CN106256837A - Solidification compound, the manufacture method of solidfied material and be firmly coated with material - Google Patents

Solidification compound, the manufacture method of solidfied material and be firmly coated with material Download PDF

Info

Publication number
CN106256837A
CN106256837A CN201610420826.2A CN201610420826A CN106256837A CN 106256837 A CN106256837 A CN 106256837A CN 201610420826 A CN201610420826 A CN 201610420826A CN 106256837 A CN106256837 A CN 106256837A
Authority
CN
China
Prior art keywords
group
compound
solidification compound
alkyl
ring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610420826.2A
Other languages
Chinese (zh)
Other versions
CN106256837B (en
Inventor
千坂博树
野田国宏
筱崎信也
盐田大
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Ohka Kogyo Co Ltd
Original Assignee
Tokyo Ohka Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of CN106256837A publication Critical patent/CN106256837A/en
Application granted granted Critical
Publication of CN106256837B publication Critical patent/CN106256837B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to solidification compound, the manufacture method of solidfied material and be firmly coated with material.The problem of the present invention is to provide a kind of solidification compound forming the excellent hard conating of bendability, toughness, case hardness and the transparency and the manufacture method of solidfied material employing above-mentioned solidification compound and is firmly coated with material.The solidification compound that the present invention relates to contains (A) Photoepolymerizationinitiater initiater and (B) polyfunctional acrylic ester compound, described polyfunctional acrylic ester compound comprises at least one in siloxane bond, aromatic rings and crosslinking saturated rings, and above-mentioned (A) Photoepolymerizationinitiater initiater comprises the compound that following formula (a-1) represents.In formula, R1For comprising the specific organic group of aromatic rings, R2It is the organic group of 1 valency, R3For hydrogen atom, the alkyl of the carbon number 1～11 can with substituent group, maybe can have the aryl of substituent group, m is 0 or 1.

