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Definitions

• the present invention relates to an acylphosphine composition, a polymerization initiator and a polymerizable composition using the acylphosphine composition, a cured product which is a curing reaction product of the polymerizable composition, and a method for producing the same.
• a polymerizable composition that can be cured by utilizing a polymerization reaction is used in various fields such as a polymerization initiator, and a cured product that is a curing reaction product of the polymerizable composition is also used in various fields. Has been done. Therefore, various studies have been conducted on the composition of the polymerizable composition.
• a polymerizable composition (water-soluble composition) containing a reactive compound (a compound having a specific reactive group) together with an acylphosphine composition (acylphosphine salt) so as to be adaptable to a wide range of light sources.
• a polymerizable composition for example, an aqueous curable composition
• a polymerizable compound containing water and a polymerizable compound together with a water-soluble photopolymerization initiator having an acylphosphine oxide type structure
• Patent Document 2 Patent Document 2
• An object of the present invention is to provide an acylphosphine composition, a polymerization initiator, a polymerizable composition, and a cured product and a method for producing the same, which can obtain excellent physical properties.
• the acylphosphine composition of one embodiment of the present invention contains a cation represented by the formula (1) and two or more kinds of anions including the acylphosphine anion represented by the formula (2), and the acylphosphine anion thereof.
• Each of Y1, Y2 and Y3 has a linear alkyl group having 1 or more and 6 or less carbon atoms, a linear alkenyl group having 2 or more and 6 or less carbon atoms, and 6 or more and 15 or less carbon atoms.
• the hydrogen groups of Y1, Y2 and Y3 may be substituted with hydroxyl groups, respectively.
• the methylene group of is optionally substituted with any of -O-, -S-, -CO- and -N + H-. Any two of Y1, Y2 and Y3 are bonded to each other. May be good.
• X1 is an aryl group having 6 or more and 15 or less carbon atoms
• each of the hydrogen groups of the aryl group is a linear alkyl group having 1 or more and 8 or less carbon atoms and 3 or more and 8 or less carbon atoms.
• X2 is a linear alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl group having 3 or more and 8 or less carbon atoms, and a linear alkoxy group having 1 or more and 8 or less carbon atoms. It is either a branched alkoxy group having 3 or more and 8 or less carbon atoms and an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group has 1 or more and 8 or less carbon atoms.
• Each of the methylene groups of X2 may be substituted with either —O— or —S—.
• the polymerization initiator of one embodiment of the present invention contains an acylphosphine composition, and the acylphosphine composition has the same composition as the above-mentioned composition of the acylphosphine composition of one embodiment of the present invention.
• the polymerizable composition of one embodiment of the present invention contains an acylphosphine composition, a reactive group-containing compound containing a reactive group represented by the formula (3), and an aqueous solvent, and the acylphosphine composition thereof is described above. It has a structure similar to that of the acylphosphine composition according to the embodiment of the present invention.
• R1 is either a hydrogen group or a methyl group.
• Z1 is either -O- or -NR2-, and R2 is either a hydrogen group and a hydrocarbon group having 1 or more and 20 or less carbon atoms.
• Z2 is an alkylene group having 1 or more and 6 or less carbon atoms.
• n is an integer of 0 or more and 30 or less. However, an asterisk (*) represents an unbonded bond.
• the cured product of one embodiment of the present invention is a cured reaction product of a polymerizable composition, and the polymerizable composition has the same constitution as the above-mentioned constitution of the polymerizable composition of one embodiment of the present invention. Is.
• the method for producing a cured product according to the embodiment of the present invention is the same as the constitution of the polymerizable composition according to the embodiment of the present invention described above, wherein the polymerizable composition is irradiated with active energy rays. It has a structure.
• the acylphosphine composition described here is used as a polymerization initiator or the like, as will be described later. However, the use of the acylphosphine composition is not limited to the polymerization initiator, and other uses may be used.
• This acylphosphine composition has a salt structure. Specifically, the acylphosphine composition contains a quaternary ammonium type cation represented by the formula (1) and two or more kinds of anions, and the two or more kinds of anions are of the formula (2). ) Includes an acylphosphine-type anion (hereinafter referred to as "acylphosphine anion").
• Each of Y1, Y2 and Y3 has a linear alkyl group having 1 or more and 6 or less carbon atoms, a linear alkenyl group having 2 or more and 6 or less carbon atoms, and 6 or more and 15 or less carbon atoms.
• the hydrogen groups of Y1, Y2 and Y3 may be substituted with hydroxyl groups, respectively.
• the methylene group of is optionally substituted with any of -O-, -S-, -CO- and -N + H-. Any two of Y1, Y2 and Y3 are bonded to each other. May be good.
• X1 is an aryl group having 6 or more and 15 or less carbon atoms
• each of the hydrogen groups of the aryl group is a linear alkyl group having 1 or more and 8 or less carbon atoms and 3 or more and 8 or less carbon atoms.
