CN102597879A - Photosensitive resin composition - Google Patents
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- CN102597879A CN102597879A CN201180004535.0A CN201180004535A CN102597879A CN 102597879 A CN102597879 A CN 102597879A CN 201180004535 A CN201180004535 A CN 201180004535A CN 102597879 A CN102597879 A CN 102597879A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
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- 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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- 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
- G03F7/075—Silicon-containing compounds
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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Abstract
Disclosed is a photosensitive resin composition-that can form a minute pattern by means of photolithography, can form a insulating film without heat treatment above 200 DEG C, and has no problems of carrier being trapped and charge mobility decreasing when used as a gate insulating film of an organic thin-film transistor-containing a photo-radical generating agent and a polysiloxane compound having units represented by the belowmentioned general formulae (1-4). (In formula 1, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkylene group having a carbon number of 1-5 that may have a substituent alkyl group. In formula 2, R3 represents a hydrogen atom or an alkyl group having a carbon number of 1-4. In formula 3, R4 represents an alkyl group having a carbon number of 1-6 or a cycloalkyl group having a carbon number of 5-6. In formula 4, R5 represents a hydrogen atom or an alkyl group having a carbon number of 1-4.)
Description
Technical field
The present invention relates to use the photosensitive polymer combination of polysiloxane compound, and then related to the negative type photoresist (particularly permanent resist) of having used this photosensitive polymer combination.
Background technology
In recent years, the research of display device such as relevant liquid crystal indicator, EL display device is extensively carried out, and as can be with one of electrically driven (operated) display device of low consumption, Electronic Paper have received concern.Electronic Paper can make the such thin thickness of paper, even and have low power consumption and cut off the electricity supply and also can keep the advantage of image, and the utilization in e-book and advertisement poster of waiting in expectation.According to thinking, if the display base plate of Electronic Paper uses plastic sheeting, the drive division of display device uses OTFT, though then can be soft and bending also can can't harm article quality and show that range of application is also wide, constantly universal.
The gate insulating film of OTFT generally is that the material of inorganic system that insulativity such as silit, silicon nitride, aluminium oxide, tantalum oxide, titanium dioxide is high is made through CVD method film forming; But because the CVD method needs large-scale vacuum systems device, so aspect manufacturing cost, have problems.In addition, the material of above-mentioned inorganic system is hard and upright and outspoken, so on being used for flexible base, board such as plastic sheeting the time, might be because of crooked damaged.
Contrast with it; The material of organic system dissolves in more in the organic solvent; So can come to carry out at low cost a large amount of manufacturings through rubbing method or print process; And bendability and the adhesiveness on plastic sheeting are good, so the organic insulation that the gate insulating film of OTFT is used is studied always widely.
Electronic Paper etc. need fine display device, require to form fine pattern on the gate insulating film of use therein OTFT.Formation method as fine pattern; Photoetching process is arranged; As the condensation product that can pass through the photosensitive polymer combination that photoetching process forms gate insulating film, know to contain alkoxy silane and the photosensitive polymer combination (reference example such as patent documentation 1～3) of photoacid generator or generated base alkaline agent.
But with regard to above-mentioned photosensitive polymer combination, remaining photoacid generator or generated base alkaline agent and their analyte might cause electric leakage.In addition, for the crosslinked photosensitive polymer combination that makes through alkoxysilyl solidifies, must about 200～500 ℃, heat-treat.Therefore, can not be with the plastic sheeting of polycarbonate, polyethylene terephthalate etc. as substrate.As can photoetching and can obtain the photosensitive polymer combination of the high dielectric film of insulativity; Known and contained the polysiloxane compound with epoxy radicals and the photosensitive polymer combination of photoacid generator; But the dielectric film that is obtained by such photosensitive polymer combination can be caught the charge carrier that forms in the semiconductor layer because of the hydroxyl that the open loop of epoxy radicals generates, so the problem that exists the electric charge degree of excursion to descend.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 6-148895 communique
Patent documentation 2: TOHKEMY 2007-43055 communique
Patent documentation 3: TOHKEMY 2007-316531 communique
Summary of the invention
The problem that the present invention will solve
Therefore; The objective of the invention is; A kind of photosensitive polymer combination is provided, and it can form fine pattern through photoetching process, and the thermal treatment that does not surpass 200 ℃ just can form dielectric film; And when using, do not have that charge carrier is hunted down and problem that the electric charge degree of excursion is descended as the gate insulating film of OTFT.
The means that are used to deal with problems
The present inventor In view of the foregoing furthers investigate, and the result has accomplished the present invention.That is, the present invention provides a kind of photosensitive polymer combination, and it contains polysiloxane compound and the optical free radical generation agent that has by the unit of formula (1)～(4) expression.
(in the above-mentioned general formula (1), R
1Expression hydrogen atom or methyl, R
2The carbon number that expression can have a substituted alkyl is 1～5 alkylidene.）
(in the above-mentioned general formula (2), R
3Expression hydrogen atom or carbon number are 1～4 alkyl.）
(in the above-mentioned general formula (3), R
4The expression carbon number is that 1～6 alkyl or carbon number are 5 or 6 naphthenic base.）
(in the above-mentioned general formula (4), R
5Expression hydrogen atom or carbon number are 1～4 alkyl.）
The effect of invention
Effect of the present invention is: can provide that a kind of can to obtain not only the transparency high, and the thermotolerance of the temperature can tolerate substrate manufacture time the and solvent resistance so as permanent resist anti-through the time variability good insulation course photosensitive polymer combination (particularly negative light-sensitive resin combination), used the negative type photoresist (particularly forever resist) of this photosensitive polymer combination.
Description of drawings
Fig. 1 be with by embodiment 1 and 2 and the film that obtains of the photosensitive polymer combination of comparative example 1 and 2 process the summary sectional view of OTFT of the bottom gate/top contact type of gate insulating film.
Embodiment
Below, according to preferred example the present invention is elaborated.
