TW584785B - Curable flame-retardant resist composition and cured product thereof - Google Patents

Abstract

A resist curable resin material composed mainly of a curable prepolymer (for example, a photocurable resin material comprising a photosensitive prepolymer having an ethylenically unsaturated terminal group originating in an acrylic monomer (A), a compound having an ethylenically unsaturated group excluding the photosensitive prepolymer (B), and a photopolymerization initiator (C)) and a flame-retarding agent containing a hydrated metal compound and a brominated epoxy compound are mixed. Alternatively, the resist curable resin material described above and a hydrated metal compound surface-treated with a surface treating agent having an amphipathic property and a polarity are mixed.

Description

584785 A7 ___B7 V. Description of the Invention (1) [Technical Field] (Please read the precautions on the back before filling out this page) The present invention relates to an anti-etching hardening resin for forming protective films for printed circuit boards and the like Composition and uses. [Background Art] In the manufacture of printed circuit boards, uranium resists used in the engraving of uranium or solder resists used in the soldering process have required various substrate protection measures. In the manufacturing process of thin-film printed circuits (flexible printed circuit board; abbreviated as FPC) used in small equipment, etc., during the soldering process of assembly parts, it is also necessary to protect the circuit-independent Part of the use of solder resist (solder resist) ° The Ministry of Economic Affairs, Intellectual Property Bureau, employee consumer cooperatives to print such a substrate to protect the means, in the past is to pierce the polyimide film as a predetermined model of the laminate A cover lay or a covet * coat that is printed with an ink composed of a heat-resistant material. Since the cover layer and the protective coating layer are both used as a protective film for the circuit after soldering, heat resistance and insulation during soldering and flexibility without cracks due to bending during the assembly of the substrate are required. Furthermore, if F R C used for equipment other than battery-powered equipment is used, it is also required to have flame retardancy. Therefore, it is desired to develop a flexible and flame retarder. Because the cover layer formed by die-cutting polyimide film can meet the above-mentioned characteristics, it is currently used the most. However, in addition to the expensive metal molds for die-cutting work, it is necessary to manually die-cut the film. There is an increase in cost due to accurate positioning and bonding, and it is difficult to form fine patterns. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -4-584785 A7 B7 V. Description of the invention ( 2) Question. In addition, since the drying process is required due to the use of screen-printed electricity for the protective coating, there are problems of high manufacturing cost and poor workability. (Please read the precautions on the reverse side before filling out this page.) To solve these problems, there have been proposals to apply a photosensitive resin composition on a substrate in a liquid state or make a thin film to attach it. According to this method, after a film is formed on a substrate and exposed, developed, and heated using photographic technology, a fine pattern cover layer or a protective coating layer can be easily formed. Therefore, various photosensitive resin compositions have been developed in the future. . Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, the existing photosensitive resin composition does not fully meet the characteristics required for F PC. Although a proposal has been made, for example, a photosensitive resin composition made of a prepolymer, a photopolymerization initiator, a diluent, and an epoxy compound that undergoes an addition reaction of a polyvalent acid anhydride in a phenolic epoxy epoxy resin for lacquer (Japanese Patent) JP 1-5 4 3 90), but although the composition has good heat resistance and insulation, it lacks flexibility and is not suitable for use as an FPC. In addition, there are adhesive systems formed of a low molecular weight copolymer of a reaction product of a copolymer formed from an ethylenically unsaturated dicarboxylic anhydride and an ethylenically unsaturated copolymer with an amine, and a high molecular weight copolymer containing a carboxylic acid. Proposal of a photosensitive resin composition equipped with an acrylic urethane monomer component, a photoinitiator, and a block polyisocyanate crosslinking agent (Japanese Patent Laid-Open No. 7-2 7 8 4 9 2 Bulletin), but the composition also lacks flame resistance and has a problem of restricted use. As a method for imparting flame retardancy to a photosensitive resin composition, a halogenated flame retarder such as a brominated epoxy resin or a flame retarder such as antimony trioxide is used in combination. Method of the flame retardant system (Japanese Patent Laid-open No. 9- 3 2 5 4 9 0, Japanese Patent Laid-open No. 1 1- 40-3. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 584785 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (3) 2 4 2 3 3 Bulletin No. 1 etc.). However, these flame retardants are sometimes inferior in reliability under high temperature environments. For example, when using antimony compounds, environmental issues related to the disposal of resin waste must be considered. In addition, if the brominated epoxy resin 尙 is to be blended in an amount to obtain a sufficient flame retardant effect, flexibility will be lost. On the other hand, there are proposals for using phosphate esters as flame retardants (Japanese Patent Laid-Open No. 9-2 3 5 4 4 9; -2 7 1 9 6 7 etc.), but the flame retardant effect is low when only phosphate ester is used, so that it cannot meet the flame retardant standards in the UL standard. As described above, it is not easy to produce an anti-etching agent that has both high flame resistance and flexibility that meets UL standards, and excellent soldering heat resistance, humidity resistance, high temperature reliability, photosensitivity, and developability. , So I have been hoping for improvement. [Disclosure of the Invention] The present invention is to provide a high level of flame retardancy and flexibility, and also has excellent soldering heat resistance, humidity resistance, high temperature reliability, photosensitivity, and developability. The subject of the subject is a transparent, hardening resin composition for etching resistance, particularly a good hardening resin composition for etching resistance, which can be used as a cover layer for FPC and a soldering flux. In addition, the present invention aims to provide a method which is useful for forming a heat-resistant protective film using the above-mentioned curable resin composition for etching resistance. As a result of diligent research, the inventors found that it is difficult to use a specific composition (please read the precautions on the back before filling this page) 4.1. # The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6-584785 A7 ____B7 V. Description of the invention (4) The fact that the use of a flammability-imparting agent can solve the above problems and complete the present invention 0 (Please read the precautions on the back before filling out this page} That is, the present invention An anti-etching curable resin composition containing an anti-etching curable resin material and a hydrated metal compound is provided. In a first aspect of the present invention, the anti-etching curable resin composition in which a brominated epoxy compound is blended in the above-mentioned configuration is provided. 1 From the above-mentioned state, a hardening resin composition for uranium resistance having excellent flame retardancy, photosensitivity, developability, flexibility, soldering heat resistance, and the like can be obtained. Further, the present invention The second state is a hardening resin composition for etching resistance in which the water and the metal compound are surface-treated with a surface-treating agent having a polarity of hydrophilicity and lipophilicity. Hardening resin composition for etching resistance such as flame retardancy, photosensitivity, developability, folding resistance, etc. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. Bureau of Intellectual Property, Ministry of Economic Affairs The employee consumer cooperative printed the hardening resin composition for etching resistance of the first aspect of the present invention, which contains a hardening resin material for etching resistance and a flame retarder. I-1 · Hardening resin for etching resistance The hardening resin material for etching resistance used in the first embodiment {mainly consists of a hardening prepolymer. Here, the hardening resin material means a light hardening resin material, an electron beam hardening resin material, X-ray hard} Paper size applies the Zhongguanjia Standard (CNS) M specification (21GX297 mm) ΓγZ ---- 584785 A7 B7 V. Description of the invention (5) Chemical resin materials, thermosetting resin materials, etc. You can also use any hardening material used as an anti-etching resin material. L U ------ ^^ 衣-(Please read the precautions on the back before filling in this page) (i) Photohardenability Resin material photocurable resin In terms of materials, 祗 is not particularly limited as long as it can be hardened by visible light, ultraviolet rays, and the like, but it is preferably a photosensitive prepolymer (A-1) having an ethylenically unsaturated terminal group derived from an acrylic monomer. ) 'The (1) photosensitive prepolymer (A-1) made of a compound (B) having an ethylenically unsaturated group other than the aforementioned photosensitive prepolymer (A-1) and a photopolymerization initiator (C) ) f The photosensitive prepolymer (A-1) used in the first embodiment is one having an ethylenically unsaturated end group derived from an acrylic monomer. The acrylic monomer referred to herein is acrylic or methyl. Acrylic acid (hereinafter referred to as "(meth) acrylic acid" in combination with acrylic acid and methacrylic acid) or derivatives thereof such as alkyl esters and hydroxyalkyl esters. For the first form of photosensitive prepolymer (A-1) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, there are no special restrictions on meeting the above conditions, but the specific examples are: polyester acrylate, Epoxy acrylate, urethane acrylate, polybutadiene acrylate, polysiloxane acrylate, melamine acrylate, etc. Among them, polysiloxane acrylate and urethane acrylate are preferred. . Further, it is preferably one having both a carboxyl group and at least two ethylenically unsaturated bonds in one molecule. Specific examples are as follows: epoxy (methyl) with carboxyl group ", this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8-584785 A7 B7 V. Description of invention (6) Acrylate compound (EA) or urethane (meth) acrylate compound (UA) having a carboxyl group. ≪ Epoxy (meth) acrylate compound (EA) having a carboxyl group > In the first embodiment The epoxy (meth) acrylate compound having a carboxyl group is not particularly limited, but for example, an epoxy (formaldehyde) obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid-containing reactant and an acid anhydride The epoxy compound is not particularly limited, but it can be exemplified by bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and phenol. Phenolic epoxy compounds for paints, phenolic epoxy compounds for cresol paints, or epoxy compounds such as aliphatic epoxy compounds. These can be used alone or in combination of two or more. Containing unsaturated groups For monocarboxylic acids, Examples: acrylic acid, acrylic acid dimer, methacrylic acid, / 3-furfuryl acrylic acid, / 3-styryl acrylic acid, cinnamic acid, crotonic acid, ^ -cyanocinnamic acid, etc. Half-ester compounds of reaction products of hydroxyacrylic acid and saturated or unsaturated dibasic acid anhydrides, such as hydroxyalkyl esters of (meth) acrylic acid, etc., containing unsaturated-glycidyl ethers and saturated or unsaturated dibasic acid anhydrides. The half-ester compound of the reaction product. These unsaturated monocarboxylic acids may be used alone or in combination of two or more. As for the acid anhydride, examples include maleic anhydride, succinic anhydride, itaconic anhydride, and xylylene. Acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl bridge tetrahydrophthalic anhydride, methyl methyl bridge tetrahydrobenzene. "This paper is applicable to Chinese national standards. (CNS) A4 size (210X297 mm) -9-

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、 1T # 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 584785 A7 __ B7 V. Description of the invention (7) (Please read the precautions on the back before filling this page) Formic anhydride, chloric anhydride, methyltetrahydrobenzene Aromatic polycarboxylic anhydrides such as dicarboxylic acid anhydrides such as dicarboxylic acid, trimellitic anhydride, pyromellitic anhydride, dibenzodione tetracarboxylic dianhydride, etc., 5- (2,5-dioxotetrafuryl) ) A 3-methyl-1, 3-dicyclohexene-1, 2-dicarboxylic anhydride, such as bridged bicyclic one [2 · 2 · 1]-hept-5-ene-2, 3-dicarboxylic anhydride, etc. Residual anhydride derivatives and the like. These may be used alone or in combination of two or more. The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group obtained in this way is not particularly limited, but it is preferably a number average molecular weight of 1,000 to 40,000, more preferably 2,000 to 5,000. Here, the number average molecular weight is a polystyrene conversion factor measured by gel permeation chromatography. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The acid value of the aforementioned epoxy (meth) acrylate compound (the meaning of solid components. The same applies below) is preferably 1 Orng κ Ο H / g or more. In the range of 45 mg ΚΟΗ / g to 160mg K〇H / g, and in the range of 50mg K〇H / g to 140m g Κ 〇 Η / g, due to the alkali solubility and alkali resistance of the cured film The reason is good, especially good. If the acid value is less than 10 mg Κ Ο Η / g, the alkali solubility will be deteriorated. On the contrary, if the acid value is too large, the combination of the constituent components of the hardening resin composition for etching resistance will be inappropriate and may decrease. Factors such as alkali resistance and electrical characteristics of the cured film as characteristics of the anti-etching agent. The epoxy (meth) acrylate compound having the aforementioned carboxyl group may constitute the photosensitive prepolymer (A-1) alone, or it may use the later-mentioned paper size and apply the Chinese National Standard (CNS) A4 specification (210X297) (Centi)-10- 584785 A7 __ B7 V. Description of the invention (8) Urethane (meth) acrylate compound having carboxyl group. In this case, the epoxy (meth) acrylate compound having a carboxyl group is preferably used in an amount of 100 parts by mass or less with respect to 100 parts by mass of the urethane (meth) acrylate compound having a carboxyl group.

