TWI378321B - Thermosetting resin composition for producing color filter for cmos image sensor, color filter comprising transparent film formed using the compositon and cmos image sensor using the color filter - Google Patents

Description

1378321 IX. Invention: [Technical field of invention:! Cross-reference of related application This non-provisional patent application is based on 35 USC clause 119 and requests for Korean patent application No. 10-2007-0059842, application date 2007 Priority is claimed on June 19, the entire disclosure of which is incorporated herein by reference. Field of invention

The present invention relates to a thermosetting resin composition for manufacturing a color filter for a complementary metal oxide semiconductor (CMOS) image sensor, 10 color filters including a transparent film formed using the composition, And a CMOS image sensor using the color filter.

BACKGROUND OF THE INVENTION The color light film used in the image sensor includes a transparent film formed below and above the surface of the color light film to improve flatness and protect the color filter. The transparent thin crucible must be optically transparent in the visible light region, have high film strength, and have sufficient heat resistance and chemical resistance to impart subsequent treatment such as heating, cleaning, development, and side after formation of the transparent film. Specifically, the underlying film of the color filter used for the image sensor must be a reflection of the violet light that can suppress the illumination used to make the pattern of the color photoresist, thus preventing various adverse factors such as Halo and standing waves cause defects in the pattern in the color filter. Japanese Patent Laid-Open Publication No. Hei 1-134306, No. Sho 62-163016, and No. Sho 63-1311 No. 3 disclose a transparent film composition for color calendering sheets, comprising f-based 5 glycerol glycosides, polyimine and melamine A mixture of resin and epoxy resin is used as a main component. The epoxy resin composition can be used to produce a protective film for a color filter having reliable adhesion strength, heat resistance, chemical resistance, and water repellency. For example, Japanese Laid-Open Patent Publication No. Hei 08-050289 discloses a hardenable resin composition comprising a glycidyl methacrylate polymer and a phenolic hardener. In addition, Japanese Patent Publication No. 8-2〇1617 discloses a tree of a transparent film, comprising an epoxy resin, a hardener and an organic solvent, wherein the hardener is a benzene (tetra)·cis dianhydride copolymer. The reaction product of the amine and the amine.逋*% oxygen resin is mixed with the hardener just before application (so-called "two-P blade composition"), and (d) is that the reaction between the epoxy resin and the hardener is fast. It is known that epoxy resins are not suitable for the preparation of a part of the composition. The treatment of the two-part group is complicated and is not suitable for the scale preparation of the secret jade industry. None of the foregoing prior art discloses that a partial composition comprising an epoxy resin can (4) satisfy the day-to-day riding, thinness, degree, and sexuality.

Physical requirements and other requirements. Further, a transparent film for a color ray film which can absorb ultraviolet light has not been developed. [Mingna J Summary of Invention 邳, provides a thermosetting resin composition for producing colored enamel sheets. The invention has the advantages of the first film „ The solid resin composition has excellent adhesive strength, transparency, enamel film 竑.. ^ ^, heat resistance, acid resistance, alkali resistance and long surface storage * 疋 tens The thermosetting resin of the present invention is an external precursor comprising an organic solvent and a self-hardening copolymer having the structural unit represented by Formulas 2, 3 and 4, wherein R is a hydrogen atom or a methyl group and η is An integer R2 from 1 to 10

〇>-〇+c-t-〇H (2) wherein R2 is a hydrogen atom or a methyl group and m is an integer from 1 to 1〇; R3’+民-

OH 〇 (3) wherein R 3 is a hydrogen atom or a methyl group; and R 4 -C- H 2 ο )-ζ (4) wherein h is a hydrogen atom or a methyl group and hydrazine is selected from the group consisting of the following groups

ΟΗ

And (5) < the self-hardening copolymer comprises from about 5 mol% to about 9 mol% of the structural unit of formula 1, about 1 mol% to about 30 mol% of the structural unit of formula 2, ^Mo Er II to About 30 moles of formula 3 structural units, and grades of 5 moles to about 2 inches of mull 1383721

The structural unit " self-hardening copolymer further comprises the structural unit of formula 6: 〇久广.

X (6) wherein X is selected from the group consisting of %, β and (^_Υ, 〇 is an integer of (8), ρ is an integer from 4 to 12, and γ is selected from a hydrogen atom, a CiQ low carbon alkyl group and a C1-C4 low. Carbon-based oxygen. The structural unit of formula 6 is present in an amount of from about 5 mole percent to about 2 mole percent. The self-hardening copolymer has a weight ranging from about 1,000 to about 1 Torr. The thermosetting resin composition of the present invention further comprises an epoxy compound. The thermosetting resin composition of the present invention comprises from about 1% to about 5% by weight of a self-hardening copolymer, and from about 1% to about 45% by weight of an epoxy compound. , and the difference is an organic solvent.

15 The epoxy compound is selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac resin type epoxy compound, a cresol novolac resin type epoxy compound, and a substituted ring. a group consisting of oxygen compounds. These epoxy compounds may be used singly or in a mixture thereof. The self-hardening copolymer further includes at least one structural unit selected from the group consisting of: (meth) acrylates including methyl (meth) acrylate, ethyl (meth) acrylate, (曱) Base) propyl acrylate, (methyl) 8 1378321

Isopropyl acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate; acryl amides include N-mercapto acrylamide, N-ethyl acrylamide, N-isopropyl propylene hydride Amine, N-methylol acrylamide, N-fluorenyl decyl acrylamide, N-ethyl decyl acrylamide, N-isopropyl decyl acrylamide, N-methylol 5 methyl Acrylamide, hydrazine, hydrazine-dimethyl methacrylate, N,N-diethyl acrylamide, hydrazine, hydrazine-dimethyl methacrylamide, and N,N-diethyl decyl propylene Hydrazine; styrene includes styrene, α-methylstyrene and hydroxystyrene; Ν-vinylpyrrolidone; Ν-vinylformamide; Ν-vinyl decylamine; and Ν-ethylene mum. sit. The composition of the present invention further comprises at least one polymer selected from the group consisting of poly(indenyl)acrylate, nylon, polyester, polyimine, and polyfluorene. The polymer is supported in an amount of about 50 parts by weight or less based on 100 parts by weight of the self-hardening copolymer. According to another aspect of the present invention, there is provided a color filter comprising a transparent film formed using the composition 15. According to still another aspect of the present invention, an image sensor using the color filter is provided. Brief Description of the Drawings Figure 1 is a schematic diagram showing the structure of a CMOS image sensor. 20 Figure 2 is a schematic diagram showing the machine rotation of pattern defects caused by light reflection. Fig. 3 shows a pattern shape obtained by applying a color refractory film of a CMOS image sensor to a transparent film formed in Comparative Example 1, and exposing and developing the color resist of the color resist. Fig. 4 shows a pattern shape obtained by applying a CMOS image sensor with a color light 9 1378321 to a transparent film formed in Example 1, and exposing and developing the colored photoresist after exposure of the color resist. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION The present invention will now be described more fully hereinafter with reference to the appended claims, Indeed, the present invention may be embodied in a variety of different forms and is not limited to the embodiments described herein; rather, these embodiments are intended to enable the present disclosure to comply with applicable statutory

10 The present invention provides a thermosetting resin composition which can be used for manufacturing a color filter for a C Μ S image sensor. Specifically, the thermosetting resin composition of the present invention contains an organic solvent and a self-hardening copolymer having an ultraviolet (UV) absorbing group. The self-hardening copolymer has the structural unit represented by the formulas 2, 3 and 4: 15 The thermosetting resin composition of the present invention comprises an organic solvent and a self-hardening copolymer having the structural unit represented by the formulas 1, 2, 3 and 4:

Ri +· 〇i-〇+C2-t^〇 (1) wherein 艮 is an argon atom or a methyl group and η is an integer from 1 to 10;

20 wherein R 2 is a hydrogen atom or a methyl group and m is an integer from 1 to 10; 10 1378321 r3

OH ο (3) wherein R 3 is a hydrogen atom or a fluorenyl group; and R 4

/-0-2 〇

Wherein R 4 is a hydrogen atom or a fluorenyl group and z is selected from the group consisting of the following groups:

Since the structural unit of Formula 1 can be thermally crosslinked with the structural units of Formulas 2, 3 and 4, the self-hardening copolymer has thermosetting properties. The self-hardening copolymer having the structural unit of Formula 1 to Formula 4 may belong to any type of copolymer such as a random copolymer, a 10 alternating copolymer, a block copolymer or a graft copolymer.

The self-hardening copolymer comprises from about 5 moles per mole to about 90 mole percent of the structural unit of formula 1, from about 1 mole percent to about 30 mole percent of the structural unit of formula 2, from about 1 mole percent to about 30 moles. % structural unit of formula 3, and from about 0.5 mole % to about 20 mole % of structural unit of formula 4 . 15 Specifically, the structural unit of Formula 4 has an ultraviolet light absorbing group (Z). The presence of the group (Z) prevents the occurrence of pattern defects due to various adverse factors. For example, referring to the machine illustrated in Figure 2, when the color resist is exposed, the unexposed portion of the color resist is not hardened by the external reflection from the underlying substrate of the violet 11 1378321. The self-hardening copolymer further comprises a structural unit of formula 6 which has improved storage stability and film hardness of the composition:

(6)

Wherein X is selected from the group consisting of Η and ό-Υ, 〇 is an integer from 1 to 4, Ρ is an integer from 4 to 12, and γ is selected from the group consisting of a hydrogen atom, a Cl-C4 lower alkyl group, and a Ci-C4 low carbon oxyhydrogen. base.

The structural unit of formula 6 is stored in an amount of from about 0.5 mole % to about 20 mole %. The self-hardening copolymer has a weight average molecular weight of from about 1,000 to about 1,000,000. When the self-hardening copolymer has a weight average molecular weight of less than about 1, ’, the self-hardening copolymer cannot be sufficiently hardened. Also, when the self-hardening copolymer has a weight average molecular weight greater than about 1, 〇〇〇, 〇〇〇, the solubility of the copolymer is reduced or it may be difficult to apply the composition to the substrate. The self-hardening copolymer may be present in the thermosetting resin composition in an amount of from about 1 Torr to about 45% by weight based on the total weight of the group. The kind of the organic solvent used in the composition of the present invention is not particularly limited. Examples of organic solvents useful in the present invention include, but are not limited to, ethylene glycols including ethylene glycol and diethylene glycol; glycol ethers including ethylene glycol monomethyl ether, 20 diethylene glycol monoterpene ether, and ethylene glycol. Alcohol diethyl ether and diethylene glycol dioxime ether; glycol ether acetates including ethylene glycol monoethyl ether acetate, diethylene glycol-ethyl shunting B 12 1378321

Acid esters, and diethylene glycol monobutyl ether acetate; propylene glycols; propylene glycol ethers including propylene glycol-method, propylene glycol-a-mystery, propylene glycol-propanol, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol Methyl ether, propylene glycol diethyl ether, and dipropylene glycol diethyl ether; propylene glycol ether acetates include propylene glycol 5-methyl ether acetate and dipropylene glycol monoethyl ether acetate; guanamines include N-methylpyrrolidone, diterpenes Ketones and dimethylacetamide; ketones such as isobutyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; petroleum solvents including toluene, xylene, and solvent naphtha The esters include ethyl acetate, butyl acetate, and ethyl lactate and mixtures thereof. 10 In addition to containing the self-hardening copolymer and other components, the organic solvent can constitute the remaining weight percent of the composition. The composition of the present invention comprises an organic solvent in an amount of from about 30% to about 99% by weight, such as from about 70% to about 98% by weight, based on the total weight of the composition. If the composition includes less than about 30% by weight of an organic solvent, it is difficult to apply the composition to the substrate. Meanwhile, if the composition of 15 contains more than about 99% by weight of an organic solvent, it is difficult to form a thick protective film. In order to improve etching resistance and alkali resistance and to adjust fluidity, the composition may further contain an epoxy compound as needed. The epoxy compound may be selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac 20 lacquer type epoxy compound, a cresol novolac resin type epoxy compound, and a substituted An epoxy compound of a group consisting of an epoxy compound or the like. These epoxy compounds may be used singly or in a mixture thereof. The epoxide has a weight average molecular weight in the range of from about 50 to about 10,000. The epoxidized composition in the thermosetting resin composition based on the total weight of the resin composition 13 1378321 ίο 15

The content of the compound is in the range of from about 1% to about 45% by weight, such as from about 5% to about 30% by weight. When the epoxy compound is present in an amount of less than about 1% by weight, the monthly b may cause the dimensional stability of the transparent film formed using the composition to be inferior. Meanwhile, when the epoxy compound is present in an amount of more than about 45% by weight, it is difficult to apply the composition to the substrate. In order to improve the properties and impart other properties to the composition such as ease of application, film hardness and affinity for the upper film and the underlying film, the X self-hardening octamer may be selected from the following At least one repeating unit (mercapto) acrylic acid vinegar of the group consisting of (mercapto)methyl acrylate, (meth)acrylic acid, (meth)acrylic acid propylene vinegar, (meth)acrylic acid Isopropyl ester '(meth) propylene; butyl acrylate, and benzyl (meth) acrylate; propylene oxime amines include N-methyl propyl sulfoxide, Ν-ethyl acrylamide, Ν-isopropyl acrylamide, Ν-A 呙 醯 土 醯 醯 醯 醯 醯 醯 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 、 、 、 、 Indoleamine, hydrazine-hydroxymethylmethacrylamide, hydrazine, hydrazine-dimethyl oxahydrazine, N,N-diethyl acrylamide, dimethyl methacrylate, and hydrazine, Ν·Diethylmethyl propyl amide, stupid ethylene including phenyl acetonitrile, \T, methyl styrene and hydroxystyrene; Μ-vinyl pyrrolidone; Ν χ 基Amines; fluorene-vinyl decylamine; and hydrazine-vinylimidazole; and mixtures thereof self-hardening copolymers can be synthesized by any suitable method known in the art. For non-limiting examples, far self-hardening copolymers can be used. The free radical polymerization initiator is used in the synthesis of the same organic solvent of the composition of the present invention, and the solid resin composition. The self-hardening copolymer for synthesizing the ultraviolet light-receiving group has 14 1378321

The solvent of the machine is not particularly limited and may be the same as the organic solvent used in the thermosetting resin composition of the present invention. In another aspect, the amount of the organic solvent in the polymerization is controlled so as to be from about 3% to about 50% by weight, for example, about 5, based on the weight of the solution of the self-hardening copolymer in an organic solvent. % to about 30% by weight of the amount present. When the concentration of the self-hardening copolymer in the solution is less than about 3% by weight, the polymerization rate is low, and thus a plurality of monomers remain unreacted. At the same time, when the concentration of the self-hardening copolymer in the solution exceeds about 50% by weight, the solution is too viscous to handle and control the reaction rate.任 Any of the known polymerization initiators can be used for self-hardening copolymers.

The synthesis includes a thermal polymerization initiator, a photopolymerization initiator, and a redox initiator. A peroxide type and an azo type radical polymerization initiator can be used in the present invention because it is easy to handle and it is easy to control the reaction rate and molecular weight. Examples of the peroxide type polymerization initiator which can be used in the present invention include isobutyl pentoxide, cyclohexanone peroxide, methylcyclohexyl peroxide, 20 acetoxyacetone peroxide, 1,1-anthracene (Third butylperoxy)_3,3,5-trimethylcyclohexene, 1,1-Penta-t-butylperoxy)cyclohexyl, 3 hexylperoxy)-3,3 , 5-trimethylcyclohexene, ^(Third-hexylperoxy)cyclohexyl, U-home (t-butylperoxy) ring 12th hospital 'isobutyl peroxide, peroxide laurel , succinic acid peroxide, 3,3,5 • trimethyl (4) peroxidation, peroxidized stupid, peroxidized (four), hard (tetra) peroxide, peroxytricarbonate diisopropyl vinegar, peroxydicarbonate Di-n-(4), peroxydicarbonate di-2-ethylhexanoic acid, peroxydicarbonate di-2-ethoxyethyl acetonate, peroxydicarbonate di- 2 soil-methyl lactyl butyl vinegar, peroxygen Dibasic carbonic acid cold (4_t-butylcyclohexyl (6), (10) Wu·15 1378321

Neodecyloxyperoxy)diisopropylbenzene, cumene peroxy neodecanoate, octyl peroxy neodecanoate, hexyl peroxy neodecanoate, third butyl peroxy neodecanoate Ester, third hexyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-indole (2-ethylhexylperoxy) Alkane, peroxy-2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl ester, peroxyperoxy-2-ethyl-trihexyl ester, hexanoic acid peroxy-2 -ethyl-tert-butyl ester, peroxy-2-ethyl-trihexyl hexanoate, peroxy-3-methyl-tert-butyl propionate, tert-butyl peroxy laurate , peroxy-3,5,5-trimethylhexanoic acid tert-butyl ester, monohexyl carbonate monoperoxyisopropyl isopropyl ester, carbon tri-tert-butyl ester peroxyisopropyl ester, 2,5 - dimethyl-2,5-fluorene (benzene 10 mercapto peroxy) hexane, tert-butyl peracetate, third hexyl perbenzoate, tert-butyl perbenzoate, etc. and mixtures thereof . A combination of a peroxide-type polymerization initiator and a reducing agent can be used as the redox initiator. Examples of the azo type polymerization initiator used in the present invention include 1,1-azo (cyclohexane-1-carbonitrile), 2,2'-azobis(2-methyl-butyronitrile), 2,2'-arsenazo 15 butyronitrile, 2,2'-arsenazo (2,4-dimethyl-pentanenitrile), 2,2'-arsenazo (2,4-dimethyl-) 4-methoxyvaleronitrile), 2,2'-arsenazo(2-indolyl-propane) hydrochloride, 2,2'-arsenazo [2-(5-mercapto-2-imidazoline) 2-yl)propane] hydrochloride, 2,2'-arsenazo [2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-arsenazo [2-( 5-methyl-2-imidazolin-2-yl)propane], 2,2'-azo贰[2-methyl-N-(l,l-贰(2-hydroxymethyl 20-yl)-2- Hydroxyethyl)propanamide, 2,2'-arsenazo [2-indolyl-N-(2-hydroxyethyl)propanamide], 2,2'-arsenazo (2-methyl-) Propylamine) dihydrate, 4,4'-arsenazo (4-cyano-pentanoic acid), 2,2'-arsenazo (2-hydroxymethylpropionitrile), 2,2'-even Nitrogen (2-methylpropionic acid) dimethyl ester (dimethyl-2,2'-arsenazo (2-mercaptopropionate)), cyano-2-propylazomethanamine, etc. And mixtures thereof. In addition to the peroxide type and azo type polymerization initiator, at least one known control agent such as chain (four), a secret polymerization accelerator may be further added during the synthesis of the second copolymer. The two: hard, the molecular weight of the copolymer is adjusted to a range such as defined above. The molecular weight controlling agent may be a thioglycolic acid, a vegetable-based propionic acid vinegar, a thioglycol, a non-undecyl mercaptan, an α-methylstyrene dimer, or the like, and a mixture thereof. . One or more solvents other than the organic solvent for the preparation of the copolymer may also be added for the purpose of adjusting the solubility of the component and controlling the leveling property and controlling the drying rate after the polymerization. The ruthenium' copolymer can be extracted into a solid form by conventional techniques for purification, storage, and dissolution. The techniques are not limited, such as spray drying, film drying, dropwise addition to a poor solvent, and re-soaking. In order to improve etching resistance and alkali resistance and adjust fluidity, the composition of the present invention further comprises poly(meth)acrylate, nylon, polyester, polyimine, based on 100 parts of 1 匕 self-hardening copolymer. Or at least one polymer content of the polybenzazole is about 50 parts by weight or less. Further, a thermosetting catalyst may be added to the thermosetting resin composition of the present invention. Examples of the thermosetting catalyst useful in the present invention include an amine compound, a phosphorus compound, a boron compound, a hydrazine compound, a carboxylic acid compound, an organic sulfonated compound, and the like, and a mixture thereof. In order to obtain good storage stability, the thermosetting catalyst is added in an amount of about 1 part by weight or less based on 1 part by weight of the self-hardening copolymer. If desired, the thermosetting resin composition of the present invention can be further formed into a film formed by using the thermosetting resin composition of the present invention with other known chemical agents such as an antioxidant, an ultraviolet stabilizer, a plasticizer, and 17 1378321. Apply to a color filter for one of the image sensors. Further details of the present invention will be described later with reference to the following examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the scope of the invention. Example [Example 1]

After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 ° C with stirring. 10 25 g of glycidyl methacrylate, 13 g of 2-hydroxyethyl methacrylate, 15 g of methacrylic acid, 9 g of 9-methyl methacrylate, 4 g of N-stupyl butadiene A mixture of amine, 9 g of styrene, 100 g of methyl methacrylate and 20 g of dimercapto-2,2'-azo (2-methylpropionic acid vinegar) was added dropwise to the flask for 1.5-2 hours. Time while maintaining the temperature at 8 °C with stirring. The resulting mixture was allowed to react for 3-4 hours with stirring while maintaining the reaction temperature at 80 ° C to obtain a solution containing the random copolymer of the formula 7.

Gel permeation chromatography (GPC) of the polymer solution indicated a polystyrene based benchmark with a weight average molecular weight of 14,500. To 20 g of the polymer solution (a), a gram epoxy resin (jER_152, JER) '0.05 g of a surfactant (R 〇 8, mc) and 5 g of propylene glycol monomethyl ether 19 1378321 acetate were added. The mixture was dissolved and filtered with thorough stirring to obtain a thermosetting resin composition (e). The thermosetting resin composition (e) was applied to a 0.7 mm thick glass substrate (#1737, Corning) using a spin coater, dried in a drier at 80 ° C for 3 minutes, and hardened at 230 ° C. Minutes to make a transparent film with a thickness of 0.5 microns. [Example 2]

After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 8 Torr with stirring. (: 30 g of glycidyl methacrylate, 1 g of 2-hydroxyethyl 10 methacrylate, 15 g of methacrylic acid, 5 g of 2-hydroxy-4-methylpropenyl oxybenzophenone, 5 g of N-styl maleimide, β g of styrene, 5 g of methyl methacrylate and 8 g of dimethyl 2,2,-arsenazo (2-mercaptopropionate) The mixture was added dropwise to the flask for 1.5-2 hours while maintaining the temperature at 80 ° C. The resulting mixture was allowed to react for 4-5 hours with stirring while maintaining the temperature of the reverse 15 at 80 ° C to obtain A solution of the random copolymer of formula 8 (b).

Gel permeation chromatography (GPC) of the polymer solution indicates a polystyrene based benchmark having a weight average molecular weight of 11,000. The thermosetting resin composition (7) was prepared in the same manner as in Example 1, except that 4 g of the polymer solution (b) was used instead of the polymer solution (8). 20 20 A transparent film of thickness ο. 5 μm was produced according to the procedure of Example 1 except that the thermosetting resin composition (f) was used instead of the thermosetting resin composition (e). [Example 3] After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 ° C with stirring. 30 g of glycidyl acrylate, 10 g of 2-hydroxyethyl methacrylate, 15 g of methacrylic acid, 100 g of methyl methacrylate '10 g of 2-(2'-hydroxy-5' Methyl propylene oxyphenyl) benzotriazole, 15 grams of N-phenyl maleimide, 33 grams of styrene, and 8 grams of dimethyl-2,2'-arsenazo ( A mixture of 2-methylpropionate) was added dropwise to the flask for 1.5-2 hours while maintaining the temperature at 8 (TC). The resulting mixture was allowed to react for 4-5 hours with stirring while maintaining the reaction temperature. A solution (c) containing a random copolymer of the formula 9 was obtained at 80 °C.

Gel permeation chromatography (GPC) of the polymer solution was determined based on a polystyrene standard with a weight average molecular weight of 9,5 Å. The thermosetting resin composition (g) was prepared in the same manner as in Example 1, except that 40 g of the polymer solution (c) was used instead of the polymer solution (a). A transparent film of 5 μm thick was produced according to the procedure described in Example 1, except that the thermosetting resin composition (g) was used instead of the thermosetting resin composition. 1378321 [Comparative Example 1] After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 with stirring. 30 g of methacrylic acid glycidol vinegar '13 g of dicyclopentanyl methacrylate, 5 12 g of styrene, 25 g of methyl methacrylate and 10 g of dimethyl-2,2'-arsenazo ( A mixture of 2-methylpropionate) was added dropwise to the flask over a period of 15 hours, while maintaining the temperature at 8 with stirring (rc^ allowing the resulting mixture to react for 4-5 hours with stirring while maintaining the reaction temperature at 8 ( Rc to obtain a solution (d) containing a random copolymer of the formula 10.

Gel permeation chromatography (GPC) of the polymer solution indicates a polystyrene based benchmark having a weight average molecular weight of 13,000. The thermosetting resin composition (h) was prepared in the same manner as in Example 1, except that 40 g of the polymer solution (d) was used instead of the polymer solution (a). 15 A transparent film of 0.5 μm thick was produced according to the procedure described in Example 1, except that the thermosetting resin composition (h) was used instead of the thermosetting resin composition (4). <Evaluation of physical properties> * The flatness, adhesion, film hardness and light transmittance of the moon-transparent film manufactured in Examples i to 3 and Comparative Example i were evaluated according to the following individual procedures. The side moon film picker makes the pattern. Calculate the number of pattern defects caused by various adverse factors such as halo effect. The result is displayed in illusion /, 22 1378321

1 Flatness evaluation Measures the difference between the red and green pixels of the dummy color filter (that is, the class height between pixels). After applying the transparent films manufactured in Examples 丨 to 3 and Comparative Example 1 to the dummy color filter, measuring the order between the pixels of the color filter <»the height of the class before applying the transparent film (dl) The ratio R of the class height (d2) after application of the transparent film is calculated by the following equation (1): R = d2 / dl (1) Thermosetting resin compositions prepared in Examples 1 to 3 and Comparative Example 1 The flattening performance is divided into five levels based on the following criteria: r>〇.4···level 1; 〇.4 New suburbs.3...level 2; 0W0.3...level 3; 0.2^0丄·grade 4; R<0.1...level 5. The higher the rating, the better the flattening performance. 2Adhesion and chemical resistance test 15 After cutting one cross and cutting the cross-shaped strips on each of the transparent films manufactured in Examples 1 to 3 and Comparative Example 1, use cell 〇 璐The tape is peeled off (cross cut test). The visual inspection checks the tear-off state of the cross-cut to evaluate the adhesion of the transparent film. When no cross cut was torn off, the adhesion was judged as "acceptable". When one or more cross cuts are torn off, the adhesion is judged as "failed". In addition, the transparent film test pieces were immersed in N_methyl 2_β ratio slightly bite _ (ΝΜΡ) as an organic solvent, 10% aqueous alkaline potassium hydroxide solution and acidic etchant> gluten solution (LCE-12K, Saintek) The company (cyantEK CORPORATION) was immersed in 40 C for 30 minutes to 'repeat the aforementioned adhesion test 23 1378321 test procedure to evaluate chemical resistance. Observe the tearing state of the cross cut. When no cleavage was torn off after each immersion, the chemical resistance was judged as "commendation j." When one or more cross-cuts were torn off after each immersion, the chemical resistance was judged as "failed". 5 3 Evaluation of film hardness The transparent films produced in Examples 1 to 3 and Comparative Example 1 were scratched using six kinds of (1H-6H) pencils (Statdler), and the film damage was observed. The film strength was divided into six levels (1H-6H) depending on the degree of damage.

□ Evaluation of pattern defects (by halo phenomenon) 10 The color photoresist of the CMOS image sensor was applied to each of the transparent films formed in Examples 1 to 3 and Comparative Example 1, and illuminated and developed to form a pattern. Observe the shape of the pattern. Calculate the number of defects that are raised by the border of the pattern. The pattern defect is caused by the reflection of ultraviolet light from the underlying substrate, as shown in Figure 2. The pattern shapes formed by using the transparent films produced in Comparative Example 1 and Example 1 are shown in Figs. 3 and 4, respectively.

Physical Properties Example 1 Example 2 Example 3 Comparative Example 1 Flatness Qualified Qualified Adhesiveness (Cross Cut) 100/100 100/100 100/100 95/100 Film Hardness (Pencil Hardness) 4H 5H 4H 2H Acid Qualified and Qualified Chemically resistant alkali qualified qualified unqualified organic solvent qualified qualified unqualified 365 nm 86.2% 91.7% 90.5% 99.5% Light transmittance 400 nm 98.6% 99.5% 99.2% 99.8% Pattern defect 3/100 8/100 7/ 100 27/100 24 1378321 It can be seen from the results of Table 1 that the transparent film made of the thermosetting resin composition produced in Examples 1 to 3 was used in terms of flatness, adhesion, light transmittance in the visible light region, and film hardness. Shows excellent features. For example, the film is substantially transparent to the passage of visible light region radiation, e.g., has a minimum light transmission of at least about 98% of visible light radiation having a wavelength of 400 nm. In addition, the transparent film absorbs 365 nm of ultraviolet light, contributing to a significant reduction in the number of pattern defects. For example, the film of the present invention has a maximum transmittance of about 92% of radiation at a wavelength of 365 nm.

As apparent from the foregoing description, the thermosetting resin composition of the present invention is easy to handle, and has a better chemical property than the two-part thermosetting resin composition conventionally used for producing a color filter. Further, the transparent film for a color filter produced by using the thermosetting resin composition of the present invention has excellent flatness, adhesion, transmittance, film strength and heat resistance. Further, the thermosetting resin composition of the present invention can absorb ultraviolet light. Therefore, when the thermosetting resin composition of the present invention 15 is used for the color filter of the image sensor, the number of pattern defects caused by the halo and standing waves of the re-reflected ultraviolet light can be reduced. It will be apparent to those skilled in the art that <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Therefore, it is to be understood that the invention is not limited to the specific embodiments disclosed, and the modifications and other embodiments are intended to be included in the scope of the appended claims. Although specific terms are employed herein, the use of the invention is in no way limiting, and the scope of the invention is defined by the scope of the claims. &lt;S) 25 1378321 I: Simple description of the drawing 3 Fig. 1 is a schematic view showing the structure of a CMOS image sensor. Figure 2 is a schematic diagram showing the machine rotation of the pattern defect caused by light reflection. Fig. 3 shows a pattern shape obtained by applying a color resist of a CMOS image sensor to a transparent film formed in Comparative Example 1, and exposing and exposing the color resist to a color resist.

Fig. 4 shows a pattern shape obtained by applying a color refractory film of a CMOS image sensor to a transparent film formed in Example 1, and exposing and developing the color resist of the color resist. 10 [Main component symbol description] (none)

&lt; S ) 26

Claims (1)

1378321 (1 year + month + 曰 曰 曰 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 097 Organic solvent and self-hardening copolymer having structural units represented by formulas 1, 2, 3 and 4: R. 5 Wherein I is a hydrogen atom or a fluorenyl group and η is an integer from 1 to 10; R2 -0H 0 (2) where is a hydrogen atom or a methyl group and m is an integer from 1 to 10 R3 A— 0H 0 (3) Wherein R3 is a hydrogen atom or a fluorenyl group; Wherein R 4 is a hydrogen atom or a fluorenyl group and z is selected from the group consisting of the following groups: (5) 〇27 1378321 Patent Application No. 097106107, the entire disclosure of which is incorporated herein by reference. Mol % Formula 1 structural unit, from about 1 mole % to about 30 mole % of the structural unit of formula 2, from about 1 mole % to about 30 mole % of the structural unit of formula 3, and from about 0.5 mole % to about 20 moles Ear % formula 5 4 structural unit. 3. The thermosetting resin composition of claim 1, wherein the self-hardening copolymer further comprises a structural unit of formula 6: (6) where X is selected from and, and 〇 is from 1 to 4 The number is 15 and ρ is an integer from 4 to 12, and the oxime is selected from the group consisting of a hydrogen atom, a CrCj lower alkyl group and a Cl-C4 low carbon alkoxy group. 4. The thermosetting resin composition of claim 3, wherein the self-hardening copolymer comprises the structural unit of the formula 6 in an amount of from about 0.5 mol% to about 20 mol%. 5. The thermosetting resin composition of claim 1, wherein the self-hardening copolymer has a weight average molecular weight ranging from about 1, 〇〇〇 to about 1,000,000. 6. The thermosetting resin composition of claim 1 further comprising an epoxy compound. 7. The thermosetting resin composition of claim 6, wherein the thermosetting resin composition comprises from about 1% to about 45% by weight of self-hardening copolymerization. 28 20 101.4.9 Patent Application No. 097106107 ... 8 such as: ^ to about peach heavy Dong epoxy compound, and the difference is organic solvent. 8. The heat-sensitive resin composition of claim 6, wherein the anthracene compound is selected from the group consisting of a double-type epoxy compound, a bis-epoxy compound, a lacquer (tetra) epoxy compound, and a methyl acid. A group consisting of a varnish resin type, a compound of the peak generation, and a mixture thereof. 9. If applying for the _ resin composition of the first item, the self-bonding hardening copolymer further comprises at least one structural unit selected from the group consisting of: (?) Miscellaneous; acrylamide; styrene, N-vinylpyrrolidone; N vinylformamide; N-vinylamine; and N-vinylimidazole. 10. The thermosetting resin composition according to claim 9 wherein the (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. a group consisting of isopropyl (meth)acrylate, butyl acetonate (meth)acrylate, and benzyl (meth)acrylate; the acrylamide is selected from N-methyl acrylamide , N-ethyl acrylamide, N-isopropyl acrylamide, N-methylol decylamine, N-methyl methacrylamide, N-ethyl methacrylamide, N-iso Propyl methacrylamide, N-methylolmethacrylamide, N,N-dimercaptopropenylamine, N,N-diethyl acrylamide, n,N- a group consisting of dimethyl decyl acrylamide and N,N-diethyl methacrylamide; and the styrene is selected from the group consisting of styrene, α-methyl styrene, and hydroxybenzene a group consisting of ethylene. 29 1378321 5 Patent Application No. 097106107 Replacing the Patent Application No. 101.4.9 11. The thermosetting resin composition of claim 1, further comprising a poly(indenyl) acrylate, a nylon, a polyester, a poly At least one polymer of an amine, polysilicon, and mixtures thereof. 12. The thermosetting resin composition of claim 1, wherein the self-hardening copolymer comprises a selected from the group consisting of a copolymer of a group consisting of a mixture thereof. 10 13. A substantially transparent film derived from a self-hardening copolymer comprising structural units represented by the formulas 2, 3 and 4: Wherein R is a hydrogen atom or a fluorenyl group and η is an integer from 1 to 10; 30 1378321 Patent Application No. 097106107 〇^〇+C-t-〇H (2) wherein R 2 is a hydrogen atom or a fluorenyl group and m is an integer from 1 to 10; R 3 OH ο (3) wherein R 3 is a hydrogen atom or a fluorenyl group; (4) wherein R 4 is a hydrogen atom or a fluorenyl group and Z is selected from the group consisting of the following groups: 10. 14. The film of claim 13, wherein the film has a maximum light transmittance of about 92% with a wavelength of 365 nm. 15. The film of claim 13 wherein the film has a minimum transmittance of at least about 98% of visible light having a wavelength of 400 nm. 16. The film of claim 13, wherein the film has a pencil hardness of at least 4H as measured by using 6 (1H-6H) pencil (Statdler) scratch film. 17. A color filter comprising a type of self-hardening copolymer 31 15 1378321 Patent Application No. 097106107 The structural unit Ri is represented by a value such as 〇^°+s2-K&gt;° (1) where Ri is a hydrogen atom or a sulfhydryl group and η is an integer from 1 to 10; r2 (2) wherein R 2 is a hydrogen atom or a fluorenyl group and m is an integer of 1 to 10; R 3 OH (3) wherein R 3 is a hydrogen atom or a methyl group; and R 4 -S; 0 t (4) wherein R 4 is a hydrogen atom or Sulfhydryl and Z are selected from the following groups 18. A color filter comprising a substantially transparent film formed using a composition of a thermosetting resin, the composition comprising an organic solvent and a self-hardening copolymer having structural units represented by Formulas 1, 2, 3 and 4: 32 1378321 Patent Application No. 097106107 Patent Application No. 1 〇 1 49 R» 〇^°+^° (1) /, is a hydrogen atom or a methyl group and 11 is an integer of 1 to 1 〇 R2 〇^~°+C-t-OH wherein R2 is a hydrogen atom or a methyl group and m is (2) an integer from 1 to 10; r3 Where R3 is a halogen atom or a methyl group; and «4 Λ~0-2 〇 (4) Wherein hydrazine is a hydrogen atom or a methyl group and hydrazine is selected from the group consisting of: 10 19. An image sensor comprising a color filter comprising a substantially transparent film derived from a self-hardening copolymer comprising structural units represented by the formulas 1, 2, 3 and 4: 33 1378321 Patent Application No. 097106107 Replacing the patent scope to replace this ιοί 4.9 Ri, +Sr+ (1) wherein Ri is a hydrogen atom or a methyl group and η is an integer from 1 to 10; R2 〇^〇+C-^〇H (2) R2 is a hydrogen atom or a methyl group and m is an integer of 1 to 10; r3 A-OH 0 (3) wherein R3 is a hydrogen atom or a methyl group; and R4 -c-h2 (4) wherein R4 is a hydrogen atom or a methyl group And Z is selected from the following groups 10 and (5). 20. An image sensor comprising a color filter comprising a substantially transparent film formed using a thermosetting resin composition. The composition comprises a fabric for use in the manufacture of a color filter. A thermosetting resin composition comprising an organic solvent and a self-hardening copolymer having the structural unit represented by the present invention, which is represented by the patent application No. 1, 2, 34, 13, 783, s, s. -〇+c+^〇(1) wherein R! is a hydrogen atom or a methyl group and η is an integer from 1 to 10; R2 〇^〇+Ct-〇H (2) wherein R2 is a hydrogen atom or a methyl group and m is 1 to An integer of 10; R3 is ____, 1_c-OH 〇(3) wherein R3 is a hydrogen atom or a methyl group; and R4 -z (4) wherein R4 is a hydrogen atom or a methyl group and Z is selected from the group consisting of group and (5). 35