CN109343308A - Organosilicon modified crylic acid resin composition - Google Patents
Organosilicon modified crylic acid resin composition Download PDFInfo
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- CN109343308A CN109343308A CN201810950964.0A CN201810950964A CN109343308A CN 109343308 A CN109343308 A CN 109343308A CN 201810950964 A CN201810950964 A CN 201810950964A CN 109343308 A CN109343308 A CN 109343308A
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- resin composition
- ester
- modified crylic
- acrylate
- crylic acid
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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
-
- 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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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a kind of organosilicon modified crylic acid resin compositions, which is characterized in that including alkali soluble resin, organosilicon modified crylic acid resin, colorant, photopolymerizable compound, Photoepolymerizationinitiater initiater.Black matrix" made by the present invention has splendid acid resistance, impregnates even across the acid (chloroazotic acid) of 20min, the characteristics such as surface state and adhesive force all do not change.
Description
Technical field
The invention belongs to light sensitivity chemical material fields, and in particular to a kind of organosilicon modified crylic acid resin composition.
Background technique
Currently, touch panel is widely used in display device as liquid crystal display etc..In current touch panel
Manufacturing process in, need to be etched the metal film after black matrix".Therefore, to resistance toization of black-matrix material
The property learned and weatherability have high requirement.
The photosensitive composition of black matrix" for general colored filter, if being diverted to touch surface
Standard requirements are often not achieved in plate, endurance.
Based on the above reasons, coloring excellent it is an object of that present invention to provide chemical resistance and that black matrix" can be used to prepare
Photosensitive polymer combination.
Summary of the invention
Goal of the invention: in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of organosilicon-modified acrylic
Resin combination.
Technical solution: in order to achieve the above object of the invention, the present invention is specifically achieved like this: a kind of organic-silicon-modified
Acrylic acid resin composition, including alkali soluble resin, organosilicon modified crylic acid resin, colorant, photopolymerizable compound,
Photoepolymerizationinitiater initiater and silane coupling agent are organosilicon modified crylic acid resin in terms of 100 parts by the quality of alkali soluble resin
Quality be 5 ~ 20 parts, colorant be 60 ~ 100 parts, 0 ~ 60 part of photopolymerizable compound, 5 ~ 15 parts of Photoepolymerizationinitiater initiater, silane
1 ~ 10 part of coupling agent.
Wherein, the organosilicon modified crylic acid resin includes at least A, B monomer, and A, the molecular formula of B monomer are as follows
A monomer is, B monomer is。
The molecular formula of a kind of preferred embodiment, the organosilicon modified crylic acid resin is。
Wherein, the alkali soluble resin molecular formula is, wherein X molecular formula be, Y is and carboxylic acid anhydrides removes anhydride group-CO-O-CO-
Residue afterwards, Z are that tetracarboxylic dianhydride removes the residue after 2 anhydride groups.
Wherein, the colorant is mill base.
Wherein, the photopolymerizable compound is methyl acrylate, methyl methacrylate, 2- hydroxy-ethyl acrylate, 2-
Hydroxyethyl methacrylate, 2- hydroxy propyl methacrylate, two base ester of 2- acrylic acid 1,2- second, methacrylic acid glycol ester,
Triethylene glycol diacrylate, double methyl methacrylate triethylene glycol ester, tetraethylene glycol diacrylate, dimethacrylate three contract
Tetraethylene glycol ester, propylene glycol diacrylate, dimethacrylate, trimethylolpropane trimethacrylate, four (three
Hydroxymethyl-propane) tetrapropylene ester, four (trimethylolpropane) tetramethyl acrylic esters, pentaerythrite mono acrylic ester, pentaerythrite
Monomethacrylates, pentaerythritol tetraacrylate, pentaerythritol tetramethylacrylate, five acrylic acid of dipentaerythrite
Ester, dipentaerythrite pentamethacrylate, six acrylate of dipentaerythrite, dipentaerythrite hexamethyl acrylic acid
Ester, 1,6- hexanediyl ester, benzyl acrylate, benzyl methacrylate, acrylic or methacrylic acid.
Wherein, the molecular formula of the Photoepolymerizationinitiater initiater, wherein X ' molecular formula beOr, R1For phenyl, alkyl ,-the CN ,-NO of C1-C202Or C1-
The halogenated alkyl of C4, R2For the alkyl of C2-C12 or the acyl group of C4-C8, R3- R7Each independently represent H, halogen atom, C1-C12
Alkyl, phenyl or C6H5S-, R8、R9Acyl respectively independently indicates the alkyl or phenyl of H, halogen atom, C1-C12.
The utility model has the advantages that the present invention, compared with traditional technology, made black matrix" has splendid acid resistance, even if
It is impregnated by the acid (chloroazotic acid) of 20min, the characteristics such as surface state and adhesive force all do not change.