< Carbamate (meth) acrylate compound (UA) having a carboxyl group > The urethane (meth) acrylate compound having a carboxyl group in the first embodiment is derived from a hydroxyl group A compound containing a (meth) acrylate unit 'and a polyol-derived unit, and a polyisocyanate-derived unit as constituent units. In detail, both ends are made of a unit derived from a (meth) acrylate having a hydroxyl group, and between the two ends are a unit derived from a polyol and a unit derived from an aminocarbamate bond. The polyisocyanate unit is composed of a repeating unit, and has a structure in which a carboxyl group is present in the repeating unit. That is, the urethane (meth) acrylate compound having the carboxyl group is represented by Ra— (〇R60〇OCNHRcNHCO) n-Ra [wherein Ra represents a (meth) acrylic acid having a hydroxyl group. "Zhuowu" 〇r6〇 means deamino residues of polyols "Rc Table 75 polyisocyanate deisocyanate residues. ] A urethane (meth) acrylate compound having a carboxyl group can be produced by reacting at least a (meth) acrylate having a hydroxyl group, a polyol, and a polyisocyanate, but here, in the polyol Or at least one of the polyisocyanates, a compound having a carboxyl group must be used. It is better that this paper size is in accordance with Chinese National Standards (CNs) A4 specification (210 X297 mm) -11-L ^ clothing-(Please read the notes on the back before filling this page) Printed by the Consumer Cooperative η 584785 A7 ----- B7 V. Description of the Invention (9) (Please read the notes on the back before filling this page) It is a polyol with a carboxyl group. By using a compound having a carboxyl group as a polyol and a polyisocyanate in this manner, a urethane (meth) acrylate compound having a carboxyl group in Rb or R C can be produced. In the above formula, η 値 is preferably about 1 to 200, and more preferably 2 to 30. If η 値 is within this range, the flexibility of the cured film made of the hardening resin composition for etching resistance will be better. Also, if at least one of a polyol and a polyisocyanate is used, two kinds of repeating unit systems are used to indicate a plurality of types, but the regularity of the plurality of units may be completely random, block, partial, etc., as appropriate according to the purpose . For the printing of the (meth) propionic acid esters with hydroxyl groups as the carbamates with carboxyl groups by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, there may be mentioned: 2-hydroxy (meth) acrylate, ( Propyl (meth) acrylate, butyl hydroxy (meth) acrylate, caprolactone or epoxide adduct of each of the aforementioned (meth) acrylates, glycerol- (meth) acrylate, glycerol di (methyl) ) Acrylate, glycidyl acrylate-acrylic adduct, trimethylolpropane mono (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane monoepoxide adduct dibis (meth) acrylate, etc. These (meth) acrylates which have a hydroxyl group can be used individually or in combination of 2 or more types. Among these, 2-hydroxy (meth) acrylate, hydroxy (meth) acrylate, and hydroxy (meth) acrylate are preferred, and 2-hydroxy (meth) acrylate is more preferred. Ethyl ester. If 2 -12- 4iG is used, this paper size is applicable to Chinese National Standard (cns) 8-4 specification (2 丨 〇> 297 mm) 584785 A7 B7 V. Description of the invention (1〇)-mesogen (methyl) Ethyl acrylate enables easier synthesis of urethane (meth) acrylic compound (UA) having a carboxyl group. (Please read the notes on the back before filling this page.) For polyols with carboxyl group urethane (meth) acrylate compounds (UA), polymer polyols and / or secondary Based compound. In terms of polymer polyols, there can be mentioned: polyether diols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyester polyols prepared from esters of polyols and polyacids; and sources Polycarbonate diols containing hexamethylene carbonate, pentamethylene carbonate and the like as constituent units; polycaprolactone diols, polybutyrolactone diols, etc. Polylactone based glycol. When a polymer polyol having a carboxyl group is used, for example, when synthesizing the above-mentioned polymer polyglycol, a polyhydric alcohol having a valence of 3 or more (anhydrous) trimellitic acid and the like can be synthesized so that the carboxyl group can remain. Compounds. Polymer polyols printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs may use one or a combination of two or more of these. For these polymer polyols, when a number average molecular weight of 2000 to 2000 is used, the flexibility of the cured film made of the hardening resin composition for etching resistance is better. It is better. Among these polymer polyols, if a polycarbonate diol is used, the cured film made of a hardening resin composition for etching resistance has high heat resistance and excellent autoclave resistance. good. Furthermore, if the constituent unit of the polymer polyol is not only a single constituent unit but a plurality of constituent units, the flexibility of a cured film made of a hardening resin composition for etching resistance will be more flexible. For better reasons. 417 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -13-584785 A7 B7 V. Description of the invention (11) For polymer polyols composed of such a plurality of constituent units, : Polyethylene glycol and the like which are derived from ethylenedi and propylene glycol-containing units as constituent units. (Please read the notes on the back before filling this page.) For dihydroxy compounds, branched or straight-chain compounds with two alcoholic hydroxyl groups can be used. Particularly preferred is the use of dihydroxy aliphatic carboxylic acids with carboxyl groups. Examples of such a dihydroxy compound include dimethylolpropionic acid and dimethylolbutanoic acid. The use of a dihydroxy fatty acid carboxylic acid having a carboxyl group allows the carboxyl group to be easily present in the urethane (meth) acrylate compound. The dihydroxy compound may be used singly or in combination of two or more kinds, and may be used together with a polymer polyol. When a polymer polyol having a carboxyl group is used, or when a polymer having a carboxyl group is used as a polyisocyanate described later, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Dihydroxy compounds such as hydroquinone without carboxyl groups. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: · Ιί For polyisocyanate which is a urethane (meth) acrylate compound (UA) having a carboxyl group, specifically: 2-4-toluene diisocyanate 2, 2, 6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (ortho, m, or para) xylene diisocyanate, methylene Base bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) ΓΤ4 ^ · 584785 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (12), 4-dimethylene diisocyanate and 1, 5-naphthalene diisocyanate. Diisocyanate. These polyisocyanates can be used singly or in combination. A polyisocyanate having a carboxyl group may also be used. The molecular weight of the urethane (meth) acrylate compound (UA) having a carboxyl group used in the first form is not particularly limited, but it is preferably a number average molecular weight of 1,000 to 40,000, more preferably 8,000 to 30. 0 0 0. Here, the number average molecular weight is a polystyrene equivalent measured by gel permeation chromatography. The acid sulfonium of the urethane (meth) acrylate is preferably 5 to 150 mg KOH / g, and more preferably 30 to 120 mg KOH / g. If the number-average molecular weight of the urethane (meth) acrylate compound having a carboxyl group is 1,000 or less, the ductility and ductility of a cured film made of a hardening resin composition for etching resistance are reduced. Strength, if it exceeds 4 0 0 0, it will become hard and may reduce flexibility. When the acid value is 5 mg K 0 Η / g or less, the alkali solubility of the hardening resin composition for etching resistance is deteriorated, and when it exceeds 150 mg K 0 Η / g, the cured film is hardened. Alkali resistance and electrical characteristics will be deteriorated. If the acid hydrazone of the urethane (meth) acrylate compound having a carboxyl group is 5 to 150 mg K 0 K, it is very suitable, but even in its range, it can improve The imageability but flexibility tends to decrease, and if the acidity is reduced, the flexibility can be improved, but the developability will be lowered, which tends to cause incomplete developability. At this time, if a urethane (meth) acrylate compound having at least two different carboxyl groups is used in combination, it may be easily produced with excellent flexibility and good r ----- --- Clothing—— (Please read the precautions on the back before filling this page)

• I 41¾ This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) -15-584785 A7 ____B7_ __ 5. Description of the invention (13) Photoresistive hardening resin composition for etching resistance. In particular, a urethane (meth) acrylate compound having a carboxyl group (hereinafter referred to as "amine") having an acid group of 5 mg K K Η / g or more and 6 O mg KOH / g or less is preferred. Carbamate (meth) acrylate compound (a) "), and a carbamate (methyl having a carboxyl group having a carboxylic acid of 60 mg KOH / g or more and 150 mg KOH / g or less ) Acrylate compounds (hereinafter referred to as "urethane (meth) acrylate compounds (b)") are each selected from at least one combination. In addition, when the urethane (meth) acrylate compound having a carboxyl group having a different acid group is used in combination, the urethane (meth) acrylate compound (UA) having a carboxyl group is preferably used. In 100 parts by mass, it is a urethane (meth) acrylate compound (a): a urethane (meth) acrylate compound (b) = 40 to 90: 60 to 10 Mass ratio (total of 100). Particularly preferred urethane (meth) acrylate compound (a) is the excess, and more preferably urethane (meth) acrylate compound (a): urethane (meth) Acrylate compound (b) = 60 to 90: 40 to 10 mass ratio. A urethane (fluorenyl) acrylate compound having a carboxyl group can be reacted by (1) mixing a (meth) acrylate having a hydroxyl group, a polyol, and a polyisocyanate together, and (2) After reacting a polyol with a polyisocyanate to produce a urethane isocyanate prepolymer containing more than one isocyanate group per molecule, the basic paper size of the amine is adapted to the Chinese National Standard (CNS) A4 specification (210X297 (Mm) "16 · L --- ** ------ ^^ clothing-- (Please read the precautions on the back before filling this page)

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• I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs «584785 A7 B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) Phenate isocyanate prepolymer and hydroxyl-specific (methyl ) A method of reacting acrylate, (3) reacting (meth) acrylic acid having a carboxyl group with a polyisocyanate to produce a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule, It is produced by a method in which this prepolymer is reacted with a polyol. (2) Compound having an ethylenically unsaturated group (B) Compound having an ethylenically unsaturated group contained in a photo-hardening component in a hardening resin composition for etching resistance, is a photosensitive prepolymer (A-1) Others are used for the purpose of adjusting the viscosity of the hardening resin composition for etching resistance, or adjusting the heat resistance and flexibility of the hardening resin composition for etching resistance as the hardened material. Preferably, a (meth) acrylate is used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, specifically: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ( Isobutyl methacrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isopropyl (meth) acrylate Alkyl (meth) acrylates such as octyl ester, 2-ethyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like; Hexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, ethyl dicyclopentenyl (meth) acrylate, etc. Alicyclic (meth) acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl (meth) propyl-17- This paper size applies to Chinese National Standard (CNS) A4 (210X297) Mm) 584785 A 7 B7 V. Description of the invention (15) (Please Read the notes on the back before filling this page) Carbitol enoate, phenyl nonyl (meth) acrylate, carbitol nonylphenyl (meth) acrylate, benzene nonyl (meth) acrylate Aromatic (meth) acrylates such as oxyesters; 2-hydroxy (meth) acrylate, hydroxy (meth) acrylate, butyl (hydroxy) (meth) acrylate, butanediol mono (meth) Acrylate, glyceryl (meth) acrylate, phenoxyhydroxy (meth) acrylate, polyethylene glycol (meth) acrylate, or glycerol di (meth) acrylate, etc. Base) acrylate; 2-dimethylamino (meth) acrylate, 2-diethylamino (meth) acrylate, 2-tert-butylamino (meth) acrylate, etc. (Meth) acrylic acid esters with amine groups; methacrylic acid ethyl phosphate phosphate, methacrylic acid ethyl bisphosphate phosphate, methacrylic acid ethyl phenyl acid phosphate (phenyl P ) And other methacrylates with phosphoric acid; ethylene glycol (meth) acrylate, two Diethylene glycol methacrylate, diethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, di (meth) acrylic acid Propylene glycol esters, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-monobutylene glycol di (meth) propylene, Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumption Cooperative, printed acrylates, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bis • glycidyl (meth) Diacrylates such as acrylates; polymethylacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, hexyl dipentaerythritol (meth) acrylate: ring of bisphenol S Ethylene oxide 4 mol modified diacrylate, bisphenol A, ethylene oxide 4 mol modified diacrylate, fatty acid modified pentaerythritol dipropylene 422. This paper size applies to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) -18-584785 A7 B7 V. Hair Instruction (16) (Please read the precautions on the back before filling this page) Orthoester, trimethylolpropane, propylene oxide 3 mol modified triacrylate 'Ξmethylolpropane, propylene oxide 6 mol Modified polyol polyacrylates such as ototropic triacrylates; bis (acryloxyethyl) -hydroxyethyl isotricyanate, ginseng (propyleneoxyethyl) isotricyanate, ε-hexyl ester modified polyacrylic acid esters with isocyanuric acid skeletons such as propylene (oxyethyl) isotricyanate groups; α, ω-dipropylene fluorene (diethylene glycol) ) Polyester acrylates such as monophthalate, α, ω-tetraacrylic acid mono (bistrimethylolpropane) -tetrahydrophthalate; glycidyl (meth) acrylate; (meth) acrylate Esters, ω-hydroxyhexanoyloxy (meth) acrylate, polycaprolactone (meth) acrylate; (meth) acrylic acid ethoxyethyl phthalate; (meth) acrylic acid ethoxyethyl amber Acid esters; 2: hydroxy-3-phenoxy propyl acrylate; ethyl phenoxy acrylate and the like. In addition, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylformaldehyde, N-vinylacetamide, polyester acrylates, urethane acrylates, epoxy acrylates, etc. may be used as Ethylenically unsaturated compounds are suitable for use. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Among them, the better ones are (meth) acrylates having hydroxyl groups, glycidyl (meth) acrylates and urethane acrylates, and As the acrylate), 2-hydroxy (meth) acrylate, hydroxy (meth) acrylate, hydroxy (meth) acrylate, and urethane acrylate may be mentioned. In addition, since heat resistance is increased, those having three or more ethylenically unsaturated groups are preferred. The blending ratio of the photosensitive prepolymer (A-1) and the compound (B) having an ethylenically unsaturated group is based on the mass ratio of (A-1): (B) 423 This paper is applicable to Chinese national standards (cns) Specification of 4 (2iox297 mm) -19-584785 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs V. Invention Description (17) = 95: 5 to 50: 50, preferably 90: 10 to 60: 40 , More preferably 85: 15 to 70: 30 (total 100). If the blending amount of the (A-1) component exceeds 95.5% by mass, the heat resistance of the brazing film of the hardened film made of the hardening resin composition for etching resistance may decrease, and the blending of the (A-1) component When the amount is 50% by mass or less, the alkali solubility of the curable resin composition for etching resistance tends to decrease. (3) As for the photopolymerization initiator (C) used in the first form of the photopolymerization initiator, dibenzodione, benzophenone benzoic acid, 4-monophenyldibenzodione, and hydroxydibenzodione , 4,4 > Dibenzodiones such as bis (dimethylamino) dibenzodione; benzoin, benzoyl methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, Benzoin alkyl ethers such as benzoin isobutyl ether, 4-monophenoxydichloroacetophenone, 2-hydroxy-2-methyl-1 monophenylpropane-1 monoketone, 1- (4-isopropyl Phenyl) 2 -Hydroxy-2 -methylpropane-1 -one, 1-[4-(2-hydroxyethoxy) phenyl] -2 -hydroxydi-2 -methyl-1 -propane-1- Ketone, 1-Cyclohexyl-phenyl ketone, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2,2-diethoxy-1, 2-di Phenylacetin, 2-fluorenyl-1, [4-mono (methylsulfanyl) phenyl], 2-morpholinopropanone, 1, 4, 3rd-butyl-dichloroethanylbenzene, 4 Tert-butyl-trichloroethylbenzene, diethoxyethyl Benzene, 2-benzyl-2-dimethylamino-1, 1- (4-morpholinephenyl), 1-butanone-1, 1-phenyl This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 (Mm) ^ 20-(Please read the precautions on the back before filling out this page) 584785 Α7 Β7 ５ 4 4 、 Instructions of the invention (18 1 2 ~ propane monoone 2-(o-ethoxyoxy carboxy) oxime, etc. Benzene 1 Thiazaanthracene, 2-Chlorothiazine S, 2-Methylthiazepine, 2,4 Methylthiazepine, etc .; Anthracene, ethyl anthraquinone, butyl anthraquinone, etc. Keen type I, 2,4,6-trimethylphenylphosphonium diphenylphosphine oxide, etc. fluorenylphosphine oxides, etc. These can be used alone or as a mixture of two or more. Also, 2, 2 ， 2-trichloro- [gongyi-4 ^-(ι, ι — monomethylethyl) phenyl] ethyl ketone, 2,2-dichloro-i- 4 — (benzyloxyphenyl) ethyl Ketones, α, α, α-tribromotolyl, 2, 4, 6-ginsyl (trichloromethyl) triphine, 2,4-trichloromethyl- (methoxybenzyl) -6-trimorphine , 2,4 Trichloromethyl— (methoxyphenethyl)-6-tri , 2, 4-trichloromethyl — (piperidyl) — 6 — three-tillage, 2, 4-trichloromethyl — (4 (please read the precautions on the back before filling out this page) methoxynaphthyl) 6 —Sangen, 2 2 〃 Monomethylfuranyl Intellectual Property Bureau, Ministry of Economic Affairs, Employees' Cooperatives Printed (Diethylamino) Benzophenone, 1 ((4-Morphinephenyl) Butanone) Ethylene —4,6 -bis (trichloromethyl) —symmetrical one-trimethylol, 2 (2 / -furylethylene)-4,6-bis (trichloromethyl) -symmetrical-trimethylol Acid generator. If necessary, a photosensitizer can also be used. Among these photopolymerization initiators, benzophenones, acetophenones, and fluorenylphosphine oxides are preferred. Specifically, it can be exemplified by 4,4-bis-benzyl-2-dimethylamino-1,1'2,4,6-dimethylbenzidinediphenyl scale oxide. The blending amount of these photopolymerization initiators (C) is preferably to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) to the paper size of the photographic paper. -21-584785 A7 B7__ V. Description of the invention (19) ( Please read the precautions on the reverse side before filling out this page) The total amount of light-hardening components made from the prepolymer (A-1) and the compound (B) with ethylenically unsaturated groups is from 100 parts by mass to 20 parts by mass Parts, more preferably from 0.2 parts by mass to 10 parts by mass. If the blending amount of the photopolymerization initiator is less than or equal to 0.1 part by mass, the curing may be insufficient. (ii) Electron-ray-curable resin material The electron-curable resin material used in the first form printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has positive and negative types, but if it can be used as an anti-etching material, Any kind can be used. Specific examples include: polyethylene cinnamate, polyethylene p-azidobenzoate, polymethyl acrylate (PMMA), polybutyl methacrylate, and methyl methacrylate-methacrylic acid copolymerization Polymer, methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-isobutylene copolymer, methyl methacrylate-methyl-α-chloroacrylate copolymer, epoxidation Butadiene (EPB), epoxidized polyisoprene, polyglycidyl methacrylate (PGMA), glycidyl methacrylate-ethyl acrylate copolymer, glycidyl methacrylic acid-styrene copolymerization Polymers, methylvinylsiloxane, polymethylcyclosiloxane (PMCA), polyvinylsiloxane (PVS), copolymers with propylene groups on the side chain, polybutadiene (PB), polymer Diaryl phthalate (PDOP), copolymer with acrylic and glycidyl groups on the side chain, allyl ester of alkyl vinyl ether-maleic anhydride copolymer, poly (butylene-1) (One mill) (PBS), poly (styrene), polyvinyl chloride, polystyrene, polypropylene Melamine, poly-α-methylstyrene, polymethacrylonitrile, cellulose acetate, polyisobutylene, polyvinyl carbazole, polyethylene 22- 42G This paper is applicable to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) 584785 A7 B7 、 Instruction of the invention (20) (Please read the precautions on the back before filling this page) Anthracene di (cyclopentadiene) ferrocene (ferrocene), polymethylisopropenyl fluorene, polypropylene Phenylamine (PMAA), poly-α-cyanoacrylate (P c EA), etc. (iii) The X-ray-curable resin material used in the first form of the X-ray-curable resin material is specifically exemplified by: methyl methacrylate (PMMA), poly (butene-1, 1) (PBS), Polyvinyl di (cyclopentadiene) ferrous iron (PVFc), polybutadiene (PS), polydiaryl phthalate (PDOP), cross-linked electronic anti-uranium etching agent (CER), ring Oxidized polybutadiene (EpB), glycidyl methacrylate-ethyl acrylate copolymer, etc. (iv) Thermosetting resin material The Ministry of Economic Affairs, Intellectual Property Bureau, Employees' Cooperative, printed the first form of heat curing Specific examples of the resin material include epoxy resin, phenol resin, polysiloxane resin, melamine derivatives (for example, hexamethoxymelamine, hexabutoxymelamine, condensed hexamethoxymelamine, etc.), urea compounds (for example, Dimethylol urea, etc.), bisphenol A-based compounds (for example, tetramethylol • bisphenol A, etc.), oxazoline compounds, oxetane compounds, etc. These thermosetting resins may be 1 It can be used alone or in combination of two or more. Preferred is epoxy resin. For epoxy resin, specific examples include: bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bis-A epoxy resin, and bisphenol F-ring. Oxygen resin, phenolic epoxy resin for lacquer This paper is in accordance with Chinese National Standard (CNS) A4 specification (21 × 297 mm) -23-584785 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 21) 'Phenolic epoxy resin for lacquer lacquer, phenolic epoxy resin for cresol lacquer, N ~ glycidyl epoxy resin, phenolic epoxy resin for lacquer bisphenol A, clamp epoxy resin , Glyoxal type epoxy resin, amine-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol type epoxy resin, polysiloxane modified epoxy resin, ε-caprolactone modified In one molecule of the epoxy resin, there are two or more epoxy compounds in the epoxy compound. In addition, it is also possible to use bis-S-type epoxy resin, diglycidyl phthalate resin, and heterocyclic epoxy resin. , Bixylenol type epoxy resin, biphenyl type epoxy resin, and tetraglycidyl xylenol Ethane resin, etc. These epoxy resins can be used singly or in combination of two or more. II-1. Flame retardant imparting agent (D) The flame retardant imparting agent (D) of the first form contains at least The hydrated metal compound (D 1) and the brominated epoxy compound (D 2) may further contain a phosphate compound (D3) if necessary. (I) The hydrated metal compound (D 1) The hydrated metal compound (D 1) used in the first aspect ( D 1) is a metal compound having crystal water, and may be, for example, a water content of 12 to 60% (mass%) per mole by thermal analysis, but it is not limited thereto. From the viewpoint of a flame-resistant effect It is preferable to use a heat-absorbing metal compound having a heat absorption of 400 J or more. It is preferable to use a hydrated metal compound of 600 to 2500 J / g. Specific examples of such hydrated metal compounds include: hydroxide. -------------- ^ ---, 玎 ------ (Please read the note on the back first Please fill in this page again for the matter) 428 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm)-24 584785 A7 B7 V. Description of invention (22) (Please read the precautions on the back before filling this page) Inscription , Magnesium hydroxide, hydroxide fishing, dorsonite, lactic acid age, 2-hydrate gypsum, zinc borate, barium metaborate, zinc hydroxystannate, kaolin, vermiculite, etc. Particularly preferred among these is aluminum hydroxide or magnesium hydroxide. As the hydrated metal compound, a hydrotalcite-based compound having a layered crystal structure and having a hydrated anion between the crystal layers is also suitable. The term "hydrotalcite" as used herein refers to a generic term that includes hydrotalcites and hydrotalcites as described below. Hydrotalcite is originally endowed with natural minerals

