CN101965375B - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents
Photosensitive resin and photosensitive resin composition comprising the same Download PDFInfo
- Publication number
- CN101965375B CN101965375B CN200980107328.0A CN200980107328A CN101965375B CN 101965375 B CN101965375 B CN 101965375B CN 200980107328 A CN200980107328 A CN 200980107328A CN 101965375 B CN101965375 B CN 101965375B
- Authority
- CN
- China
- Prior art keywords
- represent
- hydroxyl
- general formula
- fluorenes
- compound
- 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.)
- Active
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Photolithography (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a photosensitive resin which can be produced readily at a low cost, is easy to adjust its cross-linking density and acid value, and has excellent properties including high heat resistance, high transparency, a high refractive index and a low linear expansion coefficient. The photosensitive resin is produced by adding a (meth)acrylate compound having reactivity to a carboxylic acid and represented by general formula (2) to a polymeric compound, wherein the polymeric compound is produced by reacting a compound having a fluorene skeleton and represented by general formula (1) with a tetrabasic acid dianhydride. In general formula (1), the rings Z1 and Z2 independently represent an aromatic hydrocarbon group,R1a and R1b independently represent a hydrogen atom or a substituent,R2a and R2b independently represent a substituent other than a hydrogen atom,R3a and R3b independently represent a hydrogen atom or a methyl group,k1 and k2 independently represent an integer of 0 to 4,m1 and m2 independently represent an integer of 0 to 3,n1 and n2 independently represent an integer of 0 to 10,and p1 and p2 independently represent an integer of 0 to 4. In general formula (2), R4 represents a hydrogen atom or a methyl group, and R5 represents a group represented by general formula (5). In general formula (5), q, r and s independently represent an integer of 0 to 9, provided that it is impossible that all of q, r and s represent 0 simultaneously.
Description
Technical field
The photosensitive polymer combination that the present invention relates to there is the photoresist of fluorene skeleton and utilize it; in more detail; relate to character, the photoresist that can easily manufacture with low cost with various excellences and the photosensitive polymer combination that utilizes it, described photosensitive polymer combination can be used for preparing interlayer dielectric and the protective membrane (interlayer dielectric and the protective membrane that such as, use in colour filter, liquid crystal display device, integrated circuit component, solid-state imaging element etc.) etc. in liquid-crystal display and electronic unit etc.
Background technology
Known, the macromolecular compound with fluorene skeleton has the excellent physical property such as high heat resistance, high transparent, high refractive index, low linear expansion coefficient.For utilizing this characteristic and introduced the macromolecular compound with fluorene skeleton of free-radical polymerised unsaturated link(age) structure (vinyl) in molecule, advance in the research of the optical material purposes such as light-shielding agent, hard coating agent, antireflection film, eyeglass lens, optical fiber, optical waveguides, holography for optics.For example, as plastic lens material, disclose so that (methyl) acrylate chloride and 9, two (4-hydroxy phenyl) fluorenes reactions of 9-and the compound that obtains, or make after two (4-hydroxy phenyl) the fluorenes addition of ethylene oxide of 9,9-or propylene oxide, react the multipolymer (patent documentation 1) that the compound that forms is main component with (methyl) vinylformic acid.
But the molecular weight of the disclosed compound of this patent documentation is low, structure is also soft, exist not talkatively to there is sufficient specific refractory power and cause the shortcoming that cured article intensity is low and so on because cross-linking density is low.
In addition, for the macromolecular compound with fluorene skeleton, utilize the characteristic of its thermotolerance, resistance to chemical reagents excellence, also applicable to the so-called photo-resist (patent documentation 2 and 3) of liquid crystal colour filter or black matrix, solder resist etc.
Utilize the photoresist of these technology can obtain high cross-linking density, may obtain the cured article of intensity, thermotolerance, resistance to chemical reagents excellence, but due to its synthetic time that need to be very long, therefore cost is high, practical situation are to be difficult to extensively popularize.In addition, because the reason of its manufacture method can occur paintedly, therefore, be difficult to be applicable to require transparent optics, can't say the characteristic of having given full play to fluorene skeleton.
Patent documentation 1: Unexamined Patent 4-325508 communique
Patent documentation 2: No. 3673321 communique of patent
Patent documentation 3: JP 2007-264433 communique
Summary of the invention
Thereby, requirement provides photoresist, it can easily be manufactured with low cost, the adjusting of cross-linking density or acid number is easy, possesses the excellent characteristic such as the original high heat resistance of fluorene skeleton, high transparent, high refractive index and low linear expansion coefficient simultaneously, problem of the present invention is, such photoresist is provided and utilizes its photosensitive polymer combination.
In view of the practical situation that relate to, the inventor concentrates on studies repeatedly in order to solve above-mentioned problem, found that, make specifically to have the photoresist that the compound of fluorene skeleton and the specific carboxylic acid reaction of macromolecular compound addition (methyl) acrylic compound that tetraprotic acid two anhydride reactants obtain obtain, can easily manufacture with low cost, because high crosslink density obtains high strength, demonstrate the excellent characteristic such as high heat resistance, high transparent, high refractive index, low linear expansion coefficient simultaneously, thereby completed the present invention.
; the present invention is photoresist, and it is the photoresist that the macromolecular compound addition being obtained by the compound with fluorene skeleton shown in following general formula (1) and tetraprotic acid two anhydride reactants is obtained by carboxylic acid reaction (methyl) acrylic compound shown in following general formula (2).
[changing 6]
(in formula, Z
1ring and Z
2ring represents monocyclic or fused polycyclic hydrocarbon ring, R
1aand R
1brepresent hydrogen atom or alkyl, R
2aand R
2brepresent to be selected from the substituting group of alkyl, alkoxyl group, acyl group, alkoxy carbonyl, halogen atom, nitro or cyano group, R
3aand R
3brepresent hydrogen atom or methyl, k1 and k2 are identical or different, and represent 0～4 integer, and m1 and m2 are identical or different, and represent 0～3 integer, and n1 and n2 are identical or different, and represent 0～10 integer, and p1 and p2 are identical or different, and represent 0～4 integer.Wherein, work as Z
1ring and Z
2when ring is monocyclic hydrocarbon ring, p1 and p2 are 1～3; Work as Z
1ring and Z
2when ring is fused polycyclic hydrocarbon ring, Z
1encircle contained p1 sum and Z
2encircling contained p2 sum is respectively more than 1.)
[changing 7]
(in formula, R
4represent hydrogen atom or methyl, R
5represent by the group shown in following general formula (5))
[changing 8]
(in formula, q, r, s represent respectively 0～9 integer independently.But q, r, s are 0 when different.)
In addition, the present invention is photosensitive polymer combination, it is characterized in that containing above-mentioned photoresist and Photoepolymerizationinitiater initiater and/or photosensitizers.
Invention effect
The storage stability of photoresist of the present invention is high, can easily manufacture with low cost, and productivity is also excellent, has the excellent characteristic such as high heat resistance, high transparent, high refractive index, low linear expansion coefficient.And used the light sensitivity of photosensitive polymer combination of the present invention of this photoresist high, can obtain the excellent cured articles such as intensity.
Embodiment
The macromolecular compound that forms photoresist of the present invention is to make by the compound with fluorene skeleton shown in following general formula (1) and tetraprotic acid described later two anhydride reactants and the macromolecular compound obtaining.
[changing 9]
(in formula, Z
1ring and Z
2ring represents monocyclic or fused polycyclic hydrocarbon ring, R
1aand R
1brepresent hydrogen atom or substituting group, R
2aand R
2brepresent hydrogen atom substituting group in addition, R
3aand R
3brepresent hydrogen atom or methyl, k1 and k2 are identical or different, and represent 0～4 integer, and m1 and m2 are identical or different, and represent 0～3 integer, and n1 and n2 are identical or different, represent 0～10 integer, and p1 and p2 are identical or different, and represent 0～4 integer.Wherein, work as Z
1ring and Z
2when ring is monocyclic hydrocarbon ring, p1 and p2 are 1～3; Work as Z
1ring and Z
2when ring is fused polycyclic hydrocarbon ring, Z
1encircle contained p1 sum and Z
2encircling contained p2 sum is respectively more than 1.)
In above-mentioned formula (1), corresponding to by Z
1ring and Z
2the hydrocarbon of the hydrocarbon ring shown in ring is the hydrocarbon of monocyclic or fused polycyclic, for example can enumerate: the monocyclic hydrocarbon such as benzene; Fused bicyclic formula hydrocarbon (the such as C such as indenes, naphthalene
8-20fused bicyclic formula hydrocarbon, preferably C
10-16fused bicyclic formula hydrocarbon), fused tricyclic formula hydrocarbon (anthracene, phenanthrene etc.) etc. condenses 2～4 ring type hydrocarbon etc.Special in requiring in the purposes of high refractive index, high heat resistance, as preferred hydrocarbon, can enumerate fused polycyclic aromatic hydrocarbons (naphthalene, anthracene etc.), particularly preferably naphthalene.In addition, especially requiring in the purposes of high solvability and consistency and low solution viscosity, particularly preferably benzene.And, Z
1ring and Z
2ring can be the ring being same to each other or different to each other, and can be identical ring conventionally.
