CN104246609A - Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device - Google Patents

Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device Download PDF

Info

Publication number
CN104246609A
CN104246609A CN201380021084.0A CN201380021084A CN104246609A CN 104246609 A CN104246609 A CN 104246609A CN 201380021084 A CN201380021084 A CN 201380021084A CN 104246609 A CN104246609 A CN 104246609A
Authority
CN
China
Prior art keywords
methyl
acid
compound
ester
acrylate
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.)
Pending
Application number
CN201380021084.0A
Other languages
Chinese (zh)
Inventor
龟山泰弘
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.)
Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Kasei Corp
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 Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Publication of CN104246609A publication Critical patent/CN104246609A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention addresses the problem of providing a photosensitive resin composition which has a good balance between dielectric constant and high resolution that are usually in a trade-off relationship, while having high transmittance and high sensitivity. The present invention also addresses the problem of providing: a cured product that is formed using the above-described photosensitive resin composition; an interlayer insulating film that contains the cured product; a TFT active matrix substrate that comprises the interlayer insulating film; and a liquid crystal display device. The present invention is a photosensitive resin composition which contains (A) fine barium titanate particles, (B) fine zirconium oxide particles and (C) an alkali-soluble resin.

Description

Photosensitive polymer combination, solidfied material, interlayer dielectric, TFT active array base plate and liquid crystal indicator
Technical field
The present invention relates to a kind of photosensitive polymer combination.More specifically, the photosensitive polymer combination that the interlayer dielectric of a kind of scolding tin resist film for being formed in such as printed wiring board, liquid crystal display cells, plasma scope, large scale integrated circuit, thin type transistor, semiconductor package part, color filter, organic electroluminescent device etc. or coverlay and various electronic unit is useful is related to.
In addition, the present invention relates to a kind of photosensitive polymer combination useful as color filter purposes, black matrix" purposes, protective seam purposes, reinforcement purposes and spacer purposes for liquid crystal panels such as liquid crystal display.
Background technology
In the past, in the TFT active array base plate used in liquid crystal indicator, between grid and source electrode, drain electrode, form interlayer dielectric.At this, in this interlayer dielectric, employ the inorganic material of the high-ks such as silicon nitride.But, when these inorganic material are used as interlayer dielectric, need vacuum film formation apparatus when film is formed, therefore, there is the problem of manufacturing cost rising and productive capacity aspect.In addition, there are the following problems: in order to form the contact hole with the electrode being positioned at formed interlayer dielectric lower floor, needs after the photoetching process operation through employing etching resist, this etching resist is peeled off, process number increases, and therefore, manufacturing cost raises.
In order to solve the problem, requirement can not used by coating vacuum plant to form film and can form the interlayer dielectric of the high-k of contact hole by means of only exposing, developing.
As the photosensitive polymer combination of high-k, the known photosensitive polymer combination (such as with reference to patent documentation 1 ~ 3) formed containing inorganic particles in photosensitive polymer combination.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-365794 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-365796 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-57811 publication
Summary of the invention
The problem that invention will solve
But, for the photosensitive polymer combination described in patent documentation 1 ~ 3, except high-k, particularly required in TFT active array base plate purposes high resolution, high-transmission rate, highly sensitively require that performance all can not be met sometimes.
What the present inventor etc. conducted in-depth research found that: in order to carry out high-k further, must increase the content of inorganic particles, but when this content increases, the alkali-developable of photosensitive polymer combination is deteriorated, result, and resolving power reduces.
That is, there is the relation of compromise selection in the high-k of inorganic particles and resolving power.
The present invention completes in view of the foregoing, its problem is, thering is provided one to have both specific inductive capacity and high resolution, and have high-transmission rate and highly sensitive photosensitive polymer combination, there is the relation of compromise selection in wherein said specific inductive capacity and high resolution.
In addition, problem of the present invention is, provides a kind of and uses above-mentioned photosensitive polymer combination and the solidfied material, the interlayer dielectric containing this solidfied material, the TFT active array base plate containing this interlayer dielectric and the liquid crystal indicator that are formed.
The method of dealing with problems
The present inventor etc. study further to above-mentioned problem, found that: by combining specific inorganic particles, can solve above-mentioned problem, thus completing the present invention.
That is, the invention reside in following photosensitive polymer combination, solidfied material, interlayer dielectric, TFT active array base plate and liquid crystal indicator.
[1] photosensitive polymer combination, it contains: (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin.
[2] photosensitive polymer combination described in above-mentioned [1], wherein, the average primary particle diameter of (A) barium titanate microparticles and (B) zirconia particles is more than 1nm, below 1000nm independently of one another.
[3] above-mentioned [1] or the photosensitive polymer combination described in [2], it also contains: (D) has compound and (E) Photoepolymerizationinitiater initiater of ethylenically unsaturated group.
[4] solidfied material, its photosensitive polymer combination according to any one of use above-mentioned [1] ~ [3] is formed.
[5] interlayer dielectric, it contains the solidfied material described in above-mentioned [4].
[6] a TFT active array base plate, it has the interlayer dielectric described in above-mentioned [5].
[7] liquid crystal indicator, it has the TFT active array base plate described in above-mentioned [6].
The effect of invention
The present invention completes in view of the foregoing, and one can be provided to have both specific inductive capacity and high resolution, and has high-transmission rate and highly sensitive photosensitive polymer combination, and wherein said specific inductive capacity and high resolution exist the relation of compromise selection.
The present invention can also provide a kind of and use above-mentioned photosensitive polymer combination and the solidfied material, the interlayer dielectric containing this solidfied material, the TFT active array base plate containing this interlayer dielectric and the liquid crystal indicator that are formed.
Embodiment
Below, be described in detail for implementing mode of the present invention (following, working of an invention mode).It should be noted that, the present invention is not limited to following embodiment, can carry out various distortion to implement in the scope of its main points.
In the present invention, " (methyl) acryloyl " refers to one of " in acryloyl and methacryl at least ".
In addition, " total solid composition " refers to the total amount of the composition of photosensitive polymer combination in addition to the solvents.
In addition, as long as no specified otherwise, the molecular weight in the present invention refers to and uses gel permeation chromatography (GPC method) measure and be converted into the weight-average molecular weight (Mw) of polystyrene.
Photosensitive polymer combination of the present invention contains: (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin.
Photosensitive polymer combination of the present invention can be negative light-sensitive resin combination, also can be positive type photosensitive organic compound.
Then, each composition used in photosensitive polymer combination of the present invention is described.
[(A) barium titanate microparticles]
(A) barium titanate microparticles in the present invention can use with the form of particulate monomer, also can use with the form that have passed through the particulate of surface modification, to improve dispersion stabilization in a solvent.
The average primary particle diameter of (A) barium titanate microparticles that the method recorded in the item with (assay method of average primary particle diameter) described later records is generally more than 1nm, is preferably more than 10nm, more preferably more than 20nm, and is generally below 1000nm, preferably below 500nm, more preferably below 200nm.
If (A) average primary particle diameter of barium titanate microparticles is more than above-mentioned lower limit, then not easily produce cohesion, (A) specific inductive capacity of barium titanate microparticles is high, therefore preferred, in addition, if (A) average primary particle diameter of barium titanate microparticles is below above-mentioned higher limit, then the transmissivity of the interlayer dielectric obtained in visible region is good, therefore preferably.
Relative to (C) alkaline bleach liquor soluble resin 100 weight portion, (A) barium titanate microparticles is generally more than 10 weight portions relative to the match ratio of (C) described later alkaline bleach liquor soluble resin, is preferably more than 20 weight portions, is more preferably more than 50 weight portions, and is generally below 400 weight portions, is preferably below 300 weight portions, is more preferably below 200 weight portions.
If above-mentioned match ratio is more than above-mentioned lower limit, then the specific inductive capacity of the interlayer dielectric obtained is good, and in addition, if above-mentioned match ratio is below above-mentioned higher limit, then the resolving power of interlayer dielectric is good, in this preferably.
[(B) zirconia particles]
(B) zirconia particles can be simple particulate, also can be through the particulate of surface modification, to improve its dispersion stabilization in a solvent.
(B) zirconia particles in the present invention can use and such as adds the yttria (yttria) of 5 ~ 10 about % by weight relative to zirconia thus inhibit the yttria stabilized zirconia etc. of the phase transfer of zirconia under high-temperature area.
(B) average primary particle diameter of zirconia particles be generally more than 1nm, be preferably more than 10nm, be more preferably more than 20nm, and be generally below 1000nm, be preferably below 500nm, be more preferably below 200nm.
If (B) average primary particle diameter of zirconia particles is more than above-mentioned lower limit, then the specific inductive capacity of (B) zirconia particles is good, in addition, if (B) average primary particle diameter of zirconia particles is below above-mentioned higher limit, the light transmission of the interlayer dielectric then obtained in visible region is good, in this preferably.
Relative to (C) alkaline bleach liquor soluble resin 100 weight portion, (B) zirconia particles is generally more than 10 weight portions relative to the match ratio of (C) described later alkaline bleach liquor soluble resin, is preferably more than 20 weight portions, more preferably more than 50 weight portions, and is generally below 400 weight portions, is preferably below 300 weight portions, is more preferably below 200 weight portions.
If above-mentioned match ratio is more than above-mentioned lower limit, then the specific inductive capacity of the interlayer dielectric obtained is good, and in addition, if above-mentioned match ratio is below above-mentioned higher limit, then the resolving power of the interlayer dielectric obtained is good, in this preferably.
Relative to (A) barium titanate microparticles 100 weight portion, (B) zirconia particles is generally more than 5 weight portions relative to the match ratio of (A) barium titanate microparticles, is preferably more than 10 weight portions, is more preferably more than 15 weight portions, and is generally below 400 weight portions, is preferably below 300 weight portions, is more preferably below 270 weight portions.
If (B) zirconia particles is more than above-mentioned lower limit relative to the match ratio of (A) barium titanate microparticles, the resolving power of the interlayer dielectric then obtained is good, in addition, if (B) zirconia particles is below above-mentioned higher limit relative to the match ratio of (A) barium titanate microparticles, the specific inductive capacity of the interlayer dielectric then obtained is good, in this preferably.
[about particulate]
The mensuration of the average primary particle diameter of (A) barium titanate microparticles contained in photosensitive polymer combination of the present invention and (B) zirconia particles (following, sometimes they to be collectively referred to as " inorganic particles ") can be measured by example method described as follows.
(assay method of average primary particle diameter)
First, use sense photosensitive resin composition formation film, can carry out X-ray microanalysis device (XMA) mensuration by the ultra-thin section film thickness direction at this film being cut out to film cross section and transmission electron microscope (TEM) observation measures.Inorganic particles is different for the transmissivity of electron ray with resin, therefore, in tem observation image, can identify inorganic particles and resin according to the difference of contrast.When using multiple inorganic particles, the qualification of each inorganic particles and can be observed by electron ray diffraction image and carries out crystal structure analysis to carry out by the ultimate analysis that measures based on XMA.Obtain the distribution of the area of inorganic particles and the resin obtained like this according to graphical analysis, the cross section of inorganic particles can be approximately circular and go out particle diameter by areal calculation.The TEM image of evaluation to multiple 5000 times and 40000 times of particle diameter is carried out.Be histogram graph representation with 0.1 μm of scale in the TEM image of 5000 times by the multiple that is distributed in of calculated particle diameter, be the histogram graph representation with 0.01 μm of scale in the TEM image of 40000 times at multiple, the central value number of degrees being reached the level of maximum value is set to mean grain size.It should be noted that, as the evaluation assessment of domain size distribution, scanning electron microscope (SEM) can be used in the above-mentioned methods to replace TEM.