At first, describe having by the polysiloxane compound of the unit of above-mentioned general formula (1)～(4) expressions (following be also referred to as sometimes polysiloxane compound of the present invention).
In the above-mentioned general formula (1), R
1Expression hydrogen atom or methyl are because storage stability is good, so preferable methyl.R
2The carbon number that expression can have a substituted alkyl is 1～5 alkylidene.It as carbon number 1～5 alkylidene; Can enumerate out methylene, ethylidene, propylidene, butylidene and pentylidene, consider from thermotolerance, preferred carbon number is less; But the easy property consideration that obtains from industry; Preferred ethylidene, propylidene and butylidene, more preferably ethylidene and propylidene, most preferably propylidene.As R
2In the substituted alkyl that can have, can enumerate out for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group etc., but consider preferably do not have substituted alkyl from thermotolerance.
In the above-mentioned general formula (2), R
3Expression hydrogen atom or carbon number are 1～4 alkyl, are 1～4 alkyl as carbon number, can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group etc.As R
3, because going up easily, industry obtains, and the good reason of thermotolerance, preferred hydrogen atom.
In the above-mentioned general formula (3), R
4The expression carbon number is that 1～6 alkyl or carbon number are 5 or 6 naphthenic base.It as carbon number 1～6 alkyl; Can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, neopentyl, 2-amyl group, tertiary pentyl, hexyl, 2-hexyl etc.; As carbon number is 5 or 6 naphthenic base, can enumerate out cyclopentyl, cyclohexyl, methylcyclopentyl, cyclopentyl-methyl etc.As R
4, because thermotolerance is good, preferred ethyl and methyl, more preferably methyl.
In the above-mentioned general formula (4), R
5Expression hydrogen atom or carbon number are 1～4 alkyl.As carbon number is 1～4 alkyl, can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group etc.As R
5, because going up easily, industry obtains, and the good reason of thermotolerance, preferred hydrogen atom.
In polysiloxane compound of the present invention, the content of the unit of above-mentioned general formula (1) expression is preferably 0.1～5mmol/g, and more preferably 0.5～3mmol/g most preferably is 1～2.5mmol/g.The content of the unit of above-mentioned general formula (2) expression is preferably 0.01～0.8 with respect to the summation of the quantity of the unit of above-mentioned general formula (1)～(4) expression, and more preferably 0.03～0.5, most preferably be 0.05～0.3.The content of the unit of above-mentioned general formula (3) expression is preferably 0.03～0.8 with respect to the summation of the quantity of the unit of above-mentioned general formula (1)～(4) expression, and more preferably 0.07～0.7, most preferably be 0.15～0.6.The content of the unit of above-mentioned general formula (4) expression is preferably 0.01～0.6 with respect to the summation of the quantity of the unit of above-mentioned general formula (1)～(4) expression, and more preferably 0.03～0.4, most preferably be 0.05～0.25.
In addition; For the summation of the quantity of the unit of the quantity of the unit of above-mentioned general formula (2) expression and above-mentioned general formula (4) expression ratio with respect to the quantity of the unit of above-mentioned general formula (3) expression; The difference of the purposes that photosensitive polymer combination according to the present invention is used and difference, when using as negative type photoresist, this ratio is preferably 0.3～5.0; More preferably 0.5～3, most preferably be 1.5～2.5.In addition, when photosensitive polymer combination of the present invention was used as transparent materials such as lens, optical waveguides, this ratio was preferably 0.3～7.0, and more preferably 0.3～5, most preferably be 0.3～3.
When the molecular weight of polysiloxane compound of the present invention is too small; The coating of photosensitive polymer combination of the present invention and film forming become insufficient; And molecular weight is when excessive, and the property handled decline is so the matter average molecular weight of polysiloxane compound of the present invention is preferably 1000～100000; More preferably 2000～50000, most preferably be 3000～20000.In addition, among the present invention, the matter average molecular weight is meant with tetrahydrofuran (below be called THF) to be the matter average molecular weight of the polystyrene conversion of solvent when carrying out gpc analysis.
Polysiloxane compound of the present invention is on its manufacturing approach; Possible residual silanol groups (SiOH yl); But the existence of silanol group can make the storage stability of photosensitive polymer combination of the present invention descend; So the content of the silanol group in the polysiloxane compound of the present invention is preferably below the 1.0mmol/g, more preferably below the 0.1mmol/g.In addition, silanol group can through used near infrared ray spectrophotometer (with reference to TOHKEMY 2001-208683 communique, TOHKEMY 2003-35667 communique etc.) or
29The instrumental analysis of Si-NMR (with reference to TOHKEMY 2007-217249 communique etc.) is carried out quantitatively.Silanol group can as after utilize halogenated silanes compound or hydrolyzable ester to make its minimizing stating.
Owing to improving adhering reason, polysiloxane compound of the present invention preferably further has the unit by formula (5) expression.
E-SiO
3/2 (5)
(in the above-mentioned general formula (5), E representes to have the group of epoxy radicals.）
In the above-mentioned general formula (5); E representes to have the group of epoxy radicals; As group, can enumerate out the group of for example representing, owing to the big reason of adhering raising effect by formula (6)～(8) with epoxy radicals; The group of preferably representing by formula (7) and (8), the group of more preferably representing by formula (7).
(in the above-mentioned general formula (6), R
6The carbon number that expression can have a substituted alkyl is 1～5 alkylidene, and m representes 0 or 1 number.）
(in the above-mentioned general formula (7), R
7Expression hydrogen atom or methyl, R
8The carbon number that expression can have a substituted alkyl is 1～5 alkylidene, and n representes 0 or 1 number.）
(in the above-mentioned general formula (8), R
9The carbon number that expression can have a substituted alkyl is 1～5 alkylidene.）
In the above-mentioned general formula (6), R
6The carbon number that expression can have a substituted alkyl is 1～5 alkylidene.It as carbon number 1～5 alkylidene; Can enumerate out methylene, ethylidene, propylidene, butylidene and pentylidene, consider from thermotolerance, preferred carbon number is less; But the easy property consideration that obtains from industry; Preferred ethylidene, propylidene and butylidene, more preferably ethylidene and propylidene, most preferably ethylidene.As R
6In the substituted alkyl that can have, can enumerate out for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group etc., but consider preferably do not have substituted alkyl from thermotolerance.M representes 0 or 1 number, and owing to the easy reason of acquisition of raw material, m is preferably 1 number.
