Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals

Definitions

• the present invention includes a composition containing a photopolymerizable compound (A) and an inorganic fine particle (B), a photosensitive composition, a cured product of the photosensitive composition, and the above-described photosensitive composition. and a method for producing the compound.
• compositions used to form various functional materials for the purpose of imparting functionality to the materials.
• high refractive index materials are used to form optical members.
• Compositions in which metal oxide particles such as titanium oxide and zirconium oxide are dispersed in an organic component are used as high refractive materials.
• an energy ray containing a metal oxide (A) having a specific particle size, a (meth)acrylate (B), and a photopolymerization initiator (C) A curable composition has been proposed (see Patent Document 1).
• a cured product having a high refractive index can be formed as described above.
• a functional material such as a high refractive index material
• a conventionally known composition as described in Patent Document 1 when the composition is heated in the process of forming the functional material, the composition The weight of components other than the solvent in the product tends to decrease excessively.
• the conventionally known composition as described in Patent Document 1 there is also a problem that the inorganic fine particles are difficult to stably disperse over a long period of time.
• the present invention has been made in view of the above problems, and even when heated, the composition or the components in the photosensitive organism (components other than the solvent when the composition or photosensitive composition contains a solvent)
• the present inventors have proposed a composition containing a photopolymerizable compound (A) and an inorganic fine particle (B), or a photopolymerizable compound (A), an inorganic fine particle (B), and an initiator (C).
• the photosensitive composition containing a photosensitive composition containing .
• the present invention provides the following.
• a first aspect of the present invention comprises a photopolymerizable compound (A) and inorganic fine particles (B),
• the photopolymerizable compound (A) has the following formula (A1): Containing a photopolymerizable compound (A) and inorganic fine particles (B),
• the photopolymerizable compound (A) has the following formula (A1): (In formula (A1), X a is -S-, -O-, or -NH-, Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group, R a01 and R a02 each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group, or the following formula (A1a): R a03 ⁇ (X a03 ⁇ X a02 ) ma4 ⁇ (X a01 ) ma3 ⁇ (A1a) is a group represented by at least one of ma1 R a01 and ma2 R
• a second aspect of the present invention comprises a photopolymerizable compound (A), inorganic fine particles (B), and an initiator (C),
• the photopolymerizable compound (A) has the following formula (A1): (In formula (A1), X a is -S-, -O-, or -NH-, Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group, R a01 and R a02 each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group, or the following formula (A1a): R a03 ⁇ (X a03 ⁇ X a02 ) ma4 ⁇ (X a01 ) ma3 ⁇ (A1a) is a group represented by at least one of ma1 R a01 and ma2 R a02 is a group represented by formula (A1a); ma1 is 0 or 1, ma2 is 0, 1, or 2; when ma2 is 2, the two R a
• a third aspect of the present invention is a cured product of the photosensitive composition according to the second aspect.
• a fourth aspect of the present invention is the following formula (A1-1): (In formula (A1-1), X a is -S-, -O-, or -NH-, Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group, R a01 and R a02 each independently represent an aromatic hydrocarbon group, an aromatic heterocyclic group, or the following formula (A1a): R a03 ⁇ (X a03 ⁇ X a02 ) ma4 ⁇ (X a01 ) ma3 ⁇ (A1a) is a group represented by at least one of ma1 R a01 and ma2 R a02 is a group represented by formula (A1a); ma1 is 0 or 1, ma2 is 0, 1, or 2; when ma2 is 2, the two R a2 may be the same or different, at least one of ma1 and ma2 is not 0, X a01 is O; X a02 is an alkylene
• a compound represented by the following formula (A1-2a) is reacted with a compound represented by the following formula (A1-2b) in the presence of a base to obtain obtaining a compound represented by -2c);
• Substituting a terminal hydrogen atom represented by —X a03 —H in a compound represented by the following formula (A1-2c) with a group represented by R a03 is a method for producing a compound represented by HX a03 -X a02 -Hal (A1-2b) (In formula (A1-2a), formula (A1-2b), formula (A1-2c), and formula (A1-2),
• X a is -S-, -O-, or -NH-
• Ar a02 is a divalent or trivalent aromatic hydrocarbon group or a divalent or trivalent aromatic heterocyclic group
• R a04 is a hydrogen atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group
• X a01 is reacted with a compound represented by the following
• a compound represented by the following formula (A1-2a) is reacted with a compound represented by the following formula (A1-d) in the presence of a base to obtain the following formula (A method for producing a compound represented by the following formula (A1-1), comprising obtaining a compound represented by A1-1).
• R a03 -X a03 -X a02 -Hal (A1-2d) (In formula (A1-2a), formula (A1-2d), and formula (A1-2), X a is -S-, -O-, or -NH-, Ar a02 is a divalent or trivalent aromatic hydrocarbon group or a divalent or trivalent aromatic heterocyclic group, R a04 is a hydrogen atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group, X a01 is O; X a02 is an alkylene group optionally interrupted by one or more O, X a03 is O; Hal is a halogen atom; R a03 is a radically polymerizable group-containing group, In the compound represented by formula (A1-2), the total number of oxygen atoms derived from X a01 , X a02 , and X a03 is 3 or more when X a is —S—, and X a is 2 or more when is -
• a stably dispersed composition and a photosensitive composition, a cured product of the photosensitive composition, a compound preferably blended in the composition and the photosensitive composition, and a method for producing the compound can provide.
• the composition contains a photopolymerizable compound (A) and inorganic fine particles (B).
• a composition is substantially an inorganic fine particle dispersion composition, and after appropriately blending an initiator for curing the photopolymerizable compound (A), functions having properties according to the type of the inorganic fine particles (B). It is used in the formation of flexible materials.
• the photopolymerizable compound (A) includes a compound represented by formula (A1) below.
• X a is -S-, -O-, or -NH-.
• Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group.
• R a01 and R a02 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group represented by the following formula (A1a).
• At least one of ma1 R a01 and ma2 R a02 is a group represented by formula (A1a).
• ma1 is 0 or 1;
• ma2 is 0, 1, or 2;
• two R a2 may be the same or different.
• At least one of ma1 and ma2 is not zero.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• R a03 is a radically polymerizable group-containing group.
• ma3 and ma4 are each independently 0 or 1;
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) in the compound represented by formula (A1) is 1 or more.
• composition contains the compound represented by the above formula (A1), excessive weight loss of components other than the solvent is less likely to occur even when the composition is heated, and the inorganic fine particles in the composition are stable over a long period of time. disperse.
• the essential or optional ingredients that the composition may contain are described below.
• the composition contains a photopolymerizable compound (A).
• a photopolymerizable compound (A) is a compound having a radically polymerizable group-containing group.
• the radically polymerizable group-containing group typically includes a group containing an ethylenically unsaturated double bond.
• alkenyl group-containing groups including alkenyl groups such as vinyl groups and allyl groups are preferred, and (meth)acryloyl group-containing groups are more preferred.
• (meth)acrylic means both acrylic and methacrylic
• (meth)acryloyl means both acryloyl and methacryloyl
• (meth)acrylate is Both acrylates and methacrylates are meant.
• the photopolymerizable compound (A) includes a compound represented by formula (A1) below.
• the compound represented by formula (A1) is also referred to as "compound (A1)".
• X a is -S-, -O-, or -NH-.
• Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group.
• R a01 and R a02 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group represented by the following formula (A1a).
• At least one of ma1 R a01 and ma2 R a02 is a group represented by formula (A1a).
• ma1 is 0 or 1;
• ma2 is 0, 1, or 2;
• two R a2 may be the same or different.
• At least one of ma1 and ma2 is not zero.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• R a03 is a radically polymerizable group-containing group.
• ma3 and ma4 are each independently 0 or 1;
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) in the compound represented by formula (A1) is 1 or more.
• Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group.
• aromatic hydrocarbon group include groups obtained by removing (ma2+1) hydrogen atoms from aromatic hydrocarbons such as benzene, naphthalene, and biphenyl.
• aromatic heterocyclic group examples include pyridine, pyrimidine, pyridazine, pyrazine, triazine, furan, thiophene, pyrrole, oxazole, thiazole, imidazole, quinoline, isoquinoline, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, benzoxazole, and benzothiazole. , benzimidazole, indole, benzofuran, benzothiophene, isoindole, isobenzofuran, and other aromatic heterocyclic compounds from which (ma2+1) hydrogen atoms have been removed.
• aromatic hydrocarbon group for Ar a01 As the aromatic hydrocarbon group for Ar a01 described above, benzene and a group obtained by removing (ma2+1) hydrogen atoms from naphthalene are preferable.
• the aromatic heterocyclic group for Ar a01 is preferably quinoline or a group obtained by removing (ma2+1) hydrogen atoms from benzothiazole.
• R a01 and R a02 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group represented by formula (A1a) below.
• aromatic hydrocarbon groups for R a01 and R a02 include a phenyl group, a naphthyl group, and a biphenylyl group. Among these, a phenyl group, a naphthalene-1-yl group and a naphthalene-2-yl group are preferred, and a phenyl group is more preferred.
• the aromatic heterocyclic groups as R a01 and R a02 include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl and quinolinyl.
• Nil group and the like can be mentioned.
• a benzoxazolyl group, a benzothiazolyl group and a benzimidazolyl group are preferred, and a benzoxazol-2-yl group, a benzothiazol-2-yl group and a benzimidazol-2-yl group are more preferred.
• R a03 is a radically polymerizable group-containing group.
• the radically polymerizable group is as described above.
• the radically polymerizable group-containing group as R a03 is preferably a (meth)acryloyl group-containing group, more preferably a (meth)acryloyl group.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a02 is preferably an alkylene group interrupted by one or more Os.
• the number of carbon atoms in the alkylene group optionally interrupted by one or more O as X a02 is not particularly limited as long as the desired effect is not impaired.
• the alkylene group optionally interrupted by one or more O as X a02 includes an alkylene group having 1 to 4 carbon atoms, an alkanetriyl group having 1 to 4 carbon atoms, and an alkanetriyl group having 1 to 4 carbon atoms.
• ma is an integer of 2 or more and 6 or less.
• alkylene group having 1 to 4 carbon atoms include methylene group, ethane-1,2-diyl group (ethylene group), propane-1,2-diyl group and propane-1,3-diyl group. , butane-1,2-diyl group, butane-1,3-diyl group, and butane-1,4-diyl group. Among these groups, ethane-1,2-diyl group (ethylene group), propane-1,2-diyl group and propane-1,3-diyl group are preferred.
• alkanetriyl groups having 1 to 4 carbon atoms include propane-1,2,3-triyl, butane-1,2,3-triyl, and butane-1,2,4-triyl groups. Among these groups, a propane-1,2,3-triyl group is preferred.
• alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. be done. Among these groups, a methyl group and an ethyl group are preferred.
• the alkylene group optionally interrupted by one or more O as X a02 is ma alkylene groups having 1 to 4 carbon atoms and (ma-1) O connecting ma alkylene groups. It is preferable that it is a group consisting of Here, ma is an integer of 2 or more and 6 or less.
• Preferred specific examples of the alkylene group optionally interrupted by one or more Os for X a02 include the following groups. -CH2CH2 - O - CH2CH2- -( CH2CH2 - O) 2 - CH2CH2- -( CH2CH2 - O) 3 - CH2CH2- -( CH2CH2 - O) 4 - CH2CH2- -( CH2CH2 - O) 5 - CH2CH2- —C(CH 3 )HCH 2 —OC(CH 3 )HCH 2 — -(C( CH3 )HCH2 - O) 2 -C( CH3 ) HCH2- -(C( CH3 )HCH2 - O) 3 -C( CH3 ) HCH2- -(C( CH3 )HCH2 - O) 3 -C( CH3 ) HCH2- -(C( CH3 )HCH2 - O) 4 -C( CH3 ) HCH2-
• -CH2CH2 - O - CH2CH2- , -( CH2CH2 - O) 2 - CH2CH2- , -(CH 2 CH 2 -O) 3 -CH 2 CH 2 - and -CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 - are preferred, -(CH 2 CH 2 -O) 2 -CH 2 CH 2 - and -(CH 2 CH 2 -O) 3 -CH 2 CH 2 - are more preferred.