(A) barium titanate microparticles in the present invention and (B) zirconia particles can use known method and make; such as, solid reaction process, hydrothermal synthesis method, supercritical water thermal synthesis method, sol-gal process, oxalate method etc. can be used to carry out micronize.
The shape of (A) barium titanate microparticles in the present invention and (B) zirconia particles is not particularly limited, and can enumerate: spherical, granular, tabular, flakey, crystal whisker-shaped, the shape such as bar-shaped, thread.In these shapes, from the viewpoint of particulate not easily cohesion, preferably spherical, granular, sheet, flakey.
In the present invention, for (A) barium titanate microparticles and (B) zirconia particles, in order to improve dispersiveness, the interpolation of spreading agent can be carried out.
As spreading agent, can use known spreading agent without particular limitation, in addition, the adding method of spreading agent, i.e. process for dispersing also can enumerate known method, the methods such as such as ball mill, mixing method, high pressure homogenizer.
[(C) alkaline bleach liquor soluble resin]
(C) alkaline bleach liquor soluble resin contained in photosensitive polymer combination of the present invention is (following, be sometimes referred to as " composition (C) ") as long as dissolve in the resin in the solvent of alkalescence, just be not particularly limited, be preferably the resin containing carboxyl or hydroxyl.
As so alkaline bleach liquor soluble resin, can enumerate by making epoxy resin (a) and α, β-unsaturated monocarboxylic and there is at ester moiety the α of carboxyl, at least one (b) addition in β-unsaturated monocarboxylic ester also makes multi-anhydride (c) react and the Epocryl containing carboxyl of synthesis further; Containing hydroxyl or the hydroxyl of carboxyl or the vinyl group resin of carboxyl in (methyl) acrylic acid, (methyl) acrylate, (methyl) vinyl cyanide, (methyl) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide etc.; And polyamide, polyester, polyethers, polyurethane, polyvinyl butyral, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, cellulose acetate etc.These materials can be used alone a kind, or also can combine two or more use.
And, from the viewpoint of alkali-developable and image formative, be wherein preferably (C-1) Epocryl containing carboxyl and (C-2) vinyl group resin containing carboxyl.
(C-1) Epocryl containing carboxyl
Above-mentioned Epocryl is by making epoxy resin (a) and α, β-unsaturated monocarboxylic and have the α of carboxyl at ester moiety, at least one (b) addition in β-unsaturated monocarboxylic ester also makes multi-anhydride (c) react to synthesize further.Such resultant of reaction does not have epoxy radicals in fact in chemical constitution, and is not also defined as " acrylate ", but is epoxy resin and " acrylate " is typical example due to its raw material, therefore according to usual and material that is that name like this.
As being used as the epoxy resin (a) of raw material, the epoxy resin etc. shown in (adjacent, to) cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methane type epoxy resin, following formula (I) preferably can be used.
[chemical formula 1]
(in above-mentioned formula (I), p and q represents the integer of 0 ~ 4 independently of one another, R 24and R 25represent alkyl or halogen group independently of one another.
R 26and R 27represent alkylidene independently of one another, m and n represents the integer of more than 0 independently of one another.)
Wherein, be preferably the epoxy resin that phenolic resin varnish type epoxy resin or above-mentioned formula (I) represent, particularly from the viewpoint of the balance of resistance to alkaline developer adaptability and developability, preferred unsaturated link concentration is high and be adapted to carboxylic acid concentration, resin that parent nucleus is firm, is particularly preferably the epoxy resin that above-mentioned formula (I) represents.
In above-mentioned formula (I), as R 24and R 25in alkyl, be preferably the alkyl of carbon number 1 ~ 10, as halogen, can F, Cl, Br etc. be enumerated.
As R 24and R 25, be particularly preferably the alkyl of carbon number 1 ~ 5 independently of one another.
R 24and R 25alkyl, halogen group the details of the mechanism of action it be unclear that, but be speculated as 3 dimension structures had an impact, thus control the easy degree of dissolving in developer solution.Therefore, consider from above-mentioned viewpoint, p and q in above-mentioned formula (I) is preferably 1 or 2 independently of one another.
To R 24and R 25bonding position on phenyl ring is not particularly limited, but is preferably ortho position relative to following substituting group.
[chemical formula 2]
Or
[chemical formula 3]
It should be noted that, R 24and R 25can be identical group, can be also different groups, but from the viewpoint of easy to manufacture, be preferably identical group.
In addition, the multiple R contained in a part 24each other and R 25each other can be identical respectively, also can be different, but consider from easy manufacture view, preferably identical.
As R 26and R 27in alkylidene, the alkylidene of carbon number 1 ~ 10 can be enumerated.Wherein, the situation of ethylidene or propylidene is preferably.
M and n is generally more than 0 independently of one another, and is generally the integer of less than 6, preferably less than 3.
When it is in above-mentioned scope, the dissolubility in developer solution is high, and in addition, sensitivity is good, in this preferably.
In addition, R 26and R 27can be identical group, can be also different groups, but consider from easy manufacture view, be preferably identical group.
For the molecular weight of these epoxy resin (a), measure with gel permeation chromatography (GPC) and be converted into the Weight-average molecular gauge of polystyrene, being generally more than 200, being preferably more than 300, and be generally 200, less than 000,100, less than 000 is preferably.
If the molecular weight of epoxy resin (a) is more than above-mentioned lower limit, then tunicle formative is good, in addition, if the molecular weight of epoxy resin (a) is below above-mentioned higher limit, then at α, not easily there is gelation during the addition reaction of β-unsaturated monocarboxylic, easily manufacture, in this preferably.
As α, β-unsaturated monocarboxylic, itaconic acid, butenoic acid, cinnamic acid, acrylic acid, methacrylic acid etc. can be enumerated, be preferably acrylic acid and methacrylic acid, particularly acrylic acid, because reactivity is good, therefore preferably.
As the α at ester moiety with carboxyl, β-unsaturated monocarboxylic ester, can enumerate: acrylic acid-2-amber acyloxy ethyl ester, acrylic acid-2-Malaysia acyloxy ethyl ester, acrylic acid-2-O-phthalic acyl-oxygen base ethyl ester, acrylic acid-2-six hydrogen O-phthalic acyl-oxygen base ethyl ester, methacrylic acid-2-amber acyloxy ethyl ester, methacrylic acid-2-Malaysia acyloxy ethyl ester, methacrylic acid-2-O-phthalic acyl-oxygen base ethyl ester, methacrylic acid-2-six hydrogen O-phthalic acyl-oxygen base ethyl ester, butenoic acid-2-amber acyloxy ethyl ester etc., be preferably acrylic acid-2-Malaysia acyloxy ethyl ester and acrylic acid-2-O-phthalic acyl-oxygen base ethyl ester, be particularly preferably acrylic acid-2-Malaysia acyloxy ethyl ester.
At least one (b) in α, β-unsaturated monocarboxylic and ester thereof and the addition reaction of epoxy resin (a) can use known method.Such as, can under the existence of esterification catalyst, at the temperature of 50 ~ 150 DEG C, make α, at least one (b) in β-unsaturated monocarboxylic and ester thereof and epoxy resin (a) react.As esterification catalyst as used herein, the quaternary ammonium salts etc. such as tertiary amine, tetramethyl ammonium chloride, etamon chloride, DTAC such as triethylamine, trimethylamine, benzyl dimethyl amine, benzyldiethylamine can be used.
It should be noted that, epoxy resin (a), α, β-unsaturated monocarboxylic and have the α of carboxyl at ester moiety, at least one (b) in β-unsaturated monocarboxylic ester, esterification catalyst all can be used alone a kind, also can be mixed with two or more.
α, the use amount of at least one (b) in β-unsaturated monocarboxylic and ester thereof is preferably more than 0.5 equivalent relative to epoxy radicals 1 equivalent of raw material epoxy resin (a), more preferably more than 0.7 equivalent, in addition, be preferably below 1.2 equivalents, more preferably below 1.0 equivalents.
When the use amount of at least one (b) in α, β-unsaturated monocarboxylic and ester thereof is few, the import volume of unsaturated group is not enough, ensuing also insufficient with the reaction of multi-anhydride (c).In addition, remaining a large amount of epoxy radicals neither be favourable.On the other hand, when the use amount of at least one (b) in α, β-unsaturated monocarboxylic and ester thereof is many, at least one in α, β-unsaturated monocarboxylic and ester thereof is remaining as unreacted reactant.Any one situation all sees the tendency that curing characteristics is deteriorated.
As the α with addition, the multi-anhydride (c) of the epoxy resin (a) of at least one (b) in beta-unsaturated carboxylic acid and ester thereof addition further, can enumerate: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, carbic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, one kind or two or more in biphenyl tetracarboxylic dianhydride etc., be preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, biphenyl tetracarboxylic dianhydride, particularly preferred compound is tetrabydrophthalic anhydride and biphenyl tetracarboxylic dianhydride.
About the addition reaction of multi-anhydride (c), known method can be used, can by with epoxy resin (a) and α, continue reaction to obtain under the condition that the addition reaction of at least one (b) in beta-unsaturated carboxylic acid and ester thereof is same.The acid number that the addition amount of multi-anhydride (c) is preferably the Epocryl generated becomes the degree of the scope of 10 ~ 150mg-KOH/g, and then is particularly preferably 20 ~ 140mg-KOH/g.When resinous acid value is lower than above-mentioned scope, alkali-developable becomes insufficient, in addition, when it exceedes above-mentioned scope, sees the tendency that curing performance is deteriorated.
It should be noted that, when the addition reaction of this multi-anhydride, add the polyfunctional alcohols such as trimethylolpropane, pentaerythrite, dipentaerythritol, the material having imported highly branched chain structure can be formed.
(C) as alkaline bleach liquor soluble resin carboxylic Epocryl measured by GPC and the weight-average molecular weight being converted into polystyrene is generally 1, more than 000,1 is preferably, more than 500, and be generally 30, less than 000,20 are preferably, less than 000, more preferably 10, less than 000,8 are particularly preferably, less than 000.
If above-mentioned weight-average molecular weight is below above-mentioned higher limit, then the developability of photosensitive polymer combination is good, and in addition, if above-mentioned weight-average molecular weight is more than above-mentioned lower limit, then alkali resistance is good, in this preferably.
(C-2) carboxylic vinyl group resin
As carboxylic vinyl group resin, can enumerate such as: the multipolymer etc. that unsaturated carboxylic acid and vinyl compound are formed.
As unsaturated carboxylic acid, can enumerate such as: (methyl) acrylic acid, butenoic acid, methacrylate, maleic acid, maleic anhydride, itaconic acid, citraconic acid etc.These unsaturated carboxylic acids can be used alone a kind, also can be mixed with two or more.
In addition, as vinyl compound, can enumerate: styrene, α-methyl styrene, hydroxy styrenes, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) dodecylacrylate, (methyl) 2-EHA, (methyl) dihydroxypropyl methyl esters, (methyl) Hydroxyethyl Acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid N, N-dimethylamino ethyl ester, N-(methyl) acryloyl morpholine, (methyl) vinyl cyanide, (methyl) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-dimethyl aminoethyl (methyl) acrylamide, the multipolymer etc. formed with vinyl compounds such as vinyl acetates.These materials can be used alone a kind, also can be mixed with two or more.
Wherein, (methyl) acrylic acid bicyclopentyl ester give relative to development time or developer solution deterioration etc. tolerance widely in preferred.As such (methyl) acrylic acid bicyclopentyl ester, can enumerate enumerate in such as Japanese Unexamined Patent Publication 2001-89533 publication compound, such as dicyclopentadiene skeleton, Bicvclopentyl skeleton, double cyclopentenyl skeleton, double cyclopentenyl oxygen base alkyl skeleton (methyl) acrylate etc.
In above-mentioned multipolymer (carboxylic vinyl group resin), from picture shape, sensitivity, the viewpoint of cured film intensity is considered, be preferably styrene-(methyl) acrylate-(methyl) acrylic copolymer, more preferably by styrene 3 ~ 60 % by mole, (methyl) acrylate 10 ~ 70 % by mole, the multipolymer that 10 ~ 60 % by mole, (methyl) acrylic acid is formed, be particularly preferably by styrene 5 ~ 50 % by mole, (methyl) acrylate 20 ~ 60 % by mole, the multipolymer that 15 ~ 55 % by mole, (methyl) acrylic acid is formed.
In addition, as above-mentioned carboxylic vinyl group resin, film strength side chain had after the resin solidification of ethylenic unsaturated bond also raises, and diminishes as leakage current during interlayer dielectric, therefore preferred, can enumerate and such as make carboxylic polymkeric substance and allyl glycidyl ether, (methyl) glycidyl acrylate, α-ethyl glycidyl base (methyl) acrylate, butenoic acid ethylene oxidic ester, methacrylic acid glycidyl ester, crotyl glycidol ether, itaconic acid monoalkyl list ethylene oxidic ester, fumaric acid monoalkyl list ethylene oxidic ester, the aliphatics such as maleic acid mono alkyl list ethylene oxidic ester are containing the unsaturated compound of epoxy radicals, or 3,4-epoxycyclohexyl-methyl (methyl) acrylate, 2,3-epoxycyclopentyl methyl (methyl) acrylate, 5 ~ 90 % by mole of the carboxyl that the ester ring types such as 7,8-epoxy [three rings [5.2.1.0]-2-in last of the ten Heavenly stems base] oxygen ylmethyl (methyl) acrylate have with carboxylic polymkeric substance containing the unsaturated compound of epoxy radicals, preferably about 30 ~ 70 % by mole reactions and the reaction product that obtains, and make (methyl) allyl acrylate, 3-allyl oxygen base-2-hydroxypropyl (methyl) acrylate, (methyl) acrylic acid cinnamic ester, (methyl) acrylic acid crotons ester, (methyl) allyl acrylate, N, N-diallyl (methyl) acrylamide etc. has the compound of two or more unsaturated group, or vinyl (methyl) acrylate, 1-chlorovinyl (methyl) acrylate, 2-phenyl vinyl (methyl) acrylate, 1-propenyl (methyl) acrylate, butylene vinyl acid esters, the unsaturated carboxylic acids such as the compound that vinyl (methyl) acrylamide etc. has two or more unsaturated group and (methyl) acrylic acid, or and then esters of unsaturated carboxylic acids be 10 ~ 90 % by mole with the ratio that the former compound with unsaturated group is shared in entirety, preferably account for the mode copolymerization of about 30 ~ 80 % by mole and the reaction product etc. obtained.
