CN110412829A - Negative light-sensitive resin combination, photocuring pattern and image display device - Google Patents
Negative light-sensitive resin combination, photocuring pattern and image display device Download PDFInfo
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- CN110412829A CN110412829A CN201810386376.9A CN201810386376A CN110412829A CN 110412829 A CN110412829 A CN 110412829A CN 201810386376 A CN201810386376 A CN 201810386376A CN 110412829 A CN110412829 A CN 110412829A
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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
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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Abstract
The present invention provides negative light-sensitive resin combination, photocuring pattern and image display device.Above-mentioned negative light-sensitive resin combination includes adhesive resin, polymerizable compound, polymerization initiator, photoacid generator and solvent, and photoacid generator includes compound represented by chemical formula 1.In chemical formula 1, R1~R6It is each independently the alkoxy of hydrogen, the alkyl of carbon atom number 1~5, halogen or carbon atom number 1~4, the integer that n is 0~8.By having the function of the photoacid generator of the acidity improved, it is capable of forming the photocuring pattern with the physical property, curing characteristics that improve.[chemical formula 1]
Description
Technical field
The present invention relates to negative light-sensitive resin combination and the photocuring patterns formed by it.More specifically, it is related to
With the photo-curable improved and the photocuring figure being capable of the negative light-sensitive resin combination of low-temperature setting and formed by it
Case.
Background technique
In field of display, photosensitive polymer combination is used to form photoresist, insulating film, protective film, black square
The diversified photocuring patterns such as battle array, intercolumniation parting (column spacer).For example, can be by photosensitive polymer combination
By photo-mask process, selectively exposure and imaging forms desired photocuring pattern.In order to ensure desired photocuring
The physical property of pattern, above-mentioned photosensitive polymer combination need to have high sensitivity, and the pattern formed by it, which needs to have, to be improved
Heat resistance, chemical resistance etc..
Photosensitive polymer combination is divided into eurymeric and minus according to light curable type.It is formed by positive type composition photic anti-
Erosion agent is that the chemical structure of exposure portion deforms and is dissolved by the developing, and is to expose by the photoresist that negative-tone composition is formed
The degree of polymerization of the part of light increases and is cured or when developing procedure is insoluble and remain.Eurymeric and negative-tone composition may include
Respectively different adhesive resin, crosslinking agent etc..
In recent years, for example, have touch panel touch screen use increase, therefore include flexible touch screen display dress
It sets just in active development.The material for example with high molecular material flexible as various substrates can be used in flexible display
Matter, it is therefore desirable to implement various manufacturing processes under conditions of more mild.
Photosensitive polymer combination is also required to be developed to apply under low temperature curing conditions rather than previous as a result,
High temperature curing conditions, with the reactivity more improved and have adaptation, chemical resistance.
Although Ebrean Registered Patent the 10-1302508th discloses comprising using acrylate enester system monomer polymerization
Made of copolymer negative light-sensitive resin combination, but under low temperature curing conditions formed have sufficient durability figure
There is limitation in terms of case.
Existing technical literature
Patent document
Ebrean Registered Patent the 10-1302508th
Summary of the invention
Project to be solved
A project of the invention is, provides at low temperature with the reactivity improved and with excellent
The negative light-sensitive resin combination of durability.
A project of the invention is, provide the photocuring pattern formed by above-mentioned negative light-sensitive resin combination and
Image display device comprising the photocuring pattern.
The method to solve the problem
1. a kind of negative light-sensitive resin combination, it includes adhesive resin, polymerizable compound, polymerization initiator,
Photoacid generator and solvent,
Above-mentioned photoacid generator includes compound represented by following chemical formula 1,
[chemical formula 1]
In chemical formula 1, R1~R6It is each independently hydrogen, the alkyl of carbon atom number 1~5, halogen or carbon atom number 1~4
Alkoxy, the integer that n is 0~8.
2. the negative light-sensitive resin combination as described in above-mentioned 1, in above-mentioned chemical formula 1, integer that n is 2~8.
3. the negative light-sensitive resin combination as described in above-mentioned 1, the solid of the content of above-mentioned photoacid generator in composition
It is 1~5 parts by weight in 100 parts by weight of components total.
