TWI375866B - Radiation curable and developable polyurethane and radiation curable and developable photoresist composition containing the same - Google Patents

Description

Nine, invention description: [Technology street field to which the invention belongs] This is a photo-resist composition of a radiation curable development of a polyamine vinegar and an ester which can be lightly cured and developed. I Amine [Prior Art] The color filter of the liquid crystal display (10) is a general-purpose component - it can be used for liquid crystal display devices! It is the color correction back - changed to red, the color () and other two primary colors, to form the full color of the display. The production of the color film pattern layer of the bucket is mostly applied to the base material by spin coating, and the surface to be hardened is selected by pre-baking. The exposure, followed by the hardening process, is repeated three times, and the two colors of RGB are sequentially etched onto the substrate. The front color liquid crystal display device mainly uses glass as a substrate, but it has problems such as weight. In order to solve this problem, the material of the flexible display has been studied to a considerable extent, so that it is possible to achieve the advantages of light weight, difficulty in the eight-wire, and windability. In Japan, the special opening ιι_271736 two itt's have discussed the use of plastic substrates, but in general, and plastic substrates have problems that cannot be treated at high temperatures; and in Japan ^ m1. 4468 silk crepe, money Longxian-like low-temperature hardening (4) ΐ ΐ ΐ ΐ ΐ ΐ ΐ ' ' ' ' ' ' ' 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本The present invention can be completed by using a reversible curing composition. SUMMARY OF THE INVENTION "Is a radiation-curable developed polyurethane and a radiation-curable and developed photoresist composition comprising the same. TP070389 1375866 In particular, the present invention relates to a backbone comprising a carboxylic acid group and a side chain A urethane-based and carboxylic acid-based repeating unit which is composed of a random enthalpy to form a cured polyurethane. The radiation-curable developed polyurethane of the present invention is characterized by having a carboxylic acid group and a side chain in the main chain. It has an acryloyl group and a carboxylic acid group, and is composed of the following repeating units (Π) and (ΠΙ) in a random arrangement:

(m) =〇JL ο 〇ΛΊ (8) Υ° H^C=i Ο R* (ΐ) where: —R1 is C^2 straight or branched alkyl, & cycloalkyl, phenyl , biphenyl, anthranyl, xylylene, toluidine, and -Ph-A-Ph-yl (wherein A is 2 (3⁄4, -NH- or 'the group may be optionally substituted by q_6 alkyl) R is a divalent aliphatic group which may have one or more OH substituents, which in turn may be further reacted with a diisocyanate; and R3 is a straight chain having one or more 0H substituents or a Ci 6 alkyl group of a branched chain which, in turn, may further react with a diisocyanate; R4 represents hydrazine or CH3; and Τ represents one or more substituents selected from the group consisting of: -c=c —n 0 and 0. Once the polyamine is determined by GPC (gel permeation chromatography), the weight average molecule 7 1 (hereinafter referred to as Mw) is in the range of 3, 〇〇〇 4 4 〇〇, 〇〇〇; And the acid value is 5 to 120 2 mg KOH / g 〇 3 The main chain of the present invention has a carboxylic acid group and the side chain has a propylene fluorenyl group and a carboxylic acid group 4 ΤΡ 070389 1375866, a method for preparing a polyhydric alcohol (preferably Glycol) and diisocyanate The reaction, the acidity of the sulphate, the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the sulphate The reaction scheme of the reaction between the silk functional group and the acid liver is as follows: The reaction is not intended to be HO-rz^-oh