The names of Mg6Al2 (〇H) 16C03 · 4 to 5 H2〇, and later found that most of the minerals have the same crystalline structure and also have finished products. Hydrotalcite can be expressed by the following general formulae (a) and (b). [M2 + i-xM3 + x (OH) 2] x + [An_1x / n mH2〇] x '… (a) [M3 + 2 (OH) 6M1 + y] y + [An'! X / n mH2〇] " … (B) Here, 0.1 $ x $ 0.4, 0 < y < 2,0 < m, n is a natural number from 1 to 4, M1 + is Li (lithium), K (potassium), employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The consumer cooperative prints at least one kind of monovalent metal represented by R b (rivet), C s (planer), etc., and M2 + is Mg (magnesium), Ca (jin), Mn (violent), Fe (ferrous) At least one of the divalent metals represented by Co, Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), etc. 'M 3 + is A 1 (aluminum), F e (iron), C r (Chromium), I η (Indium), and at least one of the trivalent metals represented by, Αη_ is C1 (chlorine), Br (bromo) —, C03 (carbonate) 2—, No3 (nitric acid Root) 2_, S〇4 (Sulfuric acid 4:23 This paper size applies Chinese National Standard (CNS) A4 specifications (210x297 public envy) -25- 584785 A7 V. Description of the invention (23) Root) 2 —, F e (CN ) 6 (Ferrocyanate) 4-At least one of the η-valent ion exchanger anions represented by tartaric acid ions. (Please read the precautions on the back before filling this page) In the above general formula (a), the compound in which M2 is Mg 2 + and M3 + is A 1 3 + is called hydrotalcite, and the compounds of general formula (a) and general formula (b) are generally called hydrotalcites. These hydrotalcites and hydrotalcites are well-known as having a basic layer with a positive charge and a structural unit composed of an anion and an intermediate layer of crystal water which neutralize the positive charge electrically, and Except for differences in structure temperature, others have almost the same properties. In addition, these compounds are reported in the "Smectite Research Council", "Montmorillonite" (Vol. 6, No. 1) Nos. 12 to 26, published May 19, 1996), for details. Specific examples of the above hydrotalcite compounds include: stehitite, piorawlite, libectite, tacovite, onecite, iowite, etc. 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3ε The particle size of the hydrated metal compound used in the first form is not It is particularly limited, but the average particle diameter is preferably less than 4 0 // m, and more preferably 2 // m or less. If the average particle diameter exceeds 4 0 // m, the transparency of the etch-resistant hardened film will deteriorate and the light penetration will decrease, or the appearance and smoothness of the surface of the coated film may be impaired. If a hydrotalcite-based compound is used, the size of its crystal particles is preferably one with an average particle diameter of 1 0 // m or less, and more preferably 5 // m or less. If the average particle diameter exceeds 10 // m, the light transmittance of the hardened film will decrease, and at the same time, the warpage caused by the shrinkage anisotropy of the coating film during the hardening process will easily occur. The hydrated metal compound (D 1) used in the first aspect is particularly preferably a surface treated with a polar surface treating agent from the viewpoint of transparency improvement, etc.-This paper is sized to the Chinese National Standard (CNS) A4 ( 21〇 × 297 mm)

HO-CH2-CH2HD

〇-CH2 ~ CH2 ~ OH 584785 A7 B7 V. Description of the invention (24) Processor. Examples of the surface treating agent having such a polarity include a silane coupling agent such as epoxy silane, amine silane, vinyl silane, fluorenyl silane, or a titanate coupling agent. (i i) Brominated epoxy compound (D 2) The brominated epoxy compound (D 2) includes compounds represented by the following formulae (I) to (I I I). Here, in the formulae (I I) to (I I I), Y is a hydrogen atom or a group that can be represented by formula (IV), and Z is a group that can be represented by formula (IV). p is 0 or more, preferably an integer of 1 to 20, and Q is 0 or 1 or more, preferably an integer of 1 to 10. (I) (Please read the notes on the back before filling this page) H2C—CK— '

〇 * CH2-CH ~ CH2 (II) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs O-QVCH—ch2) o Br 〇Y, μ Br

(III) ch2-ch—, ch2 (IV) This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -27-Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 584785 A7 ______B7 V. Description of the invention (25) Alternatively, an acid-modified brominated epoxy resin obtained by subjecting a reaction product of the brominated epoxy compound and an unsaturated monocarboxylic acid to a saturated or unsaturated polyhydric alcohol anhydride may be used. Examples of unsaturated monocarboxylic acids include: acrylic acid, acrylic acid dimer, methacrylic acid, / 3-furfuryl acrylic acid, / S-styryl acrylic acid, cinnamic acid, crotonic acid, α-cyano Cinnamic acid and the like. For the saturated or unsaturated group-containing polyhydric alcohol anhydrides, there may be mentioned: dianhydride anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrobenzene Dicarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc. Among the above, particularly preferred brominated epoxy compounds are tetrabromobisphenol A epoxy resins having an epoxy equivalent of 200 to 3,000 and a bromine content of 40 to 60% by mass. If the epoxy equivalent is less than 2000, sufficient flexibility cannot be obtained, while if the epoxy equivalent exceeds 3,000, there is a possibility that the developability is reduced and it may be difficult to obtain. If the bromine content is 50% by mass or less, sufficient flame retardance cannot be obtained, and if it exceeds 60% by mass, it may be difficult to obtain. As the brominated epoxy compound (D 2) in the first aspect, a brominated epoxy (meth) acrylate obtained by reacting the brominated epoxy compound with an unsaturated monocarboxylic acid may be used. Compounds. Since the said brominated epoxy (meth) acrylate compound is excellent in flexibility, tetrabromo bisphenol A type epoxy (meth) acrylate and tetrabromobisphenol F type epoxy ( (Meth) acrylate, tetrabromobisphenol S-type epoxy (meth) acrylate, etc. The bromine content of the brominated epoxy (meth) acrylate compound is preferably 30 to 60% by mass. If the bromine content is below 30% by mass (1 (please read the precautions on the back before filling this page)

432 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -28- 584785 A7 __B7 V. Description of the invention (26) It is not possible to obtain sufficient flame resistance, and it is difficult to obtain more than 60% by mass Situation. (Please read the precautions on the back before filling this page) Furthermore, you can also use acid-modified bromine obtained by reacting the above-mentioned brominated epoxy (methoxy) acrylate compounds with saturated or unsaturated polyhydric alcohol anhydrides. Epoxy (meth) acrylate compound. (iii) Phosphate ester compound (D 3) In the first aspect, as the flame retardant imparting agent, in addition to the above-mentioned hydrated metal compound (D 1) and brominated epoxy compound (D 2), Rhenium may contain a phosphate ester. Compounds. In particular, when the flexibility is insufficient, it is preferable to improve the flexibility without impairing the flame retardancy due to the use of a phosphate compound. That is to say, by making a flame retardant composite system composed of three components of D1, D2, and D3, it is possible to achieve a balance between flame resistance and flexibility at a high level. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 The phosphate ester compound (D 3) used in the first form when necessary refers to a combination of "P-〇-R" (R is an organic group) in the chemical structure The meaning of the compound is usually a trivalent or pentavalent phosphorus atom. The trivalent compounds include a phosphite compound, a phosphonite compound, and a phosphinite compound. On the other hand, those having a pentavalent phosphorus atom include a phosphate compound, a phosphonate, and a phosphinate compound. Among them, from the viewpoint of storage stability, it is preferable to use a phosphate compound having a pentavalent phosphorus atom. The organic group forming the ester of these phosphate ester compounds may be any of aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic hydrocarbon group, etc., but from the flame retardant paper rule ^ applicable Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 29-584785 A7 __B7 V. Description of the invention (27) and the viewpoint of soldering heat resistance, it is preferred to have an aromatic hydrocarbon group (please read the precautions on the back before filling this page) ) Such a phosphate compound is particularly preferably a pentavalent one having an aromatic hydrocarbon group. Examples include triphenyl phosphate, resorcinol bis (diphenol) phosphate, and 2-ethylhexyl diphenyl phosphate. Base esters, and those containing a skeleton represented by the following formula (V) (in the formula (V), X may be one or more aromatic groups that are the same or different). 〇

I

X-〇-P-0-X (V) 0

I

Among them, X preferably includes a skeleton represented by the above (V), and further specifically, compounds represented by the following formulae (VI) to (VI I).