In addition, as the acid number of these carboxylic vinyl group resin, be generally 10 ~ 250mg-KOH/g, be preferably 20 ~ 200mg-KOH/g, more preferably 30 ~ 150mg-KOH/g.
In addition, as the molecular weight of these carboxylic vinyl group resin, be generally 1, more than 000, preferably 1, more than 500, more preferably 2, more than 000, and be generally 100, less than 000, preferably 50, less than 000, more preferably 30, less than 000,20 are particularly preferably, less than 000.
If the molecular weight of carboxylic vinyl group resin is in above-mentioned scope, then the high resolution of photosensitive polymer combination is good, therefore preferably.
Relative to total solid composition, the content of (C) the alkaline bleach liquor soluble resin in photosensitive polymer combination of the present invention is generally more than 10 % by weight, is preferably more than 20 % by weight, and is generally less than 60 % by weight, preferably less than 50 % by weight.
If its content is more than above-mentioned lower limit, then the repeatability of image cross section shape and thermotolerance good, therefore preferably, in addition, if its content is below above-mentioned higher limit, then the sensitivity of photosensitive polymer combination and developer dissolves speed good, therefore preferably.
The reason > that < tells on
About can provide the specific inductive capacity and high resolution that can realize having both and there is compromise selection relation by being set to formation of the present invention and be the reason of high-transmission rate and highly sensitive photosensitive polymer combination, infer as following.
By there are (A) barium titanate microparticles different 2 kind particulates such with (B) zirconia particles in photosensitive polymer combination, compared with using the situation of single particulate, with the form orientation of easier split pole.Thus, compared with the situation as single particulate, specific inductive capacity raises.
In addition, (A) barium titanate microparticles or (B) zirconia particles, owing to not having photocatalytic activity, therefore, do not suppress light reaction, and thus, sensitivity or the resolving power of photosensitive polymer combination are abundant.
And then with regard to (A) barium titanate microparticles or (B) zirconia particles, the dispersion in polymer film is easy, thus, can realize high-transmission rate.
Other composition of < >
Photosensitive polymer combination of the present invention, except above-mentioned (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin, can contain other composition further.
Other composition is different separately in negative light-sensitive resin combination and positive type photosensitive organic compound.Below, composition contained in each composition is described in detail.
< negative light-sensitive resin combination >
Negative light-sensitive resin combination of the present invention is except above-mentioned (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin, the compound containing (D) with ethylenically unsaturated group is (following, be sometimes referred to as " composition (D) ") and (E) Photoepolymerizationinitiater initiater is (below, be sometimes referred to as " composition (E) "), further as required containing following (F) ~ (H) composition.
(F) thermal cross-linking agent
(G) other composition
(H) organic solvent
[(D) has the compound of ethylenically unsaturated group]
When photosensitive polymer combination of the present invention is negative light-sensitive resin combination, there is containing (D) compound of ethylenically unsaturated group.
There is as (D) in the present invention the compound of ethylenically unsaturated group, refer in molecule the compound with more than 1 ethylenic unsaturated bond.And negative light-sensitive resin combination of the present invention contains the compound with more than 2 ethylenically unsaturated groups as required composition.
As the compound with 1 ethylenically unsaturated group, can enumerate such as: unsaturated carboxylic acid and Arrcostab, (methyl) vinyl cyanide, (methyl) acrylamide, the styrene etc. such as (methyl) acrylic acid, butenoic acid, methacrylate, maleic acid, itaconic acid, citraconic acid.
In addition, as the compound in molecule with more than 2 ethylenic unsaturated bonds, can enumerate such as: epoxy (methyl) esters of acrylic acid etc. that the ester class that unsaturated carboxylic acid and polyol are formed, polyurethane (methyl) esters of acrylic acid formed containing the phosphoric acid ester of (methyl) acryloxy, hydroxyl (methyl) acrylate compounds and polyisocyanate compound and (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides are formed.These materials can be used alone a kind, or can combine two or more use.
(D-1) the ester class that formed of unsaturated carboxylic acid and polyol
As the ester class (following, sometimes referred to as " ester (methyl) esters of acrylic acid ") that unsaturated carboxylic acid and polyol are formed, specifically following compound can be enumerated.
The reactant of above-mentioned unsaturated carboxylic acid and sugar alcohol: as sugar alcohol, can enumerate such as: ethylene glycol, polyglycol (adduct number 2 ~ 14), propylene glycol, polypropylene glycol (adduct number 2 ~ 14), trimethylene, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerine, pentaerythrite, dipentaerythritol etc.
The reactant of the epoxide addition product of above-mentioned unsaturated carboxylic acid and sugar alcohol: sugar alcohol can enumerate material same as described above.As epoxide addition product, can enumerate such as: ethylene oxide adduct or propylene oxide adduct etc.
The reactant of above-mentioned unsaturated carboxylic acid and hydramine: as alcamines, can enumerate such as diethanolamine, triethanolamine etc.
As the ester class that above-mentioned unsaturated carboxylic acid and polyol are formed, more specifically, following compound can be enumerated.
Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethyleneoxide addition three (methyl) acrylate, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, glycerol epoxy propane addition three (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc., and same butenoate, methacrylate, maleate, itaconate, citraconate etc.
In addition, as the ester class that above-mentioned unsaturated carboxylic acid and polyol are formed, can enumerate: the reactant of the aromatic polyhydroxy compounds such as above-mentioned unsaturated carboxylic acid and p-dihydroxy-benzene, resorcinol, 1,2,3,-thrihydroxy-benzene, Bisphenol F, bisphenol-A or their ethylene oxide adduct.Specifically, be such as bisphenol-A two (methyl) acrylate, bisphenol-A two [oxygen ethene (methyl) acrylate], bisphenol-A two [glycidol ether (methyl) acrylate] etc.
In addition, as the ester class that above-mentioned unsaturated carboxylic acid and polyol are formed, the reactant of the hetero ring type polyols such as above-mentioned unsaturated carboxylic acid and three (2-hydroxyethyl) isocyanuric acid ester can be enumerated.Specifically, be such as two (methyl) acrylate, three (methyl) acrylate etc. of three (2-hydroxyethyl) isocyanuric acid ester.
In addition, as the ester class that above-mentioned unsaturated carboxylic acid and polyol are formed, the reactant of above-mentioned unsaturated carboxylic acid, polybasic carboxylic acid and polyol can be enumerated.Specifically, be such as the condensation product etc. of the condensation product of (methyl) acrylic acid and phthalic acid and ethylene glycol, the condensation product of (methyl) acrylic acid and maleic acid and diethylene glycol, the condensation product of (methyl) acrylic acid and phthalic acid and pentaerythrite, (methyl) acrylic acid and hexane diacid and butylene glycol and glycerine.
(D-2) containing the phosphoric acid ester of (methyl) acryloxy
As the phosphoric acid ester containing (methyl) acryloxy, as long as the phosphate compound containing (methyl) acryloxy, just be not particularly limited, wherein, the compound that preferred following formula (IIa) ~ (IIc) represents.
[chemical formula 4]
(in formula (IIa), (IIb) and (IIc), R 11represent hydrogen atom or methyl,
P and p ' represents the integer of 1 ~ 25 independently of one another,
Q represents the integer of 1 ~ 3.)
At this, p and p ' is preferably 1 ~ 10 independently of one another, is particularly preferably 1 ~ 4.
As the concrete example of this compound, can enumerate such as: (methyl) acryloyl-oxyethyl phosphate, two [(methyl) acryloyl-oxyethyl] phosphate, (methyl) acryloyl-oxy ethylene glycol phosphate etc., these materials can individually use, and also can use as potpourri.
(D-3) polyurethane (methyl) esters of acrylic acid that formed of hydroxyl (methyl) acrylate compounds and polyisocyanate compound
As hydroxyl (methyl) acrylate compounds, can enumerate such as: hydroxyl (methyl) acrylate compounds such as (methyl) dihydroxypropyl methyl esters, (methyl) Hydroxyethyl Acrylate, tetra methylol ethane three (methyl) acrylate.
In addition, as polyisocyanate compound, can enumerate such as: the aliphatic polyisocyantes such as hexamethylene diisocyanate, 1,8-diisocyanate based-4-isocyanatomethyl octane; The ester ring type polyisocyanates such as cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, 4,4-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), isophorone diisocyanate, norbornane triisocyanate; The aromatic polyisocyanates such as 4,4-methyl diphenylene diisocyanate, three (isocyanatophenyl) thiophosphate; The hetero ring type polyisocyanates such as isocyanuric acid ester; The polyisocyanate compounds such as the allophanate-modified poly-isocyanurate manufactured by the method recorded in Japanese Unexamined Patent Publication 2001-260261 publication.
As polyurethane (methyl) esters of acrylic acid that hydroxyl (methyl) acrylate compounds and polyisocyanate compound are formed, wherein, polyurethane (methyl) esters of acrylic acid containing above-mentioned allophanate-modified poly-isocyanurate is preferably.The viscosity of polyurethane (methyl) esters of acrylic acid containing allophanate-modified poly-isocyanurate is low, dissolubility is in a solvent excellent, simultaneously, effective at least one passed through in photocuring and heat curing and the adaptation of substrate and the raising of film strength, in this preferably.
As above-mentioned polyurethane (methyl) esters of acrylic acid in the present invention, commercially available material can be used.Specifically, can enumerate such as: as KCC of Xin Zhong village manufacture trade name " U-4HA " " UA-306A " " UA-MC340H " " UA-MC340H " " U6LPA ", Bayer Japan company manufacture there is " AGROR4060 " of the compound of allophanate skeleton etc.
As above-mentioned polyurethane (methyl) esters of acrylic acid in the present invention, from the viewpoint of sensitivity, preferably there is in 1 molecule the compound of more than 4 (preferably have more than 6, more preferably have more than 8) amino-formate bonds [-NH-CO-O-] and more than 4 (preferably more than 6, more preferably more than 8) (methyl) acryloxies.Described compound can by such as making the compound of the compound of following (i) and following (ii) react to obtain.
I () 1 has the compound of more than 4 amino-formate bonds in molecule
Can enumerate such as: the diisocyanate cpd such as compound and hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate making pentaerythrite, polyglycereol etc. 1 have more than 4 hydroxyls in molecule reacts and the compound (i-1) obtained, or make to have in 1 molecules such as ethylene glycol " DURANATE 24A-100 " that the compound of more than 2 hydroxyls and Asahi Chemical Industry Co., Ltd manufacture, " DURANATE 22A-75PX ", " DURANATE 21S-75E ", biuret types such as " DURANATE 18H-70B ", " DURANATE P-301-75E ", " DURANATE E-402-90T ", there is in 1 molecules such as adduct types such as " DURANATE E-405-80T " the compound reaction of more than 3 isocyanate group and the compound (i-2) that obtains, or make the polymerizations such as isocyanatoethyl (methyl) acrylate or copolymerization and the compound (i-3) etc. obtained.
As such compound, can commercially available product be used, can enumerate such as: " DURANATE ME20-100 " that Asahi Chemical Industry Co., Ltd manufactures.
(ii) there is in 1 molecule the compound of more than 3 (methyl) acryloxies
Can enumerate such as: the compound in 1 molecules such as dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate with more than 3 (methyl) acryloxies.
At this, as the weight-average molecular weight of the compound of above-mentioned (i), be preferably 500 ~ 200,000, be particularly preferably 1,000 ~ 150,000.In addition, as the molecular weight of above-mentioned polyurethane (methyl) esters of acrylic acid, be preferably 600 ~ 150,000.
It should be noted that, such polyurethane (methyl) esters of acrylic acid such as can be manufactured by the method making the compound of the compound of above-mentioned (i) and above-mentioned (ii) react 5 minutes ~ 3 hours in the organic solvent such as toluene or ethyl acetate, at 10 ~ 150 DEG C.In this situation, preferably the mol ratio of the former isocyanate group and the hydroxyl of the latter is set to the ratio of 1/10 ~ 10/1, uses the catalyzer such as tin dilaurate normal-butyl tin as required.
(D-4) epoxy radicals (methyl) esters of acrylic acid that formed of (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides
As polyepoxides, can enumerate such as: the aliphatic polyepoxide such as (gathering) ethylene glycol polyglycidyl ether, (gathering) propylene glycol polyglycidyl ether, (gathering) tetramethylene glycol polyglycidyl ether, (gathering) pentamethylene glycol polyglycidyl ether, (gathering) dimethyltrimethylene glycol polyglycidyl ether, (gathering) hexamethylene glycol polyglycidyl ether, (gathering) trimethylolpropane polyglycidyl ether, (gathering) glycerine polyglycidyl ether, (gathering) D-sorbite polyglycidyl ether; The aromatic polyepoxide compounds such as phenol novolacs polyepoxides, brominated phenol novolaks polyepoxides, (adjacent, to) cresol novolak polyepoxides, polymer with bis phenol A epoxy compound, Bisphenol F polyepoxides; The hetero ring type polyepoxidess such as sorbitan polyglycidyl ether, triglycidyl group isocyanuric acid ester, triglycidyl group three (2-hydroxyethyl) isocyanuric acid ester; Deng polyepoxides.
The reactant formed as (methyl) acrylic acid or hydroxyl (methyl) acrylate compounds and polyepoxides and epoxy (methyl) esters of acrylic acid, can enumerate the reactant etc. of polyepoxides as described above and (methyl) acrylic acid or above-mentioned hydroxyl (methyl) acrylate compounds.
(D-5) other alefinically unsaturated compounds
As other alefinically unsaturated compounds, apart from the above, can enumerate such as: class such as allyl ester such as ethylenebis (methyl) acrylamide etc. (methyl) acrylic amide, dially phthalate etc., divinyl phthalic ester etc. containing vinyl compounds, change to thioether bond by utilizing phosphoric sulfide etc. to carry out sulfuration to the ehter bond of the alefinically unsaturated compounds of ether-containing key thus improve the compounds of the sulfur-bearing ehter bond of crosslinking rate.