In addition, in above-mentioned formula (1), as by R
1aand R
1bshown substituting group, is not particularly limited, but is generally alkyl.As alkyl, can example methyl, the C such as ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl
1-6alkyl (for example C
1-4alkyl, particularly methyl) etc.Radicals R
1aand R
1beach other can be different, also can be identical.In addition, k1 (or k2) is 2 when above, in same phenyl ring, and radicals R
1a(or R
1b) can be different, also can be identical.And, radicals R
1a(or R
1b) be not particularly limited with respect to the bonding position (the position of substitution) of the phenyl ring that forms fluorene skeleton.Preferred replacement number k1 and k2 are 0 or 1, particularly 0.And replacing number k1 and k2 can be different, but conventionally identical.
As at Z
1ring and Z
2cyclosubstituted substituent R
2aand R
2b, can enumerate the alkyl (C such as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, tertiary butyl
1-20alkyl, preferably C
1-8alkyl, further preferred C
1-6alkyl etc.), the cycloalkyl (C such as cyclopentyl, cyclohexyl
5-10cycloalkyl, preferably C
5-8cycloalkyl, further preferred C
5-6cycloalkyl etc.), the aryl [C such as phenyl, alkyl phenyl (aminomethyl phenyl (tolyl), 3,5-dimethylphenyl (xylyl) etc.)
6-10aryl, preferably C
6-8aryl, particularly phenyl etc.), the aralkyl (C such as benzyl, styroyl
6-10aryl-C
1-4alkyl etc.) etc. alkyl; Alkoxyl group (the C such as methoxyl group
1-4alkoxyl group etc.); Acyl group (the C such as ethanoyl
1-6acyl group etc.); Carbalkoxy (the C such as methoxycarbonyl
1-4carbalkoxy etc.); Halogen atom (fluorine atom, chlorine atom etc.); Nitro; Cyano group etc.
Preferred substituent R
2a(or R
2b) be alkyl (C
1-6alkyl), cycloalkyl (C
5-8cycloalkyl), aryl (C
6-10aryl), aralkyl (C
6-8aryl-C
1-2alkyl), particularly preferably C
1-4alkyl, C
1-4alkoxyl group, C
6-8aryl.Substituent R
2a(or R
2b) can be separately or two or more be combined in phenyl ring and replace.In addition, radicals R
2aand R
2bcan be same to each other or different to each other, but conventionally identical.In addition, m1 (or m2) is 2 when above, in same hydrocarbon ring, and radicals R
2a(or R
2b) can be different, also can be identical.
In addition, substituent R
2a(or R
2b) the position of substitution be not particularly limited, according to the position of substitution of hydroxyl or hydroxyl (gathering) alkylidene group oxygen base (being sometimes referred to as below hydroxyl group), can for example, replace 2～6 (2,5,2,5-position etc.) of the phenyl that forms phenol skeleton.
Substituent R
2aand R
2breplacement count m1 and m2 depends on the replacement number of hydroxyl group, but be preferably 0～2, more preferably 0～1 (particularly 0).And replacing number m1 and m2 can be different, but common identical situation is many.
As the R by hydroxyl group
3aand R
3bshown substituting group is hydrogen or methyl.And, R
3aand R
3beach other can be identical, also can be different, but conventionally identical.
Adduct number n1 and the n2 of (gathering) alkylidene group oxygen base are identical or different, can be selected from 0～10 scope, can be preferably 0～8 (for example 1～8), more preferably 0～6 (for example 1～6), the scope of (for example 1～4) particularly 0～4.In addition, n1 and n2 sum (n1+n2) can be selected from 0～20 scope, can be preferably 0～16 (for example 2～12), more preferably 0～12 (for example 2～12), the scope of (for example 2～8) particularly 0～8.And, n1 (or n2) is 2 when above, (gathering) alkylidene group oxygen base can be made up of identical alkoxyl group, also can be that different types of alkoxyl group (for example oxyethyl group and propylidene oxygen base) mixes and forms, but situation about being conventionally made up of identical alkoxyl group be many.
The scope that p1 and p2 are 0～4 is counted in the replacement of hydroxyl group, and preferably 1～4, particularly preferably 1～2.Wherein, work as Z
1ring and Z
2when ring is monocyclic hydrocarbon ring, p1 and p2 are 1～3; Work as Z
1ring and Z
2when ring is fused polycyclic hydrocarbon ring, Z
1encircle contained p1 sum and Z
2encircling contained p2 sum is respectively more than 1.In addition, p1 and p2 sum (p1+p2) are preferably 2～8, more preferably 2～4.Special in the purposes of cross-linking density that requires cured article, p1 and p2 are preferably 2～3.And replacing number p1 and p2 can be different, but common identical situation is many.The position of substitution of hydroxyl group is not particularly limited, according to the number of p1 (or p2), can be from selecting 2～6 of the phenyl of 9 replacements of fluorenes, and p1 (or p2) is 2 o'clock, for example, can be 3,4-position, 3,5-position etc.1 hydroxyl group conventionally can be 4 replacements.
And the multiple hydroxyl group that form identical phenol skeleton can be identical, also can be different.For example, multiple hydroxyl group can: (i) by the hydroxyl of n1=0 (n2=0) separately (wherein not comprising that p1 and p2 are 2 situation) form, (ii) formed by the hydroxyl of n1=0 (n2=0) and hydroxyl (gathering) alkoxyl group (2-hydroxyl-oxethyl etc.) of n1 ≠ 0 (n2 ≠ 0), (iii) formed separately by identical hydroxyl (gathering) alkoxyl group of n1 ≠ 0 (n2 ≠ 0), (iv) for example, formed by different hydroxyl (gathering) alkoxyl group [2-hydroxyl-oxethyl and 2-(2-hydroxyl-oxethyl) oxyethyl group] of n1 ≠ 0 (n2 ≠ 0).
In the compound with fluorene skeleton of above-mentioned general formula (1), especially requiring in the purposes of high refractive index, high heat resistance, preferably by the compound of the structure shown in following general formula (3).
[changing 10]
(in formula, R
1aand R
1brepresent hydrogen atom or substituting group, R
2a, R
2b, R
6aand R
6brepresent hydrogen atom substituting group in addition, R
3aand R
3brepresent hydrogen atom or methyl, k1 and k2 are identical or different, and represent 0～4 integer, m1, m2, m3 and m4 are identical or different, and represent 0～3 integer, n1, n2, n3 and n4 are identical or different, and representing 0～10 integer, p1 and p2 are identical or different, and represent 1～4 integer, p3 and p4 are identical or different, and represent 0～3 integer.)
R
1aand R
1b, R
2aand R
2b, R
3aand R
3b, k1 and k2, m1 and m2, n1 and n2 same as described above.In addition, R
6aand R
6bwith above-mentioned R
2aand R
2b, m3 and m4 and above-mentioned m1 and m2, n3 and n4 corresponding respectively with said n 1 and n2, and there is identical implication.P1 and p2 are same as described above, are preferably 1～4.P 3 and p4 are corresponding with above-mentioned p1 and p2, are preferably 0～3.
Particularly, can enumerate: two (hydroxy alkoxy base naphthyl) the fluorenes classes, 9 of 9,9-, the compound that in the above-mentioned general formulas (3) such as two (hydroxyl gathers alkoxyl group naphthyl) the fluorenes classes of 9-, p1+p2+p3+p4 is 2; Two (many (hydroxy alkoxy base) naphthyl) the fluorenes classes, 9 of 9,9-, the middle p1+p2+p3+p4 of the above-mentioned general formulas (3) such as two (many (hydroxyl gathers alkoxyl group) naphthyl) the fluorenes classes of 9-is more than 2 compound etc.
As 9, two (hydroxy alkoxy base naphthyl) the fluorenes classes of 9-, for example can enumerate 9, fluorenes { for example: 9 for 9-two (hydroxy alkoxy base naphthyl), two [6-(2-the hydroxyl-oxethyl)-2-naphthyl] fluorenes, 9 of 9-, two [6-(2-hydroxyl the propoxy-)-2-naphthyl] fluorenes, 9 of 9-, two [5-(2-the hydroxyl-oxethyl)-1-naphthyl] fluorenes, 9 of 9-, two [5-(2-hydroxyl propoxy-)-1-naphthyl] fluorenes of 9-etc. 9, two (the hydroxyl C of 9-
2-4alkoxyl group naphthyl) fluorenes etc. etc.