4. the negative light-sensitive resin combination as described in above-mentioned 1, above-mentioned adhesive resin includes the weight containing epoxy group
Answer unit and for hydrogen group.
5. the negative light-sensitive resin combination as described in above-mentioned 4, above-mentioned adhesive resin includes from selected under
The repetitive unit of at least one of the group of the composition of compound represented by chemical formula (1)~(3) monomer is stated,
(in chemical formula (1)~(3), R1For hydrogen or methyl).
6. the negative light-sensitive resin combination as described in above-mentioned 4, above-mentioned adhesive resin is further included containing oxa-
The repetitive unit of cyclobutane base.
7. the negative light-sensitive resin combination as described in above-mentioned 6, above-mentioned adhesive resin includes from selected under
The repetitive unit of at least one of the group of the composition of compound represented by chemical formula (4)~(6) monomer is stated,
(in chemical formula (4)~(6), R2For hydrogen or methyl, X1For the alkylidene of carbon atom number 1~12, X2For carbon atom number 1
~6 alkyl).
8. the negative light-sensitive resin combination as described in above-mentioned 4, above-mentioned to include the repetition list containing carboxylic acid for hydrogen group
Member.
9. the negative light-sensitive resin combination as described in above-mentioned 8, above-mentioned adhesive resin includes from selected under
The repetitive unit of at least one of the group of the composition of compound represented by chemical formula (7) and (8) monomer is stated,
(in chemical formula (7) and (8), R3For hydrogen or methyl).
10. a kind of photocuring pattern, the photosensitive polymer combination as described in above-mentioned any one of 1~9 are formed.
11. the photocuring pattern as described in above-mentioned 10, above-mentioned photocuring pattern is selected from by array planarization film pattern, protection
What film figure, insulating film pattern, photoresist pattern, black matrix pattern, intercolumniation spacer patterns and black intercolumniation parting formed
Group.
12. a kind of image display device, it includes photocuring patterns described in above-mentioned 10.
Invention effect
The negative light-sensitive resin combination of the embodiment of the present invention shows excellent reactivity in low-temperature setting, and
The pattern being produced from it has the durabilities such as chemical resistance, heat resistance, the adaptation improved.
In addition, above-mentioned negative light-sensitive resin combination includes the light of the embodiment of the present invention with the acidity improved
Acid agent realizes highly sensitive, high-resolution photoetching process by the photoacid generator.
In addition, can be formed using above-mentioned negative light-sensitive resin combination with desired precision resistance to improving
Chemically, the photocuring pattern of the fine line width of mechanical property.
Specific embodiment
The embodiment of the present invention is related to negative light-sensitive resin combination (hreinafter referred to as photosensitive composite) Ji Youqi
The photocuring pattern of formation, the negative light-sensitive resin combination include adhesive resin, polymerizable compound, following chemistry
Photoacid generator, polymerization initiator and the solvent of formula 1, promote the crosslinking of adhesive resin by above-mentioned photoacid generator, to make
Sensitivity and reactivity improve.
Hereinafter, the embodiment of the present invention is described in detail.
<negative light-sensitive resin combination>
Photoacid generator
The photosensitive composite of the embodiment of the present invention may include photoacid generator (Photo-acid Generator:
PAG).According to illustrative embodiment, above-mentioned photoacid generator can for example generate electronics by ultraviolet exposure, and can lead to
It crosses generated above-mentioned electronics and generates acid (H+)。
In a part of the embodiment, acid can be generated by aftermentioned adhesive resin by above-mentioned electronics.For example, above-mentioned viscous
What mixture resin was included can generate acid in conjunction with above-mentioned electronics for hydrogen group (proton donation group)
(proton, proton).
In a part of the embodiment, it can also be produced and the electronics generated by above-mentioned photoacid generator by solvent or other compositions
Raw acid.
For example, the oxetanes that can included with above-mentioned adhesive resin by the acid that above-mentioned photoacid generator generates
Oxygen atom contained in group and/or epoxy group in conjunction with and induce the friendship between the chain or polymer of adjacent adhesive resin
Connection reaction.Therefore, it can be improved the hardness of the organic film formed by photosensitive polymer combination, chemical resistance, close with substrate
Conjunction property etc..