• X2 is a linear alkyl group having 1 or more and 8 or less carbon atoms, a branched alkyl group having 3 or more and 8 or less carbon atoms, and a linear alkoxy group having 1 or more and 8 or less carbon atoms. It is either a branched alkoxy group having 3 or more and 8 or less carbon atoms and an aryl group having 6 or more and 15 or less carbon atoms, and each of the hydrogen groups of the aryl group has 1 or more and 8 or less carbon atoms.
• Each of the methylene groups of X2 may be substituted with either —O— or —S—.
• the two or more types of anions include acylphosphine anions, as described above.
• the type of acylphosphine anion may be only one type or two or more types.
• Aryl group is a general term for monovalent groups containing one or more aromatic rings.
• Specific examples of the aryl group are a phenyl group, a naphthyl group, an anthrasenyl group and the like because they have 6 to 15 carbon atoms.
• the carbon number of the aryl group when it contains a substituent described later is the total carbon number including the carbon number of the substituent. Therefore, for example, the trimethylphenyl group has 9 carbon atoms instead of 6.
• the definition regarding the number of carbon atoms of the aryl group described here is the same thereafter.
• Each of one or more hydrogen groups contained in the aryl group may be substituted with a substituent.
• the substituents described here are a linear alkyl group having a specific carbon number, a branched alkyl group, a linear halogenated alkyl group, and a branched alkyl halide. It is any of a group, a linear alkoxy group, a branched alkoxy group, a linear halogenated alkoxy group and a branched halogenated alkoxy group.
• a linear alkyl group is a general term for a monovalent hydrocarbon group containing one carbon atom and a monovalent hydrocarbon group in which a plurality of carbon atoms are bonded to each other so as to be linear.
• Specific examples of the linear alkyl group have 1 to 8 carbon atoms, and therefore have a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group.
• Group and n-octyl group are examples of the linear alkyl group.
• a branched alkyl group is a general term for a monovalent hydrocarbon group in which a plurality of carbon atoms are bonded to each other so as to have one or two or more side chains.
• Specific examples of the branched alkyl group have 3 to 8 carbon atoms, and therefore have an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a sec-pentyl group, an isopentyl group, a tert-pentyl group, and a neopentyl group.
• the linear alkyl halide group is a group in which one or more hydrogen groups contained in the above-mentioned linear alkyl group are each substituted with a halogen group.
• the type of halogen group is not particularly limited, but is a fluorine group, a chlorine group, a bromine group, an iodine group and the like. However, the type of the halogen group contained in the linear alkyl halide group may be only one type or two or more types.
• the branched alkyl halide group is a group in which one or more hydrogen groups contained in the above-mentioned branched alkyl group are substituted with a halogen group. Details regarding the types of halogen groups are as described above.
• a linear alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned linear alkyl group.
• Specific examples of the linear alkoxy group have 1 to 8 carbon atoms, and therefore have a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, and an n-heptoxy.
• Groups and n-octoxy groups are examples of the linear alkoxy group.
• the branched alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned branched alkyl group.
• Specific examples of the branched alkoxy group have an isopropoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-pentoxy group, an isopentoxy group, a tert-pentoxy group, since the number of carbon atoms is 3 to 8.
• the linear halogenated alkoxy group is a general term for a group in which -O- is bonded to the end of the above-mentioned linear halogenated alkyl group.
• Specific examples of the linear halogenated alkoxy group have 1 to 8 carbon atoms, and therefore have a halogenated methoxy group, a halogenated ethoxy group, a halogenated n-propoxy group, a halogenated n-butoxy group, and a halogenated n.
• -Pentoxy group, halogenated n-hexoxy group, halogenated n-heptoxy group and halogenated n-octoxy group are examples of the linear halogenated alkoxy group.
• the branched alkoxy halide group is a general term for a group in which -O- is bonded to the end of the above-mentioned branched alkyl halide group.
• Specific examples of the branched halogenated alkoxy group have 3 to 8 carbon atoms, so that the halogenated isopropoxy group, the halogenated sec-butoxy group, the halogenated isobutoxy group, the halogenated tert-butoxy group, and the halogenated sec.
• halogenated isopentoxy group halogenated tert-pentoxy group, halogenated neopentoxy group, halogenated sec-hexoxy group, halogenated isohexoxy group, halogenated tert-hexoxy group, halogenated neohexoxy group, halogenated sec-heptoxy Groups, halogenated isoheptoxy groups, halogenated tert-heptoxy groups, halogenated neoheptoxy groups, halogenated sec-octoxy groups, halogenated isooctoxy groups, halogenated tert-octoxy groups and halogenated neooctoxy groups.
• X1 is preferably an aryl group into which one or two or more linear alkyl groups are introduced, and linear alkyl groups are introduced into each of the 2-position, 4-position and 6-position. It is more preferably a phenyl group, and further preferably a phenyl group (2,4,6-trimethyl-phenyl group) in which a methyl group is introduced at each of the 2-position, 4-position and 6-position. This is because the curability of the polymerizable composition containing the acylphosphine composition described later is improved.
• Each of the one or more hydrogen groups contained in the aryl group may be substituted with a substituent as in the case described with respect to X1.
