CN113448164A - Negative photosensitive resin composition and use thereof - Google Patents
Negative photosensitive resin composition and use thereof Download PDFInfo
- Publication number
- CN113448164A CN113448164A CN202010226580.1A CN202010226580A CN113448164A CN 113448164 A CN113448164 A CN 113448164A CN 202010226580 A CN202010226580 A CN 202010226580A CN 113448164 A CN113448164 A CN 113448164A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- photosensitive resin
- acrylic
- negative
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- -1 7-oxabicyclo [4.1.0] hept-3-ylmethyl ester Chemical class 0.000 claims description 9
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 claims description 4
- LJZJMIZQMNDARW-UHFFFAOYSA-N decan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCCCC(CC)OC(=O)C(C)=C LJZJMIZQMNDARW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- FYYIUODUDSPAJQ-XVBQNVSMSA-N [(1S,6R)-7-oxabicyclo[4.1.0]heptan-3-yl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CC[C@H]2O[C@H]2C1 FYYIUODUDSPAJQ-XVBQNVSMSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- RIOOIQBUNJDFON-UHFFFAOYSA-N methyl 2-methylprop-2-enoate oxolane Chemical compound O1CCCC1.COC(C(=C)C)=O RIOOIQBUNJDFON-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- RXRIEAKKQPAUKB-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1.CO[Si](OC)(OC)CCCOCC1CO1 RXRIEAKKQPAUKB-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
A negative photosensitive resin composition comprising: (A)0.1 to 10 weight percent of an acrylic monomer or oligomer; (B)0.2 to 30 weight percent of an acrylic resin; (C)0.1 to 5 weight percent of a photoinitiator; (D)0.01 to 1 weight percent of a hot acid initiator; (E)0.1 to 5 weight percent of an epoxy monomer; and (F) the balance of an organic solvent; wherein, the content of the acrylic monomer or oligomer accounts for 25 to 45 percent of the weight sum of the acrylic monomer or oligomer and the acrylic resin. The invention also relates to the application of the negative photosensitive resin composition in a roll-to-roll process.
Description
Technical Field
The invention relates to a negative photosensitive resin composition and application thereof, in particular to a negative photosensitive resin composition for roll-to-roll process and application thereof.
Background
The base material used in the conventional electronic device (e.g., a display device, a touch device, or a touch display device) is glass, and is not flexible, and is not suitable for an electronic device with a curved surface design or a folding function. Therefore, there have been attempts to replace glass with flexible substrates (e.g., films). However, the photoresist used in the past for the glass process has the following disadvantages.
First, flexible substrates (e.g., films) often cannot withstand high temperature processing, with an upper temperature limit of less than 140 ℃. However, when the conventional photoresist material used in the glass process is used, if the baking temperature is lowered below 140 ℃, the reaction temperature is insufficient, which results in poor reliability.
In addition, when a flexible substrate (e.g., a film) is used in a roll-to-roll process, the cost of mass production can be significantly reduced. However, when the existing photoresist material capable of being cured at low temperature is used, although the photoresist material can react at a temperature below 140 ℃ and meet the reliability requirement, the photoresist material has the problem of stickiness after soft baking, and cannot be rolled up, so that the photoresist material is not suitable for roll-to-roll process.
In view of the above, there is a need to develop an optical-sensitive resin composition that can improve the above problems for roll-to-roll processes.
Disclosure of Invention
The main object of the present invention is to provide a negative photosensitive resin composition, which can form a film having non-stick property and can be applied to roll-to-roll processes.
The negative photosensitive resin composition of the present invention comprises: (A)0.1 to 10 weight percent of an acrylic monomer or oligomer; (B)0.2 to 30 weight percent of an acrylic resin; (C)0.1 to 5 weight percent of a photoinitiator; (D)0.01 to 1 weight percent of a hot acid initiator; (E)0.1 to 5 weight percent of an epoxy monomer; and (F) the balance of an organic solvent; wherein, the content of the acrylic monomer or oligomer accounts for 25 to 45 percent of the weight sum of the acrylic monomer or oligomer and the acrylic resin.