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (In the above (VI), R represents the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y represents a direct bond, an alkylene group, a phenylene group,- S —, _S〇2 —, or one C01. A r is related or different 4 M This paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) -30-584785 A 7 B7 5 2. Description of the invention (28) (Please read the notes on the back before filling out this page) The meaning of aromatic groups substituted by aromatic groups or organic groups. K and m are integers from 0 to 2 respectively, k + m is an integer of 0 or more and 2 or less. η is an integer of 0 or more.) The molecular weight of the phosphate compound (D 3) is preferably 300 or more, more preferably 350 or more, and particularly preferably 500 or more. If the total phosphate compound component contains a phosphate compound having a molecular weight of 300 or more and 50% by mass or more, it is more preferable from the viewpoints of moisture resistance and solder heat resistance, and the composition of the first form The same effect can also be obtained by preparing a phosphate ester having a trivalent phosphorus atom in the composition and making it into a phosphate ester having a 5-valent phosphorus atom by oxidation in the composition. The proportions of the above-mentioned D 1 and D 2 and the D 3 used in the flame retardant imparting agent used in the first aspect are not particularly limited, but the anti-etching curable resin material (in the photo-curable resin material) In the case, the total of the components (A 1), (B), and (C) mentioned above is 100 parts by mass, preferably D 1; 100 to 100 parts by mass, and d 2; 80 parts by mass If D3 is used; D3; 0.5 to 40 parts by mass, more preferably D1; 20 to 80 parts by mass, D2; 20 to 60 mass printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs; if D 3 is used, D 4 1 to 30 parts by mass, particularly preferably D1; 30 to 60 parts by mass, D2; 30 to 50 parts by mass, such as D3 when using D3; 5 to 20 parts by mass. In addition, if the use ratio of D 1 to D 3 based on the total amount of the flame retardant imparting agent and the hardening resin composition for etching resistance is expressed based on the above-mentioned use ratio, the following will be described. The proportion of hydrated metal compound (D 1) is not particularly limited, but if 31 paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 584785 A7 B7 V. Description of the invention (29) (Please read the back Please fill in this page again.) When the flame retardancy imparting agent (D) is composed of a hydrated metal compound (D1) and a brominated epoxy compound (D2), it is preferable to impart flame retardancy. The total amount of the agent is 11 to 91% by mass, more preferably 25 to 80% by mass, and particularly preferably 38 to 67% by mass. The proportion of the entire amount of the hydrated metal compound (D 1) of the hardening resin composition for etching resistance in the first aspect is not particularly limited, but it is preferably 5 to 48% by mass, and more preferably 11 to 40% by mass, particularly preferably 16 to 32% by mass. In addition, when the flame retardancy imparting agent is composed of a hydrated metal compound (D1), a brominated epoxy compound (D2), and a phosphate compound (D3), the proportion of the hydrated metal compound (D1) It is preferable that the total amount of the flame retardant imparting agent is 7 to 90% by mass, more preferably 18 to 79% by mass, and particularly preferably 30 to 63% by mass. The total amount of the hardening resin composition for etching resistance in the first aspect is preferably 4 to 47% by mass, more preferably 9 to 40% by mass, and particularly preferably 15 to 31% by mass. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs t-3r If the blending ratio of hydrated metal compounds is too low, the flame retardance is insufficient. As a result, the proportion of brominated epoxy compounds and / or phosphate compounds must be increased to cause acid The price is low, and the visibility is low. On the other hand, if it is too high, the cured film tends to be opaque, the flexibility is reduced, the scorability is deteriorated, and reverse warping may occur. The proportion of the brominated epoxy compound (D 2) is not particularly limited, but if the flame retardancy imparting agent is made of a hydrated metal compound (D 1) and a brominated epoxy compound (D 2), it is more Jiawei prepares 9 to 8 9% by mass of the flame retardant additive, more preferably 20 to 75% by mass, and particularly preferably ^ paper size applies Chinese National Standard (CNS) A4 specifications (21〇, 〆 297 mm) -32-'-584785 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3〇) 3 3 to 6 3% by mass. In addition, the ratio of the brominated epoxy compound (D 2) of the hardening resin composition for etching resistance in the first aspect is not particularly limited, but it is preferably 5 to 42% by mass, more preferably It is preferably 10 to 33% by mass, and particularly preferably 15 to 28% by mass. When the flame retardancy imparting agent is composed of a hydrated metal compound (D 1), a brominated epoxy compound (d 2), and a phosphate compound (D 3), the brominated epoxy compound (d 2) ) Is preferably 6 to 88 mass%, more preferably 15 to 74 mass%, and particularly preferably 27 to 59 mass%. The curable resin composition for etching resistance in the first aspect is preferably 4 to 42% by mass, more preferably 9 to 33% by mass, and particularly preferably 14 to 27% by mass. If the blending ratio of the brominated epoxy compound is too low, the flame retardance effect may be insufficient, and if it is too high, the flexibility and developability may be reduced. If a phosphate ester compound (D 3) is used, the blending ratio is not particularly limited, but the total amount of the flame retardant imparting agent is preferably 0.2 to 67 mass%, more preferably 0.7 to 43 mass %, Particularly preferably 4 to 25% by mass. The blending ratio of the entire amount of the phosphate ester compound of the hardening resin composition for anti-uranium etching in the first aspect is not particularly limited, but it is preferably 0.1 to 25% by mass, more preferably 0.4 to 18% by mass, particularly preferably 2 to 12% by mass. If the blending ratio of the phosphate compound (D 3) is too low, the flexibility may be insufficient, and if it is too high, the appearance of the coated film may be damaged due to bleeding-out. For the above-mentioned 4:37 paper size in the hardening resin composition for etching resistance in the first form, the Chinese National Standard (CNS) A4 specification (210X297 mm) -33-I. Clothing ^ Order ~ (Please read first Note on the back page, please fill in this page again) 584785 A7 _—— _B7 V. Description of the invention (31) The blending ratio of the flame retardant as a whole, preferably 17 to gg mass%, more preferably 2 9 to 6 3 mass%, particularly preferably; 39 to 57 mass%. If the blending ratio of the flame retardant is too low, the flame retardant will be deteriorated. If the ratio is too high, transparency, flexibility, strength (bending resistance), and image development will be lowered. situation. III — 1 · Other ingredients (i) Thermosetting resin (E) In the first form, the hardening resin material for uranium-resistance is a photocurable resin material, an electron beam-curable resin material, or an X-ray-curable resin. In the case of materials, the thermosetting resin (E) may be contained in the curable resin composition for etching resistance as a thermosetting component if necessary. Such a thermosetting resin (E) can be selected from the same resin materials as those used for the above-mentioned thermosetting resin materials. These thermosetting resins can be used singly or in combination of two or more kinds. Preferred among these is epoxy resin. Specific examples of the epoxy resin may be selected from those exemplified by the user as the above-mentioned thermosetting resin material. In addition, the hardening resin composition for etching resistance in the first embodiment is preferably a non-uniform system including an epoxy resin. Specifically, a state in which a solid or semi-solid epoxy resin is confirmed in an etching-resistant curable resin composition before curing is caused by unevenly mixed loops in the etching-resistant curable resin composition. The meaning of the state of oxygen resin. The particle diameter is preferably such that it does not interfere with screen printing or dry film production. For example, the entire hardening resin composition for anti-etching before curing is not the same as the standard paper size. Applicable to China National Standard (CNS) A4 (210X297 mm) = 34-:. ^^ 衣-(Please read the Note for this page, please fill in this page) Order • 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 3 £ 584785 A7 B7 V. Description of Invention (32) (Please read the notes on the back before filling this page) Sentences are transparent. Contains at least a portion that is opaque. In this way, if the hardening resin composition for etching resistance before curing has a heterogeneous phase of a phase made of epoxy resin, the shelf life of the hardening resin composition for resistance to etching will be longer. good. Among the preferred epoxy resins used for this purpose, preferred are bis-acid S-type epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, and bixylenol-type epoxy resins. Resin, biphenyl type epoxy resin, and tetraglycidyl xylenol ethane resin, and contains a phase of such epoxy resin in the hardening resin composition for etching resistance, and resists etching before hardening It becomes a non-uniform system with a curable resin composition. In this way, as a non-uniform epoxy resin which is a hardening resin composition for etching resistance before hardening, a non-uniform system is easily formed from crystals having a clear melting point, and high heat resistance of the hardened material can be obtained. From a viewpoint, it is more preferable to use a biphenyl type epoxy resin. When the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a thermosetting resin (E) in the first form of uranium-resistant hardening resin composition, the blending amount is in the case of using photocurable resin materials For a total of 100 parts by mass of the photo-hardening component (the above-mentioned photosensitive prepolymer (A-1) and the compound having an ethylenically unsaturated group) is preferably 10 to 150 parts by mass, and more preferably 10 to 50 parts by mass Serving. When the blending amount of the thermosetting resin (E) is 10 parts by mass or less, the heat resistance of the brazing film of the hardened film made of the hardening resin composition for etching resistance may be insufficient. On the other hand, if it exceeds 150 parts by mass, the shrinkage of the cured film will increase, and if the cured film is used as an insulating protective film for an F PC substrate, the curl will tend to increase. 03. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -35 _ 584785 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the hardening hardening fat (E, salt, anhydride) , Type, use. Amine grade amine. Amine, diethyltetramine, bis, tributyl 1,8 A7 B7 V. Description of the invention (33) Thermal polymerization catalyst (F) In one form, in the use of photohardenability In the case of a resin material (or an electron beam resin material or an X-ray hardening resin material), for example, when a thermal resin (E) is used, a thermal polymerization catalyst capable of performing a thermosetting effect can be used if necessary. (F). Specific use: amines, amine salts such as amines, quaternary ammonium cyclic aliphatic acid anhydrides, aliphatic acid anhydrides, aromatic acid anhydrides, polyacrylamides, imidazoles, and three farming compounds Etc. Nitrogen-containing heterocyclic compounds and organometallic compounds. These can be one type or a combination of two or more types. Examples include aliphatic and aromatic primary, secondary, and trialiphatic amines. Polymethyldiamine, polyether, etc. Diethylenetriamine, triethylenetriamine, tetraethylenepentamine, triimine, trimethylaminopropylamine, pinenyldiamine, amineethylethanol (hexamethylene) triamine , 1,3,6-Paraminylmethylhexaneylamine, 1,4-diazabicyclo [2.2 · 2] octane, diazabicyclo [5 · 4.0] undecene Ene-7-ene and the like. Examples of the aromatic amine include m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, and diaminodiphenylsulfone. As for the acid anhydride, there may be mentioned: terephthalic anhydride, trimellitic anhydride, dibenzodione tetracarboxylic anhydride, ethylene glycol bis (dehydrated trimellitate), glycerol (dehydrated trimellitate), etc. Aromatic anhydride, maleic anhydride, succinic anhydride, methylcarbamic anhydride, hexahydroterephthalic anhydride, tetrahydroterephthalic acid (please read the precautions on the back before filling this page)

4.4Q This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -36- 584785 A7 B7 V. Description of the invention (34) Formic anhydride, polyadipic anhydride, chloric anhydride, tetrabromoterephthalic acid For polyamines such as formic anhydride, a polyamine having a primary or secondary amine group obtained by subjecting a dimer acid to a polyamine such as diethylenetriamine or triethylenetetramine to a condensation reaction may be mentioned. Methylamine. As for imidazoles, specific examples are: imidazole, 2-ethyl-4 methylimidazole, N-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole Trimellitate, 2-methylimidazole_ • isocyanurate, etc. The three-tillage compound is a compound having a six-membered ring containing three nitrogen atoms, and examples thereof include melamine compounds, melamine compounds, and melamine melamine compounds. Specifically, examples of the melamine compound include melamine, N-ethylenemelamine, N, N >, N-triphenylmelamine, and the like. As for the cyanuric acid compound, cyanuric acid, isocyanuric acid, trimethyl cyanurate, paramethyl isocyanurate, triethyl cyanurate, Ginseng ethyl isocyanurate, tri (η-propyl) cyanurate, ginseng (η-propyl) isocyanurate, diethyl cyanurate, Ν, Ν & gt -Diethyl isocyanurate, methyl isocyanate, methyl isocyanurate, etc .; Examples of melamine melamine compounds include molamine reactants such as melamine compounds and melamine compounds. Examples of the organometallic compound include a metal salt of an organic acid, a metal salt of a 1,3-diketone, and a metal alkoxide. Specific examples: Dibutyltin dicinnamate, dibutyltin maleate, zinc 2-ethylhexanoate, and other organic paper sizes applicable to Chinese National Standard (CNS) A4 specifications (210 × 297 mm) -37-" "—; _-------- (Please read the notes on the back before filling in this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 584785 A7 _ B7 V. Description of the Invention (35) Acid metal salts, nickel acetoacetone nickel, zinc acetoacetone, etc. 1,3-dione metal salt, tetrabutane Alkoxy i-based metals such as titanium oxytitanium, chromium tetrabutoxy alkoxide, and aluminum butoxy alkoxide. The amount of the thermal polymerization catalyst (F) used is from 0.5 to 20 parts by mass, and preferably from 1 to 10 parts by mass, based on 100 parts by mass of the thermosetting resin (E). If the amount of the thermal polymerization catalyst (F) used is less than 0.5 parts by mass, the curing reaction will not proceed smoothly and the heat resistance will decrease. In addition, because it takes a long time to harden at high temperatures, it may cause a decrease in work efficiency. When it exceeds 20 parts by mass or more, it reacts with a carboxyl group in the hardening resin composition for etching resistance and tends to gel, which causes problems such as a decrease in storage stability. (i i i) Others In addition, in order to adjust the viscosity of the anti-etching curable resin composition, an organic solvent may be added if necessary. In this way, due to the adjustment of the viscosity, it can be easily coated or printed on an object by a roll coating method, a spin coating method, a screen coating method, a curtain coating method, a knife coating method, or a blade coating method. Examples of organic solvents include: ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; acetamyl acetate, >-butyrolactone, butyl acetate, etc. Solvents; Alcohol-based solvents such as butanol, benzyl alcohol; Carbitol acetate, methyl-cellosolve acetate, etc .; , N-dimethylformamide, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone, and other amine-based solvents; dimethyl asus; phenol, cresol, and other phenol-based solvents; Nitro Compounds This paper is sized for China National Standard (CNS) A4 (210X 297 Gong Dong 1 -38-'" (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 584785 A7 _______ B7 V. Description of the Invention (36) Department of Consortium, Coben, __ ^ toluene, hexamethylbenzene, and xiangxiang aromatic aromatic solvents Solvents for aromatic and alicyclic hydrocarbons made from hydrocarbons such as hydronaphthalene and dipentene. They can be used singly or in combination. The amount of the organic solvent used is preferably such that the viscosity of the hardening resin composition for etching resistance can be adjusted to 500 to 500,000 mPa · s [measured at 25 ° C using a Brookfield Viscometer]. More preferably, it ranges from 1,000 to 500,000 mPa · s. With such a viscosity, it is suitable for coating or printing on an object and is easy to use. In addition, the preferred amount of organic solvent used to make such a viscosity is 1.5 mass times or less the solid content other than the organic solvent. If it exceeds 1.5 mass times, the solid content concentration decreases, so that when the hardening resin composition for etching resistance is printed on the substrate, a sufficient film thickness cannot be obtained in one printing, and there are cases where multiple printing is required. In case 0, a coloring agent can be added to such an anti-etching curable resin and used as an ink. Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black. When used as an ink, its viscosity is preferably 500 to 500,000 mPa · s [measured at 25 ° C using a Brookfield Viscometer]. A flow modifier may be further added to the curable resin composition for etching resistance of the first aspect to adjust the flowability. The fluidity adjusting agent is suitable for the paper size when the hardening resin composition for etching resistance is coated on an object using a roll coating method, a screen coating method, a curtain coating method, a knife coating method, or a blade coating method, for example. Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -39-~: ——_ ^^ 衣-(Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 584785 A7 _________ B7 V. Description of the Invention (37) It is ideal to adjust the fluidity of the hardening resin composition for etching resistance. Examples of the flow regulator include inorganic and organic fillers, waxes, and surfactants. Specific examples of the inorganic concrete filler include talc, barium sulfate, barium titanate, silica, alumina, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, and oxalate compounds. Specific examples of the organic fluorene filler include polysiloxane resin, polysiloxane rubber, and fluororesin. Specific examples of fluorene include polyfluorene fluorene and polyethylene wax. Specific examples of the surfactant include polysiloxane oil, higher fatty acid esters, and amidine. These fluidity-adjusting agents can be used singly or in combination of two or more kinds. Among these, when an inorganic hafnium filler is used, it is desirable not only to improve the fluidity of the hardening resin composition for etching resistance, but also to improve properties such as adhesion and hardness. Further, additives such as a heat polymerization inhibitor, a tackifier, a defoamer, a leveling agent, and an adhesion-imparting agent may be added to the curable resin composition for resisting etching, if necessary. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone-methyl ether, tertiary butyl catechol, gallophenol, phenanthrene, and the like. In terms of tackifiers, there can be mentioned: hectorite, montmorillonite, saponite, chertite, fumemontite, tetrasilica, layered silicate with mica, etc. Processed interlayer compounds, silicon dioxide, and organic silicon oxide. Antifoaming agent is used to eliminate bubbles generated during printing, coating and hardening. Specific examples include: acrylic, polysiloxane and other surfactants. This paper applies Chinese national standard _ (CNS) A4 Specifications (210X297mm) -40-： —I, ^^ 衣-(Please read the precautions on the back before filling this page)

， 1T # Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584785 V. Description of the invention (38 Leveling agents are used to eliminate unevenness. Specific examples are: C. As for adhesiveness imparting agents, alkane coupling agents, etc. As another addition range, for example, for preservation of plasticizers, etc. Next, the product of the present invention will be described. The second type anti-etching hardening resin has the same structure as the first type: A7 B7 Printing and coating Examples of the surfactants such as olefin-based, polysiloxane-based surfactants on the surface of the coating film include imidazole-based, thiazole-based, triazole-based, and silicon-based agents. Ultraviolet rays may be added without disturbing the stability of the gist of this embodiment Preventive agent, the second form of the anti-etching hardening resin composition of the anti-etching hardening resin composition system material is blended. The explanation will be omitted.: -I.-(Please read first (Notes on the back then fill out this page)

