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

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

Technical Field

[0001] 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 cured reaction product of the polymerizable composition, and a method for producing the same.

Background Art

[0002] Polymerizable compositions that can be cured using a polymerization reaction are used in various fields such as polymerization initiators, and cured products that are cured reaction products of the polymerizable compositions are also used in various fields. For this reason, various studies have been made on the composition of the polymerizable composition.

[0003] Specifically, in order to be adaptable to a wide range of light sources, a polymerizable composition (water-soluble composition) containing a reactive compound (a compound having a specific reactive group) together with an acylphosphine composition (acylphosphinate) has been proposed (see, for example, Patent Document 1). Further, in order to obtain excellent sensitivity, a polymerizable composition (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 (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

[0005] Although studies on the constitution of a polymerizable composition containing an acylphosphine composition have been actively conducted, the physical properties of the polymerizable composition are still not sufficient. In addition, the physical properties of a polymerization initiator that can be considered as an application of the polymerizable composition and the physical properties of a cured product that is a cured reaction product of the polymerizable composition are still not sufficient. Therefore, there is room for improvement.

[0006] An object of the present invention is to provide an acylphosphine composition, a polymerization initiator, a polymerizable composition, a cured product, and a method for producing the same, which can obtain excellent physical properties.

[0007] The acylphosphine composition according to one embodiment of the present invention contains a cation represented by the formula (1) and two or more anions including an acylphosphine anion represented by the formula (2), 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.

[0008] N + HY1Y2Y3 ···(1) (Each of Y1, Y2, and Y3 is any one of a linear alkyl group having 1 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group having 7 to 13 carbon atoms. The hydrogen groups of Y1, Y2, and Y3 may be substituted by a hydroxyl group. Each methylene group of Y1, Y2, and Y3 may be substituted by any one of -O-, -S-, -CO-, and -N + H-. Any two of Y1, Y2, and Y3 may be bonded to each other.)

[0009] [Chemical formula] (X1 is an aryl group having 6 to 15 carbon atoms, and each of the hydrogen groups of the aryl group may be substituted by any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, and a branched halogenated alkoxy group having 3 to 8 carbon atoms.) (X2 is any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and each of the hydrogen groups of the aryl group may be substituted by any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, a branched halogenated alkoxy group having 3 to 8 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, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, and a heterocyclic group-containing group. Each of the methylene groups of X2 may be substituted by either -O- or -S-.)

[0010] The polymerization initiator of one embodiment of the present invention includes an acylphosphine composition, and the acylphosphine composition has a configuration similar to the configuration of the acylphosphine composition of one embodiment of the present invention described above.)

[0011] The polymerizable composition of one embodiment of the present invention includes an acylphosphine composition, a reactive group-containing compound containing a reactive group represented by formula (3), and an aqueous solvent, and the acylphosphine composition has the same configuration as the acylphosphine composition of one embodiment of the present invention described above.

[0012] [Chemical formula] (R1 is either a hydrogen group or a methyl group. Z1 is either -O- or -NR2-, and R2 is either a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms. Z2 is an alkylene group having 1 to 6 carbon atoms. n is an integer from 0 to 30. However, the asterisk (*) represents an unbonded bond.)

[0013] The cured product of one embodiment of the present invention is a cured reaction product of the polymerizable composition, and the polymerizable composition has the same configuration as the polymerizable composition of one embodiment of the present invention described above.

[0014] The method for producing a cured product of one embodiment of the present invention is to irradiate the polymerizable composition with active energy rays, and the polymerizable composition has the same configuration as the polymerizable composition of one embodiment of the present invention described above.

[0015] According to the acylphosphine composition, polymerization initiator, or polymerizable composition of one embodiment of the present invention, the acylphosphine composition contains two or more anions including the cation shown in formula (1) and the acylphosphine anion shown in formula (2), 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, so excellent physical properties can be obtained.

[0016] Also, according to the cured product of one embodiment of the present invention, since it is a cured reaction product of the above-described polymerizable composition, excellent physical properties can be obtained.

[0017] Furthermore, according to the method for producing a cured product of an embodiment of the present invention, since the above-described polymerizable composition is irradiated with active energy rays, a cured product having excellent physical properties can be obtained.

Mode for Carrying Out the Invention

[0018] Hereinafter, an embodiment of the present invention will be described in detail. The order of description is as follows. However, the details of the present invention are not limited to the aspects described below and can be changed as appropriate.

[0019] 1. Acylphosphine composition 2. Polymerizable composition 3. Cured product and method for producing the same 4. Use (polymerization initiator, etc.)

[0020] <1. Acylphosphine composition> First, the acylphosphine composition of an embodiment of the present invention will be described.

[0021] [Configuration] 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 a polymerization initiator and may be other uses.

[0022] This acylphosphine composition has a salt structure. Specifically, the acylphosphine composition contains a quaternary ammonium type cation represented by formula (1) and two or more anions, and the two or more anions include an acylphosphine type anion represented by formula (2) (hereinafter referred to as "acylphosphine anion").

[0023] N + HY1Y2Y3 ···(1) (Each of Y1, Y2, and Y3 is any one of a linear alkyl group having 1 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group having 7 to 13 carbon atoms. Each hydrogen group of Y1, Y2, and Y3 may be substituted by a hydroxyl group. Each methylene group of Y1, Y2, and Y3 may be substituted by any one of -O-, -S-, -CO-, and -N + H-. Any two of Y1, Y2, and Y3 may be bonded to each other.)

[0024] [Chemical formula] (X1 is an aryl group having 6 to 15 carbon atoms, and each hydrogen group of the aryl group may be substituted by any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, and a branched halogenated alkoxy group having 3 to 8 carbon atoms.) X2 is any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms. Each of the hydrogen groups of the aryl group may be substituted by any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, a branched halogenated alkoxy group having 3 to 8 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, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, and a heterocyclic group-containing group. Each of the methylene groups of X2 may be substituted by either -O- or -S-.

[0025] (Details regarding the anion) As described above, two or more types of anions contain an acylphosphine anion. The number of types of acylphosphine anions may be only one type or two or more types.

[0026] (Acylphosphine anion) Details regarding the structure of the acylphosphine anion are as described below.

[0027] (X1) An aryl group is a general term for monovalent groups containing one or more aromatic rings. Specific examples of aryl groups include phenyl, naphthyl, and anthracenyl groups, etc., because the number of carbon atoms is 6 to 15. However, when the aryl group contains substituents described later, the number of carbon atoms of the aryl group is the total number of carbon atoms including the carbon atoms of the substituents. For this reason, for example, the number of carbon atoms of a trimethylphenyl group is 9, not 6. The definition regarding the number of carbon atoms of the aryl group described here is the same hereinafter.

[0028] Each of the one or more hydrogen groups contained in the aryl group may be substituted by a substituent. The substituents described here are, as described above, a linear alkyl group, a branched alkyl group, a linear halogenated alkyl group, a branched halogenated alkyl group, a linear alkoxy group, a branched alkoxy group, a linear halogenated alkoxy group, and a branched halogenated alkoxy group, any of which has a carbon number within a specific range.

[0029] 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 in a linear manner. Specific examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group because the number of carbon atoms is 1 to 8.