As 9, two (hydroxyl gathers alkoxyl group naphthyl) the fluorenes classes of 9-, for example can enumerate: 9, fluorenes [for example: 9 for 9-two (hydroxyl dialkoxy naphthyl), 9-pair 6-[2-(2-hydroxyl-oxethyl) oxyethyl group] and-2-naphthyl } fluorenes, 9,9-pair 6-[2-(2-hydroxyl propoxy-) propoxy-] and-2-naphthyl } fluorenes, 9,9-pair 5-[2-(2-hydroxyl-oxethyl) oxyethyl group] and-1-naphthyl } fluorenes, 9,9-two { 5-[2-(2-hydroxyl propoxy-) propoxy-]-1-naphthyl } fluorenes etc. 9, two (hydroxyl two C of 9-
2-4alkoxyl group naphthyl) fluorenes etc.] etc. 9, two (hydroxyl dialkoxy naphthyl) the fluorenes classes of 9-; Be more than 3 compound etc. corresponding to n1, n2, n3, n4 in the above-mentioned general formula (3) of these compounds.
As 9, two (many (hydroxy alkoxy base) naphthyl) the fluorenes classes of 9-, corresponding to above-mentioned 9, the p1+p2+p3+p4 of two (hydroxy alkoxy base naphthyl) the fluorenes classes of 9-is that more than 2 compounds can be enumerated, for example 9, fluorenes [for example: 9 for 9-two (two or three (hydroxy alkoxy base) naphthyl), two [two (2-the hydroxyl-oxethyl)-2-naphthyls] fluorenes, 9 of 9-, two [two (2-hydroxyl propoxy-)-2-naphthyl] fluorenes of 9-etc. 9, two (two or three (the hydroxyl C of 9-
2-4alkoxyl group) naphthyl) fluorenes etc.] and etc. 9, two (many (hydroxy alkoxy base) naphthyl) fluorenes of 9-.
As 9, two (many (hydroxyl gathers alkoxyl group) naphthyl) the fluorenes classes of 9-, corresponding to above-mentioned 9, n1, n2, n3, the n4 of two (hydroxy alkoxy base naphthyl) the fluorenes classes of 9-is more than 2 and p1+p2+p3+p4 is that more than 2 compound can be enumerated, for example: 9, two (two or three (hydroxyl dialkoxy) naphthyl) fluorenes of 9-[for example 9, two { two [2-(2-hydroxyl-oxethyl) oxyethyl group]-2-naphthyl } fluorenes of 9-etc. 9, two (two or three (hydroxyl two C of 9-
2-4alkoxyl group) naphthyl) fluorenes etc.] and etc. 9, two (two or three (hydroxyl dialkoxy) naphthyl) the fluorenes classes of 9-; Be more than 3 compound etc. corresponding to n1, n2, n3, n4 in the described formula of these compounds (changing 3).
Wherein, preferably 9, two [6-(2-hydroxyl-oxethyl)-2-naphthyl] fluorenes of 9-etc.
In the compound with fluorene skeleton of above-mentioned general formula (1), especially requiring in the purposes of high solvability and consistency and low solution viscosity, preferably by the compound of the structure shown in following general formula (4).
[changing 11]
(in formula, R
1aand R
1brepresent hydrogen atom or substituting group, R
2a, R
2b, R
7aand R
7brepresent hydrogen atom substituting group in addition, R
3aand R
3brepresent hydrogen atom or methyl.K1 and k2 are identical or different, and represent 0～4 integer, and n1 and n2 are identical or different, and represent 0～10 integer, and p1 and p2 are identical or different, and represent 1～3 integer.)
R
1aand R
1b, R
2aand R
2b, R
3aand R
3b, k1 and k2, m1 and m2, n1 and n2 same as described above.In addition, R
7aand R
7bcorresponding to above-mentioned R
2aand R
2b, and there is identical implication.P1 and p2 are same as described above, but are preferably 1～3.
Comprise 9 by the representational compound shown in above-mentioned formula (4), two (hydroxy alkoxy base phenyl) fluorenes classes of 9-(compound of n1=n2=1 in above-mentioned general formula (4)), 9, two (hydroxyl gathers alkoxyl group dialkyl phenyl organic) fluorenes classes of 9-(in above-mentioned general formula (4), n1, n2 are respectively more than 1 compound) etc.
Two (hydroxy alkoxy base phenyl) the fluorenes classes of 9,9-for example comprise 9, two (hydroxy alkoxy base phenyl) the fluorenes classes of 9-for example 9, two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-, two [4-(the 2-hydroxyl propoxy-) phenyl] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl the propoxy-)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl) phenoxyethyl alcohol] fluorenes of 9,9-, two [4-(the 2-hydroxyl propoxy-) phenoxyethyl alcohol] fluorenes of 9,9-, two [4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl the propoxy-)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-2, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl propoxy-)-2, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 6-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl propoxy-)-2, the 6-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-2, the 4-3,5-dimethylphenyl] fluorenes of 9,9-, two [3-(2-hydroxyl propoxy-)-2, the 4-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl-oxethyl)-3, the 4-3,5-dimethylphenyl] fluorenes of 9,9-, two [2-(2-hydroxyl propoxy-)-3,4-3,5-dimethylphenyl] fluorenes of 9,9-etc. 9, two (hydroxy alkoxy alkyl phenyl) fluorenes of 9-, preferably 9, two (2-hydroxyl propoxy--bis-C of 9-
1-4alkyl phenyl) fluorenes etc. 9, two (the hydroxyl branching C of 9-
3-4alkoxyl group-dialkyl phenyl organic) fluorenes class }.
Two (hydroxyl gathers alkoxyl phenyl) the fluorenes classes of 9,9-comprise n1, n2 is more than 2 compound, and for example, two (hydroxyl dialkoxy phenyl) the fluorenes classes of 9,9-{ for example: two [4-(the 2-hydroxyl diethoxy) phenyl] fluorenes of 9,9-, two [4-(the 2-hydroxyl dipropoxy) phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl the diethoxy)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl the dipropoxy)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl diethoxy)-3, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(the 2-hydroxyl diethoxy) phenoxyethyl alcohol] fluorenes of 9,9-, two [4-(the 2-hydroxyl dipropoxy) phenoxyethyl alcohol] fluorenes of 9,9-, two [4-(2-hydroxyl the diethoxy)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl the dipropoxy)-3-aminomethyl phenyl] fluorenes of 9,9-, two [4-(2-hydroxyl diethoxy)-2, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl dipropoxy)-2, the 5-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl diethoxy)-3, the 6-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl dipropoxy)-2, the 6-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl diethoxy)-2, the 4～3,5-dimethylphenyl] fluorenes of 9,9-, two [3-(2-hydroxyl dipropoxy)-2, the 4-3,5-dimethylphenyl] fluorenes of 9,9-, two [4-(2-hydroxyl diethoxy)-3, the 4-3,5-dimethylphenyl] fluorenes of 9,9-, two [2-(2-hydroxyl dipropoxy)-3,4-3,5-dimethylphenyl] fluorenes of 9,9-etc. 9, two (the hydroxyl dialkoxy phenyl) fluorenes of 9-}.
Wherein, preferably 9, two (hydroxyl-oxethyl phenyl) fluorenes, 9 of 9-, two (hydroxyl-oxethyl-3-aminomethyl phenyl) fluorenes, 9 of 9-, two (hydroxyl-oxethyl-3, the 5-3,5-dimethylphenyl) fluorenes, 9 of 9-, two (hydroxyl-oxethyl-2-phenoxyethyl alcohol) fluorenes of 9-etc.
For form photoresist of the present invention by the compound with fluorene skeleton shown in above-mentioned general formula (1) especially requiring in the purposes of high specific refractory power, solvability and consistency and low solution viscosity, preferably R
2aand R
2bfor phenyl.
Particularly, for example, comprise 9,9-two (hydroxy alkoxy base aryl phenyl) fluorenes class (n1=n2=1 in above-mentioned general formula (4), R by the compound shown in above-mentioned general formula (4)
2a, R
2bfor the compound of phenyl), 9, (the middle n1+n2 of above-mentioned general formula (4) is more than 2 and R to two (hydroxyl gather alkoxy aryl phenyl) the fluorenes classes of 9-
2a, R
2bfor the compound of phenyl).
9, two (hydroxy alkoxy base aryl phenyl) the fluorenes classes of 9-comprise 9, two [4-(2-the hydroxyl-oxethyl)-3-phenyl] fluorenes, 9 of 9-, two [4-(2-hydroxyl the propoxy-)-3-phenyl] fluorenes, 9 of 9-, two [4-(2-hydroxyl propoxy-)-3-tolyl phenyl] fluorenes of 9-etc. 9, two (the hydroxy alkoxy base aryl phenyl) fluorenes of 9-, preferably 9, two (the 2-hydroxyl-oxethyl aryl phenyl) fluorenes of 9-} etc.