In addition, multifunctional (methyl) acrylate compounds such as will recorded in Japanese Unexamined Patent Publication 2003-221833 publication and Japanese Unexamined Patent Publication 9-100111 publication etc. can be enumerated, silicon dioxide gel [such as isopropyl alcohol dispersion Organic silica sols (Misao Kusano's system " IPA-ST ") of particle diameter 5 ~ 30nm, MEK dispersion Organic silica sols (Misao Kusano's system " MEK-ST "), methylisobutylketone dispersion Organic silica sols (Misao Kusano's system " MIBK-ST ") etc.] use the compound of isocyanate group or the silane coupling agent bonding containing sulfydryl.
This compound is by making alefinically unsaturated compounds react and bonding thus the compounds of the intensity that improve as solidfied material and thermotolerance via silane coupling agent and silicon dioxide gel.
In addition, as other alefinically unsaturated compounds, the known compound recorded in Japanese Unexamined Patent Publication 2005-165294 publication can also be used.These materials can individually use, and also can combine two or more and use.
In the present invention, as alefinically unsaturated compounds, from the viewpoint of polymerism, bridging property etc., preferably comprise in molecule the compound with more than 2 ethylenically unsaturated groups.Wherein, be preferably ester (methyl) esters of acrylic acid, the phosphoric acid ester containing (methyl) acryloxy or polyurethane (methyl) esters of acrylic acid, be more preferably ester (methyl) esters of acrylic acid.In this ester (methyl) esters of acrylic acid, particularly preferably dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, there is in 1 molecules such as dipentaerythritol six (methyl) acrylate the compound of more than 3 (methyl) acryloxies, bisphenol-A two (methyl) acrylate, bisphenol-A two [oxygen ethylidene (methyl) acrylate], the aromatic polyhydroxy compounds such as bisphenol-A two [glycidol ether (methyl) acrylate], or the reactant of they and ethylene oxide adduct.
In addition, in alefinically unsaturated compounds of the present invention, compound containing aromatic rings or containing do not replace or p (to) variable color (red colored) that causes owing to suppressing the heating of interlayer dielectric of the position compound with substituent phenyl, therefore preferably.As this alefinically unsaturated compounds, such as aliphatic multifunctional (methyl) acrylate and bisphenol-A can be enumerated or there is (methyl) acrylate compounds etc. of polyvalent alcohol of fluorene skeleton.
In photosensitive polymer combination of the present invention, the content of alefinically unsaturated compounds is generally more than 10 % by weight relative to total solid composition, is preferably more than 20 % by weight, and is generally less than 60 % by weight, preferably less than 50 % by weight.
When the content of alefinically unsaturated compounds is in above-mentioned scope, sensitivity and developer dissolves speed not easily reduce, and in addition, also not easily cause the repeatability of image surface shape to reduce, also not easily produce the residual film etc. of resist.
As the match ratio of the composition (D) in the present invention, as the use level of the composition (D) relative to composition (C) 100 weight portion, be generally below 200 weight portions, be preferably below below 170 weight portions, more preferably 150 weight portions, and be generally more than more than more than 40 weight portions, preferably 50 weight portions, more preferably 70 weight portions.
[(E) Photoepolymerizationinitiater initiater]
When photosensitive polymer combination of the present invention is negative light-sensitive resin combination, containing (E) Photoepolymerizationinitiater initiater.
As this (E) Photoepolymerizationinitiater initiater, only otherwise damage effect of the present invention, any one Photoepolymerizationinitiater initiater known all can use, and can enumerate the compound that can produce the free radical that ethylenically unsaturated group is polymerized under the effect from ultraviolet to luminous ray.
Below, the preferred concrete example of Photoepolymerizationinitiater initiater is shown, but the present invention is not limited to these.
(i) 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyl naphthyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4, the halomethylation pyrrolotriazine derivatives such as two (the trichloromethyl)-s-triazine of 6-, two (the trichloromethyl)-s-triazines of 2-(4-ethoxy carbonyl naphthyl)-4,6-.
(ii) halomethylation oxadiazole derivative, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4,5-two (3 '-methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(o-methyl-phenyl-)-4, the imdazole derivatives such as 5-diphenyl-imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer.
(iii) benzoin, the benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether.
(iv) anthraquinone derivative such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone.
(v) benzanthrone derivant.
(vi) benzophenone derivates such as benzophenone, Michler's keton, 2 methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone.
(vii) 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-methylpropiophenone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-[4 '-(methyl thio) phenyl]-2-morpholino-1-acetone, 1, the acetophenone derivs such as 1,1-trichloromethyl (to butyl phenyl) ketone.
(viii) thioxanthone derivates such as thioxanthones, 2-ethyl thioxanthones, ITX, CTX, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone.
(ix) ESCAROL 507 ethyl ester, to benzoate derivatives such as diethylamino ethyl benzoates.
The acridine derivatives such as (x) 9-phenylacridine, 9-(p-methoxyphenyl) acridine.
(xi) phenazene derivative such as 9,10-dimethylbiphenyl azophenlyene.
(xii) two (cyclopentadienyl group) titanium chloride, two (cyclopentadienyl group) diphenyl titanium, two (cyclopentadienyl group) two (2, 3, 4, 5, 6-phenyl-pentafluoride-1-base) titanium, two (cyclopentadienyl group) two (2, 3, 5, 6-phenyl tetrafluoride-1-base) titanium, two (cyclopentadienyl group) two (2, 4, 6-trifluoro-benzene-1-base) titanium, two (cyclopentadienyl group) (2, 6-difluorobenzene-1-base) titanium, two (cyclopentadienyl group) (2, 4-difluorobenzene-1-base) titanium, two (methyl cyclopentadienyl) two (2, 3, 4, 5, 6-phenyl-pentafluoride-1-base) titanium, two (methyl cyclopentadienyl) two (2, 6-difluorobenzene-1-base) titanium, two (cyclopentadienyl group) (2, the fluoro-3-of 6-bis-(pyrroles-1-base) benzene-1-base) the luxuriant titanium derivative such as titanium.
(xiii) 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 4-dimethyl aminoethyl benzoic ether, 4-dimethylamino isoamyl benzene formic ether, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoic acid ester, 2, two (the 4-diethylamino benzal) cyclohexanone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, the alpha-aminoalkyl benzophenone compounds such as 4-(diethylamino) chalkone.
(xiv) the acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxides, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide.
(xv) 1; 2-octanedione, 1-[4-(benzene sulfo-) phenyl]-; 2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-base]-, the oxime ester compound etc. recorded in 1-(O-acetyl group oxime) and Japanese Unexamined Patent Publication 2000-80068 publication, Japanese Unexamined Patent Publication 2001-233842 publication, Japanese Unexamined Patent Publication 2001-235858 publication, Japanese Unexamined Patent Publication 2005-182004 publication, No. 2002/00903rd, International Publication and Japanese Unexamined Patent Publication 2007-41493 publication.
The preferred concrete example of above-mentioned oxime ester compound is below shown, but the present invention is not limited to these compounds.
[chemical formula 5]
These Photoepolymerizationinitiater initiaters can be used alone, or combinationally use multiple.As combination, above-mentioned Photoepolymerizationinitiater initiater can be combined, in addition, the combination of polymerization initiator described in such as Japanese Patent Publication 53-12802 publication, Japanese Unexamined Patent Publication 1-279903 publication, Japanese Unexamined Patent Publication 2-48664 publication, Japanese Unexamined Patent Publication 4-164902 publication or Japanese Unexamined Patent Publication 6-75373 publication etc. can be enumerated.
Wherein, (xiv) acylphosphine oxide compound and (xv) oxime ester compound are high sensitivity for the i ray of mercury vapor lamp; therefore preferred; (xv) oxime ester compound due to image formed after heat cured film high at the light transmission of visible region, therefore particularly preferably.
The content of the Photoepolymerizationinitiater initiater in photosensitive polymer combination of the present invention is generally more than 0.1 % by weight relative to total solid composition, is preferably more than 0.5 % by weight, in addition, is generally less than 40 % by weight, is preferably less than 30 % by weight.
When the content of Photoepolymerizationinitiater initiater is more than above-mentioned lower limit, the sensitivity of photosensitive polymer combination is good, in addition, when the content of Photoepolymerizationinitiater initiater is below above-mentioned higher limit, not easily produces residue, in this preferably.
As the match ratio of composition (E) relative to composition (C), with the cooperation gauge of composition (E) relative to composition (C) 100 weight portion, be generally below 100 weight portions, be preferably below 70 weight portions, and be generally more than more than 5 weight portions, preferably 10 weight portions.
(F) thermal cross-linking agent
In order to improve thermotolerance and the resistance to chemical reagents of the film after heat curing, photosensitive polymer combination of the present invention can contain thermal cross-linking agent.
As thermal cross-linking agent, as long as based on exposure, development image formed after effect of curing under carry out cross-linking reaction, then can use known thermal cross-linking agent.Specifically, following thermal cross-linking agent can be enumerated.
(F-1) there is in molecule the compound of epoxy radicals
(following as the compound in (F-1) molecule used in the present invention with epoxy radicals, be sometimes referred to as " composition (F-1) "), can enumerate such as: poly epihydric alcohol base ester compounds monohydroxy compound or polyol and chloropropylene oxide are reacted and obtains (gathering) glycidyl ether compound, making (gathering) carboxylic acid compound and chloropropylene oxide react and obtain and (many) amines and chloropropylene oxide are reacted obtain (gathering) glycidyl amines etc. from low molecular weight substance to the compound of high molecular weight material.
(F-1-1) poly epihydric alcohol ether compound
As poly epihydric alcohol ether compound, can enumerate such as: the diglycidyl ether-type epoxide of polyglycol, the diglycidyl ether-type epoxide of two (4-hydroxy phenyl), two (3, 5-dimethyl-4-hydroxy phenyl) diglycidyl ether-type epoxide, the diglycidyl ether-type epoxide of Bisphenol F, the diglycidyl ether-type epoxide of bisphenol-A, the diglycidyl ether-type epoxide of tetramethyl bisphenol-A, the diglycidyl ether-type epoxide of ethyleneoxide addition bisphenol-A, two hydroxy fluorenes type epoxide, two hydroxy alkylidene oxygen base fluorenes type epoxide, bisphenol-A/aldehyde nobolak type epoxy compound, phenol novolak type epoxide, cresol novolak type epoxy compound.
In addition, in poly epihydric alcohol ether compound, polyglycidyl ether resins is contained.As polyglycidyl ether resins, can enumerate: the phenolic resin type epoxy resin such as polymeric epoxy resin of the polymeric epoxy resin of bisphenol-s epoxy resin, phenol novolac epoxy resins, cresol novolac epoxy, triphenol epoxy resin, phenol and dicyclopentadiene, phenol and naphthalene.
These (gathering) glycidyl ether compounds can be make remaining hydroxyl and acid anhydrides or 2 yuan of acid compounds etc. react and import the compound of carboxyl.
(F-1-2) poly epihydric alcohol base ester compounds
As poly epihydric alcohol base ester compounds, can enumerate such as: the 2-glycidyl ester type epoxide of hexahydrophthalic acid, the 2-glycidyl ester type epoxide etc. of phthalic acid.
(F-1-3) poly epihydric alcohol ylamine compounds
As poly epihydric alcohol ylamine compounds, can enumerate such as: the diglycidyl amine type epoxide of two (4-aminophenyl) methane, the triglycidyl group amine type epoxide etc. of isocyanuric acid.
(F-1-4) other
In addition, as other example, such as (methyl) glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, (methyl) acrylic acid-3 can be enumerated, 4-epoxy radicals butyl ester, (methyl) acrylic acid-4,5-epoxy radicals pentyl ester, (methyl) acrylic acid-6, the polymkeric substance that 7-epoxy radicals heptyl ester, α-ethylacrylate-6,7-epoxy radicals heptyl ester etc. make (methyl) acrylate etc. with epoxy radicals be obtained by composite reaction one kind or two or more separately.Or, the polymkeric substance also containing usual 10 ~ 70 % by mole of other comonomer, preferably 15 ~ 60 % by mole except (methyl) acrylate Component units with epoxy radicals can be enumerated.
As comonomer, can enumerate such as: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid bicyclopentyl oxygen base ethyl ester, (methyl) acrylic acid ester that (methyl) isobornyl acrylate is such, and styrene, α-methyl styrene, p-methylstyrene, the vinyl aromatic compounds that vinyl naphthalene is such.
As (methyl) acrylate with epoxy radicals, preferably enumerate (methyl) glycidyl acrylate.In addition, as preferred comonomer, can enumerate: (methyl) acrylic acid bicyclopentyl ester, α-styrene.
Composition (F-1) is (sometimes referred to as " epoxy resin ") when resin, as preferred molecular weight, as long as photosensitive polymer combination of the present invention can be coated with equably with solution state, just be not particularly limited, suitably can select according to the thickness, application conditions, object etc. of the film formed.As its molecular weight, usually preferred 2, the scope of 000 ~ 300,000, is preferably 3,000 ~ 100,000, more preferably 4,000 ~ 50,000.
In addition, the epoxy radicals used in composition used in the present invention (F-1) is generally 1,2-epoxy radicals, but in order to improve ageing stability and give flexibility etc., also 1,3-epoxy radicals (oxetanes), 4,3-epoxycyclohexyls can be used.
In addition, as the composition (F-1) in the present invention, preferably not containing aromatic rings composition or containing do not replace or p (to) position has the composition of substituent phenyl, because its variable color (red colored) that the heating of interlayer dielectric can be suppressed to cause.As such epoxy compound, such as bisphenol A type epoxy compound and epoxy resin can be enumerated, there is the epoxy compound optionally with substituent fluorene skeleton and epoxy resin, the multipolymer etc. of glycidyl (methyl) acrylate.
In photosensitive polymer combination of the present invention, containing when there is in molecule the compound of epoxy radicals, as its content, relative to total solid composition, be generally less than 60 % by weight, be preferably less than 50 % by weight, more preferably less than 30 % by weight, and be generally more than 1 % by weight.Have in molecule the content of the compound of epoxy radicals too much time, easily cause the reduction of the fissility after the reduction of the storage stability of photosensitive polymer combination and exposure, development.