• This substituent includes a linear alkyl group having a specific number of carbon atoms, a branched alkyl group, a linear alkyl halide group, a branched alkyl halide group, and a linear alkoxy group. , A branched alkoxy group, a linear halogenated alkoxy group and a branched halogenated alkoxy group.
• the substituent is any of a halogen group, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group and a heterocyclic group. Is it? Details regarding the types of halogen groups are as described above.
• each of one or more methylene groups contained in X2 may be substituted with either -O- or -S- as described above.
• 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.
• anions As long as the above-mentioned two or more types of anions contain an acylphosphine anion, they may further contain other anions other than the acylphosphine anion.
• the other types of anions may be only one type or two or more types.
• anions include, but are not limited to, halogen ions, hexafluorophosphate ions (PF 6 -), tetrafluoroborate ion (BF 4 -), bis (trifluoromethanesulfonyl) imide ion ((CF 3 SO 2) 2 N -) , trifluoromethanesulfonate ion (CF 3 SO 3 -), nonafluorobutanesulfonate ion (C 4 F 9 SO 3 - ), benzoic acid ion, 4-ethyl benzoate, p - toluenesulfonate ion and hydroxide ion (OH -) and the like.
• the halogen ions include fluorine ions (F ⁇ ), chloride ions (Cl ⁇ ), bromine ions (Br ⁇ ) and iodide ions (I ⁇ ).
• the other anion is preferably a hydroxide ion. This is because the stability of the acylphosphine composition is improved.
• the cation is a quaternary ammonium type cation (N + HY1Y2Y3).
• the type of cation may be only one type or two or more types.
• the type of Y1 may be the same as the type of Y2, or may be different from the type of Y2.
• 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.
• Specific examples of the linear alkenyl group include a vinyl group, an allyl group, an acrylic group and a methacrylic group because they have 2 to 6 carbon atoms.
• Arylalkyl group is a general term for monovalent groups in which an aryl group and a linear or branched alkyl group are bonded to each other.
• the details regarding the aryl group are as described above, and the details regarding the linear or branched alkyl group are as described above.
• Each of one or more hydrogen groups contained in each of Y1, Y2 and Y3 may be substituted with a hydroxyl group.
• the hydrogen group at the terminal may be substituted with a hydroxyl group, or the hydrogen group in the middle may be substituted with a hydroxyl group.
• Specific examples of the alkyl group in which the terminal hydrogen group is substituted with a hydroxyl group have 7 to 13 carbon atoms, and therefore have a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl.
• each of one or more methylene groups contained in each of Y1, Y2 and Y3 is substituted with any of -O-, -S-, -CO- and -N + H-. May be.
• any two of Y1, Y2, and Y3 may form a ring by being independently bonded to each other. That is, Y1 and Y2 may be bonded to each other, Y2 and Y3 may be bonded to each other, or Y1 and Y3 may be bonded to each other. In this case, one ring may be formed, or two or more rings may be formed. Further, a ring composed of a single bond may be formed. Further, a carbon-carbon double bond may be formed by bonding Y2 and Y3 to each other, and a ring may be formed by bonding the carbon-carbon double bond and Y1 to each other.
• Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and the rest of Y1, Y2 and Y3 is replaced by a hydroxyl group at one terminal hydrogen group. It is preferably a linear alkyl group having 1 to 6 carbon atoms. Further, one of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and each of the two Y1, Y2 and Y3 has a hydroxyl group at the terminal one hydrogen group. More preferably, it is a linear alkyl group having 1 to 6 carbon atoms substituted with. This is because the curability of the polymerizable composition containing the acylphosphine composition is improved.
• the ratio of the weight of the cation to the weight of the acylphosphine anion is not particularly limited, but is preferably 0.25 to 1.00. This is because the solubility of the acylphosphine composition is further improved and the stability of the acylphosphine composition is further improved.
• Each of the equivalence ratio and the weight ratio can be calculated based on the analysis result (integral ratio of 1H-NMR) of the acylphosphine composition using the nuclear magnetic resonance (NMR) method.
• acylphosphine composition is particularly limited as long as it is a composition containing a cation satisfying the conditions (Y1 to Y3, X1 and X2) shown in the formulas (1) and (2) and two or more kinds of anions. Not done.
• cations are quaternary ammonium type cations represented by each of A1 to A42.
• the cation may be a cation having another structure not mentioned as a specific example here as long as it satisfies the condition shown in the formula (1).
• acylphosphine anion examples are acylphosphine-type anions represented by B1 to B16, respectively.
• the acylphosphine anion may be an anion having another structure not mentioned as a specific example as long as it satisfies the condition shown in the formula (2).
• the method for producing the acylphosphine composition is not particularly limited. Therefore, the acylphosphine composition can be produced by using a known production method. Specific methods for producing some acylphosphine compositions will be described later.
• This acylphosphine composition contains a cation represented by the formula (1) and two or more types of anions containing the acylphosphine anion represented by the formula (2), and has an equivalent ratio of 1.005 to 1.100. Is.
• the solubility of the acylphosphine composition is improved and the stability of the acylphosphine composition is improved. Therefore, the storage stability of the polymerizable composition containing the acylphosphine composition is improved, and the curability of the polymerizable composition is also improved, so that excellent physical properties can be obtained.