In the negative photosensitive resin composition of the present invention, the ratio of the content of the acrylic monomer or oligomer to the sum of the weight of the acrylic monomer or oligomer and the weight of the acrylic resin is controlled, so that the formed film has the developing property and the non-stick property. Therefore, when the negative photosensitive resin composition of the invention is coated on a flexible substrate, the composition can be applied to a roll-to-roll process to prepare an insulating layer or a protective layer of a flexible electronic device (e.g., a display device, a touch display device, etc.).
In the negative photosensitive resin composition of the present invention, the content of the acrylic monomer or oligomer is 25% to 45% of the sum of the weight of the acrylic monomer or oligomer and the weight of the acrylic resin, i.e., < 25% < A)/(A) + (B) < 45%. When the ratio is too low, there is a problem that the development is impossible or poor; when the ratio is too high, there is a problem that the film is sticky after soft baking or easily comes off after development. In one embodiment of the present invention, the acrylic monomer or oligomer is present in an amount of 25% to 33% by weight of the sum of the acrylic monomer or oligomer and the acrylic resin, i.e., < 25% < A)/(A) + (B) < 33%.
In the negative photosensitive resin composition of the present invention, (a) the acrylic monomer or oligomer may be an acrylic monomer, an acrylic oligomer, or a combination thereof. Wherein the acrylic oligomer may contain 2 to 10 acrylic monomers.
In the negative photosensitive resin composition of the present invention, (B) the acrylic resin may include an epoxy group-containing monomer. In one embodiment of the present invention, the acrylic resin may be formed from tricyclo [5, 2, 1, 02, 6] dec-8-yl methacrylate (TCDMA), methacrylic acid (MAA), Styrene (Styrene), methacrylic acid, 7-oxabicyclo [4.1.0] hept-3-ylmethyl ester (CYCLOMER M-100), and tetrahydrofuryl methyl methacrylate (THFMA). More specifically, the acrylic resin may be polymerized from tricyclo [5, 2, 1, 02, 6] decan-8-yl methacrylate, methacrylic acid, styrene, CYCLOMER M-100, and tetrahydrofurfuryl methacrylate. In addition, the molecular weight of the acrylic resin may be between 10,000 g/mole and 20,000 g/mole.
In the negative photosensitive resin composition of the present invention, (D) the hot acid initiator is an initiator which generates an acid upon heating. Wherein the reaction temperature of the hot acid initiator may be 50 ℃ to 150 ℃ or 80 ℃ to 150 ℃. In the present invention, the thermal acid initiator may be a cationic thermal acid initiator. In addition, the acid formed after heating of the hot acid initiator can have an acid dissociation constant (pKa) of less than or equal to-20 and greater than or equal to-30, i.e., -30. ltoreq. pKa.ltoreq.20; or less than-20 and greater than or equal to-30, i.e., -30. ltoreq. pKa < -20. In one embodiment of the invention, the hot acid is initiatedThe acid radical of the agent is SbF 6-or B (C)6F5)-(ii) a The invention is not limited thereto.
In the negative photosensitive resin composition of the present invention, the type of the (E) epoxy monomer is not particularly limited as long as it is a monomer containing an epoxy group. In one embodiment of the present invention, the epoxy monomer may include Bis (3, 4-epoxycyclohexylmethyl) adipate (Bis (3, 4-epoxypropylmethyl) adipate), 3-Glycidoxypropyltrimethoxysilane (3-Glycidoxypropyltrimethoxysilane), or a combination thereof; the invention is not limited thereto.