Specific embodiment
Embodiment 1:
The structure of X is as follows；Y is that 1,2,3,6- tetrabydrophthalic anhydrides remove the residue after anhydride group；Z is biphenyl four
Formic acid dianhydride removes the residue after 2 anhydride groups,
A kind of organosilicon modified crylic acid resin composition, the alkali soluble resin including 100 parts of mass fractions, 5 ~ 20 parts have
Machine fluorine-silicon modified acrylic resin, 60 ~ 100 parts of colorant, 0 ~ 60 part of photopolymerizable compound, 5 ~ 15 parts of photopolymerization cause
Agent, 1 ~ 10 part of silane coupling agent；The wherein molecular formula of alkali soluble resin are as follows:, wherein X molecular formula be, Y is and carboxylic acid anhydrides removes anhydride group-CO-O-CO-
Residue afterwards, Z are that tetracarboxylic dianhydride removes the residue after 2 anhydride groups；The colorant is mill base；The optical polymerism chemical combination
Object is methyl acrylate, methyl methacrylate, 2- hydroxy-ethyl acrylate, 2- hydroxyethyl methacrylate, 2- methacrylic acid
Hydroxypropyl acrylate, two base ester of 2- acrylic acid 1,2- second, methacrylic acid glycol ester, triethylene glycol diacrylate, methacrylate
Triethylene Glycol, tetraethylene glycol diacrylate, dimethacrylate tetraethylene-glycol ester, propylene glycol diacrylate,
Dimethacrylate, trimethylolpropane trimethacrylate, four (trimethylolpropane) tetrapropylene esters, four (three hydroxyls
Methylpropane) tetramethyl acrylic ester, pentaerythrite mono acrylic ester, pentaerythrite monomethacrylates, pentaerythrite 4 third
Olefin(e) acid ester, pentaerythritol tetramethylacrylate, five acrylate of dipentaerythrite, dipentaerythrite pentamethyl acrylic acid
Ester, six acrylate of dipentaerythrite, dipentaerythrite hexamethacrylate, 1,6- hexanediyl ester, third
Olefin(e) acid benzyl ester, benzyl methacrylate, acrylic or methacrylic acid；The molecular formula of the Photoepolymerizationinitiater initiater, wherein X ' molecular formula beOr, R1For benzene
Alkyl ,-the CN ,-NO of base, C1-C202Or the halogenated alkyl of C1-C4, R2For the alkyl of C2-C12 or the acyl group of C4-C8, R3- R7
Each independently represent H, halogen atom, the alkyl of C1-C12, phenyl or C6H5S-, R8、R9Acyl respectively independently indicate H, halogen atom,
The alkyl or phenyl of C1-C12.
Specifically, following each ingredient is dissolved in propylene glycol methyl ether acetate/diethylene glycol ethylmethyl ether=80/20(mass
Than) in the mixed solvent, make its mass fraction of solids 15%, be stirred 3h with blender, with the film mistake of aperture 0.5um
Filter is filtered, and photosensitive polymer combination is made.
1. -100 parts of alkali soluble resin (structure is same as above) --- ---；
2. -60 parts of organosilicon modified crylic acid resin (structure is as follows :) --- ---
；
3.80 parts of styrene, 20 parts of methacrylic acids, 30 parts of methyl methacrylates, 10 parts of γ-methacryloxypropyls
The polymer of triethoxysilane (market product: SHIN-ETSU HANTOTAI's chemistry, KBE-503)；
- 60 parts of " 4. M404 " dipentaerythritol hexaacrylate (Japanese chemical drug system) --- ---；
" 5. OXE-02 " -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone -1-(0- acetyl
Oxime) 30 parts of --- ---；
6. 300 parts of colorant (Tokushiki system) --- ---.
Embodiment 2:
Formula is close with embodiment 1, does not use KBE-503；The preparation method is the same as that of Example 1.
Embodiment 3:
It is formulated, the ratio of KBE-503 5 part close with embodiment 1；The preparation method is the same as that of Example 1.
Embodiment 4:
It is formulated, the ratio of KBE-503 20 part close with embodiment 1；The preparation method is the same as that of Example 1.
Embodiment 5:
It is formulated, the ratio of KBE-503 40 part close with embodiment 1；The preparation method is the same as that of Example 1.
Embodiment 6:
Formula is close with embodiment 1, does not use organosilicon modified crylic acid resin；The preparation method is the same as that of Example 1.
Embodiment 7:
Formula is close with embodiment 1, and 20 parts of organosilicon modified crylic acid resin；The preparation method is the same as that of Example 1.
Embodiment 8:
Formula is close with embodiment 1, and 40 parts of organosilicon modified crylic acid resin；The preparation method is the same as that of Example 1.
