WO2021106678A1 - Acylphosphine composition, polymerization initiator, polymerizable composition, cured product, and method for producing cured product - Google Patents

Abstract

This acylphosphine composition contains a cation represented by formula (1) and two or more types of anion including an acylphosphine anion represented by formula (2). The ratio of the molar equivalent amount of the cation relative to the molar equivalent amount of the acylphosphine anion is 1.005-1.100.

Description

Acylphosphine composition, polymerization initiator, polymerizable composition, and cured product and method for producing the same.

The present invention relates to an acylphosphine composition, a polymerization initiator and a polymerizable composition using the acylphosphine composition, a cured product which is a curing reaction product of the polymerizable composition, and a method for producing the same.

A polymerizable composition that can be cured by utilizing a polymerization reaction is used in various fields such as a polymerization initiator, and a cured product that is a curing reaction product of the polymerizable composition is also used in various fields. Has been done. Therefore, various studies have been conducted on the composition of the polymerizable composition.

Specifically, a polymerizable composition (water-soluble composition) containing a reactive compound (a compound having a specific reactive group) together with an acylphosphine composition (acylphosphine salt) so as to be adaptable to a wide range of light sources. Has been proposed (see, for example, Patent Document 1). Further, in order to obtain excellent sensitivity, a polymerizable composition (for example, an aqueous curable composition) containing water and a polymerizable compound together with a water-soluble photopolymerization initiator having an acylphosphine oxide type structure has been proposed (for example). , Patent Document 2).

JP-A-2018-150497 International Publication No. 2017/145484 Pamphlet

Although studies on the composition of a polymerizable composition containing an acylphosphine composition have been actively conducted, the physical characteristics of the polymerizable composition are still insufficient. Further, the physical characteristics of the polymerization initiator, which is considered to be used for the polymerizable composition, and the physical characteristics of the cured product, which is a curing reaction product of the polymerizable composition, are not yet sufficient. Therefore, there is room for improvement.

An object of the present invention is to provide an acylphosphine composition, a polymerization initiator, a polymerizable composition, and a cured product and a method for producing the same, which can obtain excellent physical properties.

The acylphosphine composition of one embodiment of the present invention contains a cation represented by the formula (1) and two or more kinds of anions including the acylphosphine anion represented by the formula (2), and the acylphosphine anion thereof. The ratio of the molar equivalent of the cation to the molar equivalent of 1.005 or more and 1.100 or less.

N ⁺ HY1Y2Y3 ・ ・ ・ (1)
(Each of Y1, Y2 and Y3 has a linear alkyl group having 1 or more and 6 or less carbon atoms, a linear alkenyl group having 2 or more and 6 or less carbon atoms, and 6 or more and 15 or less carbon atoms. An aryl group and any of an arylalkyl groups having 7 or more and 13 or less carbon atoms. The hydrogen groups of Y1, Y2 and Y3 may be substituted with hydroxyl groups, respectively. Y1, Y2 and Y3, respectively. The methylene group of is optionally substituted with any of -O-, -S-, -CO- and -N ⁺ H-. Any two of Y1, Y2 and Y3 are bonded to each other. May be good.)

(X1 is an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group is a linear alkyl group having 1 or more and 8 or less carbon atoms and 3 or more and 8 or less carbon atoms. A branched alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl halide group having 3 or more and 8 or less carbon atoms, and 1 or more and 8 or less carbon atoms. A linear alkoxy group having 3 or more and 8 or less carbon atoms, a linear halogenated alkoxy group having 1 or more and 8 or less carbon atoms, and a 3 to 8 or less carbon atoms. It may be substituted with any of the branched alkoxy halide groups.
X2 is a linear alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl group having 3 or more and 8 or less carbon atoms, and a linear alkoxy group having 1 or more and 8 or less carbon atoms. It is either a branched alkoxy group having 3 or more and 8 or less carbon atoms and an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group has 1 or more and 8 or less carbon atoms. A linear alkyl group, a branched alkyl group having 3 or more and 8 or less carbon atoms, a linear halogenated alkyl group having 1 or more and 8 or less carbon atoms, and 3 or more and 8 or less carbon atoms. A branched alkyl halide group, a linear alkoxy group having 1 or more and 8 or less carbon atoms, a branched alkoxy group having 3 or more and 8 or less carbon atoms, and a straight chain having 1 or more and 8 or less carbon atoms. A halogenated alkoxy group, a branched halogenated alkoxy group having 3 or more and 8 or less carbon atoms, a halogen group, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, It may be substituted with any one of a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group and a heterocyclic group. Each of the methylene groups of X2 may be substituted with either —O— or —S—. )

The polymerization initiator of one embodiment of the present invention contains an acylphosphine composition, and the acylphosphine composition has the same composition as the above-mentioned composition of the acylphosphine composition of one embodiment of the present invention.

The polymerizable composition of one embodiment of the present invention contains an acylphosphine composition, a reactive group-containing compound containing a reactive group represented by the formula (3), and an aqueous solvent, and the acylphosphine composition thereof is described above. It has a structure similar to that of the acylphosphine composition according to the embodiment of the present invention.

(R1 is either a hydrogen group or a methyl group.
Z1 is either -O- or -NR2-, and R2 is either a hydrogen group and a hydrocarbon group having 1 or more and 20 or less carbon atoms.
Z2 is an alkylene group having 1 or more and 6 or less carbon atoms.
n is an integer of 0 or more and 30 or less.
However, an asterisk (*) represents an unbonded bond. )

The cured product of one embodiment of the present invention is a cured reaction product of a polymerizable composition, and the polymerizable composition has the same constitution as the above-mentioned constitution of the polymerizable composition of one embodiment of the present invention. Is.

The method for producing a cured product according to the embodiment of the present invention is the same as the constitution of the polymerizable composition according to the embodiment of the present invention described above, wherein the polymerizable composition is irradiated with active energy rays. It has a structure.

According to the acylphosphine composition, polymerization initiator or polymerizable composition of one embodiment of the present invention, the acylphosphine composition comprises a cation represented by the formula (1) and an acylphosphine anion represented by the formula (2). Since it contains two or more kinds of anions and the ratio of the molar equivalent of the cation to the molar equivalent of the acylphosphine anion is 1.005 or more and 1.100 or less, excellent physical properties can be obtained.

Further, according to the cured product of one embodiment of the present invention, since it is a cured product of the above-mentioned polymerizable composition, excellent physical properties can be obtained.

Further, according to the method for producing a cured product according to the embodiment of the present invention, since the above-mentioned polymerizable composition is irradiated with active energy rays, a cured product having excellent physical properties can be obtained.

Hereinafter, one embodiment of the present invention will be described in detail. The order to be described is as follows. However, the details of the present invention are not limited to the aspects described below, and can be changed as appropriate.

1. 1. Acylphosphine composition 2. Polymerizable composition 3. Hardened product and its manufacturing method 4. Applications (polymerization initiator, etc.)

<1. Acylphosphine composition>
First, the acylphosphine composition of one embodiment of the present invention will be described.

[Constitution]
The acylphosphine composition described here is used as a polymerization initiator or the like, as will be described later. However, the use of the acylphosphine composition is not limited to the polymerization initiator, and other uses may be used.

This acylphosphine composition has a salt structure. Specifically, the acylphosphine composition contains a quaternary ammonium type cation represented by the formula (1) and two or more kinds of anions, and the two or more kinds of anions are of the formula (2). ) Includes an acylphosphine-type anion (hereinafter referred to as "acylphosphine anion").

N ⁺ HY1Y2Y3 ・ ・ ・ (1)
(Each of Y1, Y2 and Y3 has a linear alkyl group having 1 or more and 6 or less carbon atoms, a linear alkenyl group having 2 or more and 6 or less carbon atoms, and 6 or more and 15 or less carbon atoms. An aryl group and any of an arylalkyl groups having 7 or more and 13 or less carbon atoms. The hydrogen groups of Y1, Y2 and Y3 may be substituted with hydroxyl groups, respectively. Y1, Y2 and Y3, respectively. The methylene group of is optionally substituted with any of -O-, -S-, -CO- and -N ⁺ H-. Any two of Y1, Y2 and Y3 are bonded to each other. May be good.)