In addition to the negative photosensitive resin composition, the present invention also provides the use of the negative photosensitive resin composition for a roll-to-roll process. In particular, the negative photosensitive resin composition of the present invention can be coated on a flexible substrate and cured at a low temperature to form an insulating layer or a protective layer. The negative photosensitive resin composition of the invention has the characteristic of non-sticky surface after low-temperature curing and baking, and can be used in roll-to-roll process and stored in a roll.
In the present invention, the flexible substrate can be a flexible substrate or a film. In addition, the material of the flexible substrate may include Polycarbonate (PC), Polyimide (PI), polypropylene (PP), polyethylene terephthalate (PET), or other plastic or polymer material; the invention is not limited thereto. Further, in the present invention, the low temperature may be 140 ℃ or less, for example: 80 ℃ to 140 ℃ or 120 ℃ to 140 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention.
In this context, unless otherwise specified, the term "or" and/or "feature" means the presence of a, either alone or in combination with B; the features A and B or AND, respectively, refer to the presence of both A and B; the terms "including", "comprising", "having" and "containing" mean including but not limited to.
In addition, a value can be the first value, the second value, or another value between the first value and the second value if the value is between the first value and the second value.
Further, as used herein, a value "about" is intended to include within + -10% of the value, and particularly within + -5% of the value. The amounts given herein are approximate amounts, i.e., the meaning of "about" may still be implied without specifically stating "about".
The present invention will be further specifically described with reference to examples, but these examples are not intended to limit the scope of the present invention. In the following preparations, examples and comparative examples, temperatures are given in degrees centigrade and parts and percentages are by weight, unless otherwise indicated. Parts by weight relate to parts by volume as kilograms relate to liters.
Examples and comparative examples
In the following examples and comparative examples of the present invention, the acrylic monomer or oligomer used was M-400(CAS No.: 29570-58-9), which has the following structure (A-1):
the acrylic resin (B-1) used in the following examples and comparative examples of the present invention was synthesized in the following manner.
In a flask equipped with a condenser and a stirrer, 4 parts by weight of thermal radical initiator 2, 2' -Azobisisobutyl (AIBN), 282 parts by weight of solvent Methylethyldiglycol (MEDG), followed by 46 parts by weight of tricyclo [5, 2, 1, 02, 6] decan-8-yl methacrylate (TCDMA), 21 parts by weight of Methacrylic acid (MAA), 3 parts by weight of Styrene (Styrene), 40 parts by weight of Methacrylic acid, 7-oxabicyclo [4.1.0] hept-3-yl Methyl ester (Methacrylic acid, 7-oxobicyclo [4.1.0] hept-3-yl Methyl ester, CYCLOMM-100, manufactured by Daicel Industries, Ltd.), 12 parts by weight of tetrahydrofuran Methyl methacrylate (tetrahydrofuran Methyl methacrylate, THF) was charged, and rapidly replaced with nitrogen at 65 ℃ for half an hour after stirring, subsequently, the temperature was raised to 75 ℃ for 2 and a half hours to obtain a resin copolymer solution (B-1) having a solid content of 31.8% by weight and an average molecular weight (Mw) of 11000.
In the following examples and comparative examples of the present invention, the photoinitiator used was: i-907(CAS No. 71686-10-5), which has the structure shown in the following formula (C-1); and ITX (CAS No. 5495-84-1) having the structure represented by the following formula (C-2):
in the examples and comparative examples of the present invention described below, the structures of the thermal acid initiators used, and the dissociation constants (pKa) of the acids and acid groups formed are shown in table 1 below.
TABLE 1
In the following examples and comparative examples of the present invention, the epoxy monomers used were: bis (3, 4-epoxycyclohexylmethyl) adipate (DM 4128E, CAS No.: 3130-19-6) having the following structure (E-1); and 3-Glycidoxypropyltrimethoxysilane (3-Glycidoxypropyltrimethoxysilane) (A-187, CAS No.: 2530-83-8) having the following structure (E-2):
in the following examples and comparative examples of the present invention, the organic solvent (F-1) used was ethyl 1-Methoxy-2-propylacetate (1-Methoxy-2-propyl acetate, PGMEA) (CAS No.: 108-65-6).