• the solubility of the acylphosphine composition is further improved and the stability of the acylphosphine composition is further improved, so that a higher effect can be obtained. it can.
• X1 is a 2,4,6-trimethylphenyl group in the formula (2), the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.
• X2 is a phenyl group in the formula (2), the curability of the polymerizable composition containing the acylphosphine composition is improved, so that a higher effect can be obtained.
• one of Y1, Y2 and Y3 is a linear alkyl group having 1 to 6 carbon atoms, and the remaining two of Y1, Y2 and Y3 are terminal 1s, respectively.
• a linear alkyl group having 1 to 6 carbon atoms in which the hydrogen groups are substituted with hydroxyl groups improves the curability of the polymerizable composition containing the acylphosphine composition, and thus has a higher effect. Obtainable.
• This polymerizable composition contains an acylphosphine composition, a reactive group-containing compound, and an aqueous solvent.
• the type of the acylphosphine composition may be only one type or two or more types. The fact that the number of types may be one or more is the same for each of the reactive group-containing compound and the aqueous solvent.
• acylphosphine composition functions as a polymerization initiator during the polymerization reaction of the polymerizable composition.
• the details regarding the composition of the acylphosphine composition are as described above.
• the content of the acylphosphine composition in the polymerizable composition is not particularly limited, but is preferably 0.1% by mass to 30% by mass, and 1% by mass to 10% by mass in the total solid content. More preferably. This is because the storage stability and curability of the polymerizable composition are improved.
• total solid content is a series of components (liquid component and solid component) constituting the polymerizable composition, excluding the aqueous solvent which is a liquid component under the conditions of 25 ° C. and 1 atm. It means all of the remaining solid components. Therefore, the content of the acylphosphine composition described above means the ratio of the mass of the acylphosphine composition to the mass of all solid components.
• the definition of total solids described here is the same in the following.
• the liquid component may contain not only an aqueous solvent but also an organic solvent or the like, if necessary.
• the reactive group-containing compound is a compound containing a reactive group represented by the formula (3), and the number of reactive groups contained in the reactive group-containing compound may be only one or two or more.
• R1 is either a hydrogen group or a methyl group.
• Z1 is either -O- or -NR2, and
• R2 is either a hydrogen group and a hydrocarbon group having 1 or more and 20 or less carbon atoms.
• Z2 is an alkylene group having 1 or more and 6 or less carbon atoms.
• n is an integer of 0 or more and 30 or less. However, an asterisk (*) represents an unbonded bond.
• R1 When the number of reactive groups is two or more, the types of two or more R1s may be the same or different from each other. Of course, when the number of reactive groups is 3 or more, only some of the types of R1 among the 3 or more R1s may be the same.
• the type of hydrocarbon group having 1 to 20 carbon atoms is not particularly limited.
• the hydrocarbon group described here is a general term for a monovalent group composed of hydrogen and carbon.
• the hydrocarbon group may be linear, branched, cyclic, or two or more of them bonded to each other.
• the hydrocarbon group may contain one or more carbon-carbon unsaturated bonds.
• the intercarbon unsaturated carbon bond may be an intercarbon double bond, an intercarbon triple bond, or both.
• the types of 2 or more Z1s may be the same or different from each other.
• the number of reactive groups is 3 or more, only some Z1 types among the 3 or more Z1s may be the same.
• hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms because the hydrocarbon group has 1 to 20 carbon atoms.
• an alkyl group having 1 to 10 carbon atoms an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, and carbon.
• Any of an aryl group having a number of 6 to 10 and an arylalkyl group having a carbon number of 7 to 10 is preferable. This is because the sensitivity of the polymerizable composition is improved.
• alkyl group have 1 to 20 carbon atoms, and therefore have a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group.
• alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an amyl group, and an isoamyl group. , Tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group and isodecyl group.
• 3-hexenyl group 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, 4-dodecenyl group, These include 3-cyclohexenyl group, 2,5-cyclohexadienyl-1-methyl group and 4,8,12-tetradecatrienylallyl group.
• alkenyl group having 2 to 10 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 4-pentenyl group, a 3-pentenyl group, and a 2-hexenyl group. These include 3-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group and 4-decenyl group.
• the cycloalkyl group having 3 to 20 carbon atoms is either a saturated monocyclic alkyl group having 3 to 20 carbon atoms or a saturated polycyclic alkyl group.
• Specific examples of the cycloalkyl group have 3 to 20 carbon atoms, and therefore have a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, and a decahydro group.
• These include naphthyl groups, octahydropentalene groups, bicyclo [1.1.1] pentanyl groups and tetradecahydroanthrasenyl groups.
• cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, and a decahydro group.
• a cycloalkylalkyl group having 4 to 20 carbon atoms is a group having 4 to 20 carbon atoms in which one or more hydrogen groups contained in the alkyl group are substituted with a cycloalkyl group. It is a general term for. Specific examples of cycloalkylalkyl groups have 4 to 20 carbon atoms, so cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl.
• cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, and cyclononylmethyl.