OCN-Ri-NCO + HO-C-j-C-OH

COOH R3 -c^-o- =0

U

COOH R<-CHj-O- =0 丄. - Bu. Seven _μ_υi〇_ called ten CH^-O COOH *

°<s^O Η,〇=( · Ο t U 丄.-CHr|〇 Λη CH^O- 0 OH HO JL^-^JLo. -N-R “ 2i〇-CH+

CHj-0-COOH

HO R4 where: (i) (n) (Π) TP070389 8 1375866 μ R1 is CH2 straight or branched alkyl, & 8 cyclic alkyl, phenyl, phenyl, naphthyl, and曱 stupyl, toluidine-based, -Ph-A-ph-based (wherein A is 2 03⁄4, -NH- or -〇_), which may be optionally substituted by c]4 silk; R is divalent An aliphatic group, which in turn may have one or more hydrazine H substituents, which in turn may be further reacted with a diisocyanate; and R3 is a straight or branched chain having one or more 0H substituents. ο 6 alkyl, the hydrazine H substituent may in turn be reacted with a diisocyanate; R4 represents hydrazine or CH3; and τ represents one or more substituents selected from the group consisting of: -(tetra)-, &' X), ¢) and 0. The polyamine ester of the present invention has a weight average molecular weight (hereinafter referred to as Mw) measured by GPC (gel permeation chromatography) in the range of 3,000 to 400,000; preferably 6,000 to 8 Å, 〇0 ;; and an acid value of 5 〜12〇mgK〇R/g, preferably 1〇~6〇mgKOH/g 〇 The invention further relates to a radiation curable developed photoresist composition comprising: (A) from formula (I), (π) And the polyamine ester of the present invention comprising (b) the repeating unit represented by (in), (B) an acrylic monomer, and (the photoinitiator of the present invention, the (A) is represented by Formula 1 , (Π) and ie) repeated, the weight ratio of the polyurethane (hereinafter referred to as polyurethane (A)) and the acrylate monomer (hereinafter referred to as acrylate monomer (B)): (9) ) for 4〇~9〇: 10~60. With respect to the total weight of the component (4) and the component (B) of 1% by weight, (c) the photoinitiator (hereinafter referred to as the photoinitiator (〇) is 1 to 5 〇 〇 / 本. The composition of the invention may optionally include one or more of the auxiliary 1), the colorant (6), the sub-agent (F), and the solvent (G). The amount of these components to be used can be varied within a wide range as long as it does not adversely affect the object to be achieved by the present invention. [Embodiment] In the present invention, in the preparation of a polyurethane having a carboxylic acid group and a side chain having a propylene fluorenyl group TP070389 9 and an acid group, and the repeating unit 1 and the polyurethane compound, the diisocyanate has a molecule A compound of two isocyanate functional groups, such as diphenylmethane diisocyanate_0, oxime, 4-phenylene diisocyanate, 4,4, _biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4, 4 , _ diphenylmethane diisocyanate, 2^4- or 2,6-dimethylphenyl diisocyanate, p-toluidine diisocyanate, I4'] diphenyl, diisocyanate, L3- or ^4-xylene diisocyanate, L3-, pentyl diisocyanate #1,4·cyclohexane diisocyanate, 1> 3_cyclohexane diiso-acid vinegar, 3-isocyanide Acid vinegar methyl _3,5,5_trif-cyclohexyl isopropyl vinegar (Isofluran-diisocyanate S), methyl 2,4·cyclohexane; ^diisocyanate , methyl 2,6-cyclo-dialkyl diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene methylene diisocyanate g | , 丨, 2_ stretch propyl "isocyanate g, 1, 2 Butyl diisocyanate, 2,3_butyl butyl diisocyanate, butyl diisocyanide, 2,4,4• or 2,2,4_three y hexa y Diisocyanate. ^Inventive + used to prepare a polyether with a main chain having a Wei group and a side chain having an acrylic acid group: an acid group and consisting of repeating units w, (11) and (m) = alcohol oxime using an average molecular 1 of 4 〇〇 ~ 5, hydrazine polyols, such as poly-bonds = such as poly (ethylene glycol), poly (propylene glycol), poly (butanediol) (pTMEG); Vinegar = diol (poly(ethylene glycol adipate) diol, poly (butylene phthalate) diol, diol, diol, poly(adipate 3 - methyl) -1,5. pentylene glycol )) ί (β 3 3_methyl_1,5_pentylene glycol vinegar) diol, polycaprolactone diol and rice (Ρ-Τ-δ-δ- Ethylene glycol vinegar; polycarbonate (hydrogenation of ί H曰ί ^ ^ f tobacco polyol such as polyethylene monomer, polypropylene multi-product it, decadiene polyol and polyisoprene) a product. The blood carboxyl chain has a Wei group and the side chain has an acryl fluorenyl group in the polyamine vinegar composed of the repeating yam, (9) and (4), and the phthalic acid compound of at least two right bases can be mentioned. For example, two (f; 曰 TP070389 10 1375866 (Dime ^ iylol propionic acid 'referred to as DMPA 'Lancaster products in the UK), CAPA HC1100 (polycaprolactone with side chain carboxylic acid functional groups, products of SOLVAY, Germany), 2-B Alcohol group 2-methyl-2•hydroxyacetic acid. In the present invention, the main chain has a carboxylic acid group and the side chain has an acryloyl group and the heavy elements (I), (H) and (10) The acrylate monomer containing an epoxy group may be, for example, Glycidylmethaciylate (GMA, a product of D〇w Chemica, USA). In the present invention, in the preparation of a polyurethane having a carboxylic acid group and a side chain having an acryloyl group and a carboxylic acid group and having a repeating unit (I), (Π) and 0Π, the acid anhydride may, for example, be trimellitic. An acid anhydride (Trimellitic anhydride, TMA, a product of Aldrich, USA) and tetrahydrophthalic anhydride (Tetrahydr〇phthalk. anhydride, referred to as THPA 'Aldrich Company, USA), succinic acid and dihydrophthalic anhydride. - a polyurethane having a carboxylic acid group and a side chain having an acryloyl group and a carboxylic acid group and having a repeating unit (Ι), (Π) and (III), having a higher molecular weight and more It is easy to form a hydrogen bond amine ester group and has an acrylic group for radiation curing and parenting, so that the chemical resistance, heat resistance and yellowing resistance of the cured product can be improved. The photocurable composition for radiation curable development according to the present invention comprises (Α) a main chain having a drum acid group and a side chain having an acryloyl group and a tick acid group and consisting of repeating units (I), (II) and (ΙΠ) And a (meth) photoinitiator. The polyamine used in the photoresist composition of the present invention is intended to be the one described above in the present invention. The acrylate monomer (B) used