(X1 is an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group is a linear alkyl group having 1 or more and 8 or less carbon atoms and 3 or more and 8 or less carbon atoms. A branched alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl halide group having 3 or more and 8 or less carbon atoms, and 1 or more and 8 or less carbon atoms. A linear alkoxy group having 3 or more and 8 or less carbon atoms, a linear halogenated alkoxy group having 1 or more and 8 or less carbon atoms, and a 3 to 8 or less carbon atoms. It may be substituted with any of the branched alkoxy halide groups.
X2 is a linear alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl group having 3 or more and 8 or less carbon atoms, and a linear alkoxy group having 1 or more and 8 or less carbon atoms. It is either a branched alkoxy group having 3 or more and 8 or less carbon atoms and an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group has 1 or more and 8 or less carbon atoms. A linear alkyl group, a branched alkyl group having 3 or more and 8 or less carbon atoms, a linear halogenated alkyl group having 1 or more and 8 or less carbon atoms, and 3 or more and 8 or less carbon atoms. A branched alkyl halide group, a linear alkoxy group having 1 or more and 8 or less carbon atoms, a branched alkoxy group having 3 or more and 8 or less carbon atoms, and a straight chain having 1 or more and 8 or less carbon atoms. A halogenated alkoxy group, a branched halogenated alkoxy group having 3 or more and 8 or less carbon atoms, a halogen group, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, It may be substituted with any one of a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group and a heterocyclic group. Each of the methylene groups of X2 may be substituted with either —O— or —S—. )

(Details about anions)
The two or more types of anions include acylphosphine anions, as described above. The type of acylphosphine anion may be only one type or two or more types.

(Acylphosphine anion)
Details regarding the composition of the acylphosphine anion are as described below.

(X1)
Aryl group is a general term for monovalent groups containing one or more aromatic rings. Specific examples of the aryl group are a phenyl group, a naphthyl group, an anthrasenyl group and the like because they have 6 to 15 carbon atoms. However, the carbon number of the aryl group when it contains a substituent described later is the total carbon number including the carbon number of the substituent. Therefore, for example, the trimethylphenyl group has 9 carbon atoms instead of 6. The definition regarding the number of carbon atoms of the aryl group described here is the same thereafter.

Each of one or more hydrogen groups contained in the aryl group may be substituted with a substituent. As described above, the substituents described here are a linear alkyl group having a specific carbon number, a branched alkyl group, a linear halogenated alkyl group, and a branched alkyl halide. It is any of a group, a linear alkoxy group, a branched alkoxy group, a linear halogenated alkoxy group and a branched halogenated alkoxy group.

A linear alkyl group is a general term for a monovalent hydrocarbon group containing one carbon atom and a monovalent hydrocarbon group in which a plurality of carbon atoms are bonded to each other so as to be linear. Specific examples of the linear alkyl group have 1 to 8 carbon atoms, and therefore have a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. Group and n-octyl group.

A branched alkyl group is a general term for a monovalent hydrocarbon group in which a plurality of carbon atoms are bonded to each other so as to have one or two or more side chains. Specific examples of the branched alkyl group have 3 to 8 carbon atoms, and therefore have an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a sec-pentyl group, an isopentyl group, a tert-pentyl group, and a neopentyl group. Group, sec-hexyl group, isohexyl group, tert-hexyl group, neohexyl group, sec-heptyl group, isoheptyl group, tert-heptyl group, neoheptyl group, sec-octyl group, isooctyl group, tert-octyl group and neooctyl group. is there.

The linear alkyl halide group is a group in which one or more hydrogen groups contained in the above-mentioned linear alkyl group are each substituted with a halogen group. The type of halogen group is not particularly limited, but is a fluorine group, a chlorine group, a bromine group, an iodine group and the like. However, the type of the halogen group contained in the linear alkyl halide group may be only one type or two or more types.

The branched alkyl halide group is a group in which one or more hydrogen groups contained in the above-mentioned branched alkyl group are substituted with a halogen group. Details regarding the types of halogen groups are as described above.

A linear alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned linear alkyl group. Specific examples of the linear alkoxy group have 1 to 8 carbon atoms, and therefore have a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, and an n-heptoxy. Groups and n-octoxy groups.

The branched alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned branched alkyl group. Specific examples of the branched alkoxy group have an isopropoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-pentoxy group, an isopentoxy group, a tert-pentoxy group, since the number of carbon atoms is 3 to 8. Neopentoxy group, sec-hexoxy group, isohexoxy group, tert-hexoxy group, neohexoxy group, sec-heptoxy group, isoheptoxy group, tert-heptoxy group, neoheptoxy group, sec-octoxy group, isooctoxy group, tert-octoxy group and neooctoxy group. Is.

The linear halogenated alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned linear halogenated alkyl group. Specific examples of the linear halogenated alkoxy group have 1 to 8 carbon atoms, and therefore have a halogenated methoxy group, a halogenated ethoxy group, a halogenated n-propoxy group, a halogenated n-butoxy group, and a halogenated n. -Pentoxy group, halogenated n-hexoxy group, halogenated n-heptoxy group and halogenated n-octoxy group.

The branched alkoxy halide group is a general term for a group in which -O- is bonded to the end of the above-mentioned branched alkyl halide group. Specific examples of the branched halogenated alkoxy group have 3 to 8 carbon atoms, so that the halogenated isopropoxy group, the halogenated sec-butoxy group, the halogenated isobutoxy group, the halogenated tert-butoxy group, and the halogenated sec. -Pentoxy group, halogenated isopentoxy group, halogenated tert-pentoxy group, halogenated neopentoxy group, halogenated sec-hexoxy group, halogenated isohexoxy group, halogenated tert-hexoxy group, halogenated neohexoxy group, halogenated sec-heptoxy Groups, halogenated isoheptoxy groups, halogenated tert-heptoxy groups, halogenated neoheptoxy groups, halogenated sec-octoxy groups, halogenated isooctoxy groups, halogenated tert-octoxy groups and halogenated neooctoxy groups.

Among them, X1 is preferably an aryl group into which one or two or more linear alkyl groups are introduced, and linear alkyl groups are introduced into each of the 2-position, 4-position and 6-position. It is more preferably a phenyl group, and further preferably a phenyl group (2,4,6-trimethyl-phenyl group) in which a methyl group is introduced at each of the 2-position, 4-position and 6-position. This is because the curability of the polymerizable composition containing the acylphosphine composition described later is improved.

(X2)
Details regarding each of the linear alkyl group, the branched alkyl group, the linear alkoxy group, the branched alkoxy group and the aryl group are as described above.

Each of the one or more hydrogen groups contained in the aryl group may be substituted with a substituent as in the case described with respect to X1. This substituent includes a linear alkyl group having a specific number of carbon atoms, a branched alkyl group, a linear alkyl halide group, a branched alkyl halide group, and a linear alkoxy group. , A branched alkoxy group, a linear halogenated alkoxy group and a branched halogenated alkoxy group. The substituent is any of a halogen group, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group and a heterocyclic group. Is it? Details regarding the types of halogen groups are as described above.

The heterocyclic group contains a monovalent group in which a ring (heterocycle) is composed of a carbon atom and one or more types of atoms other than carbon atoms, and a monovalent group containing one or more heterocycles. Atoms other than the carbon atom are nitrogen atom, oxygen atom, sulfur atom and the like. Specific examples of the heterocyclic ring-containing group include a group in which one hydrogen group is removed from each of thiazole, imidazole, oxazole, pyridine, pyrazinin, pyrimidinine, pyridadinin, thiophene, furan, bithiophene, tarthiophene and the like.

Further, each of one or more methylene groups contained in X2 may be substituted with either -O- or -S- as described above.

Among them, X2 is preferably an aryl group having 6 to 15 carbon atoms, and more preferably a phenyl group. This is because the curability of the polymerizable composition containing the acylphosphine composition is improved.

(Other anions)
As long as the above-mentioned two or more types of anions contain an acylphosphine anion, they may further contain other anions other than the acylphosphine anion. The other types of anions may be only one type or two or more types.

Other types of anions include, but are not limited to, halogen ions, hexafluorophosphate ions (PF ₆ ^-), tetrafluoroborate ion (BF ₄ ^-), bis (trifluoromethanesulfonyl) imide ion ((CF ^{_{3 SO 2) 2 N -)}} , trifluoromethanesulfonate ion (CF ₃ SO ₃ ^-), nonafluorobutanesulfonate ion ^{_{(C 4 F 9 SO 3 -}} ), benzoic acid ion, 4-ethyl benzoate, p - toluenesulfonate ion and hydroxide ion (OH ^-) and the like. The halogen ions include fluorine ions (F ⁻ ), chloride ions (Cl ⁻ ), bromine ions (Br ⁻ ) and iodide ions (I ⁻ ).

Among them, the other anion is preferably a hydroxide ion. This is because the stability of the acylphosphine composition is improved.

(Details about cations)
As described above, the cation is a quaternary ammonium type cation (N ⁺ HY1Y2Y3). The type of cation may be only one type or two or more types. The type of Y1 may be the same as the type of Y2, or may be different from the type of Y2. Similarly, the type of Y1 may be the same as the type of Y3 or different from the type of Y3, and the type of Y2 may be the same as the type of Y3 or different from the type of Y3.

Details regarding the linear alkyl group are as described above, except that the range of carbon atoms is different. The details regarding the aryl group are as described above.