• X a01 and X a03 are O in Formula (A1).
• ma1 is 0 or 1 and ma2 is 0, 1, or 2.
• two R a2 may be the same or different. At least one of ma1 and ma2 is not zero.
• ma3 and ma4 are each independently 0 or 1. It is preferable that ma1 is 0 and ma2 is 1 or 2, more preferably ma1 is 0 and ma2 is 1, since the desired effect can be easily obtained by using the compound (A1). . Moreover, it is preferable that both ma3 and ma4 are 1.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) in the compound represented by formula (A1) is 1 or more.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) is preferably 3 or more when X a is —S—, and X a is It is preferably 2 or more when —O—, and preferably 1 or more when X a is —NH—.
• the compound (A1) contains a specific amount or more of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by the formula (A1a), so that the composition is not a solvent when heated. can suppress an excessive decrease in the weight of the component of (B), and can stabilize the dispersion of the inorganic fine particles (B) in the composition.
• the upper limit of the total number of oxygen atoms derived from X a01 , X a02 and X a03 contained in the group represented by formula (A1a) is not particularly limited as long as the desired effect is not impaired.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) is, for example, preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less, and 4 6 or less is more preferable.
• X a is the same as X a in formula (A1).
• X a is preferably -S-.
• a compound in which the acryloyl group is changed to a methacryloyl group is also preferable as the compound (A1).
• the single bond or linking group between the oxygen atom attached to the aromatic ring and the acryloyloxy group is represented by -(CH 2 CH 2 -O) 3 -CH 2 CH 2 - or -CH 2
• a compound changed to CH 2 CH 2 —O—CH 2 CH 2 CH 2 — is also preferred as compound (A1).
• the acryloyl group is changed to a methacryloyl group, and the single bond or linking group between the oxygen atom attached to the aromatic ring and the acryloyloxy group is replaced by —(CH 2 CH 2 —O) 3
• a compound changed to -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -O-CH 2 CH 2 CH 2 - is also preferable as the compound (A1).
• X a is -S-, -O-, or -NH-.
• Ar a01 is a (ma2+1)-valent aromatic hydrocarbon group or a (ma2+1)-valent aromatic heterocyclic group.
• R a01 and R a02 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group represented by the following formula (A1a).
• At least one of ma1 R a01 and ma2 R a02 is a group represented by the above formula (A1a).
• ma1 is 0 or 1;
• ma2 is 0, 1, or 2;
• two R a2 may be the same or different.
• At least one of ma1 and ma2 is not zero.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• R a03 is a radically polymerizable group-containing group.
• ma3 and ma4 are each independently 0 or 1;
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 contained in the group represented by formula (A1a) is such that X a is -S It is 3 or more when X a is -, 2 or more when X a is -O-, and 1 or more when X a is -NH-.
• the total number of oxygen atoms derived from X a01 , X a02 and X a03 contained in the group represented by formula (A1a) is such that X a is -S is 3 or more when X is -, is 2 or more when X is -O-, and is 1 or more when X is -NH-; is the same as the compound
• X a is -S-, -O-, or -NH-.
• Ar a02 is a bivalent or trivalent aromatic hydrocarbon group or a bivalent or trivalent aromatic heterocyclic group.
• R a04 is a hydrogen atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• R a03 is a radically polymerizable group-containing group.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 is 3 or more when X a is —S—, and X a is 2 or more when is -O-, and is 1 or more when X a is -NH-.
• X a , X a01 , X a02 , X a03 and R a03 are the same as those in formula (A1).
• the aromatic hydrocarbon group or aromatic heterocyclic group as R a04 is the aromatic hydrocarbon group or aromatic heterocyclic group as R a01 and R a02 in formula (A1). It is the same as the cyclic group.
• Preferred specific examples of the compound represented by formula (A1-1) include the following compounds.
• X a is the same as X a in formula (A1).
• X a is preferably -S-.
• Xb is -O- or -S-.
• Xb is preferably -S-.
• a compound in which the acryloyl group is changed to a methacryloyl group is also preferable as the compound represented by formula (A1-1).
• the linking group between the oxygen atom attached to the aromatic ring and the acryloyloxy group is —(CH 2 CH 2 —O) 3 —CH 2 CH 2 — or —CH 2 CH 2 CH 2 —O—CH 2 CH 2 CH 2 — is also a compound represented by formula (A1-1). preferable.
• the acryloyl group is changed to a methacryloyl group, and an oxygen atom bonded to the aromatic ring and an acryloyloxy group
• a compound in which the linking group between is changed to —(CH 2 CH 2 —O) 3 —CH 2 CH 2 — or —CH 2 CH 2 CH 2 —O—CH 2 CH 2 CH 2 — also has the formula It is preferable as a compound represented by (A1-1).
• the method for producing the compound represented by formula (A1-1) is not particularly limited.
• a method for producing a compound represented by formula (A1-1) will be described using a compound represented by formula (A1-2) as an example.
• a preferred method for producing the compound represented by formula (A1-2) is to prepare a compound represented by formula (A1-2a) below and a compound represented by formula (A1-2b) below in the presence of a base. to obtain a compound represented by the following formula (A1-2c); substituting a terminal hydrogen atom represented by —X a03 —H of a compound represented by the following formula (A1-2c) with a group represented by R a03 .
• X a is -S-, -O-, or -NH-.
• Ar a02 is a bivalent or trivalent aromatic hydrocarbon group or a bivalent or trivalent aromatic heterocyclic group.
• R a04 is a hydrogen atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• Hal is a halogen atom.
• R a03 is a radically polymerizable group-containing group.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 is 3 or more when X a is —S—, and X a is 2 or more when is -O-, and is 1 or more when X a is -NH-.
• the method for producing the compound represented by formula (A1-2a) is not particularly limited.
• a compound represented by the following formula (A1-2a-1) and 2-mercaptoaniline, 2-hydroxyaniline, or o-phenylenediamine are combined with phosphorus oxychloride, phosphorus trichloride, and triphenyl phosphite.
• a compound represented by the formula (A1-2a) is obtained through amidation and ring closure by reacting with a dehydration condensing agent such as Amidation and ring closure may optionally be carried out in the presence of a phase transfer catalyst such as tetrabutylammonium bromide.
• a compound represented by formula (A1-2a) can also be produced using an acid halide of a compound represented by formula (A1-2a-1) below. Specifically, first, an acid halide of a compound represented by formula (A1-2a-1) below is reacted with 2-mercaptoaniline, 2-hydroxyaniline, or o-phenylenediamine to obtain an amide compound. Thereafter, the resulting amide compound is reacted with phosphorus oxychloride, phosphorus trichloride, triphenyl phosphite, and the like to cyclize the compound represented by formula (A1-2a).
• the reaction of the compound represented by formula (A1-2a) and the compound represented by formula (A1-2b) in the presence of a base is usually carried out in the presence of an organic solvent.
• the organic solvent used for the reaction between the compound represented by formula (A1-2a) and the compound represented by formula (A1-2b) is not particularly limited as long as it does not inhibit the progress of the reaction. Since the reaction is carried out in the presence of a base, the organic solvent is preferably an organic solvent that does not have an acidic group such as a carboxy group or a sulfonic acid group, or a hydroxyl group.
• an aprotic polar organic solvent is preferable because it facilitates the progress of the reaction.
• Suitable examples of aprotic polar organic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, tetrahydrofuran, cyclopentylmethyl ether, acetonitrile, and hexamethylphosphite. Holic triamide and the like.
• the amount of organic solvent used is not particularly limited.
• the amount of the organic solvent used is 0.5 times or more by mass the mass of the base, the mass of the compound represented by formula (A1-2a), and the mass of the compound represented by formula (A1-2b). It is preferably 0.7 to 20 times by mass, and even more preferably 1 to 10 times by mass.
• bases a basic compound used in so-called Williamson's ether synthesis can be used without particular limitation.
• bases include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium hydride, metallic sodium, and metallic potassium.
• the amount of the base used in the reaction between the compound represented by formula (A1-2a) and the compound represented by formula (A1-2b) is such that a desired amount of the compound represented by formula (A1-2c) is produced. It is not particularly limited as long as it can be made.
• the amount of the base to be used is, for example, preferably 0.8 mol or more and 10 mol or less, more preferably 0.9 mol or more and 5 mol or less, relative to 1 mol of the compound represented by formula (A1-2a). 3 mol or less is more preferable.
• the amount of the compound represented by formula (A1-2b) to be used is not particularly limited as long as a desired amount of the compound represented by formula (A1-2c) can be produced.
• the amount of the compound represented by the basic formula (A1-2b) to be used is, for example, preferably 0.8 mol or more and 10 mol or less, and 0.9 mol or less per 1 mol of the compound represented by the formula (A1-2a). It is more preferably 1 mol or more and 5 mol or less, and even more preferably 1 mol or more and 3 mol or less.
• the temperature at which the compound represented by formula (A1-2a) and the compound represented by formula (A1-2b) are reacted can produce a desired amount of the compound represented by formula (A1-2c). It is not particularly limited as much as possible.
• the reaction temperature is, for example, preferably 0° C. or higher and 200° C. or lower, more preferably 10° C. or higher and 180° C. or lower, even more preferably 20° C. or higher and 150° C. or lower.
• the reaction may be carried out using a pressure vessel.
• the time for reacting the compound represented by formula (A1-2a) with the compound represented by formula (A1-2b) is such that a desired amount of the compound represented by formula (A1-2c) can be produced. It is not particularly limited as much as possible.
• the reaction time is typically preferably 1 hour or more and 2 days or less, more preferably 2 hours or more and 1 day or less, and more preferably 3 hours or more and 18 hours or less.
• the terminal hydrogen atom represented by —X a03 —H of the compound represented by formula (A1-1c) obtained by the above method is substituted with a group represented by R a03 .
• the method for substituting the terminal hydrogen atom represented by —X a03 —H with the group represented by R a01 is not particularly limited.
• the method for substituting the terminal hydrogen atom represented by -X a03 -H with the group represented by R a03 is appropriately selected according to the type of radical polymerizable group-containing group represented by R a03 .
• R a03 is a (meth)acryloyl group
• a (meth)acrylic acid halide such as (meth)acryloyl chloride is added to -X a03 - in the compound represented by formula (A1-2c).
• a group represented by H By reacting with a group represented by H, a terminal hydrogen atom represented by -X a03 -H can be substituted with a (meth)acryloyl group.
• the reaction between the compound represented by formula (A1-2c) and (meth)acrylic acid halide is preferably carried out in an organic solvent.
• the type of organic solvent is not particularly limited as long as it does not react with the compound represented by formula (A1-2c) and (meth)acrylic acid halide.
• the compound represented by the formula (A1-2) can also be obtained by condensing (meth)acrylic acid and the compound represented by the formula (A1-2c) according to a well-known ester synthesis method. .
• a compound represented by the following formula (A1-2a) is reacted with a compound represented by the following formula (A1-2d) in the presence of a base to obtain a compound represented by the formula (A1-2).
• a compound represented by formula (A1-2) can also be produced by a method including obtaining the compound.
• X a is -S-, -O-, or -NH-.
• Ar a02 is a bivalent or trivalent aromatic hydrocarbon group or a bivalent or trivalent aromatic heterocyclic group.
• R a04 is a hydrogen atom, an aromatic hydrocarbon group, or an aromatic heterocyclic group.
• X a01 is O.
• X a02 is an alkylene group optionally interrupted by one or more Os.
• X a03 is O.
• Hal is a halogen atom.
• R a03 is a radically polymerizable group-containing group.
• the total number of oxygen atoms derived from X a01 , X a02 , and X a03 is 3 or more when X a is —S—, and X a is 2 or more when is -O-, and is 1 or more when X a is -NH-.