• aryl group examples are a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group and the like because they have 6 to 20 carbon atoms.
• Specific examples of the aryl group include a phenyl group and a biphenylyl group in which one or more hydrogen groups are substituted by any one or more of the above-mentioned alkyl group, alkenyl group, carboxyl group and halogen group.
• Naftyl group Naftyl group, anthryl group, etc., and more specifically, 4-chlorophenyl group, 4-carboxyphenyl group, 4-vinylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group and the like. ..
• An arylalkyl group having 7 to 20 carbon atoms is a general term for a group having 7 to 30 carbon atoms in which one or more hydrogen groups contained in the alkyl group are substituted with an aryl group. Is.
• Specific examples of the arylalkyl group include a benzyl group, an ⁇ -methylbenzyl group, an ⁇ , ⁇ -dimethylbenzyl group, a phenylethyl group and a naphthylpropyl group because they have 7 to 20 carbon atoms.
• Z2 When the number of reactive groups is two or more, the types of two or more Z2s may be the same or different from each other. Of course, when the number of reactive groups is 3 or more, only some Z2 types out of 3 or more Z2s may be the same as each other.
• the alkylene group have 1 to 6 carbon atoms, and therefore may be a linear alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, or an isopropylene group and an isopropylene group. It may be a branched alkylene group such as an isobutylene group.
• 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.
• n is an integer of 0 to 30 as described above, it may be 0.
• the type of mother to which the reactive group is bound is not particularly limited.
• the above-mentioned parent is a y-valent hydrocarbon group or the like.
• y 1, the parent is the above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, aryl group, arylalkyl group and the like, and the carbon number of each of these groups is particularly limited. Not done.
• the reactive group-containing compound is preferably one or both of an alkylene oxide-modified (meth) acrylate compound and a (meth) acrylamide compound. This is because the polymerizable composition is likely to undergo a polymerization reaction.
• alkylene oxide-modified methacrylate compound examples include diethylene oxide-modified neopentyl glycol dimethacrylate, dipropylene oxide-modified neopentyl glycol dimethacrylate, diethylene oxide-modified 1,6-hexanediol dimethacrylate and dipropylene oxide-modified 1,6-hexane. Such as diol dimethacrylate.
• NK ester A-600, A-GLY-20E and NK economyr A-PG5054E manufactured by Shin Nakamura Chemical Industry Co., Ltd. can be used.
• Z2 is preferably either an ethylene group or a propylene group in the formula (3). This is because the solubility of the reactive group-containing compound, particularly the solubility in an aqueous solvent, is improved. When Z2 is an ethylene group, the solubility of the reactive group-containing compound is significantly improved.
• the solubility of the reactive group-containing compound is guaranteed, so that the value of n is preferably 6 or more.
• the solubility of the reactive group-containing compound is guaranteed, so that the sum of the two or more n values. Is preferably 10 or more.
• the acrylamide compound is a compound in the formula (3) in which R1 is a hydrogen group, Z1 is -NR2-, and the value of n is 0.
• the methacrylamide compound is a compound in the formula (3) in which R1 is a methyl group, Z1 is ⁇ NR2-, and the value of n is 0.
• acrylamide compounds include hydroxyacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dipropylacrylamide, acryloylmorpholin, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide and the like.
• methacrylamide compounds include hydroxymethacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-butylmethacrylamide, diacetonemethacrylamide, N, N-dimethylmethacrylamide, N. , N-diethylmethacrylamide, N, N-dipropylmethacrylamide, methacrylloylmorpholin, Nn-butoxymethylmethacrylamide, N-isobutoxymethylmethacrylamide, N-methoxymethylmethacrylamide and the like.
• the content of the reactive group-containing compound in the polymerizable composition is not particularly limited, but is preferably 60% by mass to 99% by mass and 70% by mass to 95% by mass in the total solid content. Is more preferable. This is because the curability of the polymerizable composition is improved.
• Aqueous solvent is a general term for solvents containing water and an organic solvent that is miscible with water as well as being liquid under the conditions of 25 ° C. and 1 atm. That is, the aqueous solvent may be water alone, an organic solvent miscible with water, or a mixture of both.
• the organic solvent miscible with this water means an organic solvent that dissolves 0.01 g or more in 100 g of water at 20 ° C.
• the thickness of the coating film which will be described later, can be easily controlled.
• the substrate described later not only the substrate having high resistance to the organic solvent but also the substrate having low resistance to the organic solvent can be used, so that the degree of freedom regarding the type of the substrate is widened.
• the polymerizable composition is applied onto an organic material (for example, a film containing the organic material), the organic material is less likely to be attacked by the polymerizable composition.
• the aqueous solvent is environmentally friendly, the environmental load is reduced when the polymerizable composition is used.
• the type of water is not particularly limited, but specifically, it is pure water, ion-exchanged water, or the like.
• the type of organic solvent that can be mixed with water is not particularly limited, but specifically, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1, 3-Propylenediol, 2-Methyl-1,3-Propylenediol, 1,2-Pentanediol, 1,5-Pentanediol, 2,4-Pentanediol, 1,2-Hexanediol, 3,5-Diol- 3-Hexin-2,5-diol, 2,5-hexanediol, hexylene glycol, 1,6-hex
• the organic solvent miscible with water a lower alcohol having 5 or less carbon atoms is preferable. This is because the solubility in water is significantly improved.