In the above-mentioned general formula (7), R
7Expression hydrogen atom or methyl, R
8The carbon number that expression can have a substituted alkyl is 1～5 alkylidene.It as carbon number 1～5 alkylidene; Can enumerate out methylene, ethylidene, propylidene, butylidene and pentylidene, consider from thermotolerance, preferred carbon number is less; But the easy property consideration that obtains from industry; Preferred ethylidene, propylidene and butylidene, more preferably ethylidene and propylidene, most preferably ethylidene.As R
8In the substituted alkyl that can have, can enumerate out for example methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, the tert-butyl group etc., but consider preferably do not have substituted alkyl from thermotolerance.N representes 0 or 1 number, and owing to the easy reason of acquisition of raw material, n is preferably 1 number.
When polysiloxane compound of the present invention further has the unit of being represented by above-mentioned general formula (5); When the content of the unit of above-mentioned general formula (5) expression is very few; Then adhering raising effect is few, and too much the time, then makes the surface of the solidfied material after photosensitive polymer combination of the present invention solidifies viscosity might occur; So the content of the unit of above-mentioned general formula (5) expression is preferably 2000～50000 in epoxide equivalent, more preferably 3000～20000.
Polysiloxane compound of the present invention can be through being obtained by the alkoxysilane compound containing trialkylsilyl group in molecular structure of formula (1a)～(4a) expression or the hydrolysis-condensation reaction of halogenated silanes compound, so-called solgel reaction.
(in the formula, R
1And R
2Definition identical with above-mentioned general formula (1), X
1Expression halogen atom or carbon number are 1～4 alkoxy.）
(in the formula, R
3Definition identical with above-mentioned general formula (2), X
2Expression halogen atom or carbon number are 1～4 alkoxy.）
(in the formula, R
4Definition identical with above-mentioned general formula (3), X
3Expression halogen atom or carbon number are 1～4 alkoxy.）
(in the formula, R
5Definition identical with above-mentioned general formula (4), X
4Expression halogen atom or carbon number are 1～4 alkoxy.）
As alkoxysilane compound containing trialkylsilyl group in molecular structure by above-mentioned general formula (1a) expression; Can enumerate out for example (acryloyl-oxy ylmethyl) trimethoxy silane, (2-acryloxy propyl group) trimethoxy silane, (3-acryloxy propyl group) trimethoxy silane, (3-acryloxy propyl group) triethoxysilane, (methacryloxy methyl) trimethoxy silane, (2-methacryloxypropyl) trimethoxy silane, (3-methacryloxypropyl) trimethoxy silane, (3-methacryloxypropyl) triethoxysilane; As halogenated silanes compound, for example can enumerate out (3-acryloxy propyl group) trichlorosilane, (3-methacryloxypropyl) trichlorosilane etc. by above-mentioned general formula (1a) expression.As alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound by above-mentioned general formula (1a) expression; The reason good owing to reactivity and reaction is controlled easily; Preferably (3-methacryloxypropyl) trimethoxy silane and (3-methacryloxypropyl) triethoxysilane, more preferably (3-methacryloxypropyl) trimethoxy silane.
As alkoxysilane compound containing trialkylsilyl group in molecular structure by above-mentioned general formula (2a) expression; Can enumerate out for example phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three isopropoxy silane, 4-aminomethyl phenyl trimethoxy silane, 4-aminomethyl phenyl triethoxysilane, 4-aminomethyl phenyl three isopropoxy silane etc.; As halogenated silanes compound, can enumerate out for example phenyl trichlorosilane, 4-aminomethyl phenyl trichlorosilane etc. by above-mentioned general formula (2a) expression.As alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound by above-mentioned general formula (2a) expression; The reason good owing to reactivity and reaction is controlled easily; Preferred phenyltrimethoxysila,e and phenyl triethoxysilane, more preferably phenyltrimethoxysila,e.
As alkoxysilane compound containing trialkylsilyl group in molecular structure by above-mentioned general formula (3a) expression; Can enumerate out for example dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diisopropoxy silane, diethyl phenyl dimethoxy silane, diethyl diethoxy silane, diethyl diisopropoxy silane, dipropyl dimethoxy silane, dipropyl diethoxy silane, dipropyl diisopropoxy silane etc.; As halogenated silanes compound, can enumerate out for example dimethyldichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane etc. by above-mentioned general formula (3a) expression.As alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound by above-mentioned general formula (2a) expression; The reason good owing to reactivity and reaction is controlled easily; Preferred dimethyldimethoxysil,ne and dimethyldiethoxysilane, more preferably dimethyldimethoxysil,ne.
As alkoxysilane compound containing trialkylsilyl group in molecular structure by above-mentioned general formula (4a) expression; Can enumerate out for example dimethoxydiphenylsilane, diphenyl diethoxy silane, diphenyl diisopropoxy silane, two (4-aminomethyl phenyl) dimethoxy silane, two (4-aminomethyl phenyl) diethoxy silane, two (4-aminomethyl phenyl) diisopropoxy silane etc.; As halogenated silanes compound, can enumerate out for example diphenyl dichlorosilane, two (4-aminomethyl phenyl) dichlorosilane etc. by above-mentioned general formula (4a) expression.As alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound by above-mentioned general formula (4a) expression; The reason good owing to reactivity and reaction is controlled easily; Preferred dimethoxydiphenylsilane and diphenyl diethoxy silane, more preferably dimethoxydiphenylsilane.
