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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials

Definitions

• a fourth aspect of the present invention is represented by the following formula (A1): R a01 -R a02 -X a01 -Ph-CO-O-R a03 (A1)
• R a01 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group
• X a01 is O or S
• R a02 is a single bond or a divalent linking group
• R a03 is a benzyl group or a phenethyl group
• Ph is a phenylene group.
• R a03 is a benzyl group
• the group represented by —X a01 —R a02 —R a01 is a compound that is not a (meth)acryloyloxy group.
• R a01 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
• X a01 is O or S;
• R a02 is a single bond or a divalent linking group.
• R a03 is a benzyl group or a phenethyl group.
• Ph is a phenylene group.
• a 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.
• cationic polymerizable group-containing groups typically include epoxy group-containing groups, oxetanyl group-containing groups, vinyloxy group-containing groups, vinylthio group-containing groups, and the like. Among these, an epoxy group-containing group and a vinyloxy group-containing group are preferred.
• the epoxy group-containing group is preferably an alicyclic epoxy group-containing group or a glycidyl group.
• the alicyclic epoxy group is an aliphatic cyclic group in which two carbon atoms as adjacent ring-constituting atoms in the aliphatic cyclic group are bonded through an oxygen atom. That is, an alicyclic epoxy group has an epoxy group containing a three-membered ring consisting of two carbon atoms and one oxygen atom on an aliphatic ring.
• the linking group linking the acryloyloxy group or methacryloyloxy group and the aryloxy group, arylthio group, heteroaryloxy group, or heteroarylthio group is —CH 2 CH 2 —O—CH 2 CH2- , -( CH2CH2 - O ) 2 - CH2CH2- , -( CH2CH2 - O) 3 - CH2CH2- , -CH2CH2CH2 - O- CH2 CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, Compounds changed to -(CH 2 CH 2 -S) 2 -CH 2 CH 2 - or -(CH 2 CH 2 -S) 3 -CH 2 CH 2 - are also preferred as novel compounds.
• HX a01 -Ph-CO-OR a03 (A1-a) HX a02 -R a04 -Hal (A1-b) HX a02 -R a04 -X a01 -Ph-CO-OR a03 (A1-c)
• 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 temperature at which the compound represented by formula (A1-a) and the compound represented by formula (A1-b) are reacted can produce a desired amount of the compound represented by formula (A1-c). 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.
• R a01 is a glycidyl group
• the group represented by —X a02 —H in the compound represented by formula (A1-1c) is reacted with epichlorohydrin in a conventional manner to obtain —X a02 —H.
• a terminal hydrogen atom represented by can be substituted with a glycidyl group.
• reaction of the compound represented by the formula (A1-a) with the compound represented by the formula (A1-d) in the presence of a base is the reaction of the compound represented by the formula (A1- It is carried out analogously to the reaction of a compound of formula (A1-b) with a compound of formula (A1-b).
• 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.
• MA is each independently a (meth)acryloyl group
• X is each independently an oxygen atom, -NH-, or -N(CH 3 ) is -.
• 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.
• 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.
• 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 type of halogen atoms alone, or may consist of two or more types of halogen atoms.
• Another example of a suitable epoxy compound is a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group.
• alicyclic epoxy compounds include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane and bis(3,4-epoxycyclohexylmethyl)adipate , bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, ⁇ -caprolactone modification 3, 4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, ⁇ -methyl- ⁇ -valerolactone-modified 3, 4-epoxycyclohexylmethyl-3′,4′-epoxy
• Z 01 represents a single bond or a linking group (a divalent group having one or more atoms).
• R a01 to R a018 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom and an organic group.
• R a01 to R a018 are groups selected from the group consisting of hydrogen atoms, halogen atoms and organic groups.
• R a02 and R a010 may be bound together.
• R a013 and R a016 may combine with each other to form a ring.
• m a1 is 0 or 1;
• the alicyclic epoxy compound represented by the above formula (a01-2) is represented by the following formula (a01-2-1), which corresponds to a compound in which m a1 in the above formula (a01-2) is 0. are preferred.
• hydrocarbon 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 n-hexyl group.
• R a01 to R a018 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, It is more preferable that all of R a01 to R a018 are hydrogen atoms, because it is particularly easy to form a material having excellent mechanical properties using the composition.
• alicyclic epoxy compounds represented by formula (a01-2) specific examples include alicyclic epoxy compounds represented by formula (a01-2a) and formula (a01-2b) below. compound.
• alicyclic epoxy compounds represented by formula (a01-3) specific examples include S-spiro[3-oxatricyclo[3.2.1.0 2,4 ]octane-6 , 2′-oxirane] and the like.
• R a23 is a hydrogen atom or a methyl group.
• a siloxane compound is a compound having a siloxane skeleton composed of siloxane bonds (Si—O—Si) and two or more glycidyl groups or alicyclic epoxy groups in the molecule.
• 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.
• 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.
• 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)
• Suitable specific examples of the cationically polymerizable group-containing group include: -R 08 , -O- CH2CH2 - R08 , -O - CH2CH2CH2 - R08 , -O - CH2CH2CH2CH2 - R08 , -CO-O- CH2CH2 - R08 , -CO -O- CH2CH2CH2 - R08 , -CO-O - CH2CH2CH2CH2 - R08 , -NH- CH2CH2 - R08 , -NH - CH2CH2CH2 - R08 , -NH - CH2CH2CH2CH2 -R08 , -CO-NH- CH2CH2 -R08 , —CO—NH—CH 2 CH 2 CH 2 —R 08 , and A group represented by —CO—NH—CH 2 CH 2 CH 2 CH 2 —R 08 can be mentioned.
• 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).
• the -NH- groups attached to the triazine ring are attached to the aromatic rings in R A11 , R A12 and R A13 respectively.
• 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.
• 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.
• Suitable specific examples of the naphthyl group which may have a substituent include naphthalene-1-yl group and naphthalene-2-yl group.