• the content of the aqueous solvent in the polymerizable composition is not particularly limited, but is preferably 10% by mass to 99% by mass, more preferably 30% by mass to 95% by mass, and 50% by mass. It is more preferably to 90% by mass. This is because the handleability of the polymerizable composition is improved, and the thickness of the cured product formed by using the polymerizable composition is easily controlled.
• the content of the aqueous solvent in the polymerizable composition is not particularly limited, but is particularly 30% by mass to 95% by mass. It is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 80% by mass. This is because the fluidity of the ink containing the ink composition can be easily controlled.
• the polymerizable composition may further contain any one or more of the other components, if necessary.
• the types of other components can be arbitrarily set according to the use of the polymerizable composition and the like.
• the other component is a colorant.
• This colorant is a component that colors the polymerizable composition. This is because the polymerizable composition can be colored by using a colorant.
• the type of the colorant may be only one type or two or more types.
• This colorant contains any one or more of pigments and dyes. Therefore, the colorant may contain only the pigment, may contain only the dye, or may contain both the pigment and the dye.
• Each of the pigment and the dye may be an inorganic material, an organic material, or a mixture of the inorganic material and the organic material.
• the pigment is a black pigment.
• the black pigment includes carbon black produced by any one or more of the furnace method, the channel method and the thermal method, as well as acetylene black, ketjen black and lamp black.
• the black pigment may be a material in which the above-mentioned black pigment is adjusted or coated with an epoxy resin, or the above-mentioned black pigment is previously dispersed in the resin in a solvent and a resin of 20 mg / g to 200 mg / g.
• It may be a material coated with a black pigment, a material in which the above-mentioned black pigment is subjected to an acidic surface treatment or an alkaline surface treatment, or a carbon black having an average particle size of 8 nm or more and a DBP oil absorption amount of 90 ml / 100 g or less.
• carbon black may be used in which the total amount of oxygen calculated from carbon monoxide (CO) and carbon dioxide (CO 2 ) in the volatile matter at 950 ° C. is 9 mg or more per 100 m 2 of the surface area.
• the black pigment may be graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black or the like.
• pigments are colored pigments of organic pigments and inorganic pigments, and the color of the colored pigments is a color other than black.
• organic pigments and inorganic pigments include chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine blue, prussian blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, etc. Yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber and lake pigments.
• the pigment may be a commercially available product.
• Specific examples of commercially available pigments are MICROPIGMO WMMYW-5, MICROPIGMO WMRD-5, MICROPIGMO WMBN-5, MICROPIGMO WMGN-5, MICROPIGMO WMGN-5, MICROPIGMO WMBE-5, MICROPIGMO WMVER-5, MICROPIGMO WMVT-5 BLACK CW-1 (manufactured by Orient Chemical Industry Co., Ltd.), Pigment Red 1,2,3,9,10,14,17,22,23,31,38,41,48,49,88,90,97 , 112,119,122,123,144,149,166,168,169,170,171,177,179,180,184,185,192,200,202,209,215,216,217,220,223 , 224,226,227,254,228,240,254, Pigment Orange 13,31,34,36,38,43,46,48,49,51,52
• dyes are metal complex compounds and the like.
• the metal complex compound include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindolin compounds, and quinacridone compounds.
• the dye may be a commercially available product. Specific examples of commercially available dyes are WATER YELLOW 1, WATER YELLOW 2, WATER YELLOW 6C, WATER YELLOW 6CL, WATER ORANGE 18, WATER ORANGE 25, WATER RED 1, WATER RED 2 RED 27, WATER PINK 2S, WATER BROWN 16, WATER GREEN 8, WATER BLUE 3, WATER BLUE 9, WATER BLUE 105S, WATER BLUE 106, WATER BLUE 117-L, WATER VIOLER 1- , WATER BLACK 256-L, WATER BLACK R-455, WATER BLACK R-510, BONJET YELLOW 161-L, BONJET MAGENTA XXX, BONJET CYAN XXX, BONJET BLACK 891-L, VALIFAST , VALIFAST RED 2320, VALIFAST PINK 1364, VALIFAST PINK 2310N, VALIFAST
• sensitizer The type of sensitizer is not particularly limited, but specific examples thereof include thioxanthone and benzophenone.
• photopolymerization (radical) initiator The type of photopolymerization (radical) initiator is not particularly limited, and specific examples thereof include benzoin ether, benzyl acetal, ⁇ -hydroxyacetphenone, ⁇ -aminoacetophenone, and oxime ester.
• Organic solvent is a general term for solvents other than the above-mentioned aqueous solvent.
• the type of organic solvent is not particularly limited, but specifically, ketones, ether solvents, ester solvents, cellosolve solvents, alcohol solvents (excluding alcohol solvents corresponding to aqueous solvents), These include ether ester-based solvents, BTX-based solvents, aliphatic hydrocarbon-based solvents, terpene hydrocarbon oils, halogenated aliphatic hydrocarbon-based solvents, and halogenated aromatic hydrocarbon-based solvents.