A linear alkenyl group is a general term for monovalent hydrocarbon groups having an intercarbon double bond (> C = C <) and having a plurality of carbon atoms bonded to each other so as to be linear. Specific examples of the linear alkenyl group include a vinyl group, an allyl group, an acrylic group and a methacrylic group because they have 2 to 6 carbon atoms.

Arylalkyl group is a general term for monovalent groups in which an aryl group and a linear or branched alkyl group are bonded to each other. The details regarding the aryl group are as described above, and the details regarding the linear or branched alkyl group are as described above.

Each of one or more hydrogen groups contained in each of Y1, Y2 and Y3 may be substituted with a hydroxyl group. In this case, in each of Y1, Y2 and Y3, the hydrogen group at the terminal may be substituted with a hydroxyl group, or the hydrogen group in the middle may be substituted with a hydroxyl group. Specific examples of the alkyl group in which the terminal hydrogen group is substituted with a hydroxyl group have 7 to 13 carbon atoms, and therefore have a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl. A group, a hydroheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxyundecyl group, a hydroxydodecyl group and a hydroxytridecyl group.

Further, each of one or more methylene groups contained in each of Y1, Y2 and Y3 is substituted with any of ^{-O-, -S-, -CO- and -N + H-.} May be.

Note that any two of Y1, Y2, and Y3 may form a ring by being independently bonded to each other. That is, Y1 and Y2 may be bonded to each other, Y2 and Y3 may be bonded to each other, or Y1 and Y3 may be bonded to each other. In this case, one ring may be formed, or two or more rings may be formed. Further, a ring composed of a single bond may be formed. Further, a carbon-carbon double bond may be formed by bonding Y2 and Y3 to each other, and a ring may be formed by bonding the carbon-carbon double bond and Y1 to each other.

Among them, a part of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and the rest of Y1, Y2 and Y3 is replaced by a hydroxyl group at one terminal hydrogen group. It is preferably a linear alkyl group having 1 to 6 carbon atoms. Further, one of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and each of the two Y1, Y2 and Y3 has a hydroxyl group at the terminal one hydrogen group. More preferably, it is a linear alkyl group having 1 to 6 carbon atoms substituted with. This is because the curability of the polymerizable composition containing the acylphosphine composition is improved.

(Equivalent ratio, etc.)
In the acylphosphine composition described here, the ratio of the molar equivalent of the cation to the molar equivalent of the acylphosphine anion (equivalent ratio) is optimized, specifically 1.005 to 1.100. This is because the solubility of the acylphosphine composition is improved and the stability of the acylphosphine composition is improved. This equivalent ratio is calculated by the equivalent ratio = (valence of cation x number of moles of cation) / (valence of acylphosphine anion x number of moles of acylphosphine anion).

The ratio of the weight of the cation to the weight of the acylphosphine anion (weight ratio) is not particularly limited, but is preferably 0.25 to 1.00. This is because the solubility of the acylphosphine composition is further improved and the stability of the acylphosphine composition is further improved.

Each of the equivalence ratio and the weight ratio can be calculated based on the analysis result (integral ratio of 1H-NMR) of the acylphosphine composition using the nuclear magnetic resonance (NMR) method.

(Concrete example)
Specific examples of the acylphosphine composition are particularly limited as long as it is a composition containing a cation satisfying the conditions (Y1 to Y3, X1 and X2) shown in the formulas (1) and (2) and two or more kinds of anions. Not done.

Specific examples of cations are quaternary ammonium type cations represented by each of A1 to A42. However, the cation may be a cation having another structure not mentioned as a specific example here as long as it satisfies the condition shown in the formula (1).

Specific examples of the acylphosphine anion are acylphosphine-type anions represented by B1 to B16, respectively. However, the acylphosphine anion may be an anion having another structure not mentioned as a specific example as long as it satisfies the condition shown in the formula (2).

[Production method]
The method for producing the acylphosphine composition is not particularly limited. Therefore, the acylphosphine composition can be produced by using a known production method. Specific methods for producing some acylphosphine compositions will be described later.

[Action and effect]
This acylphosphine composition contains a cation represented by the formula (1) and two or more types of anions containing the acylphosphine anion represented by the formula (2), and has an equivalent ratio of 1.005 to 1.100. Is.

In this case, as compared with the case where the equivalent ratio does not satisfy the above-mentioned conditions, as described above, the solubility of the acylphosphine composition is improved and the stability of the acylphosphine composition is improved. Therefore, the storage stability of the polymerizable composition containing the acylphosphine composition is improved, and the curability of the polymerizable composition is also improved, so that excellent physical properties can be obtained.

In particular, when the weight ratio is 0.25 to 1.00, the solubility of the acylphosphine composition is further improved and the stability of the acylphosphine composition is further improved, so that a higher effect can be obtained. it can.

Further, if X1 is a 2,4,6-trimethylphenyl group in the formula (2), the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.

Further, if X2 is a phenyl group in the formula (2), the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.

Further, in the formula (2), one of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and the remaining two of Y1, Y2 and Y3 are terminal 1s, respectively. A linear alkyl group having 1 to 6 carbon atoms in which the hydrogen groups are substituted with hydroxyl groups improves the curability of the polymerizable composition containing the acylphosphine composition, and thus has a higher effect. Obtainable.

<2. Polymerizable composition>
Next, the polymerizable composition of one embodiment of the present invention using the above-mentioned acylphosphine composition will be described.

[Constitution]
This polymerizable composition contains an acylphosphine composition, a reactive group-containing compound, and an aqueous solvent. However, the type of the acylphosphine composition may be only one type or two or more types. The fact that the number of types may be one or more is the same for each of the reactive group-containing compound and the aqueous solvent.

(Acylphosphine composition)
The acylphosphine composition functions as a polymerization initiator during the polymerization reaction of the polymerizable composition. The details regarding the composition of the acylphosphine composition are as described above.

(Content)
The content of the acylphosphine composition in the polymerizable composition is not particularly limited, but is preferably 0.1% by mass to 30% by mass, and 1% by mass to 10% by mass in the total solid content. More preferably. This is because the storage stability and curability of the polymerizable composition are improved.

The "total solid content" described here is a series of components (liquid component and solid component) constituting the polymerizable composition, excluding the aqueous solvent which is a liquid component under the conditions of 25 ° C. and 1 atm. It means all of the remaining solid components. Therefore, the content of the acylphosphine composition described above means the ratio of the mass of the acylphosphine composition to the mass of all solid components. The definition of total solids described here is the same in the following. The liquid component may contain not only an aqueous solvent but also an organic solvent or the like, if necessary.

(Reactive group-containing compound)
The reactive group-containing compound is a compound containing a reactive group represented by the formula (3), and the number of reactive groups contained in the reactive group-containing compound may be only one or two or more.

(R1 is either a hydrogen group or a methyl group.
Z1 is either -O- or -NR2, and R2 is either a hydrogen group and a hydrocarbon group having 1 or more and 20 or less carbon atoms.
Z2 is an alkylene group having 1 or more and 6 or less carbon atoms.
n is an integer of 0 or more and 30 or less.
However, an asterisk (*) represents an unbonded bond. )

In equation (3), as described above, an asterisk (*) indicates an unbonded bond. Therefore, in the formula (3), the reactive group-containing compound is not shown, but only the reactive groups contained in the reactive group-containing compound are shown.

(R1)
When the number of reactive groups is two or more, the types of two or more R1s may be the same or different from each other. Of course, when the number of reactive groups is 3 or more, only some of the types of R1 among the 3 or more R1s may be the same.

(Z1)
The type of hydrocarbon group having 1 to 20 carbon atoms is not particularly limited. The hydrocarbon group described here is a general term for a monovalent group composed of hydrogen and carbon. The hydrocarbon group may be linear, branched, cyclic, or two or more of them bonded to each other. In addition, the hydrocarbon group may contain one or more carbon-carbon unsaturated bonds. The intercarbon unsaturated carbon bond may be an intercarbon double bond, an intercarbon triple bond, or both.

When the number of reactive groups is 2 or more, the types of 2 or more Z1s may be the same or different from each other. Of course, when the number of reactive groups is 3 or more, only some Z1 types among the 3 or more Z1s may be the same.

Specific examples of the hydrocarbon group are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms because the hydrocarbon group has 1 to 20 carbon atoms. A group, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and the like.

Among them, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, and carbon. Any of an aryl group having a number of 6 to 10 and an arylalkyl group having a carbon number of 7 to 10 is preferable. This is because the sensitivity of the polymerizable composition is improved.

Specific examples of the alkyl group have 1 to 20 carbon atoms, and therefore have a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group. , Tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group. Groups, octadecyl groups and icosyl groups and the like.

Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group. , Tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group and isodecyl group.

Specific examples of the alkenyl group include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, and a 2-hexenyl group because they have 2 to 20 carbon atoms. 3-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, 4-dodecenyl group, These include 3-cyclohexenyl group, 2,5-cyclohexadienyl-1-methyl group and 4,8,12-tetradecatrienylallyl group.