Embodiment 9:
Formula is close with embodiment 1, and 80 parts of organosilicon modified crylic acid resin；The preparation method is the same as that of Example 1.
Embodiment 10:
Formula is close with embodiment 1, and 120 parts of organosilicon modified crylic acid resin；The preparation method is the same as that of Example 1.
Embodiment 11:
The performance evaluation of each organosilicon modified crylic acid resin composition of embodiment 1 ~ 10
<acid resistance evaluation>
Above-mentioned photosensitive polymer combination is coated on the glass substrate using spin coater (production of 1H-360S: three large bamboo hats with a conical crown and broad brim), 90 DEG C
Under dry 2min on hot plate and form film, then, using exposure machine (USHIO productions) with the full film of exposure 50mj/cm2 progress
Exposure.After exposure, development 90sec is carried out with spray pattern with 0.04% potassium hydroxide developer solution.Then, in 240 DEG C of baking ovens
After dry 30min, form the cured film of film thickness 1.7um.
The glass substrate for forming cured film is soaked in leaching in 48 DEG C of acidic etching liquid (concentrated hydrochloric acid: concentrated nitric acid=15:2)
Bubble takes out after 2/4/6/8/10/20 minute, and air blast drying is carried out after washing, observe film surface blister formation and film adhesive force and
Surface blisters situation.
For the adhesive force variation after evaluation cured film acid soak, grid software test need to be carried out.Specifically, according to ISO2409
Cured film is cut into 100 lattice (10 × 10) with the interval of 2.0mm, then carries out acid soak by the test method of (ASTM D3359)
It tests (method is same as above).After acid soak, washing, drying, adhesive tape is adhered firmly to the crosscutting position of grid, then rapid glass
Adhesive tape, check cured film whether glass, its adhesive force is evaluated with 6 grades of grade 0B to 5B.
Cured film acid soak rear surface is observed under optical microscopy (VHX-5000, Keyemce system) and is bubbled situation, will be seen
Observe solidification film surface gassing phenomenon be considered as it is bad, cured film it is in apparent good order and condition it is (identical as not soaking out) be considered as it is good
It is good.
<formation of photosensitive resin pattern>
Above-mentioned photosensitive polymer combination is coated on the glass substrate using spin coater (production of 1H-360S: three large bamboo hats with a conical crown and broad brim), 90 DEG C
Under on hot plate dry 2min formed film, then, using exposure machine (USHIO productions) progress the exposure with exposure mask, between exposure
Gap 150um, exposure energy 50mj/cm2.After exposure, developed with 0.04% potassium hydroxide developer solution with spray pattern
90sec.Then, in 240 DEG C of baking ovens after dry 30min, form the photoresist of thickness 1.7um, line comprising line width 50um
Pattern.
Following evaluation is carried out to the photosensitive resin pattern:
Straight line traveling
Above-mentioned photosensitive resin pattern is observed with the Hitachi scanning electron microscope SEM(corporation, model SU8010),
The case where evaluating pattern lines traveling, good pattern will be formd as former state according to exposure mask is considered as well, otherwise is bad.
Configuration of surface
The coarse situation of patterned surfaces is observed in the secure execution mode (sem, it will be observed that surface is smooth, it is good to be considered as without the case where obvious rough pattern
It is good；It otherwise is bad.
The results are shown in Table 1:
。
Embodiment 4,6 ~ 10, which compares, can see, and the additive amount of organosilicon-modified acrylate increases in formula, acid resistance
Gradually increase, but pattern lines traveling is gradually deteriorated, at the same configuration of surface occur it is bad it is organic-silicon-modified must acrylate
Optimal additive amount is 40-80 parts.
Embodiment 1 ~ 5, which compares, can see, and in acrylic resin composite structure, increase the additive amount of KBE-503, most end form
At pattern acid resistance gradually increase.Optimal KBE-503 additive amount is 20-40 parts.
The organosilicon modified crylic acid resin composition being prepared by embodiment 4, the black matrix" acid resistance of formation
By force, straight line traveling is excellent, configuration of surface is good.
Claims (7)
1. organosilicon modified crylic acid resin composition, which is characterized in that including alkali soluble resin, organosilicon-modified acrylic
Resin, colorant, photopolymerizable compound, Photoepolymerizationinitiater initiater are organosilicon in terms of 100 parts by the quality of alkali soluble resin
Acrylic resin modified quality is 5 ~ 20 parts, and colorant is 60 ~ 100 parts, and 0 ~ 60 part of photopolymerizable compound, photopolymerization causes
5 ~ 15 parts of agent.