Description

Solidification compound, the manufacture method of solidfied material and be firmly coated with material
Technical field
The present invention relates to solidification compound and employ above-mentioned solidification compound solidfied material manufacture method and Firmly it is coated with material.
Background technology
At various figures such as liquid crystal display, plasma scope, CRT monitor, EL display, field-emitter displays As in display device, such as, in order to protect surface, antireflection, anti-dazzle etc., employ blooming.Examine from the viewpoint of marresistance Consider, as such blooming, use on the surface of the base material formed by triacetyl cellulose (TAC) etc., form hard conating and The hard material that is coated with become is known (for example, with reference to patent documentation 1).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2013-195550 publication
Summary of the invention
Invent problem to be solved
Typically for the hard hard conating being coated with in material and using, it is desirable to bendability, toughness, case hardness, the transparency etc. are various Excellent.But, conventional hard conating the most fully meets above-mentioned requirements.
The present invention completes in view of above-mentioned problem, it is therefore intended that provide one can form bendability, toughness, surface hard Degree and the solidification compound of the excellent hard conating of the transparency and employ the manufacture of solidfied material of above-mentioned solidification compound Method and be firmly coated with material.
For solving the means of problem
Inventors herein have recognized that, by containing specific Photoepolymerizationinitiater initiater and specific polyfunctional acrylic ester The solidification compound of compound, it is possible to resolve above-mentioned problem, thus complete the present invention.Specifically, the present invention provides with lower section Case.
The 1st aspect of the present invention is a kind of solidification compound, and it contains (A) Photoepolymerizationinitiater initiater and (B) multifunctional third Enoic acid ester compounds, described polyfunctional acrylic ester compound comprises in siloxane bond, aromatic rings and crosslinking saturated rings At least one,
Above-mentioned (A) Photoepolymerizationinitiater initiater comprises the compound that following formula (a-1) represents.
[chemical formula 1]
(R1Group that the group that represents for following formula (a-2), following formula (a-3) represent or following formula (a-4) represent Group, R2It is the organic group of 1 valency, R3For hydrogen atom, the alkyl of the carbon number 1～11 can with substituent group, maybe can have The aryl of substituted base, m is 0 or 1.)
[chemical formula 2]
(R4For hydrogen atom, nitro or the organic group of 1 valency, R5And R6Independently be chain-like alkyl, cyclic hydrocarbon group or miscellaneous Aryl, R5With R6Can be mutually bonded and form volution.)
[chemical formula 3]
(R7Independently be the organic group of 1 valency, amino, halogen atom, nitro or cyano group, A is S or O, and n is 0～4 Integer.)
[chemical formula 4]
(R8It is the organic group of 1 valency, R9For hydrogen atom, nitro or the organic group of 1 valency.)
The 2nd aspect of the present invention is the manufacture method of solidfied material, and it includes following operation:
Above-mentioned solidification compound is used to form the operation of solidification compound film；With
The operation that above-mentioned solidification compound film is exposed.
The 3rd aspect of the present invention is for be firmly coated with material, and it has base material and uses above-mentioned solidification compound at above-mentioned base The hard conating formed on material.
The effect of invention
Consolidating of the excellent hard conating of bendability, toughness, case hardness and the transparency can be formed by means of the invention it is possible to provide The property changed compositions and employ the manufacture method of solidfied material of above-mentioned solidification compound and be firmly coated with material.
Detailed description of the invention
" solidification compound "
The solidification compound that the present invention relates to contains (A) Photoepolymerizationinitiater initiater and (B) polyfunctional acrylic ester compound, Described polyfunctional acrylic ester compound comprises at least one in siloxane bond, aromatic rings and crosslinking saturated rings, above-mentioned (A) Photoepolymerizationinitiater initiater comprises the compound that above-mentioned formula (a-1) represents.By the solidification compound that the present invention relates to obtain hard The bendability of coating, toughness, case hardness and the transparency are excellent, can be suitably used for firmly being coated with material.
<(A) Photoepolymerizationinitiater initiater>
As (A) Photoepolymerizationinitiater initiater, as long as comprising the compound that above-mentioned formula (a-1) represents, just it is not particularly limited.This The solidification compound that invention relates to is owing to comprising (A) Photoepolymerizationinitiater initiater, so sensitivity is high, even with less energy Quantity of X-rays X also can fully solidify.(A) Photoepolymerizationinitiater initiater may be used alone or in combination and uses two or more.
In above-mentioned formula (a-1), R1The group or above-mentioned that the group that represents for above-mentioned formula (a-2), above-mentioned formula (a-3) represent The group that formula (a-4) represents.
As R2The example of preferred organic group, with R described later4Equally, can enumerate alkyl, alkoxyl, cycloalkyl, Cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, can have substituent group phenyl, can There is the phenoxy group of substituent group, can have the benzoyl of substituent group, can have the phenyloxycarbonyl of substituent group, permissible Benzoyl epoxide, the phenylalkyl can with substituent group with substituent group, can have the naphthyl of substituent group, can have The naphthoxy of substituted base, can have the naphthoyl of substituent group, can have the naphthoxycarbonyl of substituent group, can have The naphthoyl epoxide of substituent group, can have the naphthylalkyl of substituent group, can have the heterocyclic radical of substituent group (heterocyclyl), can have the Heterocyclylcarbonyl of substituent group, the amino replaced by 1 or 2 organic groups, morpholine- 1-base and piperazine-1-base etc..
R2During for alkyl, the carbon number of alkyl is preferably 1～20, more preferably 1～6.It addition, R2During for alkyl, permissible For straight chain, it is also possible to for side chain.As R2For concrete example during alkyl, methyl, ethyl, n-pro-pyl, isopropyl, positive fourth can be enumerated Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different pungent Base, secondary octyl, t-octyl, n-nonyl, different nonyl, positive decyl and isodecyl etc..It addition, R2During for alkyl, alkyl can be at carbon Chain comprises ehter bond (-O-).As the example of the alkyl in carbochain with ehter bond, methoxy ethyl, ethyoxyl second can be enumerated Base, methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..
R2During for alkoxyl, the carbon number of alkoxyl is preferably 1～20, more preferably 1～6.It addition, R2For alkoxyl Time, can be straight chain, it is also possible to for side chain.As R2For concrete example during alkoxyl, can enumerate methoxyl group, ethyoxyl, positive third Base epoxide, isopropyl epoxide, normal-butyl epoxide, isobutyl group epoxide, sec-butyl epoxide, tert-butyl group epoxide, n-pentyl epoxide, isoamyl Base epoxide, sec-amyl epoxide, tertiary pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide, iso-octyl epoxide, Zhong Xin Base epoxide, t-octyl epoxide, n-nonyl epoxide, different nonyl epoxide, positive decyl epoxide and isodecyl epoxide etc..It addition, R2For alkane During epoxide, alkoxyl can comprise ehter bond (-O-) in carbochain.As the example of the alkoxyl in carbochain with ehter bond, can Enumerate methoxy ethoxy, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propyl group epoxide Ethoxy ethoxy and methoxy-propyl epoxide etc..
R2During for cycloalkyl or cycloalkyloxy, the carbon number of cycloalkyl or cycloalkyloxy is preferably 3～10, more preferably 3～6.As R2For concrete example during cycloalkyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring can be enumerated pungent Base etc..As R2For concrete example during cycloalkyloxy, cyclopropyl epoxide, cyclobutyl epoxide, cyclopentyloxy, cyclohexyl can be enumerated Epoxide, suberyl epoxide and ring octyl group epoxide etc..
R2During for representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyl The carbon number of base epoxide is preferably 2～21, more preferably 2～7.As R2For concrete example during representative examples of saturated aliphatic acyl group, can Enumerate acetyl group, propiono, positive bytyry, 2-methylpropionyl, positive valeryl, 2,2-Dimethylpropanoyl, positive caproyl, just Heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, positive ten Four alkanoyls, Pentadecane acyl group and hexadecane acyl group etc..As R2For concrete example during representative examples of saturated aliphatic acyloxy, Can enumerate acetyl group epoxide, propiono epoxide, positive bytyry epoxide, 2-methylpropionyl epoxide, positive valeryl epoxide, 2,2-bis- Methylpropionyl epoxide, positive caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group epoxide, positive capryl oxygen Base, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, positive 15 Alkanoyl epoxide and hexadecane acyloxy etc..
R2During for alkoxy carbonyl, the carbon number of alkoxy carbonyl is preferably 2～20, more preferably 2～7.As R2For Concrete example during alkoxy carbonyl, can enumerate methoxycarbonyl, ethoxy carbonyl, n-pro-pyl epoxide carbonyl, isopropyl epoxide carbonyl Base, normal-butyl epoxide carbonyl, isobutyl group epoxide carbonyl, sec-butyl epoxide carbonyl, t-butyloxycarbonyl, n-pentyl epoxide carbonyl Base, isopentyl epoxide carbonyl, sec-amyl epoxide carbonyl, t-amyloxycarbonyl group, n-hexyl epoxide carbonyl, n-heptyl epoxide carbonyl Base, n-octyl epoxide carbonyl, iso-octyl epoxide carbonyl, secondary octyl epoxide carbonyl, t-octyl epoxide carbonyl, n-nonyl epoxide carbonyl Base, different nonyl epoxide carbonyl, positive decyloxycarbonyl and isodecyl epoxide carbonyl etc..
R2During for phenylalkyl, the carbon number of phenylalkyl is preferably 7～20, more preferably 7～10.It addition, R2For naphthalene During base alkyl, the carbon number of naphthylalkyl is preferably 11～20, more preferably 11～14.As R2For tool during phenylalkyl Style, can enumerate benzyl, 2-phenylethyl, 3-phenyl propyl and 4-phenyl butyl.As R2Concrete for during naphthylalkyl Example, can enumerate Alpha-Naphthyl methyl, betanaphthyl methyl, 2-(Alpha-Naphthyl) ethyl and 2-(betanaphthyl) ethyl.R2For phenylalkyl, Or during naphthylalkyl, R2Substituent group can be had further on phenyl or naphthyl.
R2During for heterocyclic radical, heterocyclic radical is 5 yuan or the monocycle of 6 yuan comprising more than 1 N, S, O, or is described monocycle Condense each other or heterocyclic radical that described monocycle and phenyl ring condense.When heterocyclic radical is condensed ring, number of rings is less than 3.Heterocyclic radical can To be aromatic group (heteroaryl), it is also possible to be non-aromatic group.As the heterocycle of the described heterocyclic radical of composition, furan can be enumerated Mutter, thiophene, pyrroles, azoles, isoxazole, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, rattle away Piperazine, benzofuran, benzothiophene, indole, iso-indoles, indolizine (indolizine), benzimidazole, benzotriazole, benzo Azoles, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines (cinnoline) and quinoxaline etc..R2For During heterocyclic radical, heterocyclic radical can have substituent group further.
R2During for Heterocyclylcarbonyl, the heterocyclic radical comprised in Heterocyclylcarbonyl and R2Situation for heterocyclic radical is identical.
R2For replaced by 1 or 2 organic groups amino time, about the preferred example of organic group, carbon can be enumerated The alkyl of atomic number 1～20, the cycloalkyl of carbon number 3～10, the representative examples of saturated aliphatic acyl group of carbon number 2～21, can have The phenyl of substituted base, can have the benzoyl of substituent group, can have the octadecyloxy phenyl of the carbon number 7～20 of substituent group Base, can have substituent group naphthyl, can have substituent group naphthoyl, can have substituent group carbon number 11～ The naphthylalkyl of 20 and heterocyclic radical etc..The concrete example of these preferred organic groups and R2Identical.As organic by 1 or 2 The concrete example of the substituted amino of group, can enumerate methylamino, ethylamino, diethylamino, n-pro-pyl amino, diη-propyl Amino, isopropylamino, n-butylamino, di-n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, the most pungent Base amino, n-nonyl amino, positive Decylamino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive bytyry Amino, positive pentanoylamino, positive caproyl amino, positive heptanoyl group amino, positive octanoylamino, positive decanoylamino, benzoyl Base amino, α-naphthoyl amino and β-naphthoyl amino etc..