Specific examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, and a 2-hexenyl group. These include 3-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group and 4-decenyl group.

The cycloalkyl group having 3 to 20 carbon atoms is either a saturated monocyclic alkyl group having 3 to 20 carbon atoms or a saturated polycyclic alkyl group. Specific examples of the cycloalkyl group have 3 to 20 carbon atoms, and therefore have a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, and a decahydro group. These include naphthyl groups, octahydropentalene groups, bicyclo [1.1.1] pentanyl groups and tetradecahydroanthrasenyl groups.

Specific examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, and a decahydro group. Such as a naphthyl group, an octahydropentalene group and a bicyclo [1.1.1] pentanyl group.

A cycloalkylalkyl group having 4 to 20 carbon atoms is a group having 4 to 20 carbon atoms in which one or more hydrogen groups contained in the alkyl group are substituted with a cycloalkyl group. It is a general term for. Specific examples of cycloalkylalkyl groups have 4 to 20 carbon atoms, so cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl. Group, cyclodecylmethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclo Decylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group , 4-Cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group, 4-cycloheptylbutyl group, 4-cyclooctylbutyl group, 4-cyclononylbutyl group, 4-cyclodecylbutyl group, 3- 3-adamanthylpropyl group and decahydronaphthylpropyl group.

Specific examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, and cyclononylmethyl. Group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3- Cyclohexylpropyl group, 3-cycloheptylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group and the like.

Specific examples of the aryl group are a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group and the like because they have 6 to 20 carbon atoms. Specific examples of the aryl group include a phenyl group and a biphenylyl group in which one or more hydrogen groups are substituted by any one or more of the above-mentioned alkyl group, alkenyl group, carboxyl group and halogen group. , Naftyl group, anthryl group, etc., and more specifically, 4-chlorophenyl group, 4-carboxyphenyl group, 4-vinylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group and the like. ..

Specific examples of the aryl group having 6 to 10 carbon atoms are a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group and the like. Specific examples of the aryl group include a phenyl group and a biphenylyl group in which one or more hydrogen groups are substituted by any one or more of the above-mentioned alkyl group, alkenyl group, carboxyl group and halogen group. , Naftyl group, anthryl group, etc., more specifically, 4-chlorophenyl group, 4-carboxyphenyl group, 4-vinylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group, etc. is there.

An arylalkyl group having 7 to 20 carbon atoms is a general term for a group having 7 to 30 carbon atoms in which one or more hydrogen groups contained in the alkyl group are substituted with an aryl group. Is. Specific examples of the arylalkyl group include a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenylethyl group and a naphthylpropyl group because they have 7 to 20 carbon atoms.

(Z2)
When the number of reactive groups is two or more, the types of two or more Z2s may be the same or different from each other. Of course, when the number of reactive groups is 3 or more, only some Z2 types out of 3 or more Z2s may be the same as each other.

Further, when the value of n is 2 or more, the types of two or more Z2s may be the same as each other or may be different from each other. Of course, when the value of n is 3 or more, only some Z2 types out of 3 or more Z2s may be the same as each other.

Specific examples of the alkylene group have 1 to 6 carbon atoms, and therefore may be a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, or an isopropylene group and an isopropylene group. It may be a branched alkylene group such as an isobutylene group. Among them, the alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably any one of an ethylene group, a propylene group and an isopropylene group. This is because the water solubility of the reactive group-containing compound is improved.

(Details about n)
Since the value of n is an integer of 0 to 30 as described above, it may be 0. When the value of n is 0, the reactive group is represented by R1-C (= CH ₂ ) -C (= O) -Z1- *.

(Concrete example)
The type of mother to which the reactive group is bound is not particularly limited. When the number of reactive groups is y, the above-mentioned parent is a y-valent hydrocarbon group or the like. When y = 1, the parent is the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, arylalkyl group and the like, and the carbon number of each of these groups is particularly limited. Not done. When y = w (w is an integer of 2 or more), the parent is from each of the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group and arylalkyl group. It is a group in which (w-1) hydrogen groups are released, and the number of carbon atoms thereof is not particularly limited.

Among them, the reactive group-containing compound is preferably one or both of an alkylene oxide-modified (meth) acrylate compound and a (meth) acrylamide compound. This is because the polymerizable composition is likely to undergo a polymerization reaction.

The alkylene oxide-modified (meth) acrylate compound is an alkylene oxide-modified acrylate compound, an alkylene oxide-modified methacrylate compound, or the like. The (meth) acrylamide compound is an acrylamide compound, a methacrylamide compound and the like.

The alkylene oxide-modified acrylate compound is a compound in the formula (3) in which R1 is a hydrogen group, Z1 is —O—, and the value of n is 1 to 30. The alkylene oxide-modified methacrylate compound is a compound in the formula (3) in which R1 is a methyl group, Z1 is —O—, and the value of n is 1 to 30.

Specific examples of the alkylene oxide-modified acrylate compound include diethylene oxide-modified neopentyl glycol diacrylate, dipropylene oxide-modified neopentyl glycol diacrylate, diethylene oxide-modified 1,6-hexanediol diacrylate and dipropylene oxide-modified 1,6-hexane. For example, diol diacrylate.

Specific examples of the alkylene oxide-modified methacrylate compound include diethylene oxide-modified neopentyl glycol dimethacrylate, dipropylene oxide-modified neopentyl glycol dimethacrylate, diethylene oxide-modified 1,6-hexanediol dimethacrylate and dipropylene oxide-modified 1,6-hexane. Such as diol dimethacrylate.

Commercially available products may be used as each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound. Specifically, NK ester A-600, A-GLY-20E and NK economyr A-PG5054E manufactured by Shin Nakamura Chemical Industry Co., Ltd. can be used.

Among them, in each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, Z2 is preferably either an ethylene group or a propylene group in the formula (3). This is because the solubility of the reactive group-containing compound, particularly the solubility in an aqueous solvent, is improved. When Z2 is an ethylene group, the solubility of the reactive group-containing compound is significantly improved.

When each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound has one reactive group, the solubility of the reactive group-containing compound is guaranteed, so that the value of n is preferably 6 or more. When each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound has two or more reactive groups, the solubility of the reactive group-containing compound is guaranteed, so that the sum of the two or more n values. Is preferably 10 or more.

The acrylamide compound is a compound in the formula (3) in which R1 is a hydrogen group, Z1 is -NR2-, and the value of n is 0. The methacrylamide compound is a compound in the formula (3) in which R1 is a methyl group, Z1 is −NR2-, and the value of n is 0.

Specific examples of acrylamide compounds include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dipropylacrylamide, acryloylmorpholin, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide and the like.

Specific examples of methacrylamide compounds include hydroxymethacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetonemethacrylamide, N, N-dimethylmethacrylamide, N. , N-diethylmethacrylamide, N, N-dipropylmethacrylamide, methacrylloylmorpholin, Nn-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, N-methoxymethylmethacrylamide and the like.

Commercially available products may be used as each of the acrylamide compound and the methacrylamide compound. Specifically, FFM-2, FFM-3, FFM-4, FFM-5 and the like manufactured by FUJIFILM Corporation can be used.

(Content)
The content of the reactive group-containing compound in the polymerizable composition is not particularly limited, but is preferably 60% by mass to 99% by mass and 70% by mass to 95% by mass in the total solid content. Is more preferable. This is because the curability of the polymerizable composition is improved.

(Aqueous solvent)
Aqueous solvent is a general term for solvents containing water and an organic solvent that is miscible with water as well as being liquid under the conditions of 25 ° C. and 1 atm. That is, the aqueous solvent may be water alone, an organic solvent miscible with water, or a mixture of both. The organic solvent miscible with this water means an organic solvent that dissolves 0.01 g or more in 100 g of water at 20 ° C.

The following advantages can be obtained by using a polymerizable composition containing an aqueous solvent. First, the thickness of the coating film, which will be described later, can be easily controlled. Secondly, as the substrate described later, not only the substrate having high resistance to the organic solvent but also the substrate having low resistance to the organic solvent can be used, so that the degree of freedom regarding the type of the substrate is widened. Third, when the polymerizable composition is applied onto an organic material (for example, a film containing the organic material), the organic material is less likely to be attacked by the polymerizable composition. Fourth, since the aqueous solvent is environmentally friendly, the environmental load is reduced when the polymerizable composition is used.

The type of water is not particularly limited, but specifically, it is pure water, ion-exchanged water, or the like.