• aromatic ring-containing group has one radically polymerizable group-containing group or one cationically polymerizable group-containing group
• suitable examples of such groups include groups of the following formulae.
• PG is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
• R A12 and R A13 are a group represented by formula (A-2e-b1) below.
• RA14 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
• R A12 and R A13 are groups represented by the formula (A-2e-b1), both R A12 and R A13 have a radically polymerizable group-containing group, or both have a cationically polymerizable group It has a containing group.
• 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.
• Suitable 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 radically polymerizable group-containing group or a cationically polymerizable group-containing group as R A14 .
• the radically polymerizable group-containing group and the cationically polymerizable group-containing group are as described above.
• Preferred specific examples of the radically polymerizable group-containing group and preferred specific examples of the cationically polymerizable group-containing group are the radically polymerizable group-containing groups described for the compound represented by formula (A-2e-a). It is the same as the preferred specific examples and preferred specific examples of the cationically polymerizable group-containing group.
• 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 a 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 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.
• 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 .
• Compounds that provide radically polymerizable group-containing groups and cationically polymerizable group-containing groups include polymerization of (meth)acrylic acid, (meth)acrylic acid halides, halogenated olefins, epichlorohydrin, glycidyl (meth)acrylate, and the like. compounds having a functional group.
• a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group and a compound having a polymerizable group
• an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, and a thioether bond are generated. reactions can be employed.
• the reaction for forming the radically polymerizable group-containing group or the cationically 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.
• 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, cationic polymerizable groups, and the like.
• an organic solvent or the like exemplified as a specific example of the solvent (S) 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.
• the composition contains inorganic fine particles (B).
• the material of the inorganic fine particles (B) is not particularly limited as long as it is an inorganic material.
• the inorganic fine particles (B) are preferably one or more selected from the group consisting of metal oxide fine particles (B1) and metal fine particles (B2).
• metal oxide fine particles (B1) it is easy to form a material with a high refractive index using the composition.
• 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.
• 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 preferable inorganic fine particles (B) include silicon fine particles (SiNC (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.
• 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).
• 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 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.
• the content of the metal oxide fine particles (B1) in the composition is 90% by mass or more is preferable, 90% by mass or more and 98% by mass or less is more preferable, and 90% 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).
• 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.
• 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 are included.
• 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 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.
• 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 c6 and R c7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl groups; 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 groups; 2-
• 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
• 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. 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).
• 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 .
• 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.
• 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).
• 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.
• 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.
• 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 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.
• Examples 1 to 22, Comparative Example 1, and Comparative Example 2 Using Compounds 1 to 11 obtained in Synthesis Examples 1 to 11 described above and 2-(2-acryloyloxyethyl)oxybiphenyl as a comparative compound, a simulated test was conducted by heating the photosensitive composition. . Incidentally, the inorganic fine particles (B) and the initiator (C) do not affect the weight reduction due to 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, A solution containing the photopolymerizable compound (A) was obtained.
• 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 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 23 to 110 and Comparative Examples 3 to 10 5 parts by mass of the photopolymerizable compound (A) of the type described in Tables 2 and 3, 20 parts by mass of inorganic fine particles (B) made of the material described in Tables 2 and 3, and an initiator (C) as 0.5 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and a solvent (S ) to obtain photosensitive compositions of Examples 13-60 and Comparative Examples 3-10.
• 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.
• 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.
• Example 111 to 121 and Comparative Example 11 2.3 parts by mass of the photopolymerizable compound (A) of the type shown in Table 4, 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 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 having a wavelength of 400 to 700 nm was obtained.
• MCPD-3000 multi-channel spectrometer

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=85804175

Family Applications (1)

Country Status (2)

Cited By (3)

Citations (2)

• 2022
  • 2022-09-13 WO PCT/JP2022/034244 patent/WO2023058418A1/ja not_active Ceased
  • 2022-09-13 JP JP2023552775A patent/JPWO2023058418A1/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events