in the photoresist composition of the present invention may, for example, be a mono-, di-, tri- or poly-acrylic functional monomer. The monoacrylic acid functional monomer may, for example, be 2-phenoxyethyl acrylate, tetrahydrofuranyl acrylate, isobornyl acrylate, isobornyl methacrylate, 2-(2-ethoxyethoxy) acrylate. ) TP070389 11 1375866 = 曰 、, 癸 癸 vinegar „, propylene glycol lauric acid vinegar and methacrylic acid lauryl-acrylic acid 8 secret army can be, for example, dipropylene glycol tripropylene glycol vinegar, propylene glycol vinegar The second olefin is called hexane diol vinegar, the second glutinous glutinous acid, the propylene glycol diethylene glycol vinegar, the propylene diethylene glycol glycol, the propylene diethylene glycol g, the trimethacrylate a glycol ester, a dipropylene, a tetraglycol vinegar, a tetraethylene glycol dimethacrylate, a tripropylene acid functional group or a propylene acrylate monomer, for example, a triacrylate Base) propylene vinegar, trimethyl bis (monomethyl) propyl vinegar, tetrapropyl benzoic acid bis (tris(propyl) propyl vinegar), penta propyl acetonide and hexamethylene diacetate diquaternary quinone vinegar vinegar, etc. The progesterate can be used alone or in combination of two or more. The reset ratio of the polyamine vinegar 'propylene' 酉曰 酉曰 (Β) which is used with the acryl fluorenyl group and the carboxylic acid group is 4 〇 9 : a range of 1 〇 to 6 。. - a photoinitiator used in the photoresist composition of the present invention (the enamel is irradiated with visible ultraviolet light, far ultraviolet light, electron beam, and xenon ray, etc. The structure may be cleaved to produce an active tmVeSite such as a radical, a cation or an anion, and may be polymerized with a polyamine ester (A) having a phenyl group in the main chain and a propylene bauxite group in the side chain, and an acrylate monomer (8). Examples of the initiator (C) include, for example, imidazoles such as 2,2,_bis(2 chlorobenzene•^) 4'4 '5,5-indole (4-methoxyphenylphenyl)_ι, 2 '_二咪嗤, 2,2,_双双(2_氯,5,5 -_(4-ethoxydylphenyl)_ι,2'_二. rice bran, 2,2,_double ( ;_ chlorophenyl)-4,4,,5,5,-indole (4-phenoxycarbonylphenyl)_U,_diimidazole i 雔(2,4·diphenyl)_4,4,, 5,5,_肆(4_methoxycarbonylphenyl M,2,c^azole, 2,2'-bis(2,4-diphenyl)-4,4',5,5,-肆(4_ethoxycarbonylphenyl H,2,-di-saliva, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-肆(4-benzene Oxyphenylphenyl)_1,2'-diimidazole, 2,2,-bis(2,4,6-trichlorophenyl)-4 ,4,,5,5,-肆(4-methyl 其 carbonyl phenyl)--dimethicillin, 2,2,_bis(2,4,6-trichlorophenyl)_4,4,,5 ,5,肆&ethoxycarbonylphenyl)-l,2V diimidazole, 2,2,·bis(2,4,6- 'trichlorobenzene^)_4,4',5,5'-肆(4-Phenoxycarbonylphenyl)-1,2'-diimidazole, 2\2,_bis(2_Molyphenyl M,4',5,5'-indole (4-methoxycarbonylbenzene) 1,1,2,-diimidazole, 2,2t double TP070389 12 r9, 55) gan 4'4,5'5-indole (4-ethoxylated phenyl hydrazine, 2'-dimiso, 2,2,-double base...'々,-肆...phenoxycarbonylphenyl from broadly diimidazole, ", · phenyl K4', 5,5'-fluorene (4々 oxydecylphenyl hydrazine) , 2'·二咪二啐1/又(2,4-二漠苯)·4,4,,5,5,·肆(4·ethoxylated phenyl)"*1, 2,-ϋ 9,,-2,f'_bis(2,4-dibromophenyl)4,4,5,5,-indole (4-phenoxycarbonylbenzene: its "7" , 2,2'-double (2,4,6·three desert phenyl>4,4,,5,5,-肆(4_methoxy odor saliva, 2,2, _ double (2,4 ,6·三漠phenyl)-4,4,,5,5,-肆(4_美V4 4%^本基>U'-diimidazole, 2,2,_double (2,4,6_ Tribromobenzene ^,,, two: (4-Anooxysilylphenyl)-1,2,-diimidine, 2,2,-bis(2-cyanodi14,4,5,5'-肆(4-methoxycarbonylphenyl) )-1,2'_diimidazole, 2,2,-double ί;^)·4/,5,5'·肆(4·ethoxycarbonyl alone W,·二味^二又(乱基Stupid base from ^' monument (4) phenoxycarbonylphenyl hydrazine ^ dim 2'2 - bis (2-methylphenyl > 4,4',5,5'肆0 methoxycarbonylphenyl) -0, 2, 2'_ bis (2_methylphenyl hydrazine, 4, 5, 5, - fluorene (4-ethoxy phenylene, 2, 2' bis (2. methyl benzene) Base >4,4',5,5'_肆(4-phenoxycarbonylindole·1,2-diimidazole, 2,2,-bis(2-ethylphenyl)_4,4,,5 ,5,-肆(4-methoxycarbenyl)^1,2,-diimidazole, 2,2,-bis(2-ethylphenyl)_4,4,5,5,·肆(4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2,-bis(2-ethylphenyl)-4,4,5,5,- 肆(4-phenoxy Carbonyl stupid base) Yizi diimidazole, 2,2,·bis (2_benzene^ stupyl^4,4',5,5'-indole (4-methoxycarbonylphenyl)-1,2,-二米峻, 2,2,_bis(2·phenyl)yl-4,4',5,5'-indole (4-ethoxycarbonylphenyl)-7-diimidazole, 2,2,_ Biphenylphenyl: ^ '^'-肆...phenoxycarbonylphenyl^glyimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-anthracene, 2,_ Diimidazole, 2,2,-bis(2,4-dichlorobenzyl)-4,4',5,5'-tetraphenyl _!, 2'_two_0 sit, 2, double ( 2,4,6_trisylphenyl): 4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2,-bis(2-bromophenyl)-4, 4,5,5,-tetraphenyl-1,2'-diimidazole, 2,2,-bis(2,4-dibromophenyl)-4,4,5,5,-tetraphenyl 1'2 - squat, 2,2 _bis(2,4,6-tribromophenyl)_4,4',5,5'·tetraphenyl-l,2,_two croup, 2, 2,-bis(2-cyanophenyl)_4,4',5,5'-tetraphenyl-1,2,-di-n-butyl salic, 2,2,-bis(2,4-dicyano Phenyl)_4,4,,5,5,-tetraphenyl-1,2,-di. Mazole, 2, 2, _ biguanium 070389 13 ^ «66 (2,4,6-tricyanophenyl)-4,4, 5 s,πη & glycyl stupid base>4,4,,5 ,5,-Tetrabenzene A,"four stupid J-1,2,-two-flavor saliva, 2,2,_bis-bisphthyl)-44,55,-tetraphenyl-,-,imidazole,2,2' _ bis (2,4-dimethylphenyl k4,, 5'5,-tetraphenylidene t-4', two; ?4(2-ethyl stupid); (10) tetraphenyl'=ylindole 4 ,,5,5,-tetraphenyl q 2,- a ,, and (,, 0 -ethyl-based H4,55,-tetraphenyl A ^ oxazole, 2, 2, bis (2-phenylene) Base >4 4, 5 5,-tetraphenylene j oxazole, 2,2,-bis(2,4,6-triphenyl phenyl 2 2 2 2 ; 4;r^ ; ^ ^ Ια^ ϊΖ;:^ Stupid base 4',5,5: benzene 1,4,6_two-milk base)-4,4,5,5'-tetraphenyl, _ imi, = = iso-T-ether And an example of a succinyl-based initiator (C), such as an acetophenone-based structure such as 22-dioxy-2-phenylacetophenone, 2_Phenyl-2-methyl-phenylphenyl]-indole, Η4_isopropylphenyl)_2_transyl-2-methylpropanoid _, 4-(2-cyanoethoxy)phenyl _(2_carbyl 2-propyl)-, 2,2-methoxybenketone, 2,2-diethoxyacetophenone, 2_Methyl_(4_Methylthiophenyl)-2-morphinyl-1-propanyl-I- ketone, 2-pyramidyl-2-dimethylamine, a certain base, butyl __嗣, 1_Phenyl hexyl phenyl hydrazine, 2 2 '-didecyloxy-1,2-diphenylethan-1-one, 4-azathiophenyl hydrazine, 4-azido-based benzene Ethyl ketone and the like and similar derivatives. Examples of the photoinitiator (C) may, for example, be diphenyl hydrazine, such as benzophenone, TP070389 14 1375866 4,4,-bis(di-m-)benzophenone. , 4,4,-bis(diethylamino) bis-methyl, 3 3, dimethyl-4-methoxybenzophenone and the like and the like.

