 6.68 (dd, 2H), 7. 45-7.54 (m, 2H), 8.10-8.26 (m, 2H).
IR (KBr, cm ⁻¹ ): 3450, 2950, 1730, 1635, 1600, 1462, 1410, 1390, 1280, 1195, 1100, 810, 770.
Mass spectrum: (EI-MS) m / z = 302M +).

(Example 5) <Example using 1,4-naphthalene diether derivative as a photopolymerization sensitizer: Trimethylolpropane triacrylate as a radical polymerizable compound and 4-methylphenyl-4-isobutyl as a photopolymerization initiator Photocuring of Photopolymerizable Composition Using Phenyliodonium Hexafluorophosphate and 4-Methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as Photopolymerization Sensitizer>
100 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 250”), 4 isolated in Example 3 0.5 parts by weight of -methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was added to prepare a uniform photopolymerizable composition. This photopolymerizable composition was applied onto a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm, Lumirror is a registered trademark of Toray Industries, Inc.) using a bar coater so as to have a film thickness of 12 μm. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time from tackiness to tackiness of the polyester film surface coated with the photopolymerizable composition (tack free time) was 7 minutes.

Example 6 <Example using 1,4-naphthalenediether derivative as photopolymerization sensitizer: alicyclic epoxy compound as cationic polymerizable compound and 4-methylphenyl-4-isobutyl as photopolymerization initiator Photocuring of Photopolymerizable Composition Using Phenyliodonium Hexafluorophosphate and 4-Methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as Photopolymerization Sensitizer>
100 parts by weight of an alicyclic epoxy compound (manufactured by The Dow Chemical Company: trade name “UVR-6105”), 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: product) 2 parts by weight of “Irgacure 250”) and 0.5 parts by weight of 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene isolated in Example 3 were added, and a uniform photopolymerizable composition was added. Adjusted. This photopolymerizable composition was applied on a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) to a film thickness of 12 μm using a bar coater. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time from tackiness to tackiness of the polyester film surface coated with the photopolymerizable composition (tack free time) was 7 minutes.

Comparative Example 1 <Trimethylolpropane triacrylate as a radical polymerizable compound, 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate as a photopolymerization initiator, and 1,4-diethoxynaphthalene as a photopolymerization sensitizer Photo-curing of photopolymerizable composition using
A photopolymerizable composition was prepared in the same manner as in Example 5 except that 0.5 part by weight of 1,4-diethoxynaphthalene as a photopolymerization sensitizer was used with respect to 100 parts by weight of trimethylolpropane acrylate. The photopolymerizable composition was applied on a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) so as to have a film thickness of 12 μm. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time from tackiness to tackiness of the polyester film surface coated with the photopolymerizable composition (tack free time) was 8 minutes.

(Comparative Example 2) <Photopolymerizable composition without addition of trimethylolpropane triacrylate as a radical polymerizable compound, 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate as a photopolymerization initiator, and a photopolymerization sensitizer Light curing of objects>
A photopolymerizable composition was prepared in the same manner as in Example 5 except that no photopolymerization sensitizer was added, and the photopolymerizable composition was prepared as a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm). It applied so that it might become a film thickness of 12 micrometers. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time (tack-free time) until the stickiness of the polyester film surface to which the photopolymerizable composition was applied after light irradiation was measured was not cured even after 30 minutes.

(Comparative example 3) <A cycloaliphatic epoxy compound as a cationic polymerizable compound, 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate as a photopolymerization initiator, and 1,4-diethoxynaphthalene as a photopolymerization sensitizer Photo-curing of photopolymerizable composition using
A photopolymerizable composition was prepared in the same manner as in Example 6 except that 0.5 part by weight of 1,4-diethoxynaphthalene as a photopolymerization sensitizer was used with respect to 100 parts by weight of the alicyclic epoxy compound. The photopolymerizable composition was applied on a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time from tackiness to tackiness of the polyester film surface coated with the photopolymerizable composition (tack free time) was 8 minutes.