In addition, further increased due to exposure process by the physics of separated exposure portion and non-exposed portion, chemical differences, from
And it for example can be improved the resolution ratio of the pattern after developing procedure, and improve the sensitivity for above-mentioned exposure process.
According to an embodiment of the invention, above-mentioned photoacid generator may include compound represented by following chemical formula 1.
[chemical formula 1]
In chemical formula 1, R1~R6It is each independently hydrogen, the alkyl of carbon atom number 1~5, halogen or carbon atom number 1~4
Alkoxy.The integer that n is 0~8.
In above-mentioned chemical formula 1, the acidity of photoacid generator increases due to the fluoroalkyl in conjunction with sulfo group, exposes so as to improve
Reactivity after light process.For example, because of electronegativity or pK due to electron-withdrawing big above-mentioned fluoroalkylaValue is lower, it is thus possible to mention
Highly acidity.
In a part of the embodiment, from the aspect of improving acidity, n can be 2~8 integer.When n is greater than 8, above-mentioned light
The molecular dimension or molecular length of acid agent increase, and may make the activity drop of polymerizable compound and/or polymerization initiator instead
It is low.
In a part of the embodiment, R1~R6In at least one can be halogen or alkoxy.Electron-withdrawing group increases as a result,
And it can be improved acidity.
In exemplary embodiments, the content of above-mentioned photoacid generator is amounted to relative to above-mentioned photosensitive composite solid component
100 parts by weight can be about the range of 1~10 parts by weight, preferably can be about the range of 1~5 parts by weight.Above-mentioned photoacid generator
Content be less than about 1 parts by weight in the case where, may cannot achieve and adequately produce sour effect.The content of above-mentioned photoacid generator is greater than
In the case where about 5 parts by weight, sour yield excessively increases and generated acid diffuses to non-exposed portion, thus exposure process or
The resolution ratio of photoetching process may be decreased.Furthermore, it is possible to interfere the effect of aftermentioned polymerization initiator and make adaptation and resistance toization
The property learned is deteriorated.
Adhesive resin
Adhesive resin is to confer to the closing force with substrate in the photosensitive composite of the embodiment of the present invention and can
The ingredient for forming film.According to illustrative embodiment, above-mentioned adhesive resin can be used as to be made in developing procedure
Alkaline-based developer assigns soluble alkali soluble resins and is provided.For example, above-mentioned adhesive resin can have for
The reactivity of light or heat, and there is alkali solubility.
About the type of above-mentioned adhesive resin, as long as the art such as negative light-sensitive resin combination field
In the adhesive resin that generally uses and be just not particularly limited in the range of not departing from the purpose of the present invention, can be this
The polymer of the usually used monomer in field or the copolymer of two or more monomers, the polymerization sequence of monomer and arrangement do not have
It is particularly limited to.
In a part of the embodiment, above-mentioned adhesive resin includes the repetitive unit containing epoxy group (or ethylene oxide), and
It may include for hydrogen group.For example, carboxylic acid repetitive unit can be used as and above-mentioned be provided for hydrogen group.
For example, above-mentioned adhesive resin may include in the monomer represented by following chemical formula (1)~(3) extremely
A kind of repetitive unit (for example, above-mentioned repetitive unit containing epoxy group) of few monomer.
In above-mentioned chemical formula (1)~(3), R1It can be hydrogen or methyl.
In a part of the embodiment, above-mentioned adhesive resin can further include the repetition list containing oxetanyl
Member.
For example, above-mentioned adhesive resin may include in the monomer represented by following chemical formula (4)~(6) extremely
A kind of repetitive unit of few monomer.
In above-mentioned chemical formula (4)~(6), R2It can be hydrogen or methyl.X1It can be the alkylidene of carbon atom number 1~12, X2
It can be the alkyl of carbon atom number 1~6.
Above-mentioned carboxylic acid repetitive unit can for example derive from monomer represented by following chemical formula (7) and (8) at least
A kind of monomer.
In above-mentioned chemical formula (7) and (8), R3It can be hydrogen or methyl.
In a part of the embodiments of the present invention, above-mentioned adhesive resin may include structure represented by following chemical formula 2.