Examples of the photoinitiator (C) include, for example, a photo-agent having an α-diketone structure such as diisopropyl carbazate, benzoyl carbazate, methotrexate, etc. And similar derivatives; light-emitting agents with a polynuclear fluorene structure such as 醌, 2-ethyl gg Kun, 2-t-butyl butyl, i, 4-naphthoquinone, etc. and similar derivatives 1 flavonoids (xanthone) a light initiator of the structure such as flavonoids, thioflavones, 24 4 -diethylthioflavonoids, 2-gas thioxanthine, and the like; and having a diazotide & -diazodiphenylamine, 4-diazo-4,-methoxydiphenyl^, 4-nitro--3-methoxy-monoamine, and the like; and light having a tristimulus structure Starting agents such as 2-(2,-furylethylidene)_4,6-bis(trichloromethyl), 2_(3',4'-dimethoxyoxystyryl)_4,6-bis ( Tri-gas violent) _s triazine, 2_0 [methoxy naphthyl M, 6-bis(trichloromethyl)-s-triazine, 2_(2'·m-methylphenyl)_4,6_ double (two Chloromethyl)-s-diindole, 2-(2'-thinylethylene)_4,6-bis(trichloromethyl)_s_triazine, and the like, and similar derivatives. '

In addition to the above-mentioned photoinitiators, it is also possible to use diazobenzaldehyde, azidopurine, bis(2,6-dimethoxybenzohydrazyl) 2,4,4-trimethyl^ Base can oxide, N-phenylthioacridone, triphenylpyrenylperchlorate, and the like, and similar derivatives. These light starters may be used singly or in combination of two or more. The photoinitiator (C) is used in an amount of 5% by weight based on 100% by weight of the total weight of the component (A) and the component (B). The photoresist composition of the present invention may further contain a secondary auxiliary agent, and examples thereof include a decane having a vinyl functional group such as vinyltrichloromethane, vinyltrimethoxyxanthene, vinyltriethoxyxanthene^ An epoxy-containing functional group such as 2-(^,4-epoxycyclohexyl)-ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxyoxy-naphthene, 3-shrinkage Glycidoxypropylmethyldiethoxydecane, 3_glycidoxypropyltriethoxy oxetane; methacryloxyl-containing alkane such as 3-methylpropenyloxypropyl Methyldimethoxydecane, 3_mercaptopropene 醯 070070389 15 1375866 oxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxy oxime, 3-mercaptopropene a methoxy propyl triethoxy oxalate; a ruthenium containing propylene oxime such as 3 · propylene methoxy propyl trimethoxy sulphide; an amine group containing an amine group such as N - (2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, Ν-(2·Aminoethyl>3-Aminopropyltrimethoxy-oxyxanthene, Ν_(2_ Aminoethyl)_3_amine Propyldiethoxy oxime, 3-aminopropyltrimethoxysulfonium, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(l,3-di Methylbutylene)propylamine, fluorenyl-phenyl-3-aminopropyltrimethoxysulfonium, hydrazine-(vinylbenzyl)_2-aminopropyldimethoxyxanthine hydrochloride; a urethane-containing functional group such as 3-ureidopropyltriethoxy oxane; a chloropropyl-functional decane such as 3-chloropropyltrimethoxynonane; a thiol-containing functional group a decane such as 3-hydrothiopropylmethyldimethoxy zeoxime, 3-hydrothiopropyltrimethoxy sulphur; a sulfur-containing functional group such as bis (diethoxy stone) Ethyl propyl) tetrasulfide; a cycloalkane containing an isocyanic acid group, such as 3-isohydroester propyl triethoxy decane, relative to component (A) and component (B) The amount of the auxiliary aid p) used is 〇丨5 to 5% by weight based on the total weight of 1% by weight.