When making alkoxysilane compound containing trialkylsilyl group in molecular structure or the halogenated silanes compound of above-mentioned general formula (1a)～(4a) expression be hydrolyzed condensation, preferably in solvent, use catalyzer such as acid or alkali to react.As operable solvent in the reaction; Can enumerate water outlet, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, acetone, MEK 、 diox, tetrahydrofuran, toluene, xylene, cyclohexane etc.; They can use a kind of, also can mix use more than two kinds.When making the solvent beyond the water,, preferably add an amount of water and react in order to promote hydrolysis-condensation reaction.
In the hydrolysis-condensation reaction of alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound; The hydrolysis and generate silanol group under the effect of water of alkoxysilyl or halo silicyl is between the silanol group of this generation or silanol group and alkoxy or the condensation of chlorosilane base and generate siloxy group (SiOSi yl).
As the catalyzer of above-mentioned hydrolysis-condensation reaction, can enumerate out inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid; Organic acids such as formic acid, acetate, oxalic acid, citric acid, methane-sulforic acid, benzene sulfonic acid, p-toluenesulfonic acid, mono phosphoric acid ester isopropyl ester; Inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, ammonia; Amines such as Trimethylamine, triethylamine, monoethanolamine, diethanolamine (organic base) type etc. can use a kind of in them, also can and with more than two kinds.The temperature of hydrolysis-condensation reaction changes according to the difference of the kind of solvent types, catalyzer and amount etc., but is preferably 0～80 ℃, more preferably 5～50 ℃, most preferably is 8～30 ℃.
When the alkoxysilane compound containing trialkylsilyl group in molecular structure of above-mentioned general formula (1a)～(4a) expression or halogenated silanes compound are hydrolyzed condensation; Each alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound are reacted respectively; React after also can mixing; Because reactant is inhomogeneous few, the reason that can stably produce was reacted after preferred the mixing.
When polysiloxane compound of the present invention further has the unit of being represented by above-mentioned general formula (5); Except that the alkoxysilane compound containing trialkylsilyl group in molecular structure of above-mentioned general formula (1a)～(4a) expression or halogenated silanes compound are hydrolyzed the condensation, the alkoxysilane compound containing trialkylsilyl group in molecular structure or the condensation of halogenated silanes compound hydrolysis of formula (5a) expression are got final product.
(in the formula, the definition of E is identical with above-mentioned general formula (5), X
5Expression halogen atom or carbon number are 1～4 alkoxy.）
As alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound by above-mentioned general formula (5a) expression; For example can enumerate out 3; 4-epoxy butyl trimethoxy silane, 2-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyltrime,hoxysilane, 2-glycidoxy-1-Methylethyl triethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane, 3; 4-epoxycyclohexyl trimethoxy silane, 3,4-epoxycyclohexyl triethoxysilane, 2-(3,4-epoxy-4-methylcyclohexyl) propyl trimethoxy silicane etc.
When the hydrolysis-condensation reaction through alkoxysilane compound containing trialkylsilyl group in molecular structure or halogenated silanes compound obtains polysiloxane compound of the present invention; Meeting residual silanol groups on manufacturing approach; Because the existence of this silanol group; The storage stability of photosensitive polymer combination of the present invention descends, so preferably silanol group is carried out end-blocking.When silanol group is carried out end-blocking, can enumerate out the method for carrying out trimethyl silylization with trimethyl chlorosilane, hexamethyldisilazane; Carry out oxyalkylated method etc. with hydrolyzable ester compounds such as orthoformate, ortho-acetate, four alkoxy methane, carbonic esters.
Below, optical free radical is produced agent describe.Among the present invention, optical free radical produces agent and is meant and can as energy-ray, can enumerates out ultraviolet ray, electron beam, X ray, radioactive ray, high-frequency ray etc. through the compound of energy-ray irradiation initiation free radical polymerization.Produce agent as optical free radical, can enumerate out acetophenone is that optical free radical produces agent, benzil is that optical free radical generation agent, benzophenone series optical free radical produce agent, thioxanthones is that optical free radical produces agent, acylphosphine oxide is that optical free radical produces agent etc.Optical free radical generation agent can only be used a kind of, also can be also with more than two kinds.
As above-mentioned acetophenone is that optical free radical produces agent; For example can enumerate out diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 4 '-isopropyl-2-hydroxy-2-methyl propiophenone, 2-hydroxymethyl-2-methyl phenyl ketone, 2; 2-dimethoxy-1,2-diphenylethane-1-ketone, to the dimethylamino benzoylformaldoxime, to tert-butyl group dichloroacetophenone, to tert-butyl group trichloroacetophenone, to oligomer of nitrine benzylidene acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethylether, benzoin propyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-[4-vinyl-(1-methyl ethylene) phenyl] acetone etc.
As above-mentioned benzil is that optical free radical produces agent, can enumerate out for example diphenyl diketone (being also referred to as benzil), two (4-methoxyphenyl) diketone (being also referred to as anisil) etc.
Produce agent as above-mentioned benzophenone series optical free radical; Can enumerate out for example benzophenone, o-benzoyl yl benzoic acid methyl esters, Michler's keton, 4; 4 '-two (diethylamino) benzophenone, 4,4 '-dichloro benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide etc.
As above-mentioned thioxanthones is that optical free radical produces agent, can enumerate out for example thioxanthones, 2-methyl thioxanthones, 2-ethyl thioxanthones, 2-clopenthixal ketone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone etc.
As above-mentioned acylphosphine oxide is that optical free radical is sent out agent; Can enumerate out for example 2-methyl benzoyl diphenyl phosphine oxide, 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2,4, monoacyl phosphine oxides such as 6-trimethylbenzoyl phenyl-phosphonic acid methyl esters are that optical free radical produces agent; Two (2,6-dimethoxy benzoyl) phenylphosphine oxide, two (2,4; The 6-trimethylbenzoyl) phenylphosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4, two acylphosphine oxide such as 4-tri-methyl-amyl phosphine oxide are that optical free radical produces agent.