(F-2) nitrogenous heat cross-linking compound
As the nitrogenous heat cross-linking compound used in the present invention, can enumerate: make melamine, benzoguanamine, glycoluril or urea and formaldehyde effect and the compound formed or their alkyl-modified compound.
Specifically, the compound formed as making melamine and formaldehyde effect or the example of its alkyl-modified thing, can enumerate: " Cymel " (registered trademark) that Cytec Industries Inc manufactures 300,301,303,350,736,738,370,771,325,327,703,701,266,267,285,232,235,238,1141,272,254,202,1156,1158, " NIKALAC " (registered trademark) E-2151, MW-100LM, MX-750LM etc. of Sanwa Chemical Co., Ltd.
In addition, as making benzoguanamine and formaldehyde effect and the example of the compound formed or its alkyl-modified thing, " Cymel " (registered trademark) 1123,1125,1128 etc. can be enumerated.
In addition, as making glycoluril and formaldehyde effect and the example of the compound formed or its alkyl-modified thing, can enumerate " Cymel " (registered trademark) 1170,1171,1174,1172, " NIKALAC " (registered trademark) MX-270 etc.
In addition, the compound formed as making urea and formaldehyde effect or the example of its alkyl-modified thing, can enumerate " UFR " (registered trademark) that Cytec Industries Inc manufactures 65,300, " NIKALAC " (registered trademark) MX-290 etc.
As (F) thermal cross-linking agent in the present invention, wherein, there is in preferred molecule-N (CH 2oR) 2the compound of base (in formula, R represents alkyl or hydrogen atom).Particularly preferably make urea or melamine and formaldehyde effect and the compound formed or its alkyl-modified thing.
In photosensitive polymer combination of the present invention containing nitrogenous heat cross-linking compound, as the content of this nitrogenous heat cross-linking compound, relative to total solid composition, be generally less than 40 % by weight, be preferably less than 30 % by weight, more preferably less than 20 % by weight.When the amount of nitrogenous heat cross-linking compound is too much, easily cause the reduction of residual film ratio when developing and the reduction of distinguishing.
Wherein, as (F) thermal cross-linking agent, as particularly preferred compound, can enumerate in molecule and there is-N (CH 2oR) 2the compound of base (in formula, R represents alkyl or hydrogen atom).Specifically, urea or melamine and formaldehyde effect is particularly preferably made and the compound formed or its alkyl-modified thing.
(G) other composition
(G-1) bonding auxiliary agent
In order to improve the adaptation with substrate, bonding auxiliary agent can be coordinated in photosensitive polymer combination of the present invention.As bonding auxiliary agent, such as silane coupling agent can be enumerated.
More specifically, can enumerate such as: trimethoxysilyl benzoic acid, γ-metacryloxy propyl trimethoxy silicane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-isocyanate group propyl-triethoxysilicane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane etc.These silane coupling agents can be used alone a kind, also can be mixed with two or more.
In addition, silane coupling agent not only has the function as bonding auxiliary agent, but also has the function of interlayer dielectric being given to suitable heat fusing (thermal fluidity), raising flatness in thermal treatment.As the silane coupling agent coordinated with such object, the silane coupling agent such as with epoxy radicals can be enumerated.More specifically, such as γ-glycidoxypropyltrime,hoxysilane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane etc. can be enumerated.
It should be noted that, when containing above-mentioned bonding auxiliary agent, as its use level, relative to total solid composition, be generally more than 0.1 % by weight, and be generally less than 20 % by weight, preferably less than 10 % by weight.
(G-2) surfactant
In order to improve as the coating of the coating fluid of composition and use sense photosensitive resin composition and the developability of the film obtained etc., photosensitive polymer combination of the present invention can contain non-ionics, anionic surface active agent, cationic surfactant, amphoteric surfactant or fluorine class or the surfactant such as silicone based.
As above-mentioned non-ionics, can enumerate such as: polyoxyethylene alkyl ether class, polyoxyethylene polyoxy-propylene class, polyoxyethylene alkyl phenyl ether class, polyxyethylated ester class, polyoxyethylene fatty acid ester class, fatty acid glyceride class, polyoxyethylene glycerol fatty esters of gallic acid, season penta tetraene fatty acid ester, polyoxyethylene season penta tetraene fatty acid ester, sorbitan fatty acid ester class, polyoxyethylene sorbitan fatty acid ester class, Span class, Polyoxyethylene Sorbitol Fatty Acid Esters class etc.As these commercially available products, the polyoxyethylene surfactants etc. such as " the EMULGEN 104P ", " EMULGEN A60 " of Kao Corp's manufacture can be enumerated.
In addition, as above-mentioned anionic surface active agent, can enumerate such as: alkyl sulfonates, alkyl benzene sulfonate, alkyl naphthalene sulfonic acid salt, polyoxyethylene alkyl ether Sulfonates, alkylsurfuric acid salt, alkyl sulfate salt, higher alcohol sulfate salt, glim salt, polyoxyethylene alkyl ether sulfate salt class, polyoxyethylene alkylphenyl ether sulfate salt class, alkyl phosphate salt, ether phosphates class, polyoxyethylene alkyl phenyl ether phosphoric acid salt, special high score subclass surfactant etc.Wherein, be preferably special high score subclass surfactant, be more preferably special polyocarboxy acid type high score subclass surfactant.
As such anionic surface active agent, commercially available product can be used, such as, alkyl sulfate salt can enumerate " Emal 10 " of Kao Corp's manufacture etc., alkyl naphthalene sulfonic acid salt can enumerate " the PELEX NB-L " of Kao Corp's manufacture etc., and special high score subclass surfactant can enumerate " the HOMOGENOL L-18 ", " HOMOGENOL L-100 " of Kao Corp's manufacture etc.
And then, as above-mentioned cationic surfactant, quaternary ammonium salt, imidazolidine derivatives class, amine salt etc. can be enumerated, in addition, as amphoteric surfactant, betaine type compounds, imidazoles can be enumerated salt, imidazolines, amino acids etc.Wherein, preferred quaternary ammonium salt, is more preferably stearyl trimethyl ammonium salt class.As commercially available surfactant, such as, alkyl amine salt can enumerate " ACETAMIN 24 " of Kao Corp's manufacture etc., and quaternary ammonium salt can enumerate " the KOTAMIN 24P ", " KOTAMIN 86W " of Kao Corp's manufacture etc.
On the other hand, as fluorine class surfactant, preferably there is at least arbitrary position of end, main chain and side chain the compound of fluoroalkyl or fluorine alkylidene.
Specifically, can enumerate such as: 1,1,2,2-tetrafluoro octyl group (1,1,2,2-tetra-fluoropropyl) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight ethylene glycol bisthioglycolates (1,1,2,2-tetrafluoro butyl) ether, six ethylene glycol bisthioglycolates (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, perfluorododecyl sodium sulfonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecane, 1,1,2,2,3,3-hexafluoro decane etc.
As these commercially available products, can enumerate: " DFX-18 " that " FC430 " that " Megafac F142D ", " Megafac F172 ", " Megafac F173 " that " BM-1000 ", " BM-1100 " that BM Chemie company manufactures, Dainippon Ink. & Chemicals Inc manufacture, " Megafac F183 ", " Megafac F470 ", " Megafac F475 ", Sumitomo 3M Co., Ltd. manufacture, NEOS company manufacture etc.
In addition, as organosilicone surfactants, can enumerate such as: " Toray Silicone DC3PA " that Toray Silicone company manufactures, " Toray Silicone SH7PA ", " Toray Silicone DC11PA ", " Toray Silicone SH21PA ", " Toray Silicone SH28PA ", " Toray Silicone SH29PA ", " Toray Silicone SH30PA ", " Toray Silicone SH8400 ", " TSF-4440 " that organosilicon Co., Ltd. of Toshiba manufactures, " TSF-4300 ", " TSF-4445 ", " TSF-444 (4) (5) (6) (7) 6 ", " TSF-4460 ", " TSF-4452 ", " KP341 " that Silicone company manufactures, " BYK323 " that BYK Chemie company manufactures, commercially available products such as " BYK330 ".
In these surfactants, from the viewpoint of the homogeneity of coating film thickness, preferred fluorine class surfactant, organosilicone surfactants.
Surfactant can be combination of more than two kinds, can enumerate: the combination etc. of organosilicone surfactants/fluorine class surfactant, organosilicone surfactants/special high score subclass surfactant, fluorine class surfactant/special high score subclass surfactant.Wherein, organosilicone surfactants/fluorine class surfactant is preferably.
In the combination of this organosilicone surfactants/fluorine class surfactant, can enumerate such as: " DFX-18 " that " TSF4460 "/NEOS company that organosilicon Co., Ltd. of GE Toshiba manufactures manufactures, " S-393 " that " BYK-300 " that BYK Chemie company manufactures or " BYK-330 "/Seimi Chemical company manufacture, " F-478 " or " F-475 " that " KP340 " that organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI manufactures/large Japanese ink Co., Ltd. manufactures, " DS-401 " that " SH7PA "/Daikin Co., Ltd that Toray Silicone company manufactures manufactures, " FC4430 " that " L-77 "/Sumitomo 3M Co., Ltd. that Nippon Unicar Co. Ltd. manufactures manufactures etc.
In photosensitive polymer combination of the present invention, the content of surfactant is preferably less than 10 % by weight relative to total solid composition, and more preferably 0.1 ~ 5 % by weight.
(G-3) hardening agent
In order to the change of the time under cripetura heat curing condition, design temperature, photosensitive polymer combination of the present invention can contain hardening agent further, and the manufacturing process according to each element suitably selects different conditions of cure.
As such hardening agent, only otherwise infringement requires function, just be not particularly limited, can enumerate such as: benzoic acid derivative, polybasic carboxylic acid (acid anhydride), polymkeric substance, thermal acid generator, amines, polyamine compounds and closed carboxylic acid etc. containing polybasic carboxylic acid (acid anhydride).Particularly when containing the above-mentioned compound containing epoxy radicals as thermal cross-linking agent, preferably use thermal curing agents.
(G-3-1) benzoic acid derivative
As benzoic acid derivative, can enumerate: benzoic acid, the position of 2 to 6 on benzoic phenyl ring have the substituent compounds such as hydroxyl, halogen group, alkyl, acyl group, acyloxy, alkoxy, aryl, allyl.Wherein, preferably there is the compound of the hydroxyl high relative to the ability to cure of epoxy radicals alternatively base, particularly preferably there is the compound of more than 2 hydroxyls.As such benzoic acid derivative, can enumerate such as: Gallic Acid, DHB, 2,6-DHBA, PCA, 2,4,6-trihydroxybenzoic acids etc.
(G-3-2) polybasic carboxylic acid (acid anhydride)
As polybasic carboxylic acid (acid anhydride), can enumerate such as: the ester ring type polybasic carboxylic acids (acid anhydride) such as methylnadic anhydride, hexahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride; The aromatic polycarboxylic acid acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tricarboxylic acid anhydride, benzophenone tetracarboxylic anhydride; The ester ring type acid anhydrides such as succinic acid, trimellitic acid, maleic acid, cyclopentane tetrabasic carboxylic acid; The hydrolysate etc. of aromatic anhydride.Wherein, trimellitic acid (acid anhydride), phthalic anhydride is preferably.
(G-3-3) polymkeric substance containing polybasic carboxylic acid (acid anhydride)
As the polymkeric substance containing polybasic carboxylic acid (acid anhydride), the part half ester can enumerating polybasic carboxylic acid (acid anhydride) part in the polymkeric substance or such polymkeric substance in the polybasic carboxylic acids (acid anhydride) such as maleic acid (acid anhydride) and molecule with the compound of more than 1 ethylenic unsaturated bond is polymer-modified etc.
As the compound in molecule with more than 1 ethylenic unsaturated bond, can enumerate such as: (methyl) acrylic acid and Arrcostab, (methyl) vinyl cyanide, (methyl) acrylamide, styrene, (gathering) alkylidene oxygen base or there is the substituent alkylidenes etc. such as alkyl.
As the polymkeric substance containing polybasic carboxylic acid (acid anhydride), wherein, from the viewpoint of transmitance, cured film intensity, preferred maleic anhydride and (gathering) alkylidene oxygen base or the multipolymer with substituent alkylidenes such as alkyl.
(G-3-4) thermal acid generator
As thermal acid generator, can enumerate such as: aromatic diazo salt, Diaryl iodonium salt, single phenyl sulfonium salt, triallyl sulfonium salt, triallyl selenium salt etc. are various salt compounds, sulphonic acid ester, halogen compound etc.
As concrete example, as aromatic diazo salt, can enumerate: chlorobenzene diazonium hexafluorophosphate, dimethylamino benzene diazonium hexafluoro antimonate, naphthyl diazonium hexafluorophosphate, dimethylamino naphthyl diazonium tetrafluoroborate etc.
In addition, as Diaryl iodonium salt, can enumerate: diphenyl iodine tetrafluoroborate, diphenyl iodine hexafluoro antimonate, diphenyl iodine hexafluorophosphate, diphenyl iodine fluoroform sulphonate, 4,4 '-di-t-butyl diphenyl iodine fluoroform sulphonate, 4,4 '-di-t-butyl diphenyl iodine tetrafluoroborate, 4,4 '-di-t-butyl diphenyl iodine hexafluorophosphate etc.
In addition, as single phenyl sulfonium salt, can enumerate: benzyl para hydroxybenzene ylmethyl sulfonium hexafluorophosphate, p-hydroxybenzene dimethyl sulfonium hexafluoro antimonate, to single phenyl sulfonium salt type or benzyl phenyl sulfonium salt types etc. such as the compounds shown in acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, benzyl para hydroxybenzene ylmethyl sulfonium hexafluoro antimonate, following formula (II).
[chemical formula 6]
(in formula, Z represents phenyl.)
In addition, as triallyl sulfonium salt, can enumerate: triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, three (rubigan) sulfonium tetrafluoroborate, three (rubigan) sulfonium hexafluorophosphate, three (rubigan) sulfonium hexafluoro antimonate, 4-tert-butyl group triphenylsulfonium hexafluorophosphate etc.
As triallyl selenium salt, can enumerate: triallyl selenium tetrafluoroborate, triallyl selenium hexafluorophosphate, triallyl selenium hexafluoro antimonate, two (chlorphenyl) phenyl selenium tetrafluoroborate, two (chlorphenyl) phenyl selenium hexafluorophosphate, two (chlorphenyl) phenyl selenium hexafluoro antimonate etc.
As sulphonic acid ester, can enumerate such as: benzoin p-toluenesulfonic acid ester, to nitrobenzyl-9,10-ethoxy anthracene-2-sulphonic acid ester, 2-nitrobenzyl p-toluenesulfonic acid ester, 2,6-dinitrobenzyl p-toluenesulfonic acid esters, 2,4-dinitrobenzyl p-toluenesulfonic acid esters etc.