As R2In comprise, substituent group time phenyl, naphthyl and heterocyclic radical have substituent group further, carbon can be enumerated The alkyl of atomic number 1～6, the alkoxyl of carbon number 1～6, the representative examples of saturated aliphatic acyl group of carbon number 2～7, carbon number 2 ～the alkoxy carbonyl of 7, the representative examples of saturated aliphatic acyloxy of carbon number 2～7, there is single alkane of the alkyl of carbon number 1～6 Base amino, there is the dialkyl amido of alkyl of carbon number 1～6, morpholine-1-base, piperazine-1-base, halogen, nitro and cyanogen Base etc..R2In comprise, the number of this substituent group that phenyl, naphthyl and heterocyclic radical are when having substituent group further, as long as not Hinder in the range of the purpose of the present invention, be not particularly limited, preferably 1～4.R2In comprise, phenyl, naphthyl and Heterocyclic radical has multiple substituent groups during multiple substituent group, can be the same or different.
It addition, as R2, further preferably cycloalkyl-alkyl, can have on aromatic rings substituent group phenoxyalkyl, The phenylsulfartyl alkyl of substituent group can be had on aromatic rings.The replacement that phenoxyalkyl and phenylsulfartyl alkyl can have Base and R2In the substituent group that can have of the phenyl that comprises identical.
In organic group, as R2, preferably alkyl, cycloalkyl, the phenyl can with substituent group or cycloalkyl-alkyl, Aromatic rings can have the phenylsulfartyl alkyl of substituent group.As alkyl, preferably the alkyl of carbon number 1～20, more excellent Select the alkyl of carbon number 1～8, the alkyl of particularly preferred carbon number 1～4, most preferable.Can have the benzene of substituent group In base, preferably aminomethyl phenyl, more preferably 2-aminomethyl phenyl.The carbon number of the cycloalkyl comprised in cycloalkyl-alkyl is preferably 5 ～10, more preferably 5～8, particularly preferably 5 or 6.The carbon number of the alkylidene comprised in cycloalkyl-alkyl be preferably 1～ 8, more preferably 1～4, particularly preferably 2.In cycloalkyl-alkyl, preferably cyclopentyl ethyl.Aromatic rings can have replacement The carbon number of the alkylidene comprised in the phenylsulfartyl alkyl of base is preferably 1～8, more preferably 1～4, and particularly preferably 2. Aromatic rings can have in the phenylsulfartyl alkyl of substituent group, preferably 2-(4-chlorophenyl sulfanyl) ethyl.
Above, to R2It is illustrated, as R2, group that preferably following formula (R2-1) or (R2-2) represent.
[chemical formula 5]
(in formula (R2-1) and (R2-2), R10And R11Being respectively organic group, p is the integer of 0～4, R10And R11It is present in During adjacent position on phenyl ring, R10With R11Can be mutually bonded and form ring, q is the integer of 1～8, and r is the integer of 1～5, S is 0～the integer of (r+3), R12For alkyl.)
About the R in formula (R2-1)10And R11The example of organic group, with R2Identical.As R10, preferably alkyl or benzene Base.R10During for alkyl, its carbon number is preferably 1～10, more preferably 1～5, particularly preferably 1～3, and most preferably 1.That is, R10Most preferably methyl.R10With R11When being bonded and form ring, this ring can be aromatic ring, it is also possible to for aliphatic ring.As R10With R11Define the preferred example of the group that the formula (R2-1) of ring represents, can enumerate naphthalene-1-base, 1,2,3,4-naphthanes- 5-base etc..In above-mentioned formula (R2-1), p is the integer of 0～4, preferably 0 or 1, more preferably 0.
In above-mentioned formula (R2-2), R12For alkyl.The carbon number of alkyl is preferably 1～10, and more preferably 1～5 are the most excellent Elect 1～3 as.As R12, preferably enumerate methyl, ethyl, propyl group, isopropyl, butyl etc., in these, more preferably methyl.
In above-mentioned formula (R2-2), r is the integer of 1～5, the integer of preferably 1～3, more preferably 1 or 2.Above-mentioned formula (R2- 2), in, s is 0～(r+3), the integer of preferably 0～3, the integer of more preferably 0～2, particularly preferably 0.Above-mentioned formula (R2-2) In, q is the integer of 1～8, the integer of preferably 1～5, the integer of more preferably 1～3, particularly preferably 1 or 2.
In formula (a-1), R3For hydrogen atom, the alkyl of the carbon number 1～11 can with substituent group, maybe can have and take The aryl of Dai Ji.As R3For the substituent group can having during alkyl, preferably enumerate phenyl, naphthyl etc..It addition, as R3For The substituent group can having during aryl, preferably enumerates the alkyl of carbon number 1～5, alkoxyl, halogen atom etc..
In formula (a-1), as R3, preferably enumerate hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, benzene Base, benzyl, aminomethyl phenyl, naphthyl etc., in these, more preferably methyl or phenyl.
In formula (a-2), R4For hydrogen atom, nitro or the organic group of 1 valency.R4Be bonded on the fluorenes ring in formula (a-2) with Be bonded in formula (a-1)-(CO)mOn 6 yuan of aromatic rings that-6 yuan of aromatic rings of group of representing are different.As long as meeting this Part, then to R in formula (a-2)4It is not particularly limited relative to the bonding position of fluorenes ring.From being readily synthesized R1Represent for formula (a-2) From the standpoint of the compound that the formula (a-1) of group represents etc., R42 be preferably in fluorenes ring relative to the bonding position of fluorenes ring.
R4During for organic group, R4Not hindering in the range of the purpose of the present invention, there is no particular restriction, can be from various organic Group suitably selects.As R4For preferred example during organic group, with R2Equally, alkyl, alkoxyl, cycloalkanes can be enumerated Base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, can have the benzene of substituent group Base, can have the phenoxy group of substituent group, can have the benzoyl of substituent group, can have the phenoxy group carbonyl of substituent group Base, can have the benzoyl epoxide of substituent group, can have the phenylalkyl of substituent group, can have the naphthalene of substituent group Base, can have the naphthoxy of substituent group, can have the naphthoyl of substituent group, can have the naphthoxy carbonyl of substituent group Base, can have the naphthoyl epoxide of substituent group, can have the naphthylalkyl of substituent group, can have the heterocycle of substituent group Base, can have the Heterocyclylcarbonyl of substituent group, the amino replaced by 1 or 2 organic groups, morpholine-1-base and piperazine- 1-base etc..The concrete example of these groups with for R2And the concrete example that illustrated is identical.
In group described above, as R4, for nitro or R13During the group that-CO-represents, have what sensitivity improved Tendency, is preferred.R13Not hindering in the range of the purpose of the present invention, there is no particular restriction, can select from various organic groups Select.About preferably as R13The example of group, the alkyl that carbon number 1～20 can be enumerated, the phenyl can with substituent group, Can have the naphthyl of substituent group and can have the heterocyclic radical of substituent group.As R13, in these groups, particularly preferred 2- Aminomethyl phenyl, thiophene-2-base and Alpha-Naphthyl.
It addition, R4During for hydrogen atom, there is the tendency that the transparency becomes good, be preferred.It should be noted that R4For Hydrogen atom and R2During for above-mentioned (R2-2), there is the tendency that the transparency becomes better.
In formula (a-2), R5And R6It is respectively chain-like alkyl, cyclic hydrocarbon group or heteroaryl.In these groups, as R5And R6, preferably chain-like alkyl.
R5And R6During for chain-like alkyl, chain-like alkyl can be straight chained alkyl, it is also possible to for branched alkyl.R5And R6For chain During shape alkyl, the carbon number of chain-like alkyl is preferably 1～20, more preferably 1～6.As R5And R6For tool during chain-like alkyl Style, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, Sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, different nonyl, positive decyl, And isodecyl etc..It addition, R5And R6During for chain-like alkyl, chain-like alkyl can comprise ehter bond (-O-) in carbochain.As at carbon Chain has the example of the chain-like alkyl of ehter bond, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, second can be enumerated Epoxide ethoxyethyl group, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..
R5And R6During for cyclic hydrocarbon group, cyclic hydrocarbon group can be aliphatic cyclic alkyl, it is also possible to for aromatic cyclic hydrocarbon Base.
R5And R6During for aromatic cyclic alkyl, aromatic cyclic alkyl is preferably phenyl or multiple phenyl ring via carbon-to-carbon Key bonding and group that the group that formed or multiple phenyl ring condense and formed.Aromatic cyclic alkyl is phenyl or multiple phenyl ring During the group being bonded or condensing and formed, the number of rings of the phenyl ring comprised in aromatic cyclic alkyl is not particularly limited, and preferably 3 Hereinafter, more preferably less than 2, particularly preferably 1.As the preferred concrete example of aromatic cyclic alkyl, phenyl, naphthalene can be enumerated Base, xenyl, anthryl and phenanthryl etc..
R5And R6During for aliphatic cyclic alkyl, aliphatic cyclic alkyl can be monocyclic, it is also possible to for polycycle.Fat The carbon number of fat race cyclic hydrocarbon group is not particularly limited, preferably 3～20, more preferably 3～10.Ring-type as monocyclic The example of alkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, Three ring nonyls (tricyclononyl group), tricyclodecyl (tricyclodecyl group), tetracyclododecyl group (tetracyclododecyl group) and adamantyl etc..
R5And R6During for heteroaryl, heteroaryl is 5 yuan or the monocycle of 6 yuan comprising more than 1 N, S, O, or is described list The heteroaryl that ring condenses each other or described monocycle condenses with phenyl ring.When heteroaryl is condensed ring, number of rings is less than 3.As structure Become the heterocycle of described heteroaryl, can enumerate furan, thiophene, pyrroles, azoles, isoxazole, thiazole, thiadiazoles, isothiazole, imidazoles, Pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, iso-indoles, indolizine, benzimidazole, Benzotriazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines and quinoxaline etc..
R5With R6Can be mutually bonded and form volution.Comprise R5With R6The group of the volution formed is preferably cycloalkylidene (cycloalkylidene group)。R5With R6When being bonded and form cycloalkylidene, the volution constituting cycloalkylidene is preferably 5 yuan Ring～6 rings, more preferably 5 rings.
R5With R6When the group being bonded and formed is cycloalkylidene, cycloalkylidene can condense with other rings of more than 1. As the example of the ring that can condense with cycloalkylidene, can enumerate phenyl ring, naphthalene nucleus, Tetramethylene. ring, Pentamethylene. ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine ring and pyrimidine ring etc..
R7During for organic group, can not hinder in the range of the purpose of the present invention, select from various organic groups.Make For R7For preferred example during organic group, the alkyl of carbon number 1～6 can be enumerated；The alkoxyl of carbon number 1～6；Carbon number 2～7 Representative examples of saturated aliphatic acyl group；The alkoxy carbonyl of carbon number 2～7；The representative examples of saturated aliphatic acyloxy of carbon number 2～7；Phenyl；Naphthyl；Benzene Formoxyl；Naphthoyl；The group being selected from the alkyl of carbon number 1～6, morpholine-1-base, piperazine-1-base and phenyl is substituted Benzoyl；There is the alkyl monosubstituted amino of the alkyl of carbon number 1～6；There is the dialkyl amido of the alkyl of carbon number 1～6；Morpholine- 1-base；Piperazine-1-base；Halogen；Nitro；Cyano group.
R7In, preferably benzoyl；Naphthoyl；Be selected from the alkyl of carbon number 1～6, morpholine-1-base, piperazine-1-base, And the substituted benzoyl of group in phenyl；Nitro, more preferably benzoyl；Naphthoyl；2-aminomethyl phenyl carbonyl；4- (piperazine-1-base) phenylcarbonyl group；4-(phenyl) phenylcarbonyl group.
It addition, n is preferably the integer of 0～3, the integer of more preferably 0～2, particularly preferably 0 or 1.When n is 1, R7Key The position closed is preferably with respect to R7The binding site that the phenyl being bonded is bonded with atom A is para-position.
A is preferably S.
R8Can select from various organic groups in the range of the purpose of the present invention not hindering.As R8Preferred example Son, can enumerate the alkyl of carbon number 1～20, the cycloalkyl of carbon number 3～10, the representative examples of saturated aliphatic acyl group of carbon number 2～20, carbon number 2～ The alkoxy carbonyl of 20, can have the phenyl of substituent group, can have the benzoyl of substituent group, can have substituent group Phenyloxycarbonyl, can have the phenylalkyl of the carbon number 7～20 of substituent group, can have the naphthyl of substituent group, can have The naphthoyl of substituent group, can have the naphthoxycarbonyl of substituent group, can have the naphthyl of the carbon number 11～20 of substituent group Alkyl, can have the heterocyclic radical of substituent group and can have the Heterocyclylcarbonyl etc. of substituent group.
R8In, the preferably alkyl of carbon number 1～20, the more preferably alkyl of carbon number 1～6, particularly preferably ethyl.