When using gate insulating film as OTFT when photosensitive polymer combination of the present invention is solidified; Produce agent as above-mentioned optical free radical, from obtaining the viewpoint of high electric charge degree of excursion, preferred acylphosphine oxide is that optical free radical produces agent; More preferably the monoacyl phosphine oxide is that optical free radical produces agent; Most preferably 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.When also producing agent with the optical free radical more than two kinds, preferred at least a is that acylphosphine oxide is that optical free radical produces agent.
In addition; When photosensitive polymer combination of the present invention is solidified during as transparent materials such as lens, waveguides; Produce agent as above-mentioned optical free radical, from obtaining the viewpoint of the high solidfied material of the transparency, preferred acetophenone is that optical free radical produces agent and acylphosphine oxide is that optical free radical produces agent; More preferably acetophenone is that optical free radical produces agent, most preferably 1-hydroxycyclohexylphenylketone.When also producing agent with the optical free radical more than two kinds, preferred at least a is that acetophenone is that optical free radical produces agent.
The content that optical free radical in the photosensitive polymer combination of the present invention produces agent produces the kind of agent, different variation of kind and intensity etc. of content, active energy beam of free-radical polymerised group in the photosensitive polymer combination of the present invention according to optical free radical; But be preferably 0.1～10 mass parts with respect to polysiloxane compound 100 mass parts of the present invention; More preferably 0.2～7 mass parts further is preferably 0.3～5 mass parts.Be lower than 0.1 mass parts if above-mentioned optical free radical produces the content of agent, then be solidified with and become insufficient,, then not only can not get and the corresponding increment effect of use level, might produce harmful effect to thermotolerance, the transparency etc. on the contrary if surpass 10 mass parts.
Photosensitive polymer combination of the present invention can also further contain organic solvent.As such organic solvent, can enumerate out for example aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene, naphthane; Saturated hydrocarbon compound such as pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, nonane, isononane, decane, isodecane, Permethyl 99A, cyclohexane, methylcyclohexane, terpane, decahydronaphthalene; Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, ether series solvents such as 4-diox; Ketone series solvents such as acetone, MEK, methyl isobutyl ketone, metacetone, dipropyl ketone, methyl amyl ketone, cyclohexanone; Ester series solvents such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate; Diol ester series solvents such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetic acid esters, diethylene glycol monoethyl ether acetate etc.Above-mentioned solvent can use separately, also can make up use more than two kinds.
When using photosensitive polymer combination of the present invention through rubbing method or print process, the content of above-mentioned organic solvent is preferably 5～200 mass parts, more preferably 10～100 mass parts with respect to polysiloxane compound 100 mass parts of the present invention.
In the photosensitive polymer combination of the present invention; Except cooperating above-mentioned organic solvent, can also cooperate composition arbitrarily such as light sensitizer, plastifier, thixotropy imparting agent, photoacid generator, hot acid agent, spreading agent, foam-breaking agent, pigment, dyestuff as required.The use level of any composition like this is preferably 0.001～1 mass parts with respect to polysiloxane compound 100 mass parts of the present invention in total amount.
For photosensitive polymer combination of the present invention, behind the layer that forms photosensitive polymer combination of the present invention on the objects such as substrate,, thus photosensitive polymer combination of the present invention is solidified through the irradiation active energy beam.Form not special qualification of method of the layer of photosensitive polymer combination of the present invention; As long as for example use that dip coated, flow coat, bristle coating, spraying coating, extrusion coated, spin coating, roller coat, rod are coated with etc.; Utilize methods such as coating of net formula or roller transfer, just can form the film that has carried out patterning.As the object of the layer that forms photosensitive polymer combination of the present invention, not special the qualification can be used silicon substrate, glass substrate, sheet metal, plastic plate etc. according to purposes.For the photosensitive polymer combination of the present invention that forms on the object the layer thickness; It is according to the difference of purposes and difference; When using as the gate insulating film of the dielectric film of semiconductor element or OTFT; With 10nm～10 μ m is target, when the core as optical waveguide uses, is target with 1～200 μ m.
When photosensitive polymer combination of the present invention contains organic solvent, after forming the layer of photosensitive polymer combination of the present invention, be that purpose is carried out heat treated (being prebake conditions sometimes) with the organic solvent of removing in the layer.The condition of heat treated can according to the thickness of the layer of the boiling point of the organic solvent that uses and vapor pressure, photosensitive polymer combination of the present invention, formed layer object heat resisting temperature and suitably selection is a target with 30 seconds～10 minutes heat treated under 60～140 ℃.
As the light source that the layer of photosensitive polymer combination is shone active energy beam; Can enumerate out extra-high-pressure mercury vapour lamp, extreme ultraviolet (Deep UV) lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, metal halide lamp, excimer laser etc., above-mentioned light source can suitably be selected according to the wavelength photoreceptor that optical free radical produces agent and sensitizer.The irradiation energy of active energy beam can produce the kind and the use amount of agent according to thickness and the optical free radical of the layer of photosensitive polymer combination and suitably select.
Through the irradiation active energy beam layer of photosensitive polymer combination is solidified, but, also can carry out heat treated (being called the back sometimes toasts) for the adhesiveness of objects such as the layer that improves solidfied material and substrate.This heat treated preferably under inactive gas atmosphere such as nitrogen, helium, argon gas, was carried out under 60～200 ℃ temperature 1 minute～2 hours.