As halogen compound, can enumerate: the chloro-2-phenyl acetophenone of 2-, 2, 2 ', 4 '-trichloroacetophenone, 2, 4, 6-tri-(trichloromethyl)-s-triazine, 2-(to methoxyl-styrene)-4, two (the trichloromethyl)-s-triazine of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4 '-methoxyl-1 '-naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-, two-2-(4-chlorphenyl)-1, 1, 1-trichloroethanes, two-1-(4-chlorphenyl)-2, 2, 2-ethapon, two-2-(4-methoxyphenyl)-1, 1, 1-trichloroethanes etc.
In these thermal acid generator, from the viewpoint of transmitance, cured film intensity, preferred single phenyl sulfonium salt type or benzyl phenyl sulfonium salt type.
(G-3-5) amines
As amines, can enumerate such as: ethylenediamine, 1,3-diaminopropanes, 1,4-diaminobutane, hexamethylene diamine, 2,5-dimethyl hexamethylene diamine, piperidines, pyrrolidine, triethylenediamine, trimethylhexamethylenediamine, dimethylcyclohexylam,ne, tetramethyl guanidine, triethanolamine, N, N '-dimethyl piperazine, two cyanamides, or derivatives thereof; DBU (1,8-diazabicyclo (5,4,0) undecene-1), the fatty amines (primary amine, secondary amine, tertiary amine) such as DBU class tetraphenyl borate salts; M-phenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamido diethyl diphenyl methane, benzyl dimethyl amine, dimethylamino paracresol, 2-(dimethyl amine dimethyl) phenol, 2,4,6-tri-(dimethylaminomethyl) phenol, pyridine, picoline, DBU (1,8-diazabicyclo (5,4,0) undecene-1), 2, the aromatic amines (primary amine, secondary amine, tertiary amine) such as three-2-ethylhexyl hydrochlorates of 4,6-tri-(dimethylaminomethyl) phenol; Glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-undecyl imidazole trimellitic acid salt, glyoxal ethyline isocyanurate, 2-phenylimidazole isocyanurate, 2,4-diamido-6-[glyoxal ethyline quinoline base-(1)]-ethyl-s-triazine, 2,4-diamido-6-[2-ethyl imidazol(e) quinoline base-(1)]-ethyl-s-triazine, 2,4-diamido-6-[2-undecyl imidazole quinoline base-(1)]-ethyl-s-triazine, 2-phenyl-4, the imidazolium compoundss such as 5-bishydroxymethyl imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis-(cyanoethoxy methyl) imidazoles; Diethylene triamine, imino group two propyl group amine, two (hexa-methylene) triamine etc.
Wherein, from the viewpoint of cured film intensity, be preferably two cyanamides, DBU class tetraphenyl borate salts.
(G-3-6) polyamine compounds
As polyamine compounds, can enumerate such as: the aromatic polyamines such as aliphatic polyamine, m-xylene diamine, xylylene diamine, xylylene diamine derivant, xylylene diamine tripolymer such as trientine, tetren, penten, dimethylamino propylamine, diethyl amino propylamine, N-aminoethylpiperazine, menthene diamines, isophorone diamine, two (4-amino-3-methylcyclohexyl) methane, diamino bicyclic hexyl amine, N, N-dimethylcyclohexylam,ne.Wherein, N, N-dimethylcyclohexylam,ne is preferably.
(G-3-7) carboxylic acid is closed
As closed carboxylic acid, can enumerate and such as utilize the method recorded in Japanese Unexamined Patent Publication 4-218561 publication, Japanese Unexamined Patent Publication 2003-66223 publication, Japanese Unexamined Patent Publication 2004-339332 publication, Japanese Unexamined Patent Publication 2004-339333 publication etc. to make above-mentioned (polynary) carboxylic acid and the carboxylic acid containing their polymkeric substance and vinyl ether addition and the closed carboxylic acid etc. that formed.
In above-mentioned hardening agent, good and high rigidity and the adaptation with supporter can be obtained from the viewpoint of the activity of curing reaction, preferably contain the polymkeric substance of polybasic carboxylic acid (acid anhydride), salt compounds, closed carboxylic acid compound, benzoic acid derivative.
More specifically, maleic anhydride can be enumerated and be selected from the polybasic carboxylic acid multipolymer of more than at least 1 vinyl compound in the ethene of alkyl, the polypropylene oxygen base propylidene of carbon number 1 ~ 15 or the polyethyleneoxy propylidene of carbon number 1 ~ 15 containing carbon number 1 ~ 20, butylene or propen compounds, styrene; The closed carboxylic acid compound be made up of the addition product of trimellitic acid or maleic acid and ethyl vinyl ether; The benzoic acid derivative such as DHB, Gallic Acid; Benzyl para hydroxybenzene ylmethyl sulfonium hexafluorophosphate, p-hydroxybenzene dimethyl sulfonium hexafluoro antimonate, to single phenyl sulfonium salts etc. such as single phenyl sulfonium salt type or benzyl phenyl sulfonium salt type such as the compounds shown in acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, benzyl-para hydroxybenzene ylmethyl sulfonium hexafluoro antimonate, following formula (II).
[chemical formula 7]
(in formula, Z represents phenyl.)
Wherein, polybasic carboxylic acid multipolymer, benzoic acid derivative with the adaptation raising of supporter in excellent, in addition, single sulfonium salt is excellent in hardness raising.
Particularly benzoic acid derivative, because Thermocurable is excellent, transmitance is high, and the impact of the color change caused by heat is low, therefore preferably.
In photosensitive polymer combination of the present invention containing hardening agent, as the content that hardening agent is shared in photosensitive polymer combination, relative to total solid composition, be generally more than 0.05 % by weight, be preferably more than 0.1 % by weight, and be generally less than 20 % by weight, preferably less than 10 % by weight.When the amount of hardening agent is very few, easily cause the reduction of the cementability to supporter, hardness, on the contrary, when it is too much, easily cause the increase that thermogravimetric reduces.
(G-4) hot polymerization inhibitor
In order to improve storage stability and improve resolving power, hot polymerization inhibitor can be coordinated in photosensitive polymer combination of the present invention.As hot polymerization inhibitor, specifically, can enumerate such as: optionally there are substituent O-hydroxyl-diphenyl ketone, p-dihydroxy-benzene, p methoxy phenol, BHT etc.As the mixing ratio of these compounds, relative to total solid composition, be generally less than 10 % by weight, be preferably less than 2 % by weight.
(G-5) polymerization accelerator
In order to improve sensitivity, polymerization accelerator can be added in photosensitive polymer combination of the present invention.As polymerization accelerator, specifically, can enumerate such as: the amino acid whose ester such as N-phenylglycine or its zwitterionic compound, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-sulfydryl benzo azoles, 3-sulfydryl-1, 2, 4-triazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene, ethylene glycol bisthioglycolate thiopropionate, trimethylolpropane tris thiopropionate, pentaerythrite tetrathio propionic esters etc. are containing the compounds of sulfydryl, ethanthiol, trimethylolpropane tris sulfo-gluconate, multi-functional thiol's compounds such as pentaerythrite tetrathio propionic ester, N, N-dialkylaminobenzoic acid esters, N-phenylglycine or its ammonium salt, the derivants such as sodium salt, phenylalanine or its ammonium salt, the salt such as sodium salt, the derivants such as ester etc. have the amino acid or derivatives thereof class etc. of aromatic rings.
In photosensitive polymer combination of the present invention, when adding polymerization accelerator, as its content, relative to total solid composition, be preferably less than 20 % by weight, more preferably 1 ~ 10 % by weight.
(G-6) ultraviolet light absorber
In photosensitive polymer combination of the present invention, ultraviolet light absorber can be contained as required.Ultraviolet light absorber is that the object controlling laser curing velocity when being exposed by the film of the photosensitive polymer combination of the present invention that substrate is formed thus is added by utilizing this ultraviolet light absorber to absorb the specific wavelength exposing the light source used.By adding ultraviolet light absorber, the exposure that can improve, develop after pattern form or remove the effects such as the residue that residues in non-exposed portion after development.
As ultraviolet light absorber, the compound such as between 250nm ~ 400nm with absorption maximum can be used.More specifically, can enumerate such as: the benzophenone cpd such as Sumisorb 130 (Sumitomo Chemical system), EVERSORB10, EVERSORB11, EVERSORB12 (Taiwan photochemistry industry forever system), Tomisorb 800 (API Corporation system), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (SHIPOR KASEI system), Sumisorb200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (Sumitomo Chemical system), JF77, JF78, JF79, JF80, JF83 (north of the city chemical industry system), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN900, TINUVIN928, TINUVIN1130 (BASF system), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (Taiwan photochemistry industry forever system), Tomisorb 100, Tomisorb 600 (API Corporation system), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, the benzotriazole cpds such as SEESORB709 (SHIPOR KASEI system), the benzoic acid ester compounds such as Sumisorb 400 (Sumitomo Chemical system), salicylic acid phenyl, the hydroxyphenyltriazinuv compounds etc. such as TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477DW, TINUVIN479 (BASF AG's system).
Wherein, preferred benzotriazole cpd, hydroxyphenyltriazinuv compound, particularly preferably benzotriazole cpd.
When adding these ultraviolet light absorbers, as its mixing ratio, relative to total solid composition, be generally more than 0.01 % by weight and less than 15 % by weight, be preferably more than 0.05 % by weight and less than 10 % by weight.
When its mixing ratio is more than above-mentioned lower limit, easily obtain at least one effect in the improvement of pattern form and removing residue, in addition, when its mixing ratio is below above-mentioned higher limit, sensitivity and residual film ratio are good, in this preferably.
(H) organic solvent
Above-mentioned each composition be usually with an organic solvent adjusted to solid component concentration be 5 ~ 60 % by weight, be preferably adjusted to the scope of 10 ~ 50 % by weight after use.
As organic solvent, as long as the solvent that above-mentioned each component dissolves, dispersion, applicability can be made good, be just not particularly limited.Specifically, can enumerate such as: methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, Propylene glycol monoacetate, propylene-glycol diacetate, diethylene glycol monobutyl ether acetic acid esters, propylene glycol monomethyl ether is (following, sometimes referred to as " PGMAc "), MEK, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, methylene chloride, ethyl acetate, methyl lactate, ethyl lactate, propionic acid 3-methoxyl methyl esters, propionic acid 3-ethoxy ethyl ester, propylene glycol monomethyl ether, methyl alcohol, ethanol, propyl alcohol, butanols, tetrahydrofuran, diethylene glycol dimethyl ether, methoxybutyl acetic acid esters, solvesso, carbitol etc.
As the boiling point of above-mentioned organic solvent, be preferably the scope of 100 ~ 200 DEG C, be more preferably the scope of 120 ~ 170 DEG C.
In addition, organic solvent can be used alone a kind, also can be mixed with two or more.As the combination of organic solvent used in combination, the solvent being such as mixed with more than the a kind organic solvent be selected from diethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetic acid esters, methoxybutyl acetic acid esters, solvesso, carbitol in PGMAc can be enumerated.
And then, in above-mentioned mixed solvent, the mixing ratio being selected from more than a kind organic solvent in diethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetic acid esters, methoxybutyl acetate, solvesso, carbitol is generally more than 10 % by weight relative to PGMAc, is preferably more than 30 % by weight, and is generally less than 80 % by weight, preferably less than 70 % by weight.
In addition, in above-mentioned mixed solvent, the mixed solvent of PGMAc and methoxybutyl acetic acid esters due to the suitable mobility of the coated film in coating drying process can be caused, therefore, in order to make the concavo-convex planarization of substrate, the mixed solvent of preferred PGMAc and methoxybutyl acetic acid esters.
< positive type photosensitive organic compound >
Positive type photosensitive organic compound of the present invention is except above-mentioned (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin, containing (I) containing photoacid generator, and as required further containing (F) thermal cross-linking agent, (G) other composition, (H) organic solvent of recording in the item of above-mentioned < negative light-sensitive resin combination >.
The concrete example of (F) thermal cross-linking agent that can contain in positive type photosensitive organic compound, (G) other composition, (H) organic solvent and preferred mode are as described above.
[(I) photoacid generator]
(I) photoacid generator in the present invention generates acidic-group by exposure thus improves the deliquescent compound relative to alkaline developer, can enumerate such as 1,2-naphthalene quinone di-azido compound, 1,2-quinonediazide compound etc.
Specifically, can enumerate: 2,3,1, the 2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3 of 4-trihydroxybenzophenone, 1, the 2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3 of 4-trihydroxybenzophenone, 1 of 4-trihydroxybenzophenone, 2-benzoquinones two nitrine-4-sulphonic acid ester, 2,3,4,1 of 4 '-tetrahydroxybenzophenone, 2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,1 of 4 '-tetrahydroxybenzophenone, 2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,1, the 2-benzoquinones two nitrine-4-sulphonic acid ester etc. of 4 '-tetrahydroxybenzophenone.
As the match ratio of the composition (I) in photosensitive polymer combination of the present invention relative to composition (C), with the cooperation gauge of composition (I) relative to composition (C) 100 weight portion, be generally below 100 weight portions, be preferably below 70 weight portions, and be generally more than more than 20 weight portions, preferably 30 weight portions.
The formation method > of < interlayer dielectric
Below, the formation method of the interlayer dielectric of negative light-sensitive resin combination that uses special in photosensitive polymer combination of the present invention is described.
[1] working procedure of coating
First, spin coater, line rod, flowing coating machine, mould is used to be coated with the apparatus for coating such as machine, slit coating machine, roll coater, flush coater on substrate, to be coated with above-mentioned photosensitive polymer combination of the present invention.The coating film thickness of photosensitive polymer combination is generally 0.2 ~ 5 μm.
[2] drying process
From above-mentioned coated film, volatile ingredient removing (drying) is formed dry coating.Vacuum drying, hot plate, IR baking oven, convection oven etc. can be used in drying.Preferred drying condition be temperature 40 ~ 150 DEG C, drying time 10 second ~ scope of 60 minutes.
[3] exposure, developing procedure
Then, the dry coating of photosensitive polymer combination layer places photomask, carry out image exposure via this photomask.After exposure, by the unexposed uncured portion of development removing, form image thus.It should be noted that, after exposure, sometimes to carry out post-exposure, to cure putting forward highly sensitive object before developing.Electric hot plate, IR baking oven, convection oven etc. can be used in the curing of this situation.Post-exposure, baking conditions be generally 40 ~ 150 DEG C, drying time 10 second ~ scope of 60 minutes.