2. organosilicon modified crylic acid resin composition according to claim 1, which is characterized in that described organic-silicon-modified
Acrylic resin includes at least A, B monomer, and A monomer is, B monomer is。
3. organosilicon modified crylic acid resin composition according to claim 2, which is characterized in that described organic-silicon-modified
The molecular formula of acrylic resin is。
4. organosilicon modified crylic acid resin composition according to claim 1, which is characterized in that the alkali-soluble tree
Rouge molecular formula is, wherein X molecular formula be, Y is and carboxylic acid anhydrides removes anhydride group-CO-O-CO-
Residue afterwards, Z are that tetracarboxylic dianhydride removes the residue after 2 anhydride groups.
5. organosilicon modified crylic acid resin composition according to claim 1, which is characterized in that the colorant is color
Slurry.
6. organosilicon modified crylic acid resin composition according to claim 1, which is characterized in that the optical polymerism
Conjunction object is methyl acrylate, methyl methacrylate, 2- hydroxy-ethyl acrylate, 2- hydroxyethyl methacrylate, 2- metering system
Sour hydroxypropyl acrylate, two base ester of 2- acrylic acid 1,2- second, methacrylic acid glycol ester, triethylene glycol diacrylate, double metering systems
Sour Triethylene Glycol, tetraethylene glycol diacrylate, dimethacrylate tetraethylene-glycol ester, propylene glycol diacrylate
Ester, dimethacrylate, trimethylolpropane trimethacrylate, four (trimethylolpropane) tetrapropylene esters, four (three
Hydroxymethyl-propane) tetramethyl acrylic ester, pentaerythrite mono acrylic ester, pentaerythrite monomethacrylates, pentaerythrite four
Acrylate, pentaerythritol tetramethylacrylate, five acrylate of dipentaerythrite, dipentaerythrite pentamethyl propylene
Acid esters, six acrylate of dipentaerythrite, dipentaerythrite hexamethacrylate, 1,6- hexanediyl ester,
Benzyl acrylate, benzyl methacrylate, acrylic or methacrylic acid.
7. organosilicon modified crylic acid resin composition according to claim 1, which is characterized in that the photopolymerization causes
The molecular formula of agent, wherein X ' molecular formula beOr
, R1For phenyl, alkyl ,-the CN ,-NO of C1-C202Or the halogenated alkyl of C1-C4, R2For the alkyl of C2-C12 or the acyl of C4-C8
Base, R3- R7Each independently represent H, halogen atom, the alkyl of C1-C12, phenyl or C6H5S-, R8、R9Acyl respectively independently indicate H,
The alkyl or phenyl of halogen atom, C1-C12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810950964.0A CN109343308A (en) | 2018-08-21 | 2018-08-21 | Organosilicon modified crylic acid resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810950964.0A CN109343308A (en) | 2018-08-21 | 2018-08-21 | Organosilicon modified crylic acid resin composition |
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| CN109343308A true CN109343308A (en) | 2019-02-15 |
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| CN201810950964.0A Pending CN109343308A (en) | 2018-08-21 | 2018-08-21 | Organosilicon modified crylic acid resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694557A (en) * | 2019-10-23 | 2021-04-23 | 常州强力先端电子材料有限公司 | Photocurable resin, photocurable resin composition, and black matrix material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191737A (en) * | 1998-12-28 | 2000-07-11 | Daicel Chem Ind Ltd | Curable resin composition |
| US20080039544A1 (en) * | 2006-08-11 | 2008-02-14 | Daxin Materials Corporation | Photosensitive resin composition |
| CN104238269A (en) * | 2014-09-19 | 2014-12-24 | 江苏博砚电子科技有限公司 | Photosensitive resin composition and application thereof |
| US20150315376A1 (en) * | 2014-04-30 | 2015-11-05 | Chi Mei Corporation | Photosensitive resin composition for color filter and application thereof |
| CN108333868A (en) * | 2017-01-18 | 2018-07-27 | 东京应化工业株式会社 | The manufacturing method of resin combination, black matrix", display device and black matrix" |
-
2018
- 2018-08-21 CN CN201810950964.0A patent/CN109343308A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191737A (en) * | 1998-12-28 | 2000-07-11 | Daicel Chem Ind Ltd | Curable resin composition |
| US20080039544A1 (en) * | 2006-08-11 | 2008-02-14 | Daxin Materials Corporation | Photosensitive resin composition |
| US20150315376A1 (en) * | 2014-04-30 | 2015-11-05 | Chi Mei Corporation | Photosensitive resin composition for color filter and application thereof |
| CN104238269A (en) * | 2014-09-19 | 2014-12-24 | 江苏博砚电子科技有限公司 | Photosensitive resin composition and application thereof |
| CN108333868A (en) * | 2017-01-18 | 2018-07-27 | 东京应化工业株式会社 | The manufacturing method of resin combination, black matrix", display device and black matrix" |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112694557A (en) * | 2019-10-23 | 2021-04-23 | 常州强力先端电子材料有限公司 | Photocurable resin, photocurable resin composition, and black matrix material |
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