Can carry out photoetching by filming of obtaining of photosensitive polymer combination of the present invention, can be used as negative type photoresist (particularly permanent resist) and use.When photosensitive polymer combination of the present invention is used as negative type photoresist; Photosensitive polymer combination of the present invention is coated on substrate etc.; When then filming of formation being shone active energy beam; Cover filming of photosensitive polymer combination with photomask; Thereby optionally shine active energy beam, the part (uncured portion) that has made then by shading is dissolved or dispersed in organic solvent or the developer solution etc. and is removed (being called development sometimes), can form the cured film of having carried out patterning thus.As the organic solvent that is partly dissolved or disperses that has made by shading; Can enumerate out for example alkaline aqueous solution, acidic aqueous solution, acetone, MEK, methyl isobutyl ketone, ethanol, isopropyl alcohol, n-propanol, benzene, propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, toluene, o-xylene, m-xylene, P-xylene, 1; 3; 5-trimethylbenzene, 1,3,4-trimethylbenzene etc.
The cured film that is obtained by photosensitive polymer combination of the present invention is because the transparency, insulativity, high index of refraction, thermotolerance, against weather, chemical proofing etc. are good, so be useful as the dielectric film of the encapsulant of LED etc., optical waveguide, optical lens, semiconductor device.Particularly, when using as semi-conductive gate insulating film, charge carrier is hunted down and problem that the electric charge degree of excursion is descended is few, is exceedingly useful as the gate insulating film of OTFT.
Embodiment
Enumerate embodiment below and comparative example further specifies the present invention, but the present invention does not receive their qualification.
[make routine A: the manufacturing of polysiloxane compound A]
In reaction vessel, add 3-methacryloxypropyl trimethoxy silane 124.2g (0.5 mole), phenyltrimethoxysila,e 39.7g (0.2 mole), dimethyldimethoxysil,ne 132.2g (1.1 moles), dimethoxydiphenylsilane 75.3g (0.2 mole) and as the 1-butanols 300g of solvent with stirrer, thermometer and return channel.Stirring also is heated to 70 ℃, drips 100 parts of 0.12% phosphate aqueous solutions then, reacts 1 hour down at 80 ℃ again.Then, add sodium hydrate aqueous solution and come neutralization reaction liquid, reacted 1 hour down at 80 ℃ then.Add toluene 300g, the water that stops to stir and remove separation then contains layer.Water 1000g washing toluene layer 3 times flows down to heat up in a steamer in 40 ℃ of decompressions at nitrogen then and desolvates.To wherein adding triethyl orthoformate 300g, descend processing after 1 hour at 130 ℃, flow down in 80 ℃ of decompressions at nitrogen and heat up in a steamer volatile ingredients such as unreacted triethyl orthoformate, obtain polysiloxane compound A of the present invention.The analysis result of GPC is, the matter average molecular weight is 7500,
1The analysis result of H-NMR is not detect silanol group.
[make routine B～I: the manufacturing of polysiloxane compound B～I]
In making routine A, except using the alkoxysilane compound containing trialkylsilyl group in molecular structure shown in the table 1, carry out same operation, the polysiloxane compound B～I shown in the synthetic table 1 with the routine A of manufacturing.The reaction mol ratio of the numeric representation alkoxysilane compound containing trialkylsilyl group in molecular structure in the table.In the polysiloxane compound of table 1, polysiloxane compound A～E is a polysiloxane compound of the present invention, and polysiloxane compound F～I is the polysiloxane compound of comparison.In addition, expression matter average molecular weight and silanol group analysis on Content result in the table 2.
Table 1
| Polysiloxane compound | A | B | C | D | E | F | G | H | I |
| The 3-methacryloxypropyl trimethoxy silane | 25 | 25 | 25 | 15 | 15 | - | - | - | - |
| Phenyltrimethoxysila,e | 10 | 10 | 25 | 15 | 70 | 10 | 10 | 10 | 10 |
| Dimethyldimethoxysil,ne | 55 | 54 | 20 | 20 | 5 | 55 | 53 | 55 | 55 |
| Dimethoxydiphenylsilane | 10 | 10 | 30 | 50 | 10 | 10 | 10 | 10 | 10 |
| 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane | - | 1 | - | - | - | 25 | - | - | - |
| 3-(glycidoxy propyl group) ethyl trimethoxy silane | - | - | - | - | - | - | - | - | 25 |
| The vinyl methyl dimethoxysilane | - | - | - | - | - | - | 25 | - | - |
| Methyldiethoxysilane | - | - | - | - | - | - | - | 25 | - |
Table 2
| The matter average molecular weight | Silanol group | |
| Polysiloxane compound A | 7500 | Do not detect |
| Polysiloxane compound B | 7600 | Do not detect |
| Polysiloxane compound C | 5600 | Do not detect |
| Polysiloxane compound D | 3200 | Do not detect |
| Polysiloxane compound E | 8300 | Do not detect |
| Polysiloxane compound F | 7600 | Do not detect |
| Polysiloxane compound G | 7500 | Do not detect |
| Polysiloxane compound H | 7700 | Do not detect |
| Polysiloxane compound I | 7900 | Do not detect |
[embodiment 1～7 and comparative example 1～5]
Use polysiloxane compound A～I, following acrylic ester A and B, produce two (2 of agent as optical free radical; 6-dimethoxy benzoyl) phenylphosphine oxide (below be designated as optical free radical produce agent 1), 1-hydroxycyclohexylphenylketone (below be designated as optical free radical produce agent 2), as photoacid generator [two (4-chlorphenyl) the sulfonium hexafluoro antimonates of 4-(2-chloro-4-benzoyl thiophenyl) phenyl], as the platinum-divinyl tetramethyl disiloxane complex compound of hydrosilylation catalysts and as the butyl acetate of solvent, according to the composition modulation embodiment 1～7 of table 3 and the photosensitive polymer combination or the compositions of thermosetting resin of comparative example 1～5.
Acrylic ester A
Acrylic ester B
Table 3
< evaluation as gate insulating film of photosensitive polymer combination >
In order to estimate photosensitive polymer combination or the characteristic as gate insulating film of compositions of thermosetting resin, the making OTFT shown in Figure 1 that obtains in the foregoing description and the comparative example with being described below.