As R7Or R8In comprise, substituent group time phenyl, naphthyl and heterocyclic radical have substituent group further, can enumerate The alkyl of carbon number 1～6, the alkoxyl of carbon number 1～6, the representative examples of saturated aliphatic acyl group of carbon number 2～7, the alkoxyl carbonyl of carbon number 2～7 Base, the representative examples of saturated aliphatic acyloxy of carbon number 2～7, there is the alkyl monosubstituted amino of the alkyl of carbon number 1～6, there is carbon number 1～6 The dialkyl amido of alkyl, morpholine-1-base, piperazine-1-base, halogen, nitro and cyano group etc..R7Or R8In comprise, phenyl, naphthalene The number of this substituent group when base and heterocyclic radical have substituent group further, as long as in the scope not hindering the purpose of the present invention In, it is not particularly limited, preferably 1～4.R7Or R8In comprise, phenyl, naphthyl and heterocyclic radical there is multiple substituent group Time multiple substituent groups, can be the same or different.
R9With R4Situation identical.
For the compound that formula (a-1) represents, when m is 0, such as, can close according to following flow diagram (scheme) 1 Become.In flow chart 1, use the compound that following formula (1-1) represents as raw material.Such as, R1The group represented for formula (a-2) Time, in flow chart 1, use the fluorene derivative that following formula (1-1-1) represents as raw material.R4For nitro or the organic group of 1 valency Time, the fluorene derivative that formula (1-1-1) represents can be by utilizing known method with R5And R6The fluorenes replacing 9 and obtain derives Thing imports substituent R4And obtain.For with R5And R6For the fluorene derivative replacing 9 and obtain, such as, work as R5And R6For During alkyl, can obtain in the following manner: as described in Japanese Unexamined Patent Publication 06-234668 publication, at alkali metal hydrogen-oxygen In the presence of compound, in aprotic polar organic solvent, fluorenes is made to react with alkylating reagent.It addition, by having at fluorenes In machine solvent solution, add alkylating reagent, the aqueous solution of alkali metal hydroxide and the tetrabutyl iodate of alkyl halide etc The phase transfer catalyst of ammonium, potassium tert-butoxide etc, is alkylated reaction, thus can get 9,9-alkyl substituted fluorene.
The halo carbonyl compounds that use formula (1-2) represents, utilizes friedel-crafts (Friedel-Crafts) anti- Should, compound formula (1-1) represented is acylated, the ketonic compound that available formula (1-3) represents.In formula (1-2), Hal is halogen Element atom.R1In the position that is acylated of the compound represented by formula (1-2) on the aromatic rings that comprises may utilize following methods and Select: suitably change the condition of Friedel-Crafts reaction, or to the compound represented by formula (1-2) on this aromatic rings Protection and deprotection are implemented in position outside the position being acylated.
It follows that the ketonic compound represented for the formula (1-3) obtained, hydroxylamine is utilized to carry out oximate and obtain following formula (1-4) oxime compound represented.Make the anhydride ((R that the oxime compound of formula (1-4) and following formula (1-5) represent3CO)2O) or under State the carboxylic acid halides (R that formula (1-6) represents3COHal, Hal are halogen atom.) reaction, the chemical combination that available following formula (1-7) represents Thing.
It should be noted that in formula (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) and (1-1-1), R1、R2、R3、R4、R5, and R6Identical with the situation of formula (a-1).
<flow chart 1>
[chemical formula 6]
For the compound that formula (a-1) represents, when m is 1, such as can be according to the 2-in-1 one-tenth of following flow diagram.Flow chart In 2, use the compound that following formula (2-1) represents as raw material.The compound that formula (2-1) represents is available same with flow chart 1 The method of sample, the compound utilizing Friedel-Crafts reaction formula (1-1) to be represented is acylated and obtains.Depositing at hydrochloric acid Under, (RONO, R are the alkyl of carbon number 1～6 to make nitrites that following formula (2-2) represents.) chemical combination that represents with formula (2-1) Thing reacts, and obtains the ketoxime compounds that following formula (2-3) represents.It follows that make ketoxime compounds that following formula (2-3) represents, The anhydride ((R represented with following formula (2-4)3CO)2Or the carboxylic acid halides (R that represents of following formula (2-5) O)3COHal, Hal are that halogen is former Son.) reaction, the compound that available following formula (2-6) represents.It should be noted that following formula (2-1), (2-3), (2-4), (2-5) and in (2-6), R1、R2, and R3Identical with the situation of formula (a-1).
When m is 1, there is following tendency: can reduce further in the curable using the compound represented containing formula (a-1) The generation of the impurity in the solidfied material that compositions is formed.
<flow chart 2>
[chemical formula 7]
As the preferred concrete example of the compound that formula (a-1) represents, following compound can be enumerated.
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
Relative to total 100 mass parts of the solid state component of solidification compound, the content of (A) Photoepolymerizationinitiater initiater is preferred It is 0.1～90 mass parts, more preferably 1～80 mass parts.(A) when the content of Photoepolymerizationinitiater initiater is above-mentioned scope, the present invention The solidification compound related to easily becomes the solidification compound that sensitivity is more excellent.
<(B) polyfunctional acrylic ester compound>
As (B) polyfunctional acrylic ester compound, as long as comprising in siloxane bond, aromatic rings and crosslinking saturated rings At least one, be not particularly limited.(B) polyfunctional acrylic ester compound is favorably improved by consolidating of the present invention relates to The bendability of hard conating, toughness and the case hardness that the property changed compositions obtains.(B) polyfunctional acrylic ester compound can individually make With or be applied in combination two or more.(B) polyfunctional acrylic ester compound can be low molecular compound, it is also possible to be to have spy The oligomer of fixed repetitive and/or polymer, it is also possible to be combinations thereof.
As (B) polyfunctional acrylic ester compound, such as, can enumerate and comprise the multifunctional acrylic acid containing siloxane bond (B) polyfunctional acrylic ester compound of ester compounds；Comprise containing at least one in aromatic rings and crosslinking saturated rings (B) polyfunctional acrylic ester compound of polyfunctional acrylic ester compound, from the characteristic easily improving the hard conating obtained From the standpoint of, preferably comprise: the polyfunctional acrylic ester compound containing siloxane bond, and containing full selected from aromatic rings and crosslinking Polyfunctional acrylic ester compound with at least one in ring.
[the polyfunctional acrylic ester compound containing siloxane bond]
Although the bendability of hard conating that raising is obtained by the polyfunctional acrylic ester compound containing siloxane bond, suppression The contribution of the effect of cure shrinkage (reduction crimpiness) is little, but the case hardness promoting this hard conating is had bigger contribution.Make For the polyfunctional acrylic ester compound containing siloxane bond, such as, (methyl) acryloyl group of comprising more than 2 can be enumerated Polysilsesquioxane (polysilsesquioxane) compound.Especially, the surface of the hard conating obtained from easier raising From the standpoint of hardness, as above-mentioned polysilsesquioxane compound, preferably comprise (methyl) acryloyl group of more than 2 The polysilsesquioxane compound of cage modle.
As above-mentioned polysilsesquioxane compound, such as, the cage modle polysilsesquioxane that following formula represents can be enumerated.
[RSiO3/2]n
(in formula, R independently be the group containing (methyl) acryloyl group or carboxyl, and n is 8,10,12 or 14, wherein, 2 Individual above R is (methyl) acryloyl group.)
As the above-mentioned group containing carboxyl, such as, the 1 valency group that-X-B-Y-COOH represents can be enumerated.
Above-mentioned X represents that (in formula, R5 and R6 represents carbon number for singly-bound, the alkylidene of carbon number 1～6, arlydene or-R5-NH-R6- The alkylidene of 1～3.R5 with R6 can be the same or different.), Y represents by removing 2 in aromatic series ring group or alcyl Each 1 hydrogen atom on individual ring carbon atom and the group of divalent that produces or the carbon number 1～4 can with side chain and/or double bond The alkylidene of divalent, B represents-NHCO-or-CONH-.Wherein, X and/or Y can have selected from (methyl) acryloyl group At least one group alternatively base in ((meth) acryl group), vinyl and epoxy radicals.
As the alkylidene of the carbon number 1～6 in above-mentioned X, specifically, methylene, ethylidene, Asia third can such as be enumerated Base, butylidene etc..It is 6～10 as the arlydene in above-mentioned X, preferably carbon number.As such arlydene, such as, can enumerate Phenylene (o-, m-or p-etc.), naphthylene (Isosorbide-5-Nitrae-, 1,5-, 2,6-etc.) etc..As-the R5-NH-R6-in above-mentioned X, concrete and Speech, such as, can enumerate-CH2-NH-CH2-、-(CH2)2-NH-(CH2)2-、-(CH2)3-NH-(CH2)3-、-CH2-NH-(CH2)2-、- (CH2)2-NH-CH2-、-(CH2)2-NH-(CH2)3-、-(CH2)3-NH-(CH2)2-、-CH2-NH-(CH2)3-、-(CH2)3-NH- CH2-etc..
As the aromatic ring in above-mentioned Y, the fragrance of the carbon number 6～10 of the substituent group can with carbon number 1～2 can be enumerated Ring (such as, phenyl ring, naphthalene nucleus, tolyl, xylyl etc.).As the alicyclic ring in above-mentioned Y, the alicyclic ring of carbon number 5～10 can be enumerated (such as, monocyclic cycloalkyl, monocyclic cycloalkenyl, 2 ring type alkyl, cage modle alkyl etc. can be enumerated, specifically, such as, can enumerate ring Pentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, bicyclopentadiene ring, norbornane ring, Norborene ring, cubane (cubane) ring, basket alkane (basketane) ring etc.).As in above-mentioned Y can have side chain and/ Or the alkylidene of the carbon number 1～4 of double bond, specifically, such as, can enumerate methylene, ethylidene, propylidene, ethenylidene, (2- Octenyl) alkylidene such as ethylidene, (2,4,6-trimethyl-2-nonenyl) ethylidene, there is the alkylidene of double bond or there is carbon The alkylidene of the side chain of several 1～9.
[containing the polyfunctional acrylic ester compound of at least one in aromatic rings and crosslinking saturated rings]
Although the polyfunctional acrylic ester compound containing at least one in aromatic rings and crosslinking saturated rings is to lifting The contribution of the effect of the case hardness of the hard conating obtained is moderate, but passes through aromatic rings and/or cross-link saturated rings so The soft skeleton such as upright and outspoken part skeleton and alkylidene (such as, methylene, ethylidene etc.), ehter bond and/or ammonia ester bond Synergism, to improving the bendability of this hard conating, suppressing cure shrinkage (reduction crimpiness) to have bigger contribution.
As aromatic rings, such as, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, fluorenes ring, furan nucleus, pyrrole ring, imidazole ring, Thiphene ring, phosphene (phosphole) ring, pyrazole ring, azoles ring, isoxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, triazine ring, tetrazine ring, benzofuran ring, isobenzofuran ring, indole ring, iso-indoles ring, benzothiophene Ring, benzo phosphene (benzophosphole) ring, benzimidazole ring, purine ring, indazole ring, benzothiazole ring, benzene And isoxazole ring, benzothiazole ring, quinoline ring, isoquinolin ring, quinoxaline ring, quinazoline ring, cinnolines ring, isocyanurate ring Deng, consider from viewpoints such as the bendability of the hard conating obtained, resistance to crimpiness, preferably isocyanurate ring, fluorenes ring and triazine ring.
As crosslinking saturated rings, such as, can enumerate norbornane ring, isoborneol alkane ring, diamantane (obsolete) ring, tristane ring, Tetracyclododecane rings etc., consider from viewpoints such as the bendability of the hard conating obtained, resistance to crimpiness, preferably tristane ring.
Relative to total 100 mass parts of the solid state component of solidification compound, (B) polyfunctional acrylic ester compound Content is preferably 10～99.9 mass parts, more preferably 20～99 mass parts.(B) content of polyfunctional acrylic ester compound is During above-mentioned scope, the solidification compound that the present invention relates to the hard conating obtained easily has more excellent bendability, toughness And case hardness.
<other compositions>
As required, the solidification compound that the present invention relates to can comprise various additive.Specifically, can enumerate molten Agent, sensitizer, curing accelerator, photocrosslinking agent, photosensitizer, dispersing aid, filler, closely sealed accelerator, antioxidant, purple Ultraviolet absorbers, deflocculant, thermal polymerization inhibitor, defoamer, surfactant etc..