The type of organic solvent that can be mixed with water is not particularly limited, but specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1, 3-Propylenediol, 2-Methyl-1,3-Propylenediol, 1,2-Pentanediol, 1,5-Pentanediol, 2,4-Pentanediol, 1,2-Hexanediol, 3,5-Diol- 3-Hexin-2,5-diol, 2,5-hexanediol, hexylene glycol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3 -Pentanediol, 2,5-dimethyl-2,5-hexanediol, sulfolane, 1,4-cyclohexanedimethanol, 2,2-thiodiethanol, 3-pyridylcarbinol, propylene glycol monomethyl ether, dipropylene glycol methyl ether , Tripropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene Glycol n-butyl ether, propylene glycol t-butyl ether, dipropylene glycol t-butyl ether, propylene glycol phenyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol Ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, triethylene glycol n-butyl ether, ethylene glycol n-hexyl ether, diethylene glycol n-hexyl ether, ethylene glycol phenyl ether and the like.

Among them, as the organic solvent miscible with water, a lower alcohol having 5 or less carbon atoms is preferable. This is because the solubility in water is significantly improved.

(Content)
The content of the aqueous solvent in the polymerizable composition is not particularly limited, but is preferably 10% by mass to 99% by mass, more preferably 30% by mass to 95% by mass, and 50% by mass. It is more preferably to 90% by mass. This is because the handleability of the polymerizable composition is improved, and the thickness of the cured product formed by using the polymerizable composition is easily controlled.

When the polymerizable composition is used as an ink composition for inkjet, the content of the aqueous solvent in the polymerizable composition is not particularly limited, but is particularly 30% by mass to 95% by mass. It is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 80% by mass. This is because the fluidity of the ink containing the ink composition can be easily controlled.

The content of the organic solvent miscible with water in the aqueous solvent is not particularly limited, but is preferably 40% by mass or less, more preferably 20% by mass or less, and 10% by mass. It is more preferably 5% by mass or less, and particularly preferably 5% by mass or less. This is because the environmental load is reduced when the polymerizable composition is used.

(Other)
The polymerizable composition may further contain any one or more of the other components, if necessary. The types of other components can be arbitrarily set according to the use of the polymerizable composition and the like.

Specifically, other components include cross-linking agents, photosensitive groups, organic acids, coupling agents, leveling agents, sensitizers, surfactants, basic compounds, colorants, photopolymerization (radical) initiators (acyls). (Excluding phosphine compositions), water-soluble preservatives, conductive substances, organic solvents, etc., any one or more. In the following, the details of the colorant will be described on behalf of the series of other components described above.

(Colorant)
The other component is a colorant. This colorant is a component that colors the polymerizable composition. This is because the polymerizable composition can be colored by using a colorant. The type of the colorant may be only one type or two or more types.

This colorant contains any one or more of pigments and dyes. Therefore, the colorant may contain only the pigment, may contain only the dye, or may contain both the pigment and the dye. Each of the pigment and the dye may be an inorganic material, an organic material, or a mixture of the inorganic material and the organic material.

Pigments are coloring materials that are insoluble in solvents. The pigments include not only inorganic and organic materials that are not required in the solvent, but also materials in which one or both of the inorganic and organic dyes are raked. The dye may be water-soluble or oil-soluble.

A specific example of the pigment is a black pigment. The black pigment includes carbon black produced by any one or more of the furnace method, the channel method and the thermal method, as well as acetylene black, ketjen black and lamp black. The black pigment may be a material in which the above-mentioned black pigment is adjusted or coated with an epoxy resin, or the above-mentioned black pigment is previously dispersed in the resin in a solvent and a resin of 20 mg / g to 200 mg / g. It may be a material coated with a black pigment, a material in which the above-mentioned black pigment is subjected to an acidic surface treatment or an alkaline surface treatment, or a carbon black having an average particle size of 8 nm or more and a DBP oil absorption amount of 90 ml / 100 g or less. Alternatively, carbon black may be used in which the total amount of oxygen calculated from carbon monoxide (CO) and carbon dioxide (CO ₂ ^{) in the volatile matter at 950 ° C. is 9 mg or more per 100 m 2 of the surface area.} Further, the black pigment may be graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black or the like.

Further, specific examples of pigments are colored pigments of organic pigments and inorganic pigments, and the color of the colored pigments is a color other than black. Specific examples of organic pigments and inorganic pigments include chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine blue, prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, etc. Yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber and lake pigments.

Among them, the pigment is preferably a black pigment, more preferably carbon black. This is because excellent light-shielding properties can be obtained.

The pigment may be a commercially available product. Specific examples of commercially available pigments are MICROPIGMO WMMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBE-5, MICROPIGMO WMVER-5, MICROPIGMO WMVT-5 BLACK CW-1 (manufactured by Orient Chemical Industry Co., Ltd.), Pigment Red 1,2,3,9,10,14,17,22,23,31,38,41,48,49,88,90,97 , 112,119,122,123,144,149,166,168,169,170,171,177,179,180,184,185,192,200,202,209,215,216,217,220,223 , 224,226,227,254,228,240,254, Pigment Orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64 , 65,71, Pigment Yellow 1,3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100,109,110 , 113,114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180,185, Pigment Green 7,10,36,58, Pigment Blue 15,15: 1,15: 2,15: 3,15: 4,15: 5,15: 6,22,24,56,60,61,62,64 , Pigment Violet 1,19,23,27,29,30,32,37,40,50 and the like.

Specific examples of dyes are metal complex compounds and the like. Specific examples of the metal complex compound include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindolin compounds, and quinacridone compounds. Antanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, azo dye, cyanine dye and the like.

The dye may be a commercially available product. Specific examples of commercially available dyes are WATER YELLOW 1, WATER YELLOW 2, WATER YELLOW 6C, WATER YELLOW 6CL, WATER ORANGE 18, WATER ORANGE 25, WATER RED 1, WATER RED 2 RED 27, WATER PINK 2S, WATER BROWN 16, WATER GREEN 8, WATER BLUE 3, WATER BLUE 9, WATER BLUE 105S, WATER BLUE 106, WATER BLUE 117-L, WATER VIOLER 1- , WATER BLACK 256-L, WATER BLACK R-455, WATER BLACK R-510, BONJET YELLOW 161-L, BONJET MAGENTA XXX, BONJET CYAN XXX, BONJET BLACK 891-L, VALIFAST , VALIFAST RED 2320, VALIFAST PINK 1364, VALIFAST PINK 2310N, VALIFAST VIOLET 1701, VALIFAST BLACK 1815, VALIFAST BLACK 1807, VALIFAST BLACK 3804, VALIFAST BLACK 3810, VALIFAST BLACK 3820, VALIFAST BLACK 3830, VALIFAST BLACK 3840, VALIFAST BLACK 3866, VALIFAST BLACK 3870, VALIFAST ORANGE 2210, VALIFAST BROWN 3402, VALIFAST BLUE 1613 and VALIFAST BLUE 1605 (all manufactured by Orient Chemical Industry Co., Ltd.), Acid Green 1, Acid Green 3, Acid Green Green 50, Acid Green A, Alizarin Cyanin Green F, Bas ic Green 1, Basic Green 5, Bromocresol Green, Bromocresol Green Sodium Salt, Erio Green B, Fast Green FCF, Fiter Blue Green Sodium Salt, Indocyanine Green, Janus Green B, Leuco Malachite Green, Malachite Green, Oxalate, Methyl Green, Palatine Chrome Green, Quinizarin Green SS, Acid Red 1, Acid Red 9, Acid Red 13, Acid Red 18, Acid Red 26, Acid Red 27, Acid Red 52, Acid Red 91, Acid Red 91, Acid Red , Acid Red 94, Acid Red 112, Acid Red 114, Acid Red 151, Acid Red 289, Alizarin, Allura Red AC, Astrazon Red 6B, Azo Rubine, Basic Leuco Red 2B, Chromotrope 2R, Congo Red, Cresol Red, Crezol Red Sodium Salt, Crocein Scarlet 3B, Direct Fast Red 3B, Direct Red 80, Direct Scarlet B, Eriochrome Red B, 4-Ethoxychrysoidine Hydrochloride, Ethyl Red, Fast Red B Salt, Fast Red ITR Base, Lake Red CBA, Lithol Rubin BCA, Methoxy Red, Methyl Red, Methyl Red Sodium Salt, Oralith Brilliant Pink R, Para Red, Phenol Red Sodium Salt, Pigment Red, Pigment Red 254, Rhodamine 6G, Sudan II, Suda n III, Sudan R, 2,3,5-Triphenyltrazolium Chloride, Acid Black 1, Acid Blue 1, Acid Blue 9, Acid Blue 92, Acid Blue 92, Acid Blue3 SolidBlueSalt, AcidBlue 7, Basic Blue 12, Basic Blue 17, Basic Blue 24, Basic Blue 26, Briliant Blue G, Brilliant Blue R, Bromocresol Blue, Bromophenol Blue, Bromothymol Blue, Chrome Pure Blue BX, Coomassie Brilliant Blue G-250, Coomassie Brilliant Blue R-250, Direct Blue 1, Direct Blue 2, Direct Blue 14, Direct Sky Blue, Disperse Blue 14, Eriochrome Blue Black B, Eriochrome Cyanine R, Evans Blue, Filter Blue Green Sodium Salt, Indigo Carmine, Indigo, Methylene Blue Hydrate , Modent Black 17, Modern Blue 13, Modent Blue 29, Omega Chrome Black Blue G, Pigment Blue 15, Quinizarin Blue, Sudan Blue, Tymothymol Blue, Thymol Blue, Thymol Blue, methylanthraquione, Astrazon Orange R, Basic Orange 14, Crocein Orange G, Ethyl Orange, Methyl Orange, Mordant Orange 1, α-naphtol Orange, Oil Orange, Orange G, Permanent Orange, Pyrazolone Orange, Sudan I and Sudan II (above, Tokyo Kasei Kogyo Co., Ltd. (Made by a formula company), etc.