[0030] 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 more side chains. Specific examples of the branched alkyl group include 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, a neopentyl group, a sec-hexyl group, an isohexyl group, a tert-hexyl group, a neohexyl group, a sec-heptyl group, an isoheptyl group, a tert-heptyl group, a neoheptyl group, a sec-octyl group, an isooctyl group, a tert-octyl group, and a neooctyl group because the number of carbon atoms is 3 to 8.

[0031] A linear halogenated alkyl group is a group in which one or more hydrogen groups contained in the above-mentioned linear alkyl group are each replaced by a halogen group. The type of halogen group is not particularly limited, and examples include a fluorine group, a chlorine group, a bromine group, and an iodine group. However, the type of halogen group contained in the linear halogenated alkyl group may be only one type or two or more types.

[0032] A branched halogenated alkyl group is a group in which one or more hydrogen groups contained in the above-mentioned branched alkyl group are replaced by a halogen group. Details regarding the type of halogen group are as described above.

[0033] 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 thus are a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptoxy group, and an n-octoxy group.

[0034] A 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 3 to 8 carbon atoms, and thus are 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, a neopentoxy group, a sec-hexoxy group, an isohexoxy group, a tert-hexoxy group, a neohexoxy group, a sec-heptoxy group, an isoheptoxy group, a tert-heptoxy group, a neoheptoxy group, a sec-octoxy group, an isooctoxy group, a tert-octoxy group, and a neooctoxy group.

[0035] 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 thus include a halogenated methoxy group, a halogenated ethoxy group, a halogenated n-propoxy group, a halogenated n-butoxy group, a halogenated n-pentoxy group, a halogenated n-hexoxy group, a halogenated n-heptoxy group, and a halogenated n-octoxy group.

[0036] The branched halogenated alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned branched halogenated alkyl group. Specific examples of the branched halogenated alkoxy group have 3 to 8 carbon atoms, and thus include a halogenated isopropoxy group, a halogenated sec-butoxy group, a halogenated isobutoxy group, a halogenated tert-butoxy group, a halogenated sec-pentoxy group, a halogenated isopentoxy group, a halogenated tert-pentoxy group, a halogenated neopentoxy group, a halogenated sec-hexoxy group, a halogenated isohexoxy group, a halogenated tert-hexoxy group, a halogenated neohexoxy group, a halogenated sec-heptoxy group, a halogenated isoheptoxy group, a halogenated tert-heptoxy group, a halogenated neoheptoxy group, a halogenated sec-octoxy group, a halogenated isooctoxy group, a halogenated tert-octoxy group, and a halogenated neooctoxy group.

[0037] Among them, X1 is preferably an aryl group into which one or more linear alkyl groups are introduced, more preferably a phenyl group into which linear alkyl groups are introduced at the 2nd, 4th, and 6th positions, and even more preferably a phenyl group into which methyl groups are introduced at the 2nd, 4th, and 6th positions (2,4,6-trimethyl-phenyl group). This is because the curability of the polymerizable composition containing the acylphosphine composition described later is improved.

[0038] (X2) Details regarding each of the linear alkyl group, branched alkyl group, linear alkoxy group, branched alkoxy group, and aryl group are as described above.

[0039] Each of one or more hydrogen groups contained in the aryl group may be substituted by a substituent, in the same manner as described for X1. This substituent is any one of a linear alkyl group, a branched alkyl group, a linear halogenated alkyl group, a branched halogenated alkyl group, a linear alkoxy group, a branched alkoxy group, a linear halogenated alkoxy group, and a branched halogenated alkoxy group, wherein the number of carbon atoms is within a specific range. Further, the substituent is any one 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-containing group. Details regarding the type of the halogen group are as described above.

[0040] The heterocyclic group-containing group is a general term for a monovalent group in which a ring (heterocyclic ring) is composed of a carbon atom and one or more atoms other than carbon atoms, and a monovalent group containing one or more heterocyclic rings. The atoms other than the carbon atom are nitrogen atoms, oxygen atoms, sulfur atoms, etc. Specific examples of the heterocyclic group-containing group are groups in which one hydrogen group has been removed from each of thiazole, imidazole, oxazole, pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, bithiophene, terthiophene, etc.

[0041] Also, each of one or more methylene groups contained in X2 may be substituted by either -O- or -S- as described above.

[0042] 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.

[0043] (Other anions) If two or more of the above-mentioned anions contain an acylphosphine anion, they may further contain other anions other than the acylphosphine anion. The type of other anions may be only one type or two or more types.

[0044] The type of other anions is not particularly limited, but halogen ions, hexafluorophosphate ions (PF6 - ), tetrafluoroborate ions (BF4 - ), bis(trifluoromethanesulfonyl)imide ions ((CF3SO2)2N - ), trifluoromethanesulfonate ions (CF3SO3 - ), nonafluorobutanesulfonate ions (C4F9SO3 - ), benzoate ions, 4-ethylbenzoate ions, p-toluenesulfonate ions and hydroxide ions (OH - ), etc. This halogen ion is a fluoride ion (F - ), a chloride ion (Cl - ), a bromide ion (Br - ) and an iodide ion (I - ), etc.

[0045] Among them, other anions are preferably hydroxide ions. This is because the stability of the acylphosphine composition is improved.

[0046] (Details regarding the cation) 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. Note that the type of Y1 may be the same as the type of Y2 or 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.

[0047] Details regarding the straight-chain alkyl group are as described above, except that the carbon number ranges are different. Also, details regarding the aryl group are as described above.

[0048] The straight-chain alkenyl group is a generic term for monovalent hydrocarbon groups in which a plurality of carbon atoms are bonded to each other so as to have a carbon-carbon double bond (>C=C<) and be straight-chain. Specific examples of the straight-chain alkenyl group include vinyl group, allyl group, acrylic group, and methacrylic group, etc. because the carbon number is 2 to 6.

[0049] The arylalkyl group is a generic term for monovalent groups in which an aryl group and a straight-chain or branched alkyl group are bonded to each other. Details regarding the aryl group are as described above, and details regarding the straight-chain or branched alkyl group are also as described above.

[0050] Each of one or more hydrogen groups contained in each of Y1, Y2, and Y3 may be substituted by a hydroxyl group. In this case, in each of Y1, Y2, and Y3, the terminal hydrogen group may be substituted by a hydroxyl group, or the intermediate hydrogen group may be substituted by a hydroxyl group. Specific examples of the alkyl group in which the terminal hydrogen group is substituted by a hydroxyl group include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group, hydroxynonyl group, hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group, and hydroxytetradecyl group because the carbon number is 7 to 13.

[0051] Also, each of one or more methylene groups contained in each of Y1, Y2, and Y3 may be substituted by any one of -O-, -S-, -CO-, and -N + H-.

[0052] Note that any two of Y1, Y2, and Y3 may independently be combined with each other to form a ring. That is, Y1 and Y2 may be combined with each other, Y2 and Y3 may be combined with each other, or Y1 and Y3 may be combined with each other. In this case, one ring may be formed, or two or more rings may be formed. Further, a ring consisting of single bonds may be formed. Furthermore, when Y2 and Y3 are combined with each other, a carbon-carbon double bond may be formed, and a ring may be formed when the carbon-carbon double bond and Y1 are combined with each other.