As solvent spendable in the solidification compound that the present invention relates to, such as, can enumerate ethylene glycol monomethyl ether, Ethylene glycol monomethyl ether, ethylene glycol n-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol list second Base ether, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, dipropylene glycol list first Base ether, dihydroxypropane single-ethyl ether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ethylether；Ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monomethyl ether Acetas, diethylene glycol monomethyl ether acetas, TC acetas, propylene glycol monomethyl ether, third (gathering) alkylene glycol monoalkyl ether acetate classes such as glycol list monoethyl ether acetate；Diethylene glycol dimethyl ether, diethylene glycol first Other ethers such as benzyl ethyl ether, diethylene glycol diethyl ether, oxolane；Methyl ethyl ketone, Ketohexamethylene, 2-heptanone, 3-heptanone Deng ketone；The lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl ester, 2 hydroxy propanoic acid ethyl ester；2-hydroxy-2-methyl ethyl propionate, 3-first Epoxide methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxyacetic acid second Ester, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetic acid 3-methyl-3-methoxybutyl, propanoic acid 3-methyl-3-first Epoxide butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, acetic acid Isopentyl ester, n-butyl propionate, ethyl n-butyrate., propyl butyrate, isopropyl isobutyrate, butanoic acid N-butyl, methyl pyruvate, acetone acid Other esters such as ethyl ester, acetone acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester；Toluene, two Toluene etc. are aromatic hydrocarbon；The amide-types etc. such as N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide. These solvents can be used alone, it is possible to is applied in combination two or more.
In above-mentioned solvent, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetic acid ester, propylene glycol monomethyl ether, Propylene glycol monoethyl acetas, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Ketohexamethylene, acetic acid 3-methoxyl group Butyl ester demonstrates the dissolubility of excellence for above-mentioned (A) composition and (B) composition, thus preferably, particularly preferably uses propylene glycol Monomethyl ether acetate, acetic acid 3-methoxybutyl.The usage amount of solvent suitably determines i.e. according to the purposes of solidification compound Can, as an example, can enumerate: relative to total 100 mass parts of the solid state component of solidification compound, be 50～900 mass About Fen.In the present invention, when using solvent, there is the tendency becoming to be easily controlled thickness.This tendency is needing filming In the case of particularly significant.During it addition, (B) composition is at room temperature solid, solvent in the present invention, is preferably used.
As thermal polymerization inhibitor spendable in the solidification compound that the present invention relates to, such as, hydroquinone, hydrogen can be enumerated Quinone list ethylether etc..It addition, respectively, as defoamer, the compound of polysiloxane series, fluorine system etc. can be enumerated；As surface Activating agent, can enumerate the compound of anion system, cation system, nonionic etc..
[preparation method of solidification compound]
The solidification compound that the present invention relates to can be prepared by mixing whole above-mentioned each compositions with blender.Need Illustrate, when the solidification compound of preparation does not contains the insoluble compositions such as filler, it is possible to use filter was carried out Filter, so that solidification compound becomes uniform.
" manufacture method of solidfied material "
The manufacture method of the solidfied material that the present invention relates to includes following operation:
The solidification compound that the present invention relates to is used to form the operation of solidification compound film；With
The operation that above-mentioned solidification compound film is exposed.
As required, can pattern for the solidfied material utilizing this manufacture method manufacture.
As the method using the solidification compound that the present invention relates to form solidification compound film, such as, can enumerate Following methods: use roll coater, reverse contact transfer printing type apparatus for coating, the rotations such as coating machine (reverse coater), bar coater Turn the painting of the non-contact type such as coating machine (rotary apparatus for coating), curtain flow coater (curtain flow coater) to arrange Put, substrate is coated with solidification compound.As substrate, it is not particularly limited, such as, substrate described later can be enumerated.
As required, it is possible to the above-mentioned solidification compound film formed is dried.Drying means is not particularly limited, Such as, following methods can be enumerated: (1) utilizes heating plate, such as, in the temperature of 80～120 DEG C, preferably 90～100 DEG C, be dried The method of 60～120 seconds；(2) a few hours～the method for a couple of days are at room temperature placed；(3) storage heater, infrared ray are put into Several tens minutes～a few hours in heater and make its method being dried；Etc..
It follows that to above-mentioned solidification compound film irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray, expose Light.For exposure, such as, the method etc. that the available mask being situated between every minus is exposed, carry out, also regioselectivity Available whole exposes and carries out.In the case of carrying out whole exposure, for example, it is possible to online (1ine) winding is formed The film base material of solidification compound film, in line procedures, carries out activity continuously for above-mentioned solidification compound film The irradiation of energy-ray.The energy-ray amount irradiated is different, the most preferably also with the difference of the composition of solidification compound It is 40～200mJ/cm2Left and right.Light source is not particularly limited, such as, high voltage mercury lamp, LED etc. can be enumerated, from save energy, From the viewpoint of alleviating environmental pressure, preferably LED.Utilize in the exposure that LED is carried out, as spendable wavelength, such as, can lift Go out 365～405nm, the wavelength in the more specifically UV region such as 385nm, 395nm, 405nm.Generally, the energy utilizing LED illumination is penetrated Line amount easily tails off.But, owing to the solidification compound that the present invention relates to contains (A) Photoepolymerizationinitiater initiater, sensitivity is excellent, Therefore, even and if use LED be exposed as light source, it is possible to fully solidify, effectively obtain that there is consolidating of good characteristic Compound.As above it is stated that as, the sensitivity of the solidification compound that the present invention relates to is excellent, therefore, by using The solidification compound of the present invention, can manufacture the hard material that is coated with efficiently as a result, the display of panel of LCD etc can be improved The productivity ratio of device.
In the case of solidification compound film is optionally exposed by position, by the film after utilizing developer solution to make exposure Development, can form the pattern of desired shape.Developing method is not particularly limited, such as, and available infusion process, nebulization Deng.Developer solution suitably can select according to the composition of solidification compound.Solidification compound comprises the alkali of alkali soluble resins etc During the composition of dissolubility, as developer solution, the developer solution of the organic systems such as monoethanolamine, diethanolamine, triethanolamine, hydrogen-oxygen can be used Change the aqueous solution of sodium, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc..
It follows that for the pattern after development, be preferable over about 200～250 DEG C and carry out after bake (post bake).
The solidfied material utilizing the manufacture method of the solidfied material that the present invention relates to prepare such as can suitably serve as and firmly be coated with material In hard conating.
" being firmly coated with material "
The hard material that is coated with that the present invention relates to has base material and uses the solidification compound that the present invention relates at above-mentioned base material The hard conating of upper formation.
As base material, it is not particularly limited, the known base material as the hard base material being coated with material can be used.Specifically, Triacetyl cellulose (TAC), polyethylene terephthalate (PET), PEN (PEN) can be enumerated, gather Amide (PA), polymethyl methacrylate (PMMA), nylon (Ny), polyether sulfone (PES), polrvinyl chloride (PVC), polypropylene (PP), the film base material such as Merlon (PC)；Glass baseplate etc..Wherein, preferably film base material, more preferably TAC film, PC film, PET film.
The hard material that is coated with that the present invention relates to can manufacture in the following manner: first, uses the curable group that the present invention relates to Compound forms solidification compound film, is then exposed by this solidification compound film.The formation of solidification compound film and exposure As the situation of the manufacture method of the solidfied material that the present invention relates to.The thickness of hard conating is preferably 1～10 μm.
" image display device "
The image display device that the present invention relates to have the present invention relates to be firmly coated with material.As image display device, can Enumerate liquid crystal display, plasma scope, CRT monitor, EL display, organic el display, field-emitter display Deng, can its display surface or its wiring protective layer on laminating the present invention relates to be firmly coated with material.
Embodiment
Below, it is shown that embodiment specifically describes the present invention further, but the scope of the present invention is not by these embodiments Limit.
[embodiment 1～12 and comparative example 1～8]
The most like that, by (A) Photoepolymerizationinitiater initiater, (B1) polyfunctional acrylic ester chemical combination containing siloxane bond Thing, (B2) containing the polyfunctional acrylic ester compound of at least one in aromatic rings and crosslinking saturated rings and (B3) its He uniformly mixes by acrylate compounds, obtains the solidification compound of solvent-free system.The numeric representation in bracket in table 1 is each The use level (unit: mass parts) of composition.
Compound 1: the Photoepolymerizationinitiater initiater that the chemical formula on the left of following the first row represents
Compound 2: the Photoepolymerizationinitiater initiater that the chemical formula on the right side of following the first row represents
Compound 3: the Photoepolymerizationinitiater initiater that the chemical formula of following second row represents
[chemical formula 15]
Irg819: the Photoepolymerizationinitiater initiater that the chemical formula in following left side represents
Irg184: the Photoepolymerizationinitiater initiater that the chemical formula of following centre represents
OXE01: the Photoepolymerizationinitiater initiater that the chemical formula on following right side represents
[chemical formula 16]
Silsesquioxane 1:R19～R26The silsesquioxane that the chemical formula in the following left side of all acryloyl group epoxides represents Alkane
Silsesquioxane 2:R19～R26The chemical formula that 30 moles of % are following right side represent group, R19～R2670 Mole % is the silsesquioxane that chemical formula acryloyl group epoxide, following left side represents
[chemical formula 17]
Tristane system: the compound that the chemical formula on the left of following the first row represents
Isocyanuric acid system 1: the compound that the chemical formula on the right side of following the first row represents
Fluorenes system: the compound that the chemical formula of following second row represents
Isocyanuric acid system 2:X represents the compound that the chemical formula of following the third line of acryloyl group epoxide represents
[chemical formula 18]
(film-forming method)
The solidification compound obtained is dropped onto on the PET film that thickness is 100 μm, enter with applicator (applicator) Row coating, obtains solidification compound film.Then, for this solidification compound film, with high voltage mercury lamp exposure machine (ORC A.B.) Or LED (wavelength 395nm) is exposed, obtain the cured film that thickness is 50 μm.This cured film is peeled off from above-mentioned PET film, Carry out following evaluation.These evaluation results are recorded in table 1.
(case hardness)
According to JIS K 5600-5-4, measure the pencil hardness of above-mentioned cured film.According to following benchmark evaluation case hardness.
◎ (the best): above-mentioned pencil hardness is more than 7H.
Zero (well): above-mentioned pencil hardness is 4H～6H.
× (bad): above-mentioned pencil hardness is below 3H.
(transparent)
Use transmissometer MCPD (big electronics system), measure above-mentioned cured film absorbance at 400nm.According to following The benchmark evaluation transparency.
◎ (the best): above-mentioned absorbance is more than 95%.
Zero (well): above-mentioned absorbance is more than 90% and less than 95%.
× (bad): above-mentioned absorbance is less than 90%.
(bendability and toughness)
Preparation radius is the stainless steel bar of n (unit be mm, n are the integer of more than 1).The each stainless steel bar prepared is rolled up Around above-mentioned cured film.Determine in the stainless steel bar that can wind in the case of rupturing not making this cured film there is least radius not Rust rod iron.According to following benchmark evaluation bendability and toughness.
◎ (the best): above-mentioned least radius is below 2mm.
Zero (well): above-mentioned least radius is 3mm～5mm.
× (bad): above-mentioned least radius is more than 6mm.
As shown in Table 1, the solidification compound that the present invention relates to the bendability of the hard conating obtained, toughness, surface are hard Degree and the transparency are excellent, can be suitably used for firmly being coated with material.