9, two (hydroxyl gathers alkoxy aryl phenyl) the fluorenes classes of 9-comprise 9, two (hydroxyl dialkoxy aryl phenyl) fluorenes classes of 9-{ for example 9,9-two { 4-[2-(2-hydroxyl-oxethyl) oxyethyl group]-3-phenyl } fluorenes etc. 9, two (the hydroxyl dialkoxy aryl phenyl) fluorenes of 9-, preferably 9, two [2-(2-hydroxyl-oxethyl) oxyethyl group aryl phenyl] fluorenes of 9-} etc.
Wherein, preferably 9, two (hydroxyl-oxethyl aryl phenyl) fluorenes of 9-etc.
As the compound reacting with the above-mentioned compound with fluorene skeleton, can use tetraprotic acid dianhydride.
As tetraprotic acid dianhydride, particularly, can example: ethylene-dimalonic acid dianhydride, pentane tetracarboxylic acid dianhydride, hexane tetracarboxylic acid dianhydride, tetramethylene tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, hexanaphthene tetracarboxylic acid dianhydride, suberane tetracarboxylic acid dianhydride, norbornane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, xenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, 5-(2, 5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic acid anhydride, 4-(2, 5-dioxo tetrahydrofuran (THF)-3-yl)-1, 2, 3, 4-tetraline-1, 2-dicarboxylic acid anhydride, naphthalene-1, 4, 5, 8-tetracarboxylic acid dianhydride, 4, 4 '-(hexafluoro isopropylidene) diphthalic anhydrides, 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-sulfobenzide tetracarboxylic acid dianhydride etc., can use one kind or two or more in them.Wherein, preferably pyromellitic acid dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid anhydride, benzophenone tetracarboxylic acid dianhydride, xenyl tetracarboxylic acid dianhydride.
Make above-mentioned compound and the tetraprotic acid dianhydride with fluorene skeleton carry out addition reaction, can obtain forming the macromolecular compound of photoresist of the present invention.In this addition reaction, the ratio that the relative 1mol of tetraprotic acid dianhydride has a compound of fluorene skeleton is preferably 0.5mol～1.5mol, 0.65mol～1.25mol more preferably.When the ratio of tetraprotic acid dianhydride is lower than 0.5mol and while exceeding 1.5mol, often can not get enough molecular weight.
In the time thering is the compound of fluorene skeleton and the addition reaction of tetraprotic acid dianhydride, also can use catalyzer.The catalyzer using is as long as promoting the material of reaction, just be not particularly limited, but as an example, can enumerate: pyridine, quinoline, imidazoles, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, accelerine, N, N-dimethyl benzyl amine, three (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0] nonene-5 amine such as grade; The quaternary ammonium compounds such as tetramethyl ammonium chloride, 4 bromide, trimethyl benzyl ammonia chloride, Tetramethylammonium hydroxide; Tributylphosphine, triphenylphosphine etc.; And their mixture.In addition, the amount of the catalyzer of use is also not particularly limited, but with respect to total amount 100 mass parts of compound and tetraprotic acid dianhydride with fluorene skeleton, the preferably scope of 0.1～2.0 mass parts.When the amount of catalyzer is during far away more than 2.0 mass parts, have and can electrical characteristic or storage stability to photoresist produce dysgenic situation.
In addition, in the time carrying out addition reaction, for solubilizing reaction raw material and reduction viscosity etc., also can use solvent.The kind of solvent only otherwise hinder reaction, is just not particularly limited, but as an example, can enumerates: the gylcol ethers such as ethylene glycol bisthioglycolate ethyl ether, diethylene glycol dimethyl ether; The glycol ether acetate classes such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary butyl ether acetic ester; The propylene glycol ethers such as dihydroxypropane single-ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, dipropylene glycol Anaesthetie Ether; The propylene glycol acetate esters such as propylene glycol monomethyl ether, propylene glycol list ethyl ether acetic ester, DPGME acetic ester, dihydroxypropane single-ethyl ether acetic ester; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; The acetate esters such as ethyl acetate, butylacetate; Dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE; And their mixture.
The amount of solvent using is also not particularly limited, but with respect to total amount 100 mass parts of compound and tetraprotic acid dianhydride with fluorene skeleton, the preferably scope of 25～150 mass parts.While being less than 25 mass parts, there is the situation that viscosity does not fully reduce.On the other hand, while exceeding 150 mass parts, have the concentration of reactant is too declined, thereby the situation of speed of response decline.
In the compound and tetraprotic acid dianhydride with fluorene skeleton, add solvent as required or catalyzer carries out addition reaction, but preferably heating in the time of reaction dissolves by heating raw, and also can fast reaction speed.Heating temperature can suitably be set according to having the compound of fluorene skeleton and the kind of tetraprotic acid dianhydride or the device of use, the scope that preferably approximately is 60～220 ℃.The more preferably scope of 90～160 ℃.When temperature of reaction is during lower than 60 ℃, often finish to need spended time to reaction.On the other hand, when temperature of reaction is during higher than 220 ℃, tend to occur the painted side reaction of Denging, maybe can there is the situation that causes reactivity to decline because of the balance of acid anhydrides closed loop.
By making by the macromolecular compound addition obtaining above, by carboxylic acid reaction (methyl) acrylic compound shown in following general formula (2), can to obtain photoresist of the present invention.
[changing 12]
(in formula, R
4represent hydrogen atom or methyl, R
5represent by the group shown in following general formula (5))
[changing 13]
(in formula, q, r, s represent respectively 0～9 integer independently.But q, r, s are 0 when different.)
As carboxylic acid reaction (methyl) acrylate by shown in above-mentioned general formula (2), specifically can enumerate: (methyl) vinylformic acid 2-hydroxyl ethyl ester glycidyl ether, (methyl) vinylformic acid 2-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 3-hydroxypropyl acrylate glycidyl ether, (methyl) vinylformic acid 4-hydroxy butyl ester glycidyl ether, polyethylene glycol-propylene glycol (methyl) acrylate glycidyl ether.
Make such carboxylic acid reaction (methyl) acrylic compound and above-mentioned macromolecular compound carry out addition reaction.The ratio of carboxylic acid reaction (methyl) acrylic compound in photoresist of the present invention is because of purposes difference, therefore cannot treat different things as the same, when for Photocurable coating agent and optical material, can make its acid number that is added to photoresist reach 0.On the other hand, in the time being applied to the purposes of alkali-developable, the scope that is preferably 30～150mgKOH/g according to the acid number of resin solids regulates.When acid number is during well below 30mgKOH/g, developing powder declines, and can have the situation that can not get the pattern needing.On the other hand, when acid number is during higher than 150mgKOH/g, become overdevelopment, the situation that can have that pattern is easily peeled off, electrical characteristic etc. also declines.And in this manual, the acid number of resin solids is the measured value based on JIS-K0070.
In the reacting of above-mentioned macromolecular compound and carboxylic acid reaction (methyl) acrylic compound, in order to promote reaction, can also use catalyzer.The kind of catalyzer is because of the kind difference of carboxylic acid reaction (methyl) acrylic compound, therefore cannot treat different things as the same, but as an example, can enumerate: pyridine, quinoline, imidazoles, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, accelerine, N, N-dimethyl benzyl amine, three (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicylo [5,4,0]-7-undecylene, 1,5-diazabicylo [4,3,0] nonene-5 amine such as grade; The quaternary ammonium compounds such as tetramethyl ammonium chloride, 4 bromide, trimethyl benzyl ammonia chloride, Tetramethylammonium hydroxide; Tributylphosphine, triphenylphosphine etc.; And their mixture.
In addition, the amount of the catalyzer of use is also not particularly limited, but with respect to described compound 100 mass parts with fluorene skeleton, is preferably the scope of 0.1～2.0 mass parts.In the time that the amount of catalyzer is too much, electrical characteristic or the storage stability that can have photoresist produce dysgenic situation.
In addition, in the time making the reaction of carboxylic acid reaction (methyl) acrylic compound, preferably add stopper.As long as suppressing the stopper of unsaturated link(age) reaction, the kind of stopper is just not particularly limited, but as an example, can enumerate: Resorcinol, hydroquinone monomethyl ether, Tert. Butyl Hydroquinone, tert-butyl catechol, (Wako Pure Chemical Industries, Ltd. produces: Q-1300) for N-methyl-N-nitrosoaniline or N-nitroso-group phenyl azanol ammonium salt, (Wako Pure Chemical Industries, Ltd. produces N-nitroso-group phenyl azanol aluminium salt: Q-1301), 2, 2, 6, 6-tetramethyl piperidine-1-oxygen base, 4-hydroxyl-2, 2, 6, 6-tetramethyl piperidine-1-oxygen base etc.Particularly preferably N-nitroso-group phenyl azanol aluminium salt, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base.The amount of stopper because of its kind and reaction conditions different, therefore cannot treat different things as the same, but with respect to whole photoresists, the preferably scope of 5～2000ppm.In the time being less than this scope, there is the situation that gelation occurs because of unsaturated link(age) reaction in the mill; When more than this scope, can there is the situation that light sensitivity declines, therefore not preferred.