[chemical formula 2]
In chemical formula 2, R1、R2And R3It each independently can be hydrogen or methyl.R4It can be for from selected from above-mentioned chemistry
The structure of monomer in compound represented by formula (1)~(3).
R5It can be for from the structure for the monomer being selected from compound represented by above-mentioned chemical formula (4)~(6).
R6It can be for from the structure for the monomer being selected from compound represented by above-mentioned chemical formula (7) or (8).
A, b and c indicate the molar ratio of repetitive unit in structure, and in a part of the embodiment, a can be 20~70mol%, b
It can be 20~60mol%, c can be 5~30mol%.
As set forth above, it is possible to by the hydrogen supply of for example above-mentioned adhesive resin and the electronics generated by above-mentioned photoacid generator
Group (for example, above-mentioned carboxylic acid repetitive unit) generates acid.By above-mentioned acid with the repetitive unit for example containing epoxy group and/or contain
Have oxetanyl repetitive unit react, so as to the adjacent structure or macromolecular chain in above-mentioned adhesive resin it
Between induce cross-linking reaction.
In one embodiment, above-mentioned adhesive resin may include the mixture or total of two or more resins different from each other
Mixed object (blend).For example, above-mentioned adhesive resin may include it is different from each other in structure represented by above-mentioned chemical formula 2
It is two or more.
Chain can be freely located within the scope of defined mole of % by each repetitive unit that bracket indicates in chemical formula 2
Any position.That is, each bracket of chemical formula 2 is to be indicated to express mole % and with a segment (block), but respectively repeat list
As long as member in the corresponding resin, then can be configured unlimitedly with segment or be individually separated.
In addition, above-mentioned adhesive resin is not precluded by this technology other than repetitive unit represented in chemical formula 2
The addition for other repetitive units that well known monomer is formed in field.
The weight average molecular weight of above-mentioned adhesive resin is not particularly limited, from the aspect of improving adaptation and developability,
The adhesive resin of about 5,000~35,000 ranges can be used.
The content of above-mentioned adhesive resin can be considered by resolution ratio, the pattern uniformity of its photocuring pattern formed and
It is appropriate to adjust.In one embodiment, the content of above-mentioned adhesive resin amounts to 100 relative to above-mentioned photosensitive composite solid component
Parts by weight can be about 20~70 parts by weight ranges.
Polymerizable compound
Polymerizable compound contained in the photosensitive composite of the embodiment of the present invention is used as can be by aftermentioned
The effect of polymerization initiator and the compound for polymerizeing or being crosslinked, can be such that crosslink density increases in manufacturing process, make photocuring
The mechanical property of pattern enhances.
Above-mentioned polymerizable compound can be without particular limitation using the substance used in the art, for example, single
Functional monomer, two functional monomers and polyfunctional monomer furthermore, type are not particularly limited, and can enumerate following chemical combination
Object.
As the example of monofunctional monomer, nonyl phenyl carbitol acrylate, 2- hydroxyl -3- phenoxy group third can be enumerated
Base acrylate, 2- ethylhexyl carbitol acrylate, 2- hydroxyethylmethacry,ate, n-vinyl pyrrolidone etc..Make
For the example of two functional monomers, can enumerate 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate,
Neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A bis- (acrylyl oxy-ethyl) ethers,
3- methyl pentanediol two (methyl) acrylate etc..As the concrete example of polyfunctional monomer furthermore, trihydroxy methyl can be enumerated
Propane three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trihydroxy methyl third
Alkane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Ji Wusi
Alcohol five (methyl) acrylate, ethoxylated dipentaerythritol six (methyl) acrylate, six (first of propoxylated dipentaerythritol
Base) acrylate, dipentaerythritol six (methyl) acrylate etc..These compounds can make individually or by two or more combinations
With.
As the example of commercially available product, KAYARAD DPHA (Japanese chemical drug (strain) manufacture) etc. can be enumerated, but is not limited to
This.
The content of above-mentioned polymerizable monomer is not particularly limited, for example, relative to photosensitive polymer combination solid component
100 parts by weight are amounted to, can be 30 parts by weight~80 parts by weight ranges.It can be improved the strong of photocuring pattern within the above range
Degree, the uniformity, resolution ratio etc..