[0053] Among them, some of Y1, Y2, and Y3 are linear alkyl groups having 1 to 6 carbon atoms, and the rest of Y1, Y2, and Y3 are preferably linear alkyl groups having 1 to 6 carbon atoms in which one hydrogen group at the terminal is substituted by a hydroxyl group. Further, it is more preferable that one of Y1, Y2, and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and each of the two of Y1, Y2, and Y3 is a linear alkyl group having 1 to 6 carbon atoms in which one hydrogen group at the terminal is substituted by a hydroxyl group. This is because the curability of the polymerizable composition containing the acylphosphine composition is improved.

[0054] (Equivalent ratio, etc.) In the acylphosphine composition described herein, the ratio (equivalent ratio) of the molar equivalent of the cation to the molar equivalent of the acylphosphine anion 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 equivalent ratio = (valence of cation × number of moles of cation) / (valence of acylphosphine anion × number of moles of acylphosphine anion).

[0055] Incidentally, the ratio of the weight of the cation to the weight of the acylphosphine anion (weight ratio) is not particularly limited, but among them, it 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.

[0056] Each of the equivalent ratio and the weight ratio can be calculated based on the analysis result (integration ratio of 1H-NMR) of the acylphosphine composition using the nuclear magnetic resonance (NMR) method.

[0057] (Specific examples) Specific examples of the acylphosphine composition are not particularly limited as long as they are compositions containing a cation and two or more anions that satisfy the conditions (Y1 to Y3, X1, and X2) shown in formulas (1) and (2).

[0058] Specific examples of the cation include quaternary ammonium-type cations represented by each of A1 to A42. However, the cation may be a cation having another structure not listed here as a specific example as long as it satisfies the conditions shown in formula (1).

[0059] [Chemical formula]

[0060] [Chemical formula]

[0061] [Chemical formula]

[0062] Specific examples of the acylphosphine anion include acylphosphine-type anions represented by each of B1 to B16. However, the acylphosphine anion may be an anion having another structure not specifically exemplified herein as long as it satisfies the conditions shown in formula (2).

[0063] [Chemical formula]

[0064] [Chemical formula]

[0065] [Production method] The production method of the acylphosphine composition is not particularly limited. Therefore, the acylphosphine composition can be produced using known production methods. Specific production methods for some acylphosphine compositions will be described later.

[0066] [Action and effect] This acylphosphine composition contains two or more anions including the cation shown in formula (1) and the acylphosphine anion shown in formula (2), and the equivalent ratio is 1.005 to 1.100.

[0067] In this case, as described above, the solubility of the acylphosphine composition is improved and the stability of the acylphosphine composition is improved as compared with the case where the equivalent ratio does not satisfy the above-described conditions. 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.

[0068] 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 higher effects can be obtained.

[0069] In addition, in formula (2), if X1 is a 2,4,6-trimethylphenyl group, the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.

[0070] In addition, in formula (2), if X2 is a phenyl group, the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.

[0071] In addition, in formula (2), if one of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and each of the remaining two of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms in which one terminal hydrogen group is substituted by a hydroxyl group, the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.

[0072] <2. Polymerizable Composition> Next, a polymerizable composition according to an embodiment of the present invention using the above-described acylphosphine composition will be described.

[0073] [Configuration] This polymerizable composition contains an acylphosphine composition, a reaction 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 type may be one type or two or more types is the same for each of the reaction group-containing compound and the aqueous solvent.

[0074] (Acylphosphine Composition) The acylphosphine composition functions as a polymerization initiator during the polymerization reaction of the polymerizable composition. The details regarding the configuration of the acylphosphine composition are as described above.

[0075] (Content) The content of the acylphosphine composition in the polymerizable composition is not particularly limited, but among them, it is preferably 0.1% by mass to 30% by mass, and more preferably 1% by mass to 10% by mass in the total solid content. This is because the storage stability and curability of the polymerizable composition are improved.

[0076] As used herein, the "total solid content" means all of the remaining solid components excluding the aqueous solvent which is a liquid component under the conditions of 25 ° C and 1 atm from a series of components (liquid components and solid components) constituting the polymerizable composition. Therefore, the content of the acylphosphine composition described above means the ratio of the mass of the acylphosphine composition to the mass of all the solid components. The definition of the total solid content described here is the same hereinafter. Note that the liquid component may include not only the aqueous solvent but also an organic solvent etc. as necessary.

[0077] (Reactive group-containing compound) The reactive group-containing compound is a compound containing a reactive group represented by formula (3), and the number of reactive groups contained in the reactive group-containing compound may be only 1 or 2 or more.

[0078] [Chemical formula] (R1 is either a hydrogen group or a methyl group. Z1 is either -O- or -NR2, and R2 is either a hydrogen group or 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, the asterisk (*) represents an unbonded bond. )

[0079] In formula (3), as described above, the asterisk (*) indicates an unbonded bond. Therefore, in formula (3), it does not indicate the reactive group-containing compound but only indicates the reactive groups contained in the reactive group-containing compound.

[0080] (R1) When the number of reactive groups is two or more, the types of two or more R1s may be the same as each other or different from each other. Of course, when the number of reactive groups is three or more, only some of the types of three or more R1s may be the same as each other.

[0081] (Z1) The types of hydrocarbon groups having 1 to 20 carbon atoms are not particularly limited. The hydrocarbon group described here is a general term for monovalent groups composed of hydrogen and carbon. This hydrocarbon group may be linear, branched, cyclic, or in a state where two or more of them are bonded to each other. Further, the hydrocarbon group may contain one or more carbon-carbon unsaturated bonds. This carbon-carbon unsaturated bond may be a carbon-carbon double bond, a carbon-carbon triple bond, or both.

[0082] When the number of reactive groups is two or more, the types of two or more Z1s may be the same as each other or different from each other. Of course, when the number of reactive groups is three or more, only some of the types of three or more Z1s may be the same as each other.

[0083] 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, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms because the number of carbon atoms is 1 to 20.

[0084] Among them, any one of 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, an aryl group having 6 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms is preferable. This is because the sensitivity of the polymerizable composition is improved.

[0085] Specific examples of the alkyl group 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, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group, etc., because the number of carbon atoms is 1 to 20.

[0086] 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, an isoamyl group, a tert-amyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, and an isodecyl group, etc.

[0087] 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, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, a 4-decenyl group, a 3-undecenyl group, a 4-dodecenyl group, a 3-cyclohexenyl group, a 2,5-cyclohexadienyl-1-methyl group, a 4,8,12-tetradecatrienyl allyl group, etc., because the number of carbon atoms is 2 to 20.

[0088] 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, a 2-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, and a 4-decenyl group, etc.

[0089] The cycloalkyl group having 3 to 20 carbon atoms is either a saturated monocyclic alkyl group or a saturated polycyclic alkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group 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, a decahydronaphthyl group, an octahydropentalenyl group, a bicyclo[1.1.1]pentanyl group, and a tetradecahydroanthracenyl group, etc., since the number of carbon atoms is 3 to 20.

[0090] In addition, 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, a decahydronaphthyl group, an octahydropentalenyl group, and a bicyclo[1.1.1]pentanyl group, etc.

[0091] The term "cycloalkylalkyl group having 4 to 20 carbon atoms" is a general term for a group having 4 to 20 carbon atoms in which one or more hydrogen groups contained in the alkyl group are substituted by a cycloalkyl group. Specific examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include, since it has 4 to 20 carbon atoms, 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-cyclodecylethyl 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-adamantylpropyl group, and decahydronaphthylpropyl group, etc.