Vapor deposition chromium (Cr) on glass substrate 6 forms the extraction electrode of wide 2mm, thick about 100nm, processes gate electrode 4.The compositions of thermosetting resin of the photosensitive polymer combination of spin coating embodiment 1,2 and comparative example 1 and comparative example 2 makes that thickness is about 1 μ m in the above, air-dry after, in embodiment 1,2 and the comparative example 1 through with 5000mJ/cm
2The irradiation high-pressure mercury-vapor lamp makes its curing, in the comparative example 2 through under nitrogen atmosphere, making its curing in 2 hours in 150 ℃ of heating, thereby form gate insulating film 5.Spin coating gathers the xylene solution of (3-hexyl) thiophene on gate insulating film 5, makes that dried thickness is 30nm, and air-dry back forms organic semiconductor film 1.Gather (3-hexyl) thiophene activation in order to make, under nitrogen atmosphere in 150 ℃ of annealing in process of carrying out 30 minutes.Gold evaporation on organic semiconductor film 1 (Au); According to channel width is 2mm, the thick 30nm of being about to form raceway groove length be source electrode 2 and the drain electrode 3 of 100 μ m, thus to embodiment 1 and 2 and comparative example 1 and 2 make the OTFT of 12 bottom gates/top contact type respectively.
For embodiment 1 and 2 and the OTFT of comparative example 1 and 2, use analyzing parameters of semiconductor appearance (Keithley corporate system, product SCS4200 by name) to measure conveying characteristic, calculate electric charge degree of excursion μ.In addition, electric charge degree of excursion μ is defined by following formula, particularly, and with leakage current I
DThe square root of absolute value be the longitudinal axis, with grid voltage V
GWhen mapping, be that electric charge degree of excursion μ is obtained on the basis with the slope of a curve in the zone of saturation for transverse axis.Mensuration is carried out under nitrogen atmosphere, under the shading state.Electric charge degree of excursion μ is set at the mean value of the OTFT that can measure conveying characteristic, and the quantity that can not measure the OTFT of conveying characteristic because of electric leakage is set at the defective products number.The result is shown in Table 4.
[mathematical expression 1]
I
D=WCμ(V
G-V
T)
2/2L
I
D: leakage current
W: transistorized channel width
L: transistorized channel length
C: the static capacity of gate insulating film
V
G: grid voltage
V
T: transistorized threshold voltage
μ: electric charge degree of excursion
Table 4
| Electric charge degree of excursion (μ) | The defective products number | |
| Embodiment 1 | 5.3×10 -3 | 0/12 |
| Embodiment 2 | 3.8×10 -3 | 0/12 |
| Comparative example 1 | 8.7×10 -4 | 0/12 |
| Comparative example 2 | 2.3×10 -4 | 6/12 |
< the hot tinting property evaluation of photosensitive polymer combination >
On the square glass substrate of 2.5cm, the photosensitive polymer combination with spinner coating embodiment 3～7 and comparative example 1 and 3～5 makes that dried thickness is about 500 μ m, makes solvent evaporates.With this test film 120 ℃ of following heat treated 30 minutes.Glass substrate top after heat treated is provided with and draws the photomask of 1mm live width, with high-pressure mercury-vapor lamp with 100mJ/cm
2Irradiation ultraviolet radiation.Then, this test film impregnated in the beaker that ethyl acetate is housed, uncured portion is removed in dissolving, with the test film of the test film after air-dry as temper tiniting property evaluation usefulness.Test film is water white, and solidfied material is as shown in table 6 in the refractive index at wavelength 837nm place.This test film is put into 150 ℃ calibration cell, and through taking out after 15 days, visual solidfied material painted estimated hot tinting property according to following metewand.The result is shown in Table 5.
< metewand >
◎: can't see paintedly, hot tinting property is low.
Zero: painted slightly, hot tinting property is high slightly.
△: obviously painted, hot tinting property is high.
*: this degree painted that can't differentiate the line of literal through solidfied material arranged, and hot tinting property is very high.
Table 5
| Embodiment | Refractive index | Hot tinting property |
| Embodiment 3 | 1.515 | ◎ |
| Embodiment 4 | 1.513 | ○ |
| Embodiment 5 | 1.557 | ◎ |
| Embodiment 6 | 1.566 | ◎ |
| Embodiment 7 | 1.520 | ◎ |
| Comparative example 1 | 1.512 | △ |
| Comparative example 3 | 1.511 | △ |
| Comparative example 4 | 1.506 | × |
| Comparative example 5 | 1.550 | × |
Shown in the result of table 4, photosensitive polymer combination of the present invention is solidified and the gate insulating film that obtains can obtain high electric charge degree of excursion.Contrast with it; The gate insulating film (comparative example 1) that the photosensitive polymer combination that contains polysiloxane compound with epoxy radicals and photoacid generator is solidified and obtain and the compositions of thermosetting resin that contains the polysiloxane compound with vinyl, the polysiloxane compound with SiH base and hydrosilylation catalysts (platinum catalyst) is solidified and the gate insulating film (comparative example 2) that obtains can only obtain low electric charge degree of excursion, particularly the latter exists the high problem of defective products rate.
In addition, shown in the result of table 5, photosensitive polymer combination of the present invention can use as negative type photoresist, and the refractive index of its solidfied material is high, even at high temperature, and hot tinting property also low (embodiment 3～7).Contrast with it makes the solidfied material (comparative example 1 and 3～5) of forming the photosensitive polymer combination curing different with photosensitive polymer combination of the present invention and obtaining have high hot tinting property.
The above results shows, photosensitive polymer combination of the present invention being used for transparent high-index material for example when lens, optical waveguide etc., even at high temperature, also can not lose transparently and use.