• Ketones include methyl ethyl ketone, acetone and cyclohexanone.
• Ethereal solvents include oxane, tetrahydrofuran and 1,2-dimethoxyethane.
• Ester-based solvents include methyl acetate, ethyl acetate and propyl acetate.
• Cellosolve-based solvents include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
• Alcohol-based solvents include methanol and ethanol.
• Examples of the ether ester solvent include ethylene glycol monomethyl acetate and ethylene glycol monoethyl acetate.
• BTX-based solvents are benzene, toluene, xylene and the like.
• Aliphatic hydrocarbon solvents include hexane, heptane, octane and cyclohexane.
• Terpene hydrocarbon oils include turpentine, D-limonene and pinene.
• Halogenated aliphatic hydrocarbon solvents include carbon tetrachloride, chloroform, trichlorethylene, methylene chloride and 1,2-dichloroethane. The halogenated aromatic hydrocarbon solvent is chlorobenzene or the like.
• the organic solvent may be aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like.
• the content of the organic solvent in the polymerization composition is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. .. This is because the environmental load is reduced when the polymerizable composition is used.
• the acylphosphine composition and the reactive group-containing compound are put into an aqueous solvent, and then the aqueous solvent is stirred. In this case, a colorant or the like may be further added to the aqueous solvent. As a result, the acylphosphine composition and the reactive group-containing compound are each dispersed or dissolved in the aqueous solvent, so that a polymerizable composition is prepared.
• an acylphosphine composition and a reactive group-containing compound are contained together with an aqueous solvent, and the acylphosphine composition has the above-mentioned constitution. Therefore, by ensuring the storage stability and curability of the polymerizable composition, a good cured product can be easily produced using the polymerizable composition, and excellent physical properties can be obtained.
• the other actions and effects of the polymerizable composition are the same as those of the acylphosphine composition.
• the cured product described here is a cured reaction product of the polymerizable composition. More specifically, the cured product is a reaction product formed by a polymerization reaction (photoradical polymerization reaction) of a reactive group-containing compound via an acylphosphine composition that functions as a polymerization initiator. Therefore, after the polymerizable composition is applied to the surface of the substrate, the polymerizable composition undergoes a polymerization reaction to form a film containing a cured reaction product (cured product) of the polymerizable composition on the surface of the substrate. Will be done.
• a polymerization reaction photoradical polymerization reaction
• the type of the substrate is not particularly limited, but for example, it is any one or more of metal, wood, rubber, plastic, glass, ceramic, paper and cloth.
• the method for applying the polymerizable composition is not particularly limited, and examples thereof include a spin coater, a bar coater, a roll coater, a curtain coater, various printing methods, and a dipping method.
• the type of active energy ray is not particularly limited, but an example is ultraviolet light using a mercury lamp or the like as a light source. Irradiation conditions such as the wavelength of ultraviolet light, irradiation intensity, and irradiation time can be arbitrarily set.
• the irradiation conditions are as follows, for example.
• the wavelength is 200 nm to 400 nm.
• the irradiation intensity is 1 mW / cm to 500 mW / cm, preferably 5 mW / cm to 300 mW / cm, and when converted to the irradiation amount, it is 10 mJ / cm 2 to 1000 mJ / cm 2 , preferably 100 mJ / cm 2 to 500 mJ. / Cm 2 .
• the irradiation time is 1 second to 500 seconds, preferably 5 seconds to 300 seconds.
• the polymerization reaction of the reactive group-containing compound proceeds via the acylphosphine composition (polymerization initiator) in the coating film, so that a cured reaction product (cured product) of the polymerizable composition is formed. Therefore, a film containing a cured product is formed.
• a plurality of coating films may be laminated on each other by repeating the above-mentioned coating film forming procedure.
• this cured product it is a cured reaction product of the polymerizable composition, and the polymerizable composition has the above-mentioned structure. Therefore, excellent physical properties can be obtained for the same reason as described with respect to the polymerizable composition.
• the other actions and effects on the cured product are the same as those on the polymerizable composition.
• the polymerization reaction of the polymerizable composition is stable, sufficient and stable according to the irradiation of the active energy. proceed. Therefore, a cured product having the above-mentioned excellent physical characteristics can be obtained.
• imaging lenses imaging lenses, antistatic films, optical films, conductive films, protective films, heat ray shielding materials, transfer foils, printing plates, insulating varnishes, insulating sheets, laminated boards, printed substrates, and flexible displays.
• the acylphosphine composition is preferably used as a polymerization initiator in applications requiring a polymerization reaction, as described above. This is because the solubility of the acylphosphine composition is ensured, and the storage stability and curability of the polymerizable composition containing the acylphosphine composition are improved. As a result, a good cured product is formed using the polymerizable composition.
• an acylphosphine composition is synthesized by the procedure described below, a polymerizable composition is prepared using the acylphosphine composition, and then a coating film (cured product) is produced using the polymerizable composition.