In the time of addition carboxylic acid reaction (methyl) acrylic compound, for fast reaction speed, preferably heating.Heating temperature can suitably be set according to the kind of carboxylic acid reaction (methyl) acrylic compound and device, but is preferably the scope of about 60～150 ℃.When temperature of reaction is during lower than 60 ℃, often finish to need spended time to reaction.On the other hand, when temperature of reaction is during higher than 150 ℃, tend to have the painted side reaction that waits occurs, maybe can there is the situation that gelation occurs because of unsaturated link(age) reaction.
The molecular weight of the photoresist of the present invention so obtaining is not particularly limited, but considers from the viewpoint of coating strength, film-forming properties or developability, is preferably 1000～200000, more preferably 2500～50000.And in this manual, the molecular weight of photoresist is to have utilized the vinylbenzene conversion weight-average molecular weight of the GPC under record condition in embodiment.
Photosensitive polymer combination of the present invention contains above-mentioned photoresist and Photoepolymerizationinitiater initiater and/or photosensitizers as neccessary composition.This Photoepolymerizationinitiater initiater and/or photosensitizers can mix with the state being dissolved or dispersed in solvent, or also chemically combination of photoresist relatively.
As can be used for Photoepolymerizationinitiater initiater of the present invention and/or photosensitizers, be not particularly limited, for example can enumerate: benzophenone, 4-dihydroxy benaophenonel, two-N, N-dimethylamino benzophenone, two-N, the benzophenones such as N-diethylamino benzophenone, 4-methoxyl group-4 '-dimethylamino benzophenone, thioxanthone, 2, the thioxanthene ketones such as 4-diethyl thioxanthone, isopropyl thioxanthone, clopenthixal ketone, isopropoxy clopenthixal ketone, EAQ, benzo anthraquinone, aminoanthraquinone, chloroanthraquinone, anthraquinone-2-sulfonic acid salt, anthraquinone-2, the Anthraquinones such as 6-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, acetophenones, the benzoin ethers such as benzoin methylether, ethoxybenzoin, bitter almond oil camphor phenylate, 2,4,6-trihalomethyl group triazines, 1-hydroxycyclohexylphenylketone, 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4, 5-bis-(m-methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4, 5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4, 5-diphenyl-imidazole dimer, 2, 4-bis-(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, 4-Dimethoxyphenyl)-4, 5-diphenyl-imidazole dimer etc. 2, 4, 5-triarylimidazoles dimer class, benzyl dimethyl ketal, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-1-acetone, 2-hydroxy-2-methyl-1-phenyl-propyl-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone, 1,2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(O-benzoyl oxime)], phenanthrenequione, 9, the bitter almond oil camphor classes such as 10-phenanthrenequione, methylbenzene acyloin, ethylbenzene acyloin, 9-phenylacridine, 1, the acridine derivatives such as two (9, the 9 '-acridyl) heptane of 7-, two acylphosphine oxides, can use one kind or two or more in them.
In photoresist of the present invention, also can further add promotor.As the example of promotor, can enumerate: ESCAROL 507 ethyl ester, ESCAROL 507 isopentyl ester, N, N-dimethylethanolamine, N methyldiethanol amine, trolamine etc.
In photosensitive polymer combination of the present invention, the polymerizable monomer (being sometimes only called below " polymerizable monomer ") in molecule with more than 1 unsaturated group can be further used, light sensitivity, resistance to chemical reagents, thermotolerance and physical strength can be improved thus.In addition, in order to regulate flow characteristics etc., also can add polymerizable monomer.As this polymerizable monomer, as long as thering is the monomer of more than 1 unsaturated link(age) in molecule, can use without particular limitation, select suitable monomer according to purposes, the object of application.For example can example: polyoxyethylene glycol two (methyl) acrylate (ethylidene number is 2～14), TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, TriMethylolPropane(TMP) oxyethyl group three (methyl) acrylate, TriMethylolPropane(TMP) propoxy-three (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, polypropylene glycol two (methyl) acrylate (propylidene number is 2～14), Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, bisphenol A polyethenoxy two (methyl) acrylate, dihydroxyphenyl propane dioxy ethene two (methyl) acrylate, dihydroxyphenyl propane three oxygen ethene two (methyl) acrylate, dihydroxyphenyl propane ten oxygen ethene two (methyl) acrylate, polycarboxylic acid (Tetra hydro Phthalic anhydride etc.) and the carboxylate of compound ((methyl) propenoic acid beta-hydroxy ethyl ester etc.) with hydroxyl and ethylenic unsaturated group, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) alkyl acrylates such as (methyl) 2-EHA, (methyl) vinylformic acid affixture of the epoxy compoundss such as ethylene glycol diglycidylether, glycol ether diglycidylether, Triethylene Glycol Diglycidyl Ether, TEG diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, dipropylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, four propylene glycol diglycidylethers, polypropylene glycol diglycidyl ether, Sorbitol Powder triglycidyl ether, glycerin triglycidyl ether, the unsaturated organic acids such as toxilic acid and acid anhydrides thereof, N methacrylamide, N-ethyl acrylamide, NIPA, N hydroxymethyl acrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, N-isopropyl methyl acrylamide, N-methylol methacrylamide, N, N-DMAA, N, N-diethyl acrylamide, N, N-dimethylmethacryl amide, N, the acrylic amides such as N-diethylmethyl acrylamide, the styrenic such as vinylbenzene, hydroxy styrenes, NVP, N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole etc., can use one kind or two or more in them.
In photosensitive polymer combination of the present invention, for the anti-ring of designability, visibility and photo-resist is dizzy etc., can also add tinting material.The kind of the tinting material adding can suitably be selected according to painted object, for example can example: phthalocyanine based dye, anthraquinone based dye, azo based dye, indigo based dye, coumarin series dyestuff, triphenyl methane based dye, phthualocyanine pigment, anthraquione pigmentss, azo pigment, quinacridone pigment, coumarin series pigment, triphenyl methane series pigments etc., can use one kind or two or more in them.
Photosensitive polymer combination of the present invention can be made the form of the paste that solution or filler etc. are mixed, and therefore can also contain solvent.The kind of the solvent using is not particularly limited, but as an example, can enumerate: the glycols such as water, ethylene glycol, glycol ether, triethylene glycol, TEG; The gylcol ethers such as ethylene glycol monomethyl ether, diglycol monotertiary methyl ether, ethylene glycol bisthioglycolate ethyl ether, diethylene glycol dimethyl ether; The glycol ether acetate classes such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diglycol monotertiary butyl ether acetic ester; The propandiolses such as propylene glycol, dipropylene glycol, tripropylene glycol; The propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol list ethyl ether, DPGME, dihydroxypropane single-ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, dipropylene glycol Anaesthetie Ether; The propylene glycol acetate esters such as propylene glycol monomethyl ether, propylene glycol list ethyl ether acetic ester, DPGME acetic ester, dihydroxypropane single-ethyl ether acetic ester; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; The lactic acid ester such as methyl lactate, ethyl lactate; The acetate esters such as ethyl acetate, butylacetate, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE; And their mixture.
In photosensitive polymer combination of the present invention, can further mix as required the known composition in the past such as stopper, softening agent, defoamer, coupling agent.
Photosensitive polymer combination of the present invention can become to assign to obtain arbitrarily by mix above-mentioned neccessary composition and solvent as required or other according to ordinary method.
When photosensitive polymer combination of the present invention according to obtaining is above used as to photo-resist, set it as solution or paste coating in substrate.Coating method is not particularly limited, but can apply silk screen printing, curtain coating, scraper coating, spin coating, spraying, proofing coating, slit coating etc.For the solution having applied or paste, can expose with UV or electron beam by the mask of regulation.While using solvent coating, can pass through drying process.By the film having exposed is developed with wet type, can form pattern.For developing method, spraying type, puddle (パ De Le, puddle) formula, impregnated etc. all can, the preferably few spraying type of residue.Also can irradiate as required ultrasonic wave etc.As developing solution, preferably use alkalescent water.For auxiliary developability, can also add organic solvent, tensio-active agent, defoamer etc.
Embodiment
Below utilize embodiment to explain the present invention, but the present invention is not subject to any restriction of these embodiment.