Claims (6)

1. solidification compound, it contains (A) Photoepolymerizationinitiater initiater and (B) polyfunctional acrylic ester compound, described multifunctional Acrylate compounds comprises at least one in siloxane bond, aromatic rings and crosslinking saturated rings,
Described (A) Photoepolymerizationinitiater initiater comprises the compound that following formula (a-1) represents:
Chemical formula 1
R1Group that the group that represents for following formula (a-2), following formula (a-3) represent or the base that following formula (a-4) represents Group, R2It is the organic group of 1 valency, R3For hydrogen atom, the alkyl of the carbon number 1～11 can with substituent group, maybe can have The aryl of substituent group, m is 0 or 1；
Chemical formula 2
R4For hydrogen atom, nitro or the organic group of 1 valency, R5And R6Independently be chain-like alkyl, cyclic hydrocarbon group or heteroaryl, R5 With R6Can be mutually bonded and form volution；
Chemical formula 3
R7Independently be the organic group of 1 valency, amino, halogen atom, nitro or cyano group, A is S or O, and n is the integer of 0～4；
Chemical formula 4
R8It is the organic group of 1 valency, R9For hydrogen atom, nitro or the organic group of 1 valency.
2. solidification compound as claimed in claim 1, wherein, described (B) polyfunctional acrylic ester compound comprise containing The polyfunctional acrylic ester compound of siloxane bond.
3. solidification compound as claimed in claim 2, wherein, the described polyfunctional acrylic ester chemical combination containing siloxane bond Thing is the polysilsesquioxane compound of (methyl) acryloyl group comprising more than 2.
4. solidification compound as claimed in claim 2, wherein, described (B) polyfunctional acrylic ester compound also comprises: contain There is the polyfunctional acrylic ester compound selected from aromatic rings with at least one in crosslinking saturated rings.
5. the manufacture method of solidfied material, it includes following operation:
The solidification compound described in claim 1 is used to form the operation of solidification compound film；With
The operation that described solidification compound film is exposed.
The most firmly being coated with material, it has base material and uses the solidification compound described in claim 1 to be formed on the substrate Hard conating.
CN201610420826.2A 2015-06-17 2016-06-13 Curable composition, method for producing cured product, and hard coating material Active CN106256837B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015121983A JP6602062B2 (en) 2015-06-17 2015-06-17 Curable composition, method for producing cured product, and hard coat material
JP2015-121983 2015-06-17