UA • 1 Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs I-2 · Etching-resistant hardening resin material (i) Photocurable resin material (1) Photosensitive prepolymer (A-2) < Urethane (meth) acrylate compound) > Combination of different urethane (meth) acrylate compounds (a) and urethane (meth) acrylate (b ) The use ratio at the time of use is preferably a urethane (meth) acrylate compound (100 mass parts) of the urethane (meth) acrylate compound having a carboxyl group ( a): Urethane (meth) acrylate compound (b) = 40 to 90: 60: 100 mass ratio. Furthermore, it is more preferable that the amino methacrylate (meth) acrylate compound (this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 41-584785 A7 B7 printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs) System V. Description of the invention (39) a): The mass ratio of urethane (meth) acrylate compound (b) = 50 to 80:50 to 20. The other matters are the same as those in the first form. (2) The compound (B) having an ethylenically unsaturated group is the same as the first embodiment. (3) The photopolymerization initiator (C) is the same as that in the first embodiment. (i i) The electron beam-curable resin material is the same as that of the first embodiment. (i i i) The X-ray curable resin material is the same as that of the first embodiment. (i v) The thermosetting resin material is the same as that of the first embodiment. I I-2 · Surface-treated hydrated metal compound In the second aspect, the surface-treated hydrated metal compound is prepared in the above-mentioned hardening resin material for etching resistance. (i) The hydrated metal compound used in the second aspect is a metal compound having crystal water, and may be exemplified by a heat absorption at thermal decomposition of more than 400 J / g, but it is not limited to this. this. Specific examples of such a hydrated metal compound are the same as those exemplified in the first embodiment. (Please read the precautions on the back and fill in this page first) 44S This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -42-584785 A7 ___B7 V. Description of the invention (4〇) (Please read the back first (Please fill in this page again for the matters needing attention) Also, in the above-mentioned hydrated metal compound, a hydrotalcite compound having a layered crystal structure and having a hydrated anion between the crystal layers, or a layered crystal structure having an organic anion between the crystal layers Hydrotalcite-based compounds are also easy to use. The hydrotalcite in the second form can be expressed by the following general formulae (c) and (d). (M2 + i-xM3 + x (OH) 2) x + (anion) ......... (c) (M3 + 2 (OH) 6M1 + y] y + (anion) y * .... ..... (d) Here, 0. · 4, 0, 0 < y < 2, M2 + is at least one kind of monovalent metal represented by Li, Na, K, Rb, Cs,] \ / 12 + is at least one of the divalent metals represented by] \ / [Gong, € 3,] \ / 111,? €, (3〇, 1 \ [: 1, 〇11, Z η, etc., M 3 + for A 1,

At least one trivalent metal represented by Fe, Ci ·, I η, etc., [ani ο η (anion)] X — and [ani ο η] y — are hydrated anions or organic anions existing between crystal layers . Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as in the first form, in the above general formula (c), the compound in which M 2 + is M g 2+ and M 3 + is A 1 3 + is called hydrotalcite. In addition, the compounds of general formulae (c) and (d) are generally called hydrotalcites. In the case of hydrotalcite compounds having hydrated anions between crystal layers, in the general formulae (C) and (d) above, [ anion] x-will become [An-χ / η · πιΗ2〇] χ-1, [anion] y_ will become the hydrated anion of TfC shown by C Α η χ / η · 1ϊΐΗ2). Therefore, this paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -43-one 584785 A7 _ B7 V. Description of the invention (41) (Please read the precautions on the back before filling this page) Between crystal layers The general formula of the hydrotalcite-based compound having a hydrated anion can be expressed by the following (e) and (f). Here, A η-is at least one of Cl-, Br_, Co-32-'N031-, s42-Fe (CN) 6 4-, and n-valent ion-exchange anion represented by tartaric acid ion. . C M2 + i-xM3 + x (OH) 2) x + [A ^^ / n mH2〇] x *… (e) [M3 + 2 (OH) 6M1 + y] y + [An '/ n mH2〇] y_ (F) Here, 0.1Sx ^ O · 4, 0 < y < 2, m is an integer of 1 or more, and n is an integer of 1 to 4. M1 +, M2 +, and M3 + have the same meaning as those in formulas (c) and (d). In the case of a hydrotalcite compound having an organic anion between the crystal layers, the organic anion is not particularly limited, but amino acids, sulfur compounds, nitrogen-containing heterocyclic compounds, and salt compounds thereof are suitable. Specifically, examples include: leucine, cystine, phenylalanine, tyrosine, aspartic acid, glutamic acid, lysine, 6-aminohexyl carboxylic acid, employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed 1 2 -aminocinnamylcarboxylic acid, N, N -dimethyl-6-aminohexylcarboxylic acid, N, N -dodecyl -N, N -dimethyl-1 0 -amine Amino derivatives such as decyl carboxylic acid, dimethyl-N-1 2 -aminocinnamyl carboxylic acid, 2-chlorobenzyl thiazole, methyl dithiocarbamic acid, dimethyl dithiocarbamic acid And other sulfur-containing compounds and their salt compounds, 2-mercaptothiazoline, 2,5-difluorenyl-1,3,4-thiadiazole, 1-carboxymethyl-5-thiol 1H-tetrafluorene , 2, 4, 6 —Ethylthio-S—Two wells The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -44-584785 A7 B7 V. Nitrogen-containing impurities such as the description of the invention (42) Ring compounds and their salt compounds. A hydrotalcite-based compound having an organic anion between the crystal layers is one that does not exist, but can be prepared by treating a hydrotalcite-based compound with an organic solvent containing a predetermined organic anion. The particle size of the surface-treated hydrated metal compound used in the second aspect is not particularly limited, but the average particle diameter is preferably from 0.05 to 40 // m, and more preferably from 0.1 to 2.0 / / m is more suitable. If the average particle diameter exceeds 3 0 // m, the transparency of the hardened film may be deteriorated, which may reduce the light transmittance or damage the appearance and smoothness of the surface of the coated film. On the other hand, if it is 0 · 0 5 // m or less, there is a disadvantage that the productivity of the powder is significantly reduced. When a hydrotalcite-based compound is used, the size of its crystal particles is preferably about 0.05 to 10 / zm, and more preferably 0.1 to 5.0 // m. If the average particle diameter exceeds 10 // m, the light transmittance of the cured film will be reduced, and at the same time, the warpage may easily occur due to the shrinkage anisotropy of the coating film during the curing process. On the other hand, if it is 0 · 0 5 // m or less, there is a disadvantage that the productivity of the powder is significantly reduced. The particle diameter of the surface-treated hydrous metal compound in the second form can be determined by a sedimentation particle size measurement method or a light scattering method in a solvent. Alternatively, a transmission electron microscope and a scanning electron microscope can also be used to directly observe the crystal particles to obtain the geometric diameter of each particle, and to obtain it from the frequency distribution or cumulative distribution of each fraction according to the number basis . The mean particle size will vary by assay. Obtained using the microscope above: _-------- (Please read the precautions on the back before filling this page)

、 1T f Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4.43 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -45-584785 A7 ______B7 V. Explanation of the Invention (43) The average particle diameter is calculated After the average of the long and short diameters of each particle, and 长 obtained from the log-normal distribution, in this embodiment, it can be measured according to any of the methods described above and can be included in the above range of average particle diameters. Among the hydrated metal compounds used in the second aspect, preferably, the heat absorption during thermal decomposition is more than 4 0 J / g, preferably 6 0 to 2 5 0 0 J / g. Metal compounds. If the heat absorption is more than 400 J / g, a high flame retardance effect may be obtained. (i i) Surface treatment agent When performing the surface treatment of the hydrated metal compound in the second aspect, a surface treatment agent can be used. When the hydrated metal compound subjected to such a surface treatment is blended in a hardening resin material, the viscosity increase during kneading can be suppressed during the manufacture of a high-concentration master batch intermediate material, and molding can be easily performed, and its transparency is also low. Will improve significantly. Furthermore, since the dispersed state of the hydrated compound particles in the curable resin composition becomes good, flexibility and flame retardancy can be greatly improved. The surface treating agent is not particularly limited, but it is preferable to use a material having a hydrophilic and lipophilic property or a material having a polarity. Specific examples of the surface-treating agent having hydrophilic and lipophilic properties include saturated fatty acids and unsaturated fatty acids having a carbon number of 8 or more; primary amines, secondary amines, tertiary amines, and salt compounds thereof; quaternary ammonium salts; It is selected from the group consisting of amino acid derivatives. More specifically, examples include: octylamine, laurylamine, tetradecylamine, cetylamine, stearylamine, oleylamine, propylamine, amine, aniline, etc. This paper standard applies to China National Standard (CNS) A4 specification (210X297 mm) "46-: ~ I. ^^ 衣-(Please read the precautions on the back before filling this page)

, 1T

• I printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy se 4 584785 Α7 B7 V. Description of the invention (44) Primary amines listed in the table; Secondary amines such as ammonium amine, N-toluidine, etc .; dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitamine, diamine Tertiary amines such as methyl stearylamine, dilauryl-methylamine, tributylamine, trioctylamine, N, N-dimethylaniline, etc .; tetrabutylammonium ion, tetrahexylammonium ion, diamine Hexyl dimethyl ammonium ion, dioctyl dimethyl ammonium ion, hexane trimethyl ammonium ion, octyl trimethyl ammonium ion, dodecyl trimethyl ammonium ion, stearyl trimethyl ammonium ion, Fluoradiene trimethyl ammonium ion, cetyl trimethyl ammonium ion, cetyl triethyl ammonium ion, cetyl ammonium ion, tetradecyl dimethyl benzyl ammonium ion, stearyl arsenide Methyl benzyl ammonium ion, dioleyl dimethyl ammonium ion, N-methyl diethanol lauryl ammonium ion, dipropanol-methyl lauryl ammonium ion, dimethyl monoethyl Tertiary ammonium such as alcohol lauryl ammonium ion, poly (ethylene oxide) dodecyl-methylammonium ion, and amine propylamine quaternary compound. In addition, exemplified are: saturated fatty acids such as hexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and their metal salts; undecylenic acid, cetylenoic acid, erucic acid, Unsaturated fatty acids such as basic acid, sorbic acid, oleic acid, linoleic acid, arachidic acid, and their metal salts; leucine, phenylalanine, tyrosine, lysine, 12-aminolaurate Carboxylic acid 'N-η-dodecyl-N, N-difluorenyl-1 0-aminodecyl residual acid, dimethyl mono-N-12-aminolaurylcarboxylic acid, etc. Derivatives, etc. Specific examples of polar surface treatment agents include: titanate coupling agent, aluminum coupling agent, zirconium aluminate coupling agent, and selected from the group consisting of silane coupling (please read the precautions on the back before filling this page), 11 f The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -47-584785 A7 ___B7 V. The group of people who made the invention (45). Examples of silane coupling agents: 3-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl ginseng (2-methoxyethoxy) Silane, 3-monomethyloxypropyltrimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxide, 3 -glycidyloxypropyldimethoxyacetate, 3- Sulfopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxyacetate, 3-ureylpropyldiethoxylate, etc. . As for the titanate coupling agent, there are: isopropyl triisostearyl titanate, isopropyl dodecane phenylthiosulfate titanate, isopropyl titanate (dioctyl pyrophosphate) ) Ester, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (tricosylphosphite) titanate, tetra (2,2-diallyloxymethyl) —1 monobutyl) bis (titanyl) phosphite titanate, bis (dioctyl pyrophosphate) oxoacetate titanate, bis (dioctyl pyrophosphate) titanium ethylene Acid esters, isopropyl dioctyl fluorenyl titanate, isopropyl dimethyl propylene isostearyl fluorinated titanate, isopropyl isostearyl fluorinated dipropylene titanate, isopropyl tri (dioctyl phosphate) ) Titanate, isopropyl anisyl phenyl titanate, isopropyl tris (N-amidinomethyl monoamine ethyl) titanate, dianisylphenoxyacetate titanate, diiso Stearin, ethylene titanate, etc. Examples of the aluminum coupling agent include acetoxyaluminum diisopropylate. Examples of the zirconium aluminate coupling agent include compounds having a skeleton represented by the following general formula. In this 'functional group (-RX)' R table cannot have a substituted alkylene group, X is an amine group, a carboxyl group, a fluorenyl group, an alkyl group, and a chain of paper. The Chinese paper standard (CNS) A4 specification (210X 297 mm) -48- I -------- • Cloth II (Please read the notes on the back before filling this page) Order • 1 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 584785 A7 ___ B7 5 Description of the invention (46) Alkenyl. R χ can be exemplified as the organic group shown below. These functional groups may have only one kind or two or more kinds. (Please read the notes on the back before filling this page)

Organic group; one (CH2) 2NH2, one (CH2) 4C00H,-(C Η 2) 1 2 C Η 3 '-C (CH3) = CH2,-(CH2) 2SH,-(CH2) 2NH2

RX

I c

/ 广: N 〇, 、 0

0H \ I I

xZr Al-OH OH / \ /

OH In addition, the use amount of the surface treatment agent is preferably from 0.1 to 5.0% by mass, and more preferably from 0.4 to 2.0% by mass for the hydrated metal compound. If the amount of the surface treatment agent used is too small, there may be a problem of poor moldability because it tends to cause an increase in viscosity when it is molded into a thin film such as a cured film. On the other hand, if the amount of the surface treatment agent used is too large, it may be caused by a decrease in the heat resistance of the film due to an increase in unreacted or out-gas during heating. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. If a hydrotalcite-based compound having an organic anion between crystal layers is used, the surface treatment is performed after applying a solvent containing an organic anion. Therefore, since the hydrotalcite compound having an organic anion between the crystal layers becomes a substance that has been subjected to a surface treatment, it is not necessary to reuse the surface treatment agent as described above for surface treatment, and it can be directly used as a "surface treatment agent." Surface-treated hydrated metal compounds ". This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -49- '584785 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ _B7 V. Description of the invention (47) (iii) Second proportion The surface-treated hydrated metal compound is preferably 100 parts by mass of 100 to 100 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 30 to 100 parts by mass of the hardening resin material for resisting etching. 60 parts by mass. If the blending ratio of the hydrated metal compound is too low, the flame retardance is insufficient. If it is necessary to obtain a high flame retardance effect, it is necessary to increase the ratio of other flame retardancy-imparting ingredients such as brominated epoxy compounds and phosphate compounds. , So that it will cause a decline in acid content of solid ingredients and a decline in imaging properties. On the other hand, if it is too high, the cured film tends to become opaque, and its flexibility is lowered, resulting in poor flexibility, which may cause warping. I I I 1 2 Other ingredients In addition to the above-mentioned hardening prepolymer and hydrated metal compound, various compounds may be blended in the hardening resin composition for uranium-resistant engraving in the second form. For example, as a flame retardant-imparting ingredient, a brominated epoxy compound and / or a phosphate compound may be blended. In combination with the above-mentioned hydrated metal compound, excellent flame retardancy imparting effect can be exhibited. In addition, in the case where the curable resin material for etching resistance is a photocurable resin material, an electron beam curable resin material, or an X-ray curable resin material, a thermosetting resin can be used as a thermosetting component when necessary. The thermal polymerization catalyst is contained in the hardening resin composition for anti-etching together: --------- clothing-- (Please read the precautions on the back before filling this page) Order • 1 4 sheets Standards are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -50-584785 A7 ___B7_ V. Description of the invention (48) (i) Brominated epoxy compounds (Please read the precautions on the back before filling this page) Bromine The blending ratio of the hardening resin composition for the anti-uranium engraving of the converted epoxy compound is not particularly limited, but it is more preferable to use 10 to 80 parts by mass of the 100 parts by mass of the hardening resin composition for the resistance to etching, more preferably It is 20 to 60 parts by mass, and particularly preferably 30 to 50 parts by mass. If the blending ratio of brominated epoxide compound is too low, the flame retardant effect may be insufficient. If it is too high, the flexibility and developability may be lowered. Others are the same as those of the first form. (i i) Phosphate ester compound A phosphate ester compound may be contained if necessary. This makes it possible to improve the flame retardancy of the hardenable material composition. In particular, when the flexibility is insufficient, it is desirable to improve the flexibility without impairing the flame resistance by using the hydrated metal compound, brominated epoxy compound, and phosphate compound. That is, a flame-retardant composite system composed of three components of a hydrated metal compound, a brominated epoxy compound, and a phosphoric acid ester compound can be used to achieve a balance between flame resistance and flexibility at a high level. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, phosphate ester compounds can be used in one or more combinations. The blending ratio of the phosphoric acid ester compound is not particularly limited, but it is preferable to use 0.5 to 40 parts by mass, and more preferably 1 to 30 parts by mass of the hardening resin composition for resisting etching. It is preferably 5 to 20 parts by mass. If the blending ratio of the phosphate ester compound is too low, the flexibility may be insufficient, and if it is too high, the appearance of the coated film may be damaged due to bleeding. Others are the same as those of the first form. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 51. — 584785 A7 B7 V. Description of the invention ⑷) (1 1 i) The thermosetting resin (E) is the same as those in the first ~ form. (iv) The thermal polymerization catalyst (F) is the same as that of the first form. (v) Others The others are the same as those in the first form. Next, a method for producing a hardening resin composition for etching resistance will be described. #Inventive composition of the first and second forms of uranium-resistant hardening resin 'Can be produced by mixing the above-mentioned ingredients in a usual manner. The method of mixing is particularly limited. It is possible to mix one component and the remaining components ′ or to mix all the components together. Specifically, it is preferable to perform melt-kneading after mixing the above components, for example, using a Bumbery mixer, a kneader, a roll press, a uniaxial or biaxial extruder, and a kneading extruder. A well-known mixture such as a press (Ko-Kneader) is used to knead the mixture to make it. The melting temperature is preferably in the range of 60 to 130 ° C. In addition, in the case where the viscosity at room temperature after dilution with a solvent is reduced to an ink-like hardening resin composition for etching resistance, it can be produced by a well-known kneading method such as three rollers or glass beads. Next, a cured film of the curable resin composition for etching resistance will be described. The hardening resin compositions for etching resistance according to the first and second aspects of the present invention can be coated on a substrate with an appropriate thickness, dried after heat treatment, and then hardened by exposure, development, and thermal hardening to form hardened materials. 4.5S This paper size is applicable to China National Standard (CNS) A4 (210X297mm) -52-(Please read the precautions on the back before filling this page) Order