Embodiment 1
In the 1000ml flask that is provided with agitator and prolong, add pyromellitic acid dianhydride (ダ イ セ Le society product: PMDA) 64g, 9, (Osaka ガ ス ケ ミ カ Le society manufactures two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-: BPEF) 136g, propylene glycol monomethyl ether 134g, under nitrogen gas stream, the oil bath with 155 ℃ is heated 4 hours while stirring.Then be cooled to after 120 ℃, add 4-dimethylaminopyridine 1g, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (ADEKA society product: ア デ カ ス タ Block LA-7RD) 0.04g, vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into society's product: 4HBAGE) 106g, stir 4 hours at 120 ℃.Next be cooled to room temperature, add propylene glycol monomethyl ether so that nonvolatile component reaches 50 quality %, obtain photoresist (A1) solution of faint yellow transparent toughness.
For the resin solution obtaining, to measure viscosity, utilized vinylbenzene conversion weight-average molecular weight and the solid of GPC to divide acid number, viscosity is 2900mPas/25 ℃, and utilizing the vinylbenzene conversion weight-average molecular weight of GPC is 12523, and it is 2.2mgKOH/g that solid divides acid number.And, the BM type viscometer that viscosimetric analysis has been used Toki Sangyo Co., Ltd. to manufacture.In addition, measure for GPC, 2 of TSKgel G7000HXL, the TSKgel GMHXL, the TSKgel G2500HXL that use TOSOH Co., Ltd to manufacture are chromatographic column, under 40 ℃ of THF eluants, 0.5ml/min flow velocity, measure.Measure acid number based on the neutralization titration of recording in JIS-K0070.
Embodiment 2
In the 1000ml flask that is provided with agitator and prolong, add xenyl tetracarboxylic acid dianhydride (Yu Buxingchan society product: BPDA) 72g, 9, two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-(Osaka ガ ス ケ ミ カ Le society produces: BPEF) 128g, 4-dimethylaminopyridine 1g, propylene glycol monomethyl ether 134g heated 4 hours with the oil bath of 155 ℃ while stirring under nitrogen gas stream.Then, be cooled to after 120 ℃, add 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (ADEKA company product: ア デ カ ス タ Block LA-7RD) 0.04g, vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into company's product: 4HBAGE) 84g, stirred 4 hours at 120 ℃.Then, be cooled to room temperature, add propylene glycol monomethyl ether so that nonvolatile component reaches 50 quality %, obtain photoresist (A2) solution of faint yellow transparent toughness.For the resin solution obtaining, to measure viscosity, utilized vinylbenzene conversion weight-average molecular weight and the solid of GPC to divide acid number, viscosity is 4200mPas/25 ℃, and utilizing the vinylbenzene conversion weight-average molecular weight of GPC is 7243, and it is 2.5mgKOH/g that solid divides acid number.
Comparative example 1
The synthesis example 1 of recording according to Unexamined Patent 4-325508 communique has obtained photoresist (A3).
Use the photoresist of embodiment 1～2 and comparative example 1, form photosensitive composite with the composition of table 1.Be coated with machine with rod this photosensitive composite is coated on to the soda-lime glass substrate that 1.1mm is thick so that dry film thickness becomes 6 μ m, make, after its dry 10 minutes, to be cooled to room temperature with the hot air dryer of 80 ℃.Then,, with ultrahigh pressure mercury lamp UV irradiating machine, irradiating integration light quantity is 300mJ/cm
2ultraviolet ray.For this cured coating film, implement pencil hardness and draw lattice-belt stripping test according to JIS-K5400, evaluate painting film strength.
[table 1]
* 1IRGACURE184 (production of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le society)
* 2 dipentaerythritol acrylates (Japanese chemical drug society produce)
* 3 propylene glycol monomethyl ether
Use the photosensitive composite of photoresist of comparative example 1 because molecular weight is low, therefore, a little less than film formation ability, if do not add other resinous principles, cannot evaluate.Used the photosensitive composite of the photoresist of embodiment 1～2 to obtain level and smooth film, and hardness, adaptation are all good.
Embodiment 7
In the 1000ml flask that is provided with agitator and prolong, add pyromellitic acid dianhydride (ダ イ セ Le society product: PMDA) 76g, 9, (Osaka ガ ス ケ ミ カ Le society manufactures two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-: BPEF) 124g, propylene glycol monomethyl ether 134g, under nitrogen gas stream, the oil bath with 155 ℃ is heated 4 hours while stirring.Then, be cooled to after 120 ℃, add 4-dimethylaminopyridine 1g, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (ADEKA company product: ア デ カ ス タ Block LA-7RD) 0.04g, vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into company's product: 4HBAGE) 106g, stirred 2 hours at 120 ℃.Then, be cooled to room temperature, add propylene glycol monomethyl ether so that nonvolatile component reaches 50 quality %, obtain photoresist (A4) solution of faint yellow transparent toughness.
For the resin solution obtaining, to measure viscosity, utilized vinylbenzene conversion weight-average molecular weight and the solid of GPC to divide acid number, viscosity is 4800mPas/25 ℃, and utilizing the vinylbenzene conversion weight-average molecular weight of GPC is 23169, and it is 75.2mgKOH/g that solid divides acid number.
Embodiment 8
In the 1000ml flask that is provided with agitator and prolong, add xenyl tetracarboxylic acid dianhydride (Yu Buxingchan society product: BPDA) 90g, 9, two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-(Osaka ガ ス ケ ミ カ Le society manufactures: BPEF) 110g, propylene glycol monomethyl ether 134g, 4-dimethylaminopyridine 1g heated 4 hours with the oil bath of 155 ℃ while stirring under nitrogen gas stream.Then, be cooled to after 120 ℃, add 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (ADEKA company product: ア デ カ ス タ Block LA-7RD) 0.04g, vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into society's product: 4HBAGE) 80g, stirred 2 hours at 120 ℃.Then, be cooled to room temperature, add propylene glycol monomethyl ether so that nonvolatile component reaches 50 quality %, obtain photoresist (A5) solution of faint yellow transparent toughness.
For the resin solution obtaining, to measure viscosity, utilized vinylbenzene conversion weight-average molecular weight and the solid of GPC to divide acid number, viscosity is 6600mPas/25 ℃, and utilizing the vinylbenzene conversion weight-average molecular weight of GPC is 18230, and it is 71.6mgKOH/g that solid divides acid number.
Comparative example 4
Use the bisphenol fluorene type epoxy resin (Osaka ガ ス ケ ミ カ Le society product: BPFG) that epoxy equivalent (weight) is 257, the synthesis example 1 and the embodiment 1 that record according to No. 3813244 communique of special permission have obtained photoresist (A6).Synthetic needs more than 20 hours, compared with embodiments of the invention 1～4, productivity is significantly low.
Comparative example 5
Use the bisphenol fluorene type epoxy resin (Osaka ガ ス ケ ミ カ Le society product: BPFG) that epoxy equivalent (weight) is 257, the synthesis example 1 and the embodiment 2 that record according to No. 3813244 communique of special permission have obtained photoresist (A7).Synthetic needs more than 21 hours, compared with embodiment 8 with embodiments of the invention 7, and productivity is significantly low.
Comparative example 6
Except the vinylformic acid 4-hydroxy butyl ester glycidyl ether 80g of embodiment 8 being replaced with to glycidyl methacrylate (レ イ ヨ Application society of Mitsubishi product: GMA) 60g, similarly react, obtained photoresist solution (A8).For the resin solution obtaining, to measure viscosity, utilized vinylbenzene conversion weight-average molecular weight and the solid of GPC to divide acid number, viscosity is 12400mPas/25 ℃, utilize the vinylbenzene conversion weight-average molecular weight of GPC is 16100, it is 74.2mgKOH/g that solid divides acid number.
Test example 1
For the photoresist of embodiment 7～8 and comparative example 4～5, be determined at the polystyrene conversion weight-average molecular weight of utilizing GPC after 1 month after firm manufacture and in room temperature preservation, study its velocity of variation.The results are shown in table 2.
[table 2]
For the photoresist of embodiment 7～8, substantially do not observe variation, but for the photoresist of comparative example 2～3, observing molecular weight increases by 25% left and right, its storage stability is poor.
Embodiment 9～12 and comparative example 7～12
Use the photoresist of embodiment 7～8 and comparative example 4～6, the cooperation of according to the form below 3 forms photosensitive composite.This photosensitive composite is coated on to the soda-lime glass substrate that 1.1mm is thick so that its dry film thickness becomes 3 μ m with spin coater, makes, after its dry 90 seconds, to be cooled to room temperature with the hot plate of 100 ℃.Next be, 15mW/cm with ultrahigh pressure mercury lamp exposure machine in ultraviolet illumination
2(365nm), integration light quantity is 20mJ/cm
2under, carry out take UGRA-OFFSET-TESTKAIL1982 as mask after soft contact exposure, immersion development 90 seconds in the 1% sodium carbonate water of 25 ℃, thus form pattern, evaluate light sensitivity with (Step) hop count of residual stage, evaluate resolving power with hachure.Result is shown in table 3 together.