Symbol description
1 organic semiconductor film (layer)
2 source electrodes
3 drain electrodes
4 gate electrodes
5 insulation courses (gate insulating film)
6 supporters (substrate)
Claims (according to the modification of the 19th of treaty)
1. (revise afterwards) a kind of photosensitive polymer combination, it contains polysiloxane compound and the optical free radical generation agent that has by the unit of formula (1)～(5) expression,
In the general formula (1), R
1Expression hydrogen atom or methyl, R
2The carbon number that expression can have a substituted alkyl is 1～5 alkylidene,
In the general formula (2), R
3Expression hydrogen atom or carbon number are 1～4 alkyl,
In the general formula (3), R
4The expression carbon number is that 1～6 alkyl or carbon number are 5 or 6 naphthenic base,
In the general formula (4), R
5Expression hydrogen atom or carbon number are 1～4 alkyl,
E-SiO
3/2 (5)
In the general formula (5), E representes to have the group of epoxy radicals.
2. (deletion)
3. (revise afterwards) photosensitive polymer combination according to claim 1; Wherein, Have polysiloxane compound by the unit of said general formula (1)～(5) expressions and be the polysiloxane compound that is hydrolyzed condensation by the alkoxysilane compound containing trialkylsilyl group in molecular structure of formula (1a)～(5a) expression or halogenated silanes compound and obtains
In the general formula (1a), R
1And R
2Definition identical with said general formula (1), X
1Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (2a), R
3Definition identical with said general formula (2), X
2Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (3a), R
4Definition identical with said general formula (3), X
3Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (4a), R
5Definition identical with said general formula (4), X
4Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (5a), the definition of E is identical with said general formula (5), X
5Expression halogen atom or carbon number are 1～4 alkoxy.
4. (revise the back) according to claim 1 or 3 described photosensitive polymer combinations; Wherein, With respect to the polysiloxane compound by the unit of said general formula (1)～(5) expression that has of 100 mass parts, the said optical free radical that contains 0.1～10 mass parts produces agent.
Claims (4)
1. photosensitive polymer combination, it contains the polysiloxane compound and the optical free radical that have by the unit of formula (1)～(4) expression and produces agent,
In the general formula (1), R
1Expression hydrogen atom or methyl, R
2The carbon number that expression can have a substituted alkyl is 1～5 alkylidene,
In the general formula (2), R
3Expression hydrogen atom or carbon number are 1～4 alkyl,
In the general formula (3), R
4The expression carbon number is that 1～6 alkyl or carbon number are 5 or 6 naphthenic base,
In the general formula (4), R
5Expression hydrogen atom or carbon number are 1～4 alkyl.
2. photosensitive polymer combination according to claim 1, wherein, the polysiloxane compound with unit of being represented by said general formula (1)～(4) is the polysiloxane compound that further has by the unit of formula (5) expression,
E-SiO
3/2 (5)
In the formula, E representes to have the group of epoxy radicals.
3. photosensitive polymer combination according to claim 1; Wherein, Have polysiloxane compound by the unit of said general formula (1)～(4) expressions and be the polysiloxane compound that is hydrolyzed condensation by the alkoxysilane compound containing trialkylsilyl group in molecular structure of formula (1a)～(4a) expression or halogenated silanes compound and obtains
In the general formula (1a), R
1And R
2Definition identical with said general formula (1), X
1Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (2a), R
3Definition identical with said general formula (2), X
2Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (3a), R
4Definition identical with said general formula (3), X
3Expression halogen atom or carbon number are 1～4 alkoxy,
In the general formula (4a), R
5Definition identical with said general formula (4), X
4Expression halogen atom or carbon number are 1～4 alkoxy.
4. according to each described photosensitive polymer combination in the claim 1～3; Wherein, With respect to the polysiloxane compound by the unit of said general formula (1)～(4) expression that has of 100 mass parts, the said optical free radical that contains 0.1～10 mass parts produces agent.
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| JP2010-049437 | 2010-03-05 | ||
| JP2010049437A JP2011186069A (en) | 2010-03-05 | 2010-03-05 | Photosensitive resin composition |
| PCT/JP2011/055074 WO2011108705A1 (en) | 2010-03-05 | 2011-03-04 | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105264648A (en) * | 2013-06-07 | 2016-01-20 | 富士胶片株式会社 | Composition for forming gate insulating film, organic thin film transistor, electronic paper, and display device |
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| JPS53134085A (en) * | 1977-07-18 | 1978-11-22 | Dainippon Printing Co Ltd | Photopolymerizable composition |
| JP2010039056A (en) * | 2008-08-01 | 2010-02-18 | Sekisui Chem Co Ltd | Photosensitive composition and method of manufacturing pattern film |
-
2010
- 2010-03-05 JP JP2010049437A patent/JP2011186069A/en active Pending
-
2011
- 2011-03-03 TW TW100107208A patent/TW201140243A/en unknown
- 2011-03-04 CN CN201180004535.0A patent/CN102597879A/en active Pending
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105264648A (en) * | 2013-06-07 | 2016-01-20 | 富士胶片株式会社 | Composition for forming gate insulating film, organic thin film transistor, electronic paper, and display device |
| CN106468857A (en) * | 2015-08-19 | 2017-03-01 | 奇美实业股份有限公司 | Photosensitive resin composition and application thereof |
| CN106468857B (en) * | 2015-08-19 | 2019-10-15 | 奇美实业股份有限公司 | Photosensitive resin composition and application thereof |
| CN109541889A (en) * | 2018-12-19 | 2019-03-29 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| CN109541889B (en) * | 2018-12-19 | 2020-06-26 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| US11644750B2 (en) | 2018-12-19 | 2023-05-09 | Jiangsu Aisen Semiconductor Material Co., Ltd. | Negative photoresist used for semiconductor encapsulation process |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201140243A (en) | 2011-11-16 |
| JP2011186069A (en) | 2011-09-22 |
| KR20110101073A (en) | 2011-09-15 |
| WO2011108705A1 (en) | 2011-09-09 |
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