• reaction of the compound represented by formula (A1-2a) with the compound represented by formula (A1-2d) in the presence of a base is the reaction of the above-described formula (A1- It is carried out in the same manner as the reaction between the compound represented by 2a) and the compound represented by formula (A1-2b).
• the compound represented by formula (A1-1) produced by the above method is blended into the composition after being purified as necessary.
• purification methods include well-known methods such as chromatography such as column chromatography and recrystallization.
• the photopolymerizable compound (A) may contain a photopolymerizable compound (A2) other than the compound (A1) described above as long as the desired effects are not impaired.
• the ratio of the mass of the compound (A1) to the mass of the photopolymerizable compound (A) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly 90% by mass or more. Preferably, 100% by weight is most preferred.
• the composition may contain other photopolymerizable compounds (A2) along with compound (A1). Since the compound (A1) has a radically polymerizable group-containing group, the other photopolymerizable compound (A2) also has a radically polymerizable group-containing group.
• the other photopolymerizable compound (A2) may be a monofunctional compound having one radically polymerizable group or a polyfunctional compound having two or more radically polymerizable groups. preferable.
• the other photopolymerizable compound (A2) having a radically polymerizable group-containing group compounds having one or more (meth)acryloyl groups such as (meth)acrylate compounds and (meth)acrylamide compounds are preferable.
• a (meth)acrylate compound having a (meth)acryloyl group is more preferred.
• Monofunctional compounds having radically polymerizable group-containing groups include, for example, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic anhydride citraconic acid, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Cyclohexyl (meth) acrylate
• Polyfunctional compounds having radically polymerizable group-containing groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di( meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexaneglycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate ) acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dip
• trifunctional or higher polyfunctional compounds are preferred because they tend to increase the strength of materials formed using the composition.
• a tetrafunctional or higher polyfunctional compound more preferably a pentafunctional or higher polyfunctional compound.
• the composition contains a compound represented by the following formula (A-2a) or the following formula (A-2b) as the photopolymerizable compound (A) having a radically polymerizable group-containing group. preferably included.
• each MA is independently a (meth)acryloyl group.
• Each X is independently an oxygen atom, -NH-, or -N(CH 3 )-.
• Each R a1 is independently an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group.
• R a2 is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or a group represented by —X—(R a1 —O) na1 —MA (where X is the same as above).
• na1 and na2 are each independently 0 or 1;
• the alkyl group having 1 to 4 carbon atoms as R a2 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl. and tert-butyl groups.
• a methyl group and an ethyl group are preferred.
• Preferred examples of the compound represented by formula (A-2a) and the compound represented by formula (A-2b) include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane. Examples include tri(meth)acrylate, glycerin tri(meth)acrylate, and compounds 1) to 32) below. In the compounds 1) to 32) below, MA is a (meth)acryloyl group.
• the mass of the compound represented by the formula (A-2a) with respect to the mass of the photopolymerizable compound (A), and the formula (A-2b) is preferably 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and even more preferably 40% by mass or more and 50% by mass or less.
• R 1 and R 2 are each independently a hydrogen atom or a methyl group.
• R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms.
• p and q are each independently 0 or 1;
• R 1 and R 2 are each independently a hydrogen atom or a methyl group. R 1 and R 2 may be different from each other or may be the same. R 1 and R 2 are preferably the same because the compound represented by formula (A-2c) is easily synthesized and available.
• R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms. R 3 and R 4 may be different from each other or may be the same. R 3 and R 4 are preferably the same because the compound represented by formula (A-2c) is easy to synthesize and obtain.
• the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 may be linear or branched.
• alkyl groups having 1 to 5 carbon atoms as R 3 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and tert-pentyl group.
• the composition contains a compound represented by formula (A-2c) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group
• the formula (A) is preferably 10% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 50% by mass or less.
• the composition contains sulfur represented by the following formula (A-2d) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group. It preferably contains (meth)acrylates.
• Ar a1 -R a21 -SR a22 -O-CO-CR a23 CH 2 (A-2d)
• Ar a1 is a phenyl group optionally substituted with a halogen atom.
• R a21 is a single bond or an alkylene group having 1 to 6 carbon atoms.
• R a22 is an alkylene group having 1 to 6 carbon atoms, and
• R a23 is a hydrogen atom or a methyl group.
• Ar a1 is a phenyl group optionally substituted with a halogen atom.
• the number of halogen atoms bonded to the phenyl group is not particularly limited.
• the number of halogen atoms bonded to the phenyl group is preferably 1 or 2, more preferably 1.
• the plurality of halogen atoms bonded to the phenyl group may consist of the same kind of halogen atoms alone, or may consist of two or more kinds of halogen atoms.
• a halogen atom that can be bonded to a phenyl group includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, and a bromine atom being preferred.
• Ar a1 is preferably an unsubstituted phenyl group.
• R a21 is a single bond or an alkylene group having 1 to 6 carbon atoms.
• alkylene group having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group and butane-1,4-diyl. , pentane-1,5-diyl groups, and hexane-1,6-diyl groups.
• R a21 is preferably a single bond and a methylene group, more preferably a single bond.
• R a22 is an alkylene group having 1 to 6 carbon atoms.
• the alkylene group having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group and butane-1,4-diyl. , pentane-1,5-diyl groups, and hexane-1,6-diyl groups.
• R a22 is preferably a methylene group, an ethane-1,2-diyl group and a propane-1,3-diyl group, more preferably an ethane-1,2-diyl group and a propane-1,3-diyl group. .
• Ar a1 is a phenyl group and R a21 is a single bond. is particularly preferred.
• sulfur-containing (meth)acrylates represented by formula (A-2d) include 2-phenylthioethyl (meth)acrylate, 3-phenylthiopropyl (meth)acrylate, 2-benzylthioethyl ( meth)acrylate, 3-benzylthiopropyl (meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate ) acrylate, 3-(2-chlorophenyl)propyl (meth)acrylate, 3-(3-chlorophenyl)propyl (meth)acrylate, 3-(4-chlorophenyl)propyl (meth)acrylate, 2-(2-fluorophenyl) ethyl (meth) acrylate, 2-(3-fluorophenyl) ethy
• the composition contains a sulfur-containing (meth)acrylate represented by formula (A-2d) as another photopolymerizable compound (A2) having a radically polymerizable group-containing group
• the photopolymerizable compound (A) The mass ratio of the sulfur-containing (meth)acrylate represented by formula (A-2d) to the mass is preferably 40% by mass or more and 50% by mass or less.
• the composition preferably contains a compound represented by the following formula (A-2e) as the other photopolymerizable compound (A2), since the composition can be used to easily form a material with a high refractive index.
• R A1 , R A2 and R A3 are each independently an organic group. At least two of the organic group as R A1 , the organic group as R A2 and the organic group as R A3 have a radically polymerizable group-containing group.
• Preferred examples of the compound represented by formula (A-2e) include compounds represented by the following formula (A-2e-a).
• R A01 is a quinolinyl group optionally having substituents, an isoquinolinyl group optionally having substituents, or a 2-substituted benzothiazolyl group optionally having substituents is.
• a 2-substituted benzothiazolyl group has a group represented by —SR A0 at the 2-position.
• R A0 is a hydrogen atom or a radically polymerizable group-containing group.
• Both R A02 and R A03 are aromatic ring-containing groups having radically polymerizable group-containing groups. The -NH- group attached to the triazine ring is attached to the aromatic rings in R A02 and R A03 .
• R A01 is a quinolinyl group optionally having substituents, an isoquinolinyl group optionally having substituents, or a 2-substituted benzothiazolyl group optionally having substituents. It is thought that this contributes to the high refractive index of the material formed using
• the quinolinyl group as R A01 includes a quinolin-2-yl group, a quinolin-3-yl group, a quinolin-4-yl group, a quinolin-5-yl group, a quinolin-6-yl group, and a quinolin-7-yl group. , and quinolin-8-yl groups.
• the raw material compound for the compound represented by the formula (A2e-a) is easily available, and the compound represented by the formula (A2e-a) is easily synthesized.
• quinolin-3-yl and quinolin-4-yl groups are preferred.
• the isoquinolinyl group as R A01 includes isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, and isoquinolin-8-yl groups.
• the quinolinyl group as R A01 and the substituent that the isoquinolinyl group may have are not particularly limited as long as the desired effect is not impaired.
• substituents include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of monovalent organic groups include alkyl groups, alkoxy groups, alkoxyalkyl groups, aliphatic acyl groups, aliphatic acyloxy groups, alkoxycarbonyl groups, alkylthio groups, and aliphatic acylthio groups.
• a radically polymerizable group-containing group, which will be described later, is also preferable as the monovalent organic group.
• the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the monovalent organic group as a substituent is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the lower limit of the number of carbon atoms is 2.
• alkyl groups as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl, n-heptyl, and n-octyl groups.
• alkoxy groups as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n- Pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy groups are included.
• alkoxyalkyl groups as substituents include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, 4-n-butyloxy-n-butyloxy groups.
• aliphatic acyl groups as substituents include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, and octanoyl group.
• aliphatic acyloxy groups as substituents include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy groups.
• alkoxycarbonyl groups as substituents include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl and sec-butyloxy. carbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl groups.
• alkylthio groups as substituents include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio and n-pentylthio. , n-hexylthio, n-heptylthio, and n-octylthio groups.
• aliphatic acylthio groups as substituents include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
• the quinolinyl group and the isoquinolinyl group have multiple substituents, the multiple substituents may be different from each other.
• the 2-substituted benzothiazolyl group as R A01 has a group represented by —S—R A0 at the 2-position.
• the 2-substituted benzothiazolyl group as R A01 may have a substituent other than the group represented by —S—R A0 at a position other than 2.
• R A0 is a hydrogen atom or a radically polymerizable group-containing group. The radically polymerizable group-containing group will be described later.
• Preferred examples of 2-substituted benzothiazolyl groups include the groups below.
• the substituent which the 2-substituted benzothiazolyl group as R A01 may have is the same as the substituent which the quinolinyl group and the isoquinolinyl group may have.
• the number of substituents is not particularly limited as long as the desired effects are not impaired.
• the number of substituents is preferably 1 or 2, more preferably 1.
• the 2-substituted benzothiazolyl group has multiple substituents, the multiple substituents may be different from each other.
• Both R A02 and R A03 are aromatic ring-containing groups having radically polymerizable group-containing groups.
• the —NH— group attached to the triazine ring is attached to the aromatic rings in R A02 and R A03 .
• the bonding position of the radically polymerizable group-containing group in the aromatic ring-containing group as R A02 and R A03 is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group as RA02 and the number of radically polymerizable group-containing groups in the aromatic ring-containing group as RA03 are not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group as RA02 and the number of radically polymerizable group-containing groups in the aromatic ring-containing group as RA03 are preferably integers of 1 or more and 3 or less, 1 or 2 is more preferred, and 1 is particularly preferred.
• the aromatic ring-containing groups as R A02 and R A03 may contain only one monocyclic aromatic ring or one condensed aromatic ring, and the monocyclic aromatic ring and/or condensed aromatic ring may include two or more.
• the aromatic ring-containing group as R A02 and R A03 contains two or more monocyclic aromatic rings and/or condensed aromatic rings, the monocyclic aromatic rings, the condensed aromatic rings, or the monocyclic
• the type of linking group that links the formula aromatic ring and the condensed aromatic ring is not particularly limited.
• the linking group may be a divalent linking group or a trivalent or higher linking group, preferably a divalent linking group.
• a group represented by —CR a001 R a002 — is also preferred as the divalent linking group.
• R a001 and R a002 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.
• R a001 and R a002 may combine with each other to form a ring.
• groups represented by —CR a001 R a002 — include methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1,1 , 1,3,3,3-hexafluoropropane-2,2-diyl, cyclopentylidene, cyclohexylidene, and cycloheptylidene groups.