[table 3]
* 4IRGACURE OXE-01 (manufacture of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le society)
Compared with having used the photosensitive composite of photoresist (A6～A8) of comparative example 4～6, use the light sensitivity of photosensitive composite of the photoresist of embodiment 7～8 (A4～A5) high, demonstrate good characteristic against corrosion.
Embodiment 13
In the 1000ml flask that is provided with agitator and prolong, add 3,3 '-4,4 ' xenyl tetracarboxylic acid anhydride (produce: BPDA) 71.8g, 9 by the emerging generation of space portion, two [4-(2-hydroxyl-oxethyl) 3-phenyl] fluorenes of 9-(Osaka ガ ス ケ ミ カ Le society produces: BOPPEF) 109.7g, propylene glycol monomethyl ether 128g, 4-dimethylaminopyridine 0.25g, has heated 4 hours with the mantle heater of 120 ℃ while stirring.Then, add p methoxy phenol (Tokyo changes into production) 0.1g, Hydroxyethyl acrylate (Tokyo changes into production) 13.7g, heated 4 hours at 120 ℃.Further add vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into company's product: 4HBAGE) 34.68g, 120 ℃ of heated and stirred 4 hours, obtain photoresist (A9) solution of faint yellow transparent toughness.
For the resin solution obtaining, measure viscosity, utilize vinylbenzene conversion weight-average molecular weight, the solid of GPC to divide and solid divides acid number, viscosity is 187100mPas/25 ℃, utilize that the vinylbenzene conversion weight-average molecular weight of GPC is 4170, solid is divided into 66.8%, solid divides acid number for 85.4mgKOH/g.
Embodiment 14
In the 1000ml flask that is provided with agitator and prolong, add 3,3 '-4,4 ' xenyl tetracarboxylic acid anhydride (produce: BPDA) 61.22g, 9 by the emerging generation of space portion, two [6-(2-hydroxyl-oxethyl) naphthyl] fluorenes of 9-(Osaka ガ ス ケ ミ カ Le society produces: BNFEO) 95.89g, propylene glycol monomethyl ether 125g, 4-dimethylaminopyridine 0.25g, has heated 4 hours with the mantle heater of 120 ℃ while stirring.Then add p methoxy phenol (Tokyo changes into production) 0.1g, Hydroxyethyl acrylate (Tokyo changes into production) 13.3g, heated 4 hours at 120 ℃.Further add vinylformic acid 4-hydroxy butyl ester glycidyl ether (Japan changes into society's product: 4HBAGE) 56g, 120 ℃ of heated and stirred 4 hours, obtain photoresist (A10) solution of faint yellow transparent toughness.
For the resin solution obtaining, measure viscosity, utilize vinylbenzene conversion weight-average molecular weight, the solid of GPC to divide and solid divides acid number, viscosity is 586700mPas/25 ℃, utilize that the vinylbenzene conversion weight-average molecular weight of GPC is 9250, solid is divided into 59.0%, solid divides acid number for 60.4mgKOH/g.
Embodiment 15～16
The photoresist that uses embodiment 13, has formed photosensitive composite with the cooperation of table 4.For this photosensitive composite, carry out the evaluation same with embodiment 9～12.
[table 4]
The light sensitivity of any one photosensitive composite is all high, and demonstrates good characteristic against corrosion.
The possibility of industrial application
Photoresist of the present invention can easily be manufactured with low cost, and the adjusting of cross-linking density or acid number is easy, and has the excellent characteristic such as high heat resistance, high transparent, high refractive index and low linear expansion coefficient.Thereby, use the resin combination of this photoresist to can be used for preparing interlayer dielectric or the protective membrane (interlayer dielectric or the protective membrane that such as, use in colour filter, liquid crystal display device, integrated circuit component, solid-state imaging element etc.) etc. in liquid-crystal display or electronic unit etc.
Claims (7)
1. photoresist, it is characterized in that, it is to make to be reacted take the ratio of the compound with fluorene skeleton with respect to 1mol, tetraprotic acid dianhydride as the mol ratio of 0.5～1.5mol by the compound with fluorene skeleton shown in following general formula (1) and tetraprotic acid dianhydride the photoresist that the macromolecular compound addition that obtains is obtained by carboxylic acid reaction (methyl) acrylic compound shown in following general formula (2)
In formula, Z
1ring and Z
2ring represents benzene or naphthalene, R
1aand R
1brepresent hydrogen atom or alkyl, R
2aand R
2brepresent to be selected from C
6-8aryl or C
1-6the substituting group of alkyl, R
3aand R
3brepresent hydrogen atom or methyl, k1 and k2 are that 0, m1 and m2 are identical or different, and represent 0～3 integer, and n1 and n2 are identical or different, and represent that 0～10 integer, p1 and p2 are 1;
In formula, R
4represent hydrogen atom or methyl, R
5represent by the group shown in following general formula (5);
In formula, q, r, s represent respectively 0～9 integer independently, but q, r, s are 0 when different.
2. photoresist as claimed in claim 1, wherein, by the compound shown in following general formula (3) of serving as reasons of the compound with fluorene skeleton shown in described general formula (1),
In formula, R
1aand R
1brepresent hydrogen atom or alkyl, R
2a, R
2b, R
6aand R
6brepresent to be selected from C
6-8aryl or C
1-6the substituting group of alkyl, R
3aand R
3brepresent hydrogen atom or methyl, k1 and k2 are that 0, m1, m2, m3 and m4 are identical or different, and represent 0～3 integer, and n1, n2, n3 and n4 are identical or different, and represent that 0～10 integer, p1 and p2 are that 1, p3 and p4 are 0.
3. photoresist as claimed in claim 1, wherein, the compound shown in following general formula (4) of serving as reasons of the compound with fluorene skeleton shown in described general formula (1),
In formula, R
1aand R
1brepresent hydrogen atom or alkyl, R
2a, R
2b, R
7aand R
7brepresent to be selected from C
6-8aryl or C
1-6the substituting group of alkyl, R
3aand R
3brepresent hydrogen atom or methyl; K1 and k2 are that 0, n1 and n2 are identical or different, and represent that 0～10 integer, p1 and p2 are 1.
4. the photoresist as described in any one in claim 1～3, wherein, the R in described general formula
2aand R
2bfor phenyl.
5. the photoresist as described in any one in claim 1～4, its acid number is 30～150mgKOH/g.
6. photosensitive polymer combination, is characterized in that, it contains the photoresist described in any one and Photoepolymerizationinitiater initiater and/or photosensitizers in claim 1～5.
