TW200937123A - Resist material and laminate - Google Patents

Abstract

Disclosed is a resist material which enables formation of a white resist film having high resolution, high solder reflow resistance and high reflectance. The resist material is also capable of forming a resist film which is hardly discolored from white to other colors when exposed to high temperatures or irradiated with light. Specifically disclosed is a resist material which is used for forming a resist film for a light-emitting diode device that emits light having a wavelength of not more than 800 nm. The resist material contains a siloxane polymer and a white filler.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist film formed in, for example, a light-emitting diode element in which a light-emitting diode wafer is laminated on a substrate having a resist film formed on its upper surface. A resist material and a laminate having a resist film formed using the resist material. [Prior Art] Previously, anti-corrosion films and the like have been widely used as protection layers for printed circuit boards, etc. In order to form the above solder resist film, a solder resist material is used. As an example of the above-mentioned solder resist material, the following patent document discloses a solder resist material containing an ultraviolet curable prepolymer as an acrylate compound, and an ultraviolet curable prepolymer, an organic polydecane oxide. And the reaction product of the aluminum chelate. Among the solder resist materials, calcium sulphate calcium carbonate, fine talc powder, bentonite, fine cerium oxide, clay, kaolin or fine asbestos may be blended as a pigment. By using the above-described solder resist material to form a solder resist film, heat resistance can be improved. ❹ Furthermore, in recent years, light-emitting diodes (hereinafter referred to as LEDs (LED) are attracting attention. In the LED element, for example, an LED b plate is laminated on a printed circuit board having a resist film formed on its upper surface. A terminal for supplying power is provided on the LED chip. The terminals of the LED chip are connected to the electrodes on the printed circuit board by, for example, solder or gold. Among the LED elements, it is desirable to effectively utilize the light emission of the LED wafer. Therefore, as the resist film, a white resist film capable of reflecting light from the LED chip with a high reflectance is preferable. 137746.doc 200937123 As an example of a resist material for forming the white resist film, Patent Document 2 listed below discloses a resist material containing an epoxy resin and a hydrolyzable alkoxysilane. An alkoxy-containing decane-modified epoxy resin obtained by a dealcoholization reaction, a polycarboxylic acid resin containing an unsaturated group, a diluent, a photopolymerization initiator, and a hardening adhesion-imparting agent. The white resist film formed using the resist material is less susceptible to yellowing even when exposed to a high temperature. Patent Document 3 discloses a solder resist material containing a carboxyl group-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, rutile type titanium oxide, and a diluent. The solder resist material is a thermosetting or photocurable resist material. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the solder resist material disclosed in the above Patent Document 1 is used, it is possible to form a solder resist film excellent in heat resistance. However, since the above-mentioned solder resist material contains an acrylate compound as a main component, even if it is a white solder resist film in an initial state, yellowing may occur if it is exposed to a high temperature. Therefore, the solder resist material disclosed in the above Patent Document 1 is not suitable for forming a white solder resist film of an LED element. The white resist film formed by using the resist material disclosed in Patent Document 2 is relatively less susceptible to yellowing even when exposed to high temperatures. The anti-contact agent material contains a decane modified epoxy resin containing an alkane 137746.doc 200937123 oxy group modified with an alkoxy decane as a main component β. Therefore, if exposed to reflow, etc. 20 (rc) The above-mentioned high temperature may cause yellowing of the anti-money film. The white solder resist film formed by using the solder resist material disclosed in the above Patent Document 3 contains an epoxy compound. Therefore, if it is exposed to reflow, etc. 〇 〇 〇 〇 〇 〇 〇 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀 抗蚀a material for a coating, and a laminate having a resist film formed using the resist material. According to the present invention, a resist material for forming light having a wavelength of 800 nm or less can be provided. The resist element of the LED element includes a siloxane polymer and a white filler. In a specific aspect of the resist material of the present invention, the above siloxane polymer is obtained by the following formula 1) represented by the obtained at least one polymeric silicon compound of Silane siloxane polymer.

Si(x)P(R)4-P·. (1) In the above formula (1), X represents a hydrolyzable group, R represents a non-hydrolyzable organic group having a carbon number of 丨-decal, and p represents 丨. An integer of ~4. When p is 2 to 4, a plurality of Xs may be the same or different. When 卩 is i or 2, the plurality of feet may be the same or different. In another specific aspect of the resist material of the present invention, the above siloxane polymer is a cyclic ether group-containing oxirane polymer. The above oxime-oxygenated polymer having a cyclic ether group is An alkane polymer obtained by polymerizing 137746.doc 200937123, wherein p in the formula (1) is an integer and at least one R is a decane compound having an organic group having a cyclic ether group. Further, in other specific aspects of the resist material of the present invention, the above-mentioned rock-oxygenated polymer having a cyclic bond group has an organic group directly bonded to a carbon atom on the stone atom, and the organic group is 10~ 80% has a cyclic ether group. In other specific aspects of the resist material of the present invention, the above-mentioned organic group having a cyclic group has an organic group having an epoxycyclohexane skeleton. In still another specific aspect of the resist material of the present invention, the above-mentioned rock-alkali-oxygenated polymer having a ring-shaped base has an organic group directly bonded to a carbonogen® on a stone atom, and the organic The base 1G ~ 嶋 has an epoxy ring burnt bone _ frame. In another specific aspect of the resist material of the present invention, the decane compound 100 represented by the above formula (1) is represented by the above formula (1) and wherein p in the above formula (1) is The content of the decane compound of 2 is in the range of 2 Å to 1 Torr. Other specific aspects of the resist material of the present invention further include a resin having a acid liver group or a thiol group and an unsaturated double bond. Further, in other specific aspects of the resist material of the present invention, the product of the solid content acid value (mg KOH/g) of the resin component and the epoxy equivalent (g/eq) of the resin component is in the range of 25,000 to 100,000. Further, in other specific aspects of the resist material of the present invention, a photoradical generator is further contained. Further, in other specific aspects of the resist material of the present invention, the photoacid generator is further contained. In other broad aspects of the etchant material, a resist 137746.doc 200937123 material is provided which contains photopolymerization of at least one oxirane represented by the following formula (1). Starting agent and white material, the above formula (1) At least one of the cerium-smelting compounds is a decane compound represented by the following formula () and having a mouth in the following formula (1), and the above-mentioned weight average molecular weight of the oxyalkylene polymer is in the range of 1,000 to 50,000. Si(x)P(R)4-P.. Formula (1) In the above formula (1), 'X represents a hydrolyzable group, R represents an organic group having a carbon number of (4), and p represents an integer of Bu. When it is 2 to 4, the plurality of X may be the same or different. When it is ..., the plurality of R may be the same or different. 0 In a specific aspect of the anti-money material of the present invention, the above formula (1) The total content of the decane compound is 100 m〇l%*, and the content of the decane compound represented by the above formula (1) and P in the above formula (1) is 2 to 1 〇〇. The anti-(four) 丨 of the present invention The other sample of the material, the oxy-fired polymer containing the oxy-oxygenated polymer having an unsaturated double bond, and the above-mentioned oxaxy-oxygenated polymer having an unsaturated double bond is obtained by the above formula (1) p is an integer of U, and at least one R is a siloxane polymer obtained by polymerizing a luminescent compound having an organic group having an unsaturated double bond. Further, in the other specific state of the anti-reagent material of the present invention, the above-mentioned and the unsaturated double-bonded oxime-oxygenated polymer has an organic group directly bonded to a cerium atom: a carbon atom, and the organic group 5 to 8 % by weight of the unsaturated double bond. In still other specific aspects of the anti-money agent material of the present invention, the above-mentioned alkaloid I37746.doc 200937123 alkane polymer contains an acid anhydride group or a carboxyl group, and an unsaturated double bond. The oxirane polymer, the above-mentioned oxirane polymer having an acid anhydride group or a carboxyl group, and an unsaturated double bond is obtained by making 卩 in the above formula (1) an integer of 丨 〜3 and at least one R having an acid anhydride The decane compound of the organic group of a group or a carboxyl group is a oxoxane polymer obtained by polymerizing a decane compound in which the p in the above formula (1) is an integer of 1 to 3 and at least one R is an organic group having an unsaturated double bond. In other specific aspects of the resist material of the present invention, the above-mentioned oxirane polymer having an acid anhydride group or a carboxyl group and an unsaturated double bond has an organic group to which a carbon atom is directly bonded to a ruthenium atom ©, and The organic group is 1 to 25. /. There is an acid anhydride group or a carboxyl group, and 5 to 8 % by weight of the organic group has an unsaturated double bond. In another specific aspect of the resist material of the present invention, the above siloxane polymer comprises a siloxane polymer having a cyclic ether group, and the above-described oxirane polymer having a cyclic ether group is The p-oxane polymer obtained by polymerizing the decane compound in which the p in the formula (1) is an integer of 丨3 to 3 and at least one R is an organic group having a cyclic ether group. Further, in other specific aspects of the resist material of the present invention, the above-mentioned oxo-oxygenated polymer having a cyclic fluorenyl group has an organic group directly entangled with a carbon atom on the cerium atom, and the organic group 5 to 8 % by weight has a cyclic ether group. In another specific aspect of the resist material of the present invention, the above-mentioned oxoxane poly η 3 has a siloxane polymer having an acid anhydride group or a carboxyl group, an unsaturated double bond, and a cyclic ether group, and the above has an acid anhydride group. Or a carboxyl group, an unsaturated double bond, and a cyclic oxyalkylene polymer are obtained by making ρ in the above formula (1) an integer of 1 to 3 and at least one R is an organic group having an acid anhydride group or a carboxyl group. The calcined CT article wherein p in the above formula (1) is an integer of 1 to 3 and at least one R is a decane compound having an organic group having an unsaturated double bond, and P in the above formula (1) is An alkoxysilane polymer obtained by polymerizing a decane compound having an integer of 1 to 3 and at least one of an organic group having a cyclic ether group. In still other specific aspects of the resist material of the present invention, the above-described oxirane polymer having an acid anhydride group or a carboxyl group, an unsaturated double bond, and a cyclic ether group has a carbon atom directly bonded to a ruthenium atom. The organic group has 1 to 25% of the organic group having an acid anhydride group or a carboxyl group, and 5 to 8 % by weight of the organic group has an unsaturated double bond, and 5 to 8 % by weight of the organic group has a cyclic ether group. ► In other specific aspects of the resist material of the present invention, the product of the solid content acid value (mg KOH/g) and the epoxy equivalent (g/eq) of the resin component is in the range of 30,000 to 500,000. In still another specific embodiment of the resist material of the present invention, the content of the white filler is from 150 to 1000 parts by weight based on 1 part by weight of the above-mentioned oxy-oxygenated polymer. The laminate of the present invention comprises a printed circuit board and a resist film deposited on the surface of the printed circuit board and formed by using a resist material formed in accordance with the present invention (effect of the invention) Since the resist material of the present invention contains a siloxane polymer and a white filler, a white resist film can be formed, for example, by applying a resist material on a substrate and performing exposure. Further, the resist film has high heat resistance. Therefore, when the resist film is exposed to a high temperature, it is difficult to cause discoloration from white. Therefore, by using the resist material of the present invention to form a resist film of an LED element, light from the LED chip can be efficiently reflected, thereby improving the conversion efficiency of the light of the LED element. When the siloxane polymer contains a siloxane having a cyclic ether group, and the above-mentioned oxirane polymer having a cyclic ether group is an integer of 1 to 3 by the above formula (1) and at least When a decane compound obtained by polymerizing a decane compound having an organic group having a cyclic ether group is formed, a resist film which is less likely to be discolored from white even when exposed to the same dish can be formed. Further, it is possible to form a resist film which is less likely to be discolored from white even when it is irradiated with light. When the organic group having a cyclic ether group is an organic group having an epoxycyclohexane skeleton, an anti-surname film which is less likely to be discolored from white even when exposed to a high temperature can be formed. Further, it is possible to form a resist film which is less likely to be discolored from white even when irradiated with light. According to other broad aspects of the present invention, the resist material contains a siloxane polymer, a photopolymerization initiator, and a white filler obtained by polymerizing the above specific decane compound, and the weight of the oxime polymer is averaged. Since the molecular weight is in the range of 7,000 to 50,000, the developability is excellent. Further, by applying the anti-residue material of the present invention to a substrate and performing exposure, a white resist film having high reflow resistance and high reflectance can be formed. By forming the resist film of the LED element using the anti-caries material of the present invention, light from the LED chip can be efficiently reflected, thereby improving the electro-optical conversion efficiency of the LED element. When the resist film formed by using the resist material of the present invention is exposed to light at a south temperature or the like, or when it is irradiated with light, it is less likely to cause discoloration from white, and the reflectance is not easily lowered. [Embodiment] 137746.doc -10- 200937123 Hereinafter, the details of the present invention will be described. The anti-money agent material of the present invention contains a rock oxide polymer and a white filler. (a siloxane polymer) The above-mentioned oxaxy oxy-polymer is a compound obtained by polymerizing at least one of the following formula (1), and the compound can be used only for one type; It is also possible to use two or more types of the first oxygen-containing compound in combination of two or more types. ❹

Si(X)P(R)4-p." Formula (1) wherein X represents a non-hydrolyzable group, a non-hydrolyzable organic group having a carbon number of 1 to 30, and p represents an integer of Η . When plural, they may be the same or different. When p is 1 or 2, the plural commissions may be the same or different. The X in the above formula (1) is usually a group which is heated to room temperature (10) to (10) in the presence of excess water in the absence of a catalyst. (d), hydrolysis based. The condensed water can form a sulphuric oxygen bond. Examples of the hydrolyzable group include a burnt base. The oxy group having a carbon number of 1 to 6 may be exemplified as the oxy group of the compound. The alkoxy group having 1 to 6 carbon atoms may, for example, be a methoxy group, an ethoxy group or a propoxy group. j = the cleavable group may be a hydrolyzable group other than the morpho oxy group, and examples of the hydrolyzable group other than the saponin group include a dentate group such as a gas or a hydrazine group, an acetamino group, a hydroxyl group or an isocyanate group. . The non-hydrolyzable organic group is an organic group having a carbon number of 1 to 3 Å which is a hydrophobic group which is hard to be hydrolyzed and stabilized. 137746.doc •11· 200937123 The above-mentioned organic group having a carbon number of 丨% is exemplified by an alkyl group having a carbon number of 丨~3〇, an alkyl group, an aromatic substituted alkyl group, an aryl group, and a vinyl group. The organic group, the organic group containing an epoxy group, the organic group containing an amine group, or an organic group containing a mercapto group or the like. Examples of the alkyl group having a carbon number of 丨~" include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, a pentyl group, a decyl group, a dodecyl group, and a tetradecyl group. Cetyl group, octadecyl group, eicosyl group, etc. Examples of the above-mentioned dentate alkyl group include a fluorinated alkyl group, a vaporized alkyl group or a brominated alkyl group. Examples of the aromatic-substituted alkyl group include a 3-benzyl group, a 6-propyl group, a 6-cyclohexyl group, and a 6,6,6-trifluorohexyl group. Examples of the aromatic substituted alkyl group include a benzyl group and a benzobenzyl group. Examples of the benzobenzyl group include a 4-benzylidene group and a 4-bromobenzyl group. Examples of the aryl group include a phenyl group, a fluorenylphenyl group, a decyl group, a naphthyl group, and the like. Specific examples of the decane compound to be represented include, for example, triphenylethoxy decane, tridecyl ethoxy decane, triethyl ethoxy decane, triphenyl methoxy decane, and triethyl hydrazine. Base decane, ethyl dimethyl methoxy decane, decyl diethyl methoxy decane, ethyl dimethyl ethoxy decane, methyl diethyl ethoxy decane, Dimethyl methoxy oxime, stupidyl diethyl methoxy (tetra), phenyl: methyl ethoxy shixi, phenyl diethyl ethoxy decane, methyl diphenyl methoxy decane , ethyl diphenyl methoxy decane, decyl diphenyl ethoxy decane, ethyl diphenyl ethoxy decane, third butoxy trimethyl decane, butoxy trimethyl decane, Methyl ethoxy decane, methoxy dimethyl vinyl decane, ethoxy dimethyl vinyl decane, diphenyl diethoxy decane, phenyl diethoxy fluorene 137746.doc 12 200937123 alkane, Dimethyldimethoxy decane, diethyl methoxy decyl decane diethoxy methyl decane, 3-cyclopropyl dimethoxymethyl decane, gas methyl diethoxy methyl decane, two Ethoxy dimethyl decane, = ethoxycarbonyl methyl vinyl decane, diethoxy methyl vinyl decane, diethoxy diethyl decane, dimercapto dipropoxy decane, dimethoxy Methyl phenyl decane, methyl trimethoxy decane, methyl triethoxy decane, decyl _ tri-n-propoxy decane, ethyl trimethoxy decane, ethyl triethoxy Base decane, ethyl tri-n-propoxy decane, propyl trimethoxy decane, propyl triethoxy decane, propylene 1- 1-tri-n-propoxy decane, butyl trimethoxy decane, butyl triethyl Oxydecane, butyltripropoxydecane, isobutyltrimethoxydecane isobutyltriethoxydecane, isobutyltripropoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxy Decane, n-hexyltripropoxydecanecyclohexyldimethoxydecane, cyclohexyltriethoxydecane, cyclohexyltripropoxydecaneoctyldimethoxydecane, octyltriethoxydecane, octyl Tripropoxydecane, dodecyltrimethoxydecane, dodecyltriethoxysulfonium alkane, undecyldipropoxydecane,tetradecyltrimethoxydecane, fourteen yards Triethoxy zephyr, tetradecyl tripropoxy sulphate, hexadecanyl if 1 hydrazine & hexadecyltriethoxy hydrazine & hexadecyltripropoxydecane , octadecyltrimethoxy decane, octadecyltriethoxy decane, octadecyldipropoxydecane, eicosyltrimethoxy decane Twenty-octyl diethoxy zephyr, decantyl tripropoxy zebra, 6 hexyl methoxy decane, 6,6,6-trifluorohexyltrimethoxy decane, benzyl trimethoxy矽, 4- benzyl benzyl trimethoxy decane, 4-bromobenzyl-tri-n-propoxy oxalate, stupid dimethoxy oxime, phenyl triethoxy sulphur, ethylene 137746.doc • 13· 200937123 Trimethoxy dream, B suspected base = Yimei feces #师丞oxydecane, γ-glycidoxypropyltrimethoxy zexi, γ-mercaptopropyloxypropyltriethyl Alkyloxy, Ν-β-(aminoethyl)aminopropyltrimethoxy)aminopropyltriethoxy ketone, γ.aminopropyl trisole, γ-aminopropyltri Ethoxylated sulphur, methyl triethyl ethoxylate, Ethyl ethoxylate, Ν·β·phenylaminopropyltrimethoxy sulphide, γ _ propyl propyl Oxygen I, γ-benzyl propyl trimethoxy (tetra), triethyl hexadecane, trimethoxy decane, triisopropoxy decane, tri-n-propoxy decane, triethoxy decane, tetramethyl Oxydecane, tetraethoxy oxime Tetra-n-propoxy zephyr, tetraisopropoxy zexi, tetraethyl ethoxylate, M3,4-epoxycyclohexyl)ethyltrimethoxy oxime & 2,34 epoxycyclohexyl Ethyltrimethoxydecane, 3' glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl fluorenyl = ethoxy ishixiyuan, 3_glycidoxypropyl triethoxy Decane, triethoxydecyloxypropoxybutane, dimethoxydecyloxypropoxybutane, p-styryltrimethyloxydecane, 3-methylpropenyloxy Propylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropenyloxypropylmethyldiethoxylate, 3-methylpropene Oxyl propyl triethoxy oxalate, 3 · propylene methoxy propyl trimethoxy decane, hydrazine 2 (aminoethylamino propyl methyl dimethoxy decane, Ν 2 (aminoethyl) )_3_Aminopropyl dimethoxydecane, anthracene-2-(aminoethyl)_3_aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3•amino group Propyltriethoxydecane, 3-diethoxy矽alkyl_ν_(1,3·didecyl-butylene)propylamine, Ν_phenyl-3-aminopropyltrimethoxydecane, 3-ureidopropyltriethoxyphosphonium 137746.doc 200937123 , 3-mercaptopropyl decyl decyloxydecane, 3-mercaptopropyltrimethoxy zeoxime, 3·mercaptopropyltriethoxy decane, 3-isocyanatepropyltriethoxy decane or 3-(trimethoxydecyl)propyl succinic anhydride trimethoxy fluorene, 3-vinyloxypropyl trimethoxy decane or 3 · glycidoxypropyl decyl dimethoxy decane. More preferably, the above-mentioned aromatized polymer is an alkoxydecane condensate obtained by condensing an alkoxydecane. Further, it is preferred that at least one X in the above formula is an alkoxy group, the decane compound is an alkoxy decane, and the oxirane polymer is an alkoxy decane condensate obtained by condensing the alkoxy decane. When these alkoxydecane condensates are used, the heat resistance of the resist film can be further improved. When an alkoxydecane condensate is obtained, one type of alkoxy oxime may be used, or two or more types may be used in combination. The decane compound represented by the above formula (1) is preferably an alkoxy group > pentane represented by the following formula (1A). The alkoxysilane polymer is preferably an alkoxydecane condensate obtained by condensing an alkoxydecane represented by the following formula (1A). Si(Rl)s(R2)t(R3)4-s_t Formula (1A) In the above formula (1A), 'R1 represents hydrogen or a non-hydrolyzable organic group having a carbon number of 丨~, and R2 represents an alkoxy group. , Rule 3 represents a hydrolyzable group other than the alkoxy group, s represents an integer of 0 to 3, and t represents an integer of 1 to 4, and s + t$4. When s is 2 or 3, the plural R1s may be the same or different. When (2 to 4), the plurality of R2 may be the same or different. When s + g 2 , the plurality of R3 may be the same or different. R2 and R3 in the above formula (1A) are usually as follows: under the condition of excess water coexistence and without catalyst, 'heating to room temperature (25〇c)~1〇〇, 137746.doc • 15- 200937123, which can be hydrolyzed to form a group of the base group; or further condensed to form a group of a hydrazone bond. As R2 in the above formula (1A), a calcination as exemplified in the above formula (1) In the above formula (1A), a hydrolyzable group other than the alkoxy group which is exemplified as the X in the above formula (1), and R1 in the above formula (1A) can be mentioned. The non-hydrolyzable organic group of the same formula R in the above formula (1). The above-mentioned alkoxysilane polymer preferably contains a rhodium oxide polymer having a cyclic ether group. The alkane polymer is preferably a decane which is an integer of U in the above formula (1) and which is an integer of U and at least one of which is an organic group having a ring 2 ether group. The oxirane polymer obtained by polymerizing a compound can further improve the heat resistance of the resist film when it contains a siloxane polymer having a cyclic ether group. The cyclic ether group is preferably an epoxy group. The organic group (4) is an organic group having an epoxycyclohexane skeleton. The organic group having a cyclic ring group is preferably an organic group having an anthracene epoxy ring. The Xixi oxygen-fired polymer is preferably a stone-oxygenated polymer having a 2-epoxy ring hexagram skeleton. The above-mentioned money-burning polymer having an epoxy ring hexanin f frame is preferably obtained by making the above formula (1) Wherein P is an integer and at least one R is an anthrax oxidized polymer obtained by polymerizing a ceramsite-containing material having an organic group of an epoxy ring-fired skeleton. When it contains an oxygen having an epoxy Z-hexane skeleton In the case of an alkane polymer, the thermal properties of the resist film can be further improved. Preferably, the above-mentioned cyclooxygenated polymer having a cyclic ether group has an organic group to which a carbon atom is directly bonded to a germanium atom, and the organic group is 137746.do< -16· 200937123 10~80% has a cyclic ether group. When the ratio of the organic group of the base is less than 10%, the compatibility of the siloxane polymer with other components is lowered. When the ratio of the organic group having a cyclic ether group exceeds 80%, there is a film resistant to the film. In the case where the financial durability is lowered, it is preferred that the above-mentioned naphthenic polymer having a cyclic ether group has an organic group to which a carbon atom is directly bonded to a ruthenium atom, and the organic group has -10 80/0 Epoxy cyclohexane skeleton. When the proportion of the organic group having an epoxycyclohexane skeleton is less than 10%, there is a case where the compatibility of the siloxane polymer with other components β < When the ratio of the organic group of the hexane skeleton exceeds 80%, the durability of the resist film may be lowered. The decane compound represented by the above formula (1) is 1 〇〇 m 〇 1% in the above formula (1) and in the above formula G). The content of the decane compound of 2 is preferably in the range of 5 to 100 mol%, more preferably in the range of 2 〇 to 1 〇〇 m〇i%. What is represented by the above formula (1) and in the above formula (1)? When the amount of the material is too small, the crack resistance of the resist film is lowered. Further, when Φ is a total of 100 m〇l% of the decane compound represented by the above formula (1), which is represented by the above formula (1) and in the above formula (1)? When the content ratio of the decane compound of 2 is less than mG1%, at least two kinds of the money compounds represented by the above formula (1) are used. The weight average molecular weight of the above siloxane polymer is preferably in the range of from 2,000 to 50,000, more preferably in the range of from 2 to 嶋. When the weight average molecular weight of the oxalate polymer is too small, there is a case where the resist film exhibits a more viscous property. When the weight average molecular weight of the Shixi oxygenated polymer is too large, the compatibility of the polymer with other components is reduced. 137746.doc -17- 200937123 Shape. The at least one decane compound represented by the above formula (1) contains the cerium compound represented by the above formula (1) and 4 in the above formula (1). In the total of 100 mol% of the decane compound represented by the above formula (1), it is preferred that the content of the decane compound represented by the above formula (丨) and p in the above formula (丨) is 5 to 1 〇〇m. In the range of 〇i%2, it is better that the content is in the range of 2〇~1〇〇1%. When the amount of the pA2 and the elemental bismuth in the above formula (1) is too small, the heat-resistant cracking resistance of the anti-supplement film is further reduced, and the total decane compound represented by the above formula (1)丨〇〇m〇l% in the above formula (1) and in the above formula (1)? The content of the decane compound of 2 is less than 100%. /. At the time, at least two kinds of the astaxane compounds represented by the above formula (1) are used. Examples of the decane compound represented by the above formula (1) and having a valence of 2 in the above formula (1) include diphenyldiethoxy (tetra), dimethyl-methoxy sulphur, and diethyl Oxy-dimethyl dimethyl dream, diethoxymethyl ethyl phenyl sylvestre, ethoxydiethyl; dimethyldipropoxy sylvestre, dimethoxymethylphenyl decane, 3 _ glycidoxypropylmethyldiethoxylate, N-2-(aminoethyl)_3_aminopropylmethyldi-foxy (tetra) or % sulfopropylmethyldimethoxy Base decane and the like. The above-mentioned siloxane polymer has a weight average molecular weight of from 1 Å to 5 Å. When the weight average molecular weight of the siloxane polymer is too small, there is a case where the viscosity of the resist film is lowered. When the weight average molecular weight of the siloxane polymer is too large, there is a decrease in the compatibility of the siloxane polymer with other components 137746.doc -18- 200937123. A preferred upper limit of the weight average molecular weight of the above siloxane polymer is 20,000 〇. The above siloxane polymer is more preferably an alkoxy decane condensate obtained by condensing an alkoxy decane. Further, it is preferred that at least one X in the above formula (1) is an alkoxy group, the above decane compound is an alkoxydecane, and the above siloxane polymer is a condensation of an alkoxy decane obtained by condensing the alkoxy decane. Things. When these alkoxylated condensates are used, the heat resistance of the anti-film can be further improved. When an alkoxydecane condensate is obtained, one alkoxy oxime may be used. Alternatively, two or more alkoxydecane may be used in combination. The above-mentioned Shishi milk-fired polymer is preferably a shihua oxygen-fired polymer having an unsaturated double bond. The above naphthenic polymer having an unsaturated double bond is preferably a decane having an organic group having an unsaturated double bond by making the oxime in the above formula (1) an integer of 丨 〜3 and at least one ft. The oxygen crater polymer 0 obtained by polymerizing the compound can eliminate the developability of the anti-money material and the viscosity of the resist film when the above-mentioned siloxane polymer having an unsaturated double bond is contained. The above siloxane polymer is preferably a siloxane polymer having an acid anhydride group or a carboxyl group and an unsaturated double bond. The above naphthenic polymer having an acid anhydride group or a carboxyl group and an unsaturated double bond is preferably one obtained by making P in the above formula (1) an integer of from 1 to 3 and at least one R having an acid anhydride group or a carboxyl group. The organic decane compound, a oxoxane polymer obtained by polymerizing a calcined compound having an integer of from 1 to 3 in the above formula (1) and at least one R being an organic group having an unsaturated double bond. When δ contains the above-mentioned oxygenated 137746.doc -19-200937123 sulphide having an acid needle group or a thiol group and an unsaturated double bond, the developability of the resist material can be further improved. Further, when the above-mentioned naphthenic polymer having an acid anhydride group or a mercapto group and an unsaturated double bond is contained, a large amount of white filler can be filled, so that a resist film having a higher reflectance of light when irradiated with light can be formed. . The above naphthenic polymer is preferably a polyoxyalkylene polymer having a cyclic ether group. The above-mentioned alkoxysilane polymer having a cyclic ether group is preferably obtained by using p in the above formula (1) as an integer of 1 to 3 and at least one R is an organic group having a cyclic ether group. The naphthenic polymer obtained by polymerizing a decane compound. When the rhodium-containing alkane polymer having a cyclic ether group is contained, the heat resistance of the resist film can be further improved. The cyclic ether group is preferably an epoxy group. The above naphthenic polymer having a cyclic ether group is preferably used in combination with the above-mentioned nonoxyxane polymer having an unsaturated double bond. Further, the above-mentioned naphthenic polymer having a cyclic ether group is preferably used in combination with the above-described naphthenic polymer having an acid anhydride group or a carboxyl group and an unsaturated double bond. The above siloxane polymer is preferably a siloxane polymer having an acid anhydride group or a carboxyl group, an unsaturated hydrazine double bond, and a cyclic ether group. The above naphthenic polymer having an acid anhydride group or a carboxyl group, an unsaturated double bond, and a cyclic ether group is preferably such that ρ in the above formula (1) is an integer of i to 3 and at least one r is a decane compound having an organic group of an acid anhydride group or a carboxyl group, a decane compound in which p is an integer of 1 to 3 and at least one R is an organic group having an unsaturated double bond, and the above formula (1) The oxime polymer obtained by polymerizing a decane compound having an organic group having a cyclic ether group is an integer of 〜3. When it contains an acid anhydride group or a carboxyl group, an unsaturated double bond, and a ring-shaped radical (4), the thermal resistance of the anti-caries film can be further improved. The cyclic ether group is preferably an epoxy group. The above-mentioned nonoxyl alkane polymer having an unsaturated double bond, the above-mentioned alkoxyalkyl polymer having an acid anhydride group or a carboxyl group, and an unsaturated double bond, and the above-mentioned anhydride group or The methoxy group polymer having a carboxyl group, an unsaturated double bond, and a cyclic ether group preferably has an organic group in which a carbon atom is directly bonded to a ruthenium atom, and 5 to 80% of the organic group has no Saturated double bond. The developability of the resist material and the crack resistance of the resist film can be further improved by using a cerium oxide polymer having an organic group having an unsaturated double bond in the range of 5 to 80%. The unsaturated double bond is preferably an olefinic double bond. Preferably, the above-mentioned oxy-fired polymer having an acid Sf group or a slow group and an unsaturated double bond, and the above-mentioned oxalate-oxygenated polymer having an acid-hepatic group or a carboxyl group, an unsaturated double bond, and a cyclic group are preferably An organic group having a carbon atom directly bonded to a ruthenium atom and having 1 to 25% of the organic group has an acid anhydride group or a carboxyl group. By using a siloxane polymer having an organic group having an acid anhydride group or a carboxyl group in the range of 1 to 25%, the heat-resistance and electrical insulating properties of the resist film can be further improved. The above oxime-oxygenated polymer having a cyclic ether group and the above-mentioned oxirane polymer having an acid anhydride group or a carboxyl group, an unsaturated double bond, and a cyclic ether group preferably have a bond directly bonded to a ruthenium atom. An organic group of a carbon atom, and 5 to 80% of the organic group has a cyclic ether group. When the ratio of the organic group having a cyclic ether group is less than 5%, there is a case where the heat resistance of the resist film is not sufficiently obtained. When the proportion of the organic group having a cyclic ether group exceeds 80 ° /. At the time, there is a case where the developability of the anti-residue material is lowered. The product of the solid content of the resin component contained in the resist material of the present invention is 137746.doc -21 - 200937123 (mg KOH / g) and the epoxy equivalent (g / eq) is preferably at 30,000 - 500,000. Within the scope. By making the product of the solid acid value and the epoxy equivalent in the range of 30,000 to 500,000, the electrical insulating property of the resist film can be further improved. The above-mentioned "resin component" specifically means a resin component other than the white filler contained in the resist material. The anti-agent material preferably contains a resin having an acid anhydride group or a carboxyl group, and an unsaturated and double bond. When the above resin having an acid anhydride group or a carboxyl group and an unsaturated double bond is contained, the developability of the resist material can be further improved, and the adhesion of the anti-surname film can be lowered. The acid value of the solid content of the resin component (mg KOH/g) when the oxy-oxygenated polymer is an epoxy group-containing oxirane polymer and contains the above-mentioned resin having an acid anhydride group or a carboxyl group and an unsaturated double bond. The product of the epoxy equivalent (g/eq) of the resin component is preferably in the range of 25,000 to 100,000. The term "resin component" as used herein means a resin component other than the white filler contained in the resin composition. At this time, the durability of the resist film can be further improved. If the upper 述 product is less than 25,000, there is a case where the compatibility of the siloxane polymer with other components is lowered, or the residual film after prebaking exhibits a high viscosity. If the above product is more than 100,000, the durability of the resist film may be lowered. The resin composition of the present invention may further contain a curing accelerator to facilitate the reaction of the cyclic ether group with the acid anhydride group or the carboxyl group. (White Filler) The white filler contained in the resist material of the present invention is not particularly limited as long as it is white. 137746.doc -22- 200937123 As a white filler, for example, ruthenium, titanium ruthenium, sA bismuth Titanium, talc, sulfuric acid dream, clay, carbonic acid: micro-powder oxygen-cutting, amorphous zinc dioxide, niobium niobium (four), oxidation #, oxyhydroxide, neodymium hydroxide, nitrogen cutting, nitriding Leading fault, ammonia oxidation town, mica, Φ mother powder 2 rolls, Shixi acid wrong, oxygen materials. Among them, the dioxide:organic powder or the organic resin filler can be preferably used alone with two reflectances. White can be used to fill the sputum, and it can be used in combination of two or more. : = resin filler' can be exemplified by: polystyrene-based organic resin, organic tree, acid S, organic resin filler, (benzoic resin, filler, acrylic, rubber, rubber, rubber, organic, rubber, rubber, organic, organic The amount of the above-mentioned white filler is preferably in the range of 100 to 1,500 parts by weight, more preferably in the range of 100 to 700 parts by weight, particularly preferably (10). If the amount of the white filler is too small, the reflectance of the anti-slip film may not be sufficiently improved. If the amount of the white filler is too large, the developability of the resist material may be lowered. When the Shixia oxy-fired polymer is a diarrhea polymer having an unsaturated double bond, the white filler can be filled with high density without excessively reducing the hardenability of the anti-surname material. For example, relative to having an unsaturated The white filler may be added in an amount of from 3 to 15 parts by weight based on 100 parts by weight of the double-bonded siloxane polymer. (Other components) The resist material of the present invention preferably contains a polymerization initiation. Polymerization initiator The cross-linking component in the resin composition is crosslinked by an external stimulus. 137746.doc -23- 200937123 is not particularly limited. The polymerization initiator may be used singly or in combination of two or more. Examples thereof include light such as heat, visible light or ultraviolet light, ultrasonic waves, microwaves, etc. The above polymerization initiator is preferably a photopolymerization which crosslinks crosslinking components in a resist material by irradiation of light. Starting agent.

The content of the above polymerization initiator is preferably in the range of 0.1 to 100 parts by weight based on 1 part by weight of the above-mentioned oxy-oxygenated polymer. If the amount of the polymerization initiator is too small, there is a case where the resist material cannot be sufficiently cured by external stimulation. If the amount of the polymerization initiator is too large, it may be difficult to apply the resist material uniformly or to generate a residue after development. The above polymerization initiator is preferably a photoradical generator which generates a radical by irradiation of light. When a photoradical generator is used, the radical material can be crosslinked by radicals generated by a photoradical generator by exposure to harden the resist material. Further, a resist material is applied onto the substrate and partially exposed and developed, whereby a pattern film can be formed. Specific examples of the photo-radical generating agent include a mercaptophosphine oxide derivative, a methylated tri-negative derivative, a sec-methylated oxadiazole derivative, a rice saliva, a benzoin, and a benzoin base bond. Class, onion-derived derivatives, benzofluorenone derivatives, benzophenone-bio, #乙晴生物, 9: oxysulfur such as star derivatives, benzoate derivatives, acridine derivatives, cultivating organisms , a dimoxine derivative, an α-amine-based benzene (tetra) compound or a derivative thereof. The photoradical generator may be used singly or in combination of two or more. As the above fluorenyl phosphine oxide derivative, 2,4,6-trioxazolidine benzoyldiarylphosphine oxide '2,4,6-trimethylbenzimidyldiphenyl I37746 .doc -24- 200937123

Phosphine oxide (for example, manufactured by BASF, "Lucirin"), bis(2,4,6-tri-C1-2 alkylbenzylidene) arylphosphine oxide, bis(2,4,6-trimethyl) Benzyl hydrazino)-phenylphosphine oxide (for example, "Irgacure 819" manufactured by Ciba Specialty Chemicals Co., Ltd.), 2,4,6-tri-C1-2 alkylbenzylidene aryl alkoxyphosphine oxide, 2,4,6-trimethylbenzimidylethoxyethoxyphosphine oxide, bis(2,6-di-C1-2 alkoxyphenyl)-branched C6-12 alkylphosphine oxide , bis(2,6-monomethoxybenzhydryl)_2,4,4-trimethylpentylphosphine oxide (BAPO), bis(2,4,6-tri-C1-2 alkyl benzoyl) Base Cl-6 alkylphosphine oxide, bis(2,4,6-trimethylbenzylidene)methylphosphine oxide, bis(2 4 6 trimethylbenzylidene)ethylphosphine oxide or double (2,4,6-trimethylbenzylidene)_Ν_τ-based phosphine oxide. The above-mentioned tooth methylated ruthenium ruthenium derivative may, for example, be 2—(4-methoxyphenyl)-4,6-bis(trimethylmethyl)_all three tillage, 2—(4-methoxynaphthalene) Base) 46•Bis(trismethyl)--tris-, 2-(4·ethoxynaphthyl)·4 6·bis (tri-methyl)_ 2, or 2-(4-B Oxycarbylnaphthyl)_46·bis (trioxane methyl bromide, etc. as the above-mentioned imadan derivative) may be exemplified by 2_(o-phenyl)-4,5-diphenyl(tetra)dimer, Oxygen stupid base)·4,5•bis(3._methoxyphenyl) mouth rice olfactory dimer, 2-(o-fluorophenyl)-4'5·diphenylimidazole dimer, 2_ (o-methoxyphenyl K5-dipyridyl iodide dimer, or 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. As a benzoin alkyl ether, Listed: benzoin musk phenyl ether, benzoin isobutyl ether or benzoin isopropyl ether, etc. As the above derivatives, 2H^, 2_ethyl onion 137746.doc 200937123, 2-tert-butyl fluorene醌 or ι_气蒽醌, etc. As the above benzophenone derivative, there may be mentioned: benzamidine, mazinone, 2-methylbenzophenone 3. Yue Yue Si diphenyl, 4-methyl benzophenone, 2-diphenyl gas Yue-one, 4-bromo-carboxy benzophenone or benzophenone 2_ _ the like.

❹ As the above acetophenone derivative, 2,2-dimethoxyphenylacetophenone, 2,2-diethoxyacetophenone, hydrazine hydroxycyclohexyl phenyl ketone, and hydroxy-2 are exemplified. -methylphenylacetone, hydrazine-hydroxy-hydrazine-methylethyl (p-isopropylphenyl) ketone, 1-hydroxy-indole-dodecylphenyl)-, 2-methyl-(4, _($thio)phenyl)-2-morpholinyl-1-propanamine, or trimethylol (p-butylphenyl) ketone, and the like. Examples of the above-mentioned 9-oxothiop-indene derivative include 9-oxythiolane, 2-ethyl-9-oxosulfide, hawthorn, 2·isopropyl-9-oxathiazin p, 2_. Gas _9_ oxysulfonate, 2,4-dimercapto-9-oxothiopurine, 2,4-diethyl-9-oxythione or 2,4·isopropyl-5 - Oxygen sulphur mountain v star. The benzoate derivative may, for example, be p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester. The acridine derivative may, for example, be 9-phenyl acridine or (p-methoxyphenyl) acridine or the like. Examples of the above-mentioned morphing derivative include 9,10-dimethylbenzinodine and the like. Examples of the above titanocene derivative include dicyclopentadienyl titanium dihydride, dicyclopentadienyl bisphenyl titanium, and dicyclopentadienyl bis (2 3,4 5,6-pentafluoro). Benz-1-yl)titanium, dicyclopentadienyl bis(23,5,6 tetrafluorophenyl) chin, bicyclol; ^ dilute bis (2,4,6-trisole) Tricyclopentadienyl-(2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyl-(24•difluorobenzene·fluorenyl) 137746.doc -26· 200937123 Titanium, II ( Methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(indenylcyclopentadienyl)bis(2,6-difluorobenzene- 1-based) or dicyclopentadienyl-[2,6-difluoro-3-(.pyrrol-1-yl)-phenyl-1-yl]titanium. Examples of the above α-amine-based alum-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-indolylpropan-1-one and 2-benzyl. 2--2-dimethylamino 1-(4-morpholinylphenyl)-butanone, 2·benzyl-2·dimethylamino-1-(4·morpholinylphenyl)butane 1-ketone, 4-dimethylaminoethyl benzoate, 4· dimethylaminoisoamyl benzoate, 4-diethylamino acetophenone, 4-dimethyl Aminopropiophenone, 2-ethylhexyl_ι,4-didecylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethyl Aminoamino 3-(4-diethylaminobenzyl) coumarin, or diethylamino) chalcedony and the like. Examples of the above anthracene derivatives include anthracene, 2-dioctane-1-[4(phenylthio)carbyl]-2-(anthracene-branched), or ethyl ketone_ι_[9 Base_6_(2_methylbenzhydryl)_9H-carbazole·3·yl]_!_(〇_乙醯基肟) and the like. When the photoradical generator is contained, the content of the above photoradical generator is preferably in the range of 〇丨~chuan by weight relative to 1 part by weight of the above-mentioned siloxane polymer, and more preferably 15 parts by weight of (4). If the amount of the photo radical generating agent is too small, there is a case where a sufficient amount of radicals are not generated after the exposure. If the amount of the photo radical generating agent is too large, it is difficult to apply the resist material uniformly or after development. The situation of the residue. The above polymerization initiator is preferably an acid generator which generates an acid by external stimulation. When an acid generator for generating an acid by external stimulation is used, the resin composition can be hardened by imparting an external stimulus to the resin composition. 137746.doc -27· 200937123 The above acid generator is preferably an acid photoacid generator which is produced by irradiation of light. The resist material containing a photoacid generator is a photosensitive composition which is photosensitive by exposure. At this time, the resist material can be hardened by exposing the resist material to crosslink the siloxane polymer. Further, a resist material is applied onto the substrate and partially exposed and developed, whereby a pattern can be formed. The photoacid generator is not particularly limited. Specific examples of the photoacid generator include the trade name "TPS-φ 105" (CAS No. 66003-78-9) and "TPS-109" (CAS No. l44317-) manufactured by Midori Chemical Co., Ltd.

44-2), "MDS-105" (CAS No. 116808-67-4), "MDS-205" (CASN〇.81416-37_7), "DTS-105" (CASN〇.111281-12-0) , "NDS_105" (CAS No. 195057-83-1) and "NDS-165" (CAS No. 316821-98-4) and other sulfonium salt compounds; the brand name "DPI-105" (CAS No) manufactured by Midori Chemical Co., Ltd. .66003-76-7), "DPI-106" (CAS No.214534-44-8), "DPI-109" (CAS

No.194999-82-1), "DPI-201" (CAS No. 6293-66-9), "BI-105" (CAS No. 154557-16-1), "MPI-105" (CAS No.) 1 15298-63-0), "MPI-106" (CAS No.260061-46-9),

* "MPI-109" (CAS No.260061-47-0), "BBM05" (CAS

No.84563-54-2), "BBI-106" (CAS No.185195-30-6), "BBI-109" (CAS No.194999-85-4), "BBI-110" (CAS No.) 213740-80-8) and bismuth salt compounds such as "BBI-201" (CAS Ν〇·102342_33·4); the product name "ΝΑΙ·106" manufactured by Midori Chemical Co., Ltd. (naphthalene diimide camphor sulfonate, CAS No. 83697-56-7), "ΝΑΙ- 137746.doc • 28 - 200937123 100" (CAS No. 83697-53-4), "NAI-1002" (CAS No. 76656-48-9), "NAI- 1004" (CAS No. 83697-60-3), "NAI-101" (CAS No. 555 72-4), "NAI-105" (CAS No. 85342-62-7), "NAI-109" (CAS No. 171417-91-7), "NI-101" (CAS No. 131526-99-3), "NI-105" (CAS No. 85342-63-8), "NDI-

* 101" (CAS No. 141714-82-1), "NDI-105" (CAS • No.133710-62-0), "NDI-106" (CAS No. 210218-57-8),

"NDI-109" (CAS No.307531-76-6), "PAI-01" (CAS Φ No.17512-88-8), "PAI-101" (CAS No.82424-53-1), " PAI-

106" (CAS No.202419-88-3), "PAI-1001" (CAS

No.193222-02-5), "SI-101" (CAS 550·55048·39-0), "SI_105" (CASN〇.34684_40-7), "SI-106" (CASN〇.179419- 32-0), "SI-109" (CAS No. 252937-66-9), "PI_105" (CAS No. 41580-58-9) and "PI-106" (CAS No. 83697-51-2) , sulfonate-based compounds such as "CGI1397", "CGI1325", "CGI1380", "CGI1311", "CGI263" and "CGI268" manufactured by Ciba Specialty Chemicals; the product name "DTS200" manufactured by Midori Chemical Co., Ltd. (CAS No. 203573-06-2), and the product name "RHODORSIL PHOTOINITIATOR-2074" (CAS No. 178233-72-2) manufactured by Rhodia Japan Co., Ltd., etc., BF4- as a counter ion compound. The photoacid generator may be used singly or in combination of two or more. When the photoacid generator is contained, the photoacid generator is preferably contained in an amount of from 0.1 to 1 part by weight based on 1 part by weight of the alkoxysilane polymer. If the amount of the photoacid generator is too small, there is a case where the resist material after exposure is not sufficiently sensitized by 137746.doc -29-200937123. If the amount of the photoacid generator is too large, it may be difficult to apply the resist material uniformly or to generate a residue after development. When the above photoradical generator is used, the resist material preferably contains no photoacid generator. At this time, acid and alkali are not left in the formed resist film. Therefore, even if the metal contacts the resist film, migration of the metal can be suppressed. In addition to the photopolymerization initiator, a sensitizer may be further added to the resist material. When the sensitizer is used, the sensitivity of the resist material can be further improved by 9 degrees. The above sensitizer is not particularly limited. Specific examples of the sensitizer include: benzamidine, p, p, _ tetramethyldiaminobenzhydrazide, p, p'-tetraethylaminodiphenyl hydrazine _, 2 • Gas · 9. Oxygen sulfur _, fluorenone, 9 ethoxy hydrazine, 蒽 ', 芘, 茈, thiophene, benzoin, thioflavin-diphenyl onion, " 2 "Xiao Jidi, 5 nitro-nuclear, stupid, 2K nitro-l-amine, 沁乙-based _ p-nitroaniline, p-nitroaniline, N• ethyl ketone _4 • nitro] • naphthyl Amine, 2 from trinitrophenylamine, onion, 2_ethyl onion, 2_t-butyl onion, 1,2-benzoindole, 3_methyl_u·digas-] , stupid and onion ketone, diphenyl fluorenyl propyl, 12 - eucalyptus, q V silver 1 ^ one go... Wei 3, 3_ county _ double (5,7 · oxycarbonyl scent • 2 · vegetarian) Or other components. (Other components that can be added) The resist material of the present invention may contain a solvent. The coating of the material containing the resolving agent becomes easy. ^: For the above solvent, an aromatic hydrocarbon compound, A saturated or unsaturated compound, an ether, an anthracene or an ester may be used in combination of two or more. 4 Solvents may be used only 137746.doc 30-200937123 The aromatic hydrocarbon compound may, for example, be stupid, xylene, toluene, ethylbenzene, styrene, trimethylbenzene or diethylbenzene. Examples of the saturated or unsaturated hydrocarbon compound include :Huanjiyuan, Huanji, Erqi, Zhengba, Isabi, Zhengji, Alien, Zhenggeng, Yigengyuan, Zhengxinyuan, Qixin, Zhengyi, Yiqi , n-decane, isodecane, tetrahydrofuran, tetrahydronaphthalene or ergophane, etc. As the above mystery, it can be exemplified: Eryi shout, di-n-propyl shim, diisopropyl ether: two top, Ethylpropionate, diphenyl, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, two Propylene glycol dibutyl ether, dipropylene glycol methyl sulfonate, ethylene glycol dimethyl sulfonate, ethylene glycol diethyl bond, ethylene glycol dipropylene, ethylene glycol methyl ether, tetrahydrofuran, dioxane, propylene glycol monomethyl ether acetate Ester 1 ethylene glycol monoethyl ether acetate, dipropylene glycol oxime ether acetate, diethylene glycol monoether acetic acid, ethyl cyclohexane曱-cyclohexane, p-menthane, o-menthane, m-menthane, dipropyl ether or dibutyl ether, etc. As the above-mentioned class, a propylene net, a methyl ethyl ketone, a methyl isobutyl network may be mentioned. , diethyl _, dipropyl hydrazine, methyl amyl group, cyclopentanyl cyclohexanone or cyclobutanone, etc. 酽: description of the class, can be cited: ethyl acetate, methyl acetate, butyl acetate Known, cyclohexyl acetate, strontium acetate cellosolve, ethyl acetate, fiber, butyl cellosolve, ethyl lactate, lactic acid, lactic acid, butyl lactate, isoamyl lactate, or succinate Examples of the above alcohols include pentanol, ene alcohol, isoamyl alcohol, isobutyl isopropanol, deca-ol, ethanol, 2-ethylbutanol, 2-ethylhexanol, 137746.doc • 31 - 200937123 2- Octanol, n-octanol, shrinkage ς踣 glycerol cyclohexanol, 3,5-dimethyl-1·hexyne -3-ol, n-nonanol, tetra|sugar age, sugar alcohol, ... terpineol 'ne pentanol, sterol, fusel oil, butanol, decyl alcohol, l-propyl alcohol, miscellaneous, ^ J ^ sterol, heptanol, benzyl alcohol, pentanol, decyl alcohol, fluorenyl fluorene z T violence 1-butanol, 3-methyl-2_ol' 3 -Methyl-1·butyne·3_ol, j alcohol, 4-methyl-2-pentanol or 3-methylindole-3-ol. X-shaped, for example, is suitable for uniformly coating the anti-reagent material on the substrate.

It is preferable to set the content of the above solvent to a range in which the solid content of the anti-(four) material is in the range of 10 to 90% by weight, and the solid content is preferably in the range of 3 to 85% by weight. Inside the way to contain. The resist material of the present invention may be easily contained in the resist material in order to easily react the cyclic ether group with the acid anhydride group or the carboxyl group. In the resist material of the present invention, other additives may be further added as needed. Examples of the additives include dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersing aids, surface modifiers, plasticizers, plasticizing accelerators, and sagging resistance. Agent, antioxidant or adhesion aid. (LED Element) The resist material of the present invention is suitably used for forming an anti-silver film of an LED element emitting light having a wavelength of 8 Å or less. Namely, the anti-money agent material of the present invention can be suitably used as a resist material for forming a resist film for an LED element. The resist material of the present invention can be better used as a solder resist material for forming a solder resist film of an LED element. 137746.doc -32- 200937123 Fig. 1 is a partially cutaway front cross-sectional view schematically showing an LED element having an anti-surname film formed using a resist material according to an embodiment of the present invention. In the LED element 1 shown in Fig. 1, a resist film 3 formed of the above resist material is laminated on the upper surface 2a of the substrate 2. The resist film 3 is a pattern film. Thereby, the resist film 3 does not exist on a partial region on the upper surface 2a of the substrate 2. In the region where the resist film 3 is not present, the electrodes 4a, 4b are provided on the upper surface * 2a of the substrate 2. The resist material of this embodiment contains a photopolymerization initiator. Therefore, the resist film 3 as the pattern film can be formed by an exposure step and a development step which will be described later. The LED element 1 has a substrate 2 and a resist film 3 which are laminated on the surface of the substrate 2 and formed by the above-mentioned anti-surname material. The substrate 2 is a glass epoxy laminate. Specific examples of the glass epoxy laminate are FR-4 or FR-5. Instead of the glass epoxy laminate, a laminate plate having an aluminum plate and a heat dissipation plate laminated on the name plate may be used. Further, as shown in Fig. 2, a single-layer resin sheet 21 may be used instead of the glass epoxy laminate. Further, a laminate in which a plurality of resin sheets are laminated may be used. An LED chip 7 is laminated on the upper surface 3a of the resist film 3, and the resist film 3 is interposed, and the LED wafer 7 is laminated on the substrate 2. Terminals 8a, 8b are provided in the vicinity of the outer periphery of the lower surface 7a of the LED wafer 7. The terminals 8a and 8b are electrically connected to the electrodes 4a and 4b provided on the upper surface 2a of the substrate 2 by solders 9a and 9b, respectively. Electric power can be supplied to the LED chip 7 by the electrical connection. A partial region of the lower surface of the terminals 8a, 8b is located in a region where the resist film 3 is not present. Therefore, part of the lower surface of the terminals 8a, 8b is not in contact with the resist 3 . The electrode 8& is connected to the 137746.doc-33-200937123 electrode 4a by solder 9a at a portion not in contact with the resist film 3. Further, the terminal 8b is connected to the electrode 4b by the solder 9b at a portion not in contact with the resist film 3. Other metals such as gold or silver may be used instead of the solders 9a and 9b, and the terminals 8a and 8b may be connected to the electrodes 4a and 4b, respectively. Alternatively, the terminals 8a and 8b may be connected to the electrodes 4a and 4b by wiring. In the present embodiment, the anti-corrosion crucible 3 is white. Further, when soldering or the like is performed, the resist film 3 is less likely to be discolored from white even when exposed to a high temperature. Light is emitted from the LED wafer 7 as indicated by the arrow of FIG. In particular, as indicated by an arrow a, light reaching the resist film 3 side can be efficiently reflected by the resist film 3. Therefore, the light emission of the LED chip 7 can be effectively utilized in the LED element 1. (Manufacturing Method of LED Element) When the LED element 1 is served, first, for example, as shown in FIG. 3(a), an anti-surname material layer U having a specific thickness is formed on the substrate 2. As a method of forming the above-described resist material layer u, for example, a method of applying a resist material on the substrate 2 can be mentioned. As a method of applying a resist material on the substrate 2, a usual coating method can be used. For example, it can be applied by curtain coating, screen printing, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating or gravure coating. A resist material is applied. The thickness of the resist material layer is 10 nm to 50 μίη & right. When the resist material layer 11 contains a solvent, in order to remove the solvent, it is preferred to heat-treat the resist material layer η before exposure. The heat treatment temperature before exposure is usually in the range of 40 to 20 (rc. The heat treatment temperature before exposure "T is appropriately selected depending on the boiling point of the solvent and the vapor pressure. 137746.doc •34· 200937123 Next, as shown in Fig. 3(b) When the partial exposure of the resist material layer 11 is performed using the mask 12, the mask 12 has an opening portion 12a and a light blocking portion 12b. The resist material layer 11 is irradiated with light by using the mask 12'. The exposure portion 11a and the unexposed portion lib which is not irradiated with light are partially exposed. Here, the resist material layer formed on the portion of the substrate 2 on which the electrodes 4a and 4b are formed is unexposed. The portion lib of the resist material formed on the portion of the substrate 2 on which the electrodes 4a and 4b are not formed is the exposed portion 11 a 〇Ο as the mask 12, and a commercially available conventional mask can be used. In the resist material layer 11 of the exposed portion 11a which is irradiated with light, an acid or a radical is generated by a photoacid generator or a photo radical generating agent. The resist material layer 11 of the unexposed portion lib which is not irradiated with light Medium photoacid generator or photoradical generator does not produce acid or free In the resist material layer 11 of the exposure portion 11a, the above-mentioned oxy-fired polymer is crosslinked by the action of an acid or a radical generated by a photoacid generator or a photoradical generator. When the above-mentioned stone oxide polymer is crosslinked, the resist material layer 11 of the exposed portion 11a is hardened. As a result, the resist material layer 11 of the exposed portion ua is insoluble in the developer. The resist of the unexposed portion lib The material layer "is not sensitized. Therefore, the layer 11 of the anti-money material of the unexposed portion lib is not hardened and is soluble in the developer". When exposed, the light source for illuminating the active energy rays such as ultraviolet rays or visible rays is not Particularly limited. As the above light source, an ultrahigh pressure mercury lamp, a Deep UV (deep ultraviolet) lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp or an excimer laser can be used. The light sources 137746.doc • 35 · 200937123 can be appropriately selected according to the photosensitive wavelength of the constituent components of the resist material. The irradiation energy of light can be appropriately selected by the required film thickness or the composition of the resist material. The irradiation energy of light is usually In the range of 1 〇 to 3 〇〇〇 mj/cm 2 , if the irradiation energy of light is less than 1 〇 mj/cm 2 , there is a case where the resist material layer 11 of the exposed portion 1 丨 & If the irradiation energy of light exceeds 3000 mj/cm2, the exposure time may be too long, and the manufacturing efficiency per unit time of the pattern film may be lowered. Next, the resist material layer u is developed by the developer. When development is performed, the resist material layer u of the unexposed portion lib is removed by being dissolved in the developer. As a result, as shown by 囷3(c), the resist film 3 as a pattern film can be obtained. This pattern is referred to as a negative pattern β because the resist material layer 11 of the unexposed portion 11b is removed. The operation of developing the resist material layer 11 by using a developing solution such as an alkaline aqueous solution. Examples of the operation for developing include an operation of immersing the resist material layer U in the developer, an operation of rinsing the surface of the resist material layer U with the developer, or spraying and developing the surface of the resist material layer u. Liquid operation, etc. Further, the developer is a liquid which dissolves the anti-surname material core of the unexposed portion 11b after partial exposure to the material layer u. The material layer u of the exposed portion (1) is hardened, so it is not dissolved in the developer. The developer is not limited to the aqueous solution. A solvent can also be used as the developing solution. Examples of the solvent include the above various solvents. The aqueous solution of the solution can be suitably used as the (four) liquid. When using an aqueous solution, it is not necessary to use explosion-proof equipment, and it can reduce the burden of equipment caused by corrosion, etc. I37746.doc -36- 200937123. The above-mentioned aqueous test solution may, for example, be a tetramethylammonium hydroxide solution, an aqueous solution of a solution of sodium arsenoate, an aqueous solution of sodium hydroxide, an aqueous solution of aqueous hydroxide or an aqueous solution of sodium carbonate. The development time can be appropriately set depending on the thickness of the anti-(4) material layer or the kind of the solvent. In order to be able to develop efficiently, and to achieve high manufacturing efficiency, the development time is preferably in the range of seconds to 1 minute. After the development, it is preferred to wash the pattern film 3 by steaming water, thereby removing the developer such as an aqueous solution remaining on the pattern film 3. Then, as shown in Fig. 3(d), the LED chips 7 on which the terminals 8a and 8b are provided on the lower surface 7a of the resist film 3 are laminated. Thereafter, the electrodes 8a, 8b provided on the lower surface 7a of the LED chip 7 and the electrodes provided on the upper surface 2a of the substrate 2 on the portion where the resist film 3 is not formed are irradiated by the solders 9a, 9b. Sexual connection. Thus, the LED element 1 shown in Fig. 1 can be obtained. Further, when the resist material contains the photoacid generator or the photoradical generator, the anti-surname material layer may be formed only on a specific portion without the entire surface of the substrate 2. It is also possible to expose the entire surface of the resist material layer formed on a specific portion. Hereinafter, the present invention will be exemplified by exemplifying specific examples and comparative examples of the present invention. The invention is not limited to the following examples. (Example 1) (1) Preparation of alkoxydecane condensate In a 100 ml flask equipped with a condenser, '7 g of phenyltriethoxydecane, 47 g of decyltriethoxydecane, 〇· 2 g of oxalic acid, 15 ml of water and 14 ml of propylene glycol monomethyl ether acetate. The semi-circular mechanical stirrer was used to stir the solution of 137746.doc -37- 200937123, and the solution was reacted for 7 hours using a heating mantle at 7 (rc). Secondly, an evaporator was used to generate a condensation reaction with water. The ethanol and residual water were removed. Thereafter, the flask was placed until room temperature was reached, and a solution containing an alkoxydecane condensate having a solid concentration of 70% by weight was obtained. The obtained alkoxydecane was obtained by gel permeation chromatography. The condensate was measured to have a polystyrene-equivalent weight average molecular weight Mw of 3,500. Thus, it was confirmed that an alkoxydecane condensate was obtained. (2) Preparation of a resist material as a resin composition: 10 parts by weight A solution containing alkoxydecane condensate as a siloxane polymer (solid content: 70% by weight), 0.7 parts by weight of a photoacid generator as a polymerization initiator (manufactured by Midori Chemical Co., Ltd., model: PAI -101), 10 parts by weight of titanium dioxide as a white filler (manufactured by Ishihara Sangyo Co., Ltd., model: CR-50), and 0.14 parts by weight of dibutoxy hydrazine as a sensitizer (Kawasaki Chemical Co., Ltd.) After the mixing was carried out for 2 minutes by a mixer, mixing was carried out using a three-roll mill. Thereafter, the mixture was defoamed for 3 minutes using a mixer (manufactured by Thinky Corporation, 'Degassing Stirling SP-500), thereby obtaining resistance. Etchant material (Comparative Example 1) (1) Preparation of varnish A 40 parts by weight of acrylamide phthalate (XP-4000B), 40 parts by weight of epoxy acrylate (SUMIFLASH A), and 3 parts by weight Aluminum integrator (ALCH), which was stirred and heated under normal pressure for 13 minutes at 13 (TC) to produce varnish A. (2) Manufacture of solder resist ink I37746.doc -38 - 200937123 formulated 20 parts by weight of polybutadiene acrylate (R_45ACR), 1 part by weight of epoxy acrylate (SP-1509), 30 parts by weight of barium sulfate, 15 parts by weight of pentaerythritol tetraacrylate, 20 parts by weight Polyethylene glycol diacrylate, 4 parts by weight of gel varnish, 酞 part by weight of phthalocyanine green, 4 parts by weight of 2-ethyl hydrazine, 50 parts by weight of the varnish obtained in the above (1) A, and 1 part by weight of the surfactant, by a conventional method by a three-roll mill Mixing • The formulation is uniformly dispersed to thereby produce a solder resist ink as a resist material. β (Evaluation) (1) Production of resist film The obtained resist material is obtained by screen printing. Coating on a substrate formed of glass in a thickness of 3 Å. Screen printing is performed under the following conditions, that is, a squeegee speed: 25 〇 mm / sec, a squeegee pressure · 0.17 MPa, Blade pressure: 〇17 MPa, back pressure: 〇.1〇MPa, blade speed: 50 mm/sec, and clearance: 17 mm. After coating, the resist material was dried in an oven at 8 Torr for 20 minutes to form a resist material layer on the substrate. Next, the resist material layer was irradiated with a wavelength of 365 nmi by ultraviolet illuminance of 100 mW/cm 2 by ultraviolet ray illumination of 100 mW/cm 2 via a photomask having a specific pattern using an ultraviolet ray irradiation device to achieve an irradiation energy of 5 〇〇 mJ/cm 2 . Ultraviolet light. After the ultraviolet ray was irradiated, in Example 1, the resist material layer was heated by a heating plate of 1 ° C for 2 minutes. Thereafter, when the resist material of the example was used, the resist material layer was immersed in a 2 38% aqueous solution of tetramethylammonium hydroxide for development, when the resist material of the comparative example was used. The resist layer 137746.doc -39· 200937123 was immersed in 1 〇/ of sodium carbonate. Development is carried out in an aqueous solution to remove the anti-material material layer of the unexposed portion, thereby forming a resist film on the substrate. (2) Heat resistance test of resist film The obtained resist film was allowed to stand at 27 (TC for 2 minutes to obtain an evaluation sample. Further, an evaluation sample obtained by placing the obtained resist film at 288 ° C for 2 minutes was prepared. - For the newly formed resist film (initial), the resist film (27 (TC, 2 minutes), and 288 after standing at 270 ° C for 2 minutes. (: Resist film® after 2 minutes of placement) °C, 2 minutes) 'Colorimetric colorimeter (manufactured by K〇nica Minolta Co., Ltd., CR-400) was used for colorimetry. The color representation method of the XYZ color system (CIE 1931) specified in JIS Z8701 was obtained. In addition, the chromaticity coordinates (X, y) indicate hue and color, and the tristimulus value Y indicates reflectance and brightness. The colorimetric results are shown in Table 1 below. The chromaticity diagram of the χγζ color system shows the chromaticity coordinates (X, y) of the resist films of the examples and comparative examples before and after the heat resistance test. Further, Fig. 5 schematically shows the enamel color. Chromaticity diagram of the system. 137746.doc -40- 200937123 [Table 1] Example 1 Comparative Example 1 Initial Y 89.51 80.24 X 0.3118 0.3132 y 0.3298 0.3332 270°C, 2 minutes Y 88.78 76.98 X 0.3130 0.3182 y 0.3318 0.3395 ΔΥ -0.73 -3.26 △X 0.0012 0.0050 Δy 0.0020 0.0063 288°C, 2 minutes Υ 88.31 77.25 X 0.3121 0.3237 y 0.3308 0.3450 ΔΥ -1.2 -2.99 △X 0.0003 0.0105 △y 0.0010 0.0118

△ Υ, Δχ, and Ay respectively represent the change in the value of x, y before the start of the heat resistance test (initial), and the resist film formed using the resist material of Example 1, and the anti-surname film before and after the heat resistance test. The change in chromaticity coordinates y and y) is small, and both Αχ and Ay are 0.005 or less, and the degree of discoloration is extremely small. In the visual observation, the resist film of Example 1 before the heat resistance test was white, and yellowing was not observed in the resist film of Example 1 after the heat resistance test. On the other hand, using the resist film formed of the resist material of Comparative Example 1, the change in the chromaticity coordinates (X, y) of the resist film before and after the heat resistance test was larger than that of 137746.doc -41 - 200937123. Both Ay and Ay exceeded 0.005, and the degree of discoloration was extremely large. When visually observed, yellowing was confirmed in the resist film of Comparative Example 1 after the heat resistance test. Next, when the resist materials of Examples 2 to 33 and Comparative Examples 2 to 4 were prepared, the following materials were prepared. For the synthesis of decane polymers 1 to 21, as a decyl decane, 3_(glycidoxypropyl)trimethoxydecane (GTMS), 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxaloxane (EpTMS), 3-(glycidoxypropyl)methyldimethoxyxanthine (GMDMS), mercaptotrimethoxyphthalate (MTMS) and dimethyldimethoxydecane (DMDMS) At least one of them. (Hydrane polymer 1) In a 1000 ml flask equipped with a condenser, 0.16 m·l of GTMS, 0.24 mol of MTMS, 0.6 mol of DMDMS, and 87.4 ml of propylene glycol monoterpene ether acetate were obtained. Solution. Using a semicircular mechanical stirrer, while stirring the above solution, an aqueous solution in which 0.28 g of potassium hydroxide was dissolved in 43.2 ml of water was slowly added dropwise. Thereafter, the solution was heated at 5 °C for 3 hours by heating the jacket. Then, using a vaporizer at a pressure of 2000 Pa, 40 ((: and 1 hour), a condensation reaction with water was carried out. The methanol and the residual water were removed. Thereafter, the flask was placed until the room temperature was reached, and the solution containing the oxime polymer yttrium obtained was a solid solution concentration of 50% by weight. Oxyalkane Polymers 2, 4, 6 to 8, 10, 12, 17, 21) The types and amounts of alkoxydecane were changed as shown in Table 2 below, and the resin solids after condensation reached 50% by weight. In addition, the amount of the propylene glycol 137746.doc-42-200937123 monomethyl ether acetate was adjusted, and in the same manner as the oxime polymer 丄, the siloxane-containing polymer 2, 4, 6 was obtained. a solution of ～8, 1〇, 12, 17, 21, and the obtained solid solution concentration of the solution containing the siloxane polymer of 2, 4, 6~8, 1〇, 12, 17, 21 is 5 〇 weight 0/矽 (矽 烷 聚合物 3 3 矽 矽 矽 矽 矽 矽 矽 矽 矽 GT GT GT GT GT GT GT GT GT GT GT GT GT GT GT GT GT GT 0.11 m〇iiDMDMS, 2〇〇ml of toluene, and 67 3 of propylene glycol monoterpene ether acetate were obtained to obtain a solution. Using a semicircular mechanical stirrer, the solution was slowly added dropwise while dissolved in 43.2 ml of water. · 28 g of an aqueous solution of potassium hydroxide. Thereafter, the solution was reacted at 5 (TC for 3 hours by heating the jacket. Then, using an evaporator at a pressure of 2000 Pa, 40. (: and 1 hour, The methanol and residual water produced by the condensation reaction with water are removed. Thereafter, the flask is placed until it reaches the temperature to obtain a solution containing the oxalate polymer 3. The solid solution of the obtained solution containing the siloxane polymer 3 The concentration of the substance was 5% by weight. (Hexane polymer 5, 9, 11, 14 to 16) The type and amount of the alkoxy decane were changed as shown in the following Table 2, and the resin solid after condensation was used. The addition amount of the propylene glycol early-family acetate was adjusted in such a manner as to achieve 50% by weight. In addition, the siloxane-containing polymer 5, 9, 11, 14 was obtained in the same manner as the siloxane polymer 3. The solution containing 16 is obtained from a siloxane polymer 5 The solid concentration of the solution of 9, 11, 14 to 16 is 50% by weight. (Hexane polymer 13) 137746.doc •43- 200937123 In a 1000 ml flask equipped with a condenser, 0. 26 mol is added. GTMS, 0.26 mol of EpTMS, 0.48 mol of DMDMS, 100 ml of toluene, and 53.7 ml of propylene glycol monomethyl ether acetate were used to obtain a solution. Using a semicircular mechanical stirrer, the solution was slowly added dropwise in 43.2 ml of water while stirring. An aqueous solution of 0.28 g of potassium hydroxide was dissolved. Thereafter, the solution was reacted at 50 ° C for 3 hours by means of a heating mantle. Next, the sterol and residual water formed by the condensation reaction with water were removed using an evaporator at a pressure of 2000 Pa, 40 ° C and 1 hour. Thereafter, the flask was placed until it reached room temperature, and a solution containing the siloxane polymer 13 was obtained. The resulting solution containing the decane polymer 13 had a solid concentration of 50% by weight. (Hexane polymer 18) In a 1000 ml flask equipped with a condenser, 0.26 mol of GTMS, 0.26 mol of EpTMS, and 0.48 mol of DMDMS were added to obtain a solution. * Stir the above using a semicircular mechanical stirrer. The solution was slowly added dropwise to an aqueous solution of 0.28 g of potassium hydroxide dissolved in 43 · 2 ml of water. Thereafter, the solution was reacted at 50 ° C for 3 hours by means of a heating mantle. Next, using an evaporator, removing sterol and residual water formed by condensation reaction with water under a pressure of 2000 Pa, 40 ° C and 1 hour, adding 53.7 ml of propylene glycol monomethyl ether acetate and stirring After making it a homogeneous solution, the flask was placed until it reached room temperature, and a solution containing the siloxane polymer 18 was obtained. The resulting solution containing the siloxane polymer 18 had a solid concentration of 50% by weight. 137746.doc 200937123 (Hexane Polymer 19) In a 1000 ml flask equipped with a condenser, 0.26 mol of GTMS, 0.26 mol of EpTMS, 〇·48 mol of DMDMS, 300 ml of toluene, and 53.7 ml were added. Propylene glycol monomethyl ether acetate to obtain a solution. Using a semicircular mechanical stirrer, while stirring the above solution, an aqueous solution in which 0.28 g of potassium hydroxide was dissolved in 43.2 ml of water was slowly added dropwise. Thereafter, the solution was reacted at 50 ° C for 3 hours by means of a heating mantle. Next, using an evaporator at a pressure of 2000 Pa, 4 (TC and 1 hour, will be

The methanol and residual water produced by the condensation reaction of water are removed. Thereafter, the flask was placed until it reached room temperature, and a solution containing the siloxane polymer 19 was obtained. The resulting solution containing the siloxane polymer 19 had a solid concentration of 50% by weight. (Hexane polymer 20) To a 1000 ml flask equipped with a condenser, 0.26 mol of GTMS, 0.26 mol of EpTMS, and 0.48 mol of DMDMS were added to obtain a solution. Using a semicircular mechanical stirrer, while stirring the above solution, an aqueous solution in which 0.28 g of potassium hydroxide was dissolved in 43.2 ml of water was slowly added dropwise. Thereafter, the solution was reacted at 50 ° C for 3 hours by means of a heating mantle. Next, methanol and residual water generated by condensation reaction with water were removed using an evaporator at a pressure of 1000 Pa, 40 ° C and 2 hours. After adding 53.7 ml of propylene glycol monomethyl ether acetate and stirring it to make a homogeneous solution, the flask was placed until it reached room temperature, and a solution containing the siloxane polymer 20 was obtained. The solid solution concentration of the resulting solution containing the siloxane polymer 20 was 50 137746.doc -45 · 200937123% by weight. The details of the obtained aspartic acid-fired polymers 1 to 21 are shown in Table 2 below. In the following Table 2, the above formula (!), and the above formula (1), are shown in the total of 1 〇〇mol% of the fragment compound represented by the above formula (1) for synthesizing a siloxane polymer. The ratio of the decane compound in which p is 2. Further, the weight average molecular weight Mw of the polystyrene oxide #1 measured by the gel permeation chromatograph using the gel permeation chromatograph is shown in Table 2 below. Further, the ratio of the organic group having a cyclic ether group in the organic group 〇〇% of the carbon atom directly bonded to the ruthenium oxide polymer 1 to 21 on the ruthenium atom, and the epoxy ring The ratio of the organic groups of the shelves is shown in Table 2 below.

137746.doc -46- 200937123 [CNi epoxide equivalent ^Ti Ον ίΝ 卜卜2 00 ^Τί (Ν <Ν CN (Ν (Ν gsg V〇(N § ov〇(NT·^ CN 1 5 〇 weight average MMW 5500 4500 8000 4800 7800 5700 4700 4800 8000 6100 8400 2700 5100 7600 7800 2000 10000 50000 1500 70000 3000 D body ratio (mol%) ^3 Ο r"H % TH o TH 〇rH V〇 hide ^ ^ ^ nD W ^ 减 蛘 蛘 〇Ο rn rn rn 〇 〇 Ο rn rn tn CN v〇CS v〇o 00 Os 00 00 00 00 00 1 JlX sm cup when -6- 〇 pen ^ S 靖-U — 1 w ^袋铃Ο 00 v〇〇\ Ο 00 m οο cn g 'O (N 00 l〇mm ro P; 00 in m in mmm cn 1 Composition (mixing unit: mol) DMDMS ο inch ο [0.11" o ν〇ο Inch ο c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c c o GMDMS <Ν Ο 1 (Ν d> cs ο 卜 o EpTMS 1 0.16 1 (Ν Ο ο I 0.89 I r < o as o 10.26 JI 0.22 II 0.22 II 0.26 II 0.26 II 0.26 1 I 0.26 II 0.26 I GTMS 1 0.16 1 inch Ο I 0.89 1 o ON Ο CN d> I 0.26 | I 0.22 II 0.22 I 1 0.26 I 1 0.26 II 0.26 1 I 0.26 II 0.26 I Μ Η•Η I Hexane polymer No. »·—Η (Ν ro Ό Ό 〇 00 00 Os o 1—H rj m 2 v〇 oo Os • π Η' «5? Η ※ 冢q4 W#φ^^· ^«3 嫦&ν·δ-( ι )^-r 长喵友(ι )<,«-6-0/OOS 岂一^黎荽^^越^^^长^友二:^^ ^^案^铋域^^哒^食阳长^^※ 瓦5忘硪_枇w 驷 驷 domain tatirfti cup *«-B-%ool 硪 杯 cupwff® enough 垅 垅 璁 璁 屮噼铪 屮噼铪 屮噼铪婵^※ 137746.doc •47- 200937123 (Materials other than Shixia Oxygenated Polymer) 828 (Double-type A-type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.) YX8000 (Hydrogenated Double A-type Epoxy Resin, Japan Manufactured by Epoxy Resin Co., Ltd. _(Double-F-type epoxy resin manufactured by Nippon Epoxy Co., Ltd.) Z300 (Resin with reductive double bond on side bond, manufactured by Chemical Industry Co., Ltd.) DPHA (dipentaerythritol) Hexaacrylate) CR-5 8 (rutile titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd.) KS- 69 (composite defoamer, manufactured by Shine Etsus Co., Ltd.) Photopolymerization initiator (photoradical generator, τρ〇, manufactured by Siberuhegner Co., Ltd.) Solvent (propylene glycol monoterpene ether acetate) (Example) 2) Blending 72 parts by weight of a naphthenic polymer 1, 1 part by weight of z3 〇〇 ((meth)acrylic resin having a repulsive group and having an unsaturated double bond in a side chain] Diasel Chemical Industry Co., Ltd. Manufactured), 1 part by weight of 〇ρηα (dipentaerythritol hexaacrylate), 12 parts by weight of cr-58 (rutile-type dioxin chins), 5 parts by weight of KS-69 (composite type) Antifoaming agent, manufactured by Shin-Etsu Silicones Co., Ltd., and 9 parts by weight of a photopolymerization initiator (photo-free radical generator, TPO, manufactured by Siberuhegner Co., Ltd.)' by stirring and stirring Taro SP_500 (manufactured by Thinky Co., Ltd.) After mixing for 2 minutes, 'mixing was carried out using a three-roll mill. Thereafter, the mixture was defoamed for 3 minutes using SP-500 to obtain a resist material as a resin composition. 137746.doc -48- 200937123 (Examples 3 to 33 and Comparative Examples 2 to 4) The materials used in the following paragraphs 3 to 6 are changed as shown in the following Tables 3 to 6, and the examples are the same as the examples. 2 A resist material was obtained in the same manner. (Evaluation) (1) Compatibility The resist material was placed and placed, and at this time, whether or not layer separation occurred was observed, and the compatibility was evaluated according to the following evaluation criteria. [Evaluation criteria for compatibility] ® 〇: Layer separation did not occur after 2 hours of standing △: Layer separation occurred between 1 hour and 2 hours after leaving X: Layer separation occurred within 1 hour of placement (2) Reflectance by net The printing method applied the obtained resist material to a substrate formed of glass. After coating, it was dried in an oven at 80 ° C for 20 minutes to form a layer of resist material on the substrate. Next, a mask having a specific pattern is interposed, and an ultraviolet irradiation device is used to irradiate the resist material layer for 4 seconds at a wavelength of 400 mJ/cm 2 with an ultraviolet illuminance of 100 mW/cm 2 for 365 nm. UV rays. After the ultraviolet ray is irradiated, the resist material layer is immersed in a 1% by weight aqueous solution of sodium carbonate to develop, and the anti-money material layer of the unexposed portion is removed, whereby a pattern of a resist film is formed on the substrate. Thereafter, the resist film was post-hardened by heating in an oven at 150 ° C for 1 hour, thereby obtaining a resist film. The thickness of the obtained resist film was 2 Å μηη. The reflectance of the obtained evaluation sample was measured using a color-color difference meter (manufactured by Konica Minolta Co., Ltd., CR-400) 137746.doc • 49- 200937123. (3) Heat resistance at 27 〇t, the evaluation sample obtained by the above (2) reflectance was subjected to heat treatment. 3 A color-color difference meter (manufactured by Konica Minolta Co., Ltd., CR_4 〇〇) was used to measure the evaluation sample before heat treatment. L*, a*, and b*e are also measured for L*, a*, and b* of the evaluation sample after the heat treatment, and are evaluated as "the following evaluation samples after the heat treatment based on the two measured values". ◎", when it is more than 3 and is 4 or less, it is evaluated as "〇", and when it exceeds 4 and is 5 or less, it is evaluated as "△", and when it exceeds 5, it is evaluated as "χ", and the evaluation result is shown in the following Table 3~ 6. (4) Weather resistance The evaluation sample obtained in the above (2) reflectance was irradiated with light having a wavelength of 365 nm by using an ultraviolet (Ultra Violet) irradiator so that the irradiation energy reached 100 J/cm2. L*, a*, b* of the evaluation sample before UV irradiation were measured using a color-color difference meter (manufactured by Konica Minolta Co., Ltd., CR-400). Further, L*, a*, and b* of the s parity sample after the irradiation were measured, and ΔΕ-ab was obtained from the two measured values. When the evaluation sample after UV irradiation was north, the evaluation was "◎", and when it was more than 1 and 2 or less, it was evaluated as "〇", and when it was more than 2 and 3 or less, it was evaluated as "△". The evaluation was "X" at 3 o'clock, and the evaluation results were not in Tables 3 to 6 below. (5) Developability The obtained resist material was applied onto a glass substrate by a screen printing method to a thickness of 2 〇 瓜 137746.doc cn 200937123. Screen printing was carried out under the following conditions: i.e., squeegee speed: 250 mm/sec, squeegee pressure: 0.17 MPa, to knife pressure: ο"? MPa, back pressure: 〇 1〇 MPa, scraper speed: 50 mm/sec, and clearance: i 7 mm. After coating, it was dried in an oven at 80 ° C for 20 minutes to form an anti-surname material layer on the substrate. Next, 'the mask having a pattern (the width of the opening is 100 μm, the width of the mask is 1 μmηη), and the ultraviolet irradiation device is used so that the irradiation energy reaches 400 mJ/cm 2 , 1 〇紫外线mW/cm2 ultraviolet illuminance The resist material layer was irradiated with ultraviolet rays having a wavelength of 365 nm for 4 seconds. Thereafter, the resist material layer was immersed in a 1% by weight aqueous solution of sodium carbonate to develop, and the unreacted portion of the anti-money material layer was removed, whereby a resist film having a thickness of 20 μm was formed on the substrate. After the development, the resist film was subjected to heat treatment at 150 ° C for 60 minutes. When the resist film was obtained, it was observed whether or not a pattern was formed after development using an electron microscope, whereby the developability was evaluated in accordance with the following evaluation criteria. [Evaluation criteria for developability] 〇: Pattern of L/S 100 μηι was formed Δ: Although a pattern of L/S 100 μm was formed, the length dimension of the pattern was 10% or more uneven X: L/ was not formed Pattern of S 100 μm (6) Viscosity In the evaluation of the above (5) developability, after heating at 80 ° C for 20 minutes, the layer of the anti-detergent material was pressed with a finger (after heating at 80 ° C for 20 minutes) The surface of the button film was evaluated for viscosity according to the following evaluation criteria. 137746.doc •51 · 200937123 [Evaluation Criteria for Viscosity] 〇: No finger touch on the resist film △• A slight finger touch on the resist film X: Significant finger touch marks on the resist film (7) Moisture and heat resistance The substrate obtained in the above (5) developability s parity was obtained under the conditions of 130 ° C and a relative humidity of 85% RH using an aging test apparatus (EHS-211M, manufactured by Espec Co., Ltd.). The resist film was subjected to heat treatment for 72 hours, 48 hours or Μ hours to obtain an evaluation sample. Whether or not the obtained evaluation sample was cracked was observed, and the heat and humidity resistance was evaluated based on the following evaluation criteria. ° [Evaluation criteria for resistance to source heat] ◎ : After the heat treatment for 72 hours, the resist film was not cracked. After the heat treatment for 72 hours, the resist film was cracked, but the resist film was not cracked after 48 hours of heat treatment. △ : 48 hours The resist film was cracked after the heat treatment, but the resist film was not cracked after the heat treatment for 24 hours, and the results of the crack evaluation of the resist film after the heat treatment for X: 24 hours are shown in Tables 3 to 6 below. 137746.doc •52· 200937123 [Table 3] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 -1 - _ 72 ΊΓ 29 24 4 108 S 23 a 6 74 7 30 8 — 31 9 25 III No. 10 11 调 Mixing 13 14 into a 15 minutes 16 17 Amount W 18 19 A 20 21 R?8 YX8000 806 Z3〇<L——100 100 100 100 100 100 100 100 100 dpha 10 10 10 10 10 10 10 10 10 CR-5B 120 120 120 120 120 120 120 120 120 KS-69 5 5 5 5 5 5 5 5 5 Photopolymerization Start Sword 9 9 9 9 9 9 9 9 9 Solvent value (mgKOH/g) 54 78 82 43 83 53 77 76 81 Epoxy equivalent (g/eq) 1055 726 653 1320 666 1062 719 715 726 Acid value X epoxy equivalent ※l 56518 56828 53412 56172 55086 56098 55151 54334 58729 compatibility 〇〇〇Δ 〇〇 〇〇 Viscosity 〇〇〇〇〇〇〇〇〇 Evaluation developability 〇〇〇〇〇〇〇〇〇 reflectance (%) 80 83 84 78 84 80 83 83 84 Heat resistance 〇〇〇〇〇 ◎ 〇〇 ◎咐 热 ◎ ◎ ◎ Δ ◎ ◎ ◎ ◎ Weather resistance 〇〇〇〇〇 ◎ 〇〇 ◎ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 137746.doc •53- 200937123 [Table 4]

Formulation amount 彖 Example · 12 f1 Example ' 13 Cases ^ 14 Example ^ 15 f Shi (4) · 16 f Example 17 Appreciation Example 18 18 Example 19 1 III No. 2 1 3 4 5 6 7 8 9 10 110 11 25 12 27 13 32 14 34 15 34 16 32 17 32 18 32 19 20 21 828 YX8000 806 Z300 100 100 100 100 100 100 100 100 100 dpha 10 10 10 10 10 10 10 10 10 CR-58 120 120 120 120 120 120 120 120 120 KS-69 5 5 5 5 5 5 5 5 5 Photopolymerization initiator 9 9 9 9 9 9 9 9 9 Solvent value (mgKOH/g) 42 81 79 75 74 74 75 75 75 Epoxy equivalent (g/eq) 1327 689 785 747 762 744 809 747 747 Acid value X epoxy equivalent ※1 55629 55747 62107 56129 56116 54800 60787 56129 56129 Evaluation of compatibility △ 〇〇〇〇〇〇〇〇 viscous 〇 〇〇〇〇〇〇〇〇 developability 〇〇〇〇〇〇〇〇〇 reflectivity (%) 78 84 83 82 81 81 82 82 82 Heat resistance 〇 ◎ 〇〇〇〇〇〇〇 Heat and humidity resistance ◎ △ ◎ ◎ ◎ A ◎ ◎ ◎ 候 〇 〇〇〇〇〇〇〇 〇〇〇〇〇〇〇 l ※l resin The product of the solid acid value of the component (mgKOH/g) and the epoxy equivalent of the resin component (g/eq) 137746.doc -54- 200937123 [Table 5]

Example & Example 20 Example 21 Example 22 Greedy Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 1 ΊΓ .3 4 5 7 Ϊ 16 25 37 47 62 8 78 III 11 No 12 Adjustment 13 Distribution Component amount W T5 16 17 18 19 32 20 32 21 828 YX8000 806 Z300 100 100 100 100 100 100 100 100 100 DPHA 10 10 10 10 10 10 10 10 10 CR-58 120 120 120 120 120 120 120 120 120 A KS-69 5 5 5 5 5 5 5 5 5 Photopolymerization initial lean J 9 9 9 9 9 9 9 9 9 Solvent value (mgKOH/g) 75 75 90 81 72 65 58 99 51 Epoxy Equivalent (g/eq) 747 747 1174 833 638 549 471 2123 421 Acid value X epoxy equivalent ※l 56129 56129 105272 67374 45523 35837 27167 210543 21594 Compatibility 〇Δ 〇〇〇〇〇〇Δ Viscosity Δ 〇〇〇〇 〇〇〇 Δ Evaluation of developability 〇〇〇〇〇〇〇〇〇 reflectance (%) 82 82 84 84 82 81 80 84 79 Heat resistance 〇〇〇〇〇〇〇〇〇 Moisture resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ ◎ Weather resistance 〇〇 〇〇〇〇 〇〇〇〇 〇 l l l l l 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂

----- Example 29 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 30 Example 31 Example 32 Example 33 The amount of the formulated component was 1 2 3 Τ" 5 6 7 8 31 31 31 31 9 10 11 12 13 14 15 16 17 18 19 20 21 31 828 17 YX80〇〇~~~ 19 806 15 Ζ300 100 100 100 100 100 100 100 100 DPHA 10 10 10 10 10 10 10 10 CR-58 120 120 120 120 47 95 145 250 KS-69 5 5 5 5 5 5 5 5 Photopolymerization start 刽9 9 9 9 9 9 9 9 Solubility 7 8 7 Acid value (mgKOH/g) 82 79 84 76 76 76 76 Epoxy equivalent (g/eq ) - 712 712 682 715 715 715 715 Acid 乇 χ χ Epoxy equivalent ※1 0 58001 56289 57387 54334 54334 54334 54334 Evaluation of compatibility Δ 〇〇〇〇〇〇〇 viscous 〇〇〇〇〇〇〇〇 developability 〇〇 〇〇〇〇Δ Δ reflectance (%) 83 83 83 82 72 78 86 92 Heat resistance ◎ XXX 〇 ◎ ◎ ◎ Moisture and heat resistance △ ◎ ◎ ◎ ◎ 〇 〇 Δ Weather resistance ◎ X △ X △ 〇 ◎ ◎ * The product of the solid content acid value (mgKOH/g) of the resin component and the epoxy equivalent (g/eq) of the resin component 137746 .doc •56· 200937123 Next, when preparing other anti-materials, prepare the following materials. To synthesize the following alkoxylate polymers 22 to 32, as the alkoxydecane, methyltrimethoxydecane, dimercaptodimethoxydecane, and 3 (trimethoxyxanthene)propyl sulphate were used. Acid Xuan Trimethoxy Money (Shin-Etsu Chemical Industry Co., Ltd.

Manufacture, X12-967), 3· mercapto propylene oxide oxypropyl trimethoxy sulphur, 3-mercapto propylene methoxy propyl methyl decyl oxy decane, propylene methoxy propyl three曱oxydecane, 3·vinyloxypropyltrimethoxydecane, 3′glycidoxypropyltrimethoxy ketone, 3•glycidoxypropylmethyldimethoxy oxime&, 2- (3,4-epoxycyclohexyl)ethyl " at least one of methoxy decane. (Hexane polymer 22) In a 100 ml flask equipped with a condenser, 15 guanidine methyltrimethoxy was added.矽, 5 mol of tris(trimethoxydecyl)propyl succinic anhydride trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., Χ12·967), 8〇m〇i23_ methacryloxypropylmethyl group A solution was obtained by using a decyloxydecane, 15 ml of water, and 2 ml of propylene glycol monomethyl ether acetate. The solution was stirred while stirring at 80 ° C using a semi-circular mechanical stirrer while stirring the solution. 3 hours. Secondly, using an evaporator, methanol and residuals formed by condensation reaction with water at a pressure of 2000 Pa, 4 (TC and 1 hour) The water was removed. Thereafter, the flask was placed until it reached room temperature, and a solution containing the siloxane polymer 22 was obtained. The solid solution concentration of the obtained solution containing the siloxane polymer 22 was 70% by weight. Alkyl polymer 23~37 and 44~46) The type and amount of alkoxy decane are changed as shown in the following Tables 7 to 10, 137746.doc -57- 200937123 Other than 'with a siloxane polymer 22 A solution containing Dream Oxygen Polymers 23 to 37 and 44 to 46 was obtained in the same manner, and the obtained solid solution containing the oxy-fired polymers 23 to 37 and 44 to 46 had a solid concentration of 70 wt%/〇. Oxyalkane polymer 38) In a 100 ml flask equipped with a condenser, add 39 mol of decyltrimethoxymethane, 40 mol of dimethyl methoxymethyl, 1 mol of 3-(trimethoxydecyl) ) propyl succinic anhydride trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., X12-967), 5 mol of 3-methylpropenyloxypropyltrimethoxydecane, 15 mol of 2-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, 15 ml of water, 1,5 mol of potassium hydroxide, and 20 ml of propylene glycol monomethyl ether acetate, to obtain a solution Using a semi-circular mechanical stirrer, the resulting solution was stirred while heating at 80 ° C for 3 hours. Then, acetic acid was added until the solution became neutral, followed by 'using an evaporator at 2 〇. The pressure of 〇〇Pa, 40 ° C and 1 hour, the sterol and residual water formed by the condensation reaction with water were removed. After that, the flask was placed until it reached room temperature, and the salt formed was filtered. 'The solution containing the siloxane polymer 38 is thus obtained. The resulting solution containing the siloxane polymer 38 had a solid concentration of 70% by weight. (Neteroxane polymers 39 to 43 and 47 to 53) The same as the azeoxane polymer 38, except that the type and the amount of the alkoxydecane are changed as shown in the following Tables 9 and 10. A solution containing the arsine-oxygenated polymers 39 to 43 and 47 to 53 was obtained. The solid solution concentration of the obtained solution containing the agglomerated oxygen polymers 39 to 43 and 47 to 53 was 7 〇 〇 /0. 137746.doc •58· 200937123 The details of the obtained oxoxane polymers 22 to 53 are shown in the following Table 7 to Tables 7 to 10 below, which are represented by (1) for synthesizing a siloxane polymer. The ratio of the decane compound represented by the above formula (the formula of (1) and p of 2 in the above formula (1) in a total of 100 mol% of the compound of the ceramsite compound. Further, the obtained oxirane polymer is obtained by gel permeation chromatography. The polystyrene-equivalent weight average molecular weight Mw measured at 22 to 53 is shown in the following Tables 7 to 10. Further, the obtained anthracene oxygen-fired polymer 22 to 53 is directly bonded to the organic group having a carbon atom at a halogen atom. The ratio of the organic group having an unsaturated double bond, the ratio of the organic group having an acid group or a thio group, and the ratio of the organic group having a cyclic ether group are shown in the following Tables 7 to 1 〇. .doc -59- 200937123

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Inch ※(roK^^w^il^lE f#q1«砩赛^^硪篇荽蛘枇^ Forget 屮^芑一砩 杷^屮噼 enough 杷龙黎璁一:一-屮噼^蛘Inch ※ 壬宕 壬宕 赛 赛 赛 硪癍嘁硪 硪癍嘁硪 « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « Cup W^^vg-^K·枇4 guest+%001 cupping cup^屮噼镩杷垅convenient one: one-屮噼备蛘^※ f#^w 荽<0^ domain preparation SZ 礞d >-&-(a) βΜ长硌茫(I )<, 菠-&-%os 〇〇14*璨#Φ^^^>长硌^(荽伞铋^念^一※ 137746. Doc -63- 200937123 (Acrylic resin) Acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "MSP-5969") (Epoxy resin) Epoxy oxirane (manufactured by Shin-Etsu Chemical Co., Ltd., r KF-101 ” • Hydrogenated double-prepared A-type epoxy resin (manufactured by Nippon Epoxy Co., Ltd., trade name “YX8000”) alicyclic epoxy resin (manufactured by Daisel Chemical Industry Co., Ltd., trade name “Celloxide 2021Ρ”) isocyanide Acid epoxy resin (manufactured by Nissan Chemical Co., Ltd., trade name "TEPIC-SP") Double-decreasing 'A type epoxy resin (Japan epoxy Manufactured by the company, trade name "828") (polymerization initiator) Light 5^ starter (photo-free radical generator, manufactured by Japan §iberuhegner Co., Ltd., trade name "TPO") (white filler) Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name r CR_97) (Example 34) 100 parts by weight of a siloxane polymer 22, 2 parts by weight of a photopolymerization initiator (photoradical generator, Siberuhegner & Manufactured under the name "TPO", and 300 parts by weight of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., trade name "CR-97"), mixed with a stirrer for 2 minutes, and then mixed by a three-roll mill. The mixture was subjected to defoaming for 3 minutes using a defoaming stirring Taro sp_137746.doc 200937123 5〇〇 (manufactured by Thinky Co., Ltd.), thereby obtaining a resist material. (Examples 35 to 74 and Comparative Examples 5 to 8) A resist material was obtained in the same manner as in Example 34 except that the materials used were changed as shown in FIGS. 11 to 17. (Evaluation) (1) The initial reflectance preparation size was 80 mm x 90 mm, and the thickness was 1 .〇min glass base The obtained resist material was printed on the glass substrate in a β pattern by screen printing method using a 100 mesh polyester oblique screen cloth, and then dried in a hot air oven at 80 ° C for 20 minutes. Next, 'Ultraviolet irradiation apparatus (HMW-680GX, manufactured by ORC Co., Ltd.) was used to irradiate the ultraviolet illuminance of 50 mW/cm2 for 12 seconds to 365 11111 in such a manner that the irradiation energy reached 6 〇〇mJ/cm2. UV rays. Next, weigh 1 of 30 °C. The sodium carbonate aqueous solution was used as a developing solution for 9 seconds in a developing machine using a printed circuit board, and then dried in a hot air oven for 1 minute for 60 minutes to obtain a sample having a film thickness of 2 〇μπΐ2. Using a spectrophotometer (Shimadzu Corporation) The initial reflectance of the obtained evaluation sample was measured by the company's manufacture, trade name "UVPC-3101C". (2) The light-resistant color change and the light-resistant reflectance change are performed by using an ultraviolet irradiation device (Sp〇t Cure SP-5, manufactured by USHI〇T, Inc.) to make the irradiation energy reach 1〇〇J/cm2. 137746.doc 65 200937123 Ultraviolet illuminance of mWW The ultraviolet ray having a wavelength of 365 nm was obtained by irradiating the sample for 500 seconds in the initial reflectance of the above (1). Using a color difference meter (Konica Minolta Co., Ltd., product name "CR-400") to measure the y^ of the evaluation sample before light irradiation, and 'measuring L*, a*, b of the evaluation sample after light irradiation, Based on these two measured values, AE*ab is obtained. When the evaluation sample 热处理E*ab is not full after heat treatment, it is evaluated as "〇", when it is 1 > 5 or more and less than 2 =

When it is "△", it is evaluated as "χ" when it is 2 or more, and the evaluation results are shown in the following Tables 11 to 17. Further, the reflectance of the evaluation sample after the light irradiation was measured using a spectrophotometer (manufactured by Shimadzu Corporation, trade name "UVPC-3101C"). When the reflectance of the evaluation sample after light irradiation is lower than the initial reflectance of the evaluation sample before light irradiation, the change (decrease value) is less than 5%. When it is 5 %, it is evaluated as "〇", and when it is 0.5% or more When it was less than 2%, it was evaluated as "△", and when it was the above, it was evaluated as "X", and the evaluation results are shown in Tables 11 to 17 below. (3) Change in color tone and change in heat-resistant reflectance The evaluation sample obtained in the above (1) initial reflectance was placed under 27 Torr for 5 minutes to heat-treat. L* and 0 n of the evaluation sample before heat treatment were measured using a color difference meter (manufactured by K〇nica Min〇lta & Division, trade name "CR-400"), and the evaluation sample after the heat treatment was measured. , a*, b*, and find ΔΕ*&1) based on the two measured values. When ΔE*ab of the evaluation sample after heat treatment was less than 1, it was evaluated as “〇”, and when it was i.5 or more and less than 2, it was evaluated as “Δ”, and when it was 2 or more, it was evaluated as “χ”, and evaluation was evaluated as “χ”. The results are shown in the following Tables 13 to 17 of 137746.doc -66 - 200937123. Further, the reflectance of the evaluation sample after the heat treatment was measured using a spectrophotometer (manufactured by Shimadzu Corporation, trade name "UVPC-3101C". The reflectance of the evaluation sample after the heat treatment was compared with the initial reflectance of the evaluation sample before the heat treatment. When the change (reduction value) is less than 5%, it is evaluated as "〇", and when it is 0.5% or more and less than 2%, it is evaluated as "△", and when it is 2% or more, it is evaluated as "X". 'Evaluation results are shown in the following Table 丨~丨7. (4) Viscosity & After applying the obtained resist material on the substrate, it was dried in a hot air oven at 8 °<»c for 20 minutes on the substrate. The evaluation sample was obtained by pressing the evaluation sample on the obtained substrate with a finger. The viscosity was determined according to the following evaluation criteria. [Evaluation criteria of viscosity] 〇: no stickiness △: slightly sticky X: markedly sticky (5) Evaluation of developability A printed circuit board having a copper circuit having a thickness of 40 μm, a size of mm×90 mm, and a thickness of 1.0 mm was formed on the upper surface. By screen printing method, a polyester mesh of 100 mesh was used. Mesh-making plate The material is printed on the upper surface of the printed circuit board in a β pattern, and then dried in a hot air oven at 8 ° C for 20 minutes. Secondly, the mask is provided with a specific mask to expose the coating film. And the method of the unexposed portion, using an ultraviolet irradiation device (manufactured by ORC Co., Ltd., 137746.doc -67·200937123, HMW-680GX), so that the irradiation energy reaches 600 mJ/cm2, and the ultraviolet illuminance is applied at 50 mW/cm2. The film was partially irradiated with ultraviolet rays having a wavelength of 365 nm for 12 seconds. Thereafter, a weight of 30 ° C of a weight / 〇 sodium carbonate aqueous solution was used as a developing solution, and a developing machine for a printed circuit board was used at 0.2 MPa for 90 seconds. Development, 'then dried in a hot air oven at 150 ° C for 60 minutes to obtain an evaluation sample having a film thickness of 20 μm. When the above resist film was obtained, an electron microscope was used to observe whether or not β was patterned after development, thereby The developability was evaluated by the following evaluation criteria. [Evaluation criteria for developability] 〇: Pattern of L/S 100 μm was formed Δ: A pattern of L/S 100 μη was formed, but the length dimension of the pattern was 10% or more. Do not One X: L/S 100 μm pattern was not formed (6) Reflowability The resist film obtained in the evaluation of the above (5) developability was passed through a reflow furnace together with a printed circuit board (preheating 150 ° C X for 100 seconds) +Reflow soldering [maximum temperature: 260 ° C] 3 times. ' Thereafter, whether or not peeling of the resist film or cracking of the resist film occurred was observed, whereby the heat-resistant peeling or cracking property was evaluated according to the following evaluation criteria. [Evaluation criteria for heat-resistant peeling or cracking] 〇: peeling of resist film or crack of resist film △: peeling of resist film or crack of resist film X: visible resist film on the entire surface Peeling or cracking of the resist film 137746.doc -68 - 200937123 Further, the obtained evaluation sample was evaluated for the adhesion of the resist to the substrate. According to JIS K 5400, the resist film was cut by using a cutter in a size of i mm x 1 mm in a plan view. After the tape was attached to the divided resist film, the tape was peeled off, whereby the adhesion was evaluated based on the following evaluation criteria. [Evaluation Criteria for Heat-Resistant Adhesion] 〇: Among the 100 resist films after the division, the unpeeled resist film is i 00 Δ: 100 pieces of the resist film after the division are 'the unpeeled resist film is 80 ~99® X: Among the 100 resist films after splitting, the unpeeled resist film is ~79 (7) electrically insulating using the comb-shaped electrode B sample of the IPC B-25 test pattern In addition to the printed circuit board, an evaluation sample was obtained under the same conditions as the evaluation of the developability of the above (5). A bias voltage of DC 500 V was applied to the evaluation sample to measure the leakage current. Further, the electrical insulation properties were evaluated based on the measured values of the leakage current in accordance with the following evaluation criteria. _ [Evaluation criteria for electrical insulation] ◎: Leakage current is less than 1.0x10-6 A/cm2 〇: Leakage current is 1.0x10-6 A/cm2 or more and less than 1.5x10-6 A/cm2 △: Leakage current 1.5x10-6 A/cm2 or more and less than 2.0x10-6 A/cm2 X : Leakage current is 2.OxlO-6 A/cm2 or more The results are shown in the following Tables 11 to 17 » 137746.doc -69- 200937123 [Table 11]

EXAMPLES EXAMPLES EXAMPLES Examples 34 35 36 37 38 39 40 22 100 23 100 24 100 25 100 26 100 27 100 28 100 29 30 31 32 33 Oxide polymerization with unsaturated double bonds Compound No. 34 Compound 35 36 37 38 Adjust 39 Component amount 40 41 42 43 44 45 46 Acrylic resin cyclodecane hydrogenated bisphenol A epoxy resin alicyclic epoxy resin isotrimeric decanoic acid epoxy Resin bisphenol A type epoxy resin compound having cyclic ether group 47 48 49 siloxane polymer No. 50 51 52 53 titanium dihalide 300 300 300 300 300 300 300 Photopolymerization initiator 20 20 20 20 20 20 20 solid acid value and epoxy equivalent *1 - - - - - - - Initial reflectance 90 90 90 90 90 90 90 Light resistance hue change (ΔΕ+ab) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Light reflectance change ◎ ◎ ◎ ◎ ◎ ◎ ◎ Heat-resistant color change (AE ^ab) 〇〇〇〇〇〇〇 / / (# heat-resistant reflectance change 〇〇〇〇〇〇〇 developability 〇〇〇〇〇 Δ Δ reflow-resistant heat-resistant peeling or cracking 〇〇〇〇〇〇 〇 heat-resistance △ △ △ Δ △ △ Δ Viscous 〇〇〇〇〇〇〇 Electrical insulation Δ Δ Δ Δ Δ Δ Δ *1 Solid content acid value (KOHmg / g) and epoxy equivalent of resin component ( g/eq) product -70- 137746.doc 200937123 [Table 12]

EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Example 41 42 43 44 45 46 47 Formulation Amount of compound having an unsaturated double bond, a siloxane polymer No. 22 23 24 25 26 27 28 29 100 30 100 31 100 32 100 33 100 34 100 35 100 36 37 38 39 40 41 42 43 44 45 46 Acrylic resin compound with cyclic ether group Epoxy siloxane argon bisphenol A epoxy resin alicyclic epoxy resin Iso-trimeric decanoic acid ring-rolling resin bisphenol A type epoxy resin siloxane polymer No. 47 48 49 50 51 52 53 Titanium dioxide 300 300 300 300 300 300 300 Photopolymerization initiator 20 20 20 20 20 20 20 Solid Acid value and epoxy equivalent slightly ※1 Evaluation initial reflectance 90 90 90 90 90 90 90 Light resistance hue change (ΔΕ%!)) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Change in light reflectance ◎ ◎ ◎ ◎ ◎ ◎ ◎ Change in heat-resistant color tone (△Ehb) Change in heat-resistant reflectance 〇〇〇〇〇〇〇 developability A 〇〇〇〇〇〇 Reflow-resistant heat-resistant peeling or cracking 〇△ 〇〇〇〇Δ Heat-resistance △ △ Δ △ Δ Δ Δ Viscosity △ 〇〇〇〇〇〇 Electrical insulation A △ Δ Δ △ Δ Δ *1 Resin composition Product of solid acid value (KOHmg/g) and epoxy equivalent (g/eq) • 71 - 137746.doc 200937123 [Table 13] EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Examples 48 49 50 51 52 53 54 22 23 24 25 26 27 28 29 30 31 32 33 decane polymer with unsaturated double bond No. 34 Compound 35 36 100 37 100 38 100 Adjust 39 100 Formulation amount 40 100 41 100 42 100 4344 45 46 Acrylic resin epoxy oxirane argon bisphenol A epoxy resin alicyclic epoxy resin isotrifluorofluoric acid cyclic bisphenol A type epoxy resin Compound 48 with cyclic ether group 47 49 Hydroxide polymer No. 50 51 52 53 Titanium dioxide 300 300 300 300 300 300 300 Photopolymerization initiator 20 20 20 20 20 20 20 Product of solid acid value and epoxy equivalent ※1 - - - - - - - Initial reflectance 90 90 90 90 90 90 90 Light-resistant color change (AEbb) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Change in light reflectance ◎ ◎ ◎ ◎ ◎ ◎ ◎ Change in heat-resistant color tone (ΔΕ*αΙ>) 〇〇〇〇〇〇 〇Refractive heat reflectance change 〇〇〇〇〇〇〇 developability 〇 Δ 〇〇〇〇〇 Reflow resistance Heat-resistant peeling or cracking 〇〇〇〇〇〇〇 Heat-resistance Δ Δ 〇〇〇〇〇 〇〇〇〇〇 Electrical conductivity Δ Δ Δ Δ Δ Δ Δ

*1 Product of solid content acid value (KOHmg/g) and epoxy equivalent (g/eq) of resin component -72-137746.doc 200937123 [Table 14] ❹. Example ~55~ Example~56~~ Implementation Example ~57~ Example "58~22 Mutual"26~~28" ~29~ 100 100 100 Example ~59~ 60 100 100 100 Compound with no double bond and dream oxygen polymer No. Blending ingredients (parts by weight) 311Γ1Γ1ΓJTj£jTjT "39~ 42IT "44""45""46* 100 Acrylic resin epoxy oxime __ argon bisphenol A epoxy resin alicyclic ring Oxygen resin isocyanuric acid epoxy resin bisphenol ring eucalyptus tree ~ 15 25 compound oxoxane polymer having cyclic ether group No. 47 48 49 50 51 52 53 15 titanium dioxide photopolymerization initiator solid acid Value and Epoxy When Dong Zhijing 1 Initial Reflectance Light Tolerance Change (AE*ab) Light Resistance Reflectance Change Heat Tolerance Change (AE*ab) 300 20 90 ◎ 300 300 300 20 300 300 20 300 190000 ◎ ◎ 136000 180000 190000 180000 165000 ◎ ◎ ◎ ◎ 90 Δ △ 90 ◎ Evaluation of heat-resistant reflectivity, developability, reflow resistance, heat-resistant peeling or turtle 〇〇 〇〇 〇 〇 〇 Δ Δ Δ Δ 〇〇Ο 〇 △ △ Ο 〇 Δ 黏 viscous electrical insulation heat-resistant adhesive 〇 〇Ο 〇〇〇〇〇Ο 〇 〇 〇 〇 1 1 1 1 1 1 1 The product of solid acid value (KOHmg/g) and epoxy equivalent (g/eq) I37746.doc -73· 200937123 [Table 15]

实施 EXAMPLES EXAMPLES EXAMPLES EMBODIMENT EXAMPLES Example 62 63 64 65 66 67 68 m Formulation* A compound having an unsaturated double bond oxirane polymer No. 22 23 24 25 26 100 100 100 100 100 100 100 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 Acrylic resin compound with cyclic ether group Epoxy decane bisphenol A type epoxy resin grease Ring epoxy resin isotrimeric decanoic acid ring resin double test type A ring gas oxime siloxane polymer No. 47 48 15 49 12 50 200 51 250 52 10 53 30 400 titanium dioxide 300 300 300 300 300 300 300 300 Photopolymerization initiator 20 20 20 20 20 20 20 Solid shape evaluation of acid value and ring equivalent weight ※1 219000 116000 165000 148000 275000 165000 25000 Initial reflection耐 耐 耐 耐○ ◎ ◎ ◎ ◎ ◎ Development △ Γ 〇〇〇 △ △ △ Reflow resistance, heat-resistant peeling, cracking, heat resistance, "〇" 〇〇 △ 〇〇 〇, the product of the solid acid value of the electrically insulating enamel resin component (KOHmg/g) and the epoxy equivalent (g/eq) -74- 137746.doc 200937123实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施100 100 100 1〇〇27 28 29 30 31 ——- _32 33 34 35 36 37 38 39 40 41 42 43 4 4 1 45 46 缂 缂 缂 糸 具有 具有 具有 具有 具有 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼 盼Rolled resin siloxane polymer No. 47 48 49 50 51 52 53 320 20 15 30 30 30 Two-rolled bismuth 100 300 300 100 1000 1200 Photopolymerization initiator A·20 20 20 20 20 20 Product with epoxy equivalent ※1 - 31000 490000 670000 165000 165000 165000 Evaluation of initial reflectance 1 90 90 90 80 95 96 Change in hue (AE*ab) — ◎ — ◎ ◎ ◎ ◎ ◎ Change in light reflectance — ◎ ◎ ◎ ◎ ◎ ◎ Change in hot color (ΔΕ* & 1)) ◎ ◎ ◎ ◎ ◎ ◎ Change in heat-resistant reflectance ◎ ◎ ◎ ◎ ◎ ◎ 影 影 - 〇〇〇〇 Δ Reflow resistance * 热 离Or a 〇〇 〇〇〇 〇〇〇 热 热 r r \ r 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 y ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 Product of solid content acid value (K0Hmg/g) and epoxy equivalent (g/eq) of resin component 137746.doc -75· 200937123 [Table 17] Comparative example Comparative example Comparative example Comparative example 5 6 7 8 Formulation component 1 amount Compound decane polymer having an unsaturated double bond No. 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 100 45 100 46 100 Acrylic resin 100 Epoxy oxime Oxylkane argon bisphenol A type epoxy resin alicyclic epoxy resin isotrimeric decanoic acid epoxy resin bisphenol A type epoxy resin 10 compound having a ring puzzle 47 48 49 siloxane polymer No. 50 51 52 53 Titanium dioxide 300 300 300 300 Photopolymerization initiator 20 20 20 20 Product of acid value and epoxy equivalent of solids *1 - _ - - Initial reflectance 90 90 90 90 Light tonal change (△Ehb) ◎ ◎ ◎ X Light resistance reflectance change ◎ ◎ ◎ X Heat resistant color tone Change (AE*ab) ◎ ◎ © X Heat-resistant reflectance change ◎ ◎ ◎ X Developability 〇 XX 〇 Reflow-resistant heat-resistant peeling or cracking X 〇〇〇 Heat-resistant adhesiveness Δ Δ Δ 〇 Viscous 〇 X 〇 〇Electrical insulation Δ Δ Δ 〇

*1 Product of solid content acid value (KOHmg/g) and epoxy equivalent (g/eq) of resin component -76-137746.doc 200937123 [Simplified description of the drawings] Fig. 1 is a schematic view showing the use of the present invention. A portion of the LED element of the resist film formed by the resist material of one embodiment lacks a front cross-sectional view. Fig. 2 is a partial front cross-sectional view showing a modification of an LED element having a resist film formed by using an anti-surname material of an embodiment of the present invention. 3(a) to 3(d) are diagrams showing a part of each step of manufacturing an LED element. FIG. 3(a) is a view showing a state in which a layer of a resist material is formed on a substrate. 3(b) is a view showing a state in which a resist material layer formed on a substrate is exposed, and FIG. 3(c) is a view showing a state in which a resist film is formed on the substrate, and FIG. 3 (FIG. 3) d) is a view showing a state in which an LED chip is laminated on the anti-caries film. Fig. 4 is a graph showing the chromaticity coordinates (X, y) of the resist films of the examples and comparative examples before and after the heat resistance test in the chromaticity diagram of the XYZ color system. Fig. 5 is a view schematically showing a chromaticity diagram in the XYZ color system. ^ [Main component symbol description] 1 LED element 2 Substrate 2a Upper surface 3 Resist film 3a Upper surface 4a ' 4b Electrode 7 LED wafer 137746.doc •77· 200937123 7a 8a ' 8b 9a, 9b 11 11a * lib • 12 12a O 12b

21 A Lower surface Terminal Solder Resist material layer Exposure part Unexposed part Mask Opening part Mask part Resin board Light emitted by LED 137 137746.doc -78-

Claims (1)

200937123 VII. Scope of Application: 1. An anti-surname material used to form an anti-money film of a light-emitting diode element emitting light having a wavelength of _ nm or less, and containing a siloxane polymer and a white filler. . 2. The anti-residue material of claim 1, wherein the above-mentioned oxaxy-oxygenated polymer is a siloxane polymer obtained by polymerizing at least a compound of the above formula (4), Si(X) p(R)4_p. Formula (1) ❹ In the above formula (1), X represents a hydrolyzable group, r represents a non-hydrolyzable organic group having a carbon number of u, and p represents an integer of Bu 4; It can be the same or different when it is cured; when the mouth is in the case, the plural r can be the same or different. 3. The anti-residue material of claim 2, wherein the oxidized polymer is a cyclooxyl polymer having a cyclic ether group, and the oxy-fired polymer having a cyclic ether group is The p-formula of the above formula (1) is a oxyalkylene polymer obtained by polymerizing a decane compound having an integer of 1 to 3 and at least one R is an organic group having a cyclic ether group. 4. The resist material according to claim 3, wherein the above-mentioned naphthenic polymer having a cyclic ether group has an organic group in which a carbon atom is directly bonded to a germanium atom and the organic group is 1 to 80. % has a cyclic ether group. 5. The resist material according to Item 3 or 4, wherein the organic group having a cyclic ether group contains an organic group having an epoxycyclohexane skeleton. 6. The resist material of claim 5, wherein the above-mentioned naphthenic polymer having a cyclic ether group has an organic 137746.doc 200937123 group having a carbon atom directly bonded to a ruthenium atom, and the organic group is 10 ~80% has an epoxycyclohexane skeleton. 7. The resist material according to any one of claims 2 to 6, wherein 100% by mole of the decane compound represented by the above formula (1), represented by the above formula (1) and p in the above formula (1) The content of the decane compound of 2 is in the range of 2 Å to 10 〇 m 〇 1%. 8. The resist material according to any one of claims 1 to 7, which further contains a resin having an acid anhydride group or a carboxyl group and an unsaturated double bond. 9. The resist material of claim 8, wherein the product of the solid content acid value (mgKOH/g) of the resin component and the epoxy equivalent (g/eq) of the resin component is in the range of 25,000 to 100,000. The resist material according to any one of claims 1 to 9, which further contains a photo radical generating agent. The resist material according to any one of claims 1 to 9, which further contains a photoacid generator. A resist material comprising a siloxane polymer obtained by polymerizing at least one decane compound represented by the following formula (1), a photopolymerization initiator, and a white filler, wherein the above formula (1) Is the at least one decane compound represented by the following formula (1) and in the following formula (1)? Is a decane compound of 2, and the weight average molecular weight of the above-mentioned siloxane polymer is in the range of 1000 to 50000, Si(X)P(R)4-p... Formula (1), X(tetra)hydrolyzable group in the above formula (1) , R represents a non-hydrolyzable organic group having a carbon number of ~3〇, p represents an integer of Bu 4; when ...~4, 137746.doc -2- 200937123, a plurality of X may be the same or different; when ... or 2 It can also be different. The plurality of R may be the same 13 14. ❹ 15. The resist material of the Si item 1 wherein the alkane represented by the above formula (1) is 2: 20,000, and the P alkane represented by the above formula (1) and the above formula (1) The content of the compound is 5 to 1 〇〇mol. /. Within the scope. The anti-surname material according to claim 1 or 2, wherein the above-mentioned decyl alkane polymer contains a money-burning polymer having a saturated double bond, and the above-mentioned anthracene-oxygenated polymer having an unsaturated double bond is caused by the above formula (1) The p-oxyalkylene polymer obtained by polymerizing a decane compound having an organic group of an unsaturated double bond and having an integer of from 1 to 3 and wherein R is an organic group having an unsaturated double bond. The resist material of claim 3, wherein the above-mentioned unsaturated double bond 16. The siloxane polymer has an organic group directly bonded to a ruthenium atom with a carbon atom and 5 to 80% of the organic group Has an unsaturated double bond. The resist material according to claim 1 or 2, wherein the above-mentioned siloxane polymer contains a siloxane polymer having an acid anhydride group or a carboxyl group and an unsaturated double bond, ❹ 17. the above having an acid anhydride group or a thiol group, and The above-mentioned formula (1) is a decane compound in which P in the above formula (1) is an integer of 1 to 3 and at least one R is an organic group having an acid anhydride group or a carboxyl group, and the above formula ( 1) A p-oxyalkylene polymer obtained by polymerizing a decane compound in which p is an integer of 1 to 3 and at least one R is an organic group having an unsaturated double bond. The resist material of claim 16, wherein the above-mentioned oxalate-oxygenated polymer having an acid-hepatic group or a thiol group and an unsaturated double bond has an organic group directly bonded to a carbon atom at an atom, the organic group 1 to 25% has an acid radical 137746.doc 200937123 or a carboxyl group, and 5 to 80% of the organic group has an unsaturated double bond. The resist material according to any one of the preceding claims, wherein the above-mentioned siloxane polymer contains a cyclooxygen polymer having a cyclic thiol group, and the above-mentioned oxirane polymer having a cyclic ether group is The pyrithione polymer obtained by polymerizing p in the above formula (1) as an integer of 3 and at least one R is an organic group having a cyclic group. A. The anti-silver agent material of claim 18, wherein the above-mentioned rocky oxygen-fired polymer having a ring-shaped mystery has an organic group directly bonded with a carbon atom on the stone atom, and the organic group is 5 to 8 Å. % has a cyclic ether group. The resist material according to any one of claims 1 to 6, wherein the above-mentioned hafnoxy polymer contains a neodymium oxide polymer having an acid group or a county, an unsaturated double bond, and a cyclic hetero group The above-mentioned anthraquinone-oxygenated polymer having an acid-hepatic group or a thiol group, an unsaturated double bond, and a cyclic bond group is obtained by making p in the above formula (1) an integer of 3 and at least - R is an acid A hepatic-based or ruthenium-based organic compound of the Shixia compound, wherein P in the above formula (1) is an integer of 1 to 3 and at least one R is an organic group having an unsaturated double bond, and the above formula (1) The p-oxyalkylene polymer obtained by polymerizing a decane compound having an integer of 1 3 and at least one of which is an organic group having a cyclic squaring group. The anti-silver agent material according to claim 9, wherein the above-mentioned acid anhydride group or thiol group, unsaturated double bond, and cyclic oxyalkylene polymer have a carbon atom directly bonded to the stone atom. The organic group has an acid anhydride group or a carboxyl group, and 5 to 8 % of the organic group has an unsaturated double bond ' and 5 to 8 % by weight of the organic group has a cyclic mystery. 127746.doc 200937123 22. The resist material of claim 10, wherein the product of the solid content acid value (mgKOH/g) of the resin component and the epoxy equivalent (g/eq) is between 300 〇〇 and 5 〇〇〇. Within the scope of 〇〇. The resist material according to any one of claims 12 to 22, wherein the content of the above white filler is in the range of 150 to 1000 parts by weight with respect to 100 parts by weight of the above-mentioned australis. A laminated body comprising a printed circuit board and a resist film formed on a surface of the printed circuit board and using a resist material according to any one of the above. to 137746.doc