• I Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 584785 A7 B7 V. Description of the invention (50) The hardening resin composition for etching resistance of the present invention can be used in various applications. It has excellent image properties, and has excellent adhesion to the substrate, insulation, anti-warp deformation, and flexibility when it is cured to form a thin film. It is suitable for use as an insulating protective film for printed circuit boards. In order to form an insulating protective film, the substrate may be formed on a substrate on which a circuit is formed by a conductor, and a uranium-resistant hardening resin composition or ink is applied at a thickness of 10 // m to 100 / zm. The temperature range from 60 ° C to 100 ° C is heat treated for 5 to 30 minutes and dried to a thickness of 5 to 7 0 // m, and then a negative mask with a desired exposure pattern is applied. (Nega mask) and exposure, using a developing solution to remove the unexposed part for development, and heat curing at a temperature range of 100 ° C to 180 ° C for 10 to 40 minutes to harden it Methods. Since the hardening resin composition for etching resistance is not only incombustible, but also has excellent flexibility when used as a hardened material, and is superior to flexibility, it is particularly suitable for use as an insulating protective film for FPC substrates. An FPC board with less warpage and excellent handling properties is produced. Alternatively, it may be used as an insulating resin layer between layers of a multilayer printed circuit board. As the active light used for exposure, active light generated by well-known active light sources, such as carbon arc, mercury vapor arc, gas arc (Xenon arc), and the like can be used. Due to the sensitivity of the photopolymerization initiator (C) contained in the photosensitive layer, it is usually the largest in the ultraviolet field. At this time, the active light source is preferably one that can effectively emit ultraviolet rays. Of course, if the photopolymerization initiator (C) this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm)-53--(Please read the precautions on the back before filling this page), 11 Ministry of Economic Affairs wisdom Printed by the Consumer Cooperative of the Property Bureau 584785 A7 B7 V. Description of Invention (51) (Please read the notes on the back before filling this page) Those who can feel visible light, for example, 9,10-phenanthrenequinone, etc. Visible light is used as the active light, and as the light source, other than the aforementioned active light source, a stray light bulb for photography, a sun lamp, or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, phosphate, sodium silicate, ammonia, or amine can be used. The curable resin composition for etching resistance of the present invention can also be used as a photosensitive layer of a photosensitive dry film. A photosensitive dry film is a support made of a polymer film and having a photosensitive layer made of a hardening resin composition for etching resistance. The thickness of the photosensitive layer is preferably 10 to 70 / zm. Examples of the polymer film used for the support include films made of polyester resins such as polyethylene terephthalate, aliphatic polyester, and polyolefin resins such as polypropylene and low-density polyethylene. Among these, a film made of polyester and low-density polyethylene is preferred. In addition, since these polymer films must be removed from the photosensitive layer later, those that can be easily removed from the photosensitive layer are preferred. The thickness of these polymer films is usually 5 to 100 / m, preferably 10 to 30 / m. The photosensitive dry film printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can be manufactured by forming a photosensitive layer on the support and drying the photosensitive resin layer for drying. In addition, a cover-film may be provided on the formed photosensitive layer, and a support, a photosensitive layer, and a cover film may be laminated in this order to produce a photosensitive dry film having films on both sides of the photosensitive layer. The cover film is a person who will be peeled off when the photosensitive film is used. However, since the cover film is provided on the photosensitive layer before use, the photosensitive layer can be protected, and as a result, it is a photosensitive dry film with excellent shelf life. The cover film can be used with the polymer used in the above-mentioned support. 455 paper sizes are applicable to China National Standard (CNS) A4 specifications (210X297 mm) -54-584785 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 4 A7 B7 5. Description of the invention (52) If the film is the same, the covering film and the support may be the same material or different materials, and the thickness may be the same or different. If you want to use a photosensitive dry film for the insulation and protection film and form it on the printed circuit board_h, first perform the bonding process of laminating the photosensitive layer and the photosensitive dry film. Here, if a photosensitive dry film provided with a cover film is used, the cover film is peeled off first and the photosensitive layer is exposed before contacting the substrate. Then, using a pressure roller or the like, the photosensitive layer and the substrate are thermocompression-bonded at about 40 to 120 ° C, and the photosensitive layer is laminated on the substrate. Then, the exposure process of exposing the photosensitive layer through a negative mask with a desired exposure pattern, the process of peeling the support from the photosensitive layer, and using a developing solution to remove unexposed portions for development The image processing process and the thermal curing process of thermally curing the photosensitive layer can produce a printed circuit board having an insulating protective film on the surface of the substrate. In addition, such a photosensitive dry film can be used to form an insulating resin layer between layers of a multilayer printed wiring board. Here, the same can be used for the active light and the developer used for the exposure. The curable resin composition for etching resistance of the present invention has excellent film moldability and transparency, and has high flame retardancy. In addition, if a flame retardant is used, it has excellent flame resistance, can maintain appearance and high flexibility, and is superior to light sensitivity and developability. Moreover, it can also form a heat resistant electrical insulation. It is a hardened film with properties such as adhesiveness to circuit boards. In addition, the cured film is particularly transparent, flame-resistant, flexible, and has electrical insulation and appearance. Therefore, even if the circuit is as thin as an FPC substrate, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 55--(Please read the precautions on the back before filling this page) Order f 584785 A7 B7 V. Description of the invention (53) When the board is not warped, it can form a flexible insulating protective film with excellent electrical properties and handling properties. (Please read the notes on the back before filling out this page.) Examples Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. Production Examples 1 to 3 Synthesis of a photosensitive prepolymer (A-1, A-2) having a carboxyl group. Production Example 1 < E A — 1 > Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Put a flask with a gas introduction tube, a stirring device, a cooling tube, and a thermometer in the Schübbach < Bisphenol A-type epoxy compound (trade name ·· Alar Taidou # 2600 ") manufactured by < Stock > 291g, bisphenol A: 129g and triethylamine 0.20 g as catalyst, in 150 to 16 The reaction was performed at 0 ° C for 1 hour to obtain a bisphenol A epoxy compound having a softening point of 97 ° C and an epoxy equivalent of 100 g / equivalent. This was charged with 30 g of acrylic acid, 0.45 g of monomethyl ether hydroquinone as an inhibitor, and 1.65 g of triphenylphosphine as an esterification catalyst, and reacted at 12 CTC for 5 hours to prepare A reactant of 1 mg of KOH / g was obtained. Furthermore, 168 g of tetrahydroterephthalic anhydride was charged at this temperature and the reaction was carried out at 120 ° C until the acid hydrazone reached 100 mg g K〇 / g. This reaction takes 3 hours. In this regard, as a solvent, 2 6 5 g of ethylene glycol monomethyl ether acetate and a box of 0. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -56-584785 A7 B7 V. Invention Explanation (54) 14g of super sol # 1800 1 made by Mitsubishi Petroleum Co., Ltd., epoxy acrylate resin (EA-1) was prepared. (Please read the precautions on the back before filling out this page) Manufacturing Example 2 < UA — 1 > A polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.) is installed in a reaction vessel equipped with a stirring device, a thermometer, and a condenser. PTMG-850, molecular weight 850) 2500 g (= 3 moles), 670 g (= 5 moles) of dimethylolpropionic acid as a hydroxyl compound having a carboxyl group, isophorone diisocyanate as a polyisocyanate 1 7 76 g (= 8 moles) and 2-hydroxyethyl acrylate as a (meth) acrylate with a carboxyl group 2 3 8 g (= 2.05 moles), then p-methoxyphenol and two third Each butyl hydroxytoluene was charged with 1.0 g. After heating to 60 ° C. with stirring, stop and add 1.6 g of dibutyltin dilaurate. If the temperature in the reaction vessel starts to decrease, it will be heated again, and continue to stir at 80 ° C. Use infrared absorption spectrum to confirm that the absorption spectrum of isocyanate group (2 2 0 0 cm-1) has disappeared, and the solid will be obtained. Hydroxyl-containing photosensitive prepolymer with a solid acid concentration of 60 mg KOH / g and a solid content concentration of 60% < U A-1 >. The viscosity of the prepolymer (25 ° C) was 25,000 m · Pa. Manufacturing Example 3 < UA-2 > Except for each use as a polymer polyol, a polycarbonate diol containing a unit derived from hexamethylene carbonate and pentamethylene carbonate at a ratio of 1: 1 (molecular weight 800) 800 g ( = 1 mole), as the standard of this paper with carboxyl group, the Chinese National Standard (CNS) A4 specification (210X297 mm) -57-584785 A7 B7 V. Description of the invention (55) (Please read the notes on the back before filling This page) 9 3 8 g (= 7 moles) of dimethylolpropionic acid as a base compound, 1 9 9 8 g (= 9 moles) of isophorone diisocyanate as a polyisocyanate, and Except for 238 g of (meth) acrylic acid 2-monohydroxyethyl acrylate (= 2.05 mole), the rest are the same as those in Production Example 1. < U A-1 > Synthesis was performed in the same manner. The resulting amino formate < UA-1 > The number average molecular weight was 18,000, and the acid sulfonium was 90 Mg KOH / g. Next, adjustment of the curable resin composition for etching resistance is performed. Examples 1 to 10, Comparative Examples 1 to 4 The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the blending ratio (parts by mass) shown in Table 1 as a photosensitive prepolymer (A-1 with a carboxyl group) ) And in the manufacturing examples 1 to 3 above, the manufacturing K < EA-1, UA-1, UA-2 >, and a compound (B) having an ethylenically unsaturated group, and a photopolymerization initiator (C), and a hydrated metal compound (D1), and a brominated epoxy The compound (D2), the phosphate compound (D3), and the thermosetting resin (E), the thermopolymerization catalyst (F), and the solvent are mixed to prepare a curable resin composition. Here, although a solvent is used in the synthesis of the (A-1) component and the preparation of the composition, the mixing ratios in Table 1 are expressed in terms of the dried solid component conversion. The compound (B) having an ethylenically unsaturated group is an epoxy acrylate: Ripochisi SP-4 0 1 0 (manufactured by Showa High Polymer Co., Ltd.), and a carbamate: EB 1 2 9 0 K (Dasil Chemical Industry Co., Ltd.). 4. (;? This paper size applies Chinese National Standard (匸 灿) 8 4 specifications (210 father 297 mm) -58-584785 A7 ---_.__ B7 V. Description of the invention (56) (Please read the back Please fill in this page again.) Photoinitiator (C), 2,4,6-trimethylbenzene phenylphosphine oxide: TP0 (manufactured by BASF), 2-benzylmethylamine —1— (4 —morpholinophenyl) —butanone-1 (Irgaga 3,69, manufactured by Chiba · Special Chemicals Co., Ltd.), 1 (Irga seeking 184, Chiba • Special Chemicals (stock) system.) Hydrated metal compounds (D 1) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, using aluminum hydroxide: Hutch Ryder H ~ 4 3 STE (manufactured by Showa Denko), magnesium hydroxide · Kisma 5 A (manufactured by Kyowa Chemical Industry Co., Ltd.), hydrotalcite: d Η T -4 A (manufactured by Kyowa Chemical Industry Co., Ltd.). The brominated epoxy compound (D 2) 'is a bisphenol A-type brominated epoxy resin: Ebigold E-5050 (bromine content 49% by mass, epoxy equivalent 390, Japanese epoxy resin ( )), Bisphenol A-type brominated epoxy acrylate: Shinpoll 83 19S (bromine content 41 · 1% by mass, manufactured by Yobijia (Japan)), carboxyl-containing bisphenol A-type brominated epoxy Acrylic acid ester: Neopol 8318S (32.2 mass% bromine content, solid content acid 値 8 2. 7 M g KOH / g, made by Japan's Ubisoft (stock)). Phosphate ester compound (D 2), system Aromatic Condensed Phosphate: PX-200 (manufactured by Daiha Chemical Industry Co., Ltd.) and Orthophosphate: Triphenyl Phosphate TPP (manufactured by Daiha Chemical Industry Co., Ltd.). Thermosetting resin (E), system Bisphenol epoxy resin YL6121H (made by Japan Epoxy Resin) is used. Thermal polymerization catalyst (F) is melamine (made by Nissan Chemical Industry Co., Ltd.). This paper size applies Chinese National Standard (CNS) A4 specification (210x 297 male *) -59- 584785 Α7 Β7 V. Description of the invention (57) Test example 1 < Production of photosensitive dry film > (Please read the precautions on the back before filling in this page) In the above-mentioned Examples 1 to 10 and Comparative Examples 1 to 4, fluorenyl cellulose solinoacetate was used as the solvent. The prepared resin composition (viscosity 5,000 mPa · s, 25 ° C) was coated on a polyethylene terephthalate cover using a doctor blade, and dried at 80 ° C After 7 minutes to form a photosensitive layer, a 2 5 // m thick polyethylene film (low-density polyethylene film) was laminated thereon to make a photosensitive dry film with a cover film. The film thickness of the photosensitive layer after drying is 4 0 ± 1 // m 〇 < Production of laminated test piece > The cover film of the photosensitive dry film was peeled off, and the photosensitive layer was heated at 70 ° C. On the other hand, the substrate for heating evaluation was 60 ° C, and pressure was applied. The laminating machine of the roll was bonded to the photosensitive layer and the substrate for evaluation to obtain a laminated test piece. Here, the evaluation substrate is printed using the following (1) and (2) ° Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy (1) The copper foil (thickness 3 5 #m) laminated on one side Printing board made of sulfonimide (thickness of 50 / m) (Ubisole (registered trademark) N, manufactured by Ube Kosan Co., Ltd.) was washed with a 1% sulfuric acid aqueous solution, and washed with water in an air stream. The dry ones. (2) 2 5 // m thick polyimide film (Cabodon (registered trademark) 100%, manufactured by Toray DuPont). 4M: This paper size applies Chinese National Standard (CNS) A4 specification (210x297 mm) -6〇_584785 A7 B7 V. Description of the invention (58) < Exposure, development, and thermal hardening of laminated test pieces > (Please read the precautions on the back before filling out this page} Using an exposure machine with a metal halide lamp (made by Oak Corporation) HMw-6 8 The exposure of each of the obtained laminate test pieces was performed at 0 GW at 50 Om J / cm2. Next, each of the laminate test pieces was subjected to a 1% by mass sodium carbonate aqueous solution at 30 ° C for 30 seconds, and then 30 ° The water of C was sprayed for 30 seconds to remove unexposed parts and developed. Thereafter, heat treatment was performed at 150 ° C for 30 minutes to obtain a copper-clad laminated board (using an evaluation substrate (1 )) And polyimide laminated board (using the evaluation substrate (2)). Here, the stouffei * 21 step input board (step tablet) for exposure. For the production of the solder heat resistance evaluation sample, a negative pattern of 4 cmx 6 cm in the range of 1 cmx 1 cm square and 2 cm in length of 1 mm / lmm (row / space) is used as a negative pattern. For electrical insulation, IPC (electronic circuit wiring and Packaging Society) specifications I P C-C. In the production of other evaluation samples, negative patterns were not used. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs < Physical property evaluation > The physical property evaluation is performed as follows. The results are shown in Table 2. In each of the following evaluations, "flammability", "flexibility", and polyimide were evaluated, and electrical insulation was used on a commercially available substrate. (I PC-C) is provided with the above-mentioned Examples 1 to 8 for comparison. 4 ^ This paper size applies the Chinese national standard (milk milk) 8 4 specifications (210 '/ 297 mm) -61-584785 A7 --- ---- B7_ V. Description of the invention (59) ^ 1 Μ 4 of each hardenable resin composition layer (layer thickness is 4 C) // m). The other evaluations are performed on copper-clad laminates. Evaluation items • Flame resistance The test piece was prepared by the following method. On both sides of a polyimide film (made by Toray DuPont, Capton 1 0 0H) with a thickness of 2 5 // m, 2 0 mm × 5 O mm, a hardenable resin composition layer with a thickness of 4 0 // m, Then, it was irradiated with UV (ultraviolet) at 500 m J / cm 2, and then heat-cured at 150 ° C. for 30 minutes. After adjusting the state of the sample at 70 ° C for 168 hours, a soldering shock treatment was performed in a sand bath at 260 ° C for 10 seconds, and it was used as a sample for the flame resistance test. . The combustion characteristics are evaluated using the flame retardant test method of the polymer material in accordance with the American Insurer Laboratories Co., Ltd. (abbreviated as U L) 9 4 U L-V T M test. Here, the “VTM” and “NOT” in Table 2 are based on the following criteria. "V T Μ -〇": Those who can all meet the following requirements (1) All test pieces will not be flamed for more than 30 seconds after each flame interruption. (2) When a total of 10 flame exposures are performed on 5 test pieces in each group, the total flame burning time does not exceed 250 seconds. (3) Flames or red hot burning will not reach the marking line of 125 mm. (4) Absorbent cotton will not catch fire due to flame dripping. This paper size applies to China National Standard (CNS) A4 (210x297 mm) -62-㈣〇 -------- Φ | 丨 (Please read the precautions on the back before filling this page) Order the wisdom of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau 584785 A7 _____ B7 V. Description of the invention (60) (5) After the second flame stop, the total flame and red heat of each sample will not exceed 60 seconds . (Please read the precautions on the back before filling in this page) (6) If only 1 test piece in a group of 5 test pieces does not meet the requirements, or the total flame time is between 2 5 1 seconds and 2 5 5 In the range of seconds, 5 test pieces are to be tested, and all of them need to comply with (1) to (5). "VTM-2" ... Those who can all meet the following requirements. (1) All test pieces will not be flamed for more than 30 seconds after each flame stop. (2) When a total of 10 flame exposures are performed on 5 test pieces of each group, the total flame burning time does not exceed 250 seconds or more. (3) Flames or red hot combustion will not reach the mark of 125 mm. (4) Absorbent cotton can catch fire due to flame dripping. (5) After the second flame stop, the total of flame and red heat burning of each sample will not exceed 60 seconds. (6) If only one of the five test pieces in a group fails to meet the requirements, or the total time of the flame is in the range of 251 seconds to 255 seconds, it is printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. System, then test five more test pieces, and all of them need to meet (1) to (5) 0 "NOT": Those who fail the above grades. • The photosensitivity is a negative pattern. (Stouffei *) 2 1-stage step input board is superimposed on the sample. The shape of the copper-clad laminated board measured after exposure and development processing is 4.g7. This paper scale applies Chinese national standards. (CNS) A4 specification (210X297 mm) 63 584785 A7 • _B7 V. Description of the invention (61) (Please read the precautions on the back before filling this page) The number of segments of the step input board of the light-hardened film. The photosensitivity of the curable resin composition was evaluated. The photosensitivity is expressed by the number of steps of the step input board '. The higher the number of steps of the step input board, the higher the photosensitivity. • Developability In the evaluation of photosensitivity, the state of the coating film after developing for 1 minute by using a 1% by mass sodium carbonate aqueous solution as a developing solution during development and developing at a spray pressure of 2 kg / cm 2 Make a visual judgment. The symbols in Table 2 indicate the following meanings. 