Comparative Example 4 <A photopolymerizable composition containing no alicyclic epoxy compound as the cationic polymerizable compound, 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate as the photopolymerization initiator, and no photopolymerization sensitizer. Light curing of objects>
A photopolymerizable composition was prepared in the same manner as in Example 6 except that no photopolymerization sensitizer was added, and the photopolymerizable composition was prepared as a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm). It applied so that it might become a film thickness of 12 micrometers. Next, under a nitrogen atmosphere, the polyester film coated surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 460 nm, 1 W, irradiation height: 1 cm). The time (tack-free time) until the stickiness of the polyester film surface to which the photopolymerizable composition was applied after light irradiation was measured was not cured even after 30 minutes.

(Example 7) <Sublimation resistance test of cured product of photopolymerizable composition using 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as a photopolymerization sensitizer>
In the same manner as in Example 4, 100 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 250”), A uniform photopolymerizable composition was prepared by adding 0.5 parts by weight of 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene isolated in Example 3. This photopolymerizable composition was applied onto a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm and cured in the same manner as in Example 6. I let you. The cured polyester film was placed in an oven at 200 ° C., the polyester film was taken out after 10 minutes, and the UV spectrum was measured. In the UV spectrum, the absorption intensity at 330 nm due to 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was measured and used as a photopolymerization sensitizer from the difference in absorption intensity before and after heating in an oven. The sublimation rate of the added 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was measured. As a result, 6% of 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was sublimed.

(Comparative Example 5) <Sublimation resistance test of cured product of photopolymerizable composition using 1,4-diethoxynaphthalene as photopolymerization sensitizer>
As in Comparative Example 1, 100 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 250”), 1 , 4-diethoxynaphthalene 0.5 parts by weight was added to prepare a uniform photopolymerizable composition. This photopolymerizable composition was applied onto a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm and cured in the same manner as in Example 6. I let you. The cured polyester film was placed in an oven at 200 ° C., and after 10 minutes, the polyester film was taken out and the UV spectrum was measured. In the UV spectrum, the absorption intensity at 330 nm due to 1,4-diethoxynaphthalene was measured, and the sublimation of 1,4-diethoxynaphthalene added as a photopolymerization sensitizer from the difference in absorption intensity before and after heating in the oven The rate was measured. As a result, 59% of 1,4-diethoxynaphthalene was sublimated.

(Example 8) <Sublimation resistance test of a cured product of a photopolymerizable composition using 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as a photopolymerization sensitizer>
In the same manner as in Example 5, 100 parts by weight of an alicyclic epoxy compound, 2 parts by weight of 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 250”), A uniform photopolymerizable composition was prepared by adding 0.5 parts by weight of 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene isolated in Example 3. This photopolymerizable composition was applied onto a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm and cured in the same manner as in Example 6. I let you. The cured polyester film was placed in an oven at 200 ° C., and after 10 minutes, the polyester film was taken out. A portion of the photopolymerizable composition on the coated surface was scraped off with a spatula, and its UV spectrum was measured. In the UV spectrum, the absorption intensity at 330 nm due to 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was measured and used as a photopolymerization sensitizer from the difference in absorption intensity before and after heating in an oven. The sublimation rate of the added 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was measured. As a result, 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene was 5% sublimated.

(Comparative Example 6) <Sublimation resistance test of cured product of photopolymerizable composition using 1,4-diethoxynaphthalene as photopolymerization sensitizer>
As in Comparative Example 3, 100 parts by weight of an alicyclic epoxy compound, 2 parts by weight of 4-methylphenyl-4-isobutylphenyliodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 250”), 1 , 4-diethoxynaphthalene 0.5 parts by weight was added to prepare a uniform photopolymerizable composition. This photopolymerizable composition was applied onto a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm and cured in the same manner as in Example 6. I let you. The cured polyester film was placed in an oven at 200 ° C., and after 10 minutes, the polyester film was taken out. A portion of the photopolymerizable composition on the coated surface was scraped off with a spatula, and its UV spectrum was measured. In the UV spectrum, the absorption intensity at 330 nm due to 1,4-diethoxynaphthalene was measured, and the sublimation of 1,4-diethoxynaphthalene added as a photopolymerization sensitizer from the difference in absorption intensity before and after heating in the oven The rate was measured. As a result, 55% of 1,4-diethoxynaphthalene was sublimated.

The results of Examples 5 and 6 and Comparative Examples 1 to 4 are shown in Table 1.