[0092] In addition, 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, 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, and 4-cyclohexylbutyl group, etc.

[0093] Specific examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, and a phenanthrenyl group, etc., because the number of carbon atoms is 6 to 20. Further, specific examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, etc., in which one or more hydrogen groups are substituted by any one or two or more of the above-described alkyl group, alkenyl group, carboxyl group, and halogen group. More specifically, they are a 4-chlorophenyl group, a 4-carboxylphenyl group, a 4-vinylphenyl group, a 4-methylphenyl group, and a 2,4,6-trimethylphenyl group, etc.

[0094] Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, etc. Further, specific examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, etc., in which one or more hydrogen groups are substituted by any one or two or more of the above-described alkyl group, alkenyl group, carboxyl group, and halogen group. More specifically, they are a 4-chlorophenyl group, a 4-carboxylphenyl group, a 4-vinylphenyl group, a 4-methylphenyl group, and a 2,4,6-trimethylphenyl group, etc.

[0095] The 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 by an aryl group. 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, etc., because the number of carbon atoms is 7 to 20.

[0096] (Z2) When the number of reactive groups is two or more, the types of two or more Z2 may be the same as each other or different from each other. Of course, when the number of reactive groups is three or more, only the types of some of the three or more Z2 may be the same as each other.

[0097] When the value of n is 2 or more, two or more types of Z2 may be the same as each other or different from each other. Of course, when the value of n is 3 or more, only some of the three or more types of Z2 may be the same as each other.

[0098] Specific examples of the alkylene group may be linear alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group because the number of carbon atoms is 1 to 6, or branched alkylene groups such as an isopropylene group and 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.

[0099] (Details regarding n) As described above, since the value of n is an integer from 0 to 30, it may be 0. When the value of n is 0, the reactive group is represented by R1-C(=CH2)-C(=O)-Z1-*.

[0100] (Specific examples) The type of the parent body to which the reactive group is bonded is not particularly limited. When the number of reactive groups is y, the above parent body is a y-valent hydrocarbon group or the like. When y = 1, the parent body is the above alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, arylalkyl group, etc., and the number of carbon atoms in each of these groups is not particularly limited. When y = w (w is an integer of 2 or more), the parent body is a group in which (w - 1) hydrogen groups are removed from each of the above alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, and arylalkyl group, etc., and the number of carbon atoms in them is not particularly limited.

[0101] 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 becomes more likely to undergo a polymerization reaction.

[0102] The alkylene oxide-modified (meth)acrylate compound includes the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound. The (meth)acrylamide compound includes the acrylamide compound and the methacrylamide compound.

[0103] The alkylene oxide-modified acrylate compound is a compound in which in formula (3), 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 which in formula (3), R1 is a methyl group, Z1 is -O-, and the value of n is 1 to 30.

[0104] 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-hexanediol diacrylate.

[0105] 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-hexanediol dimethacrylate.

[0106] As each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, commercially available products may be used. Specifically, NK Ester A-600, A-GLY-20E, and NK Economer A-PG5054E manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

[0107] Among them, in each of the alkylene oxide-modified acrylate compound and the alkylene oxide-modified methacrylate compound, in formula (3), Z2 is preferably either an ethylene group or a propylene group. This is because the solubility of the reactive group-containing compound, particularly its solubility in an aqueous solvent, is improved. When Z2 is an ethylene group, the solubility of the reactive group-containing compound is remarkably improved.

[0108] 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 ensured, so the value of n is preferably 6 or more. Further, 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 ensured, so the total of the values of two or more n is preferably 10 or more.

[0109] The acrylamide compound is a compound in which, in formula (3), R1 is a hydrogen group, Z1 is -NR2-, and the value of n is 0. The methacrylamide compound is a compound in which, in formula (3), R1 is a methyl group, Z1 is -NR2-, and the value of n is 0.

[0110] Specific examples of the acrylamide compound include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide, acryloylmorpholine, N-n-butoxymethylacrylamide, N-isobutoxymethylacrylamide, and N-methoxymethylacrylamide.

[0111] Specific examples of the methacrylamide compound include hydroxymethacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetonemethacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N,N-dipropylmethacrylamide, methacryloylmorpholine, N-n-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, and N-methoxymethylmethacrylamide.

[0112] As each of the acrylamide compound and the methacrylamide compound, commercially available products may be used. Specifically, FFM-2, FFM-3, FFM-4, FFM-5, etc. manufactured by Fujifilm Corporation can be used.

[0113] (Content) The content of the reactive group-containing compound in the polymerizable composition is not particularly limited, but among them, it is preferably 60% by mass to 99% by mass, and more preferably 70% by mass to 95% by mass in the total solid content. This is because the curability of the polymerizable composition is improved.

[0114] (Aqueous solvent) The aqueous solvent is a general term for a solvent that is liquid under the conditions of 25°C and 1 atm and includes water and an organic solvent miscible with water. That is, the aqueous solvent may be only water, only an organic solvent miscible with water, or a mixture of both. This organic solvent miscible with water means an organic solvent that dissolves 0.01 g or more in 100 g of water at 20°C.

[0115] By using a polymerizable composition containing an aqueous solvent, the following advantages can be obtained. First, the thickness of the coating described below can be easily controlled. Second, as the substrate described below, not only a substrate highly resistant to organic solvents but also a substrate having low resistance to organic solvents can be used, so the degree of freedom in selecting the type of the substrate is widened. Third, when applying the polymerizable composition onto an organic material (for example, a film containing an 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 using the polymerizable composition.

[0116] The type of water is not particularly limited, but specifically, it is pure water, ion-exchanged water, and the like.

[0117] The types of organic solvents that are miscible with water are not particularly limited. Specifically, they include 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-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 3,5-dimethyl-3-hexyn-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, and ethylene glycol phenyl ether, etc.

[0118] 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 remarkably improved.

[0119] (Content) The content of the aqueous solvent in the polymerizable composition is not particularly limited, but among them, it is preferably 10% by mass to 99% by mass, more preferably 30% by mass to 95% by mass, and still more preferably 50% by mass to 90% by mass. This is because the handleability of the polymerizable composition is improved and the thickness of the cured product formed using the polymerizable composition is easily controlled.

[0120] 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 among them, it is preferably 30% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and still more preferably 60% by mass to 80% by mass. This is because the fluidity of the ink containing the ink composition is easily controlled.

[0121] In addition, the content of the organic solvent miscible with water in the aqueous solvent is not particularly limited, but among them, it is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% 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.

[0122] (Others) Note that the polymerizable composition may further contain any one or two or more of other components as necessary. The types of other components can be arbitrarily set according to the use of the polymerizable composition and the like.

[0123] Specifically, the other components are any one or more of a crosslinking agent, a photosensitive group, an organic acid, a coupling agent, a leveling agent, a sensitizer, a surfactant, a basic compound, a colorant, a photopolymerization (radical) initiator (excluding acylphosphine compositions), a water-soluble preservative, a conductive substance, and an organic solvent. Hereinafter, the details of the colorant will be described by taking the above series of other components as a representative.

[0124] (Colorant) Moreover, 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 the colorant. The type of the colorant may be only one type or two or more types.

[0125] This colorant contains any one or more of a pigment and a dye. Therefore, the colorant may contain only a pigment, only a dye, or both a pigment and a dye. Each of the pigment and the dye may be an inorganic material, an organic material, or a mixture of an inorganic material and an organic material.