Publications (2)

Publication Number Publication Date
CN106256837A true CN106256837A (en) 2016-12-28
CN106256837B CN106256837B (en) 2020-04-10

Family

ID=57714196

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610420826.2A Active CN106256837B (en) 2015-06-17 2016-06-13 Curable composition, method for producing cured product, and hard coating material

Country Status (3)

Country Link
JP (1) JP6602062B2 (en)
KR (1) KR102503973B1 (en)
CN (1) CN106256837B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110785376A (en) * 2017-07-14 2020-02-11 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110799453A (en) * 2017-07-14 2020-02-14 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110799454A (en) * 2017-07-14 2020-02-14 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN111918769A (en) * 2018-03-30 2020-11-10 富士胶片株式会社 Hard coat film, article having hard coat film, image display device, and method for producing hard coat film
CN113853302A (en) * 2019-05-17 2021-12-28 富士胶片株式会社 Hard coat film, article provided with hard coat film, and image display device
CN114075398A (en) * 2020-08-21 2022-02-22 广东华润涂料有限公司 Coating composition and coated article including coating layer formed by coating composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101788399B1 (en) * 2015-09-23 2017-10-19 (주)경인양행 Oxime ester compound having improved heat stability, photopolymerization initiator and photoresist composition comprising the same
JP6677047B2 (en) * 2016-03-30 2020-04-08 三菱ケミカル株式会社 Alicyclic polyfunctional (meth) acrylate compounds
WO2020235383A1 (en) * 2019-05-17 2020-11-26 富士フイルム株式会社 Resin composition, hard coating film and polyorganosilsesquioxane
KR20220031925A (en) * 2019-09-27 2022-03-14 후지필름 가부시키가이샤 A composition for forming a hard coat layer, a hard coat film, a method for producing a hard coat film, and an article comprising the hard coat film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008019292A (en) * 2006-07-10 2008-01-31 Fujifilm Corp Photocurable composition and pattern forming method using it
CN102477252A (en) * 2010-11-29 2012-05-30 Jsr株式会社 Laminated film for hard coating forming, film coil and curing composition for hard coating forming
CN102804066A (en) * 2010-03-22 2012-11-28 株式会社Lg化学 Photocurable and thermocurable resin composition, and dry film solder resist
CN103293855A (en) * 2013-05-20 2013-09-11 常州强力先端电子材料有限公司 Acrylic ester photocuring composition
CN103703029A (en) * 2011-07-11 2014-04-02 株式会社德山 Photochromic curable composition