The photoresist composition of the present invention may further contain a coloring agent (E), which may use an organic pigment having heat resistance, such as CI Pigment Yellow (Pigment Ye), 83, CI Pigment Yellow 110, CI Pigment Yellow 138, CI·Pigment Yellow 139, CI Pigment Yellow 150 and CI Pigment Yellow 155; CI Pigment Orange 71; CI Pigment Violet 19 and CL Pigment Violet 23, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48: 3, CI Pigment Red 48:4, CI Pigment Red 122·, CI Pigment Red l7/, c丄 Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 224, and CI•Pigment Red 254; Pigment Blue and CI Pigment Blue 15:6; CI Pigment Green 7 and CI Pigment Green 36; c丄 Pigment Grab 23 and C.I_Pigment Brown 25; CI Pigment Black 1 and CI Pigment Black 7. (c/ is an announcement made by jhe Society f Dyers _ Colourists Co.). The above colorants (E) may be used singly or in combination of two or more. The amount of the coloring agent used was 7 〇 to 6 〇〇 TP070389 16 1375866% by weight based on the total weight of the component (B). The photoresist composition of the present invention may further contain a dispersing agent (F), and examples thereof include, for example, S32000 produced by Avecia, Inc., which is a cationic poly(alkylimine) and a hydroxystearic acid having a free carboxyl group. The indole-type surfactant formed by the ester reaction, after being added and grinded by a grinder, can help the colorant to stably disperse. The dispersant (F) is used in an amount of 3 to 15% by weight based on 100% by weight of the total weight of the component (A) and the component (8).

The photoresist composition of the present invention may optionally contain a solvent (G) for knowing that it remains liquid and controls the viscosity of the composition at a suitable spray. The solvent to be used is that the hydrazine can dissolve or disperse the components contained in the above composition, does not participate in the reaction, and has appropriate volatility.

The solvent (g) used in one y is, for example, a (poly)alkylene glycol monoalkyl ether such as ethylene glycol monomethyl hydrazine, ethylene glycol monoethyl phthalate, ethylene glycol mono-n-propyl hydrazine, ethylene two Alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol based scale, diethylene glycol mono-n-butyl anthracene, triethylene glycol monomethyl group , triglycol monoethyl ether, propylene glycol monodecyl ether, propylene glycol monoethyl ether, propylene di monopropyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-f-ether, dipropylene glycol, Dipropylene glycol mono-n-propyl (tetra), dipropylene glycol mono-n-butyl test, tri-, diol monomethyl ether and tripropylene glycol monoethyl acid; (poly) extended diol diol single burning squamous acid from the purpose,甲甲乙乙, 乙 glycol monoethyl sulphate acetate, = diol monomethyl hydrazine acetate vinegar and propylene glycol monoethyl acetal acetate, · other such as phenyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol diethyl ether and tetraterpene ketones such as methyl ethyl ketone, cyclohexanone, 2 g gem and emulsified vinegar such as 2 • thioglycolate Vinegar and 2_acetic acid ethyl vinegar; vinegar = 3 2- -2-methylpropionic acid ethyl vinegar, 3-methoxypropionic acid methyl vinegar, 3- methoxy group, ethyl ester, 3 · ethoxy propionic acid methyl ke, · 3 ethoxy, 2 maid 3 _ Methyl butyl butyrate, acetic acid S ^ propionic acid 3 - methyl _ 3 - methoxy butyl vinegar, acetic acid ethyl acetate, ethylene I n = 1 day, acetic acid isobutyl vinegar, formic acid equivalent, acetic acid Propionic acid TP070389 17 1375866 Butyl ester, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, decyl acetate, B Ethyl acetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as anthraquinone and diphenylbenzene; guanamines such as N-methyl benzoprotamine (NMP), N, N-dimethyl Formamide and N,N-dimercaptoacetamide and the like. The solvent (G) may be used singly or in combination of two or more. The amount of the solvent to be added is not particularly limited as long as the desired viscosity can be obtained. The solvent (G) is generally preferably used in an amount of from 200 to 2,500% by weight based on 100% by weight based on the total weight of the component (A) and the component (B). The amount of the solvent (G) herein is the total amount of the solvent to be added and the amount of the solvent originally present in the polyurethane (A) and the color former (E). The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. In the following examples, DiPhenylmethaneDiisocyanate (MDI) was purchased from BASF Corporation; Polypropylene GlyC〇l (PPG) PPG4 was purchased from Stable Polymer Chemical Industry Co., Ltd. The company has a molecular weight of 100 gram/mole; polycaprolactone diol (PCL di〇l) CAPA® 2101A is a product of SOLVAY with a molecular weight of about 1000 g/mole and a hydroxyl value of 110 mg KOH. / gram; polycarbonate diol (p〇lycarb〇nate diob referred to as PC diol) PC-diol-1000 is a product purchased from Japan Asahi Kasei Corporation 'molecular weight is about 1000 g / mol' hydroxy price is 1 〇〇 ~ 12〇 KOH/g; PolyTetramethylene-ether-Glycol (PTMEG) PTMEG-1000 is a product of BASF with a molecular weight of about 1000 g/mole and a hydroxyl value of 107-118 mg KOH/ a dimethylol propionic acid (DMPA) system derived from a Lancaster product, which is a methyl group of an epoxy group-containing acetoacetate monomer. Propionate glycidol vinegar (Gl Ycidol methacrylate (GMA) is a product of Dow Chemical Company with a molecular weight of 142 g/mole; and TP070389 18 1375866 anhydride compound SiSL (Tetrahydrophthalicanhydride, THPA) is purchased from Aldrich; The compound trimellitic anhydride (TMA) was purchased from Aldrich; the other solvent used was propanol early methyl acetate vinegar ^pr0pylene Glycol