• the aromatic ring-containing group as R A02 and R A03 has a radically polymerizable group-containing group.
• the radically polymerizable group-containing group is as described above.
• Preferable examples of the radically polymerizable group-containing group include groups represented by the following formula (AI) or the following formula (A-II), which are not vinyloxy group-containing groups. -(A 01 ) na -R 01 (AI) -(A 01 ) na -R 02 -A 02 -R 01 (A-II)
• R 01 is an alkenyl group having 2 to 10 carbon atoms.
• R 02 is an alkylene group having 1 to 10 carbon atoms.
• a 01 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
• a 02 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
• na is 0 or 1;
• the radically polymerizable group-containing group include: —OR 03 , -SR 03 , —O—CH 2 CH 2 —OR 03 , —O—CH 2 CH 2 CH 2 —OR 03 , —O—CH 2 CH 2 CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 CH 2 CH 2 —OR 03 , -O- CH2CH2 - NH- R03 , -O- CH2CH2CH2 - NH - R03 , -O - CH2CH2CH2CH2 - NH - R03 , -CO-O- CH2CH2 - NH- R03 , -CO-O- CH2CH2 - NH- R03 , -CO-O- CH2CH2 - NH- R03 , -CO-O- CH2CH2
• R A02 and R A03 When the aromatic ring-containing group as R A02 and R A03 has one radically polymerizable group-containing group, preferred examples of R A02 and R A03 include groups of the following formulae.
• PG is a radically polymerizable group-containing group.
• X A is a group selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylthio group, and a 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group. be.
• the method for producing the compound represented by formula (A-2e-a) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 . These plural types of amines may be reacted with the cyanuric halide simultaneously or sequentially with the cyanuric halide, preferably with the cyanuric halide sequentially.
• a cyanuric halide such as cyanuric chloride
• aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 .
• R A02 and R A03 in formula (A-2e-a) are, after reacting an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxy group, or an amino group, with a cyanuric halide, It can also be produced by reacting these functional groups with a compound that provides a radically polymerizable group-containing group.
• Compounds that provide radically polymerizable group-containing groups include compounds having radically polymerizable groups such as (meth)acrylic acid, (meth)acrylic acid halides, and halogenated olefins.
• the reaction to form the radically polymerizable group-containing group may be a multistage reaction. For example, after reacting a cyanuric halide with an aromatic amine having a phenolic hydroxyl group, the phenolic hydroxyl group is reacted with epichlorohydrin to glycidylate, and then the glycidyl group is reacted with acrylic acid to obtain the following formula.
• a radically polymerizable group-containing group represented by can be introduced onto the aromatic ring.
• -O-CH 2 -CHOH-CH 2 -O-CO-CH CH 2
• the above reaction is just an example, and the radically polymerizable group-containing group can be formed by carrying out a combination of various reactions.
• the compound represented by formula (A-2e-a) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• an organic solvent or the like exemplified as a specific example of the solvent (S) described later can be used.
• the temperature at which the aromatic amines are reacted is not particularly limited. Typically, the reaction temperature is preferably from 0°C to 150°C.
• R A11 , R A12 and R A13 each represent an aromatic ring-containing group. At least one of R A12 and R A13 is a group represented by the following formula (A-2e-b1).
• R a11 and R a12 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• nA1 and nA2 are each independently an integer of 0 or more and 4 or less.
• R a13 and R a14 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• R a13 and R a14 may combine with each other to form a ring.
• RA14 is a radically polymerizable group-containing group.
• both R A12 and R A13 are groups represented by formula (A-2e-b1), both R A12 and R A13 have radically polymerizable group-containing groups.
• R A11 , R A12 and R A13 are each aromatic ring-containing groups.
• the —NH— groups attached to the triazine ring are attached to the aromatic rings in R A11 , R A12 and R A13 , respectively.
• the aromatic ring-containing group is a group other than the group represented by formula (A-2e-b1), the aromatic ring-containing group is not particularly limited as long as it satisfies the given requirements above.
• Aromatic ring-containing groups other than the group represented by formula (A-2e-b1) may contain only one monocyclic aromatic ring or one condensed aromatic ring, monocyclic aromatic ring, and/or may contain two or more fused aromatic rings.
• the aromatic ring-containing group contains two or more monocyclic aromatic rings and/or condensed aromatic rings, the monocyclic aromatic rings together, the condensed aromatic rings together, or the monocyclic aromatic ring and the condensed aromatic ring
• the type of the linking group that links the is not particularly limited.
• the linking group may be a divalent linking group or a trivalent or higher linking group, preferably a divalent linking group.
• Preferred examples of the aromatic ring-containing group include optionally substituted quinolinyl groups, optionally substituted isoquinolinyl groups, and optionally substituted 2-substituted benzothiazolyl groups. These groups include an optionally substituted quinolinyl group, an optionally substituted isoquinolinyl group, and a substituted 2-substituted benzothiazolyl group.
• aromatic ring-containing group examples include an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted biphenylyl group, and an optionally substituted phenyl group.
• optionally substituted phenylthiophenyl group optionally substituted phenoxyphenyl group, optionally substituted phenylsulfonylphenyl group, optionally substituted benzothiazolyl group, optionally substituted a benzoxazolyl group which may be substituted, a terphenyl group which may have a substituent, and the like.
• substituents are the same as the substituents that the quinolinyl group and the isoquinolinyl group may have.
• these groups have multiple substituents the multiple substituents may be different from each other.
• Suitable specific examples of the naphthyl group which may have a substituent include naphthalene-1-yl group and naphthalene-2-yl group.
• biphenylyl group optionally having a substituent include a 4-phenylphenyl group, a 3-phenylphenyl group, a 2-phenylphenyl group, a 4-(4-nitrophenyl)phenyl group, a 3-(4 -nitrophenyl)phenyl, 2-(4-nitrophenyl)phenyl, 4-(4-cyanophenyl)phenyl, 3-(4-cyanophenyl)phenyl, and 2-(4-cyanophenyl)phenyl groups.
• phenylsulfonylphenyl group which may have a substituent include a 4-phenylsulfonylphenyl group, a 3-phenylsulfonylphenyl group, and a 2-phenylsulfonylphenyl group.
• the aromatic ring-containing group other than the group represented by formula (A-2e-b1) may have a radically polymerizable group-containing group as a substituent.
• the bonding position of the radically polymerizable group-containing group in the aromatic ring-containing group is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group is not particularly limited.
• the number of radically polymerizable group-containing groups in the aromatic ring-containing group is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1.
• aromatic ring-containing group has one radically polymerizable group-containing group
• suitable examples of such a group include groups of the following formulae.
• PG is a radically polymerizable group-containing group.
• R A12 and R A13 are a group represented by formula (A-2e-b1) below.
• R a11 and R a12 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• nA1 and nA2 are each independently an integer of 0 or more and 4 or less.
• R a13 and R a14 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• R a13 and R a14 may combine with each other to form a ring.
• RA14 is a radically polymerizable group-containing group. When both R A12 and R A13 are groups represented by formula (A-2e-b1), both R A12 and R A13 have radically polymerizable group-containing groups.
• alkyl groups having 1 to 4 carbon atoms as R a11 and R a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -Butyl group.
• the alkoxy group having 1 to 4 carbon atoms as R a11 and R a12 includes a methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group and sec-butyloxy group. , and tert-butyloxy groups.
• Halogen atoms as R a11 and R a12 include fluorine, chlorine, bromine and iodine atoms.
• alkyl group having 1 to 4 carbon atoms for R a13 and R a14 are the same as the specific examples of the alkyl group having 1 to 4 carbon atoms for R a11 and R a12 .
• halogenated alkyl group having 1 to 4 carbon atoms for R a13 and R a14 include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 3,3,3-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group and the like.
• Preferred examples of the group represented by formula (A-2e-b1) include groups represented by the following formula.
• the group represented by formula (A-2e-b1) has a radical polymerizable group-containing group as R A14 .
• the radically polymerizable group-containing group is as described above.
• Preferred specific examples of the radically polymerizable group-containing group are the same as the preferred specific examples of the radically polymerizable group-containing group described for the compound represented by formula (A-2e-a).
• X A is selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylthio group, a 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group, and a glycidyloxy group.
• Y A is quinolin-3-yl group, phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 3,4-dicyanophenyl group, 4-nitrophenyl group, 4-methoxyphenyl group, 4-phenylthiophenyl group, 4-phenylsulfonylphenyl group, 4-iodophenyl group, benzothiazol-2-yl group, 2-mercaptobenzothiazol-5-yl group, 4-phenylphenyl group, 4-( 4-nitrophenyl)phenyl group, 4-(4-cyanophenyl)phenyl group, naphthalen-1-yl group, and 4-(4-phenylphenyl)phenyl group.
• the method for producing the compound represented by formula (A-2e-b) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 . These plural types of amines may be reacted with the cyanuric halide simultaneously or sequentially with the cyanuric halide, preferably with the cyanuric halide sequentially.
• a cyanuric halide such as cyanuric chloride
• an aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 .
• an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group is halogenated.
• a radically polymerizable group-containing group can also be produced by reacting these functional groups with a compound that provides a radically polymerizable group-containing group after the reaction with cyanuric acid.
• Compounds that provide radically polymerizable group-containing groups include compounds having radically polymerizable groups such as (meth)acrylic acid, (meth)acrylic acid halides, and halogenated olefins.
• the reaction to form the radically polymerizable group-containing group may be a multistage reaction. For example, after reacting a cyanuric halide with an aromatic amine having a phenolic hydroxyl group, the phenolic hydroxyl group is reacted with epichlorohydrin to glycidylate, and then the glycidyl group is reacted with acrylic acid to obtain the following formula.
• a radically polymerizable group-containing group represented by can be introduced onto the aromatic ring.
• -O-CH 2 -CHOH-CH 2 -O-CO-CH CH 2
• the above reaction is just an example, and the radically polymerizable group-containing group can be formed by carrying out a combination of various reactions.
• the compound represented by formula (A-2e-b) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• an organic solvent or the like exemplified as a specific example of the solvent (S) can be used.
• cyanuric halide and aromatic amines represented by R A11 —NH 2 , R A12 —NH 2 , and R A13 —NH 2 , etc.
• the temperature at which the aromatic amines are reacted is not particularly limited. Typically, the reaction temperature is preferably from 0°C to 150°C.
• the content of the photopolymerizable compound (A) in the composition is not particularly limited as long as the desired effects are not impaired.
• the content of the photopolymerizable compound (A) in the composition is 0.1 parts by mass or more and 50 parts by mass or less when the mass of the composition excluding the mass of the solvent (S) described later is 100 parts by mass. It is preferably 0.5 parts by mass or more and 40 parts by mass or less, and particularly preferably 1 part by mass or more and 25 parts by mass or less.
• the composition contains the metal fine particles (B2)
• the material formed using the composition is imparted with conductivity, or the material formed using the composition enhances light absorption at a specific wavelength. Therefore, a composition containing fine metal particles (B2) is used to form a material that can be applied to a bandpass filter.
• the type of metal oxide that constitutes the metal oxide fine particles (B1) is not particularly limited as long as the desired effects are not impaired.
• Preferred examples of the metal oxide fine particles (B1) include at least one selected from the group consisting of zirconium oxide fine particles, titanium oxide fine particles, barium titanate fine particles, cerium oxide fine particles, and niobium pentoxide fine particles.
• the type of metal constituting the fine metal particles (B2) is not particularly limited as long as the desired effect is not impaired.
• the metal that constitutes the fine metal particles (B2) may be a single substance or an alloy.
• Preferred examples of the metal fine particles (B2) include gold fine particles and platinum fine particles.
• Other preferred inorganic fine particles (B) include silicon fine particles (silicon nanoparticles) which are semimetal fine particles.
• the composition may contain one type of these inorganic fine particles (B) alone, or may contain two or more types in combination.