Polymerization initiator
As long as polymerization initiator can for example by exposure process induce above-mentioned polymerizable compound cross-linking reaction or
Polymerization reaction, so that it may use without particular limitation.For example, above-mentioned polymerization initiator can be used selected from by acetophenone system
Close object, benzophenone based compound, triazine based compound, bisglyoxaline based compound, thioxanthones based compound, oxime ester based compound
Oxime ester based compound preferably can be used at least one of group of composition compound.
In one embodiment, in order to improve the sensitivity of photosensitive composite, it can also add and be helped using photopolymerization initiation
Agent.As above-mentioned photopolymerization initiator, can enumerate selected from by amine compounds, carboxylic acid compound and with the organic sulfur of sulfydryl
One or more of the group of compound composition compound.
The content of above-mentioned polymerization initiator is not particularly limited, for example, relative to above-mentioned photosensitive composite solid at
Divide and amount to 100 parts by weight, may include 0.1 parts by weight~10 parts by weight, preferably may include 0.1 parts by weight~5 parts by weight.In
In above-mentioned content range, the durability of above-mentioned adhesive resin or photocuring pattern will not be hindered, and can be improved exposure work
The efficiency and resolution ratio of sequence.
Solvent
It, can be without particular limitation using in the art in the photosensitive polymer combination of the embodiment of the present invention
Usually used solvent.
As the concrete example of above-mentioned solvent, ethylene glycol monoalkyl ether class can be enumerated;Diethylene glycol dialkyl ether class;Second two
Alcohol alkylether acetates class;Aklylene glycol alkylether acetates class;Propylene-glycol monoalky lether class;Propylene glycol dialkyl ether;
Propylene glycol alkyl ether propionic acid ester;Butanediol monoalkyl ethers;Butanediol monoalkyl ether acetate class;Butanediol monoalky lether third
Esters of gallic acid;The dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether;The aromatic hydrocarbons such as benzene,toluene,xylene, mesitylene
Class;Ketone;Alcohols;Esters;The ring-type ethers such as tetrahydrofuran, pyrans;Ring-type esters such as gamma-butyrolacton etc..These solvents can be with
Individually or it is used in combination of two or more.
The content of above-mentioned solvent is not particularly limited, and content can be in addition to above-mentioned ingredient and other additive components
Surplus in addition.For example, it is contemplated that the coating of composition, drying property, relative to whole 100 parts by weight of photosensitive composite,
It may include 40 parts by weight~95 parts by weight, preferably may include 45 parts by weight~85 parts by weight.
Additive
For consolidating for the photocuring pattern that further increases the photosensitive composite of the embodiment of the present invention or formed by it
The characteristics such as change degree, smoothness, adaptation, solvent resistance, chemical resistance may include additive in above-mentioned photosensitive composite.
It is inhaled for example, above-mentioned additive may include antioxidant, levelling agent, curing accelerator, surfactant, filler, ultraviolet light
Receive agent, anti-coagulants, chain-transferring agent etc..
<photocuring pattern and image display device>
The embodiment of the present invention provides the photocuring pattern manufactured by above-mentioned photosensitive composite.Furthermore reality of the invention
It applies example and the image display device comprising above-mentioned photocuring pattern is provided.
The photocuring pattern manufactured by above-mentioned photosensitive composite has the pattern line-width uniformity improved, and has excellent
The adaptation of different chemical resistance, heat resistance and substrate.Therefore, above-mentioned photocuring pattern may be used as image display device
Various patterns, such as adhesive layer, array planarization film, protective film, insulating film pattern etc., be also used as photoresist,
Black matrix, intercolumniation spacer patterns, black intercolumniation spacer patterns etc., but it is not limited to this, it is particularly possible to effectively serve as photic anti-
Lose agent pattern.
When forming above-mentioned photocuring pattern, above-mentioned photosensitive polymer combination can be coated on substrate, by preceding
It dries (pre-baking) process and forms light-sensitive surface.Later, by implementing exposure process, developing procedure as needed can be with
Photocuring pattern is formed, postexposure bake (post exposure baking:PEB) process can also be further implemented.