Table 2 shows the results of Examples 7 and 8 and Comparative Examples 5 and 6.

From Table 1, the following is clear. That is, when a photopolymerizable composition using 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as a photopolymerization sensitizer is photocured, a radical polymerizable compound and a cationic polymerizable compound are obtained. In any case, it can be cured in 7 minutes, and it can be seen that the curing rate is equal to or higher than the comparative example using 1,4-diethoxynaphthalene known as a photopolymerization sensitizer. On the other hand, in Comparative Examples 2 and 4 in which no photopolymerization sensitizer was used, it was not cured even after 30 minutes, and therefore 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) of the present invention Naphthalene can be said to be useful as a photopolymerization sensitizer.

From Table 2, the following is clear. That is, a photopolymerizable composition using 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene as a photopolymerization sensitizer uses 1,4-diethoxynaphthalene as a photopolymerization sensitizer. Compared to the photopolymerizable composition thus obtained, it can be said that it is a photopolymerization sensitizer that has a sublimation rate of 5% that is remarkably low even when heated at 200 ° C. for 10 minutes, that is, it is difficult to sublime, that is, excellent in sublimation resistance.

Example 9 <Example using 1,4-naphthalenediether derivative as radical polymerizable compound: 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene and trimethylol as radical polymerizable compound Evaluation of Photocuring of Photopolymerizable Composition Using Propane Triacrylate and Bis (2,4,6-Trimethylbenzoyl) -Phenylphosphine Oxide as Photopolymerization Initiator and Adhesion of Photocured Product to Film>
1 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals: trade name “Irgacure 819”) as a photopolymerization initiator and 4-methoxy- as a radical polymerizable compound A photopolymerizable composition containing 100 parts by weight of 1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene and 50 parts by weight of trimethylolpropane triacrylate was prepared. This photopolymerizable composition was applied on a polyester film (Toray Industries, Inc .: trade name “Lumirror” film thickness 100 μm) to a film thickness of 12 μm using a bar coater. Subsequently, the polyester film coating surface was irradiated with light using a high-pressure mercury lamp (center wavelength of irradiation light: 366 nm, 1 W, irradiation height 1 cm) in a nitrogen atmosphere. The time (tack-free time) until the stickiness of the polyester film surface to which the photopolymerizable composition was applied after light irradiation was eliminated was 2 minutes. Next, streaks of 1 cm were put on the coated surface with a knife, and an adhesive tape (trade name: cello tape (registered trademark), manufactured by Nichiban Co., Ltd.) was attached so that no air remained on the coated surface. After 5 minutes, the pressure-sensitive adhesive tape was peeled off, and the adhesion of the coated material was evaluated based on whether or not the coated material on the film-like coated surface was peeled off. The results are shown in Table 3.

Example 10 <Example using 1,4-naphthalene diether derivative as radical polymerizable compound: 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene and trimethylol as radical polymerizable compound Evaluation of Photocuring of Photopolymerizable Composition Using Propane Triacrylate and Bis (2,4,6-Trimethylbenzoyl) -Phenylphosphine Oxide as Photopolymerization Initiator and Adhesion of Photocured Product to Film>
In the same manner as in Example 9, except that 100 parts by weight of 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene and 50 parts by weight of trimethylolpropane triacrylate were used as the radical polymerizable compound. The photopolymerizable composition was prepared, applied onto a polyester film using a bar coater, and irradiated with light. The time (tack-free time) until the stickiness of the polyester film surface to which the photopolymerizable composition was applied after light irradiation was eliminated was 2 minutes. Next, the adhesive tape was affixed similarly to Example 9. After 5 minutes, the pressure-sensitive adhesive tape was peeled off, and the adhesion of the coated material was evaluated based on whether or not the coated material on the film-like coated surface was peeled off. The results are shown in Table 3.