• the physical properties of the acylphosphine composition, the polymerizable composition and the cured product were evaluated.
• a pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.0 g (173.4 mmol) (Experimental Example 2).
• a pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.1 g (174.3 mmol) (Experimental Example 3).
• Light yellow crystals were obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 28.3 g (175.2 mmol) (Experimental Example 4).
• a pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 29.4 g (182.1 mmol) (Experimental Example 5).
• a pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 30.2 g (187.3 mmol) (Experimental Example 6).
• a pale yellow crystal was obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 30.8 g (190.7 mmol) (Experimental Example 7).
• Light yellow crystals were obtained by the same procedure except that the amount of butyldiethanolamine added was changed to 33.6 g (208.1 mmol) (Experimental Example 8).
• a pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 17.5 g (173.4 mmol) (Experimental Example 10). Light yellow crystals were obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 17.6 g (174.3 mmol) (Experimental Example 11). Light yellow crystals were obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 18.1 g (178.6 mmol) (Experimental Example 12). A pale yellow crystal was obtained by the same procedure except that the amount of 4-methylmorpholine added was changed to 19.2 g (189.01 mmol) (Experimental Example 13).
• a pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.2 g (173.4 mmol) (Experimental Example 17).
• a pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.3 g (174.3 mmol) (Experimental Example 18).
• a pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 33.9 g (176.9 mmol) (Experimental Example 19).
• Light yellow crystals were obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 36.5 g (190.7 mmol) (Experimental Example 20).
• a pale yellow crystal was obtained by the same procedure except that the amount of 1-benzyl-4-hydroxypiperidine added was changed to 39.8 g (208.1 mmol) (Experimental Example 21).
• a pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 15.4 g (173.4 mmol) (Experimental Example 23).
• a pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 15.5 g (174.3 mmol) (Experimental Example 24).
• Light yellow crystals were obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 16.0 g (178.6 mmol) (Experimental Example 25).
• a pale yellow crystal was obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 17.0 g (190.7 mmol) (Experimental Example 26).
• Pale yellow crystals were obtained by the same procedure except that the amount of dimethylethanolamine added was changed to 18.6 g (208.1 mmol) (Experimental Example 27).
• White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.4 g (23 mmol) (Experimental Example 35). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.5 g (23.1 mmol) (Experimental Example 36). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.6 g (24 mmol) (Experimental Example 37). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 3.7 g (25 mmol) (Experimental Example 38). White crystals were obtained by the same procedure except that the amount of sodium iodide added was changed to 4.2 g (28 mmol) (Experimental Example 39).
• a pale yellow crystal was obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.47 g (86.7 mmol) (Experimental Example 41). Pale yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.50 g (87.1 mmol) (Experimental Example 42). Light yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 7.80 g (92.8 mmol) (Experimental Example 43). Pale yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 8.22 g (95.4 mmol) (Experimental Example 44). Light yellow crystals were obtained by the same procedure except that the amount of piperazine anhydride added was changed to 8.97 g (104.1 mmol) (Experimental Example 45).
• the acylphosphine compositions (C1 to C5) used here contain other anions (hydroxide ions) together with the anions (acylphosphine anions) shown in each of C1 to C5.
• compositions (C6 and C7) were used instead of the acylphosphine compositions (C1 to C5).
• the other compositions (C6 and C7) used here contain other anions (hydroxide ions) along with the anions (acylphosphine anions) shown in C6 and C7, respectively.
• the cured state of the cured product was determined by visually and palpating the state of the cured product. Specifically, since the polymerizable composition was sufficiently cured, it was determined to be A when a uniformly transparent film was obtained. When the polymerizable composition was cured but the surface of the coating was cloudy, it was determined to be B. When the polymerizable composition was not sufficiently cured, that is, the polymerizable composition was uncured, and the film was sticky, it was determined to be C.
• the "Comprehensive evaluation” column shown in Tables 1 and 2 shows the comprehensive evaluation of physical properties (solubility, storage stability and curability). Specifically, when the solubility determination result, the storage stability determination result, and the curability determination result were all A, the overall evaluation was set to A. On the other hand, when any of the solubility determination result, the storage stability determination result, and the curability determination result was B or C, the overall evaluation was set to B.
• the polymerizable composition does not contain the acylphosphine composition of the present invention, that is, when the polymerizable composition contains another composition (Experimental Examples 34 to 45), it is soluble. Since good results were not obtained in terms of storage stability and curability, a good overall evaluation could not be obtained.
• the polymerizable composition contains the acylphosphine composition of the present invention (Experimental Examples 1 to 33), the solubility, storage stability and curability each vary depending on the equivalent ratio. did.
• the acylphosphine composition contains the cation represented by the formula (1) and two or more types of anions containing the acylphosphine anion represented by the formula (2), and the equivalent ratio.
• the value was 1.005 to 1.100, excellent solubility was obtained.
• excellent storage stability was obtained in the polymerizable composition containing the acylphosphine composition, and excellent curability was obtained in the coating film (cured product) formed by using the polymerizable composition.
• excellent curability was obtained in the coating film (cured product) formed by using the polymerizable composition.

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