Usually, to the line reproducibility of the image request 20 μm of fabric widths obtained after development.In addition, in order to realize the display of high image quality, there is the tendency requiring the line reproducibility of more fine.On the basis of the fine rule of stable reproduction fine, as the cross sectional shape of the fine rule image after development, preferably non-image and contrast that is image portion be rectangle clearly because its development time, developer solution through time, the development latitude such as the physical stimulation that sprays of development is wide.
As the light source of the exposure process for dry coating, can enumerate such as: the LASER Light Source etc. such as the lamp source such as xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp or argon laser, YAG laser, excimer laser, N_2 laser.When only using the light of specific wavelength, also light filter can be utilized.
As the solvent for development treatment, preferred use alkaline developer, can enumerate the aqueous solution such as containing organo-alkali compounds such as inorganic alkali compound or diethanolamine, triethylamine, triethanolamine, Tetramethylammonium hydroxide such as sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, potassium silicate, NaOH, potassium hydroxide.
It should be noted that, in alkaline developer, also can contain surfactant, water miscible organic solvent, wetting agent as required, there is the low molecular compound etc. of hydroxyl or carboxylic acid group.Particularly preferably add surfactant, because its large multipair developability, distinguishing, residue etc. have improve effect.
As the surfactant used in developer solution, can enumerate such as: have sodium naphthalene sulfonate base, benzene sulfonic acid sodium salt base anionic surface active agent, there is the nonionic surfactant of polyalkylene oxide base, there is the cationic surfactant etc. of tetraalkyl ammonium.
The method of development treatment is not particularly limited, usually by 10 ~ 50 DEG C, preferably under the development temperature of 15 ~ 45 DEG C, utilize the methods such as the development of immersion development, paddle, spray development, fur brush development, supersonic wave development to carry out.
[4] heat treatment step
By exposure, developing procedure has carried out the photosensitive polymer combination film that image formed then becomes solidfied material (heat cured film) through bakingout process (firmly curing) operation.It should be noted that, after development, before firmly curing, sometimes carry out whole exposure, generation degassed during to suppress firmly to cure.
When before firmly curing whole exposure, as light source, ultraviolet light or visible ray can be used, can enumerate such as: the LASER Light Source etc. such as the lamp source such as xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp or argon laser, YAG laser, excimer laser, N_2 laser.
Or, hot plate, IR baking oven, convection oven etc. can be used in firmly curing.As hard baking conditions, be generally 100 ~ 250 DEG C, drying time 30 second ~ scope of 90 minutes.
< TFT active array base plate and liquid crystal indicator (panel) >
Below, the TFT active array base plate of the present invention containing interlayer dielectric (film containing above-mentioned solidfied material) formed as described above and liquid crystal indicator (panel) are described.
Liquid crystal indicator of the present invention is usually containing TFT active array base plate.
First, TFT active array base plate is formed as follows: on the substrate defining TFT element array, above-mentioned solidfied material is formed as interlayer dielectric, forms ito film thereon, then utilizes photoetching process to form ITO wiring.
And liquid crystal indicator of the present invention can by forming liquid crystal cells by above-mentioned TFT active array base plate and subtend baseplate-laminating, injecting liquid crystal in the liquid crystal cells formed, completing counter electrode wiring.
As subtend substrate, usually preferably use the colour filtering chip basic board with alignment films.
As alignment films, the resin molding of preferred polyimide etc.
When the formation of alignment films, usually adopt at least one in gravure processes and flexographic printing method, the thickness of alignment films is set to several 10nm.Burnt into the solidification process of row alignment films by forged, then by irradiation ultraviolet radiation or utilize the process of friction cloth to carry out surface treatment, be processed into the surface state of the inclination that can adjust liquid crystal.It should be noted that, in alignment films, interlayer dielectric similar to the above can be formed further.
As the laminating gap of above-mentioned TFT active array base plate and subtend substrate, different from the purposes of liquid crystal indicator, usually select in the scope of less than 8 μm more than 2 μm.After subtend baseplate-laminating, the part beyond liquid crystal injecting port utilizes the encapsulant encapsulation such as epoxy resin.
As such encapsulant, usually using can by carrying out UV irradiation and adding at least one of hankering and the material solidified, and liquid crystal cells periphery is sealed.After liquid crystal cells after peripheral sealing is cut into panel unit, reduce pressure in vacuum chamber, above-mentioned liquid crystal injecting port be impregnated in liquid crystal, make to put vacuum in vacuum chamber, liquid crystal can be injected in above-mentioned liquid crystal cells thus.
As the degree of decompression in liquid crystal cells, be generally 1 × 10 -2more than Pa, preferably 1 × 10 -3more than Pa, and be generally 1 × 10 -7below Pa, preferably 1 × 10 -6the scope of below Pa.In addition, preferably when reducing pressure, liquid crystal cells is heated.As the heating-up temperature in this situation, be generally more than 30 DEG C, be preferably more than 50 DEG C, and be generally less than 100 DEG C, the preferably scope of less than 90 DEG C.
As heating conservation condition during decompression, be generally more than 10 minutes and the scope of less than 60 minutes.Then, liquid crystal cells is impregnated in liquid crystal.Liquid crystal injecting port seals by making UV cured resin solidify by the liquid crystal cells being filled with liquid crystal.Like this, liquid crystal indicator (panel) can be completed.
It should be noted that, the kind of liquid crystal is not particularly limited, the liquid crystal that the fragrant same clan, aliphatic category, polycyclic compound etc. are known at present can be used, can be lyotropic liquid crystal, thermotropic liquid crystal etc. any one.In thermotropic liquid crystal, there will be a known nematic crystal, smectic crystal and cholesteryl liquid crystal etc., can be any one.
Embodiment
Below, enumerate embodiment and comparative example, the present invention is more specifically described, as long as but the present invention is no more than its purport, be not limited to following embodiment.
(with reference to synthesis example 1)
Polycaprolactone 40 weight portion of polyethyleneimine 50 weight portion and n=5 with molecular weight about 5000 is mixed with PGMAc210 weight portion, at 150 DEG C, under nitrogen atmosphere, has stirred 3 hours.The weight-average molecular weight (Mw) of the Resin A obtained is 9000.
(preparation of barium titanate microparticles dispersion liquid)
High-purity perovskite YKT-50 (Sakai Chemical Industry Co., Ltd.'s manufacture, average primary particle diameter 50nm) 23 weight portions are prepared, as Resin A 7.5 weight portion, PGMAc 69.5 weight portion that synthesize in the above-mentioned reference synthesis example 1 of spreading agent.The liquid bead mill apparatus be prepared into (employing the zirconium oxide bead of 0.5mm φ) is implemented dispersion treatment with peripheral speed 10m/s, 3 hours hold-up times, obtains barium titanate microparticles dispersion liquid (A1).
(embodiment 1 ~ 7, comparative example 1 ~ 3)
Photosensitive polymer combination has been prepared according to following table 1.
The photosensitive polymer combination obtained is coated on the glass substrate of color filter glass plate AN100 (Asahi Glass Co., Ltd's system), 130 DEG C of drying 60 seconds on hot plate, obtains the coated film of dry film thickness 1 μm.Then, 3kW high-pressure mercury-vapor lamp is used to expose from coated film side across the mask of the thread pattern with line width 5 μm ~ 50 μm.As conditions of exposure, be 20mW/cm by the image surface illumination that the illuminometer of wavelength 365nm measures 2, be set to the exposure becoming optimum exposure described later.
Then, use the tetramethylammonium hydroxide aqueous solution of 2.38 % by weight as developer solution, at 25 DEG C, substrate be impregnated in developer solution for 90 seconds, implement development thus, obtain exposed film by pure water rinsing further.The exposed film obtained is heated 30 minutes in 230 DEG C in convection oven, resulting in heat cured film.
Various evaluation is carried out to above-mentioned photosensitive polymer combination, exposed film and heat cured film.Result is recorded in table 1 in the lump.
Below, carry out describing to the details of each composition used in embodiment and comparative example and evaluation method.
The details > of < composition
(A) barium titanate microparticles
A1: utilize the dispersion liquid (containing barium titanate microparticles 23.0 % by weight) that the preparation method of above-mentioned barium titanate microparticles dispersion liquid is prepared by high-purity perovskite YKT-50 (Sakai Chemical Industry Co., Ltd.'s manufacture, average primary particle diameter 50nm).
(B) zirconia particles
B1:NANOUSE OZ-S30K-AC (Nissan Chemical Ind Ltd's manufacture)
Methyl ethyl ketone solution containing 30.0 % by weight zirconia particles (average primary particle diameter 10nm)
(C) alkaline bleach liquor soluble resin
C1: styrene/methacrylic acid methyl/methacrylic acid (mol ratio 45/35/20) multipolymer
[chemical formula 8]
Acid number: 111
Molecular weight (Mw): 6600
37 % by weight PGMAc solution
C2: methyl methacrylate/2-hydroxyl-metacrylate/methacrylic acid (mol ratio 75/15/10) multipolymer
[chemical formula 9]
Acid number: 35
Molecular weight (Mw): 11000
30 % by weight PGMAc solution
(D) there is the compound of ethylenically unsaturated group
D1:KAYARAD DPHA (Nippon Kayaku K. K's system)
[chemical formula 10]
The potpourri of a=5, b=1 and a=6, b=0
D2: epoxy radicals ester 3000A (chemistry society of common prosperity society system)
[chemical formula 11]
(E) Photoepolymerizationinitiater initiater
E1:IRGACURE OXE02 (BASF AG's manufacture)
[chemical formula 12]
(G) other composition
(G-4) hot polymerization inhibitor
G1: methyl hydroquinone
(G-6) ultraviolet light absorber
G2:TINUVIN384-2 (BASF AG's manufacture)
[chemical formula 13]
(H) organic solvent
H1: propylene glycol methyl ether acetate (PGMAc)
< evaluation method >
(acid number)
For alkaline bleach liquor soluble resin, measure according to JIS-K0070 (benchmark grease test method(s)).
(light transmission)
Be coated with photosensitive polymer combination of the present invention on the glass substrate, dry film thickness is made to be 1 μm, measure the light transmission of the heat cured film obtained in above-mentioned (embodiment 1 ~ 7, comparative example 1 ~ 3) item with spectrophotometer UV3100PC (Shimadzu Seisakusho Ltd.'s manufacture), obtain the minimum transmittance (%) in wavelength 600nm ~ 400nm scope.
(sensitivity)
Be coated with photosensitive polymer combination of the present invention on the glass substrate, make dry film thickness be 1 μm, on hot plate in 130 DEG C, cure under the condition in 60 seconds.Then, utilize high-pressure mercury-vapor lamp with 20mW/cm 2illumination expose.As conditions of exposure, be 10mJ/cm at exposure energy 2to 100mJ/cm 2scope in, with every 2 1/2interval setting exposure energy doubly exposes.After exposure, impregnated in 90 seconds in the 2.38wt% tetramethylammonium hydroxide aqueous solution of 25 DEG C, by pure water rinsing, determine the thickness of remaining cured film (exposed film).
Mark and draw the thickness of the exposed film obtained relative to exposure, by certain exposure and its 2 1/2the film thickness difference of the exposed film in exposure is doubly that the minimum exposure amount within 10% is defined as sensitivity (mJ/cm 2).
(distinguishing)
The image of the heat cured film utilizing observation by light microscope to be obtained by the forming step of above-mentioned heat cured film, is set to distinguishing by the minimum line width (μm) differentiated.
(pattern form)
By the line pattern shape of the line width of 20 μm of heat cured film obtained by the forming step of above-mentioned heat cured film with sem observation, its pattern form according to following benchmark evaluation.
A: rectangularity is good, does not have crease base
B: rectangularity is good, but has crease base a little
C: rectangularity is bad, maybe can not differentiate
(residue)
The line of the line width of 20 μm of the heat cured film utilizing observation by light microscope to be obtained by the forming step of above-mentioned heat cured film and void pattern, according to the residue of following its gap portion of benchmark evaluation.
A: without residue
B: see residue a little at resist periphery
C: also see residue at gap portion central portion
(specific inductive capacity)
The evaporation substrate of chromium forms heat cured film according to the forming step of above-mentioned heat cured film to glass.The heat cured film obtained utilizes ion plating machine with the thickness gold evaporation of 100nm, form the circular electrode of diameter 6mm.Between the chromium film and the golden film on upper strata of lower floor, apply the alternating voltage of 1kHz, determine the static capacity of heat cured film with LCR measurement, obtained specific inductive capacity thus.
As shown in table 1, for the interlayer dielectric using photosensitive polymer combination of the present invention to be formed, have both the specific inductive capacity as the relation of compromise selection and high resolution, and there is high-transmission rate and high sensitivity.
In addition, the pattern form of photosensitive polymer combination of the present invention and residue also good.
It can thus be appreciated that the solidfied material that the above-mentioned photosensitive polymer combination of use of the present invention is formed, the interlayer dielectric containing this solidfied material and the TFT active array base plate containing this interlayer dielectric are high-quality.
With reference to specific embodiment, the present invention is illustrated in detail, but to those skilled in the art, various change or correction can be carried out in the scope not departing from the spirit and scope of the present invention.The Japanese patent application (Japanese Patent Application 2012-101699) that the application applied for based on April 26th, 2012, its content is introduced in this as reference.