The above acrylic monomer or oligomer, acrylic resin, photoinitiator, thermal acid initiator, epoxy monomer and organic solvent were formulated into negative photosensitive resin compositions of examples 1 to 9 and comparative examples 1 to 5 according to the formulation shown in table 4 below.
Test example
Firstly, a substrate is prepared, wherein an ITO film is formed on the surface of the substrate, and the surface of the substrate is cleaned by deionized water and acetone. Then, the negative photosensitive resin compositions prepared in examples 1 to 9 and comparative examples 1 to 5 were uniformly coated on the substrate by spin coating. Then, soft-baked at 80 ℃ for 5 minutes, and directly applied to a high-pressure mercury lamp (exposure energy: 100 mJ/cm) using a photomask2) Exposing the negative photosensitive resin composition coated on the surface of the substrate. Next, development was performed with 1% ENPD 23 for 100 seconds. Hard baking was carried out at 140 ℃ for 30 minutes. Finally, obtaining a required sample, wherein the thickness of the sample is 1.5-2.0 μm.
Adhesion test
The samples obtained after soft baking were subjected to a tack test. The scoring criteria are shown in table 2 below.
TABLE 2
Test for etching resistance
The sample prepared by the process is treated by aqua regia or aluminic acid (40 ℃ for 160 seconds), the test piece is cleaned by ultrapure water and dried, then the stripping agent N-300(60 ℃ for 135 seconds) is treated, and then the test piece is cleaned by ultrapure water and dried, and then the Baige test is carried out. The evaluation criteria of the etching resistance test are shown in the following table 3.
TABLE 3
TABLE 4
As shown in the results of table 4, when the ratio of the content of the acrylic monomer or oligomer to the sum of the weights of the acrylic monomer or oligomer and the acrylic resin (i.e., (a)/(a) + (B)) is 20% (comparative example 1), the negative photosensitive resin composition is poor in developability. When the ratio exceeds 45% (comparative examples 2 to 5), the formed film tends to be sticky. However, when the ratio is controlled in the range of 25% to 45% (examples 1 to 9), the negative photosensitive resin composition has excellent anti-tackiness in addition to good developability. Therefore, the negative photosensitive resin composition of the present invention can be effectively applied to a roll-to-roll process.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A negative photosensitive resin composition comprising:
(A)0.1 to 10 weight percent of an acrylic monomer or oligomer;
(B)0.2 to 30 weight percent of an acrylic resin;
(C)0.1 to 5 weight percent of a photoinitiator;
(D)0.01 to 1 weight percent of a hot acid initiator;
(E)0.1 to 5 weight percent of an epoxy monomer; and
the balance of organic solvent;
wherein, the content of the acrylic monomer or oligomer accounts for 25 to 45 percent of the weight sum of the acrylic monomer or oligomer and the acrylic resin.
2. The negative-type photosensitive resin composition of claim 1, wherein the thermal acid initiator is a cationic thermal acid initiator.
3. The negative-type photosensitive resin composition of claim 1, wherein an acid dissociation constant of an acid formed by heating the hot acid initiator is less than or equal to-20 and greater than or equal to-30.
4. The negative-type photosensitive resin composition of claim 3, wherein an acid formed by heating the hot acid initiator has an acid dissociation constant of less than-20 and greater than or equal to-30.
5. The negative-type photosensitive resin composition according to claim 1, wherein the acid group of the thermal acid initiator is SbF6 -Or B (C)6F5)-。
6. The negative photosensitive resin composition of claim 1, wherein the acrylic monomer or oligomer is present in an amount of 25% to 33% based on the sum of the weight of the acrylic monomer or oligomer and the weight of the acrylic resin.
7. The negative photosensitive resin composition of claim 1, wherein the acrylic resin has a molecular weight of between 10,000 g/mol and 20,000 g/mol.
8. The negative photosensitive resin composition of claim 1, wherein the acrylic resin comprises an epoxy-containing monomer.
9. The negative photosensitive resin composition of claim 1, wherein the acrylic resin is formed of tricyclo [5, 2, 1, 02, 6] dec-8-yl methacrylate (TCDMA), methacrylic acid (MAA), Styrene (Styrene), methacrylic acid, 7-oxabicyclo [4.1.0] hept-3-ylmethyl ester (CYCLOMER M-100), and tetrahydrofurmethyl methacrylate (THFMA).
10. The negative photosensitive resin composition of claim 1, wherein the epoxy monomer comprises bis (3, 4-epoxycyclohexylmethyl) adipate, 3-glycidoxypropyltrimethoxysilane, or a combination thereof.
11. Use of the negative-type photosensitive resin composition according to any one of claims 1 to 10 for a roll-to-roll process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010226580.1A CN113448164A (en) | 2020-03-26 | 2020-03-26 | Negative photosensitive resin composition and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010226580.1A CN113448164A (en) | 2020-03-26 | 2020-03-26 | Negative photosensitive resin composition and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113448164A true CN113448164A (en) | 2021-09-28 |
Family
ID=77807681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010226580.1A Pending CN113448164A (en) | 2020-03-26 | 2020-03-26 | Negative photosensitive resin composition and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113448164A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060128715A (en) * | 2005-06-10 | 2006-12-14 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition |
| CN1987650A (en) * | 2005-12-20 | 2007-06-27 | 财团法人工业技术研究院 | Negative light resistance agent composition |
| KR20070100042A (en) * | 2006-04-06 | 2007-10-10 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition |
| KR20110038252A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
| US20110294067A1 (en) * | 2010-06-01 | 2011-12-01 | Everlight Usa, Inc. | Photosensitive resin composition |
| CN102636955A (en) * | 2011-02-10 | 2012-08-15 | 台湾永光化学工业股份有限公司 | Photosensitive resin composition |
| CN102692819A (en) * | 2011-03-24 | 2012-09-26 | 东京应化工业株式会社 | Photosensitive resin composite and liquid crystal board |
| CN104423158A (en) * | 2013-08-30 | 2015-03-18 | 台湾永光化学工业股份有限公司 | Photosensitive resin composition |
| CN104570596A (en) * | 2013-10-25 | 2015-04-29 | 台湾永光化学工业股份有限公司 | Negative thick film resist composition and use thereof |
| JP2016161939A (en) * | 2015-03-05 | 2016-09-05 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | Negative photosensitive resin composition, photocuring pattern formed using the same, and image display device comprising the same |
| CN107957656A (en) * | 2016-10-18 | 2018-04-24 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
| WO2019117018A1 (en) * | 2017-12-11 | 2019-06-20 | Ａｇｃ株式会社 | Negative photosensitive resin composition |
| JP2019116533A (en) * | 2017-12-26 | 2019-07-18 | 株式会社クラレ | Methacryl resin composition |
-
2020
- 2020-03-26 CN CN202010226580.1A patent/CN113448164A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060128715A (en) * | 2005-06-10 | 2006-12-14 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition |
| CN1987650A (en) * | 2005-12-20 | 2007-06-27 | 财团法人工业技术研究院 | Negative light resistance agent composition |
| KR20070100042A (en) * | 2006-04-06 | 2007-10-10 | 주식회사 동진쎄미켐 | Negative photosensitive resin composition |
| JP2007279728A (en) * | 2006-04-06 | 2007-10-25 | Dongjin Semichem Co Ltd | Negative photosensitive resin composition |
| KR20110038252A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