[0126] The pigment is a coloring material that is insoluble in a solvent. This pigment contains not only inorganic materials and organic materials that are unnecessary for the solvent, but also materials in which one or both of an inorganic dye and an organic dye are lakeified. The dye may be water-soluble or oil-soluble.

[0127] Specific examples of the pigment are black pigments. This black pigment includes, in addition to carbon black produced by any one or two or more of the furnace method, channel method, and thermal method, acetylene black, ketjen black, lamp black, and the like. Further, the black pigment may be a material in which the above-described black pigment is adjusted or coated with an epoxy resin, or a material in which the above-described black pigment is previously dispersed in a resin in a solvent and coated with a resin of 20 mg / g to 200 mg / g, or a material in which the above-described black pigment is subjected to an acidic surface treatment or an alkaline surface treatment, or carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, or carbon black having a total oxygen amount calculated from carbon monoxide (CO) and carbon dioxide (CO2) in the volatile matter at 950 °C of 9 mg or more per 100 m 2 2 of the surface area. Furthermore, 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, and the like.

[0128] In addition, specific examples of the pigment are colored pigments of organic pigments and inorganic pigments, and the color of the colored pigment is a color other than black. Specific examples of the organic pigment and the inorganic pigment include chromium oxide green, Prussian blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, ultramarine blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber, and lake pigments.

[0129] Among them, the pigment is preferably a black pigment, and more preferably carbon black. This is because excellent light-shielding properties can be obtained.

[0130] Note that the pigment may be a commercially available product. Specific examples of commercially available pigments include MICROPIGMO WMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBK-5, MICROPIGMO WMBE-5, MICROPIGMO WMVT-5, MICROPIGMO WMWE-1, BONJET BLACK CW-1 (all manufactured by Orient Chemical Industries, 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, etc.

[0131] Specific examples of the dye include metal complex compounds and the like. Specific examples of the metal complex compounds include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acid, azo dyes, cyanine dyes, and the like.

[0132] Note that 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 2S, WATER RED 3, WATER RED 9, WATER 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 VIOLET 7, WATER BLACK 31, WATER BLACK 191-L, 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 YELLOW 1101, VALIFAST YELLOW 3150, VALIFAST RED 1308, 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 (manufactured by Orient Chemical Industries Co., Ltd.), Acid Green 1, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 27, Acid Green 50, Acid Green A, AlizarinCyanin Green F, Basic 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 87, Acid Red 88, Acid Red 91, Acid Red 92, 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 Red 5, Benzopurpurine 4B, Bordezux Red, Chlorantine Fast Red 5B, Chromotrope 2B, Chromotrope 2R, Congo Red, Cresol Red, Cresol 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 Red254, Rhodamine 6G, Sudan II, Sudan III, Sudan R, 2,3,5-Triphenyltetrazolium Chloride, Acid Black 1, Acid Blue 1, Acid Blue 9, Acid Blue 92, Acid Blue 3 Sodium Salt, Acid Red 91, Azo Blue, Basic Blue 1, Basic Blue 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, Mordant Black 17, Mordant Blue 13, Mordant Blue 29, Omega Chrome Black Blue G, Pigment Blue 15, Quinizarin Blue, Sudan Blue, Thymol Blue, Xylene Cyanol FF, Acid Orange 5, Acid Orange 7, 1-Amino-2-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, PyrazoloneSuch as Orange, Sudan I, and Sudan II (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0133] (Sensitizer) The type of the sensitizer is not particularly limited, but specifically, it is thioxanthone, benzophenone, etc.

[0134] (Photopolymerization (radical) initiator) The type of the photopolymerization (radical) initiator is not particularly limited, but specifically, it is benzoin ether, benzyl ketal, α-hydroxyacetophenone, α-aminoacetophenone, oxime ester, etc.

[0135] (Organic solvent) The organic solvent described here is a general term for solvents other than the above-mentioned aqueous solvents. The type of the organic solvent is not particularly limited, but specifically, it is ketones, ether solvents, ester solvents, cellosolve solvents, alcohol solvents (excluding alcohol solvents corresponding to aqueous solvents), ether ester solvents, BTX solvents, aliphatic hydrocarbon solvents, terpene hydrocarbon oils, halogenated aliphatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, etc.

[0136] Ketones include methyl ethyl ketone, acetone, cyclohexanone, etc. Ether solvents include oxane, tetrahydrofuran, 1,2-dimethoxyethane, etc. Ester solvents include methyl acetate, ethyl acetate, propyl acetate, etc. Cellosolve solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. Alcohol solvents include methanol, ethanol, etc. Ether ester solvents include ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, etc. BTX solvents include benzene, toluene, xylene, etc. Aliphatic hydrocarbon solvents include hexane, heptane, octane, cyclohexane, etc. Terpene hydrocarbon oils include turpentine oil, D-limonene, pinene, etc. Halogenated aliphatic hydrocarbon solvents include carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Halogenated aromatic hydrocarbon solvents include chlorobenzene, etc. In addition, the organic solvent may also be aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc.

[0137] The content of the organic solvent in the polymerizable composition is not particularly limited, but among them, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. This is because the environmental load is reduced when the polymerizable composition is used.

[0138] [Manufacturing method] When producing this polymerizable composition, after charging the acylphosphine composition and the reaction group-containing compound into an aqueous solvent, the aqueous solvent is stirred. In this case, a colorant or the like may be further added to the aqueous solvent. Thereby, since each of the acylphosphine composition and the reaction group-containing compound is dispersed or dissolved in the aqueous solvent, a polymerizable composition is prepared.

[0139] [Function and effect] According to this polymerizable composition, it contains an acylphosphine composition and a reaction group-containing compound together with an aqueous solvent, and the acylphosphine composition has the above-described configuration. Therefore, since the storage stability and curability of the polymerizable composition are ensured, it becomes easy to produce a good cured product using the polymerizable composition, and thus excellent physical properties can be obtained. In addition, other actions and effects regarding the polymerizable composition are the same as other actions and effects regarding the acylphosphine composition.

[0140] <3. Cured Product and Its Manufacturing Method> Next, a cured product and its manufacturing method according to an embodiment of the present invention using the above-described polymerizable composition will be described.

[0141] [Configuration] The cured product described here is, as described above, a cured reaction product of the polymerizable composition. More specifically, the cured product is a reaction product formed by a polymerization reaction (photo radical polymerization reaction) of a reaction 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, a film containing the cured reaction product (cured product) of the polymerizable composition is formed on the surface of the substrate by the polymerization reaction of the polymerizable composition.

[0142] [Manufacturing Method] When manufacturing this cured product, first, the polymerizable composition is prepared by the above-described procedure. Subsequently, after applying the polymerizable composition to the surface of the substrate, the polymerizable composition is dried . Thereby, a coating film containing the polymerizable composition is formed on the surface of the substrate.

[0143] The type of the substrate is not particularly limited. For example, it is any one type or two or more types of metal, wood, rubber, plastic, glass, ceramic, paper, and cloth. The coating method of the polymerizable composition is not particularly limited. For example, it includes a spin coater, a bar coater, a roll coater, a curtain coater, various printing methods, and a dipping method.