Monomethyl Ether Acetate (pma) is a product of DOW CHEMICAL. The solvent 1^-methyl 11 is more than the bite ketone. _111 her 丫1_2*^111〇 and 〇116, referred to as NMP) is the product of BASF. [Example 1] 31.9 g of MDI (diphenylmethane diisocyanate) and 80 g of PMA (propylene glycol monomethyl ether acetate) were placed in a 500 mL four-neck separable reaction flask to raise the temperature. Stir to 60 ° C with a mechanical stirrer until the MDI is completely dissolved. Subsequently, the instillation of 16.2 g of DMPA 〇 (methyl) propionic acid and PG PPG-1000 (1000 in the molecule) which had been thoroughly mixed with 50 g of NMP (N-methyl guanoxarone) was started. After the completion of the dropping, it was judged whether or not the NCO (isocyanate functional group) was completely reacted by FTIR (Fourier Transform Infrared Spectrometer). After the reaction is completed, the temperature is finally raised to 100. (: and add 8.3 g of GMA (glycidyl methacrylate)' to maintain the temperature until the acid value of the solution is about 18 mg KOH/g, then add 6.7 g of TMA (trimellitic anhydride) and raise the reaction temperature to 11 〇. The synthesis is completed after 小时 and J hours, at which time the acid value of the solution is about 39 mg KOH/g. The radiation curable developed polyurethane 1 of the present invention is obtained, which is composed of the following repeating units in a random arrangement, and The weight average molecular weight (Mw) determined by GpC (gel permeation chromatography) was 8,700. TP070389 19 1375866

(a) u) B 0 (N68sz.odl [Example 2] 31.9 g of MDI and 80 g of PMA were placed in a 500 mL four-neck separable reaction flask. The temperature was raised to 60 ° C and disturbed with a mechanical stirrer. Mix until the MDI is completely dissolved. Then, start to drip 16.2 g of DMPA and 13.6 g of CAPA® 2101A (molecular weight 1000) which have been thoroughly mixed before 5 g of N^p, and judge whether the NCO is completely reacted by FTIR after the completion of the drop. After the reaction is completed, the temperature is finally raised to 100 ° C and 8.3 g of GMA is added, and the temperature is maintained until the acid value of the solution reaches about 18 mg KOH/g, and then 6.7 g of TMA is added and the reaction temperature is raised to 110 C and 1 hour to complete the synthesis. At this time, the acid value of the solution was about 39 mg KOH/g. The radiation-curable developed polyurethane 2 of the present invention was obtained, and Mw was determined by GPC (gel permeation chromatography) as fentanyl. [Example 3] Place 31.9 g of MDI and 80 g of PMA in a 500 mL four-neck separable reaction flask, warm the temperature to 60 ° C and stir with a mechanical stirrer until the MDI is completely dissolved. Then 'start the infusion before it is completely mixed Dunke ^^ of 16.2 g of DMPA and 13.6 g of PC-diol (molecular weight of 1000), and judged by FTIR after dripping No NCO has completely reacted. After the reaction is completed, finally heat up to 100 ° C and add 8.3 g of GMA, maintain the temperature until the acid value of the solution reaches about 18 mg KOH / g, then add 6.7 g of TMA and raise the reaction temperature to u〇 The synthesis was completed after 1 hour, at which time the acid value of the solution was about 39 mgKOH/g. The radiation-curable developed polyurethane 3 of the present invention was obtained, and the Mw was 45,000 as determined by GPC (gel permeation chromatography). 4] Place 31.9 g of MDI and 80 g of PMA in a 500 mL four-neck separable reaction flask, warm the temperature to 60 ° C and stir with a mechanical stirrer until the MDI is completely dissolved. Then 'start the infusion before mixing completely At 50 g]S|]Mp, 16.2 g DMPA and 13.6 g PTMEG (molecular weight 1 〇〇〇)' and after the completion of the drop, judge whether the NCO has completely reacted by FTIR. After the reaction is completed, the temperature is raised to TP070389 21 1375866. At 100 ° C and adding 8.3 g of GMA, maintaining the temperature until the acid value of the solution reaches about 18 mg KOH / g, adding 6.7 g of TMA and increasing the reaction temperature to n 〇 ° 0 and 1 hour, the synthesis is completed, at this time the acid value of the solution About 39 mg KOH / g. The radiation curable developed polyurethane of the present invention is obtained. 4, and the Mw was 68,000 as determined by GPC (gel permeation chromatography). [Example 5] 31 g of MDI and 80 g of PMA were placed in a four-neck separable reaction flask of 500 mT, and the temperature was raised to 60. °C and stir with a mechanical stirrer until the MDI is completely dissolved. Subsequently, 16.2 g of DMPA. and 13.6 g of PPG-1000 (having a molecular weight of 1 Å) which had been completely mixed with 5 g of NMP beforehand were started to be dropped, and it was judged by FTIR whether or not the NCO was completely reacted after the dropwise addition. After the reaction is completed, the temperature is finally raised to 100 ° C and 8.3 g of GMA is added, and the temperature is maintained until the acid value of the solution reaches about 18 mg KOH / g, and then 5.3 g of THPA (tetrahydrophthalic anhydride) is added and the reaction temperature is raised. Synthesis was completed to 11 (TC and 1 hour later, at which time the acid value of the solution was about 29 mg KOH/g. The radiation-curable developed amine ester 5 of the present invention was obtained, and GPC (gel permeation chromatography) was used. The Mw was determined to be 11,000.