When above-mentioned exposure process, as described above, by having the photoacid generator of the acidity improved to generate acid, so as to
To induce the cross-linking reaction of adhesive resin.In addition, by the effect of above-mentioned photoacid generator and polymerization initiator, exposure portion and non-
The Wuli-Shili-Renli system approach difference of exposure portion increases and can be improved the resolution ratio of exposure process.
In above-mentioned exposure process, the ultraviolets such as g line (wavelength: 436nm), h line, i line (wavelength: 365nm) can be used
Source.Above-mentioned developing procedure includes liquid additive process, infusion process, spray-on process etc., and can be by inorganic and/or organic basic compound
For developer solution.
For example, above-mentioned inorganic alkaline compound may include alkali metal salt, above-mentioned organic basic compound can wrap containing
Machine hydroxide based compound.
According to an embodiment of the invention, can be realized low-temperature solid since curability is improved because of above-mentioned photoacid generator
Chemical industry sequence.For example, the temperature relative reduction of cured above-mentioned PEB process will can be used to add.In one embodiment, above-mentioned PEB
Process can be implemented in a low temperature of 100 DEG C~150 DEG C.
As with the image display device for using above-mentioned pattern in above-mentioned photocuring pattern or manufacturing process, there is liquid crystal
Showing device, OLED, flexible display etc., but not limited to this, may be exemplified all figures as known in the art applicatory
As display device.
Hereinafter, the experimental example including preferred embodiment and comparative example is disclosed in order to help to understand the present invention, but
These embodiments only illustrate the present invention, are not intended to limit appended claims range, think in scope of the invention and technology
Think in range, to embodiment various modifications may be made and amendment, this it will become apparent to those skilled in the art that
Certainly such deformation and amendment also belong to scope of the appended claims.
Production Example 1: the manufacture of adhesive resin (A-1)
In the flask for the 1L for having reflux condenser, dropping funel and blender, supplied with 0.02L/ minutes flows
Nitrogen and form nitrogen atmosphere, be added diethylene glycol methyl ethyl ether 150g, be heated to 70 DEG C while stirring.Then, under investment
State mixture (molar ratio 50:50) 210.2g (0.95mol) and methacrylic acid 14.5g of chemical formula 3 and chemical formula 4
(0.17mol), makes it dissolve and manufactures solution.
[chemical formula 3]
[chemical formula 4]
Manufactured above-mentioned solution is added dropwise in flask using dropping funel, then makes 2 as polymerization initiator,
Bis- (2, the 4- methyl pentane nitrile) 27.9g of 2'- azo are dissolved in diethylene glycol methyl ethyl ether 200g, and are leaked by other dropping liquid
Bucket through when be added dropwise in flask within 4 hours.After the completion of dropwise addition of polymerization initiator, is maintained 4 hours at 70 DEG C, be cooled to room later
Temperature obtains the solution of the copolymer of 41.6 mass % of solid component, 65 ㎎-KOH/g of acid value (solid component conversion).Resulting tree
The weight average molecular weight (Mw) of rouge A-1 is 8,300, molecular weight distribution 1.85.
At this point, the measurement of the weight average molecular weight (Mw) and number-average molecular weight (Mn) of resin uses HLC-8120GPC (Tosoh
(strain) manufacture) device, column uses the column that TSK-GELG4000HXL and TSK-GELG2000HXL are connected in series, column temperature 40
DEG C, mobile phase solvent is tetrahydrofuran, and flow velocity is 1.0ml/ minutes, and injection rate is 50 μ l, and detector uses RI, and measurement sample is dense
Degree be 0.6 mass % (solvent=tetrahydrofuran), calibration standard substance migration TSK standard polystyren F-40, F-4, F-1,
A-2500, A-500 (Tosoh (strain) manufacture).The ratio between the weight average molecular weight of acquisition and number-average molecular weight are defined as molecular weight distribution
(Mw/Mn)。
Production Example 2: the manufacture of curable epoxide type alkali soluble resins (A-2)
As monomer, mixture (molar ratio 50:50) 132.2g of above-mentioned chemical formula 3 and chemical formula 4 is used
(0.60mol), methacrylic acid (3- ethyl -3- oxetanyl) methyl esters 55.3g (0.30mol) and methacrylic acid 8.6g
(0.10mol) in addition to this implements process identical with Production Example 1, obtains 41.8 mass % of solid component, 62 ㎎ of acid value-
The copolymer solution of KOH/g (solid component conversion).The weight average molecular weight of the Resin A -2 of measurement is 8,000, and molecular weight distribution is
1.82。
Embodiment and comparative example
According to the negative light-sensitive resin combination of composition the manufacture embodiment and comparative example recorded in following table 1.As
Solvent is used in the same manner 3:7 (weight ratio) mixed liquor (group of diethylene glycol methyl ethyl ether and propylene glycol monomethyl ether
It closes object and amounts to 60 parts by weight in 100 parts by weight).