[0144] Finally, the coating film is irradiated with active energy rays. The type of the active energy rays is not particularly limited, and for example, it is ultraviolet light using a mercury lamp or the like as a light source. Irradiation conditions such as the wavelength, irradiation intensity, and irradiation time of the ultraviolet light can be arbitrarily set.

[0145] 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 in terms of the irradiation dose, it is 10 mJ / cm 2 ~1000 mJ / cm 2 and preferably 100 mJ / cm 2 ~500 mJ / cm 2 The irradiation time is 1 second to 500 seconds, preferably 5 seconds to 300 seconds.

[0146] Thereby, in the coating film, the polymerization reaction of the reaction group-containing compound proceeds through the acylphosphine composition (polymerization initiator), so that a cured product (cured material) of the polymerizable composition is formed. Therefore, a film containing the cured material is formed.

[0147] In addition, when forming a film, a plurality of films may be laminated on each other by repeating the above-described film formation procedure.

[0148] [Actions and Effects] According to this cured material, it is a cured product of the polymerizable composition, and the polymerizable composition has the above-described configuration. Therefore, for the same reasons as described for the polymerizable composition, excellent physical properties can be obtained. In addition, other actions and effects regarding the cured material are the same as those regarding the polymerizable composition.

[0149] Further, according to the method for producing the cured material, since the polymerizable composition is irradiated with active energy rays, the polymerization reaction of the polymerizable composition proceeds stably, sufficiently, and stably in response to the irradiation of the active energy. Therefore, a cured material having the above-described excellent physical properties can be obtained.

[0150] In this case, in particular, in order to obtain a cured product having excellent physical properties, not only can the polymerization composition be simply irradiated with active energy rays, but also the irradiation amount of the active energy rays with respect to the polymerization composition can be reduced, so that a cured product having excellent physical properties can be easily and stably produced. That is, the manufacturing process of the cured product is shortened, and in addition to the substrate being less likely to be damaged, advantages can be obtained in that patterning (manufacturing a cured product to have a desired pattern) becomes possible.

[0151] <4. Uses (such as polymerization initiators)> The uses of the above-mentioned acylphosphine composition, polymerization composition, and cured product are not particularly limited. For example, they are various lenses, various films, and various functional films.

[0152] Specifically, glasses, imaging lenses, antistatic films, optical films, conductive films, protective films, heat ray shielding materials, transfer foils, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, substrates for flexible displays, substrates for touch panels, printing masks, molding materials, putties, building materials, nail materials, cosmetics, sidings, glass fiber impregnants, caulking agents, passivation films for semiconductors and solar cells, interlayer insulating films, protective films, prism lens sheets for backlights of liquid crystal display devices, Fresnel lens sheets for screens of projection TVs, lens parts of lens sheets for lenticular lens sheets, backlights using those sheets, etc., protective films / spacers for liquid crystal color filters, DNA separation chips, microreactors, nanobiodevices, recording materials for hard disks, solid-state imaging devices, solar cell panels, light-emitting diodes, organic light-emitting devices, electrode protective materials, luminescent films, fluorescent films, MEMS elements, actuators, holograms, plasmon devices, polarizing plates, polarizing films, alignment films, microlenses, optical elements, retardation films, optical connectors, optical waveguides, casting agents for optical shaping, foods, beverage containers, food packaging materials, dental materials, sanitary ceramics, housing equipment, etc. This housing equipment is a bathtub, etc.

[0153] In particular, as described above, the acylphosphine composition is preferably used as a polymerization initiator in applications that require a polymerization reaction. This is because the storage stability and curability of the polymerizable composition containing the acylphosphine composition are improved while ensuring the solubility of the acylphosphine composition. As a result, a good cured product is formed using the polymerizable composition.

Examples

[0154] Hereinafter, the examples of the present invention will be described in detail.

[0155] (Experimental Examples 1 to 45) First, an acylphosphine composition was synthesized according to the procedure described below. After preparing a polymerizable composition using the acylphosphine composition, a film (cured product) was produced using the polymerizable composition, and the physical properties of each of the acylphosphine composition, the polymerizable composition, and the cured product were evaluated.

[0156] [Synthesis of acylphosphine composition] Five types 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.

[0157]

Chemical formula

[0158] When synthesizing the acylphosphine composition shown in C1, first, in a nitrogen atmosphere, 50.0 g (173.4 mmol) of phenyl(2,4,6-trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and were charged. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve 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, after removing the solvent from the reaction solution, it was dried under reduced pressure (drying temperature = 40°C) to obtain pale yellow crystals, which are the acylphosphine composition shown in C1 (Experimental Example 1).

[0159] Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 28.0 g (173.4 mmol) (Experimental Example 2). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 28.1 g (174.3 mmol) (Experimental Example 3). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 28.3 g (175.2 mmol) (Experimental Example 4). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 29.4 g (182.1 mmol) (Experimental Example 5). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 30.2 g (187.3 mmol) (Experimental Example 6). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 30.8 g (190.7 mmol) (Experimental Example 7). Pale yellow crystals were obtained by the same procedure except that the addition amount of butyldiethanolamine was changed to 33.6 g (208.1 mmol) (Experimental Example 8).

[0160] When synthesizing the acylphosphine composition shown in C2, first, in a nitrogen atmosphere, 50.0 g (173.4 mmol) of phenyl(2,4,6-trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and were added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve phenyl(2,4,6 - trimethylbenzoyl)phosphinic acid. Subsequently, after adding 15.8 g (156.1 mmol) of 4 - methylmorpholine into the reaction flask, the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, after removing the solvent from the reaction solution, it was dried under reduced pressure (drying temperature = 40 °C) to obtain pale yellow crystals, which are the acylphosphine composition shown in C2 (Experimental Example 9).

[0161] Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 17.5 g (173.4 mmol) (Experimental Example 10). Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 17.6 g (174.3 mmol) (Experimental Example 11). Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 18.1 g (178.6 mmol) (Experimental Example 12). Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 19.2 g (189.01 mmol) (Experimental Example 13). Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 19.3 g (190.7 mmol) (Experimental Example 14). Pale yellow crystals were obtained by the same procedure except that the addition amount of 4 - methylmorpholine was changed to 21.0 g (208.1 mmol) (Experimental Example 15).

[0162] When synthesizing the acylphosphine composition shown in C3, first, in a nitrogen atmosphere, into the reaction flask, 50.0 g (173.4 mmol) of phenyl(2,4,6 - trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and were added. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve 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 obtain a reaction solution. Finally, after removing the solvent from the reaction solution, it was dried under reduced pressure (drying temperature = 40°C) to obtain pale yellow crystals, which are the acylphosphine composition shown in C3 (Experimental Example 16).

[0163] Pale yellow crystals were obtained in 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). Pale yellow crystals were obtained in 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). Pale yellow crystals were obtained in 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). Pale yellow crystals were obtained in 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). Pale yellow crystals were obtained in 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).

[0164] When synthesizing the acylphosphine composition shown in C4, first, in a nitrogen atmosphere, 50.0 g (173.4 mmol) of phenyl(2,4,6-trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and were introduced. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve phenyl(2,4,6-trimethylbenzoyl)phosphinic acid. Subsequently, after adding 14.0 g (156.1 mmol) of dimethylethanolamine into the reaction flask, the mixture in the reaction flask was stirred at room temperature (stirring time = 5 hours) to obtain a reaction solution. Finally, after removing the solvent from the reaction solution, it was dried under reduced pressure (drying temperature = 40 °C) to obtain pale yellow crystals, which are the acylphosphine composition shown in C4 (Experimental Example 22).