TP070389 22 1375866

1375866 [Example 6] 31.9 g of MDI and 80 g of PMA were placed in a 500 mL four-neck separable reaction flask, and the temperature was raised to 60 ° C and scrambled with a mechanical stirrer until the MDI was completely dissolved. Subsequently, the dropwise addition of 16.2 g of DMPA and 13.6 g of CAPA® 2101A (molecular weight of 1000) which had been thoroughly mixed in advance to 5 g of nmp was started, and after the completion of the dropping, the FTIR was used to judge whether or not the NCO was completely reacted. After the reaction is completed, the temperature is finally raised to 1 ° C and 8.3 g of GMA' is added to maintain the temperature until the acid value of the solution reaches about 18 mg KOH/g. 'Additional 5.3 g of THPA and raise the reaction temperature to 110 ° C and 1 hour. The synthesis is completed immediately after the acid value of the solution is about 29 mg KOH/g. The radiation curable developed polyurethane 6 of the present invention was obtained, and the Mw was 28,500 as determined by GPC (gel permeation chromatography). [Example 7] 31.9 g of MDI and 80 g of PMA were placed in a 500 mL four-neck separable reaction flask. The temperature was raised to 60 ° C and stirred with a mechanical stirrer until the MDI was completely dissolved. Subsequently, 16.2 g of DMPA and 13.6 g of PC-diol (having a molecular weight of 1 Å) which had been previously thoroughly mixed with 5 g of NMP were added dropwise, and after the completion of the dropping, it was judged by FTIR whether or not the NCO was completely reacted. After the reaction was completed, the temperature was finally raised to 100 ° C and 8.3 g of GMA' was added to maintain the temperature until the acid value of the solution reached about 18 mg KOH / g, and then 5.3 g of hydrazine was added and the reaction temperature was raised to 11 ° C and 1 hour later. That is, the synthesis is completed, and the acid value of the solution is about 29 mg KOH/g. The radiation curable developed polyurethane 7 of the present invention was obtained, and the Mw was 43,000 as determined by GPC (gel permeation chromatography). [Example 8] 31.9 g of MDI and 80 g of PMA were placed in a 500 mL four-neck separable reaction flask. The temperature was raised to 6 (TC and stirred with a mechanical stirrer until the MDI was completely dissolved. After P was started, The drops were previously thoroughly mixed with 50 g of 16.2 g of DMPA and 13.6 g of PTMEG (molecular weight of 1000), and after the completion of the dropwise addition, it was judged by FTIR whether or not NC0 was completely reacted. After the reaction was completed, the temperature was finally raised to 100 ° C and 8.3 g was added. GMA, maintaining the temperature until the acid value of the solution reaches TP070389 24 1375866, about 1.8 mg KOH/g, adding 5.3 g of hydrazine and increasing the reaction temperature to ii 〇 ° C and 1 hour later, the synthesis is completed. Approximately 29 mg KOH/g. The radiation curable developed polyurethane 8 of the present invention was obtained, and the Mw was determined by Gpc (gel permeation chromatography) to be 59,00 (^ [Examples 9 to 16]. 1, 2, 3, 4, 5, 6, 7, and 8 of the amount of polyamine vinegar 2, 3, 4, 5, 6, 7, and 8 and the amounts and ingredients shown in Table 2 The amount shown is such that the total amount of the component (A) and the component (B) is 1% by weight, and the amount of the remaining components is 1% by weight relative to the total weight of (4) and (8). ) Was sufficiently mixed 'by grinding the grinding wheel with appropriate control of the particle size distribution dispersant 200nm or less' obtained resist composition j, 2,3,4,5,6, Table 1 workers'

TP070389 25 1375866 Table 2 Example 13 Example 14 Example 15 Example 16 Photoresist composition 5 Photoresist composition 6 Photoresist composition 7 Photoresist composition 8 Polyamine 5 (8) 67 - _ . Polyurethane 6 - 67 Polyurethane 7 - - 67 Polyurethane 8 - - 67 IPGDA (B) 33 33 33 33 Igacure 907 (C) 16.7 16.7 16.7 16.7 KBM503 (D) 3.3 3.3 3.3 3.3 CI Pigment Green 36 (E) 150 150 150 150 S32000 (F) 10 10 10 10 PMA (G) 800 800 800 800 Viscosity (cps/25°C) 6.2 7.9 11.3 13.8 Note:

(C), (D), (E), (F), (G)% by weight are based on 100% by weight of the total weight of the component (A) + (B) (ie, (A) + (B) The ratio of the ingredients as a benchmark). TPGDA: Tripropylene glycol diacrylate, manufactured by Xinlimei Technology Co., Ltd. KBM503: 3-methacryloxypropyltriethoxydecane, a product of Japan Shin-Etsu Corporation.