7. photosensitive polymer combination as claimed in claim 6, wherein also contains the polymerizable monomer in molecule with more than 1 unsaturated group.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-078692 | 2008-03-25 | ||
| JP2008078692 | 2008-03-25 | ||
| PCT/JP2009/055877 WO2009119622A1 (en) | 2008-03-25 | 2009-03-25 | Photosensitive resin and photosensitive resin composition comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101965375A CN101965375A (en) | 2011-02-02 |
| CN101965375B true CN101965375B (en) | 2014-05-28 |
Family
ID=41113814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980107328.0A Active CN101965375B (en) | 2008-03-25 | 2009-03-25 | Photosensitive resin and photosensitive resin composition comprising the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4733231B2 (en) |
| KR (1) | KR101254054B1 (en) |
| CN (1) | CN101965375B (en) |
| TW (1) | TWI384008B (en) |
| WO (1) | WO2009119622A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5469517B2 (en) * | 2010-04-12 | 2014-04-16 | 大阪ガスケミカル株式会社 | Polyester resin having fluorene skeleton and method for producing the same |
| JP5859280B2 (en) * | 2011-11-14 | 2016-02-10 | 新日鉄住金化学株式会社 | Photosensitive material, holographic recording medium, and holographic recording method |
| JP6175259B2 (en) * | 2012-03-26 | 2017-08-02 | 大阪ガスケミカル株式会社 | Acid anhydride-modified fluorene-containing acrylic resin and method for producing the same |
| JP6031807B2 (en) * | 2012-04-13 | 2016-11-24 | Jsr株式会社 | Coloring composition, color filter and display element |
| JP5838923B2 (en) * | 2012-06-22 | 2016-01-06 | Jsr株式会社 | Coloring composition, color filter and display element |
| TWI568802B (en) * | 2012-04-13 | 2017-02-01 | Jsr股份有限公司 | Colored composition, color filter, and display element |
| JP6123620B2 (en) * | 2013-09-30 | 2017-05-10 | Jsr株式会社 | Radiation-sensitive resin composition, display element insulating film, method for forming the same, and display element |
| JP2015069181A (en) * | 2013-09-30 | 2015-04-13 | Jsr株式会社 | Radiation-sensitive resin composition, cured film, method for forming the same and display element |
| CN103980473B (en) * | 2014-05-27 | 2016-03-02 | 张家港康得新光电材料有限公司 | Containing the polyester acrylate oligomers and its preparation method and application of fluorenes |
| CN103980472B (en) * | 2014-05-27 | 2016-03-02 | 张家港康得新光电材料有限公司 | Containing the epoxy acrylate oligomer and its preparation method and application of fluorenes |
| JP6487308B2 (en) * | 2014-10-20 | 2019-03-20 | 大阪ガスケミカル株式会社 | Polyester poly (meth) acrylate having fluorene skeleton, curable composition and cured product thereof, and production method thereof |
| JP6677535B2 (en) * | 2015-03-04 | 2020-04-08 | 大阪ガスケミカル株式会社 | Curable composition, cured product thereof, and method for improving hardness |
| JP6588719B2 (en) * | 2015-03-30 | 2019-10-09 | 日鉄ケミカル＆マテリアル株式会社 | Photosensitive material, holographic recording medium, and holographic recording method |
| JP6599785B2 (en) * | 2016-02-04 | 2019-10-30 | 大阪ガスケミカル株式会社 | Carboxyl group-containing fluorene polyester resin and method for producing the same |
| JP6875929B2 (en) * | 2016-06-02 | 2021-05-26 | 大阪ガスケミカル株式会社 | Photosensitive resin composition |
| CN106397752B (en) * | 2016-10-14 | 2019-03-29 | 常州强力电子新材料股份有限公司 | Photoresist, preparation method containing fluorenes and the Photocurable composition and photoresist with it |
| KR102227606B1 (en) | 2018-04-06 | 2021-03-12 | 주식회사 엘지화학 | Cardo-based binder resin, photo-sensitive resin composition comprising the same, black matrix, color filter and display device |
| EP3932972A4 (en) * | 2019-02-27 | 2022-03-02 | Teijin Limited | Thermoplastic resin and optical member |
| CN112694557B (en) * | 2019-10-23 | 2022-05-10 | 常州强力先端电子材料有限公司 | Photocurable resin, photocurable resin composition, and black matrix material |
| CN115368583B (en) * | 2021-05-18 | 2024-04-09 | 常州强力先端电子材料有限公司 | Multi-branched polymer, alkali-soluble resin, and photocurable composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005048144A (en) * | 2003-07-31 | 2005-02-24 | Fuji Photo Film Co Ltd | Polymerizable composition |
| CN1711295A (en) * | 2002-11-14 | 2005-12-21 | 东洋合成工业株式会社 | Photosensitive resin composition and process for the formation of hydrogel |
| WO2006025236A1 (en) * | 2004-09-03 | 2006-03-09 | Toyo Boseki Kabushiki Kaisha | Active ray-curable hyperbranched polymer and active ray-curable resin composition using same |
| CN1890206A (en) * | 2003-10-01 | 2007-01-03 | 大阪瓦斯株式会社 | Multifunctional (meth)acrylate and method for producing same |
| CN101018824A (en) * | 2004-07-15 | 2007-08-15 | 帝人化成株式会社 | Resin composition and molded object thereof |
| CN101048679A (en) * | 2004-10-21 | 2007-10-03 | 大阪瓦斯株式会社 | Infrared absorbing filter |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100359217B1 (en) * | 2000-12-18 | 2002-11-04 | 제일모직주식회사 | Photosensitive resin composition for overcoating CCD color filter and the CCD color filter |
| JP4776899B2 (en) * | 2003-07-31 | 2011-09-21 | 富士フイルム株式会社 | Planographic printing plate precursor |
| JP4727344B2 (en) * | 2005-06-09 | 2011-07-20 | 東京応化工業株式会社 | Photosensitive composition |
| TW200801068A (en) * | 2006-04-11 | 2008-01-01 | Wako Pure Chem Ind Ltd | Polymerizable unsaturated compound and method for producing the same |
| JP4936448B2 (en) * | 2007-01-29 | 2012-05-23 | 花王株式会社 | Polyester for toner |
| JP2008214451A (en) * | 2007-03-02 | 2008-09-18 | Teijin Fibers Ltd | Aromatic copolyester |
-
2009
- 2009-03-25 CN CN200980107328.0A patent/CN101965375B/en active Active
- 2009-03-25 KR KR1020107022039A patent/KR101254054B1/en active IP Right Grant
- 2009-03-25 WO PCT/JP2009/055877 patent/WO2009119622A1/en active Application Filing
- 2009-03-25 TW TW98109756A patent/TWI384008B/en active
- 2009-03-25 JP JP2010505696A patent/JP4733231B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711295A (en) * | 2002-11-14 | 2005-12-21 | 东洋合成工业株式会社 | Photosensitive resin composition and process for the formation of hydrogel |
| JP2005048144A (en) * | 2003-07-31 | 2005-02-24 | Fuji Photo Film Co Ltd | Polymerizable composition |
| CN1890206A (en) * | 2003-10-01 | 2007-01-03 | 大阪瓦斯株式会社 | Multifunctional (meth)acrylate and method for producing same |
| CN101018824A (en) * | 2004-07-15 | 2007-08-15 | 帝人化成株式会社 | Resin composition and molded object thereof |
| WO2006025236A1 (en) * | 2004-09-03 | 2006-03-09 | Toyo Boseki Kabushiki Kaisha | Active ray-curable hyperbranched polymer and active ray-curable resin composition using same |
| CN101048679A (en) * | 2004-10-21 | 2007-10-03 | 大阪瓦斯株式会社 | Infrared absorbing filter |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI384008B (en) | 2013-02-01 |
| KR101254054B1 (en) | 2013-04-12 |
| CN101965375A (en) | 2011-02-02 |
| JPWO2009119622A1 (en) | 2011-07-28 |
| KR20110013363A (en) | 2011-02-09 |
| JP4733231B2 (en) | 2011-07-27 |
| TW201003310A (en) | 2010-01-16 |
| WO2009119622A1 (en) | 2009-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101965375B (en) | Photosensitive resin and photosensitive resin composition comprising the same | |
| TWI667534B (en) | Photosensitive composition for forming a shading screen, a light shielding screen, and a display device | |
| TWI577747B (en) | Colorant dispersion | |
| CN106574125B (en) | Color material dispersion liquid, colored resin composition for color filter, and display device | |
| JP6157193B2 (en) | (Meth) acrylate polymer, composition containing the polymer and use thereof | |
| KR101038692B1 (en) | Photosensitive resin composition and color filter using the same | |
| CN103172626B (en) | dye compound | |
| TWI820050B (en) | Photosensitive coloring composition for color filter, and color filter | |
| TWI612104B (en) | Colorant, coloring composition for color filter, color filter and display element | |
| TW201214045A (en) | Coloring composition, color filter, and display element | |
| CN103869617B (en) | Active energy ray-curable resin composition and the display element spacer and/or protective films of color filters for using it | |
| TW201144390A (en) | Coloring composition for use in color filter and color filter | |
| TW201406801A (en) | Curable composition, curable film and display element | |
| KR20130016045A (en) | Polymer compounds comprising dye and curable resin composition comprising the same | |
| CN106471398B (en) | Join carbazole compound, Photocurable composition, its solidfied material, solidification compound and plastic lens for plastic lens | |
| TW200902579A (en) | Colored photosensitive composition | |
| JP6031807B2 (en) | Coloring composition, color filter and display element | |
| TW201040151A (en) | Coloring composition, color filter, and color liquid crystal display element | |
| JP2017115163A (en) | Polymer, photosensitive composition, pattern formation method and color filter | |
| KR102674718B1 (en) | Black photosensitive resin composition and black column spacer prepared therefrom | |
| CN103901720A (en) | Active energy ray-cured resin compound, and coloring partition and black matrix for display element | |
| TW201738281A (en) | Coloring composition, colored cured film, display element, and solid-state imaging element | |
| CN105384728A (en) | Ethylene carboxylic acid ester compound, resin composition containing the ethylene carboxylic acid ester compound and hardened materials of the resin composition | |
| KR102344248B1 (en) | Resin, photosensitive resin composition, cured resin film and image display device | |
| CN101970532A (en) | Photosensitive resin and photosensitive resin composition comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160829 Address after: Osaka Patentee after: Osaka Gas Co., Ltd. Address before: Tokyo, Japan Patentee before: Soken Chemical & Engineering Co., Ltd. Patentee before: Osaka Gas Co., Ltd. |