(Comparative Example 7) <4-Methoxy-1- (2-acryloyloxyethoxy) naphthalene and trimethylolpropane triacrylate as a radical polymerizable compound, and bis (2,4,6-trimethylbenzoyl) -phenyl as a photopolymerization initiator Evaluation of photocuring of photopolymerizable composition using phosphine oxide and adhesion of photocured product to film>
As a radical polymerizable compound, 100 parts by weight of 4-methoxy-1- (2-methacryloyloxyethoxy) naphthalene (compound described in Example 4 of JP2008-1640) and 50 parts by weight of trimethylolpropane triacrylate A photopolymerizable composition was prepared in the same manner as in Example 9 except that it was used. The photopolymerizable composition was applied onto a polyester film using a bar coater and irradiated with light. The time (tack-free time) until the stickiness of the polyester film surface to which the photopolymerizable composition was applied after light irradiation was eliminated was 1 minute. Next, the adhesive tape was affixed similarly to Example 9. After 5 minutes, the pressure-sensitive adhesive tape was peeled off, and the adhesion of the coated material was evaluated based on whether or not the coated material on the film-like coated surface was peeled off. The results are shown in Table 3.

From Table 3, the following is clear. That is, photopolymerization using 4-methoxy-1- (2-hydroxy-3-acryloyloxypropoxy) naphthalene or 4-methoxy-1- (2-hydroxy-3-methacryloyloxypropoxy) naphthalene as the radical polymerizable compound. When the curable composition is photocured, it can be said that the adhesiveness with the substrate is excellent as compared with the comparative example using 4-methoxy-1- (2-methacryloyloxyethoxy) naphthalene as the radical polymerizable compound.

The 1,4-naphthalene diether derivative of the present invention is useful as a photopolymerization sensitizer or a radical polymerizable compound, and the photopolymerizable composition containing the 1,4-naphthalene diether derivative is obtained by light irradiation. An industrially useful photopolymerizable composition that can be easily photocured and has excellent sublimation resistance can be provided.

Claims (13)

1,4-naphthalenediether derivative represented by the following general formula (1).
(In General Formula (1), one of Z ¹ and Z ² represents a hydrogen atom, the other represents a (meth) acryloyl group, and R ¹ represents a halogen atom, a hydroxyl group, an alkoxy group, an aryl group, and an aryloxy group. An alkyl group which may have one or two or more substituents selected from a group, and X and Y may be the same or different; a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Indicates an aryloxy group or an arylthio group.) The 1,4-naphthalenediether derivative according to claim 1, wherein, in the general formula (1), Z ¹ is a hydrogen atom and Z ² is a (meth) acryloyl group. The 1,4-naphthalenediether derivative according to claim 1, wherein, in the general formula (1), Z ¹ is a (meth) acryloyl group and Z ² is a hydrogen atom. The 4-substituted-1-glycidyloxynaphthalene derivative represented by the following general formula (2) is reacted with acrylic acid or methacrylic acid. A method for producing a 4-naphthalenediether derivative.
(In General Formula (2), R ¹ represents an alkyl group which may have one or two or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group and an aryloxy group, and X and Y may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an arylthio group. The 4-substituted-1-naphthol derivative represented by the following general formula (3) is reacted with glycidyl acrylate or glycidyl methacrylate. A method for producing naphthalene diether derivatives.
(In General Formula (3), R ¹ represents an alkyl group which may have one or two or more substituents selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryl group and an aryloxy group; Y may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an arylthio group.   A photopolymerization sensitizer containing at least the 1,4-naphthalenediether derivative according to any one of claims 1 to 3 as an active ingredient.   A photopolymerization initiator composition comprising the photopolymerization sensitizer according to claim 6 and a photopolymerization initiator. The photopolymerization initiator composition according to claim 7, wherein the photopolymerization initiator is an onium salt.   The photopolymerization composition containing the photoinitiator composition of Claim 7 or Claim 8, and a cationically polymerizable compound and / or a radically polymerizable compound. The photopolymerizable composition containing the 1, 4- naphthalene diether derivative as described in any one of Claims 1-3 as a photoinitiator and a radically polymerizable compound.   The 1,4-naphthalene diether derivative according to any one of claims 1 to 3 is contained as a photopolymerization initiator and a radical polymerizable compound, and radical polymerization other than the 1,4-naphthalene diether derivative is further included. A photopolymerizable composition containing a compound.   A curing method comprising curing the photopolymerizable composition according to any one of claims 9 to 11 by irradiation with an active energy ray.   Hardened | cured material which hardened the photopolymerizable composition as described in any one of Claims 9-11 by irradiation of an active energy ray.