[0165] Pale yellow crystals were obtained by the same procedure except that the addition amount of dimethylethanolamine was changed to 15.4 g (173.4 mmol) (Experimental Example 23). Pale yellow crystals were obtained by the same procedure except that the addition amount of dimethylethanolamine was changed to 15.5 g (174.3 mmol) (Experimental Example 24). Pale yellow crystals were obtained by the same procedure except that the addition amount of dimethylethanolamine was changed to 16.0 g (178.6 mmol) (Experimental Example 25). Pale yellow crystals were obtained by the same procedure except that the addition amount of dimethylethanolamine was changed to 17.0 g (190.7 mmol) (Experimental Example 26). Pale yellow crystals were obtained by the same procedure except that the addition amount of dimethylethanolamine was changed to 18.6 g (208.1 mmol) (Experimental Example 27).

[0166] When synthesizing the acylphosphine composition shown in C5, first, in a nitrogen atmosphere, into the reaction flask, 50.0 g (173.4 mmol) of phenyl(2,4,6-trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and were introduced. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve 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, after removing the solvent from the reaction solution, it was dried under reduced pressure (drying temperature = 40°C) to obtain pale yellow crystals, which are the acylphosphine composition shown in C5 (Experimental Example 28).

[0167] Pale yellow crystals were obtained by the same procedure except that the addition amount of tert-butyldiethanolamine was changed to 28.0 g (173.4 mmol) (Experimental Example 29). Pale yellow crystals were obtained by the same procedure except that the addition amount of tert-butyldiethanolamine was changed to 28.1 g (174.3 mmol) (Experimental Example 30). Pale yellow crystals were obtained by the same procedure except that the addition amount of tert-butyldiethanolamine was changed to 28.6 g (178.6 mmol) (Experimental Example 31). Pale yellow crystals were obtained by the same procedure except that the addition amount of tert-butyldiethanolamine was changed to 30.8 g (190.7 mmol) (Experimental Example 32). Pale yellow crystals were obtained by the same procedure except that the addition amount of tert-butyldiethanolamine was changed to 33.6 g (208.1 mmol) (Experimental Example 33).

[0168] [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.

[0169] When synthesizing other compositions shown in C6, first, 7.3 g (23 mmol) of ethyl 2,4,6-trimethylbenzoyl phenylphosphinate and 40 g of 2-butanone (methyl ethyl ketone) were charged into a reflux reaction flask. Subsequently, the mixture in the reflux reaction flask was stirred under a nitrogen stream and at room temperature to completely dissolve ethyl 2,4,6-trimethylbenzoyl phenylphosphinate. Subsequently, after adding 3.3 g (22 mmol) of sodium iodide into the reflux reaction flask, the mixture in the reflux reaction flask was stirred at room temperature (stirring time = 15 minutes). Subsequently, after raising the temperature of the reaction solution to 65 °C, the reaction solution was stirred at that temperature (stirring time = 8 hours) to obtain a reaction solution. Finally, after cooling the temperature of the reaction solution to room temperature, the precipitate in the reaction solution was filtered to obtain white crystals, which are the other composition shown in C6 (Experimental Example 34).

[0170] White crystals were obtained by the same procedure except that the addition amount of sodium iodide was changed to 3.4 g (23 mmol) (Experimental Example 35). White crystals were obtained by the same procedure except that the addition amount of sodium iodide was changed to 3.5 g (23.1 mmol) (Experimental Example 36). White crystals were obtained by the same procedure except that the addition amount of sodium iodide was changed to 3.6 g (24 mmol) (Experimental Example 37). White crystals were obtained by the same procedure except that the addition amount of sodium iodide was changed to 3.7 g (25 mmol) (Experimental Example 38). White crystals were obtained by the same procedure except that the addition amount of sodium iodide was changed to 4.2 g (28 mmol) (Experimental Example 39).

[0171] When synthesizing other compositions shown in C7, first, in a nitrogen atmosphere, 50.0 g (173.4 mmol) of phenyl(2,4,6-trimethylbenzoyl)phosphinic acid and 500 ml of dichloromethane (= 500 cm 3) and the like were introduced. Subsequently, the mixture in the reaction flask was stirred at room temperature to completely dissolve 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, after the reaction solution was desolvated, it was dried under reduced pressure (drying temperature = 40 °C) to obtain pale yellow crystals, which are the other compositions shown in C7 (Experimental Example 40).

[0172] Pale yellow crystals were obtained in the same procedure except that the addition amount of piperazine anhydride was changed to 7.47 g (86.7 mmol) (Experimental Example 41). Pale yellow crystals were obtained in the same procedure except that the addition amount of piperazine anhydride was changed to 7.50 g (87.1 mmol) (Experimental Example 42). Pale yellow crystals were obtained in the same procedure except that the addition amount of piperazine anhydride was changed to 7.80 g (92.8 mmol) (Experimental Example 43). Pale yellow crystals were obtained in the same procedure except that the addition amount of piperazine anhydride was changed to 8.22 g (95.4 mmol) (Experimental Example 44). Pale yellow crystals were obtained in the same procedure except that the addition amount of piperazine anhydride was changed to 8.97 g (104.1 mmol) (Experimental Example 45).

[0173] [Preparation of Polymerizable Composition] When preparing the curable composition, first, 70 parts by mass of an aqueous solvent (ion-exchanged water), 22.5 parts by mass of a reactive group-containing compound (acryloylmorpholine ACMO (registered trademark) manufactured by KJ Chemicals Co., Ltd.), 5.7 parts by mass of a reactive group-containing compound (alkoxylated glycerin acrylate A-GLY-20E manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.5 parts by mass of a polymerization initiator (acylphosphine composition shown for each of C1 to C5), and 0.3 parts by mass of a leveling agent (polyether-modified polysiloxane copolymer TEGOglide100 manufactured by EVONIC) were weighed. The acylphosphine composition (C1 to C5) used here contains other anions (hydroxide ions) together with the anions (acylphosphine anions) shown for each of C1 to C5. Subsequently, after introducing the reactive group-containing compound, the polymerization initiator, and the leveling agent into the aqueous solvent, the aqueous solvent was stirred (temperature of the aqueous solvent = 25°C, stirring time = 10 minutes). Finally, the curable composition was obtained by filtering the aqueous solvent using a 0.45-μm filter.

[0174] For comparison, a curable composition was prepared in the same procedure except that other compositions (C6 and C7) were used instead of the acylphosphine composition (C1 to C5). The other compositions (C6 and C7) used here contain other anions (hydroxide ions) together with the anions (acylphosphine anions) shown for each of C6 and C7.

[0175] [Manufacture of cured product] After applying the curable composition to the surface of a substrate (glass plate Eagle XG manufactured by Corning) using a coating device (spin coater), the curable composition was dried (drying temperature = 90°C, drying time = 2 minutes). Thereby, a coating film (thickness = 2 μm) of the curable composition was formed. Thereafter, using a high-pressure mercury lamp as a light source, active energy rays (ultraviolet light, illuminance = 20 mW / cm 2 , irradiation dose = 500 mJ / cm 2) was irradiated. As a result, in the polymerizable composition, the reaction group-containing compound underwent a polymerization reaction via a polymerization initiator (acylphosphine composition and other compositions), and thus a film containing a cured product was formed.