[table 1]
Experimental example
By length and width be respectively 2 inches glass substrate (Eagle 2000, Corning Incorporated manufacture) successively with neutral detergent,
It is dry after water and ethyl alcohol cleaning.The photonasty manufactured in the embodiment of spin coating table 1 and comparative example respectively on above-mentioned glass substrate
Composition, then utilize hot plate (Hot plate), 80 DEG C front baking 120 seconds.Substrate after above-mentioned front baking is cooled to room temperature
Afterwards, 100 μm will be set as with the interval of quartz glass photomask, using exposure machine (MA6,Company's manufacture),
With 30mJ/cm2Light exposure (365nm benchmark) irradiation light.When implementing above-mentioned exposure, using in the same plane to be spaced apart from each other
The photomask of the opening portion pattern (sectional hole patterns) of 100 μm of regular quadrangles comprising 10 μm of square.
After light irradiation, in 2.38% tetramethylammonium hydroxide aqueous solution, film will be formed by and impregnated 60 seconds at 25 DEG C
Develop, after washing and drying, using clean baking oven in 100 DEG C of implementation, 120 minutes PEB.It is formed by the height of pattern
It is 1.5 μm.Evaluation of physical property is implemented as follows for the pattern obtained by above-mentioned operation, and the results are shown in following table 2.
(1) adaptation is evaluated
For the pattern formed as described above, according to ASTM D-3359-08 ortho-test, using by cutting machine
The method confirmation adaptation torn after surface mount adhesive tape (Tape) after cutting (cutting).In Cutting/Tape test,
Establishing criteria test method(s) provides degree that the removing of film is occurred according to 0B~5B and is judged as follows.
<evaluation criteria>
5B: removing 0%
4B: removing is less than 5%
3B: removing 5% is more than and less than 15%
2B: removing 15% is more than and less than 35%
1B: removing 35% is more than and less than 65%
0B: 65% or more removing
(2) surface damage is evaluated
It for the pattern formed as described above, is observed using scanning electron microscope (SEM), and following evaluation table
Whether surface damage occurs.
<evaluation criteria>
When ◎: SEM observation, patterned surfaces is absolutely not damaged
When zero: SEM observation, damage is observed in the patterned surfaces less than 3% in 100 samples
When △: SEM observation, the patterned surfaces in 100 samples 10~30% observes damage
When X:SEM is observed, the patterned surfaces in 100 samples 50% or more observes damage
(3) chemical resistance is evaluated
After the composition of coating Examples and comparative example, the film of curing schedule will be heated 1 hour and have passed through at 100 DEG C
In HNO3It is handled 45 minutes/2 minutes in/HCL aqueous solution.Later, according to ASTM D-3359-08 standard test conditions, using
The method torn after surface mount adhesive tape after being cut by cutting machine evaluates chemical resistance as follows.
<evaluation criteria>
5B: removing 0%
4B: removing is less than 5%
3B: removing 5% is more than and less than 15%
2B: removing 15% is more than and less than 35%
1B: removing 35% is more than and less than 65%
0B: 65% or more removing
(4) film shrinks evaluation
Compare the pattern that will be formed as described above in HNO3In/HCl etching solution (etchant) aqueous solution before and after the processing
Film thickness change is evaluated as follows.