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005215147A (en) * 2004-01-28 2005-08-11 Fuji Photo Film Co Ltd Polymerizable composition
JP2006241406A (en) * 2005-03-07 2006-09-14 Fuji Photo Film Co Ltd Ink composition, inkjet recording method, printed article, method for producing planographic printing plate and planographic printing plate
JP4899100B2 (en) * 2007-05-29 2012-03-21 ナガセケムテックス株式会社 Photosensitive composition
WO2009131189A1 (en) * 2008-04-25 2009-10-29 三菱化学株式会社 Ketoxime ester compound and use thereof
JP2009286976A (en) * 2008-05-30 2009-12-10 Fujifilm Corp Polymerizable liquid crystal composition, optically anisotropic film, optical element and liquid crystal display device
CN102459171B (en) * 2009-06-17 2014-07-09 东洋油墨Sc控股株式会社 Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern
TWI475006B (en) * 2009-09-08 2015-03-01 Nippon Steel & Sumikin Chem Co Photopolymerization initiator and photosensitive composition
JP5515714B2 (en) * 2009-12-16 2014-06-11 Ｊｓｒ株式会社 Coloring composition, color filter and color liquid crystal display element
JP2011170334A (en) * 2010-01-20 2011-09-01 Fujifilm Corp Black curable composition for wafer-level lens, and wafer-level lens
JP5222922B2 (en) * 2010-10-12 2013-06-26 富士フイルム株式会社 Pattern forming method, pattern forming material, and photosensitive film, pattern film, low refractive index film, optical device, and solid-state imaging device using the same
JP5890297B2 (en) * 2011-12-22 2016-03-22 東京応化工業株式会社 Photosensitive resin composition, color filter and display device using the same, oxime ester compound, and photopolymerization initiator
JP2013195550A (en) 2012-03-16 2013-09-30 Toppan Printing Co Ltd Optical film and optical display device
JP6127130B2 (en) * 2012-05-03 2017-05-10 コリア リサーチ インスティテュート オブ ケミカル テクノロジー Novel oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition
KR20140077246A (en) * 2012-12-12 2014-06-24 동우 화인켐 주식회사 A colored curable resin composition, color filter and display device
JP5890457B2 (en) * 2013-08-05 2016-03-22 東京応化工業株式会社 Pigment dispersion, photosensitive resin composition containing the same, and dispersion aid
JP6339346B2 (en) * 2013-11-05 2018-06-06 太陽インキ製造株式会社 Curable composition for printed wiring board, cured coating film using the same, and printed wiring board
JP6400289B2 (en) * 2013-12-24 2018-10-03 日立化成株式会社 Base material for touch panel with cured film and method for producing the same, photosensitive element and touch panel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008019292A (en) * 2006-07-10 2008-01-31 Fujifilm Corp Photocurable composition and pattern forming method using it
CN102804066A (en) * 2010-03-22 2012-11-28 株式会社Lg化学 Photocurable and thermocurable resin composition, and dry film solder resist
CN102477252A (en) * 2010-11-29 2012-05-30 Jsr株式会社 Laminated film for hard coating forming, film coil and curing composition for hard coating forming
CN103703029A (en) * 2011-07-11 2014-04-02 株式会社德山 Photochromic curable composition
CN103293855A (en) * 2013-05-20 2013-09-11 常州强力先端电子材料有限公司 Acrylic ester photocuring composition

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110799453B (en) * 2017-07-14 2022-12-27 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110799453A (en) * 2017-07-14 2020-02-14 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110799454A (en) * 2017-07-14 2020-02-14 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110785376A (en) * 2017-07-14 2020-02-11 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
US11945718B2 (en) 2017-07-14 2024-04-02 Fujifilm Corporation Surface-modified inorganic nitride, composition, thermally conductive material, and device with thermally conductive layer
US11945717B2 (en) 2017-07-14 2024-04-02 Fujifilm Corporation Surface-modified inorganic nitride, composition, thermally conductive material, and device with thermally conductive layer
CN110785376B (en) * 2017-07-14 2023-03-31 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN110799454B (en) * 2017-07-14 2022-12-30 富士胶片株式会社 Surface-modified inorganic nitride, composition, heat-conducting material and device with heat-conducting layer
CN111918769A (en) * 2018-03-30 2020-11-10 富士胶片株式会社 Hard coat film, article having hard coat film, image display device, and method for producing hard coat film
US11530334B2 (en) 2018-03-30 2022-12-20 Fujifilm Corporation Hardcoat film, article and image display device having hardcoat film, and method for manufacturing hardcoat film
CN111918769B (en) * 2018-03-30 2022-06-24 富士胶片株式会社 Hard coat film, article having hard coat film, image display device, and method for producing hard coat film
CN113853302B (en) * 2019-05-17 2024-01-02 富士胶片株式会社 Hard coat film, article provided with hard coat film, and image display device
CN113853302A (en) * 2019-05-17 2021-12-28 富士胶片株式会社 Hard coat film, article provided with hard coat film, and image display device
CN114075398A (en) * 2020-08-21 2022-02-22 广东华润涂料有限公司 Coating composition and coated article including coating layer formed by coating composition

Also Published As

Publication number Publication date
JP6602062B2 (en) 2019-11-06
JP2017008134A (en) 2017-01-12
CN106256837B (en) 2020-04-10
KR20160149147A (en) 2016-12-27
KR102503973B1 (en) 2023-02-28

Similar Documents

Publication Publication Date Title
CN106256837A (en) Solidification compound, the manufacture method of solidfied material and be firmly coated with material
KR101700476B1 (en) High photosensibility carbazole oxime ester photoinitiator, preparation and use thereof
EP2845845B1 (en) Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same
KR102197059B1 (en) Fluorene photoinitiator, preparation method thereof, photocurable composition having same, and use thereof in the field of photocuring
KR101860511B1 (en) Dual oxime esters photoinitiator and preparation method and use thereof
KR100563019B1 (en) Photopolymerizable photosensitive thermosetting liquid compositions
CN110066225B (en) Dioxime ester photoinitiator, preparation method, photosensitive resin composition and application
KR20160066482A (en) Black photosensitive resin composition, black matrix and image display device comprising thereof
CN104918914A (en) Sulfonium salt, photoacid generator, curable composition, and resist composition
TW201540704A (en) Bicarbazole compound, photo-curable composition, cured product thereof, curable composition for plastic lens, and plastic lens
CN106749776B (en) A kind of oxime ester lightlike initiating agent containing fluorenes
CN101717362A (en) Novel light initiator
KR20160037104A (en) Curable Compositions Comprising Vinyl Group-Containing Compound
CN109134712B (en) Fluorene multifunctionality photoinitiator, preparation method and application thereof
JP6828467B2 (en) Active energy ray polymerization initiator, active energy ray curable composition, cured product and benzoin thioether compound
CN104102091A (en) Composition Used For Formation Of Transparent Insulation Membrane
JP7082582B2 (en) Active energy ray-curable composition and cured product for adhesives
CN108503577B (en) Oxime ester compound and photocurable composition containing same
CN108395394B (en) Oxime ester compound and photocurable composition containing the oxime ester compound
JP6900684B2 (en) Sulfur atom-containing compounds, active energy ray polymerization initiators, active energy ray-curable compositions, cured products and benzointhioether compounds
CN105911817A (en) Photo-electric sensitivity composition, hardening film making method, hardening film, touch screen and display screen
KR20150145414A (en) Oxime ester compound and a photopolymerizable composition comprising the same
CN113372259B (en) Soluble chiral diastereoisomeric oxime ester compounds and mixtures thereof
JP7358583B2 (en) Photosensitive resin composition and equipment for applying it
JP5273431B2 (en) Novel acrylate compound, production intermediate thereof, and production method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant