TW381112B - Coating composition (1) - Google Patents

Abstract

This invention provides a coating composition having an excellent adhesion, wear resistance, staining resistance, chemical resistance, heat resistance and smoothness.In the coating composition comprising (a) polymer and (b) solvent as the essential component, wherein said polymer component is a polymer at least comprises segment represented by the following formula I or II, or a copolymer comprises at least acrylic acid and/or methacrylic acid and a monomer represented by the following formula III, IV, V and VI, wherein R is alkyl, cycloalkyl, aromatic hydrocarbon group, alkyl containing hydroxy or a group represented by the formula, wherein m is an integer of 1~10, n is an integer of 1 to 5), or aromatic hydrocarbon group containing hydroxy group; wherein R1 is alkyl, aromatic hydrocarbon group, alkyl containing hydroxy group or aromatic hydrocarbon group containing hydroxy group, at least one of organosiloxane compounds represented by the general formula (1), wherein R1 and R6 are same or different and are groups selected from unsubstituted alkyl or alkyl substituted by amino, hydroxy, alpha-mercapto or glycidyl group, unsunstituted phenyl or phenyl substituted by dimethylsilyl group, (p-acryloxy methyl) phenethyl, alkyl phenethyl, benzyl, vinyl, R2-óÓ5 are same or different, and represent hydrogen, alkyl, aryl, fluoroalkyl, or siloxanyl group substituted by alkyl group; n is an integer of 1-13), the content of the organosiloxane compound is 0.1~20wt% based on the weight of non-solvent component.

Description

A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () 1 I Technical scope of the invention 1 1 The invention relates to a coating composition that is used to form a protective film that is smooth and transparent. Table 1 1 surface 9 Especially for color filters formed on glass or transparent materials .. Please 1 first 1 coating composition for protective film 0 read 1 K Zhizhishu back 1 | 1 In recent years 9 AV equipment, electronic equipment such as personal computers 9 Prevailing application fluid Note 1 | Crystal display element 9 Especially due to the good visibility of color displays, abundant matters 1 | The amount of rich information, etc. 9 The acceptance is extended sharply 0 — 'Generally, the color display is%% {本1 Mounting 9 is on a substrate such as transparent glass. 9 Printing by dyeing method, page N_✓ 1 I pigment For example, a parallel or stripe-shaped filter I 1 0 is usually formed by a method such as a parallel filter or a stripe filter. The filter is usually made to about 1 mm in diameter. Quality (pigmentation, etc.) has an effect. 1 If you do not want to produce mottled display 9 Surface flatness must be suppressed to less than 0.1 microns 1 or less 0 Usually a smooth surface 9 is coated with thermosetting 1 I acrylic resin Flatten the surface 0 and not limited to the liquid crystal display element 1 I The color filter surface needs to be protected even 9 of the solid-state imaging element 9 must be treated in the latter 1 1 manufacturing steps such as solvent N acid N test solution immersion treatment f 9 or When the electrode layer is formed by sputtering 9 Severe conditions such as high temperatures 1 f Provide a protective film to protect the color filter 0 1 1 This protective film requires smooth and strong m 9 transparency Good 9 Does not change color for a long time 1 I \ Does not deteriorate 9 and has excellent heat resistance and chemical resistance meets these requirements 1 1 Only using thermosetting resins containing epoxy fluorene copolymers 0 1 1 Other aspects 9 About mini discs (MD) 9 Main substrates such as compact discs (CDs) * In 1 I during the production step 3 9 Need a good protective film »to protect 1 1 1 1 1 1 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) ) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (X) 1 1 I Surface 0 Protective film material must be easy to coat > Mechanical and chemical 1 1 I (waterproof, oxygen barrier) protection The surface of the main substrate »and can be easily peeled off. 01 1 Although this coating composition 9 is not concerned, JP 6- 2 1 3 6 1 6 has previously requested that 1 1 contain a photopolymerization initiator and heat or light 9 Make Organic Polysiloxane Compounds Read 1 1 To Each Other Polymerization reaction 9 to obtain a photosensitive resin composition 9 Improving the back surface 1 1 Heat resistance and transparency 0 Caution 1 Matter 1 In addition, Japanese Patent Application Laid-Open No. 7- 1 1 132 contains a tree item to improve adhesion. The grease itself is modified in advance with a silicon dioxide institute 9 to obtain a color filter with no turbidity. This is a coloring paste. However, this technology will increase the synthetic step 9. The disadvantage is that it requires a page 1 I a large cost. 1 I The above-mentioned bulletin related to the protective film 9 completely did not teach the use of organic (poly) silica 1 1 Qiyuan 01 Prescribed lessons to be solved M.1 The problems of the above-mentioned conventional protective film such as the activity of the photosensitive protective film 1 1 After irradiation 9 due to insufficient allowable range of development time »In development 1 I. Steps will occur unevenly t and stuck to the protective film Other important characteristics are flatness 1 1 frankness and tightness of the substrate or filter 1 The conventional protective film fails to obtain the full-tV *-characteristics. The present invention is to solve such problems 1 I provide cheap Λ Materials with high reliability, flatness, and high adhesion. 1 1 Means for solving problems 1 I To solve these problems 9 The present invention provides a mixture of I 1 with the following composition to obtain heat resistance and chemical resistance, Protective film with excellent transparency, flatness, tightness, etc. 〇1 I means the present invention. 1 1 1 1 1 1 This paper is applicable to China with (a) polymer and (b) solvent-4-agent as essential ingredients. National Standard (CNS) Λ4 specification (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs __ ^ _, V. Description of the invention (4) The coating composition contains the organosilicon oxygen represented by the general formula (1) At least one alkane compound. R2 R4 II 6 RHsi—〇) ^ — Si —R6 Formula (1) R3 R5 (where R1 and R6 are the same or different and are selected from the group consisting of unsubstituted alkyl groups, or amine groups, amino groups, hydroxyl groups, α-hydrothio or glycidyl substituted radical, unsubstituted phenyl, or alkylphenyl substituted with dimethylsilyl, (p-propenyloxymethyl) phenethyl, alkyl Phenethyl, benzyl, vinyl, R2 to R5 are the same or different, are hydrogen atom, alkyl, aryl, fluoroalkyl, or siloxyalkyl substituted with alkyl or aryl, η is 1 to 13 Integer, preferably an integer from 1 to 9. In addition, the coating composition provides a thermosetting coating composition further containing (c) a thermal cross-linking agent. Furthermore, among the thermosetting coating composition, (a) a polymer 僳A polymer soluble in an alkaline aqueous solution or at least swellable, and further provided (d) a photosensitive coating composition containing an active ray irradiation initiator. The photosensitive coating composition contains (e) a polymerizable unsaturated bond compound According to the present invention, the problem of the conventional protective film can be solved. The organosiloxane compound preferably used in the present invention is In formula (1), R1 and R6 are substituted Ci-Czo alkyl groups, preferably Ct-C10, wherein the substituents are amine group, hydroxyl group, α-hydrosulfide group, and cyano group. This paper scale is applicable China National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling, as shown on this page). Packing. Order printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economy A7 B7 _ I 1. V. Description of the invention (Heart) In addition, when the polymerization degree (η) of the silane is too large, a sufficient effect cannot be obtained. The polymerization degree of the silane is 1 to 13, preferably 1 to 9, and particularly preferably 1 to 5 The added amount of the selected organosiloxane compound is preferably 0.1 to 20% by weight relative to the non-solvent component, and preferably 0.2 to 10% by weight. U) The polymer is aldehyde varnish resin, polyhydroxystyrene or its Derivatives, styrene-anhydrous maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing (meth) acrylic strip resin, (meth) acrylic acid and (meth) acrylic acid ester copolymer, Fully introduce unsaturated bonds which can polymerize with these polymers, become soluble in aqueous solution or at least swell The polymer or resin, phenol resin, polyimide, polyurethane, melamine resin, unsaturated polyester resin. In particular, biphenol A type epichlorohydrin resins such as biphenol A type epichlorohydrin resins, epoxy phenolic resins, and brominated biphenol A type epoxy resins can be used as the epoxy resin. The polymer component (a) is preferably a polymer containing at least the general formula (I) or (II). — (CH2 — CH) —

I co2h ⑴ Produce 3 One (CH〗 ONE C). —— I (II) co2h This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)

Hi--I I I I I 装 I (谙 Please read the notes on the back before filling in this page)

T5. Description of the invention (5) A7 B7 Especially the polymer component (a) to have at least acrylic acid and / or methacrylic acid, and the general formula (III) ch3

III CH2 = c-COOR [wherein R is an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, and has a hydroxyl group or the following formula

-0 (C (CH2) m〇) nH 〇 (wherein a is an integer of 1 to 1Q, η is an integer of 1 to 5) alkyl group, or an aromatic hydrocarbon group having a hydroxyl group]; general formula (IV) CH 2 = CH-C00R (where R is the same as above); general formula (V) IV) (Please read the precautions on the back before filling in S: this page)

, 1T 〇 CH = CH2 (V) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and a copolymer of at least one monomer represented by the general formula (VI)

CH 3 ch2 = C-coo

(VI) This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. A7 __ ^ _ B7 _'___ 5. Description of the invention () (where R 'is an alkane Group, aromatic hydrocarbon group, alkyl group having hydroxyl group or aromatic hydrocarbon group having hydroxyl group). The alkyl group of the general formulae (III) to (VI) in the present invention is preferably a Ci-C15 alkyl group, particularly a Ci-C10 alkyl group. Especially, the polymer component (a) is preferably a molecule. A reaction product of a compound having a polymerizable unsaturated bond in the structure. More preferred examples include (meth) acrylic acid- (meth) acrylate copolymers such as poly (methacrylic acid-co-methyl methacrylate), and poly (methacrylic acid-co-methyl acrylate). ), Poly (methacrylic acid-co-butyl acrylate), poly (acrylic acid-co-methyl methacrylate), poly (acrylic acid-co-methyl acrylate), poly (methacrylic acid-co-benzyl methyl) Acrylate), poly (methacrylic acid-co-methylol methacrylate), etc .; (meth) acrylic acid-lactone modified hydroxyethyl (meth) acrylate copolymers, such as Shown by: R7 R7

I I — (CCH2) p— (CCH2) q —

C〇2H C〇2CH2〇 (C (CH2) 5〇) nH 〇 (where R7 is a hydrogen atom or a methyl group, p and q are degrees of polymerization, and n is an integer of 1 to 5); and (meth) acrylic acid -Styrene copolymers and the like. (b) The solvent can be ethyl lysinolysin, propylene glycol methyl ether acetate (PGMEA). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page. )-Order A7 B7 V. Description of the invention (7, ethyl lactate, polyethylene glycol, polypropylene glycol, cyclohexanone, polypropylene glycol methyl ether, etc., can be used alone or in a mixed solvent type. The mixture of the present invention can also be added with stability , Plasticizer, antioxidant, etc. (c) The thermal cross-linking agent can be a block isocyanate, or a compound having at least two residues of an alkane group and an alkoxy group, such as bis, three, or four (Hydroxymethyl) substituted aromatic compound or plural ring or aromatic compound, bis, tri or tetra (acetaldehydeoxymethyl) substituted aromatic compound or plural ring aromatic compound, having N-methylol honey Amines, melamines with N-alkoxymethyl groups, or melamines with N-alkoxymethyl groups, phenolic type ring gas resins, biphenol A type ring gas resins, halogenated biphenol A type epoxy resins, Epoxy-containing compounds such as alicyclic epoxy resins, polyvinyl butyral Such as acetal resin. It can be used alone or in combination of two or more kinds. Blocked isocyanate can be used for various isocyanates, such as isophoryl diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, etc. Blocking agents such as ethanol, butanol, dimethyl malonate, oxazole, caprolactam, methyllysin, ethylene glycol, etc. are used for blocking. In addition, hexamethylene diisocyanate is blocked. Can be replaced with benzaldehyde over-gas, para-gas benzaldehyde over-gas, acetaldehyde over-gas, lauryl hydrazone peroxide, and other over-gases. (D) Radiation polymerization initiated by the activation of thorium, azide compounds, halogen Shenyl oxazole compounds, halomethyl-s-triazine compounds, anchor salts, benzoin ethers, benzophenones, ketones, acetophenone derivatives and other compounds. Azide compounds are specific For example, the following: 4,4, -di || Nitrogen transport, 4,4, -diazide stilbene-2,2, -disulfonic acid-^-This paper size applies to China National Standard (CNS) A4 (210X297) Li) Please read the precautions before i order the A7 printed by the Consumer Standards Cooperative of the Central Bureau of Economic Affairs Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards __B7_ V. Description of the Invention (?) Ethylenediamine Diethylene Oxide, 4,4, -Diazanitrogen | -2,2, -Disulfonic Acid-N-propylhydroxyl Amidoamine, 4,4, -diazimidine 1,2,2, -di transverse acid, 4,4, -diazide 1-2, 2, -disulfonic acid-N, N-diethylamidamine , 4,4, -Diazide-2,2'-disulfonic acid sodium salt and other β nitrogen knots and their derivatives; 2,6-bis (p-azidophenylene) cyclohexanone, 2,6 -Di (p-azidophenylene) -4 -methylcyclohexanone, 2,6 -di (p-diazine) -4-pentylcyclohexanone, 2,6-di (p-azidecinnamon) Fork) 4-tertiary cyclohexanone and other diazabenzyl cyclohexanone and its derivatives, azidocinnamocyclohexanone and its derivatives; p-azabenzylacetophenone, p-azepine Isoproline _, 4,4'-diazide chalcone, 2,6-bis (4'-azidophenylene) acetone, 2, 6-bis (4 ·, azidophenylene) propane_- 2'-sulfonic acid-Ν, Ν-diethylene oxoethylamidine, 2, 6 -bis (4'-azepine)-acetone-2,21-disulfonic acid-Ν, Ν-diethylene Diazepam and its derivatives such as oxoethylamidine. Alternatively, an azide group may be introduced using a polymer chain. Halomethyloxazole compounds are 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5 (p-fluorenylstyryl) -1 , 3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like. In addition, halomethyl-s-triazine compounds, especially trihalomethyl-s-triazine compounds, have, for example, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S -Triazine, 2,4-bis (triazamethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2,4-bis (Trichloromethyl) -6- (p-phenylstyryl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-S-triazine, 2,4- Bis (trifluoromethyl) -6-phenyl-s-triazine, 2 -1 0-Please read the note first

I i (bound paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm)) Printed by A7 _ B7 _ 'of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy [5] Description of the invention (9) [2' (5'- Methylfuryl) ethylidene-4,6-bis (trifluoromethyl) -3-triazine, 2 (2- · furylethylidene) -4,6- (fluorene methyl) -S- Triazine, 5, 7-bis (tribromomethyl) -s-tripylazolo [l, 5-a] pyrimidine, etc. These can be used alone or in combination. Benzoin ether Examples include benzoin methyl ether, benzoin isobutyl ether, and the like. Benzophenones include, for example, acetaldehyde benzene, 2,2-dimethylamino-2-phenylacetophenone, 1,1-bis Gas acetaldehyde benzene, mignonone, o-benzoyl methyl benzoate, etc. xanthones are xanthone, thioxanthone, 2-xanthone xanthone, 2-alkylthio Xanthone, 2,4-dialkylthioxanthone, etc. "Acetylbenzene derivatives include, for example, acetophenone, trigas acetaldehyde benzene, 2,2-diethoxyacetone, 2, 2-Dimethoxy-2-phenylacetophenone, etc. Tweezer salts include various phosphonium salts, iodine sharp salts, and diazonium salts. Specific examples include triphenylsulfonium trifluoromethanesulfonate, Benzyl-4-hydroxyphenylmethylfluorene hexafluorosulfonate, methyl-4-hydroxyphenylmethylfluorene hexafluorosulfonate (or hexafluoroantimonate), diphenyl-tert-butylbenzene Hydrazone trifluoromethanesulfonate, diphenylmethylaminophenyl hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, di-tert-butylphenyliodonium trifluoromethanesulfonate (or Hexafluoroantimonate or hexafluoroborate), methoxyphenylphenyliodonium trifluoromethanesulfonate, diphenyliodotrifluoromethanesulfonate, aminophenylbenzene diazonium salt tetrafluoro Borates, tetrafluoroborates, etc. These can be used alone or in combination. In addition, in order to increase the sensitivity of the active-line irradiation polymerization initiator of component (d), it can also be combined. Use sensitizers. Examples of sensitizers are 2-nitropyrene, 2, 4,7-trinitroone, benzoxanthone, picramine, 1,2-benzoxol, -11-benzyl Paper X degree applies Chinese National Standard (CNS) Α4ϋ 格 (210X297 mm) (Please read the notes on the back before filling in, write this page) Xin · Order Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __B7_, 5 , Invention description (, σ) 11-chloro-6-hydroxybenzoxanthone, phenanthrene, 4- (4-butoxyphenyl) -2,6-diphenyl cadoxin iron perchlorate. (e) Examples of compounds that polymerize unsaturated bonds include various vinyl monomers and vinyl oligomers. Specific examples include acrylate monomers and methacrylate monomers, and include polyols such as ethylene glycol and trimethylolpropane. Esters of acrylic acid and methacrylic acid, and the above-mentioned esters of polymers or oligomers having alcoholic hydroxyl groups such as polyvinyl alcohol. The present invention further includes acrylate melamine, methacrylate melamine, and amine methacrylic acid Ester, urethane acrylate, etc. Specific examples include 2-hydroxyethyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, diethylene glycol dimethacrylate, and polyethylene glycol methyl ester. Methacrylate, trimethylolethane tetramethacrylate, tetramethylolmethane tetrapropylene, and the like. These can be used alone or in combination of two or more. The coating composition of the present invention, especially the coating composition for a color filter protective film, is preferably added with a leveling agent. Because of the addition of a leveling agent, better surface flatness can be obtained. The leveling agents include, for example, silane homogenizers, polyether modified dimethylpolysiloxane strips BYK 300, BYK 301, BYK 306, BYK. 307, BYK 335, BYK 330, BYK 331, BYK 341, BYK 344, BYK 346, BYK 3 0 2, BYK 164, etc. BYK 3 2 0, polyether modified dimethyl alkyl polysiloxane BYK 3 2 5, BYK 0 7 7, polyester modified dimethyl alkyl polysilazane 烷基 BYK 370, polyester modified dimethyl alkyl polysilazane 糸 BYK 322, BYK 075 ( (By BYK Chemical Company). In addition, fluorinated fluorene homogenizers include fluoroalkylcarboxylic acids, disodium N-perfluorooctanesulfonium glutamate, sodium 3- [ω-fluoroalkanoyl] -1-alkylsulfonate, and perfluoro Carboxylic acid, perfluorooctane sulfonate diethanolammonium amine, perfluoroalkyl sulfonamide propyl tri-12- The X degree of this paper applies to the Chinese National Standard (CNS) A4i ^ grid (210X297 mm) ---- ------ / ------ tT ------ / --- \, (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ——_; ______ 丨, V. Description of the invention (11) Methyl saddle salt, monoperfluoroalkyl ethyl phosphate, etc. β When the coating composition of the present invention is used for protective films for main substrates such as MD and CD, It may not contain a thermal crosslinking agent, a polymerization initiator, or the like. Using a suitable method such as spin coating or spray coating, the composition is coated on the main substrate to a thickness of 0.5-20 / zb at about 60. 〇 Dry for 1 to 10 minutes to form a protective film. After the work, peel off the protective film. It can be carried out with a wide range of organic solvents such as NMP, y-butyrolactone, acetone, isopropylamine (IPA), ethanol, butanol, methanol, dimethylacetone, etc. To facilitate removal, it is also possible to use an ultrasonic tank or the like. This protective film has a heat resistance of about 200-C and has mechanical strength. In addition, it can be easily applied and peeled. The thermosetting coating composition and the photosensitive coating composition of the present invention are mainly used as a color filter protective film. The composition of the present invention is applied on a substrate such as a glass substrate forming a color filter, and is suitable for spray coating, flow coating, pad coating, spin coating, dip coating, and the like, and the coating thickness is, for example, 0.5 to 10 # B. Next, the solvent is removed by evaporation, and a material for forming a pattern remains on the substrate. Removal of the solvent may be facilitated by heating or reduced pressure as necessary. The main point of the heating temperature is not to cause the deterioration of the above-mentioned forming material and the substrate, and it can be heated to 150 * 0, for example. In the case of a photosensitive resin, the layer is irradiated with an active line to reflect a pattern. Next, the layer was treated with a developing solution, and the irradiated portion was not dissolved, and the unirradiated portion was dissolved, and a protective film pattern appeared. In addition, it can also be imaged after being irradiated and heated, thereby heating, for example, the sensitivity can be further improved. The heating temperature is preferably not to cause surface shape, substrate degradation, etc., for example, can be performed at 2 fl (TC or less. The light source used for the above irradiation is, for example, 1 90-450Π ·, more preferably 2 0 0-4 0 0nia -13 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before writing this page)-Binding and ordering M Β7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Explanation of the invention (12) 1 1 1 Ultraviolet radiation in the field »% In addition, it can also be irradiated with electron rays or X-rays. 1 1 I 〇 In order to stabilize the tilt of the end of the case 9 Usually ultraviolet rays of several Μ Β 1 1 Time > It is also possible to irradiate with active rays at the distance of the mask on the surface of the layer. 1 1 The distance between the surface of the layer and the mask 9 depends on the required shape, generally 1 I 0 · 2--200 μ In addition, using a step-by-step, imaging projection, and other active line back-illuminating device 1> Adjusting the imaging position of the circular pattern up and down the layer can make the image end pay attention to 1 j The inclination of the part is stable, and the pattern obtained by the 1 I development is reheated by f or hardened by active line irradiation, etc .: This' 1 development> is conducive to improving crack resistance, solvent resistance, etc. 1 I can be used, such as osmium and / or aging earth metal 9 especially silicates of ammonium ions R | t, 1 1 I silicate hydride hydrogen phosphate, gas, etc. 0 without gold ions 1 The developer 9 can be used, for example, known in US Pat. No. 472 994 1 and European Patent Application No. 6273 3. In addition, «4 1 surfactant, detergent, Organic solvents, etc. 〇1 developer solution 9 added for the purpose of the above example. For example, non-ionic% active agent t ion% active agent, alcohol, 1 carboxylic acid 9 amine, etc. 9 and its derivatives 9 specific examples include polyalkylene glycol And its esters, 1 1 polyoxyalkylenes, polyhydric alcohol ester ring gas addition products t alcohol naphthene addition products, ] Alkyl phenol epoxy compound adduct sulfonate, sulfonate carboxylate, carboxylic acid 1 I salt, alkyl aldehyde amine ring gas fired adduct alkylamine etc. 0 1 can be added separately Or two or more types are added in combination. At this time, the added amount is preferably 0.1 to 1 0.3% by weight of the developing solution. 1 1 In terms of thermosetting resin, t can also be removed after brushing. 1 1 Unwanted parts of the protective film can be removed. 0 Wipe method can be purchased with commercially available machinery. Part 〇 After drying the solvent at about 100ec ~ 1 1 -14- 1 II 1 The paper size is in accordance with Chinese National Standards (CNS) A4 specifications (210X297 mm) A7 B7 5. Description of the invention (〇), at 190 Heat-treated on a hot plate at ° C to 250 ° C for 10 to 20 minutes, a protective film with excellent heat resistance and chemical resistance can be obtained. As a photosensitive resin, a heat-resistant and chemical-resistant protective film can be obtained by heat-treating on a hot plate at 19Q ° C to 250 ° C for 10 to 20 minutes after development. When an organosiloxane compound is added according to the present invention, the photosensitive resin protective film or even the thermosetting resin protective film can expand the allowable range of the development time and improve the adhesiveness. The adhesiveness of the general substrate and the protective film can be explained. That is, if the allowable range of the development time is small, the adhesion to the substrate is weak, and the developing solution during development may enter the substrate and the protective film, or between the color filter and the protective film, causing peeling. The addition of the compound of the present invention can improve the interface adhesion with the substrate or the color filter, and improve the allowable range and adhesion of the development time. Example The present invention will be specifically described based on examples. Examination Example 1 The following samples were prepared as a photosensitive coating composition. Polymer I (glycidyl acrylate adduct of methacrylic acid-methyl methacrylate copolymer: acid value 8G, molecular weight 20,000, bis equivalent 500) 91 g of block hexamethylene diisoisocyanate (Cronedol 2507, made by Japan Polyurethanes Corporation) 3 g 2,4-bis (trichloromethyl) -6-styryl-s-triazine 5 g 1,3-bis (3-aminopropyl) tetra Methyldisilaxane (Toshiba Silicone TSL 9306, molecular weight 248.5) 1 gram This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) Please read the precautions on the back and then the page for economical binding Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China V. Description of Invention (w) A7 B7 The central government bureau of the Ministry of Economic Affairs printed the consumer co-operatives of the Ministry of Economic Affairs by adding propylene glycol methyl ether acetate as a solvent to the above composition and preparing it to contain the above-mentioned non-solvent ingredients2 0% by weight of the composition 〇 The above composition is respectively formed on a substrate forming a 1.2 color filter with a spin coating film thickness of 1.5 > um 9 on a hot plate at 100 ° C Dry for 1 minuteBy using a predetermined photomask, a high-pressure mercury lamp was used to perform a proximity exposure on the photosensitive coating for about 100 groups. Secondly, the photosensitive coating 9 was exposed at a TMAH of 0.0505. 〇 Then 9 on a hot plate at 230 ° C, heat harden for 10 minutes. Thereby, adhesive adhesion, abrasion resistance, pollution resistance, and chemical resistance are both excellent. 9 and a protective film with smooth edges is used. Example 2 Polymer I 84 g of blocky methylenediisophosphonate (Cronedot 25 0 7 manufactured by Polyurethane Co., Ltd.) 3 g of -J- * methoxymethylmelamine 7 g of 2, 4-bis ( Tris (methyl) -6-styryl-s-triazine 5 g 1,3-bis (3-aminopropyl) tetramethyldisilazane 1 g propylene glycol methyl ether acetate was added to the above composition As a solvent, a composition containing 20% by weight of the above-mentioned non-solvent component was prepared. Exposure development. 〇 As a result, a pattern with excellent adhesion, abrasion resistance, stain resistance, and chemical resistance was obtained. 9 The edges were smooth. Example 3 The following samples were prepared as a photosensitive coating composition: -16- This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) ----------- ^-1 -----, 玎 .------ 嗲 1 (read first M read the back Note on this page will be written on this page) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (called 1 I polymer I 82 g 1 f trimethylaminomethyltri (2-hydroxyethyl acrylate) 1 1 Methyl) melamine 3g /-V Please 1 First 1 2,4-Bis (trichloromethyl) -6-phenethylidene-s-triazine 5g 1% Blocked methylated Diisocyanate (Cronedel 1 I of I 2 5 0 7 product of this polyurethane company) 9 g Note 1 I 1, 3-bis (3-aminopropyl) tetramethyl 1 gram of silicon dioxide compound and then 1 1 Add propylene glycol methyl ether acetate as a solvent to the above composition, and prepare it as a% wo 1% of this composition containing 20% by weight of the above non-solvent component for proximity exposure 9 pages 1 I development 〇 Adhesive abrasion resistance, stain resistance, chemical resistance 1 1 are all 9 excellent and smooth edge pattern 〇 1 1 Travel example 4 1 Order and prepare the following samples as light Coating composition 1 polymer I 8 2 g 1 1 trimethoxymethyltris (2-hydroxyethyl acrylate methyl 1 I) melamine 3 g I 1 2, 4-bis (trigasmethyl) -6 'Phenylethyl_S-triazine 5 g I Blocked methylene diisocyanate (Cronedo 1 | 2 5 0 7, B Polyurethane Products) 9 g 1 1 1, 3-bis ( 3-aminopropyl) tetramethyldisilazane 1 g 1 1 added to the above composition Glycol methyl ether acetate as the solvent system to a 1 1 I modulation containing the above non-solvent component of 28% by weight of the composition. Proximity exposure, 1 1 development. 0 Adhesive abrasion resistance, stain resistance, chemical resistance 1 I -1 7- 1 1 1 1 1 1 This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4) Letter of excellence. In particular, chemical resistance can be stabilized in D.5N sodium hydrogen hydride aqueous solution for more than 5 hours. In addition, by using adjacent exposure, a pattern with smooth edges can be obtained. According to the electron microscope photograph of the slope of the vulgar edge. The inclination angle of the inclination is 0.05N potassium hydroxide. 40 seconds. From this curve, it can be seen that the critical luminosity is 2 Q G m j, and it can be seen that it has high sensitivity. Example 5 The following samples were prepared as a thermosetting coating composition: Polymer I 92 g of biphenol A epichlorohydrin 5 g of block hexamethylene diisocyanate (Cronedor 2507, product of Japan Polyurethane Corporation) 2 g 1, 1 gram of 3-bis (3-aminopropyl) tetramethyldisilazane was added to the above composition as a solvent, and propylene glycol methyl ether acetate was added as a solvent to prepare a composition containing 2 G% by weight of the above-mentioned non-solvent composition. The composition was spin-coated on the substrates forming 1.2; um color filters to a thickness of 1.5 // m. Next, it was dried on a hot plate at 100 ° C for 1 minute, and then heat-hardened on a 2 3D ° C hot plate for 15 minutes. The protective film pattern thus obtained is excellent in adhesiveness, abrasion resistance, stain resistance, and chemical resistance, and a protective film with good transparency in visible light of 40 μηη or more can be obtained. Β 啻 Example β is shown in Example 1 In the photosensitive coating composition, 0.25 g of a homogenizer BΥK 164 was mixed to prepare a composition. The above composition was subjected to proximity exposure and development in the same manner as in Example 1. Surface flatness can be improved from ± 0.1 # m to ± Q.Q5; um, adhesion, abrasion resistance, pollution resistance, chemical resistance _ 1 8 _ This paper size applies to China National Standard (CNS) A4 specifications (210X297 (Mm) (please read the notes on the back before filling in this page) Order A7 B7 V. Description of the invention (· 7) A pattern with good quality and smooth edges. Example 7 Please read the back notes first, then fill in, write, this page. The thermosetting coating composition of Example 5 was mixed with 0.25 g of a homogenizer BYK 164 to prepare the composition. The composition was formed into a film in the same manner as in Example 11. As a result, a protective film with excellent surface flatness from ± 0.1; um to ± 0.05 / iin, and excellent adhesion, abrasion resistance, stain resistance, chemical resistance, and transparency can be obtained.啻 旆 Example 8 The composition of Example 1 was changed except that the polymer I was changed to the following polymer, and the photosensitive coating composition was prepared in the same manner as in Example 1, and subjected to proximity exposure to develop. It has excellent adhesion, abrasion resistance, pollution resistance, and chemical resistance, and it has good transparency and visible stability in the above visible light. Polymer: 1. Poly (methacrylic acid) 〇 < 25-co- (benzyl methacrylate) 〇β · 75 molecular weight about 30,000 2 · poly (methacrylic acid) 〇.3-co- ( Methyl methacrylate) 0 «7 Molecular weight about 25,000 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 3 · poly (styrene) 0,8-co- (methacrylic acid) 〇2 Molecular weight about 15,000 4. Poly (methacrylic acid) 0β2-co- (butyl methacrylate) 0> 8 Molecular weight approximately 45,000 Miyazaki Example 9 In the composition of Example 5, except the polymer I, the following polymerization was used instead.物 -1 9- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of invention (, <?) Example 1 A thermosetting coating composition was prepared in the same manner to obtain a protective film. It has good adhesion, stain resistance, and chemical resistance, and it has good transparency and visible edges when the light is above 400 # ιη. Polymer: 1. Poly (methacrylic acid) Q # 25-co- (benzyl methacrylate) Qj5, molecular weight about 3 0, 0 0 G, 2. poly (methacrylic acid) 0β3-co- (methyl Methyl acrylate) 0β7 with a molecular weight of about 25,000 3 · poly (styrene) 〇β8-co- (methacrylic acid) 〇β2 with a molecular weight of about 15,000 4. Poly (methacrylic acid) 0β2-co- (methacrylic acid) Butyl ester) 0ί8 Molecular weight about 45, 000 Example 1 In the composition of Example 1, except for the organosiloxane used, the "? -Bis (3-aminopropyl) polydimethylsiloxane was used. Except for alkane (TSL 9 3 8 6, molecular weight 802, average polymerization degree 8) of Toshiba Silicone Co., the photosensitive coating composition was prepared in the same manner as in Example 1 and subjected to proximity exposure and development. It has excellent adhesion, abrasion resistance, pollution resistance, and chemical resistance, but it has good transparency and visible edges when the visible light is above 400 ^ 111. Example 1 1 In the composition of Example 5, in addition to the organosilane used, the following ", ω_bis (3-aminopropyl) polydimethylsiloxane (Toshiba Silicone TSL 9386, molecular weight) 802, average degree of polymerization 8), the rest was prepared in the same manner as in Example 5 to obtain a protective film. Get tightness and resistance -20- This paper size applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ^ δΐϋ 2 A7 B7 '' V. Description of the Invention (β) Excellent pollution resistance and chemical resistance, and good transparency in visible light above 40Q / iffl, and smooth edges picture of. Example 1 2 A composition consisting of 99 g of polymer I and 1 g of 1,3-bis (3-aminopropyl) tetramethyldisilazane was prepared by adding propylene glycol methyl ether acetate as a solvent to prepare A composition containing 20% by weight of the above-mentioned non-solvent component. This composition was coated on the main substrate for MD by a spray method, and dried at 60 ° C to form a protective film. Then, the surface of the main substrate for MD with a protective film is exposed to a transportation environment. Soak in acetone and remove the membrane for about 15 minutes. To facilitate the removal of the membrane, the membrane can be removed by immersing it in acetone in an ultrasonic bath for about 1 minute. The upper protective film shows sufficient strength against mechanical damage, and has high adhesion. It is easy to remove in organic solvents such as acetone, and is convenient for work. g Every bright effect 巣 The photosensitive coating composition of the present invention and its layering step. Due to the above-mentioned structure, a protective film having excellent adhesion, resistance, stain resistance, and chemical resistance, excellent properties, heat resistance, and smoothness can be used. The industrial use value is great. In addition, the smooth edge of the end, which has always been regarded as difficult, can be achieved without problems such as disconnection of the conductive wire film. This paper size applies to China National Standard (CNS) A4 (210X297 mm) I I 11 —M 11 I I (Please read the precautions for rain before filling this page) ''

Claims (1)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Please read this paper first to apply Chinese National Standard (CNS) A4 size (210X297 mm). Note on the %% of this page. Binder A8 B8 C8 D8 h8ili2 Patent Application Range (where R is an alkylcycloalkyl, aromatic Hydrocarbon group, having a hydroxyl group or an alkyl group represented by the following formula or an aromatic hydrocarbon group having a hydroxyl group), 0 (C (CH2) m〇) nH Ο (where "1 is an integer from 1 to 10, and 11 is an integer from 1 to 5 Integer), general formula (IV) CH2 = CH-COOR (IV) (where R is the same as above) general formula (V) 〇V- CH = CH2 (V) and general formula (VI) CH 3 ch2 = c »COO (VI, --------- 1 ------, 1T ------- ^ (Please read the precautions on the back before filling in r). '' Central Bureau of Standards, Ministry of Economic Affairs A copolymer of a monomer represented by an employee consumer cooperative (where r1 is an alkyl group, an aromatic hydrocarbon group, an alkyl group having a hydroxyl group, or an aromatic hydrocarbon group having a hydroxyl group), which is characterized by the weight of non-solvent components. In other words, it contains 0.1 to 20% by weight of at least one organosiloxane compound represented by the general formula (1): This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) miti2 patent application scope A8 B8 C8 D8 R2 R4 R] -fSi —〇々 一 Si-r6 (1) (wherein R1 and Re are the same or different and are selected from the group consisting of unsubstituted or unsubstituted or amine, hydroxyl, α-hydrothio or Glycidyl is either substituted alkyl, unsubstituted phenyl, or dimethylsilyl. Substituted phenyl, (p-propenyloxymethyl) phenethyl, alkylphenethyl, Benzyl, vinyl; R2 to R5 are the same or different, and are a hydrogen atom, a radical, an aryl group, a fluoroalkyl group, or a siloxyalkyl group substituted with an alkyl group or an aryl group, η is a whole number from 1 to 9 (2) If the coating composition in the scope of patent application No. 1 contains U), please read it first, read the precautions of I, I, and then page the booklet printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs a ) 物 ”) Formula / IV Θ 合 {通 U 聚 有 有, contains the material solution and contains. Its ° group of water, is expected to be · alkali agent alkane coated on hair. The gas-introduced group is a silicon item inflated material machine 2 can be polymerized and coated with the number 3 of the least shot, or the number of items according to the item _ 1 or the line 3 key 1 And the fifth perimeter melts the perimeter. Fan Ke} Fan Bu Fan 1 The profit (d Li Heli is a special agent with a special polymer η, please contact us if you want to submit a request to the CCCC and apply for it} Hot like, such as: 如 如 ί • · The size of the paper used in the paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) A8 Βδ S81112_〇8 _____ VI. Application for patent scope 6. If the coating composition of the first patent scope is applied, the general formula ( 1) At least one of R 1 and 1 ^ is a compound having an amine alkyl group. / 7. The coating composition according to item 1 of the patent application scope, wherein (a) _ polymer component 僳 and molecular structure have Those who can polymerize unsaturated bond compounds. ---------- 0 ------ 17 ------- cast ''.: | (Please read the back first (Note ^^ page), 'Central Standards of the Ministry of Economy 印 Printed by Employee Consumer Cooperatives -4- This paper size uses the Chinese National Standard (CNS) A4 specification (210X297 mm)