| US20110294067A1 (en) * | 2010-06-01 | 2011-12-01 | Everlight Usa, Inc. | Photosensitive resin composition |
| CN102636955A (en) * | 2011-02-10 | 2012-08-15 | 台湾永光化学工业股份有限公司 | Photosensitive resin composition |
| CN102692819A (en) * | 2011-03-24 | 2012-09-26 | 东京应化工业株式会社 | Photosensitive resin composite and liquid crystal board |
| CN104423158A (en) * | 2013-08-30 | 2015-03-18 | 台湾永光化学工业股份有限公司 | Photosensitive resin composition |
| CN104570596A (en) * | 2013-10-25 | 2015-04-29 | 台湾永光化学工业股份有限公司 | Negative thick film resist composition and use thereof |
| JP2016161939A (en) * | 2015-03-05 | 2016-09-05 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | Negative photosensitive resin composition, photocuring pattern formed using the same, and image display device comprising the same |
| CN107957656A (en) * | 2016-10-18 | 2018-04-24 | 台湾永光化学工业股份有限公司 | Negative photosensitive resin composition and use thereof |
| WO2019117018A1 (en) * | 2017-12-11 | 2019-06-20 | Ａｇｃ株式会社 | Negative photosensitive resin composition |
| JP2019116533A (en) * | 2017-12-26 | 2019-07-18 | 株式会社クラレ | Methacryl resin composition |
Non-Patent Citations (2)
| Title |
|---|
| MATUSEVICH, YU I等: "A photosensitive material based on methyl methacrylate-acrylic acid copolymer", RUSSIAN JOURNAL OF APPLIED CHEMISTRY, vol. 86, no. 8, pages 1262 - 1267 * |
| 李伟杰;周光大;李伯耿;: "水溶性丙烯酸酯类感光干膜的制备及其性能研究", 影像科学与光化学, no. 02, pages 54 - 62 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4181152B2 (en) | Negative resist composition | |
| JP4983798B2 (en) | Photosensitive insulating resin composition and cured product thereof | |
| TWI506373B (en) | Photosensitive resin composition and display unit | |
| US20130236674A1 (en) | Adhesive composition for touch panel, adhesive film, and touch panel | |
| TWI704414B (en) | Chemically amplified photosensitive resin composition and insulation layer prepared from the same | |
| TWI643876B (en) | Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern | |
| JP2006113547A (en) | Thermosetting one-solution type composition for protective film of color filter and color filter using the same | |
| JP2007186542A (en) | Thermosetting resin composition, method of forming protective film for color filter and the protective film | |
| TW201825528A (en) | Photo-initiators and photosensitive resin composition for light shield comprising the same | |
| JPH10316721A (en) | Alkali-soluble resin and image-forming material using the same | |
| CN107203096B (en) | Negative photosensitive resin composition and photocured pattern made therefrom | |
| CN108931885B (en) | Low-temperature-cured photosensitive resin composition and application thereof | |
| CN113448164A (en) | Negative photosensitive resin composition and use thereof | |
| JP3321858B2 (en) | Thermosetting resin composition | |
| TWI739360B (en) | Negative photosensitive resin composition and use thereof | |
| CN113088200B (en) | High-temperature-resistant UV (ultraviolet) viscosity-reducing adhesive | |
| CN112940628B (en) | High-temperature-resistant UV (ultraviolet) viscosity-reducing adhesive capable of improving initial viscosity | |
| JP2008031417A (en) | Thermosetting resin composition, protective film and method for forming protective film | |
| JP5867750B2 (en) | Negative photosensitive resin composition | |
| JP6427953B2 (en) | Flexible transparent substrate | |
| KR101842249B1 (en) | Adhesive composition, adhesive layer and polarizing plate using the same | |
| JP6427956B2 (en) | Flexible transparent substrate | |
| JP2022132753A (en) | Composition for peeling layer formation and peeling layer | |
| JP2022132755A (en) | Composition for peeling layer formation and peeling layer | |
| JP2022136498A (en) | Release layer-forming composition and release layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |