TWI361334B - Radiosensitive resin composition - Google Patents

Description

17256pif.doc IX. Description of the Invention: [Technical Field] The present invention relates to a radiation sensitive resin composition. [Prior Art] A radiation sensitive resin composition can be used as a production having curing characteristics. The raw material of the resin, for example, can be used to produce a thin film transistor (hereinafter referred to as TFT), a TFT type liquid crystal display heat insulating film, a diffusing plate of a reflective TFT substrate, an organic EF insulating film, and a solid-state image sensor (hereinafter abbreviated) Protective film for CCD), etc. (see Japanese Patent No. H09-152625, paragraphs 0001 and 〇〇10). For the cured resin structure, the cross-sectional shape is tapered or gradually thickened or the like. Depending on the different uses described above, there will be different design choices. Therefore, when a certain cured resin is prepared by using a radiation-sensitive resin composition, the structure of the cured resin, that is, its cross-sectional shape must strictly conform to the design requirements. It is known that when a binder resin containing an acrylic acid or methacrylic acid-based alkaline soluble group is used in a conventional radiation-sensitive resin composition, the development range is very narrow. To solve this problem, a polymer with active methylene groups has been used (see JP-B, pp. 06.54382, page 3, left line 15 to the right). Line 17). However, when the above-mentioned polymer is used to prepare a radiation-sensitive resin composition, there arises a problem that the development range is narrow. SUMMARY OF THE INVENTION It is an object of the present invention to provide a radiation sensitive resin composition having a pattern having a broad range of 1361334 17256 pif.doc.

The present invention provides a radiation-sensitive resin composition capable of solving the above problems, and the radiation-sensitive resin composition contains a copolymer composed of two structural units, and a copolymer structural unit consists of an active methylene group. And / or a methine unsaturated compound derived from al, another structural unit derived from an unsaturated compound containing a light and / or heat sensitive reactive group, called a2, this composition Having a Large Development Range 0 Specifically, the present invention provides the contents as described in [1] to [12]. [1] A radiation-sensitive resin composition comprising a copolymer (A) consisting of two structural units, one of which has at least one of the following compounds, i.e., an active methylene group and/or an active methine group ( Active methine groups) derived from unsaturated compounds, called al; another structural unit derived from unsaturated compounds containing light and/or heat sensitive reactive groups, called a2; and quinonediazide Compound (B).

[2] Further, a cationic catalytic polymerization initiator (C) is further added to the radiation-sensitive resin composition described in [1]. [3] The radiation-sensitive resin composition according to [1] or [2], wherein the unsaturated compound which forms the structural unit a1 contains at least one of an active methylene group and an active methine group. The structure of this unsaturated compound is as shown in formula (I) or (Π): R1—X-R2—R—CH2—R4 (I)

(Π) (!) p61334 17256pif.doc In the structural formulae (i) and (Π), R1 is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; R2 is a single bond or contains 1 to 20 carbon atoms a divalent hydrocarbon group; R3 is any divalent group of the formula (1-1) to the formula (1-3);

(1-1) (1-2) (!-3)

R4 is a group of any one of formula (1-4) to formula (1-7);

(1-5) —CN —N〇2 (1-6) (1-7)

In the structural formulae (1-4) and (1-5)', R1 is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms: X is a formula (1-8) or (1-9).

[4] The radiation-sensitive resin composition of any one of [1] to [3], wherein the unsaturated compound having a light- and/or heat-sensitive reactive group forming the structural unit a2 has at least one of the following groups An oxetane-containing unsaturated compound (a21) and an epoxy group-containing unsaturated compound (a22). [5] The radiation-sensitive 7 1361334 17256 pif. doc resin composition of any one of [1] to [4], the moiré of the component (al) and (a2) in the copolymer (A) For 5: 95 to 95: 5. [6] The radiation-sensitive resin composition according to any one of [1] to [5], wherein the copolymer (A) is composed of the following structural unit, and one structural unit contains at least one of the following groups, that is, An unsaturated compound derived from an active methylene group and/or a methine group is referred to as al; the other structural unit is derived from an unsaturated compound containing a light- and/or heat-sensitive reactive group, and is referred to as A2; The third structural unit is formed from a copolymerized compound called a3. [7] The radiation-sensitive resin composition described in [6], wherein the compound forming the structural unit (a3) is at least one selected from the group consisting of maleic imine containing a polymerizable unsaturated carbon-carbon bond. A compound, a carboxylate compound, an aromatic compound, and a vinyl cyanide compound. [8] The radiation-sensitive resin composition according to any one of [6] or [7], wherein the molar percentage of the structural unit a1 in the copolymer A is 15 to 70 mol%, and the structural unit a21 is occupied. The percentage of moir is 20 to 80 mol%, and the percentage of structural unit a3 is 0.01 to 60 mol%. [9] The radiation-sensitive resin composition according to any one of [1] to [8], which further comprises a cationic catalytic polymerization initiator (C) 〇 [10] for the composition described in [9] A radiation-sensitive resin composition in which the weight percentage of the copolymer (A) is 60 to 96.9, and the weight percentage of the quinonediazide (B) is 3 to 30, and the cationic catalytic polymerization initiator (C) accounts for The weight percentage is 0.1 to 10.

8 (D) a cured resin obtained by using any of the radiation-sensitive resin compositions described in [1] to [10]. [12] A liquid crystal display comprising the cured resin according to [11] The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the preferred embodiments of the present invention. The copolymer (A) used in the present invention, a structural unit (hereinafter simply referred to as structural unit a1) is formed by breaking an unsaturated chemical bond of an unsaturated compound, and the unsaturated compound contains at least the following groups. One: an active methylene group or an active methine group, and another structural unit (hereinafter simply referred to as structural unit a2) is derived from an optically or thermally sensitive unsaturated compound. One contains at least one of the following groups : an active methylene group or an active methine group, and the unsaturated compound derived from the structural unit a1 is preferably a compound represented by the formula (I) or (β): X-R2—R^-CH 2 —R 4 (1)

In the formulae (I) and (n), R1 is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms; H2 is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms' 1361334 17256pif.doc R3 represents any one of divalent groups from structural formula (ii) to structural formula (1-3);

(1-1) (1-2) (1.3) R4 represents any one of the groups from the structural formula (1-4) to the structural formula (1-7);

(1-4) (1-5) (4) (1-7) In the structural formulae (1-4) and (1-5), it represents a hydrogen atom or a hydrocarbon group of 1 to 24 carbon atoms; the X structure is a formula ( 1-8) or (1-9).

(1-8) (1-9) The hydrocarbon group having 1 to 24 carbon atoms may be a methyl group, an ethyl group, a propyl group, a butyl group or the like. The divalent hydrocarbon group having 1 to 20 carbon atoms may be a methylene group, a vinyl group, a propenyl group, a butenyl group, a pentylene group, a hexylene group, a cyclized hexylene group, a dicyclopentyl group or the like. In the present invention, the unsaturated compound having an active methylene group or an active methine group which forms the copolymer structural unit (al) may be any of the following: 1361334 17256pif.doc

Preferably, 2-(methylpropoxy)ethyl acetate (formula 17256pif.doc (1)) is used to form a structural unit (al) ° as described above, to form a copolymer structural unit (a2) As the unsaturated compound containing a light- and/or heat-sensitive reactive group, an unsaturated compound containing an epoxy group or an oxetanyl group and an unsaturated group which is sensitive to light and/or heat is preferably used. The unsaturated compound which can form the structural unit a2 includes: glycidyl methacrylate, methacrylic acid-4 monohydroxybutyl ester glycidyl ether, methyl acrylic acid (3 '4-epoxycyclohexyl) methyl ester, 3 —(Meth) propylene methoxymethyl oxetane '3-methyl-3-(meth) propylene methoxymethyl oxetane, 3-ethyl-3-(methyl) Acryloxymethyloxetane '2-phenyl-3-(methyl)propenyloxymethyloxetane, 2-trifluoromethyl-3-(methyl)propene醯oxymethyloxetane, 2-pentafluoroethyl-3-(methyl)propenyloxymethyloxetane, 3-methyl-3-(methyl)propene oxime Ethyloxyoxetane, 3-methyl-3-(meth)propenyloxyethyloxetane, 2-phenyl-3-(methyl)propenyloxyethyloxy Heterocyclobutane, 2-trifluoromethyl-3-(methyl)propenyloxyethyloxetane, 2-pentafluoroethyl-3-(methyl)propenyloxyethyloxy Heterocyclobutane and other similar compounds, preferably 3-(meth) propylene oxime Oxymethyloxetane, 3-methyl-3-(methyl)propenyloxymethyloxetane, 3-ethyl-3-(methyl)propenyloxymethyl Oxetane, 2-phenyl-3-(methyl)propenyloxymethyloxetane 2 -trifluoromethyl-3(meth)propenyloxymethyloxalate Cyclobutane '2-pentafluoroethyl-3-(meth)acrylomethoxymethyl oxetane' 12 17256pif.doc 3_methyl-3-(methyl)propenyloxyethyl Oxetane, 3-methyl-3-(meth)propenyloxyethyloxetane, 2-phenyl-3-(methyl)propenyloxyethyloxetane , 2-trifluoromethyl-3-(methyl)propenyloxyethyloxetane, 2-pentafluoroethyl-3-(methyl)propene, brewing, I-ethyloxycyclohexane Ding Yuan. Other light and/or heat sensitive reactive groups may contain unsaturated chemical bonds. The above unsaturated chemical bond may be an unsaturated double bond and an unsaturated triple bond, and preferably an unsaturated double bond. The unsaturated bond may be introduced into the copolymer (A), for example, a compound having both an unsaturated bond and a carboxyl group in the molecule may be further reacted with the light and/or heat sensitive group of the structural unit (a2) in (A), thereby The copolymer (A) is introduced into a side chain. When methacrylic acid is introduced as the photosensitive and/or heat-sensitive group, it is exemplified as follows. The structural unit (al) derived from an unsaturated compound containing at least one active methylene group or active methine group may react with an unsaturated compound containing at least one of the following groups to form a copolymer: oxetanyl group Unsaturated compound (a21) and epoxy group-containing unsaturated compound (a22) ° The oxetanyl moiety or epoxy moiety of the above copolymer may be reacted with an olefinic acid to introduce a polymerizable double bond, thereby allowing copolymerization The substance (A) introduces a side chain. In the above copolymer, the chemical reaction of xanthene butyl or epoxy group with methacrylic acid, the latter and the former Moerby 値 recommended to use 1:0·05 ～1: 0.95, more preferably 1: 〇. 1~1: 0.5. The amount of methacrylic acid may depend on the final product, i.e., the acidity and alkalinity of the copolymer (A), the molecular weight, or its physical quantity of 1361334 17256 pif.doc. Also, for other compounds having an unsaturated chemical bond and a carboxyl group in the molecule, the copolymer (A) containing a polymerizable double bond can be obtained by a reaction similar to the above reaction. As the unsaturated compound having an oxetanyl group from which the structural unit (a2) can be derived, 3-ethyl-3-methylpropoxymethyl oxetane is preferably used. In the copolymer of the present invention, the compound from which another structural unit (a3) is derived may be copolymerized with the above (al) and (a2). Such a compound is at least one of the following compounds: a carboxylic acid having an unsaturated bond, a maleimide compound, a carboxylic acid ester, an aromatic compound containing a polymerizable carbon-carbon unsaturated bond, and a vinyl cyanide compound. The above maleimide compounds include: N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(ethylidenephenyl)maleimide, N-(2,6-diethylphenyl)male Yttrium, N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, N-succinimide-3-maleimidobenzoate , N_Amber quinone imino-3, maleimide propionate, N-succinimide-4, maleimide butyrate, N-succinimide-4 - maleic acid iminohexanoate, N_(1-anilinophthyl-4)maleimide, N-[4-(2-benzoxazolyl)phenyl]maleimide, N-(9-acridinyl)maleimide and the like and compounds similar thereto. The carboxylic acid ester compound described above includes an unsaturated carboxylic acid ester such as methyl 1361334 17256 pif.doc methyl acrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, benzyl methacrylate. Ester, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate; aminoalkyl unsaturated ester such as aminoethyl (meth) acrylate; vinyl carboxylic acid ester such as vinyl Acid ester, vinyl propionate. The aromatic compounds containing a polymerizable carbon-carbon unsaturated bond as described above include vinyl aromatic compounds such as styrene 'α-methylstyrene and vinyl toluene. The vinyl cyanide compound described above may be acrylonitrile, methacrylonitrile, α-chloromethacrylonitrile or the like. Among these compounds, Ν·cyclohexylmaleimide and Ν-phenylmaleimide are preferably raw materials for introducing the structural unit (a3). In the case of polymerizing (al), (a2) and (a3), the above compounds may be used singly or in combination of plural kinds. Further, the copolymer (A) in the present invention has a structural unit (a5) which is derived from an unsaturated carboxylic acid which does not affect the effects of the present invention. An unsaturated carboxylic acid from which structural unit (a5) can be derived, including acrylic acid 'methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, methyl maleic acid, methyl Fumaric acid or other unsaturated carboxylic acid having a similar structure. The ratio between the different structural units in the copolymer (A) is as follows: The structural unit (al) accounts for 1% to 90% of the total molar amount of all structural units, and the optimum range is 20 to 60%. The structural unit (a2) accounts for 9 〇 15 8 17256 pif.doc 〜 10 of the sum of all structural units, and the optimum range is 25 to 75 percent. When the structural unit (a3) is activated, it accounts for 0.01 to 60 percent of the sum of all structural unit molars, and the optimum range is 0.01 to 45 percent. ^ When the copolymer structural unit (al) and (in the present invention) When the molar percentage of a2) is in the above range, the diffusion speed in the developing solution and the developing edge are both satisfactory, and the higher curing property of the formed structure will make the resin superior. Reliability. The preparation of the copolymer in the present invention can be carried out according to an existing method (e.g., Jp_A No. 2001-302712 or the like). A known amount of a compound, a copolymerization initiator, and a solvent for deriving a desired structural unit of the copolymer may be added to a reaction vessel, and the oxygen in the reactor is replaced by nitrogen, stirred, heated, and maintained at a temperature, and charged. The copolymer described in the present invention can be produced by oxygen. In the present invention, the copolymer of the structural units a1 and a2 or a1 and a3 includes: acetamidineacetic acid 2-(methacryloxy)ethyl ester/methyl propylene succinic acid glycidyl ester copolymer acetamidine acetic acid- 2-(Methethyloxy)ethyl ester/mono(3,4-epoxycyclohexyl)methyl methacrylate copolymer, acetonitrile acetic acid 2-(methacryloxy)ethyl ester/3 _Ethylmethylpropoxymethyl oxetane copolymer, acetamidineacetic acid 2- 2 (methacryloxy)ethyl ester / glycidyl methacrylate / 3-ethyl-methyl Propyloxymethyloxetane copolymer, acetonitrile acetic acid (methacryloxy)ethyl ester/glycidyl methacrylate/methyl propyl succinic acid (3 '4-epoxycyclohexyl) Methyl ester copolymer, acetamidineacetic acid (methacryloxy)ethyl methacrylate/methacrylic acid mono(3,4-epoxycyclohexyl) 1361334 17256pif.doc methyl ester/3-ethyl-3-methyl Propyloxymethyloxetane copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropyl methoxymethyl oxetane Alkane/N-phenyl mala Amine copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-cyclohexylmala Amine copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3 - ethyl 3-methoxypropoxymethyl oxetane / N-benzyl malayan Amine copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3 monoethyl-3-methoxypropoxymethyl oxetane / N-phenyl malayan Amine/styrene copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-cyclohexyl醯imine/styrene copolymer, acetamidineacetic acid-2-(methacryloxy)ethyl ester / 3_ethyl-3-methoxypropoxymethyl oxetane / N- Benzyl maleimide/styrene copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropyl methoxymethyl oxetane /N-phenylmaleimide/cyclohexyl methacrylate copolymer, acetamidineacetic acid 2-(methacryloxyloxy) Ethyl ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-cyclohexylmaleimide / cyclohexyl methacrylate copolymer, acetonitrile acetic acid 1- 2 ( Methyl propylene oxime) ethyl ester / 3 - ethyl - 3 - methyl propyl methoxy methyl oxetane / N - benzyl maleimide / cyclohexyl methacrylate copolymer, Ethylacetate - 2 - (methacryloxy) ethyl ester / 3-ethyl 3-methoxypropoxymethyl oxetane / N-phenyl maleimide / methacrylic acid Methyl ester copolymer, acetonitrile acetic acid 2-(methacryloxy)ethyl ester / 3_ 17 1361334 17256pif.doc Ethyl 3-methylpropoxymethyl oxetane / N-benzene Kamalimide/benzyl methacrylate copolymer, acetonitrile acetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropoxymethyloxycarbonyl Butane/N-cyclohexylmaleimide/benzyl methacrylate copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methoxypropyl oxime Methyl oxetane / N-benzyl maleimide / benzyl methacrylate Copolymer, acetonitrile acetic acid 2-(methacryloxy)ethyl ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-phenylmaleimide /Dicyclopentyl methacrylate copolymer, acetamidineacetic acid - (methacryloxy)ethyl ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-benzyl Kamalimide/dicyclopentyl methacrylate copolymer, acetonitrile acetic acid 2-(3,4-epoxycyclohexylpropenyloxy)ethyl ester / 3-ethyl-3-methylpropane醯oxymethyloxetane/N-phenylmaleimide copolymer, acetamidineacetic acid 2-(3,4-epoxycyclohexylpropenyloxy)ethyl ester / 3-ethyl a 3-methylpropoxymethyl oxetane/N-cyclohexylmaleimide copolymer, acetonitrile acetic acid 2-(3'4-epoxycyclohexyl propylene oxy)B Ester / 3-ethyl-3-methylpropoxymethyl oxetane / N-benzyl maleimide copolymer, and the like. Among them, preferred is acetonitrile acetic acid 2-(methacryloxy)ethyl ester/glycidyl methacrylate copolymer, acetonitrile acetic acid 2-(methacryloxy)ethyl ester/methacrylic acid ( 3,4·epoxycyclohexyl)methyl ester copolymer, acetamidineacetic acid 2-(methacryloxy)ethyl ester/3-ethyl-3-methylpropoxymethyl oxetane An alkane copolymer; most preferably ethylene-2-ylidene 2-(methacryloxy)ethyl ester//3-ethyl-3-methylpropene 1361334 17256pif.doc 醯oxymethyloxetane Copolymer. The average molecular weight in terms of polystyrene is usually from 2,000 to 100,000, preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000, as measured by gel chromatography. While maintaining the residual film ratio at the time of development, when the average molecular weight is lowered within the above range, the development speed is high. In the radiation-sensitive resin composition, the percentage of the total weight of the solid composition of the radiation-sensitive resin composition of the copolymer (A) is preferably from 50 to 90, more preferably from 60 to 90. Here, the radiation-sensitive resin composition solid composition means a radiation-sensitive resin composition excluding a volatile component. In the present invention, the quinonediazide compound (B) includes 1,2-benzoquinonediazide sulfonate, 1,2-naphthoquinonediazide sulfonate, 1,2-benzoquinonediazide sulfonium sulfonate Amine, 1,2-naphthoquinonediazidesulfonamide, and the like. Specific examples include 1,2-naphthoquinonediazide sulfonate of trihydroxybenzophenone, such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate , 2,3,4-trihydroxybenzophenone-; 1,2-naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone Nitro-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc.; 1,2-naphthoquinone of tetrahydroxybenzophenone Azidosulfonate, such as 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2',4,4'-four Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,2',4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate Acid ester, 2,2',4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-four 8 19 1361334 17256pif. Doc hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate Acid ester, 2,3,4,2'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide: 4-sulfonate, 2,3,4,2'-tetrahydroxybenzene Ketone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide 4-sulfonate, 2, 3, 4, 4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc.; pentahydroxybenzoic acid a 1,2-naphthoquinonediazide sulfonate of a ketone, such as 2,3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2, 3,4,2',6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, etc.; 1,2-naphthoquinonediazide of hexahydroxybenzophenone Sulfonates such as 2, 4, 6, 3', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4, 6,3' , 4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 3,4,5,3,4',5,-hexahydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonate, 3,4,5,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate Acid ester, etc.; 1,2-naphthoquinonediazide sulfonate of polyhydroxyphenylalkane, such as bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate Acid ester, di(2,4-dihydroxyl) Methane-1,2-naphthoquinonediazide-5-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, di(p-hydroxybenzene) Methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1 , 2-naphthoquinonediazide-4-sulfonate, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2' - bis(2,3,4-trihydroxyphenyl)propane 8 20 1361334 17256pif.doc -1,2-naphthoquinonediazide·4-sulfonate, 2,2'-di(2,3,4 -Trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate, i,! , 3_tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide_4· sulfonate, 1,1,3-tri 2,5-Dimethyl-4-hydroxyphenyl)·3-phenylpropanol-1,2·naphthoquinonediazide-5-sulfonate, 4,1'-{ΐ_[4-(1 -[4-hydroxyphenyl]-1_methylethyl)phenyl]acetal}diphenol-1,2-naphthoquinonediazide-5-sulfonate, di(2,5-dimethyl 4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2 -hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3',3'-tetramethyl-1,1'-spirobi-5,6,7 ,5,6,7,-hexaol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3',3'-tetramethyl-1, 1'.茚-5,6,7,5',6',7'-hexaol-1,2-naphthoquinonediazide-5-acid vinegar, 2,2,4-trimethyl-7,2' '4'-Di-based fravane-Ι, 2-naphthoquinonediazide-4-sulfonate, 2,2,4-trimethyl-7,2,,4,-trihydroxyfravane-1,2 - Naphthoquinonediazide-5-sulfonate and the like. The above quinonediazide compound (B) may be used singly or in combination of two or more. The percentage of the total weight of the solid composition of the radiation-sensitive resin composition of the quinonediazide compound (B) in the present invention is preferably 2 to 50, more preferably 5 to 40. When the percentage of the quinonediazide compound (B) is in the range described above, the development residual film ratio will increase due to an increase in the difference in the diffusion speed between the unirradiated portion and the irradiated portion. The cationically catalyzed polymerization initiator (C) of the present invention includes a key cation salt. The phosphonium salt is a combination of a key cation and an anion formed by a Lewis acid. 21 1361334 17256pif.doc The key cation salt described above includes a diphenyl iodine gun and a di(p-tolyl) splicing. Specific examples of the above-mentioned key cation include diphenyl iodide, bis(p-tolyl)-determined iron'-(p-tert-butylphenyl), which is identified as 'one (p-octylphenyl) iodine, and two (for ten) Octaphenylphenyl) iodine, bis(p-octyloxyphenyl) iodine gun, di(p-octadecyloxyphenyl) iodine, phenyl p-octadecyloxyphenyl) iodine, p-Tolyl) (p-isopropylphenyl) iron iodide, triphenylsulfonium, tris(p-tolyl)fluorene, tris(p-isopropylphenyl)phosphonium, tris(2,6-dimethylphenyl)镝, tris(p-tert-butylphenyl) fluorene, tris(p-chlorophenyl) hydrazine, dimethyl methoxy hydrazine, dimethyl ethoxy hydrazine, dimethyl propoxy hydrazine, dimethyl Butoxy oxime, dimethyl octyloxy oxime, dimethyl octadecyloxy fluorene, dimethyl isopropoxy hydrazine, dimethyl cyclohexyloxy hydrazine, dimethyl fluoromethoxy hydrazine, Dimethyl (2-chloroethoxy) hydrazine, dimethyl (3-bromopropyloxy) hydrazine, dimethyl (4-cyanobutoxy) hydrazine, dimethyl (8-nitrooctyloxy) Bismuth, dimethyl (10-trifluoromethyloctadecyloxy) hydrazine, dimethyl (2-hydroxyl) Isopropoxy)indole, diphenyl(4-phenylphenylthio)anthracene, diphenyl(4-phenoxyphenyl)fluorene, dimethyl(tris(trichloromethyl)methyl) mirror Wait. Preferred key cations include: bis(p-tolyl) iodine, (p-tolyl) (p-isopropylphenyl) iodine, di(p-tert-butylphenyl) ruthenium, triphenyl guanidine, three (p-tert-butylphenyl) hydrazine and the like. The anionic raw material Lewis acid as described above includes hexafluorophosphoric acid, hexafluoroarsenic acid, hexafluoroantimonic acid, tetrakis(pentafluorophenyl)boron or the like, preferably hexafluoroantimonic acid or tetrakis(pentafluorophenyl)boron. .

22 1361334 17256pif.doc The key cations described above and the anions formed by Lewis acids can be combined as desired. As described above, the cationic polymerization initiator (C) includes a diphenyl iodine hexafluorophosphate, bis(p-tolyl) iodine iron hexafluorophosphate, bis(p-tert-butylphenyl) iodonium hexafluorophosphate, and six Di(p-octylphenyl) iodine fluorophosphate, di(p-octadecylphenyl)iodonium hexafluorophosphate, bis(p-octyloxyphenyl) iodine hexafluorophosphate, hexafluorophosphate Octadecyloxyphenyl) iodine, hexafluorophosphate phenyl (p-octadecyloxyphenyl) iron iodide, hexafluorophosphoric acid (p-tolyl) (p-isopropylphenyl) iodine, hexafluoro Methylnaphthyl phosphate iodine, ethyl cyano iodine hexafluorophosphate, triphenyl sulfonium hexafluorophosphate, tris(p-tolyl) hexafluorophosphate, tris(p-isopropylphenyl) hexafluorophosphate , tris(2,6-dimethylphenyl)phosphonium hexafluorophosphate, tris(p-tert-butylphenyl)phosphonium hexafluorophosphate, tris(p-cyanophenyl)phosphonium hexafluorophosphate, tris(hexafluorophosphate) p-Chlorophenyl)anthracene, dimethylnaphthylphosphonium hexafluorophosphate, dimethylmethoxysulfur hexafluorophosphate, hexafluoro-p-acid monomethylethoxy mirror, hexa-gas dimethyl propyloxy Helium, hexafluoride Acid dimethylbutoxy fluorene, dimethyl octyloxy hexafluorophosphate, dimethyl octadecyloxy hexafluorophosphate, dimethyl isopropoxy hexafluorophosphate, dimethyl hexafluorophosphate Tert-butyloxy oxime, dimethyl(cyclopentyloxy)phosphonium hexafluorophosphate, dimethyl(cyclohexyloxy)phosphonium hexafluorophosphate, dimethyl(fluoromethoxy)phosphonium hexafluorophosphate, six Dimethyl (2-chloroethoxy) fluorophosphate, dimethyl(3-bromopropoxy)phosphonium hexafluorophosphate, dimethyl(4·cyanobutoxy)phosphonium hexafluorophosphate, hexafluoro Dimethyl (8-nitrooctyloxy)phosphonium phosphate, dimethyl (10-trifluoromethyloctadecyloxy)phosphonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) hexafluorophosphate毓, dimethyl hexafluorophosphate (three 23 1361334 17256 pif.doc (trichloromethyl) methyl) hydrazine and the like. Diphenyl iodine hexafluoroarsenate, bis(p-tolyl) iodine hexafluoroarsenate, bis(p-tert-butylphenyl) iodine hexafluoroarsenate, bis(p-octylphenyl) hexafluoroarsenate Iodine gun, hexafluoroarsenic acid di(p-octadecylphenyl) iron iodide, hexafluoro-anthryl acid (block octyloxyphenyl) master key, hexafluoroarsenic acid II Iodine gun, hexafluoroarsenic acid phenyl (p-octadecyloxyphenyl) iodine, hexafluoroarsenic acid (p-tolyl) (p-isopropylphenyl) iodine, hexafluoroarsenate methyl Naphthyl iodonium, ethylnaphthyl iodine hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate bis(p-tolyl) hexafluoroarsenate, tris(p-isopropylphenyl) hexafluoroarsenate镝, tris(2,6-dimethylphenyl)phosphonium hexafluoroarsenate, tris(p-tert-butylphenyl)phosphonium hexafluoroarsenate, tris(p-cyanophenyl)phosphonium hexafluoroarsenate, six Tris(p-chlorophenyl)fluorene fluoroarsenate, dimethylnaphthyl hexafluoroarsenate, diethylnaphthyl hexafluoroarsenate, dimethyl methoxy hexafluoroarsenate, hexafluoroarsenic acid Dimethylethoxy hydrazine, dimethylpropoxy hexafluoroarsenate, dimethyl hexafluoroarsenate Oxime, dimethyloctyloxyphosphonium hexafluoroarsenate, dimethyloctadecyloxyphosphonium hexafluoroarsenate, dimethylisopropoxy ruthenium hexafluoroarsenate, dimethyl hexafluoroarsenate Tert-butoxy fluorene, dimethyl(cyclopentyloxy)phosphonium hexafluoroarsenate, dimethyl(cyclohexyloxy)phosphonium hexafluoroarsenate, dimethyl(fluoromethoxy)phosphonium hexafluoroarsenate , dimethyl(2-chloroethoxy)phosphonium hexafluoroarsenate, di-methyl(3-bromopropoxy)phosphonium hexafluoroarsenate, dimethyl(4-cyanobutyrate) hexafluoroarsenate锍, bis(8-nitrooctyloxy)phosphonium hexafluorophthalate, dimethyl(10-trifluoromethyloctadecyloxy)phosphonium hexafluoroarsenate, dimethyl hexafluoroarsenate (2-hydroxyisopropoxy) hydrazine, hexafluoroarsenic acid dimethyl (tris(trichloromethyl)methyl) mirror, and the like. 24 1361334 17256pif.doc hexafluoroantimonate diphenyl iodine, hexafluoroantimonate di(p-tolyl) iodine, hexafluoroantimonate di(p-tert-butylphenyl) iodonium, hexafluoroantimonate di P-octylphenyl) iodine, hexafluoroantimonate di(p-octadecylphenyl) iodine, hexafluoroantimonate di(p-octyloxyphenyl) iodine, hexafluoroantimonate II (to ten Octaoxyphenyl) iodine gun, hexafluoroantimonate phenyl (p-octadecyloxyphenyl) iron iodide, hexafluoroantimonic acid (p-tolyl) (p-isopropylphenyl) iodine, six Methylnaphthyl iodonium fluoroantimonate, ethylnaphthyl iodine hexafluoroantimonate, triphenyl sulfonium hexafluoroantimonate, tris(p-tolyl) hexafluoroantimonate, hexafluoroantimonate Propylphenyl)anthracene, tris(2,6-dimethylphenyl) hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, tris(p-cyanobenzene)镝, bis(p-chlorophenyl) hydrazine hexafluoroantimonate, dimethylnaphthyl hexafluoroantimonate, diethyl naphthyl hexafluoroantimonate, dimethyl methoxy ruthenium hexafluoroantimonate , dimethyl ethoxy hexafluoroantimonate, dimethyl propoxy ruthenium hexafluoroantimonate, Dimethylbutoxyfluoride fluoroantimonate, dimethyloctyloxy hexafluoroantimonate, dimethyloctadecyloxy hexafluoroantimonate, dimethylisopropoxy ruthenium hexafluoroantimonate, Dimethyl tert-butoxy hexafluoroantimonate, dimethyl(cyclopentyloxy)phosphonium hexafluoroantimonate, dimethyl(cyclohexyloxy)phosphonium hexafluoroantimonate, dimethyl hexafluoroantimonate (fluoromethoxy)anthracene, dimethyl(2-chloroethoxy)phosphonium hexafluoroantimonate, dimethyl(3-bromopropoxy)phosphonium hexafluoroantimonate, dimethyl hexafluoroantimonate 4-cyanobutoxy)indole, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroantimonate, dimethyl(10-trifluoromethyloctadecyloxy)phosphonium hexafluoroantimonate, Dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroantimonate, dimethyl(tris(trichloromethyl)methyl) hexafluoroantimonate, and the like. Tetrakis(pentafluorophenyl)boron diphenyl iodine, tetrakis(pentafluorophenyl)boron 2 25 1361334 17256pif.doc (p-tolyl) iodine, tetrakis(pentafluorophenyl)boron di(p-tert-butyl) Phenyl) iodine, tetrakis(pentafluorophenyl)boronium di(p-octylphenyl) iodine, tetrakis(pentafluorophenyl)boron di(p-octadecylphenyl)iodoferrate, tetrakis(pentafluoro) Phenyl) boron di(p-octyloxyphenyl) iodonium, tetrakis(pentafluorophenyl)boron di(p-octadecyloxyphenyl) iodine, tetrakis(pentafluorophenyl)boron phenyl (pair Octadecyloxyphenyl) iodine, tetrakis(pentafluorophenyl)boron (p-tolyl) (p-isopropylphenyl) iodine, tetrakis(pentafluorophenyl)borylmethylnaphthyl iodide, Tetrakis(pentafluorophenyl)borylethylnaphthyl iodonium, tetrakis(pentafluorophenyl)boron triphenylphosphonium, tetrakis(pentafluorophenyl)boron tris(p-tolyl)anthracene, tetrakis(pentafluorophenyl) Boron tris(p-isopropylphenyl)anthracene, tetrakis(pentafluorophenyl)boron tris(2,6-dimethylphenyl)anthracene, tetrakis(pentafluorophenyl)boron tris(p-tert-butylbenzene)锍, tetrakis(pentafluorophenyl)boron tris(p-cyanophenyl)anthracene, tetrakis(pentafluoro Phenyl) boron tris(p-chlorophenyl)anthracene, tetrakis(pentafluorophenyl)boron dimethylnaphthyl anthracene, tetrakis(pentafluorophenyl)boron diethylnaphthyl anthracene, tetrakis(pentafluorophenyl) Boron dimethyl methoxy fluorene, tetrakis(pentafluorophenyl)boron dimethyl ethoxy fluorene, tetrakis(pentafluorophenyl)boron dimethylpropoxy mirror, tetrakis(pentafluorophenyl)boron Methylbutoxy fluorene, tetrakis(pentafluorophenyl)boron dimethyloctyloxy fluorene, tetrakis(pentafluorophenyl)boron dimethyloctadecyloxy fluorene, tetrakis(pentafluorophenyl)boron Methyl isopropoxy fluorene, tetrakis(pentafluorophenyl)boron dimethyl tert-butoxy fluorene, tetrakis(pentafluorophenyl)boron dimethyl (cyclopentyloxy) fluorene, tetrakis(pentafluorophenyl) Boron dimethyl (cyclohexyloxy) fluorene, tetrakis(pentafluorophenyl)boron dimethyl (fluoromethoxy) fluorene, tetrakis(pentafluorophenyl)boron dimethyl (2-chloroethoxy)锍, tetrakis(pentafluorophenyl)boron dimethyl(3-bromopropoxy)fluorene, tetrakis(pentafluorophenyl)boron dimethyl(4-cyanobutoxy)anthracene, tetrakis(pentafluoro) Phenyl)boron dimethyl 8 26 1361334 17256pif.doc (8-nitrooctyloxy)anthracene, tetrakis(pentafluorophenyl)boron Methyl (1〇-trifluoromethyloctadecyloxy)phosphonium, tetrakis(pentafluorophenyl)boron dimethyl(2-hydroxyisopropoxy)phosphonium, tetrakis(pentafluorophenyl)boron Base (tris(trichloromethyl)methyl) mirror, etc. Preferred is bis(p-tolyl) iodonium hexafluorophosphate, hexafluorophosphate (p-tolyl) (p-isopropylphenyl) iodine gun, bis(p-butylphenyl) hexafluorophosphate, hexafluorophosphate Triphenylphosphonium phosphate, tris(p-tert-butylphenyl)phosphonium hexafluorophosphate, bis(p-tolyl) hexafluoroarsenate, hexafluoroarsenic (p-tolyl) (p-isopropylphenyl) Iodine, bis(p-tert-butylphenyl) iodine hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris(p-tert-butylphenyl)phosphonium hexafluoroarsenate. Di(p-tolyl) hexafluoroantimonate, hexafluoroantimonic acid (p-tolyl) (p-isopropylphenyl) iodine, hexafluoroantimonate di(p-tert-butylphenyl) iodine, six Triphenylphosphonium fluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, tetrakis(pentafluorophenyl)boronium di(p-tolyl)iodine, tetrakis(pentafluorophenyl)boron Tolyl) (p-isopropylphenyl) iodine, tetrakis(pentafluorophenyl)boron di(p-tert-butylphenyl) iodine, tetrakis(pentafluorophenyl)borontriphenylphosphonium, four (five Fluorophenyl) boron tri(p-tert-butylphenyl) hydrazine and the like. More preferred is bis(p-tolyl) iodine hexafluoroantimonate, hexafluoroantimonic acid (p-tolyl) (p-isopropylphenyl) iodine, hexafluoroantimonate di(p-tert-butylphenyl) Iodine, triphenylsulfonium hexafluoroantimonate, tris(p-tert-butylphenyl)phosphonium hexafluoroantimonate, tetrakis(pentafluorophenyl)boronium di(p-tolyl)iodine, tetrakis(pentafluorobenzene) Boron (p-tolyl) (p-isopropylphenyl) iodine gun, tetrakis(pentafluorophenyl)boron di(p-tert-butylphenyl) iodine, tetrakis(pentafluorophenyl)boron triphenyl锍, tetrakis(pentafluorophenyl)boron tri(p-tert-butylphenyl) 8 27 1361334 17256pif.doc spectroscopy and other β-cation catalyzed polymerization initiator (C) accounted for as a percentage of the total weight of the solid composition of the radiation-sensitive resin composition It is usually 0.01 to 10, preferably in the range of 0.1 to 5. When the percentage of the total weight of the solid composition of the radiation-sensitive resin composition is in the above range, the decrease in resolution at the time of heat curing is suppressed due to an increase in the heat curing speed, and the solvent resistance of the cured resin film It will be further improved. The radiation sensitive resin composition usually also contains a solvent (H). The solvent (H) described above includes an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; ethylene glycol dialkyl Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate such as methoxyethanol acetate, ethoxylate Acetyl acetate; acetate of propylene glycol alkyl ether such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, xylene, 1, 3,5-trimethylbenzene; ketones such as methyl ethyl ketone, ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, Cyclohexanol, ethylene glycol, glycerol; esters such as methyl 2-hydroxyisobutyrate, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; Γ-butyrolactone and the like. Among these solvents, methyl 2-hydroxyisobutyrate, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and γ-butyrolactone are preferably used. The solvent (Η) described above may be used singly or in combination of two or more. Solvent (Η) radiant-sensitive resin composition solid state 8 28 17256 pif.doc The percentage of the total weight of the composition is preferably 50 to 95 Å, more preferably 60 to 90. In the present invention, a sensitizer (D) may also be used, including thioxanthone derivatives such as thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethyl Thioxanthone, 2,4-diethylthiazolone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2~cyclohexylthioxanthone, 4_cyclohexylthiazide Tons of ketones, etc.; benzophenone derivatives, such as benzophenone, 4,4,--(-*methyl-methyl)-benzamide (commonly known as Michler嗣), 4, 4'- (Diethylamino)benzophenone (commonly known as Michler ketone), 4,4'-bis(ethylmethylamino)benzophenone or the like. If sensitizer (D) is used, its percentage of the total weight of the solid composition of the radiation-sensitive resin composition is preferably 0.01 to 15, more preferably 0.01 to 10. If the percentage of (D) meets the above requirements, the thermal curing speed of the resin film will be accelerated due to the strengthening action of the cationic catalytic polymerization initiator, the dissolution rate will be suppressed, and the solvent resistance of the cured resin film will be suppressed. It will be further improved. The radiation-sensitive resin composition of the present invention may further contain a polyhydric phenol (E), a crosslinking agent (F), and a polymerizable monomer (G), if necessary. The polyvalent quinone compound (E) preferably contains two or more phenolic hydroxyl groups. The above polyhydric phenol compound (E) includes polyhydric phenols such as trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, and (polyhydroxyphenyl) olefin, which are combined with quinonediazide compound. The compounds mentioned are similar. The polyhydric phenol (E) described above includes a polymer in which the polymerizable monomer is hydroxystyrene. The polyhydric phenol (E) includes a resin obtained by polymerizing hydroxystyrene 17256 pif.doc such as polyhydroxystyrene, hydroxystyrene/methyl methacrylate copolymer, hydroxystyrene/cyclohexyl methacrylate copolymer, hydroxyl group Styrene/styrene copolymer and hydroxystyrene/alkoxystyrene copolymer. Further, the polyhydric phenol (E) can also be obtained by polycondensation of at least one of the following compounds into a novolak resin. These compounds may be: phenol, cresol, calecho acetaldehyde, ketone or other similar compounds. After the polyphenol (E) is obtained, the percentage of the total weight of the solid composition of the radiation-sensitive resin composition is preferably from 〜1 to 40, more preferably from 1 to 25. When the weight percentage reaches this range, the visible light transmittance of the film product is improved. The crosslinking agent (F) described above may be a methylol compound and other similar compounds. The methylol compound described above may be an alkoxymethylated amino resin such as an alkoxymethylated melamine formaldehyde resin or an alkoxymethylated urea-formaldehyde resin. The alkoxymethylated amino resin herein includes a methoxymethylated amino resin-based resin, an ethoxymethylated amino resin, a propoxymethylated amino resin, butoxymethylated ammonia, and the like; The alkoxymethylated urea-formaldehyde resin includes a methoxymethylated urea-formaldehyde resin, an ethoxymethylated urea-formaldehyde resin, a propoxymethylated urea-formaldehyde resin, and a butoxymethylated urea-formaldehyde resin. All of the crosslinking agents (F) described above may be used singly or in combination of two or more kinds. In the radiation-sensitive resin composition, if the crosslinking agent (F) described above is used, the percentage of 1361334 17256 pif.doc in the total weight of the solid composition of the radiation-sensitive resin composition is preferably 0.01 to 15, more preferably It is preferably 0.1 to 1 Torr. When the weight percentage reaches this range, the visible light transmittance of the film product is improved. The polymerizable monomer (G) described above includes a monomer capable of undergoing a cationic polymerization reaction and capable of undergoing a radical polymerization reaction upon heating. It is preferred to use a polymerizable monomer capable of undergoing cationic polymerization. - The above-mentioned monomer capable of radical polymerization contains a polymerizable carbon-carbon unsaturated bond, which may be a monofunctional monomer, a bifunctional monomer or a multifunctional having three or more functional groups The group polymerizes the monomer. These monomers may be used singly or in combination of two or more. Monofunctional polymerizable monomers include, mercaptophenyl carbitol acrylic acid, ester, nonylphenyl carbitol methacrylate, 2-methyl-3-phenoxypropyl acrylate, methacrylic acid 2-Hydroxy-3-phenoxypropyl ester, 2-ethyl ♦ hexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, '2-hydroxyethyl acrylate' methacrylate 2 - hydroxyethyl ester, N-vinyl pyrrolidone, and the like. #双functional group polymerizable monomers include '1' 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethyl propylene acid Ester, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, bisphenol A bis(propylene oxy group) Ethyl)ether, 3-methylpentanediol diacrylate, 3-methylpentanediol dimethacrylate, and the like. The three or multifunctional polymerizable monomers include 'trimethylolpropane triacrylate, trimethylolpropane trimethylpropionate, pentaerythritol tripropylene 1361334 17256pif.doc enoate, pentaerythritol trimethyl Acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethyl propylene vinegar, pentaerythritol pentapropionate, pentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Among the above polymerizable monomers, a bifunctional or multifunctional polymerizable monomer is preferably employed. In particular, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or other similar polymerizable monomer may be used, most preferably dipentaerythritol hexaacrylate. In addition, a dual function group, a multi-functional group, and a single-functional group polymerizable monomer can be used in combination. The monomer which can be subjected to cationic polymerization contains a cationic polymerization function such as a vinyl ether, a propenyl ether, an epoxy group, an oxetanyl group or the like. The vinyl ether group-containing compound includes triethylene glycol diethylene ether 1,4-dimethylol cyclohexane divinyl ether, 4-hydroxybutyl ethylene acid, dodecyl vinyl ether And the like; specific examples of the propylene ether-based compound include 4-(4-propenyloxymethyl) 1,3-dioxolan-2-one; specific examples of the epoxy group-containing compound include bisphenol A type epoxy resin and phenol Phenolic resin type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, etc.; special case of oxetanyl compound Including, bis{3-(3-ethyloxabutyl)methyl}ether, 1,4-di{3-(3-ethyloxabutyl)methoxy}benzene, 1,4_2 {3_(3-Ethyloxabutyl)methoxy}methylbenzene, anthracene, 4_bis{3_(3 ethyloxabutyl)methoxy}cyclohexane, 1,4-di{ 3-(3-ethyloxabutyl)methoxy}methylcyclohexane, 3-(3-ethyloxabutyl)methylated phenol awake resin, and the like. 8 32 1361334 17256pif.doc When the above-mentioned polymerizable monomer (G) is selected, it is preferably in the total weight of the solid composition of the radiation-sensitive resin composition as 〇〇1 to 20 °, if necessary, in the present invention The radiation-sensitive resin composition may contain other structural monoterpenes, such as additives containing a series of properties that improve the adhesion characteristics, such as surfactants, fluororesins, anions, cations, nonionic groups or Other similar surfactants), antioxidants, anti-diffusion accelerators, UV absorbers, adhesion promoters (eg, decane coupling agents), electron donors, and the like. For the preparation of the radiation-sensitive resin composition, the copolymer (A) can be dissolved in the solvent (H), the quinonediazide compound (B) can be dissolved in the solvent (H), and the cationic catalytic polymerization initiator (c) can be dissolved. The solvent (H) and the sensitizer (D) are also dissolved in the solvent (H) to complete. It is also possible to add the solvent (H) to the compound which has been prepared in advance. After all the solutions have been uniformly mixed, the heating method can be used to accelerate the diffusion rate of the solute. In addition, it is recommended to remove the precipitated material by filtration after the compound is uniformly mixed. The screening procedure used should have a pore size of S3 microns, preferably 0.1 to 2 microns. The solvent used in the mixing process described above may be the same or different, and the principle is that the solute is easily dissolved. When the radiation-sensitive resin composition forms a cured transparent resin, for example, the above-mentioned radiation-sensitive resin composition layer (1) is formed on a substrate (2) such as glass (see FIG. 1A); the layer is covered by the mask (3) (1) Perform radiation (4) irradiation for exposure (see Figure 1B); then develop (see Figure 1C) 〇33 8 1361334 17256pif.doc The substrate (2) may be a transparent glass plate, a plastic film, a ruthenium film, etc. . A current loop can be generated on the substrate, such as a TFT or CCD, a color filter or the like. The radiation-sensitive resin composition layer (1) can be formed by, for example, coating a radiation-sensitive resin composition on the substrate (2). The coating operation may be carried out by a spin coating method, an intermediate mold coating method, a roll coating method, a scratch/spin coating method or a knife coating method (also referred to as a wafer coating method or a curtain coating method). The formation of the radiation-sensitive resin composition layer (1) also requires heat (preheating) drying, or heating after coating, and then sent to a vacuum box to be dried to volatilize the solvent and other unnecessary substances therein. Further, the radiation-sensitive resin composition layer (1) described above has a thickness of about 1 to 5 μm. Subsequently, the radiation-sensitive resin composition layer (1) will be irradiated with radiation (4) through the mask (3). The pattern of the mask (3) may depend on the desired pattern of the cured resin. The illumination uses light, which can be g-rays, i-rays, and the like. It is recommended to use a mask aligner or a stepper for the irradiation to make the entire radiation-sensitive resin composition layer (1) uniformly irradiated by radiation. After the exposure, the radiation-sensitive resin composition layer can be subjected to the development operation. This process can be accomplished by agitation, wetting, spraying or other methods that work. Since the developer is in the liquid phase, an alkaline solution is usually employed. The alkaline solution used is an aqueous solution of a basic substance. Such alkaline substances can be either inorganic or organic. Inorganic alkaline substances include sodium hydroxide, potassium hydroxide, hydrogen phosphate 2 8361334 17256pif.doc sodium, sodium dihydrogen phosphate, diammonium phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, cesium phosphate Sodium 'carbonate' potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, and the like. Organic alkaline substances include tetramethylammonium hydroxide, 2-hydroxymethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoisopropylamine, diisopropyl Amine, ethanolamine, and the like. The above basic substances may be used singly or in combination of two or more. 1〜5。 The weight percentage of the alkaline substance is 0.01 to 10, preferably in the range of 0. 1~5. Surfactants such as nonionic surfactants, cationic, anionic surfactants and the like are also included in the liquid developer. Nonionic surfactants include polyoxyethylene derivatives such as polyoxyethylene terephthalyl ether, polyoxyethylene phenyl ether, polyoxyethylene phenyl ether, ethylene oxide/propylene oxide block copolymer; sorbitan Fatty acid esters; polyoxyethylene sorbitan fatty acid esters; polyoxyethylene alkylamines, and the like. Cationic surfactants include amine salts such as natural stearylamine hydrochlorides, quaternary ammonium salts such as twelfth trimethylammonium chloride, and the like. Anionic surfactants include sulfonate salts of higher alcohols such as the sodium salt of dodecyl sulfonate or the sodium salt of oleyl sulfonate; alkyl sulfonates such as sodium dodecyl sulfate, dodecyl Ammonium sulfonate; alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, and the like. These surfactants may be used singly or in combination of two or more. The liquid developer may also contain an organic solvent. These organic solvents can be dissolved in 8 35 17256 pif.doc water' including methanol, ethanol and the like. In the developing process, the resin pattern (5) is formed by the dissolution of the irradiation region (12) (the above-described radiation irradiation region) on the radiation-sensitive resin composition layer (1), but the irradiation region (11) is not irradiated. Without exposure to radiation, this area will not dissolve in the liquid developer during development (see Figure 1C). Since the quinonediazide compound (B) is present in the radiation-sensitive resin composition, the irradiation region (12) is also highly soluble when the radiation-sensitive resin composition layer (1) has been in contact with the liquid developer for a short period of time. With transfer. Further, because of the presence of the diazide-based ruthenium compound (B), the non-irradiation region (11) does not disappear under the condition that the radiation-sensitive resin composition layer (1) is in contact with the liquid developer for a long time. After development with an alkaline material, the sample usually needs to be washed and dried with water. Then, it is necessary to further irradiate the entire resin pattern (5) or a part thereof with a wavelength of 250 to 380 μm. After the resin pattern (5) is treated as described above, it is preferred to carry out a heat treatment (post-baking treatment) to increase the heat resistance and solvent resistance of the final product. The heat treatment may be carried out by further irradiating the resin pattern (5) or a part thereof with a heat pad or a clean electric furnace to heat the substrate. The heat treatment temperature is usually 150 to 250 ° C, and the preferred temperature range is 18 Torr. (: 〜24〇t. The heat treatment duration is usually 5 to 120 min, preferably 15 to 90 min. After heat treatment, the resin pattern (5) will be further cured to a cured resin pattern (6). 1361334 17256pif.doc In a process, the cross section of the cured resin pattern (6) is perpendicular to the radiation sensitive resin composition layer substrate, and the angle between them can be easily changed by changing the amount of radiation, that is, irradiating the entire area or part of the resin pattern (5). The amount of radiation is controlled (for example, by changing the amount of radiation or the light source). It is particularly noted that increasing the amount of radiation of the entire area or part of the pattern of the illuminating resin pattern (5) may result in a cross section of the cured resin pattern (6). Radiation-sensitive resin composition. The increase in the angle Θ between the layers of the substrate is previously 90°, as shown in Fig. 2; it may also cause a change in the cross-sectional shape of the cured resin pattern (6), although this The angle between the cross section and the substrate is still 90°; reducing the amount of radiation of the entire area or part of the pattern of the illuminating resin pattern (5) may result in a cross section of the cured resin pattern (6) and radiation sensitivity. The angle Θ between the substrates of the lipid composition layer is reduced, and its number is 90° before; the cross-sectional shape of the cured resin pattern (6) is also controlled, and the angle between the cross section and the substrate is still 90°. The cured resin pattern (6) obtained by curing the radiation-sensitive resin composition is a very useful cured resin pattern. The cured resin pattern (6) can be used for a TFT substrate, a heat-insulating film with an organic EL element, a CCD protective film, and the like. The cured resin formed by the radiation-sensitive resin composition of the present invention has a broad developing range. The cured resin component formed from the radiation-sensitive resin composition containing the copolymer (A) has a high visible light transmittance, and is suitable for use. For the production of photographic partitions, coatings, microscope filters and organic thermal insulation layers of liquid crystal displays, etc. 8 37 1361334 17256pif.doc Examples The following examples are presented to illustrate the invention, but the scope of application of the invention is not limited thereto. The following contents were added to a 200 ml four-necked flask equipped with a stirring, a condenser and a thermometer, and the oxygen in the flask was replaced with nitrogen. The flask was placed in an oil bath. The internal temperature of the flask was maintained at 75 ° C to 85 ° C, and then continuously stirred for 5 hours under a nitrogen stream I to form a resin solution A1. The weight average molecular weight of A1 measured by polystyrene conversion was 11,000. (Molecular weight distribution: 2.0). Ethylacetate-2-(methacryloxy)oxyethyl ester 20.85g « 3-ethyl-3-methylpropenyloxymethyloxetane 17.94g Lactic acid B Ester 90.51g azobisisobutyronitrile 〇.7g ' The average molecular weight of the product was determined by GPC method using polystyrene scale standard. The experimental conditions were: # Instrument: MLC-8120GPC (manufactured by Tosoh) Column: TSK GEL G4000HXL+TEK -GEL G2000HXL (in series)

Column temperature: 40 ° C Solvent: Tetrahydrofuran Flow rate: l. 〇 ml / min Injection volume: 50 μ1 Monitor: RI 8 38 1361334 17256 pif.doc Test sample concentration: 0.6 wt% (solvent is tetrahydrofuran) Reference material: TSK standard is poly Styrene F-40, F-4, F-1, A-2500, A-500 (manufactured by T〇son Co., Ltd.). As described above, the ratio of the weight average molecular weight to the number average molecular weight of the product measured by polystyrene calibration is called the molecular weight distribution coefficient. Synthesis Example 2 A resin solution A2 was prepared by the method of Synthesis Example 1, except that the composition was changed as shown below. The internal temperature of the flask was 80 to 90 °C. The weight average molecular weight of A2 measured by polystyrene calibration was 12,000 (molecular weight distribution: 2.1). Methacrylic acid 7.10g Cyclohexyl methacrylate 15.86g 3-ethyl-3-methylpropenyloxymethyloxetane 21.71g Ethyl lactate 104_25g Azobisisobutyronitrile 1.06 Example 1 A1 solution 333 parts by weight (100 parts of resin), 20 parts of the diazide oxime compound represented by the following structural formula (22), and 1 part of Sun-Aid ST-100L (produced by SANSHIN CHEMICAL INDUSTRY CO., LTD.) ADEKA OPTOMER SP-172 - part (produced by Asahi Denka Co., Ltd.), 133 parts of γ-butyrolactone, 13 parts of ethyl lactate, all the above materials were mixed at room temperature 23 ° C, then The mixture was subjected to pressure filtration on a polytetrafluoroethylene cartridge with a pore size of 1.0 μηι 8 391 17256 pif.doc program to obtain a radiation-sensitive resin composition^

In the formula, 'Q4 represents the following structural formula (2^).

The surface of the substrate (2) was spray coated with a radiation-sensitive resin composition prepared by the above method, heated by a hot plate, and held at 100 ° C for 2 minutes to form a radiation-sensitive resin composition layer ( 1). The thickness measured by a Lambda Ace VM-8000J thickness gauge manufactured by DAINIPPON SCREEN MFG Co., Ltd. was 2.6 μm (see Fig. 1A for details). Then, through the mask (3), the newly formed radiation-sensitive resin composition layer (1) is irradiated with radiation (4) by using an i-ray stepper (NSR-175517A (NA = 0.5), manufactured by Nikon Corporation). To perform exposure (see Figure 1B). A contact hole was provided on the mask to provide a straight line having a width of 3 μm every 9 μm on the surface of the resin pattern. After irradiation with radiation, it was at room temperature 23. (: The solution was placed in an aqueous solution of tetramethylammonium chloride in an amount of 2·38 for 70 seconds for development, and then washed with 17256 pif.doc purity water and dried. After the development operation, the film thickness of the unirradiated portion was 2.57 micron. The effective sensitivity of the radiation to the protective layer is 120m/cm2 for the small hole with a diameter of 3 microns on the protective layer. After drying, use a deep ultraviolet lamp (wavelength 313nm, intensity 600 mJ/cm2) (UXM) -501MD; produced by Ushio Inc.) The product is then heated in a clean electric furnace at a temperature of 22 ° C for 30 minutes to form a cured resin pattern (6) (see Fig. 1D). (6) The thickness measured by the thickness gauge is 2.3 μm. The angle Θ of the cross section of the cured resin perpendicular to the cured resin substrate is located at the cross-section edge and the substrate surface, and the measured 値 is 60 degrees. The method (but without using a light stepper), a microscopic spectrophotometer (OSP-200; manufactured by Olympus) measured the visible light of the cured resin film on a transparent glass substrate (# Π 37; manufactured by Coning) The light transmittance is measured by a thickness gauge (DEKTAK3; manufactured by ULVC Co., Ltd.). The cured resin film measured by the above method has a visible light transmittance of 99.5% per micrometer under irradiation with a wavelength of 400 to 750 nm. Therefore, the cured resin film exhibited high visibility and no color development was found. Comparative Example 1 Radiation-sensitive resin compounds were obtained in the same manner as in Example 1, except that they used different solutions, and Example 1 employed a resin solution A1, For example, the resin solution A2 was used. 'Because of the same operation procedure as in Example 1, the film thickness was 2.60 1361334 17256 pif.doc micron before development, and the film thickness of the unirradiated area after development was 1.70 μm. It can be seen that the film thickness before and after development was improved. The large variation indicates that the film has a narrow development range. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and those skilled in the art without departing from the spirit and scope of the present invention. In the meantime, when some changes and refinements can be made, the scope of protection of the present invention is defined by the scope of the patent application attached. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A to Fig. 1D show a flow chart for preparing a transparent film using a radiation sensitive resin composition. Fig. 2 shows an angle between a cross section of a cured resin cross section and a plane of the substrate. Θ is 90. [Main component symbol description] 1 : Radiation sensitive resin composition layer 11 : Unirradiated area: Irradiation area 2 : Substrate 3 : Mask 4 : Radiation 5 : Resin pattern 6 : Cured resin pattern θ : The angle between the cross-section edge of the hardened resin and the plane of the substrate 8 42

Claims (1)

136133 Zhihe Yuebo Correction Toxic j 4 17256pif.doc is the 94th No. 1165 Chinese patent scope without a slash correction This revision period: December 15th, 100. Patent scope: 1·-radiation sensitive resin The composition comprises: a copolymer (A) comprising acetoacetic acid-2-(methacryloxy)ethyl ester as a structural unit (al), and derived from a light- and/or heat-sensitive reactive group a structural unit (a2) of an unsaturated compound; and a quinonediazide compound (B). 2. The radiation-sensitive resin composition as described in claim 1 further comprising a cationic polymerization initiator (C). 3. The radiation-sensitive resin composition according to claim 1 or 2, wherein the unsaturated compound containing the light- and/or heat-sensitive reactive group of the structural unit (a2) is at least contained An unsaturated compound selected from the group consisting of an oxetanyl unsaturated compound (a21) and an epoxy group-containing unsaturated compound (a22). 4. The radiation-sensitive resin composition according to claim 1 or 2, wherein the molar ratio of the structural unit (al) to the structural unit (a2) in the copolymer (A) is 5: 95 ~95: 5. 5. The radiation-sensitive resin composition according to claim 1 or 2, wherein the copolymer (A) is composed of a structural unit (al), a structural unit (a2) and a structural unit (a3), the structure The unit (a2) is derived from an unsaturated compound containing a light- and/or heat-sensitive reactive group, and the structural unit (a3) is derived from a copolymerized compound. 6. The radiant-sensitive resin composition according to claim 5, wherein the compound forming the structural unit (a3) is at least in the range of the Chinese patent of No. 121165. Wire Correction This correction date is a compound selected from the group consisting of an amine compound, a carboxylate compound, a polymerizable carbon-carbon unsaturated bond aromatic compound, and a vinyl nitrile compound on December 15, 100. 7_ The radiant-sensitive resin composition as described in claim 3, wherein the structure mono- (al), structural unit (a2l), and structural unit (a3) account for the total number of moles of the copolymer (A) The percentage of ears is 15 to 70 mol%, 20 to 80 mol%, and 〇.〇1 to 60 mol%. 8. The radiation-sensitive resin composition according to claim 2, wherein the copolymer (A), the quinonediazide compound (B) and the cationic polymerization initiator (C) respectively constitute a solid-state radiation-sensitive resin composition. The total weight of the object is 60 to 96.9%, 3 to 30%, and 0.1 to 1% of the summer. 9- A cured resin pattern which is produced by using the radiation-sensitive resin composition described in any one of claims 1 to 8. A liquid crystal display device characterized by containing the cured resin pattern described in claim 9 of the patent application. 44