〇: Can be developed △: There are some incomplete development X. · There are incomplete development. • Flexibility. The polyimide laminate is made of a cured film made of a photosensitive layer and is bent at 180 ° and inspected. The presence or absence of blushing of the hardened film. 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 0: The foggy white without the hardened film. X: The matte white with the hardened film. The test method of 6 4 8 1 is to float the copper-clad laminated board on a solder bath at 260 ° C for 10 seconds as a cycle, and to blister the hardened film of the solder float after 1 cycle and 3 cycles, respectively. Tightness is based on total -64-Ming S This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 584785 A7 __B7 V. Description of the invention (62) Judgment and evaluation are included. ◎: No change at all 0: Slight change (please read the precautions on the back before filling this page) △: Less than 10% of the cured film has been peeled off X: Completely peeled of the cured film • Electrical insulation (Insulation resistance) I PC — C (comb-type pattern) of a commercially available substrate (I PC standard) was provided with each hardening resin composition layer of Examples 1 to 8 and Comparative Examples 1 to 4, and The laminated board was left at 85 ° C and 100% relative humidity for 192 hours, and the insulation resistance was measured before and after such treatment to evaluate the electrical insulation. The measurement of the insulation resistance 施加 is performed by applying a 100 V DC voltage to the substrate before and after disposal, and holding it for 1 minute, and using an electrical insulation meter while the voltage is applied. Test Example 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs < Production of laminated test pieces > Each of the curable resin compositions (viscosity 2 0, 2) prepared in Examples 1, 2, 8, 9 and Comparative Examples 1 and 2 using carbitol acetate as a solvent 0 0 0 m P a · s), using a silk screen printing with a 150 mesh polyester plate, and coated on the substrate for evaluation in such a way that the film thickness after drying can be about 40 // m. The applied curable resin composition was dried at 70 ° C for 30 minutes to prepare a laminate test piece. The final film thickness of the photosensitive layer is 4.53. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -65-584785 A7 B7 V. Description of the invention (63) 40 ± 2 // m. For the evaluation substrate, one of the above (1) and (2) is used. These were evaluated in the same manner as in Test Example 1. The results are shown in Table 2 (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -66 584785 A7 B7 V. Explanation of the invention (64) Comparative example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇12.0 〇ppp ρ Η 10.0 ρ CO 30.0 o ρ · ρ ρ 22.0 ο ο ρ ι—Η CN1 sr—H r —H ο ο ρ r—H r—H ^ 〇1 § sr—H ρ Η ρ 〇§ r—Η ppp 22.0 22.0 ο od τ—Η ρ Ο ο ρ 〇 \ 〇ν〇O CN § pp ρ 22.0 22.0 ρ ο ο ρ τ—Η 〇〇Ο νο oopp ρ 22.0 22.0 ο ο ρ bl ^ ο.οΊ pp ρ 22.0 \ 72.〇] ο ο ρ 30.0 | opr— ^ p ρ 22.0] 22.0 ο ρ Implementation / wn "30.0" pp ρ Η | 22.〇1 22.0 10.01 ρ inch 20.0 pp ρ r—H rH 10.0 ο 1—Η CO 34.0 § 〇 < N Ο οό 1 ο ο ρ (N1 § rH s rH ρ 1— (ο τ—Η rH | 3 ^ 〇 | 18.0 S, i in 10.0 ο EA-1 UA-1 UA-2 epoxy acrylate amine Urethane Acrylate Photopolymerization Initiator-1 (TP0) Photopolymerization Initiator-2 (EAB-F) Photopolymerization Initiator-3 (Ilga seeking 184) Gas Oxidation Magnesium Hydroxide Hydrotalcite Ebiko Germany 5050 New Boer 8319S New Boer 8318S PG-200 TPPP epoxy melamine g Q § Q g 丨-(Please read the precautions on the back before filling this page) Order 4.7 ^ This paper size is applicable to Chinese national standards (〇 Chan) 8 specifications (210/297 mm) -67-584785 A7 B7 V. Invention Description (65 Printed by CS1 General Insulation Resistance Disposal (Ω) 2.3X1011 4.4X1010 8.1 ΧΙΟ10 4.5 ΧΙΟ10 2.9 ΧΙΟ11 8.8 × 109 6.9 ΧΙΟ10 2.9 ΧΙΟ12 8.7 ΧΙΟ10 1.6 ΧΙΟ12 4.6 ΧΙΟ10 2.2 ΧΙΟ11 4.9 ΧΙΟ10 4.6 × ΙΟ10 8.3 × ΙΟ10 4.9 X1011 6.0 X1011 8.6 X10 10 8.6 X10 10 8.6 X10 10 8.6 X10 Ο14 1.5 ΧΙΟ14 4.6 ΧΙΟ14 4.4 ΧΙΟ14 7.5 ΧΙΟ13 3.0 ΧΙΟ13 4.1 ΧΙΟ13 8.0 ΧΙΟ13 3.8 × 1014 8.0 ΧΙΟ13 5.6 ΧΙΟ13 2.1 × 1014 1.7 X1013 7.5 X1013 3.0 X1013 5.0 X1014 8.9 × 1012 3 ◎ ◎ ◎ ◎ ◎ < 〇 〇 ◎ ◎ < ◎ < X 〇 〇 〇 〇 < 〇 Manufacturing: it 1 cycle ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Flexibility 〇 < 〇 〇 〇 〇 〇 〇 〇 〇 < XXX 〇〇〇〇〇〇〇 XX developability 0.0000000 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 sensitization CNI rH r-ο ο ο Ν ΝΝΟΝ ΟΟ ο ΟΟ ο CO 〇〇CS Flammability 94VTM VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 1 VTM-0 1 1 VTM-0 1 1 VTM-0 1 1 VTM-0 1 1 VTM-0 1 1 NOT 1 1 NOT 1 1 NOT 1 1 NOT 1 1 VTM-0 1 | VTM-0 I | VTM-0 I VTM-0 NOT NOT Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 1 Example 8 1 Example 9 1 Example 10 1 Comparative Example 1 1 1 Comparative Example 2 1 1 Comparative Example 3 1 Comparative Example 4 Example 1 | Example 2 1 | Example 8 1 Example 9 Comparative Example 1 Comparative Example 2 Test example 1 (film) _______ Test example 2 (ink) I --------- 9 ---- Ί--1T ------ (Please read the precautions on the back before filling in this (Page) The standard one country and the country one in the world-suitable II rule paper I body, | centimeter 68 584785 A7 _____B7 V. Description of the invention (66) Examples 1 1 to 18, Comparative Examples 5 to 8 (please first (Read the notes on the back and fill in this page.) Secondly, according to the allocation ratio shown in Table 3. In the above-described Production Example 1-3 produced 2) - parts by mass), having a carboxyl group as a photosensitive prepolymer (A < EA-1, UA-1, UA-2 >, and a compound (B) having an ethylenically unsaturated group, and a photopolymerization initiator (C) ', a hydrated metal compound, and a brominated epoxy compound, and Phosphate ester compound ', thermosetting resin (E), and thermal polymerization catalyst (F) to prepare a curable resin composition. Here, although a solvent is used in the synthesis of the photosensitive prepolymer or in the preparation of the composition, the blending ratios in Table 3 are expressed in terms of solid content after drying. The compound (B) having an ethylenically unsaturated group is based on dipentaerythritol hexyl acrylate: M-400 (manufactured by Toa Synthetic Co., Ltd.), and urethane: EB 1 2 9 0 K (Daisher Chemical Industry (Share) system). The photopolymerization initiator (C) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs uses 2,4,6-trimethylphenylphosphonium phenylphosphine oxide: TPO (Photopolymerization Initiator-1) manufactured by BASF, Chiba · Special Chemicals (Stock) 2 -benzyl-2 dimethylamino-1 1- (4-morpholinophenyl) monobutanone 1 1 (brand name "Irgaga 3 6 9 ";" Ilgaqiu "is a registered trademark) (Photopolymerization Initiator-20), 1-Hydroxy-cyclohexyl-phenyl-methanone (trade name" Ily Elgar asks 1 8 4 ″) (photopolymerization initiator one 3). < Ammonia oxidation—1, 1,2, and 3> The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm 1 -69-" 584785 A7 B7) 5. Description of the invention (67) (Please read first Note on the back page, please fill in this page again) Hydrated metal compounds, using aluminum hydroxide • Hexletter 4 -4 3 Μ (Showa Denko Corporation) [using a scanning electron microscope (J SM- 5 5 0 OLV) Observe the secondary electron image at an acceleration voltage of 20KV, and calculate the average particle diameter obtained from the length-to-length ratio; 0.6 // m]. The surface treatment agent uses (1) hard Fatty acid (hydrophilic and lipophilic compound; pure chemical (stock) test reagent), (2) 3-glycidyloxypropyltrimethoxysilane A-187 (silane coupling agent made by Uyouka (Japan)), (3) 3 types of 3-methylaminopropyldimethoxysilane A-1 8 9 (silane coupling agent made by U-Nippon, Japan). The surface treatment agents (1) to (3) are used in this manner. The aluminum hydroxide treated with the surface treatment agent is referred to as aluminum hydroxide-1, -2, -3. Here, the surface treatment is carried out in the following manner. If using stearic acid, feed aluminum hydroxide and stearic acid (3% by mass) to a 20 liter Henschel mixer, and heat to 100 ° C ± 5 t while stirring to dissolve the stearic acid. Acid for the surface treatment of aluminum hydroxide. In the case of the silane coupling agent printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, first take 1% by mass of the above aluminum compound in the amount of aluminum hydroxide, in = 1/9 (volume / volume) solution was diluted 4 times. Next, the above 10% by mass aqueous dispersion of aluminum hydroxide was prepared, and the silane coupling agent was charged while stirring. To be completely filled with silane After the coupling agent was' stirred for 5 hours and filtered, vacuum-dried at 80 ° C for 12 hours to prepare a sample. In addition, for 3-glycidyloxypropyltrimethoxysilane A-1 8 7, no diluent was used. After loading the silane coupling agent, heat the Henschel mixer to 80 ° C for processing. 4. This paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -70-584785 A7 B7 V. Description of the invention (68) < Hydrolite—1, — 2 > (Please read the notes on the back before filling this page) (1) Use magnesium nitrate, aluminum nitrate and sodium hydroxide as raw materials' and follow the literature [S. Miyata: Clay and clay minerals, No. 23, pp. 365-375, 1975]. The dropping rate of sodium hydroxide was adjusted to 5 Om 1 / min, and after aging at 60 ° C for 6 hours, a structural formula [Mg0.77A 10.3 (OH) 2 ( NO 3) 1.0 · 6 η 2 〇] hydrotalcite (untreated product). The secondary electron image observation of the particle size of this single crystal particle was performed using a transmission electron microscope (CX2 0 0 manufactured by Bento Electronics) at an acceleration voltage of 120 kV. The average particle diameter calculated from the aspect ratio was 0 · 4 // m. To this hydrotalcite crystal, stearic acid was mixed at a ratio of 3% by mass, and the temperature was increased to 100 ° C. with stirring by a Henschel mixer, and the mixture was stirred for 5 minutes to prepare a sample (hydrotalcite 1 1). (2) D, L-phenyl group of P Η 1 〇 prepared by mixing with sodium hydroxide in a mixed aqueous solution of magnesium nitrate and aluminum nitrate (Morbi 3: printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 1). An aqueous solution of alanine (pure chemical reagent) to co-precipitate hydrotalcite using D, L-phenylalanine as interlayer ions. An appropriate amount of sodium hydroxide was dropped into the mixed solution to keep the pH at 10, and after ripening at 60 ° C for 6 hours, it was repeatedly washed, filtered, dried, and pulverized to obtain a sample (hydrotalcite -2). The brominated epoxy compound is a bisphenol A-type brominated epoxy resin · Ebigold E-5 0 50 (made by Japan Epoxy Resin Co., Ltd.). Phosphate ester 3 This paper is in accordance with Chinese National Standard (CNS) A4 (210X mm) -71-584785 A7 B7 V. Description of the invention (69) The compound is an aromatic condensed phosphate · p X-2 〇〇 ( Big Eight Chemical Industry (stock) system). (Please read the precautions on the back before filling this page.) The thermosetting resin (E) is a biphenyl epoxy resin YL6 12 1H (made by Japan Epoxy Resins). Thermal polymerization catalyst (F) uses melamine (manufactured by Nissan Chemical Industries, Ltd.). < Production of photosensitive dry film > For Examples 11 to 18 and Comparative Examples 5 to 8, the same procedures as in Examples 1 to 10 and Comparative Examples 1 to 4 were also used to prepare photosensitive films. . < Production of laminated test pieces > For Examples 11 to 18 and Comparative Examples 5 to 8, the same steps as those of Examples 1 to 10 and Comparative Examples 1 to 4 were used to make laminated tests. sheet. < Exposure, development, and thermal hardening of laminated test pieces > Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, using an exposure machine with a metal halide lamp [made by Oak (Stock)] HMW-6 8 0 GW to The exposure of each of the obtained laminate test pieces was performed at 50 Om J / cm2. Next, a 1% by mass sodium carbonate aqueous solution was developed at 30 ° C for 1 minute, and the unexposed part was removed and developed. Then, the heat treatment was performed at 150 ° C for 30 minutes to obtain a copper-clad laminated board ( Use evaluation substrate (1)) and polyimide laminate (use evaluation substrate (2)) ° 47S This paper size applies to China National Standard (CNS) A4 (210X297 mm) -72-584785 A7 B7 5 2. Description of the invention (70) In addition, in the production of evaluation samples of photosensitivity and developability, a negative 1-step input board made by Hitachi Chemical Co., Ltd. was used as a negative pattern for exposure. (Please read the note on the back first (Fill in this page again) < Physical property evaluation > The physical property evaluation is performed as follows. The results are not as shown in Table 4. • The flammability test was performed only once with 5 test pieces as a set, and for the purpose of comparing the flame resistance, 5 fire test pieces were used for fire resistance. Except for the total time and the number of fire test pieces among the 5 test pieces, the rest were evaluated in the same manner as in the above-mentioned Examples 1 to 10 and Comparative Examples 1 to 4. • Photosensitivity Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. As a negative pattern, a 21-step step input board made by Hitachi Kasei Co., Ltd. was superimposed on the sample and exposed at 500 m J / cm2. Next, use 1 mass% sodium carbonate aqueous solution at 30 ° C for 1 minute. After removing the unexposed parts, measure the number of steps of the light-hardened film formed on the copper-clad laminated board and input the number of steps to evaluate the hardenability. Photosensitivity of the resin composition. • Developability As far as Examples 1 to 18 and Comparative Examples 5 to 8 were evaluated, the same methods as those of Examples 1 to 10 'and Comparative Examples 1 to 4 were evaluated. This paper size is in accordance with Chinese National Standard (CNS) A4 (210x 297 mm) -73-584785 A7 B7 V. Description of the invention 折) • Folding resistance samples are on both sides of a polyimide film with a thickness of 2 5 / zm After the anti-etching agent was laminated, the test piece exposed, developed, and hardened under the above conditions was cut into a width of 15 mm and a length of 110 mm for modulation. At the time of the evaluation, the J I S C 5 〇 1 6 bending resistance test was performed using an ITO-type rubbing fatigue tester s type manufactured by Toyo Seiki Seisakusho Co., Ltd. and evaluated. The sample was mounted on a bending device with an opening of 0.25 mm and R = 0.38, and it was bent repeatedly from left to right at a load of 4 to 9N and a speed of 175 cpm. The bending test is suspended every 10 times, and the bending space of each § type test piece is observed with a microscope. Read the maximum number of bends in the anti-etching layer without cracks. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -74 · 478 This paper size applies to China National Standard (CNS) A4 (2! 〇χ 297 mm) 584785 A7 B7 V. Description of the invention (72) Comparative example printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇〇 〇12.0 0 MD ppp 1 1 1 1 20.0 〇§ p 1 0 VO 〇CN 〇ppp 1 1 § rH 1 1 0 οί § 0 L ^ oJ 1 1 § 1 ppp 1 1 1 1 20.0 ο cs § § p un 34.0 1 1 1 ppp 1 1 〇1 1 H § § p rH 00 1 0 0 〇 4 0 MD ppp 1 1 1 20.0 1 s § p Lml 1 1 1 ppp 1 1 1 20.0 1 rH § § CZJ 34.0 1 1 § 1 p H pp 1 1 1 20.0 1 1 12.0 § Η p Η 1 〇VO 0 〇j 0 MD ppp 1 § Η 1 1 1 r-H § p IK 1 〇VO 0 S pppr-H 16.0 1 1 1 1 rH § p CO Η 34.0 1 1 1 CD rH pp 1 § Η 1 1 〇〇o4 § § 0 1 i CN1 rH ^ 4OJ 1 1 S 1 ppr—H p 16.0 1 1 1 1 S rH § § p 1—H rH r—H L3i〇J 1 1 1 ppp ο VO 1 1 1 1 1 t—H § § p EA-1 UA-1 UA-2 Season 2 Tetraolurethane photopolymerization initiator-1 photopolymerization initiator-2 photopolymerization initiator-3 aerobic bromide-1 oxyoxidation Ming-2 aluminum hydroxide-3 aluminum hydroxide (H-43M) hydrotalcite -1 Hydrotalcite-2 Hydrotalcite (untreated) Brominated epoxy tree S purpose (E-5050) Phosphate ester (PX-200) Epoxy resin (YL6121H) Melamine g U r—HQQ sg £ (Please read first Note on the back, please fill in this page again), 1 '473 paper sizes are applicable to Chinese National Standards (cns), 8-4 specifications (210X297 mm) -75-584785 A7 B7 V. Description of invention (73 Intellectual Property Bureau, Ministry of Economic Affairs, employee consumption Folding tolerance of printed coops (times) ο r—H 8 1 '' < csi 〇SS Clarity 1_ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Sensitivity 1 cs CO r-HH οα o Burning test 94VTM-Class 1_ VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 NOT Total flame exposure time (S) CO inch CN οό 17.4 cn id OO 26.9 23.3 20.7 42.8 45.5 53.6 Number of fire test pieces / 5 ^ Τ) un wn ^ T) CO Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 'I ---- ---- Φ ---- Ί--, 玎 ------ ^ 9— (Please read the precautions on the back before filling this page) 4SS · This paper size applies to China National Standard (CNS) A4 specifications (210X 297mm) -76-584785 A7 B7 V. Explanation of the invention (74) Industrial application The hardening resin composition for etching resistance of the present invention has good photosensitivity and alkali developability. In addition, a protective film having excellent flame resistance, flexibility, and solder heat resistance can be formed. It is especially useful for capping and solder resist for F PC. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4㈣ This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -77-