(Sensitizer)
The type of sensitizer is not particularly limited, but specific examples thereof include thioxanthone and benzophenone.

(Photopolymerization (radical) initiator)
The type of photopolymerization (radical) initiator is not particularly limited, and specific examples thereof include benzoin ether, benzyl acetal, α-hydroxyacetphenone, α-aminoacetophenone, and oxime ester.

(Organic solvent)
The organic solvent described here is a general term for solvents other than the above-mentioned aqueous solvent. The type of organic solvent is not particularly limited, but specifically, ketones, ether solvents, ester solvents, cellosolve solvents, alcohol solvents (excluding alcohol solvents corresponding to aqueous solvents), These include ether ester-based solvents, BTX-based solvents, aliphatic hydrocarbon-based solvents, terpene hydrocarbon oils, halogenated aliphatic hydrocarbon-based solvents, and halogenated aromatic hydrocarbon-based solvents.

Ketones include methyl ethyl ketone, acetone and cyclohexanone. Ethereal solvents include oxane, tetrahydrofuran and 1,2-dimethoxyethane. Ester-based solvents include methyl acetate, ethyl acetate and propyl acetate. Cellosolve-based solvents include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Alcohol-based solvents include methanol and ethanol. Examples of the ether ester solvent include ethylene glycol monomethyl acetate and ethylene glycol monoethyl acetate. BTX-based solvents are benzene, toluene, xylene and the like. Aliphatic hydrocarbon solvents include hexane, heptane, octane and cyclohexane. Terpene hydrocarbon oils include turpentine, D-limonene and pinene. Halogenated aliphatic hydrocarbon solvents include carbon tetrachloride, chloroform, trichlorethylene, methylene chloride and 1,2-dichloroethane. The halogenated aromatic hydrocarbon solvent is chlorobenzene or the like. In addition, the organic solvent may be aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.

The content of the organic solvent in the polymerization composition is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. .. This is because the environmental load is reduced when the polymerizable composition is used.

[Production method]
In the case of producing this polymerizable composition, the acylphosphine composition and the reactive group-containing compound are put into an aqueous solvent, and then the aqueous solvent is stirred. In this case, a colorant or the like may be further added to the aqueous solvent. As a result, the acylphosphine composition and the reactive group-containing compound are each dispersed or dissolved in the aqueous solvent, so that a polymerizable composition is prepared.

[Action and effect]
According to this polymerizable composition, an acylphosphine composition and a reactive group-containing compound are contained together with an aqueous solvent, and the acylphosphine composition has the above-mentioned constitution. Therefore, by ensuring the storage stability and curability of the polymerizable composition, a good cured product can be easily produced using the polymerizable composition, and excellent physical properties can be obtained. The other actions and effects of the polymerizable composition are the same as those of the acylphosphine composition.

<3. Hardened product and its manufacturing method>
Next, a cured product of one embodiment of the present invention using the above-mentioned polymerizable composition and a method for producing the cured product will be described.

[Constitution]
As described above, the cured product described here is a cured reaction product of the polymerizable composition. More specifically, the cured product is a reaction product formed by a polymerization reaction (photoradical polymerization reaction) of a reactive group-containing compound via an acylphosphine composition that functions as a polymerization initiator. Therefore, after the polymerizable composition is applied to the surface of the substrate, the polymerizable composition undergoes a polymerization reaction to form a film containing a cured reaction product (cured product) of the polymerizable composition on the surface of the substrate. Will be done.

[Production method]
When producing this cured product, first, a polymerizable composition is prepared by the above-mentioned procedure. Subsequently, the polymerizable composition is applied to the surface of the substrate, and then the polymerizable composition is dried. As a result, a coating film containing the polymerizable composition is formed on the surface of the substrate.

The type of the substrate is not particularly limited, but for example, it is any one or more of metal, wood, rubber, plastic, glass, ceramic, paper and cloth. The method for applying the polymerizable composition is not particularly limited, and examples thereof include a spin coater, a bar coater, a roll coater, a curtain coater, various printing methods, and a dipping method.

Finally, irradiate the coating film with active energy rays. The type of active energy ray is not particularly limited, but an example is ultraviolet light using a mercury lamp or the like as a light source. Irradiation conditions such as the wavelength of ultraviolet light, irradiation intensity, and irradiation time can be arbitrarily set.

The irradiation conditions are as follows, for example. The wavelength is 200 nm to 400 nm. The irradiation intensity is 1 mW / cm to 500 mW / cm, preferably 5 mW / cm to 300 mW / cm, and when converted to the irradiation amount, it is 10 mJ / cm ² to 1000 mJ / cm ² , preferably 100 mJ / cm ² to 500 mJ. / Cm ² . The irradiation time is 1 second to 500 seconds, preferably 5 seconds to 300 seconds.

As a result, the polymerization reaction of the reactive group-containing compound proceeds via the acylphosphine composition (polymerization initiator) in the coating film, so that a cured reaction product (cured product) of the polymerizable composition is formed. Therefore, a film containing a cured product is formed.

When forming a coating film, a plurality of coating films may be laminated on each other by repeating the above-mentioned coating film forming procedure.

[Action and effect]
According to this cured product, it is a cured reaction product of the polymerizable composition, and the polymerizable composition has the above-mentioned structure. Therefore, excellent physical properties can be obtained for the same reason as described with respect to the polymerizable composition. The other actions and effects on the cured product are the same as those on the polymerizable composition.

Further, according to the method for producing a cured product, since the above-mentioned polymerizable composition is irradiated with active energy rays, the polymerization reaction of the polymerizable composition is stable, sufficient and stable according to the irradiation of the active energy. proceed. Therefore, a cured product having the above-mentioned excellent physical characteristics can be obtained.

In this case, in particular, in order to obtain a cured product having excellent physical properties, it is not only necessary to irradiate the polymerizable composition with active energy rays, but also to irradiate the polymerizable composition with active energy rays. Since the amount is small, a cured product having excellent physical properties can be easily and stably produced. That is, there are advantages in that the manufacturing process of the cured product is shortened, the substrate is less likely to be damaged, and patterning (manufacturing the cured product so as to obtain a desired pattern) becomes possible. can get.

<4. Applications (polymerization initiator, etc.)>
The uses of the above-mentioned acylphosphine composition, polymerizable composition and cured product are not particularly limited, but examples thereof include various lenses, various films and various functional films.

Specifically, for glasses, imaging lenses, antistatic films, optical films, conductive films, protective films, heat ray shielding materials, transfer foils, printing plates, insulating varnishes, insulating sheets, laminated boards, printed substrates, and flexible displays. Substrate, touch panel substrate, printing mask, molding material, putty, building material, nail material, cosmetics, siding, glass fiber impregnant, sealant, passivation film for semiconductors and solar cells, interlayer insulating film, protective film , Prism lens sheet for backlight of liquid crystal display device, Frenel lens sheet for projection TV screen, lens part of lens sheet for lenticular lens sheet, backlight using those sheets, etc. Protective film for liquid crystal color filter -Spacer, DNA separation chip, microreactor, nanobiodevice, recording material for hard disk, solid-state imaging device, solar cell panel, light emitting diode, organic light emitting device, electrode protective material, luminescent film, fluorescent film, MEMS element, actuator, hologram , Plasmon device, polarizing plate, polarizing film, alignment film, microlens, optical element, retardation film, optical connector, optical waveguide, casting agent for optical modeling, food, beverage container, food packaging material, dental material, Sanitary ware, housing equipment, etc. This housing equipment is a bathtub or the like.

In particular, the acylphosphine composition is preferably used as a polymerization initiator in applications requiring a polymerization reaction, as described above. This is because the solubility of the acylphosphine composition is ensured, and the storage stability and curability of the polymerizable composition containing the acylphosphine composition are improved. As a result, a good cured product is formed using the polymerizable composition.

Hereinafter, examples of the present invention will be described in detail.

(Experimental Examples 1 to 45)
First, an acylphosphine composition is synthesized by the procedure described below, a polymerizable composition is prepared using the acylphosphine composition, and then a coating film (cured product) is produced using the polymerizable composition. The physical properties of the acylphosphine composition, the polymerizable composition and the cured product were evaluated.