Igacure 907 : 2-methyl-(4-methylthienyl)-2-morpholinylpropanone, product of ciba. S32000: Dispersant' is a product of Avecia PMA: propylene glycol monomethyl ether acetate vinegar. Test Example - Chemical resistance test, heat resistance test and yellowing resistance test TP070389 26 1375866

Lu

The photoresist compositions 1, 2, 3, 4, 5, 6, 7, and 8 obtained above are applied to a glass sheet in a thickness of 1 to 3 μm, and pre-baked for 1 to 3 seconds, ! 50~200mJ/cm2 exposure 'developed by Na〇H developer 2〇~15〇 second, then ^200~250°C for post-baking 20~40 minutes, and the coated glass piece contains various kinds in Han The solvent (8G °C water, propylene glycol monomethyl (10), Nn ratio argon, _ 〇 gt) or tetramethylammonium hydroxide (TMAH) 2.38%) lasted 5~2 〇 minutes (that is, the chemical resistance test) ) or exposed to various environments (17 〇 in air, 〇, 1 hour, that is, heat resistance test) 'test its yellowing resistance, the results are shown in Table 3 and Table 4 below. Table 3 Photoresist composition 4 Photoresist composition 1 (ΔE*ab) Photoresist composition 2 (ΔE*ab) Photoresist composition 3 (△E*ab)

Table 4 Photoresist composition 5 (ΔE*ab) Photoresist composition 6 (ΔE*ab) Photoresist composition 7 (ΔE*ab) Photoresist composition 8 80 ° C water 0.96 0.63 0.61 1 03 PM 1.04 1.38 1.25 1 78 NMP 1.16 1.55 1.49 1 68 TMAH2.38% 0.52 0.65 0.61 1 49 170°C in air 0.60 0.71 0.62 1.08 TP070389 27 rI375866 Note: The above AE*ab values for yellowing resistance are classified by Otsuka Electronics. The spectral characteristics of the photodetector MCPD-3000 measured before and after the test for chemotaxis and heat resistance (the color difference ΔEbb value represented by L*a*b*). According to the above test, in the photoresist compositions 1 to 8 prepared by the polyamine esters ι 8 obtained in Examples 1 to 8 of the present invention, the ratio of the polyurethane is only 10% by weight based on the total weight of the photoresist composition, but the polyurethane 1~ The multiple amine ester groups (providing hydrogen bonds) and acrylic acid functional groups in the structure of 8 itself provide excellent heat resistance, chemical resistance and yellowing resistance (i.e., S3). In addition, it has a single phase throughout the system, indicating that the photoresist composition of the present invention has high compatibility. The polyurethane according to the present invention is a radiation-curable highly crosslinked resin, and the resin is used as a main component of the photoresist composition, and the pigment can be firmly adhered to the glass substrate to improve the chemical resistance and heat resistance after film formation. In addition, if the radiation-curable highly cross-linked polyurethane resin of the present invention is similarly used as a main component of a photoresist liquid, and further with a suitable dispersant and a subsequent auxiliary agent, after a low temperature (<150 ° C) ripening hardening process, That is, first at 70~1〇〇. (: pre-bake 100~300 seconds~> 50~200mJ/cm2 exposure + NaOH developer development 20~150 seconds + then 50~200mJ/cm2 exposure·> Finally to 150. (: After the flooding 20~60 minutes' The photoresist composition is flexible and can be formed on a plastic substrate (such as polyacrylonitrile (PI), polysulfide (PES) film, polycarbonate (pc) film). [Simple description of the diagram] [Explanation of main component symbols] TP070389 28

Claims (1)

/^866 K〇H/g 〇. A radiation-resistant ID-developing photoresist composition comprising the following as an effective knife-forming. (A) Polyamine vinegar according to any one of claims 1 to 3. And (8) a propane monomer, and (C) a photoinitiator; wherein the weight ratio of the polyurethane (A) to the acryl monomer (B) ((A): (B)) is 40 to 90: 10 -60; and the photoinitiator is used in an amount of 1 to 50% by weight based on the total weight of the component (A) and the component (B) of 1% by weight. 5. The photoresist composition according to item 4 of the patent application, further comprising a further auxiliary agent (D), which is based on a total weight of the component (A) and the component (B) of 100% by mass, and the auxiliary agent (D) The amount used is 0.1 to 5% by weight. 6. The photoresist composition of claim 4, which further comprises a colorant (E), the colorant (E) based on the total weight of the component (A) and the component (B): 1% by weight The amount of use is 7〇~6〇〇% by weight. 7. The photoresist composition according to item 4 of the patent application, further comprising a dispersant (F), relative to the total weight of the component (A) and the component (B) The dispersant (F) is used in an amount of from 3 to 15% by weight based on 100% by weight. The photoresist composition of claim 4, which further comprises a solvent. (G) The solvent (6) is used in an amount of 200 to 2500% by weight based on the total weight percent of the component (A) and the component (9). 30 TP070389