Claims (1)

Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584785 A8 B8 C8 ____ D8 VI. Patent Application No. 9 1 1 1 3 792 Patent Application Chinese Application Patent Scope Amendment August 20, 1992 Amendment A curable resin composition for etching, comprising at least one photosensitive prepolymer comprising a urethane (meth) acrylate having an ethylenically unsaturated terminal group derived from an acrylic monomer and a carboxyl group. Hydration from clusters of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, dorsonite, calcium aluminate, 2-hydrated gypsum, zinc borate, barium metaborate, zinc hydroxystannate, kaolin, vermiculite, and hydrotalcite-based compounds Metal compounds. · 2 · The hardening resin composition for etching resistance described in item 1 of the scope of patent application, which contains a brominated epoxy compound. 3. The hardening resin composition for etching resistance according to item 1 of the scope of patent application, which is a urethane (methyl group having an ethylenically unsaturated end group derived from an acrylic monomer and a carboxyl group ) An acrylic prepolymer, a compound having an ethylenically unsaturated group in addition to the aforementioned photosensitive prepolymer, and a photopolymerization initiator. 4. The hardening resin composition for etching resistance according to item 1 of the scope of patent application, wherein the solid content of the urethane (meth) acrylate compound having the aforementioned carboxyl group is 5 to 150 mg. K 0 Η / g 0 5 · The hardening resin composition for etching resistance as described in item 1 of the scope of the patent application, wherein the photosensitive prepolymer contains: a solid component acid 値 at 5 ni g K〇H / g above, 60 mg · K〇Η / g carboxyl carbamate (meth) acrylate compounds, and this paper size applies Chinese National Standard (CNS) A4 & grid (2) 0; <; 297 public ^ 1 ~ 1 (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584785 A8 B8 C8 _ D8 6. The scope of the patent application has a carboxylic acid group with a solid content of acid 値 above 60 mg K〇Η / g, and carboxy group below 150 mg K〇Η / g Those with urethane (meth) acrylate compounds. 6. The etching-resistant curable resin composition according to item 1 of the scope of patent application, wherein the etching-resistant curable resin material is an electron beam-curable resin material. 7. The hardening resin composition for etching resistance according to item 1 of the scope of the patent application, wherein the hardening resin material for etching resistance is an X-ray hardening resin material. · 8 · The etch-resistant curable resin composition according to item 1 of the scope of patent application, which contains a thermosetting resin and a thermal polymerization catalyst. 9 'The hardening resin composition for etching resistance according to item 1 of the scope of patent application, which contains an organic solvent. 1 0. The hardening resin composition for etching resistance as described in item 1 of the scope of patent application, wherein the heat absorption amount during the thermal decomposition of the aforementioned hydrated metal compound is 400 J / g or more. 1 1 · The hardening resin composition for etching resistance according to item 1 of the patent application scope, wherein the hydrated metal compound is at least one of aluminum hydroxide and magnesium hydroxide. 1 2 The hardening resin composition for etching resistance according to item 1 of the scope of the patent application, wherein the hydrous metal compound has a layered crystalline structure, and a hydrotalcite or a hydrotalcite-based compound having a hydrated anion between the crystal layers . 1 3 · Hardness for etching resistance as described in item 1 of the scope of patent application 1 Paper size Standard for Financially Friendly Households (CNS) A4 Secret (2) 〇297297 | '一' (Please read the precautions on the back before (Fill in this page) 584785 A8 B8 C8 D8 VI. Patent application scope (please read the precautions on the back before filling this page) Resin composition, which contains 100 parts by mass of the aforementioned hardening resin material for anti-etching, and is prepared with the aforementioned hydrated metal compound 1 〇 to 100 parts by mass. 14. The hardening resin composition for etching resistance according to item 2 of the scope of patent application, wherein the aforementioned brominated epoxy compound is an epoxy equivalent of 2000 to 3,000, and a bromine content of 40 to 60% by mass. Bromobisphenol A epoxy resin. 15 · The hardening resin composition for etching resistance according to item 2 of the scope of patent application, wherein the aforementioned brominated epoxy compound is a multifunctional epoxy (meth) acrylate having a bromine content of 30 to 60% by mass. Compounds. 16 · The etching-resistant curable resin composition according to item 2 of the scope of patent application, wherein 100 parts by mass of the aforementioned etching-resistant curable resin material is blended with the aforementioned brominated epoxy compound 10 to 8 0 mass parts 0.1 7 · The hardening resin composition for etching resistance according to item 1 of the scope of patent application, which contains a phosphate compound. 1 8 _ The printed resin composition of the consumer cooperative of the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Ministry of Economic Affairs for hardening of etching resistance as described in the scope of application for patents, wherein the phosphorus atom of the aforementioned phosphate compound is a pentavalent one. The hardening resin composition for etching resistance described in claim 18, wherein the phosphate compound is an aromatic group. 20. The hardening resin composition for etching resistance as described in item 17 of the scope of the patent application, wherein the hardening resin material for etching resistance is 100%. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297). (Mm) 584785 8 8 8 8 ABCD VI. Patent Application Amounts “Parts formulated with the aforementioned phosphate compound 0.5 to 40 parts by mass. 2 1 · A hardening resin composition for etching resistance according to item 2 of the scope of patent application, in which a phosphate compound is contained. 2 2. Hardening resistance for uranium engraving as described in item 1 of the scope of patent application. Resin composition 'wherein the viscosity is 5,000 to 50000 mPa · s (25 ° C) . 2 3 · The uranium-resistant hardening resin composition described in item 1 of the scope of the patent application, wherein the aforementioned hydrated metal compound is surface-treated with a surface-treating agent having a hydrophilicity, lipophilicity, or less than g of polarity. . -2 4 · The hardening resin composition for etching resistance according to item 23 of the scope of patent application, wherein the surface-treating agent having hydrophilic and lipophilic properties is selected from the group consisting of: saturated fatty acids having a carbon number of 6 or more; unsaturated fatty acids and The salts thereof; those of primary amines, secondary amines, tertiary amines, and the like; quaternary ammonium salts; amine compounds; and amino acid derivatives. 2 5 · The hardening resin composition for etching resistance as described in item 23 of the scope of the patent application, wherein the polar surface treatment agent is selected from the group consisting of a titanate coupling agent, an aluminum coupling agent, and an aluminate coupling agent. Mixture and silane coupling agent. 2 6 _ The hardening resin composition for etching resistance as described in item 23 of the patent application range, wherein the aforementioned hydrated metal compound is a layered crystalline mixture, and an organic anion hydrotalcite or water is present between the crystalline layers. Talc compounds. · 27. The hardening resin composition for etching resistance as described in item 26 of the patent application scope, wherein the aforementioned organic anion is selected from the group consisting of amino acids, and this paper is also applicable to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) 2 Γ ~ (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 584785 A8 B8 C8 D8 &, among those applying for patents covering sulfur compounds, nitrogen-containing heterocyclic compounds, and their salts. Fill in this page again) 2 8. The hardening resin composition for etching resistance as described in item 23 of the scope of patent application, wherein the average particle size of the aforementioned hydrated metal compound is between 0.1 and 3 0 // m. 2 9. A hardened material, characterized in that the hardened material is a hardened resin composition for etching resistance as described in item 1 of the scope of patent application. 30. A composition characterized by containing a hardening resin composition for etching resistance as described in item 1 of the scope of patent application and a coloring agent. 3 1. A hardening method for an anti-etching curable resin composition, characterized in that it has the anti-etching curable resin composition as described in item 1 of the scope of patent application or the 30 item in the scope of patent application The composition is coated on the substrate at a thickness of 10 to 100 0 // m, and dried at a temperature range of 60 ° C to 100 ° C for 5 to 30 minutes to form 5 to 7 ◦ // m thickness, the process of exposure and development, and thermal curing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 32. A dry film characterized by having a photosensitive layer formed on the support by a hardening resin composition for etching resistance as described in item 1 of the scope of patent application . 33. The dry film according to item 32 of the scope of patent application, wherein the aforementioned support system is a film made of polyester or polyethylene. 3 4. A method for manufacturing a photosensitive dry film, comprising: forming a photosensitive layer on the support and drying the photosensitive layer, the hardening resin composition for etching resistance as described in item 1 of the scope of patent application; . This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 584785 A8 B8 C8 D8 ------; ----, patent application scope 3 5. An insulation protection film, characterized by: It is made of a hardening resin composition for etching resistance as described in Patent Application No. 1. 36. A printed circuit board characterized by having an insulating protective film as described in item 35 of the patent application. 37. A flexible printed circuit board characterized by having an insulating protective film as described in Item 35 of the scope of patent application. 38. — A method for manufacturing a printed circuit board, characterized in that it has a lamination process for laminating the photosensitive layer of a dry film as described in item 32 of the patent application scope with a ® board, and The exposure process of the exposure, the development process after the exposure process, and the thermal curing process of thermally curing the photosensitive layer. (Please read the precautions on the back before filling out this page.) Appropriate, 1T printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.