• the average particle size of the inorganic fine particles (B) is preferably 500 nm or less from the viewpoint of the transparency of the material formed using the composition and the stability of dispersion of the inorganic fine particles (B) in the composition. , 2 nm or more and 100 nm or less.
• the metal oxide fine particles (B1) those whose surfaces are modified with ethylenically unsaturated double bond-containing groups are preferred.
• the surface of the metal oxide fine particles (B1) is modified with an ethylenically unsaturated double bond-containing group, it is preferable in that aggregation of the metal oxide fine particles (B1) hardly occurs.
• metal oxide fine particles (B1) For example, by allowing a capping agent containing an ethylenically unsaturated double bond to act on the surface of the metal oxide fine particles (B1), the surface is formed with an ethylenically unsaturated double bond through a chemical bond such as a covalent bond. Metal oxide fine particles (B1) modified with containing groups are obtained.
• the method of bonding the capping agent containing an ethylenically unsaturated double bond to the surface of the metal oxide fine particles (B1) via a chemical bond such as a covalent bond is not particularly limited. Hydroxyl groups are usually present on the surface of the metal oxide fine particles (B1). By reacting the hydroxyl group with the reactive group of the capping agent, the capping agent is covalently bonded to the surface of the metal oxide fine particles (B1).
• a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group
• a dialkoxysilyl group such as a dimethoxysilyl group and a diethoxysilyl group
• a trialkoxysilyl group, a dialkoxysilyl group, a monoalkoxysilyl group, a trihalosilyl group, a dihalosilyl group, and a monohalosilyl group form a siloxane bond with the surface of the metal oxide nanoparticles (B).
• a carboxy group and a halocarbonyl group form a bond represented by (metal oxide--O--CO--) with the surface of the metal oxide fine particles (B1).
• a hydroxyl group forms a bond represented by (metal oxide —O—) with the surface of the metal oxide fine particles (B).
• the groups that bind to the above reactive groups include hydrogen atoms and various organic groups.
• the organic group may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
• the groups that bind to the above reactive groups include, for example, linear or branched alkyl groups that may be interrupted by oxygen atoms (—O—), linear or branched an alkenyl group optionally interrupted by an oxygen atom (--O--), may be linear or branched, and is interrupted by an oxygen atom (--O--) alkynyl groups, cycloalkyl groups, aromatic hydrocarbon groups, heterocyclic groups, etc., which may be substituted.
• substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
• substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
• the number of substituents is not particularly limited.
• R b1 , R b2 , R b3 and Rb4 are each an organic group which may be the same or different.
• organic groups include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group and tolyl group; Epoxy group-containing groups such as propyl group; (meth)acryloyloxy group and the like.
• r and s in the above formula are each independently an integer of 0 or more and 60 or less. Both r and s in the above formula cannot be zero.
• capping agents include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane. Unsaturated groups such as silane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc.
• alkoxysilane Containing alkoxysilane; unsaturated group-containing alcohols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol (meth)acrylic acid; (meth)acrylic acid halides such as (meth)acrylic acid chloride;
• the amount of the capping agent used when bonding the capping agent to the surface of the metal oxide fine particles (B1) via a chemical bond such as a covalent bond is not particularly limited. Preferably, a sufficient amount of the capping agent is used to react with almost all hydroxyl groups on the surface of the metal oxide fine particles (B1).
• the content of the inorganic fine particles (B) in the composition is not particularly limited as long as the object of the present invention is not impaired.
• the content of the inorganic fine particles (B) in the composition is preferably 5% by mass or more and 95% by mass or less, and 35% by mass or more and 93% by mass or less with respect to the mass of the composition excluding the mass of the solvent (S). is more preferable, and 40% by mass or more and 90% by mass or less is even more preferable.
• the content of the inorganic fine particles (B) in the composition is within the above range, it is easy to obtain a composition in which the inorganic fine particles (B) are stably dispersed. It is easy to form a material that has the desired effect provided by the use of B).
• the content of the metal oxide fine particles (B1) in the composition is 70% by mass or more is preferable, 75% by mass or more and 98% by mass or less is more preferable, and 80% by mass or more and 95% by mass or less is even more preferable with respect to the mass excluding the mass of the solvent (S).
• the surface of the metal oxide fine particles (B1) is modified with an ethylenically unsaturated double bond-containing group, the ethylenically unsaturated double bond-containing groups present on the surface of the metal oxide fine particles (B1) is included in the mass of the metal oxide fine particles (B1).
• the composition may contain a plasticizer (D).
• the plasticizer (D) is a component that reduces the viscosity of the composition without significantly impairing various physical properties such as a high refractive index of the material formed using the composition.
• a compound represented by the following formula (d-1) is preferable as the plasticizer (D).
• D the plasticizer
• R d1 and R d2 are each independently a phenyl group optionally having 1 to 5 substituents.
• the substituent is selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
• R d3 and R d4 are each independently a methylene group or an ethane-1,2-diyl group.
• r and s are each independently 0 or 1
• Xd is an oxygen atom or a sulfur atom.
• the viscosity of the composition is reduced without significantly impairing various physical properties such as a high refractive index of the material formed using the composition.
• the viscosity of the plasticizer (D) measured by an E-type viscometer at 25° C. is preferably 10 cP or less, more preferably 8 cP or less, and even more preferably 6 cP or less.
• the boiling point of the plasticizer (D) under atmospheric pressure is preferably 250° C. or higher because the plasticizer (D) is less likely to volatilize and the viscosity-lowering effect of the composition is easily maintained. °C or more is more preferable.
• the upper limit of the boiling point of the plasticizer (D) under atmospheric pressure is not particularly limited, it may be, for example, 300° C. or lower, or 350° C. or lower.
• R d1 and R d2 in formula (d-1) are each independently a phenyl group optionally having 1 to 5 substituents.
• the substituent bonded to the phenyl group is a group selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
• the number of substituents is not particularly limited.
• the number of substituents is 1 or more and 5 or less, preferably 1 or 2, and preferably 1.
• R d1 and R d2 are each preferably an unsubstituted phenyl group.
• alkyl group having 1 to 4 carbon atoms as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. mentioned.
• alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert- A butyloxy group is mentioned.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R d3 and R d4 in formula (d-1) are each independently a methylene group or an ethane-1,2-diyl group. Moreover, r and s are 0 or 1 each independently.
• X d in formula (d-1) is an oxygen atom or a sulfur atom.
• Preferred specific examples of the compound represented by formula (d-1) described above include diphenyl ether, diphenyl sulfide, dibenzyl ether, dibenzyl sulfide, diphenethyl ether, and diphenethyl sulfide. Among these, diphenyl sulfide and/or dibenzyl ether are more preferred.
• the content of the plasticizer (D) in the composition is preferably more than 0% by mass and 35% by mass or less in terms of both viscosity adjustment and dispersibility of the inorganic fine particles (B) with respect to the total mass of the composition. , more preferably 5% by mass or more and 15% by mass or less.
• the composition is an amine compound (E1) represented by the following formula (e1) and/or represented by the following formula (e2). may contain the imine compound (E2) as the nitrogen-containing compound (E).
• NR e1 R e2 R e3 (e1) R e4 ⁇ N CR e5 R e6 (e2)
• R e1 , R e2 and R e3 are each independently a hydrogen atom or an organic group.
• R e4 , R e5 and R de6 are each independently a hydrogen atom or an organic group.
• R e1 , R e2 , R e3 , R e4 , R e5 , and R de6 are organic groups
• the organic groups are within a range that does not impair the desired effect. and can be selected from a variety of organic groups.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms.
• a group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the organic group include an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted naphthyl group, An optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and the like can be mentioned.
• the number of carbon atoms in the alkyl group as the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• the structure of the alkyl group may be linear or branched. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl group.
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• the number of carbon atoms in the cycloalkyl group as the organic group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
• the number of carbon atoms in the phenylalkyl group as the organic group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• the number of carbon atoms in the naphthylalkyl group as the organic group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups.
• naphthylalkyl groups include ⁇ -naphthylmethyl, ⁇ -naphthylmethyl, 2-( ⁇ -naphthyl)ethyl, and 2-( ⁇ -naphthyl)ethyl groups.
• the phenylalkyl group or naphthylalkyl group may further have a substituent on the phenyl group or naphthyl group.
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• a heterocyclyl group as an organic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is preferably a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclyl group in which such monocyclic rings are condensed with each other or such monocyclic rings and a benzene ring are condensed.
• the heterocyclyl group is a condensed ring, it has up to 3 rings.
• Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
• the substituent may be an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• a halogenated alkyl group having 1 to 6 carbon atoms a halogenated alkoxy group having 1 to 6 carbon atoms
• a saturated aliphatic acyl group having 2 to 7 carbon atoms a saturated aliphatic acyl group having 2 to 7 carbon atoms
• alkoxycarbonyl group saturated aliphatic acyloxy group having 2 to 7 carbon atoms
• monoalkylamino group having alkyl group having 1 to 6 carbon atoms dialkylamino group having alkyl group having 1 to 6 carbon atoms
• a benzoyl group a halogen atom, a nitro group, a cyano group, and the like.
• the number of substituents is not particularly limited, and is preferably from 1 to 4.
• the phenyl group, naphthyl group and heterocyclyl group contained in the organic group have multiple substituents, the multiple substituents may be the same or different.
• R e1 , R e2 and R e3 are each independently a hydrogen atom or an organic group, and at least one of R e1 , R e2 and R e3 is an aromatic group-containing group.
• R e4 , R e5 , and R de6 are each independently a hydrogen atom or an organic group, and at least one of R e4 , R e5 , and R de6 is an aromatic group-containing group.
• the aromatic ring in the aromatic group-containing group may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A hydrocarbon group is preferable as the aromatic group-containing group.
• Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
• Aralkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl groups.
• R e1 , R e2 and R e3 is preferably a group represented by A e1 —CH 2 —.
• R e4 is preferably a group represented by Ar e1 —CH 2 —.
• Ar e1 is an aromatic group optionally having a substituent.
• the aromatic group for Ar e1 may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
• the aromatic group for Ar e1 is preferably an aromatic hydrocarbon group.
• Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
• the substituents that the aromatic group as Ar e1 may have include the organic groups as R e1 , R e2 , R e3 , R e4 , R e5 and R e6 as phenyl group, naphthyl group and heterocyclyl group. In some cases, it is the same as the substituents these groups may have.
• amine compound represented by formula (e1) include triphenylamine, N,N-diphenylbenzylamine, N-phenyldibenzylamine, tribendialumine, N,N-dimethylphenylamine, N -methyldiphenylamine, N,N-dimethylbenzylamine, N-methyldibenzylamine, N-methyl-N-benzylphenylamine, N,N-diethylphenylamine, N-ethyldiphenylamine, N,N-diethylbenzylamine, N-ethyldibenzylamine, and N-ethyl-N-benzylphenylamine.
• imine compounds represented by formula (e2) include N-benzylphenylmethanimine, N-benzyldiphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropane-2-imine. is mentioned.
• the content of the nitrogen-containing compound (E) in the composition is not particularly limited as long as the desired effects are not impaired.
• the content of the nitrogen-containing compound (E) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, relative to the mass of the photopolymerizable compound (A). .
• the composition may contain a compound represented by the following formula (F1) as the triazine compound (F).
• R F1 , R F2 and R F3 are each independently a monocyclic aromatic group optionally having a substituent or a condensed aromatic group optionally having a substituent is. However, R F1 , R F2 and R F3 do not contain radically polymerizable group-containing groups. When a monocyclic aromatic group or a condensed aromatic group has substituents, the substituents do not contain an aromatic ring.
• the three —NH— groups attached to the triazine ring are attached to the aromatic rings in R F1 , R F2 and R F3 respectively.
• the monocyclic aromatic groups as R F1 , R F2 and R F3 may be aromatic hydrocarbon groups or aromatic heterocyclic groups.