<evaluation criteria>
◎: the film thickness change of etching solution before and after the processing is less than 1%
Zero: the film thickness change 1~2% of etching solution before and after the processing
△: the film thickness change 3~4% of etching solution before and after the processing
X: the film thickness change 5~6% of etching solution before and after the processing
(5) membrane left rate is evaluated
After the composition of coating Examples and comparative example, after 80 DEG C are heated 120 seconds on hot plate, film thickness is measured
(A), and measurement have passed through the film thickness (B) after exposure and imaging step, calculates its ratio, which is known as membrane left rate and (is stayed
Film rate=(B)/(A) * 100).
[table 2]
Referring to table 2, for the embodiment comprising photoacid generator of the embodiment of the present invention, with comparative example phase
Than having generally formed film or pattern with excellent chemistry, mechanical property.For the comparative example 1 without photoacid generator
In the case where, worst result is measured in all assessment items.
On the other hand, comprising the repetitive unit containing epoxy group and containing the weight of oxetanyl for adhesive resin
In the case where the embodiment 2 of both multiple units, it is be evaluated as having most excellent hardness, chemical resistance, membrane left rate, machinery resistance to
Long property.It can predict that it is more efficiently promoted due to the cross-linking reaction induced and the ring-opening reaction based on photoacid generator
Into.
N is 0 (trifluoromethyl (CF in above-mentioned chemical formula 13) in conjunction with sulfo group) and embodiment 3 in the case where, with embodiment 1
It compares, is unable to ensure sufficient acidity, adaptation slightly reduces.The case where including embodiment 4 of slight excess of photoacid generator
Under, compared with Example 1, adaptation, chemical resistance and membrane left rate slightly reduce.
On the other hand, in the case where the comparative example 4 that n is 10 in above-mentioned chemical formula 1, compared with 1~comparative example of comparative example 3,
It observes the characteristic improved, but the acidity due to being excessively increased, reduced adaptation, table is shown compared with embodiment
Face characteristic, chemical resistance.
Claims (12)
1. a kind of negative light-sensitive resin combination, it includes adhesive resin, polymerizable compound, polymerization initiator, light to produce
Sour agent and solvent,
The photoacid generator includes compound represented by following chemical formula 1,
Chemical formula 1
In chemical formula 1, R1~R6It is each independently the alcoxyl of hydrogen, the alkyl of carbon atom number 1~5, halogen or carbon atom number 1~4
Base,
The integer that n is 0~8.
2. negative light-sensitive resin combination according to claim 1, in the chemical formula 1, integer that n is 2~8.
3. negative light-sensitive resin combination according to claim 1, content the consolidating in composition of the photoacid generator
It is 1~5 parts by weight in 100 parts by weight of body components total.
4. negative light-sensitive resin combination according to claim 1, described adhesive resin includes to contain epoxy group
Repetitive unit and for hydrogen group.
5. negative light-sensitive resin combination according to claim 4, described adhesive resin include from selected from by
The repetitive unit of at least one of the group of the composition of compound represented by following chemical formula (1)~(3) monomer,
In chemical formula (1)~(3), R1For hydrogen or methyl.
6. negative light-sensitive resin combination according to claim 4, described adhesive resin is further included containing aerobic
The repetitive unit of azetidinyl.
7. negative light-sensitive resin combination according to claim 6, described adhesive resin include from selected from by
The repetitive unit of at least one of the group of the composition of compound represented by following chemical formula (4)~(6) monomer,
In chemical formula (4)~(6), R2For hydrogen or methyl, X1For the alkylidene of carbon atom number 1~12, X2For carbon atom number 1~6
Alkyl.
8. negative light-sensitive resin combination according to claim 4, described to include the repetition containing carboxylic acid for hydrogen group
Unit.
9. negative light-sensitive resin combination according to claim 8, described adhesive resin include from selected from by
The repetitive unit of at least one of the group of the composition of compound represented by following chemical formula (7) and (8) monomer,
In chemical formula (7) and (8), R3For hydrogen or methyl.
10. a kind of photocuring pattern, is formed by photosensitive polymer combination according to any one of claims 1 to 9.
11. photocuring pattern according to claim 10, the photocuring pattern is selected from by array planarization film pattern, protects
Cuticula pattern, insulating film pattern, photoresist pattern, black matrix pattern, intercolumniation spacer patterns and black intercolumniation parting composition
Group.
12. a kind of image display device, it includes photocuring patterns described in any one of claim 10.
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Cited By (1)
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