[0176] [Evaluation of Physical Properties] When the physical properties (solubility) of the acylphosphine composition, the physical properties (storage stability) of the polymerizable composition, and the physical properties (curability) of the cured product were evaluated, the results shown in Tables 1 and 2 were obtained. However, similarly, when other compositions were used, the solubility, storage stability, and curability were evaluated.

[0177] 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 dissolution state of the acylphosphine composition was determined by visually observing the state of the ion-exchanged water. Specifically, when the acylphosphine composition was uniformly dissolved and no insoluble matter remained, it was determined as A. When the acylphosphine composition was not uniformly dissolved and insoluble matter remained, it was determined as B.

[0178] When examining the storage stability, the polymerizable composition was stored in a low-temperature environment (temperature = 5°C) for 10 days. As a result, the storage state of the polymerizable composition was determined by visually observing the state of the polymerizable composition. Specifically, when the color of the polymerizable composition was uniformly transparent and its state had not changed from the state after preparation, it was determined as A. When the polymerizable composition was turbid or precipitates had occurred in the polymerizable composition and its state had changed from the state after preparation, it was determined as B.

[0179] When examining the degree of curing, the state of the cured product was visually and palpated to determine the curing state of the cured product. Specifically, since the polymerizable composition was sufficiently cured, when a uniformly transparent film was obtained, it was judged as A. When the polymerizable composition was cured but the surface of the film was cloudy, it was judged as B. When the polymerizable composition was not sufficiently cured, that is, when the polymerizable composition was uncured and the film was sticky, it was judged as C.

[0180] In addition, in the column of "Comprehensive Evaluation" shown in Table 1 and Table 2, a comprehensive evaluation regarding physical properties (solubility, storage stability, and curability) is shown. Specifically, when all of the determination results of solubility, storage stability, and curability were A, the comprehensive evaluation was set as A. On the other hand, when any of the determination results of solubility, storage stability, and curability was B or C, the comprehensive evaluation was set as B.

[0181]

Table 1

[0182]

Table 2

[0183] [Discussion] As shown in Table 1 and Table 2, each of solubility, storage stability, and curability varied greatly depending on the composition of the polymerizable composition.

[0184] Specifically, when the polymerizable composition did not contain the acylphosphine composition of the present invention, that is, when the polymerizable composition contained other compositions (Experimental Examples 34 to 45), good results were not obtained for all of solubility, storage stability, and curability, and thus a good comprehensive evaluation was not obtained.

[0185] On the other hand, when the polymerizable composition contains the acylphosphine composition of the present invention (Experimental Examples 1 to 33), solubility, storage stability, and curability each varied depending on the equivalent ratio.

[0186] Specifically, when the equivalent ratio did not satisfy the appropriate conditions (equivalent ratio = 1.005 to 1.100) (such as Experimental Examples 1, 2, 8, etc.), good results were still not obtained for all of solubility, storage stability, and curability, so a good overall evaluation was not obtained. However, when the equivalent ratio satisfied the appropriate conditions (such as Experimental Examples 3 to 7, etc.), good results were obtained for all of solubility, storage stability, and curability, so a good overall evaluation was obtained.

[0187] In particular, when the equivalent ratio satisfied the appropriate conditions, sufficient results were obtained for all of solubility, storage stability, and curability when the weight ratio also satisfied the appropriate conditions (weight ratio = 0.25 to 1.00).

[0188] [Summary] From the results shown in Table 1 and Table 2, when the acylphosphine composition contains two or more anions including the cation shown in formula (1) and the acylphosphine anion shown in formula (2), and the equivalent ratio is 1.005 to 1.100, excellent solubility is obtained. In this case, excellent storage stability was obtained in the polymerizable composition containing the acylphosphine composition, and excellent curability was obtained in the film (cured product) formed using the polymerizable composition. Also, excellent curability was obtained in the film (cured product) obtained by irradiating the above-mentioned polymerizable composition with active energy rays. Therefore, excellent physical properties were obtained in each of the acylphosphine composition (polymerization initiator), polymerizable composition, and cured product, and a cured product having excellent physical properties was obtained by the method for producing the cured product.

[0189] As described above, the present invention has been described with one embodiment and examples, but the aspects of the present invention are not limited to the aspects described in the embodiment and examples, and various modifications are possible with respect to those aspects.

[0190] This application claims priority based on Japanese Patent Application No. 2019-212569, filed with the Japan Patent Office on November 25, 2019, and incorporates by reference all of the contents of this application into this application.

[0191] Those skilled in the art can conceive of various modifications, combinations, sub-combinations, and changes according to design requirements and other factors, and it is understood that they are included within the spirit of the appended claims and the scope of their equivalents.

Claims

1. a cation represented by formula (1), two or more anions including an acylphosphine anion represented by formula (2), 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, an acylphosphine composition. N + H Y1 Y2 Y3 ··· (1) (Each of Y1, Y2, and Y3 is any one of a linear alkyl group having 1 to 6 carbon atoms, a linear alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an arylalkyl group having 7 to 13 carbon atoms. Each hydrogen group of Y1, Y2, and Y3 may be substituted by a hydroxyl group. Each methylene group of Y1, Y2, and Y3 may be substituted by any one of -O-, -S-, and -CO. Any two of Y1, Y2, and Y3 may be bonded to each other.) 【Chemical Formula 1】 (X1 is an aryl group having 6 to 15 carbon atoms, and each hydrogen group of the aryl group may be substituted by any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, and a branched halogenated alkoxy group having 3 to 8 carbon atoms.) X2 is any one of a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and each of the hydrogen groups of the aryl group is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a linear halogenated alkyl group having 1 to 8 carbon atoms, a branched halogenated alkyl group having 3 to 8 carbon atoms, a linear alkoxy group having 1 to 8 carbon atoms, a branched alkoxy group having 3 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, a branched halogenated alkoxy group having 3 to 8 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, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, and a heterocyclic group-containing group. Each of the methylene groups of X2 may be substituted by either -O- or -S-. The equivalent ratio is calculated by (valence of cation × number of moles of cation) / (valence of acylphosphine anion × number of moles of acylphosphine anion).

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 Claim 2.

4. X2 is a phenyl group. The acylphosphine composition according to any one of Claims 1 to 3.

5. One of Y1, Y2, and Y3 is a linear alkyl group having 1 to 6 carbon atoms. Each of the remaining two of Y1, Y2, and Y3 is a linear alkyl group having 1 to 6 carbon atoms in which one of the terminal hydrogen groups is substituted by the hydroxyl group. The acylphosphine composition according to any one of claims 1 to 4. 。

6. A polymerization initiator comprising the acylphosphine composition according to any one of claims 1 to 5. A 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 formula (3), An aqueous solvent and a polymerizable composition. 【Chemical formula 2】 (R1 is either a hydrogen group or a methyl group. Z1 is either -O- or -NR2, and R2 thereof is either a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms. Z2 is an alkylene group having 1 to 6 carbon atoms. n is an integer from 0 to 30. However, the asterisk (*) represents an unbonded bond.)

8. A cured product which is a cured reaction product of the polymerizable composition according to claim 7. A cured product.

9. A method for producing a cured product by irradiating the polymerizable composition according to claim 7 with active energy rays. A method for producing a cured product.

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