• Monocyclic aromatic groups include phenyl, pyridinyl, pyridinyl, pyrazinyl, pyridazinyl, furanyl, thienyl, oxazolyl, and thiazolyl groups.
• substituents that the monocyclic aromatic group may have include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
• the monovalent organic group does not contain an aromatic ring.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Monovalent organic groups include alkyl groups, alkoxy groups, alkoxyalkyl groups, aliphatic acyl groups, aliphatic acyloxy groups, alkoxycarbonyl groups, alkylthio groups, and aliphatic acylthio groups.
• the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
• the number of carbon atoms in the monovalent organic group as a substituent is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
• the lower limit of the number of carbon atoms is 2.
• alkyl groups as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl, n-heptyl, and n-octyl groups.
• alkoxy groups as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n- Pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy groups are included.
• alkoxyalkyl groups as substituents include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, 4-n-butyloxy-n-butyloxy groups.
• aliphatic acyl groups as substituents include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, and octanoyl group.
• aliphatic acyloxy groups as substituents include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy groups.
• alkoxycarbonyl groups as substituents include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl and sec-butyloxy. carbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl groups.
• alkylthio groups as substituents include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio and n-pentylthio. , n-hexylthio, n-heptylthio, and n-octylthio groups.
• aliphatic acylthio groups as substituents include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
• the number of substituents is not particularly limited as long as the desired effect is not impaired.
• the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
• the multiple substituents may be different from each other.
• Examples of the monocyclic aromatic group which may have a substituent explained above include a phenyl group, a 4-cyanophenyl group, a 3-cyanophenyl group, a 2-cyanophenyl group, a 2,3-dicyanophenyl group, 2,4-dicyanophenyl group, 2,5-dicyanophenyl group, 2,6-dicyanophenyl group, 3,4-dicyanophenyl group, 3,5-dicyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-iodophenyl group, 3-iodo phenyl, 2-iodophenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphen
• phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group and 2-nitrophenyl group are preferred, and phenyl and 4-cyanophenyl groups are more preferred.
• the condensed aromatic groups as R F1 , R F2 and R F3 are groups obtained by removing one hydrogen atom from a condensed polycyclic ring in which two or more aromatic single rings are condensed.
• the number of aromatic monocyclic rings that constitute the condensed aromatic group is not particularly limited.
• the number of aromatic monocyclic rings constituting the condensed aromatic group is preferably 2 or 3, more preferably 2. That is, the condensed aromatic group is preferably a bicyclic condensed aromatic group or a tricyclic condensed aromatic group, more preferably a bicyclic condensed aromatic group.
• the condensed aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
• Bicyclic fused aromatic groups include, for example, naphthalene-1-yl group, naphthalene-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5 -yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, isoquinolin-1-yl, isoquinolin-3-yl group, isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group and isoquinolin-8-yl group, benzoxazol-2-yl group, benzoxazol-4-yl group, benzoxazol-5-yl group, benzoxazole -6-yl group, benzoxazol-7-yl group, benzothiazol-2-yl group, benzothiazol-4-yl group,
• tricyclic condensed aromatic groups examples include anthracen-1-yl group, anthracen-2-yl group, anthracen-9-yl group, phenanthrene-1-yl group, phenanthrene-2-yl group, phenanthrene-3 -yl group, phenanthren-4-yl group, phenanthren-9-yl group, acridin-1-yl group, acridin-2-yl group, acridin-3-yl group, acridin-4-yl group, and acridin-9 -yl group.
• the substituents that the polycyclic condensed aromatic group such as the bicyclic condensed aromatic group and the tricyclic condensed aromatic group may have are the substituents that the monocyclic aromatic group may have. It is the same.
• naphthalene-1-yl group naphthalene-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinoline -4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, benzothiazol-2-yl group, 2-mercaptobenzothiazol-6- An yl group is preferred.
• a naphthalene-1-yl group a quinolin-3-yl group, a quinolin-4-yl group, and a 2-mercaptobenzothiazol-6-yl group are preferred, and a naphthalen-1-yl group is more preferred.
• R F1 , R F2 , R F1 , R F2 , R F1 , R F2 , and R F3 are optionally substituted naphthyl groups, and one or two of R F1 , R F2 and R F3 are 4-cyanophenyl groups, or Compounds which are benzothiazolyl groups are preferred.
• a naphthalene-1-yl group is preferable as the naphthyl group which may have a substituent.
• Suitable specific examples of the compound represented by formula (F1) include the compound represented by the following formula.
• the method for producing the compound represented by formula (F1) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R F1 —NH 2 , R F2 —NH 2 and R F3 —NH 2 . These plural kinds of amines may be reacted with cyanuric halide simultaneously or sequentially with cyanuric halide, and it is preferable to react with cyanuric halide sequentially.
• the compound represented by formula (F1) is usually synthesized in an organic solvent.
• an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, and the like.
• an organic solvent or the like exemplified as a specific example of the solvent (S) described later can be used.
• cyanuric halide and aromatic amines such as aromatic amines represented by R F1 —NH 2 , R F2 —NH 2 and R F3 —NH 2
• the reaction temperature is preferably from 0°C to 150°C.
• the content of the triazine compound (F) in the composition is not particularly limited as long as the desired effects are not inhibited.
• the content of the triazine compound (F) in the composition is, for example, 0.1 parts by mass or more and 30 parts by mass or less when the mass of the composition excluding the mass of the solvent (S) described later is 100 parts by mass. It is preferably 0.3 parts by mass or more and 20 parts by mass or less, and even more preferably 0.5 parts by mass or more and 15 parts by mass or less.
• the composition may contain a solvent (S) for the purpose of adjusting applicability.
• the type of solvent (S) is not particularly limited as long as the desired effects are not inhibited.
• Suitable examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol.
• the solvent (S) preferably contains a solvent having a boiling point of 140° C. or higher under atmospheric pressure, and a high solvent having a boiling point of 170° C. or higher under atmospheric pressure, from the viewpoint of good application by an inkjet printing method. More preferably, it contains a boiling point solvent (S1).
• solvents having a boiling point of 140° C. or higher under atmospheric pressure include ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether (HO—CH 2 CH 2 CH 2 —O—CH 3 ), propylene glycol monoethyl ether (HO —CH 2 CH 2 CH 2 —O—CH 2 CH 3 ), propylene glycol mono-n-propyl ether (HO—CH 2 CH 2 CH 2 —O—CH 2 CH 2 CH 3 ), propylene glycol mono-n-propyl ether (HO—CH 2 CH 2 CH 2 —O—CH 2 CH 2 CH 3 ), propylene glycol mono-n-prop
• the high boiling solvent (S1) include ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol mono-n-butyl ether (HO--CH 2 CH 2 CH 2 --O--CH 2 CH 2 CH 2 CH 3 ), propylene glycol mono-n-butyl ether (HO--C(CH 3 )HCH 2 —O—CH 2 CH 2 CH 2 CH 3 or H 3 CH 2 CH 2 CH 2 C—O—C(CH 3 )HCH 2 —OH), dipropylene glycol monoethyl ether (HO—(CH 2CH 2 CH 2 —O) 2 —CH 3 ), dipropylene glycol monomethyl ether (HO—(CH 2CH 2 CH 2 —O) 2
• the mass ratio of the solvent having a boiling point of 140° C. or higher or the high boiling point solvent (S1) having a boiling point of 170° C. or higher is preferably 20% by mass or more, and 30 It is more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
• the content of the solvent (S) is preferably an amount such that the concentration of components other than the solvent (S) in the composition is 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 50% by mass or less. , more preferably 10% by mass or more and 30% by mass or less.
• the composition may contain various additives as components other than the above components.
• Additives include sensitizers, curing accelerators, fillers, dispersants, adhesion promoters such as silane coupling agents, antioxidants, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, etc. are mentioned.
• the amount of these additives to be used is appropriately determined in consideration of the amount of these additives normally used in the composition.
• the photosensitive composition contains a photopolymerizable compound (A), inorganic fine particles (B), and an initiator (C).
• the initiator (C) is a component that cures the photopolymerizable compound. Preferred aspects and usage amounts of the photopolymerizable compound (A) and the inorganic fine particles (B) are as described above for the above composition.
• the photosensitive composition is further selected from the group consisting of a plasticizer (D), a nitrogen-containing compound (E), a triazine compound (F), a solvent (S), and other ingredients, each previously described for the composition above. It may contain one or more ingredients. Preferred aspects and usage amounts of these components are respectively as described above for the composition.
• the photosensitive composition contains an initiator (C). Since the photopolymerizable compound (A) has a radically polymerizable group, a radical polymerization initiator is used as the initiator (C). As the initiator (C), a photoinitiator can be used as the initiator (C) because it can perform site-selective curing of the photosensitive composition and there is no concern about deterioration, volatilization, sublimation, etc. of the components of the photosensitive composition due to heat. is used.
• the initiator (C) is not particularly limited, and conventionally known various polymerization initiators can be used.
• Photoradical polymerization initiators useful as radical polymerization initiators include, specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-( 2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4 -dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1 -[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1 -[6-(2-methylbenzoyl)-9-ethyl-9H
• oxime ester compounds are preferred from the viewpoint of the sensitivity of the photosensitive composition.
• a compound having a partial structure represented by the following formula (c1) is preferable.
• n1 is 0 or 1.
• R c2 is a monovalent organic group.
• R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group. * is a bond.
• the compound having the partial structure represented by formula (c1) preferably has a carbazole skeleton, fluorene skeleton, diphenyl ether skeleton, or phenyl sulfide skeleton.
• the compound having the partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).
• Compounds having a partial structure represented by formula (c1) include compounds represented by the following formula (c2).
• R c1 is a group represented by the following formula (c3), (c4), or (c5).
• n1 is 0 or 1;
• R c2 is a monovalent organic group.
• R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
• R c4 is a monovalent organic group.
• R c5 is a monovalent organic group, a halogen atom, or a nitro group.
• n2 is an integer of 0 or more and 3 or less. When n2 is 2 or 3, multiple R c5 may be the same or different, and multiple R c5 may combine with each other to form a ring. * is a bond.
• R c6 and R c7 are each independently a chain alkyl group optionally having a substituent, a chain alkoxy group optionally having a substituent, a chain optionally having a substituent A good cyclic organic group or a hydrogen atom.
• R c6 and R c7 may combine with each other to form a ring.
• R c7 and the benzene ring in the fluorene skeleton may combine with each other to form a ring.
• R c8 is a nitro group or a monovalent organic group.
• n3 is an integer of 0 or more and 4 or less. * is a bond.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
• A is S or O; n4 is an integer of 0 or more and 4 or less. * is a bond.
• R c4 is a monovalent organic group.
• R c4 can be selected from various organic groups as long as the objects of the present invention are not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms.
• a group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• R c4 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and a carbon atom
• a saturated aliphatic acyl group optionally having 2 to 20 substituents, an alkoxycarbonyl group having 2 to 20 carbon atoms and optionally having a substituent, a phenyl group optionally having a substituent , an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, having a substituent optionally substituted naphthyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, substituted a heterocyclyl group optionally having a group, a heterocyclylcarbonyl group optionally having a substituent, and the like.
• an alkyl group having 1 to 20 carbon atoms is preferable.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group as R c4 is preferably 2 or more, more preferably 5 or more, and 7 because the compound represented by formula (c3) has good solubility in the photosensitive composition. The above are particularly preferred. Further, from the viewpoint of good compatibility between the compound represented by formula (c3) and other components in the photosensitive composition, the number of carbon atoms in the alkyl group as R c4 is 15 or less. is preferred, and 10 or less is more preferred.
• R c4 has a substituent
• substituents include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms.
• the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
• the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. is a heterocyclyl group.
• the heterocyclyl group is a condensed ring, it has up to 3 rings.
• Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
• R c4 is a heterocyclyl group
• substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
• R c4 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups. Further, n-octyl group and 2-ethylhexyl group are preferred, and 2-ethylhexyl group is more preferred, from the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive composition.