[Synthesis of acylphosphine composition]
Five kinds of acylphosphine compositions represented by C1 to C5 were synthesized. The equivalent ratios and weight ratios for the acylphosphine compositions are as shown in Tables 1 and 2, respectively.

When synthesizing the acylphosphine composition shown in C1, first, in a nitrogen atmosphere, in a reaction flask, 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphine acid was added. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 26.6 g (164.8 mmol) of butyldiethanolamine was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is the acylphosphine composition shown in C1 (Experimental Example 1).

A pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.0 g (173.4 mmol) (Experimental Example 2). A pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.1 g (174.3 mmol) (Experimental Example 3). Light yellow crystals were obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.3 g (175.2 mmol) (Experimental Example 4). A pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 29.4 g (182.1 mmol) (Experimental Example 5). A pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 30.2 g (187.3 mmol) (Experimental Example 6). A pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 30.8 g (190.7 mmol) (Experimental Example 7). Light yellow crystals were obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 33.6 g (208.1 mmol) (Experimental Example 8).

When synthesizing the acylphosphine composition shown in C2, first, in a nitrogen atmosphere, in a reaction flask, 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphinic acid was added. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 15.8 g (156.1 mmol) of 4-methylmorpholine was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is the acylphosphine composition shown in C2 (Experimental Example 9).

A pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 17.5 g (173.4 mmol) (Experimental Example 10). Light yellow crystals were obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 17.6 g (174.3 mmol) (Experimental Example 11). Light yellow crystals were obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 18.1 g (178.6 mmol) (Experimental Example 12). A pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 19.2 g (189.01 mmol) (Experimental Example 13). A pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 19.3 g (190.7 mmol) (Experimental Example 14). A pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 21.0 g (208.1 mmol) (Experimental Example 15).

When synthesizing the acylphosphine composition shown in C3, first, in a nitrogen atmosphere, in a reaction flask, 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphinic acid was added. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 29.9 g (156.1 mmol) of 1-benzyl-4-hydroxypiperidine was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to prepare the reaction solution. Got Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is the acylphosphine composition shown in C3 (Experimental Example 16).

A pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.2 g (173.4 mmol) (Experimental Example 17). A pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.3 g (174.3 mmol) (Experimental Example 18). A pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.9 g (176.9 mmol) (Experimental Example 19). Light yellow crystals were obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 36.5 g (190.7 mmol) (Experimental Example 20). A pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 39.8 g (208.1 mmol) (Experimental Example 21).

When synthesizing the acylphosphine composition shown in C4, first, in a nitrogen atmosphere, in a reaction flask, 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphinic acid was added. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 14.0 g (156.1 mmol) of dimethylethanolamine was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is the acylphosphine composition shown in C4 (Experimental Example 22).

A pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 15.4 g (173.4 mmol) (Experimental Example 23). A pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 15.5 g (174.3 mmol) (Experimental Example 24). Light yellow crystals were obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 16.0 g (178.6 mmol) (Experimental Example 25). A pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 17.0 g (190.7 mmol) (Experimental Example 26). Pale yellow crystals were obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 18.6 g (208.1 mmol) (Experimental Example 27).

When synthesizing the acylphosphine composition shown in C5, first, in a nitrogen atmosphere, in a reaction flask, 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphinic acid was added. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 25.2 g (156.1 mmol) of tert-butyldiethanolamine was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is the acylphosphine composition shown in C5 (Experimental Example 28).

Pale yellow crystals were obtained by the same procedure except that the amount of tert-butyldiethanolamine added was changed to 28.0 g (173.4 mmol) (Experimental Example 29). Light yellow crystals were obtained by the same procedure except that the amount of tert-butyldiethanolamine added was changed to 28.1 g (174.3 mmol) (Experimental Example 30). Light yellow crystals were obtained by the same procedure except that the amount of tert-butyldiethanolamine added was changed to 28.6 g (178.6 mmol) (Experimental Example 31). Light yellow crystals were obtained by the same procedure except that the amount of tert-butyldiethanolamine added was changed to 30.8 g (190.7 mmol) (Experimental Example 32). Light yellow crystals were obtained by the same procedure except that the amount of tert-butyldiethanolamine added was changed to 33.6 g (208.1 mmol) (Experimental Example 33).

[Synthesis of other compositions]
For comparison, other compositions represented by C6 and C7 were also synthesized. The equivalent ratios and weight ratios for the other compositions are as shown in Table 2.

When synthesizing the other compositions shown in C6, first, in a reaction flask with reflux, 7.3 g (23 mmol) of 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester and 2-butanone (2-butanone) Methyl ethyl ketone) 40 g was added. Subsequently, the mixture in the reaction flask with reflux was stirred under a nitrogen stream and at room temperature to completely dissolve the 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester. Subsequently, 3.3 g (22 mmol) of sodium iodide was added to the reaction flask with reflux, and then the mixture in the reaction flask with reflux was stirred at room temperature (stirring time = 15 minutes). Subsequently, the temperature of the reaction solution was raised to 65 ° C., and then the reaction solution was stirred (stirring time = 8 hours) at that temperature to obtain a reaction solution. Finally, the temperature of the reaction solution was cooled to room temperature, and then the precipitate in the reaction solution was filtered to obtain white crystals, which is another composition shown in C6 (Experimental Example 34). ..

White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.4 g (23 mmol) (Experimental Example 35). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.5 g (23.1 mmol) (Experimental Example 36). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.6 g (24 mmol) (Experimental Example 37). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.7 g (25 mmol) (Experimental Example 38). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 4.2 g (28 mmol) (Experimental Example 39).

When synthesizing the other compositions shown in C7, first, in a nitrogen atmosphere, in a reaction flask, add 50.0 g (173.4 mmol) of phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. , 500 ml of dichloromethane (= 500 cm ³ ) and added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve the phenyl (2,4,6-trimethylbenzoyl) phosphinic acid. Subsequently, 7.10 g (82.4 mmol) of piperazine anhydride was added to the reaction flask, and then the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, the reaction solution was desolvated and then dried under reduced pressure (drying temperature = 40 ° C.) to obtain pale yellow crystals, which is another composition shown in C7 (Experimental Example 40).

A pale yellow crystal was obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.47 g (86.7 mmol) (Experimental Example 41). Pale yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.50 g (87.1 mmol) (Experimental Example 42). Light yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.80 g (92.8 mmol) (Experimental Example 43). Pale yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 8.22 g (95.4 mmol) (Experimental Example 44). Light yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 8.97 g (104.1 mmol) (Experimental Example 45).

[Preparation of polymerizable composition]
When preparing a polymerizable composition, first, 70 parts by mass of an aqueous solvent (ion-exchanged water) and 22.5 parts by mass of a reactive group-containing compound (acryloylmorpholin ACMO (registered trademark) manufactured by KJ Chemicals Co., Ltd.) And 5.7 parts by mass of a reactive group-containing compound (alkoxylated glycerin acrylate A-GLY-20E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and a polymerization initiator (acylphosphine composition shown in each of C1 to C5) 1 .5 parts by mass and 0.3 parts by mass of the leveling agent (polyether-modified polysiloxane copolymer TEGOglide100 manufactured by EVONIC) were weighed. The acylphosphine compositions (C1 to C5) used here contain other anions (hydroxide ions) together with the anions (acylphosphine anions) shown in each of C1 to C5. Subsequently, the reactive group-containing compound, the polymerization initiator and the leveling agent were added to the aqueous solvent, and then the aqueous solvent was stirred (temperature of the aqueous solvent = 25 ° C., stirring time = 10 minutes). Finally, a polymerizable composition was obtained by filtering the aqueous solvent using a 0.45 μm filter.

For comparison, a polymerizable composition was prepared by the same procedure except that other compositions (C6 and C7) were used instead of the acylphosphine compositions (C1 to C5). The other compositions (C6 and C7) used here contain other anions (hydroxide ions) along with the anions (acylphosphine anions) shown in C6 and C7, respectively.

[Manufacturing of cured product]
After applying the polymerizable composition to the surface of the substrate (Glass plate Eagle XG manufactured by Corning Inc.) using a coating device (spin coater), the polymerizable composition is dried (drying temperature = 90 ° C., drying time = 2 minutes). ). As a result, a coating film (thickness = 2 μm) of the polymerizable composition was formed. After that, a high-pressure mercury lamp was used as a light source to irradiate the coating film with active energy rays (ultraviolet light, illuminance = 20 mW / cm ² , irradiation amount = 500 mJ / cm ² ). As a result, the reactive group-containing compound was polymerized in the polymerizable composition via the polymerization initiator (acylphosphine composition and other compositions), so that a film containing a cured product was formed.

[Evaluation of physical properties]
When the physical properties (solubility) of the acylphosphine composition, the physical properties of the polymerizable composition (storage stability), and the physical properties of the cured product (curability) were evaluated, the results shown in Tables 1 and 2 were obtained. Was done. However, even when other compositions were used, the solubility, storage stability and curability were evaluated in the same manner.

When examining the solubility, 5 g of the acylphosphine composition was added to 95 g of ion-exchanged water (temperature = 25 ° C.), and then the ion-exchanged water was stirred (stirring time = 1 hour). As a result, the dissolved state of the acylphosphine composition was determined by visually observing the state of the ion-exchanged water. Specifically, since the acylphosphine composition was uniformly dissolved, it was determined to be A when no insoluble matter remained. Since the acylphosphine composition was not uniformly dissolved, if an insoluble matter remained, it was determined to be B.

When examining the storage stability, the polymerizable composition was stored in a low temperature environment (temperature = 5 ° C.) (storage time = 10 days). As a result, the storage state of the polymerizable composition was determined by visually observing the state of the polymerizable composition. Specifically, since the color of the polymerization composition is uniform and transparent, it was determined to be A when the state of the polymerizable composition did not change from the state after preparation. When the polymerization composition was cloudy or precipitates were generated in the polymerizable composition, and the state of the polymerizable composition had changed from the state after preparation, it was determined to be B.

When examining the curability, the cured state of the cured product was determined by visually and palpating the state of the cured product. Specifically, since the polymerizable composition was sufficiently cured, it was determined to be A when a uniformly transparent film was obtained. When the polymerizable composition was cured but the surface of the coating was cloudy, it was determined to be B. When the polymerizable composition was not sufficiently cured, that is, the polymerizable composition was uncured, and the film was sticky, it was determined to be C.

The "Comprehensive evaluation" column shown in Tables 1 and 2 shows the comprehensive evaluation of physical properties (solubility, storage stability and curability). Specifically, when the solubility determination result, the storage stability determination result, and the curability determination result were all A, the overall evaluation was set to A. On the other hand, when any of the solubility determination result, the storage stability determination result, and the curability determination result was B or C, the overall evaluation was set to B.

[Discussion]
As shown in Tables 1 and 2, each of the solubility, storage stability and curability varied greatly depending on the composition of the polymerizable composition.

Specifically, when the polymerizable composition does not contain the acylphosphine composition of the present invention, that is, when the polymerizable composition contains another composition (Experimental Examples 34 to 45), it is soluble. Since good results were not obtained in terms of storage stability and curability, a good overall evaluation could not be obtained.

On the other hand, when the polymerizable composition contains the acylphosphine composition of the present invention (Experimental Examples 1 to 33), the solubility, storage stability and curability each vary depending on the equivalent ratio. did.

Specifically, if the equivalent ratio does not meet the proper conditions (equivalent ratio = 1.005 to 1.100) (Experimental Examples 1, 2, 8 etc.), it is still soluble, storage stable and cured. Good overall evaluation was not obtained because good results were not obtained for all of the sexes. However, when the equivalent ratio satisfies the appropriate conditions (Experimental Examples 3 to 7, etc.), good results were obtained in all of solubility, storage stability, and curability, so that a good comprehensive evaluation was obtained. Was done.

In particular, when the equivalent ratio satisfies the appropriate conditions, and when the weight ratio also satisfies the appropriate conditions (weight ratio = 0.25 to 1.00), the solubility, storage stability and curability are improved. Sufficient results were obtained for all.

[Summary]
From the results shown in Tables 1 and 2, the acylphosphine composition contains the cation represented by the formula (1) and two or more types of anions containing the acylphosphine anion represented by the formula (2), and the equivalent ratio. When the value was 1.005 to 1.100, excellent solubility was obtained. In this case, excellent storage stability was obtained in the polymerizable composition containing the acylphosphine composition, and excellent curability was obtained in the coating film (cured product) formed by using the polymerizable composition. Was done. Further, in the coating film (cured product) obtained by irradiating the above-mentioned polymerizable composition with active energy rays, excellent curability was obtained. Therefore, excellent physical properties were obtained in each of the acylphosphine composition (polymerization initiator), the polymerizable composition, and the cured product, and a cured product having excellent physical properties was obtained by the method for producing the cured product. It was.

Although the present invention has been described above with reference to one embodiment and examples, since the embodiments of the present invention are not limited to the embodiments described in the embodiments and examples, various modifications can be made to the embodiments.

This application claims priority on the basis of Japanese Patent Application No. 2019-212569 filed on November 25, 2019 at the Japan Patent Office, and the entire contents of this application are referred to in this application. Incorporate for application.

One of ordinary skill in the art can conceive of various modifications, combinations, sub-combinations, and changes, depending on design requirements and other factors, but they are the purpose of the appended claims and the scope of their equivalents. It is understood that it is included in.

Claims (9)

1. The cation represented by the formula (1) and
   Including two or more kinds of anions including an acylphosphine anion represented by the formula (2),
   The ratio of the molar equivalent of the cation to the molar equivalent of the acylphosphine anion is 1.005 or more and 1.100 or less.
   Acylphosphine composition.
   N ⁺ HY1Y2Y3 ・ ・ ・ (1)
   (Each of Y1, Y2 and Y3 has a linear alkyl group having 1 or more and 6 or less carbon atoms, a linear alkenyl group having 2 or more and 6 or less carbon atoms, and 6 or more and 15 or less carbon atoms. An aryl group and any of an arylalkyl groups having 7 or more and 13 or less carbon atoms. The hydrogen groups of Y1, Y2 and Y3 may be substituted with hydroxyl groups, respectively. Y1, Y2 and Y3, respectively. The methylene group of is optionally substituted with any of -O-, -S-, -CO- and -N ⁺ H-. Any two of Y1, Y2 and Y3 are bonded to each other. May be good.)
   

   

   (X1 is an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group is a linear alkyl group having 1 or more and 8 or less carbon atoms and 3 or more and 8 or less carbon atoms. A branched alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl halide group having 3 or more and 8 or less carbon atoms, and 1 or more and 8 or less carbon atoms. A linear alkoxy group having 3 or more and 8 or less carbon atoms, a linear halogenated alkoxy group having 1 or more and 8 or less carbon atoms, and a 3 to 8 or less carbon atoms. It may be substituted with any of the branched alkoxy halide groups.
   X2 is a linear alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl group having 3 or more and 8 or less carbon atoms, and a linear alkoxy group having 1 or more and 8 or less carbon atoms. It is either a branched alkoxy group having 3 or more and 8 or less carbon atoms and an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group has 1 or more and 8 or less carbon atoms. A linear alkyl group, a branched alkyl group having 3 or more and 8 or less carbon atoms, a linear halogenated alkyl group having 1 or more and 8 or less carbon atoms, and 3 or more and 8 or less carbon atoms. A branched alkyl halide group, a linear alkoxy group having 1 or more and 8 or less carbon atoms, a branched alkoxy group having 3 or more and 8 or less carbon atoms, and a straight chain having 1 or more and 8 or less carbon atoms. A halogenated alkoxy group, a branched halogenated alkoxy group having 3 or more and 8 or less carbon atoms, a halogen group, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, It may be substituted with any one of a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group and a heterocyclic group. Each of the methylene groups of X2 may be substituted with either —O— or —S—. )
2. The ratio of the weight of the cation to the weight of the acylphosphine anion is 0.25 or more and 1.00 or less.
   The acylphosphine composition according to claim 1.
3. X1 is a 2,4,6-trimethylphenyl group.
   The acylphosphine composition according to claim 1 or 2.
4. The X2 is a phenyl group.
   The acylphosphine composition according to any one of claims 1 to 3.
5. One of the Y1, Y2 and Y3 is a linear alkyl group having 1 or more and 6 or less carbon atoms.
   Each of the remaining two of Y1, Y2 and Y3 is a linear alkyl group having 1 or more and 6 or less carbon atoms in which one of the terminal hydrogen groups is substituted with the hydroxyl group.
   The acylphosphine composition according to any one of claims 1 to 4.
6. The acylphosphine composition according to any one of claims 1 to 5.
   Polymerization initiator.
7. The acylphosphine composition according to any one of claims 1 to 5.
   A reactive group-containing compound containing a reactive group represented by the formula (3),
   A polymerizable composition comprising an aqueous solvent.
   

   

   (R1 is either a hydrogen group or a methyl group.
   Z1 is either -O- or -NR2-, and R2 is either a hydrogen group and a hydrocarbon group having 1 or more and 20 or less carbon atoms.
   Z2 is an alkylene group having 1 or more and 6 or less carbon atoms.
   n is an integer of 0 or more and 30 or less.
   However, an asterisk (*) represents an unbonded bond. )
8. A curing reaction product of the polymerizable composition according to claim 7.
   Hardened product.
9. Irradiate the polymerizable composition according to claim 7 with active energy rays.
   Method for manufacturing cured product.