Claims (7)

1. a photosensitive polymer combination, it contains: (A) barium titanate microparticles, (B) zirconia particles and (C) alkaline bleach liquor soluble resin.
2. photosensitive polymer combination according to claim 1, wherein, the average primary particle diameter of (A) barium titanate microparticles and (B) zirconia particles is more than 1nm and below 1000nm independently of one another.
3. photosensitive polymer combination according to claim 1 and 2, it also contains: (D) has compound and (E) Photoepolymerizationinitiater initiater of ethylenically unsaturated group.
4. a solidfied material, it uses the photosensitive polymer combination according to any one of claim 1 ~ 3 to be formed.
5. an interlayer dielectric, it contains solidfied material according to claim 4.
6. a TFT active array base plate, it has interlayer dielectric according to claim 5.
7. a liquid crystal indicator, it has TFT active array base plate according to claim 6.
CN201380021084.0A 2012-04-26 2013-04-25 Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device Pending CN104246609A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012101699 2012-04-26
JP2012-101699 2012-04-26
PCT/JP2013/062296 WO2013161968A1 (en) 2012-04-26 2013-04-25 Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device

Publications (1)

Publication Number Publication Date
CN104246609A true CN104246609A (en) 2014-12-24

Family

ID=49483267

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380021084.0A Pending CN104246609A (en) 2012-04-26 2013-04-25 Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device

Country Status (4)

Country Link
JP (1) JP6304026B2 (en)
KR (1) KR102006046B1 (en)
CN (1) CN104246609A (en)
WO (1) WO2013161968A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106444279A (en) * 2015-08-13 2017-02-22 太阳油墨制造株式会社 Photosensitive resin composition, dry film, and printed circuit board (PCB)
CN107272342A (en) * 2016-03-30 2017-10-20 东友精细化工有限公司 Negative-type photosensitive resin composition
CN109682868A (en) * 2017-10-18 2019-04-26 东友精细化工有限公司 The manufacturing method of evaluation unit
CN111722482A (en) * 2019-03-20 2020-09-29 富士施乐株式会社 Electrophotographic photoreceptor, process cartridge, and image forming apparatus

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6274039B2 (en) * 2014-06-12 2018-02-07 Jsr株式会社 Radiation-sensitive resin composition, insulating film and display element
CN105467765B (en) * 2014-09-30 2020-04-24 富士胶片株式会社 Photosensitive composition, method for producing cured film, and use thereof
NL2015885A (en) 2014-12-23 2016-09-22 Asml Netherlands Bv Lithographic patterning process and resists to use therein.
JP6660000B2 (en) * 2015-11-06 2020-03-04 Jsr株式会社 Liquid crystal display device and radiation-sensitive resin composition
JP6954273B2 (en) * 2017-03-29 2021-10-27 東レ株式会社 Photosensitive composition, cured film and organic EL display device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006210044A (en) * 2005-01-26 2006-08-10 Toray Ind Inc Photosensitive dielectric paste and manufacturing method of electronic circuit component using it
CN1934659A (en) * 2004-03-29 2007-03-21 日本化学工业株式会社 Inorganic dielectric powder for composite dielectric material and composite dielectric material
CN101109879A (en) * 2006-07-19 2008-01-23 株式会社日立显示器 Liquid display device and fabrication method thereof
WO2008117710A1 (en) * 2007-03-26 2008-10-02 Murata Manufacturing Co., Ltd. Photosensitive dielectric paste and electronic part made with the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52109197A (en) * 1976-03-09 1977-09-13 Nichicon Capacitor Ltd Highhdielectric ceramic composition
JPH05213669A (en) * 1992-01-31 1993-08-24 Asahi Chem Ind Co Ltd Dielectric porcelain composition
JP4565211B2 (en) 2001-06-05 2010-10-20 Ｊｓｒ株式会社 Composition for forming photosensitive dielectric, dielectric and electronic component
JP4565212B2 (en) 2001-06-05 2010-10-20 Ｊｓｒ株式会社 Photosensitive transfer film, dielectric and electronic parts
JP4565213B2 (en) 2001-08-13 2010-10-20 Ｊｓｒ株式会社 Composition for forming photosensitive dielectric, transfer film, dielectric and electronic component
JP5256646B2 (en) * 2006-05-31 2013-08-07 三菱化学株式会社 Liquid crystal display
JP5256645B2 (en) * 2006-05-31 2013-08-07 三菱化学株式会社 Thermosetting composition for protective film, cured product, and liquid crystal display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1934659A (en) * 2004-03-29 2007-03-21 日本化学工业株式会社 Inorganic dielectric powder for composite dielectric material and composite dielectric material
JP2006210044A (en) * 2005-01-26 2006-08-10 Toray Ind Inc Photosensitive dielectric paste and manufacturing method of electronic circuit component using it
CN101109879A (en) * 2006-07-19 2008-01-23 株式会社日立显示器 Liquid display device and fabrication method thereof
WO2008117710A1 (en) * 2007-03-26 2008-10-02 Murata Manufacturing Co., Ltd. Photosensitive dielectric paste and electronic part made with the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106444279A (en) * 2015-08-13 2017-02-22 太阳油墨制造株式会社 Photosensitive resin composition, dry film, and printed circuit board (PCB)
CN107272342A (en) * 2016-03-30 2017-10-20 东友精细化工有限公司 Negative-type photosensitive resin composition
CN109682868A (en) * 2017-10-18 2019-04-26 东友精细化工有限公司 The manufacturing method of evaluation unit
CN111722482A (en) * 2019-03-20 2020-09-29 富士施乐株式会社 Electrophotographic photoreceptor, process cartridge, and image forming apparatus

Also Published As

Publication number Publication date
KR102006046B1 (en) 2019-07-31
JPWO2013161968A1 (en) 2015-12-24
KR20150003744A (en) 2015-01-09
JP6304026B2 (en) 2018-04-04
WO2013161968A1 (en) 2013-10-31

Similar Documents

Publication Publication Date Title
CN101390017B (en) Heat curable composition for protective film, cured product, and liquid crystal display device
CN104246609A (en) Photosensitive resin composition, cured product, interlayer insulating film, tft active matrix substrate and liquid crystal display device
CN101395535B (en) Heat curable composition for protective film, cured product and liquid crystal display device
JP4826918B2 (en) Photopolymerizable composition
KR101352147B1 (en) Negative photosensitive resin composition
CN101395534B (en) Heat curable composition for protective film, cured product and liquid crystal display device
CN102236259A (en) Radiation sensitivity resin composition for display element, interlayer insulation film, protective film and spacer and forming method thereof
CN107636536A (en) The display device of resin combination and the black dyke including being manufactured by using it
JP2013534326A (en) Negative photosensitive resin composition
CN105911818A (en) Photoresist composition, hardening film making method, hardening film and application thereof
JP4992518B2 (en) Photopolymerizable composition
KR20090114494A (en) Negative photosensitive resin composition
CN105911819A (en) Photoresist composition, hardening film making method, hardening film and application thereof
CN106933031A (en) Photosensitive composite, cured film preparation method, cured film, Trackpad and display device
JP2013167786A (en) Curable resin composition for organic insulating film, cured material, tft active matrix substrate, and liquid-crystal display
CN101025567A (en) Radiation-sensitive resin composition, method for forming spacer and spacer
JP2006251536A (en) Thermosetting composition for protective film, color filter, and liquid crystal display device
CN109564385B (en) Photosensitive resin composition, cured product, interlayer insulating film, TFT active matrix substrate, and image display device
JP4992534B2 (en) Photopolymerizable composition
JP2007241084A (en) Heat-curable composition for protective film, color filter and liquid crystal display device
KR20070038903A (en) Curable resin composition, process for forming a cured film, and cured film
TW202116830A (en) Photosensitive resin composition
KR20240013372A (en) Novel polymer and photosensitive resin composition comprising the same
KR20190052727A (en) Photosensitive resin composition and method of forming pattern using the same
KR20100072960A (en) Ink jet resin composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: Tokyo, Japan

Applicant after: MITSUBISHI CHEMICAL Corp.

Address before: Tokyo, Japan

Applicant before: MITSUBISHI RAYON Co.,Ltd.

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20170822

Address after: Tokyo, Japan

Applicant after: MITSUBISHI RAYON Co.,Ltd.

Address before: Tokyo, Japan

Applicant before: MITSUBISHI CHEMICAL Corp.

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20141224