• R c5 is a monovalent organic group, a halogen atom, or a nitro group.
• the monovalent organic group for R c5 can be selected from various organic groups as long as the object of the present invention is not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms.
• a group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Examples of monovalent organic groups suitable as R c5 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents.
• R c5 is an alkyl group
• the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• R c5 is an alkyl group, it may be linear or branched. Specific examples of R c5 being an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl groups.
• R c5 is an alkyl group
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• R c5 is an alkoxy group
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
• R c5 is an alkoxy group, it may be linear or branched.
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 being an alkoxy group
• R c5 isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group.
• R c5 is an alkoxy group
• the alkoxy group may contain an ether bond (--O--) in the carbon chain.
• alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
• R c5 is a cycloalkyl group or a cycloalkoxy group
• the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
• Specific examples of R c5 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 being a cycloalkoxy group
• R c5 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group
• the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less.
• R c5 is a saturated aliphatic acyl group
• R c5 is a saturated aliphatic acyl group
• examples of when R c5 is a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n -hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Noyl group, n-hexadecanoyl group and the like.
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 being a saturated aliphatic acyloxy group
• R c5 is an alkoxycarbonyl group
• the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less.
• Specific examples of R c5 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyl oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbony
• R c5 is a phenylalkyl group
• the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
• R c5 is a naphthylalkyl group
• the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
• Specific examples of R c5 being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group.
• R c5 when R c5 is a naphthylalkyl group include an ⁇ -naphthylmethyl group, a ⁇ -naphthylmethyl group, a 2-( ⁇ -naphthyl)ethyl group, and a 2-( ⁇ -naphthyl)ethyl group.
• R c5 when R c5 is a phenylalkyl group or a naphthylalkyl group, R c5 may further have a substituent on the phenyl group or naphthyl group.
• R c5 is a heterocyclyl group
• the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
• R c5 is a heterocyclylcarbonyl group
• the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c5 is a heterocyclyl group.
• R c5 is an amino group substituted with 1 or 2 organic groups
• preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms
• amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino
• the substituent includes a group represented by HX 2 C-- or H 2 XC-- (eg, HX 2 C— or H 2 XC—, a halogenated alkoxy group containing a group represented by HX 2 C— or H 2 XC—, a halogenated alkyl group containing a group represented by HX 2 C— or H 2 XC—), Alkyl group, alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated fat having 2 to 7 carbon atoms group acyloxy group, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, pipe
• the number of substituents is not limited as long as the object of the present invention is not impaired, and is preferably 1 to 4.
• the phenyl group, naphthyl group and heterocyclyl group contained in R c5 have multiple substituents, the multiple substituents may be the same or different.
• Substituents contained in R c5 when the benzoyl group further has a substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group. (thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group and phenyl group.
• the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, etc., and is preferably a fluorine atom.
• the substituent containing a group represented by HX 2 C-- or H 2 XC-- includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, HX 2 C-- or H 2 XC- A group having a halogenated alkoxy group including a group represented by -, a halogenated alkyl group including a group represented by HX 2 C- or H 2 XC-, represented by HX 2 C- or H 2 XC- and a group having a halogenated alkyl group containing a group, such as a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, or represented by HX 2 C-- or H 2 XC-- More preferably, it is a group having a halogenated alkoxy group containing group.
• the group having a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--.
• aromatic groups eg, phenyl group, naphthyl group, etc.
• cycloalkyl groups substituted with halogenated alkyl groups including groups represented by HX 2 C-- or H 2 XC-- eg, cyclopentyl group, cyclohexyl groups, etc.
• the group having a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--.
• aromatic groups e.g., phenyl group, naphthyl group, etc.
• alkyl groups substituted with halogenated alkoxy groups including groups represented by HX 2 C- or H 2 XC- e.g., methyl group, ethyl group , n-propyl group, i-propyl group, etc.
• a cycloalkyl group substituted with a halogenated alkoxy group including a group represented by HX 2 C- or H 2 XC- e.g., cyclopentyl group, cyclohexyl group, etc.
• Rc5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R c5 may have.
• R c5 is an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an aromatic ring which may have a substituent.
• Good phenylthioalkyl groups are preferred.
• the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, most preferably a methyl group. preferable.
• the optionally substituted phenyl groups a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred.
• the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6.
• the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• a cyclopentylethyl group is preferred.
• the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
• a 2-(4-chlorophenylthio)ethyl group is preferred.
• examples of the formed ring include a hydrocarbon ring and a heterocyclic ring. be done. Heteroatoms contained in heterocycles include, for example, N, O and S. Aromatic rings are particularly preferred as the ring formed by combining a plurality of R c5 s. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferred. Specific examples of the case where a plurality of R c5 in formula (c3) are bonded to each other to form a benzene ring are shown below.
• R c8 is a nitro group or a monovalent organic group.
• R c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by —(CO) n1 — on the condensed ring in formula (c4).
• the bonding position of R c8 is not particularly limited.
• the group represented by formula (c4) has one or more R c8 , one of the one or more R c8 is fluorene, because the compound represented by formula (c4) is easily synthesized. Attachment to the 7-position of the backbone is preferred.
• the group represented by formula (c4) when the group represented by formula (c4) has 1 or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are multiple R c8s , the multiple R c8s may be the same or different.
• R c6 , R c7 , R c8 and n3 are the same as R c6 , R c7 , R c8 and n3 in formula (c4).
• R c8 is not particularly limited as long as the object of the present invention is not impaired.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the monovalent organic group for R c8 include the same preferred examples of the monovalent organic group as R c5 in formula (c3).
• R c6 and R c7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic It is an organic group or a hydrogen atom. R c6 and R c7 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as R c6 and R c7 . When R c6 and R c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
• R c6 and R c7 are unsubstituted chain alkyl groups
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less.
• Specific examples of R c6 and R c7 being chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
• n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group.
• R c6 and R c7 are alkyl groups
• the alkyl group may contain an ether bond (--O--) in the carbon chain.
• alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
• R c6 and R c7 are chain alkyl groups having a substituent
• the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
• the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group.
• a chain alkyl group having a substituent is preferably linear.
• the substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups.
• Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred.
• Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclyl groups. Specific examples of the cycloalkyl group are the same as the preferred examples when R c8 is a cycloalkyl group.
• aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
• heterocyclyl group are the same as the preferred examples when R c8 is a heterocyclyl group.
• R c8 is an alkoxycarbonyl group
• the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• the number of substituents is not particularly limited.
• the preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group.
• the number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
• R c6 and R c7 are chain alkoxy groups having no substituents
• the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable.
• R c6 and R c7 being chain alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert -butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
• R c6 and R c7 are alkoxy groups
• the alkoxy groups may contain an ether bond (--O--) in the carbon chain.
• alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
• R c6 and R c7 are chain alkoxy groups having substituents
• the substituents that the alkoxy groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
• R c6 and R c7 are cyclic organic groups
• the cyclic organic group may be an alicyclic group or an aromatic group.
• Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups.
• R c6 and R c7 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
• the aromatic hydrocarbon group is either a phenyl group or a group formed by combining a plurality of benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings.
• the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings
• the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable.
• Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
• R c6 and R c7 are aliphatic cyclic hydrocarbon groups
• the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic.
• the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less.
• Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like can be mentioned.
• R c6 and R c7 are heterocyclyl groups
• the same heterocyclyl groups as R c5 in formula (c3) can be mentioned.
• R c6 and R c7 may combine with each other to form a ring.
• a group consisting of a ring formed by R c6 and R c7 is preferably a cycloalkylidene group.
• the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.
• the ring may be either an aromatic ring or an aliphatic ring.
• the cycloalkylidene group may be fused with one or more other rings.
• rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine.
• R c6 and R c7 examples include groups represented by the formula -A 1 -A 2 .
• a 1 is a linear alkylene group
• a 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
• the number of carbon atoms in the linear alkylene group for A 1 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• A2 is an alkoxy group
• the alkoxy group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
• A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
• the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
• the halogenated alkyl group may be linear or branched, preferably linear.
• A2 is a cyclic organic group
• examples of the cyclic organic group are the same as the cyclic organic groups that Rc6 and Rc7 have as substituents.
• A2 is an alkoxycarbonyl group
• examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that Rc6 and Rc7 have as substituents.
• R c6 and R c7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl
• Alkyl group 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl
• R c6 and R c7 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.
• A is S because it is easy to obtain a photopolymerization initiator with excellent sensitivity.
• R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
• R c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups within the range that does not impede the object of the present invention.
• the organic group a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the organic group represented by Rc9 in formula (c5) include the same monovalent organic groups as Rc5 in formula (c3).
• R c9 substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; benzoyl group; nitro group; optionally substituted benzofuranylcarbonyl group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group a 4-(phenyl)phenylcarbonyl group is more preferred.
• n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.
• the position to which R c9 is bonded is preferably para to the bond to which the phenyl group to which R c9 is bonded is bonded to an oxygen atom or a sulfur atom.
• the monovalent organic group as Rc2 is not particularly limited as long as it does not impair the object of the present invention.
• a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. A group consisting of is more preferred.
• the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
• Preferred examples of the monovalent organic group as Rc2 include the same monovalent organic groups as Rc5 in formula (c3).
• Rc2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
• the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are those in which the phenyl group, the naphthyl group and the heterocyclyl group contained in R c5 in the formula (c3) further have a substituent. It is the same as the base.
• R c2 is a substituent containing the group represented by HX 2 C— or H 2 XC—, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or A cycloalkylalkyl group and a phenylthioalkyl group optionally having a substituent on the aromatic ring are preferred.
• Alkyl group optionally substituted phenyl group, number of carbon atoms in cycloalkyl group contained in cycloalkylalkyl group, number of carbon atoms in alkylene group contained in cycloalkylalkyl group, cycloalkylalkyl group, aromatic Regarding the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group optionally having substituents on the ring, or the phenylthioalkyl group optionally having substituents on the aromatic ring, the formula (c3 ) is the same as R c5 .
• A3 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group.
• A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
• the alkylene group may be linear or branched, preferably linear.
• the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
• Preferred examples of A 4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• Preferred specific examples of A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl.
• Preferable specific examples of the group represented by -A 3 -CO-OA 4 include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n -butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-
• R c2 a group represented by the following formula (c7) or (c8) is also preferable.
• R c10 and R c11 are each independently a monovalent organic group.
• n5 is an integer of 0 or more and 4 or less. When R c10 and R c11 are present at adjacent positions on the benzene ring, R c10 and R c11 may combine with each other to form a ring.
• R c12 is a monovalent organic group.
• n6 is an integer of 1 or less and 8 or less.
• n7 is an integer of 1 or more and 5 or less.
• n8 is an integer from 0 to (n7+3).
• R c10 and R c11 in formula (c7) are the same as R c8 in formula (c4).
• R c10 includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--, an alkyl group, or A phenyl group is preferred.
• the ring may be either an aromatic ring or an aliphatic ring.
• n5 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.
• R c12 is an organic group.
• the organic group include the same organic groups as those described for R c8 in formula (c4).
• alkyl groups are preferred.
• Alkyl groups may be straight or branched.
• the number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.
• R c12 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.
• n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
• n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0.
• n6 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.
• R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
• a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when R c3 is an aliphatic hydrocarbon group.
• R c3 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, Cyclohexylmethyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like are preferably exemplified. Among these, a methyl group or a phenyl group is more preferable.
• Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R c1 include the following compounds.
• a phosphine oxide compound is also preferable from the viewpoint of good deep-part curability of the photosensitive composition.
• a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.
• R c21 and R c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic group having 7 to 20 carbon atoms. group acyl groups. However, both R c21 and R c22 are not aliphatic acyl groups or aromatic acyl groups.
• the number of carbon atoms in the alkyl groups of R c21 and R c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less.
• the alkyl groups as R c21 and R c22 may be linear or branched.
• alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert- pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and An n-dodecyl group can be mentioned.
• the number of carbon atoms in the cycloalkyl groups for R c21 and R c22 is preferably 5 or more and 12 or less.
• Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.
• the number of carbon atoms in the aryl groups of R c21 and R c22 is preferably 6 or more and 12 or less.
• the aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.
• the number of carbon atoms in the aliphatic acyl groups for R c21 and R c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less.
• Aliphatic acyl groups may be straight or branched. Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, and tetradecanoyl groups. , pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl groups.
• the number of carbon atoms in the aromatic acyl groups for R c21 and R c22 is 7 or more and 20 or less.
• the aromatic acyl group may have a substituent.
• substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and the like.
• Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6- Trimethylbenzoyl, ⁇ -naphthoyl, and ⁇ -naphthoyl groups are included.
• the phosphine oxide compound containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, fin oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like.
• the phosphine oxide compound containing the structural moiety represented by formula (c9) is an ⁇ -hydroxyalkylphenone-based compound such as 2-hydroxy-2-methylpropiophenone.
• the mass ratio of the phosphine oxide compound containing the structural moiety represented by formula (c9) to the total is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and 40% by mass. % or more and 60 mass % or less is more preferable.
• the content of the initiator (C) in the photosensitive composition is not particularly limited.
• the content of the initiator (C) is appropriately determined depending on the type of the radically polymerizable group and the type of the initiator (C).
• the content of the initiator (C) in the photosensitive composition is 0.01 parts by mass or more and 20 parts by mass when the mass of the photosensitive composition excluding the mass of the solvent (S) described later is 100 parts by mass. The following is preferable, 0.1 to 15 parts by mass is more preferable, and 1 to 10 parts by mass is even more preferable.
• the photopolymerizable compound (A), the inorganic fine particles (B), the initiator (C), and optional components blended as necessary are uniformly mixed and dispersed in desired amounts, respectively, for photosensitizing.
• a sexual composition is obtained.
• a cured product After molding the photosensitive composition described above into a desired shape, a cured product can be produced by exposing the photosensitive composition according to the type of the initiator (C).
• the method for molding the photosensitive composition is not particularly limited, and is appropriately selected according to the shape of the cured product.
• Examples of the molding method include coating and casting into a mold.
• a method for producing a cured film will be described as a representative example of the method for producing a cured product.
• the photosensitive composition is applied onto a desired substrate to form a coating film, and then, if necessary, at least part of the solvent (S) is removed from the coating film to form a coating film.
• the method of applying the photosensitive composition onto the substrate is not particularly limited.
• the curable composition is applied to the substrate using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater.
• a coating film can be formed by coating on the substrate so as to have a desired film thickness.
• a printing method such as a screen printing method or an inkjet printing method can be applied.
• the photosensitive composition described above dries rapidly and is less likely to thicken or solidify in an inkjet head. Therefore, by using the above-described photosensitive composition, it is possible to satisfactorily perform coating by an inkjet printing method.
• the coating film After coating the photosensitive composition on the substrate, it is preferable to bake the coating film as necessary to remove at least part of the solvent (S) from the coating film.
• the baking temperature is appropriately determined in consideration of the boiling point of the solvent (S) and the like. Baking may be performed at low temperature under reduced pressure conditions.
• the baking method is not particularly limited, and includes, for example, a method of drying using a hot plate at a temperature of 80°C to 150°C, preferably 85°C to 120°C for 60 seconds to 500 seconds.
• the thickness of the coating film formed as described above is not particularly limited.
• the film thickness of the coating film is appropriately determined according to the intended use of the cured film.
• the thickness of the coating film is typically adjusted as appropriate so that a cured film having a thickness of preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.2 ⁇ m to 5 ⁇ m is formed.
• a cured film can be obtained by exposing the coating film after forming the coating film by the above method.
• the conditions for exposing the coating film are not particularly limited as long as the curing progresses satisfactorily. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light.
• the energy dose to be irradiated is not particularly limited, but is, for example, 30 mJ/cm 2 or more and 5000 mJ/cm 2 or less.
• the exposed coating film may be baked by the same method as heating after coating.
• compound IM1 (5.0 g, 0.014 mol), acryloyl chloride (1.89 g, 0.021 mol), and 4-N,N-dimethylaminopyridine (DMAP, 0.021 mol) were added to a reactor with a capacity of 100 mL. 07 g) and 35 mL of tetrahydrofuran were mixed. The resulting solution was cooled with an ice bath. To the cooled solution, triethylamine (2.64 g, 0.026 mol) was added dropwise while maintaining the internal temperature below 10°C. After the solution was stirred at room temperature for 2 hours, water was added to the solution.
• DMAP 4-N,N-dimethylaminopyridine
• Example 2 Compounds IM2 and 2 below were obtained in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 2-(2-hydroxyphenyl)benzoxazole. The yield of compound 2 below was 4.8 g (83% yield). The measurement results of 1 H-NMR of compound 2 are as follows.
• Example 3 The compound IM3 below and the compound 3 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 2-(2-hydroxyphenyl)-1H-benzimidazozole. Obtained. The yield of compound 3 below was 4.4 g (yield 76%).
• the measurement results of 1 H-NMR of compound 2 are as follows.
• Example 4 Compound IM4 below and Compound 4 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 2-hydroxy-3-(benzothiazol-2-yl)naphthalene. got The yield of compound 4 below was 4.7 g (yield 83%).
• the measurement results of 1 H-NMR of compound 4 are as follows.
• Example 5 The compound IM5 below and the compound 5 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 3,4-bis(benzothiazol-2-yl)phenol. Obtained. The yield of compound 5 below was 4.5 g (81% yield). The measurement results of 1 H-NMR of compound 5 are as follows.
• Example 6 Compound IM6 below and Compound 6 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 2,4-bis(benzothiazol-2-yl)phenol. Obtained. The yield of compound 6 below was 4.4 g (yield 79%). The measurement results of 1 H-NMR of compound 6 are as follows.
• Example 7 Compound IM7 below and Compound 7 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 6-(benzothiazol-2-yl)-2-hydroxynaphthalene. got The yield of compound 7 below was 4.6 g (yield 81%).
• the measurement results of 1 H-NMR of compound 7 are as follows.
• Example 8 Compound IM8 below and Compound 8 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 2-(benzothiazol-2-yl)-1-hydroxynaphthalene. got The yield of compound 8 below was 4.6 g (yield 81%).
• the measurement results of 1 H-NMR of compound 8 are as follows.
• Example 9 Compound IM9 below and Compound 9 below were prepared in the same manner as in Example 1, except that 2-(2-hydroxyphenyl)benzothiazole was changed to 1-hydroxy-2-(benzothiazol-2-yl)naphthalene. got The yield of compound 9 below was 4.4 g (yield 78%).
• the measurement results of 1 H-NMR of compound 9 are as follows.
• Examples 10 to 15, Comparative Example 1, and Comparative Example 2 Using compound 1, compound 2, and compound 3 obtained in Examples 1 to 3 above and 2-(2-acryloyloxyethyl)oxybiphenyl as a comparative compound, a photosensitive composition was heated to simulate conducted a test. Incidentally, the inorganic fine particles (B) and the initiator (C) do not affect the weight reduction by heating at 110°C. Specifically, 150 mg of the photopolymerizable compound (A) of the type shown in Table 1 is dissolved in the solvent (S) of the type shown in Table 1 so that the solid content concentration is 10% by mass, and A solution containing the polymerizable compound (A) was obtained. As the solvent (S), the following S-1 and S-2 were used. S-1: propylene glycol monomethyl ether acetate S-2: HO-(CH 2 CH 2 CH 2 -O) 2 -CH 3 (dipropylene glycol monomethyl ether)
• the resulting solution was dropped onto a weighed glass substrate, heated at 110°C for 10 minutes, and the glass substrate was weighed again.
• the mass of the photopolymerizable compound (A) reduced by heating was calculated from the weight of the glass substrate before and after heating. From the mass of the photopolymerizable compound (A) decreased by heating, the rate of decrease in mass of the photopolymerizable compound (A) due to heating was calculated.
• the reduction rate values are given in Table 1.
• the composition containing the photopolymerizable compound (A) having the structure included in the above formula (A1) had the above formula ( It can be seen that the weight of the components other than the solvent (S) due to heating is remarkably suppressed as compared with the composition containing the photopolymerizable compound having a structure that does not correspond to the structure of A1).
• Examples 16 to 39 and Comparative Examples 3 to 10 5 parts by mass of the photopolymerizable compound (A) of the type shown in Table 2, 20 parts by mass of inorganic fine particles (B) made of the material shown in Table 2, and bis(2,4,4,4) as the initiator (C) 0.5 parts by mass of 6-trimethylbenzoyl)-phenylphosphine oxide was dissolved and dispersed in the type of solvent (S) shown in Table 2 so that the solid content concentration was 10% by mass. Photosensitive compositions of Examples 35-132 and Comparative Examples 3-10 were obtained.
• the average particle size of the gold microparticles, platinum microparticles, zirconium oxide microparticles, and titanium oxide microparticles used as the inorganic microparticles (B) was all 10 nm.
• As the zirconium oxide fine particles and the titanium oxide fine particles surface-treated zirconium oxide fine particles and surface-treated titanium oxide fine particles were used.
• the resulting photosensitive composition was allowed to stand in a constant temperature device at a temperature of 40° C. for 3 months, and the dispersion state of the inorganic fine particles in the photosensitive composition was visually observed after 1 month and 3 months. , and the dispersion stability of the inorganic fine particles (B) in the photosensitive composition was evaluated according to the following criteria.
• the inorganic fine particles (B) is stably dispersed over a long period of 3 months at 40° C., whereas a photosensitive composition containing a photopolymerizable compound having a structure that does not correspond to the structure of formula (A1) described above can be dispersed at 40° C. for 3 months. It can be seen that the inorganic fine particles (B) separate or sediment during storage.
• Examples 40 to 42 and Comparative Example 11 2.3 parts by mass of the photopolymerizable compound (A) of the type shown in Table 3, 7.5 parts by mass of titanium oxide fine particles as the inorganic fine particles (B), and bis(2,4,4,4) as the initiator (C). 0.2 parts by mass of 6-trimethylbenzoyl)-phenylphosphine oxide, the photopolymerizable compound (A), the inorganic fine particles (B), and the initiator (C) with respect to the mass of the photosensitive composition.
• the photosensitive compositions of Examples 40 to 42 and Comparative Example 11 were obtained by dispersing and dissolving in the aforementioned solvent S-1 (propylene glycol monomethyl ether acetate) so that the total ratio was 10% by mass. rice field. Using the obtained photosensitive composition, the transmittance of the cured film, the surface appearance of the cured film, and the heat resistance of the cured film were evaluated according to the following methods. These evaluation results are shown in Table 3.
• a photosensitive composition was applied onto a glass substrate using a spin coater. Next, the film made of the photosensitive composition was heated at 110° C. for 2 minutes to obtain a coating film having a thickness such that a cured film having a thickness of 0.3 ⁇ m was formed. The coating film thus obtained was exposed to light using a high-pressure mercury lamp so that the cumulative exposure amount was 100 mJ/cm 2 . The coated film after exposure was heated at 110° C. for 2 minutes to obtain a cured film having a thickness of 0.3 ⁇ m.
• the light transmittance of the resulting cured film was measured using a multi-channel spectrometer (MCPD-3000) manufactured by Otsuka Electronics Co., Ltd., and the average transmittance of light with a wavelength of 400 to 700 nm was obtained.
• MCPD-3000 multi-channel spectrometer
• the photosensitive composition containing the photopolymerizable compound (A) having the structure contained in the above formula (A1) had light transmittance, surface appearance, and a cured product with excellent heat resistance, whereas the photosensitive composition containing a photopolymerizable compound having a structure that does not correspond to the structure of the above formula (A1) has poor surface appearance and heat resistance. I know I can give you something.

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