JP2014028938A - Active energy ray-curable resin composition for printed resist, method for forming resist pattern using the same, printed resist laminate and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed resist layer which can be patterned by printing, requires no firing or drying process for curing, which exhibits adhesiveness to a conductor such as copper and aluminum after cured with UV rays, which is durable against an etching process or an electrolytic plating process, and which can be easily stripped afterward.SOLUTION: The active energy ray-curable resin composition for a printed resist comprises: a condensate (A) obtained by hydrolyzing and condensing a thiol group-containing alkoxysilane (a1) expressed by general formula (1):RSi(OR)(where Rrepresents a hydrocarbon group having 1 to 4 carbon atoms, having at least one thiol group; and Rrepresents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), wherein hydrolysis is not carried out when all of Ris a hydrogen atom; and a compound (B) having at least one carboxyl group and at least one carbon-carbon double bond in the molecule.

Description

  The present invention relates to an active energy ray-curable resin composition for resist for printing a resist layer patterned by curing on a substrate or a conductor layer, a method for forming a resist pattern using the same, and a printing resist lamination Body and printed wiring board.

The patterned resist layer is generally used in industrial fields such as a printed wiring board, a lead frame, and an LCD. Usually, the resist layer is patterned by a photolithography method comprising at least three processing steps. In other words, long and complicated processes are required, such as a process of coating a solution type resist on a substrate, a process of transferring a pattern to a resist by performing photomask exposure on the coated layer, and a process of developing a resist. There is a problem in terms. Further, when the resist is not a permanent resist, that is, for a printed board or a lead frame, a base material etching step, a plating step and a resist stripping step are required. Also, the photolithographic process for LCDs increases the cost of LCD display manufacturing because it requires photomask exposure, development, and usually drying and baking of the patterned layer.

  On the other hand, a method of forming a resist pattern by a letterpress reverse printing method without using photolithography has been proposed (see Patent Document 1). However, since the resist ink contains a solvent, if the baking is not sufficient during the resist forming process, the resist film strength becomes weak. Therefore, it takes a long time for the baking process, which is not desirable from the viewpoint of production efficiency.

JP 2010-116525 A

  In the present invention, a pattern can be formed by a printing method, and a resist layer is formed by UV curing, which eliminates the need for baking and drying processes, has adhesion to conductors such as copper and aluminum, and is suitable for etching processes and electrolytic plating processes. An object of the present invention is to provide a printing resist layer that can withstand the stress and can be easily peeled later.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a hydrolysis-condensation product of a thiol group-containing alkoxysilane, at least one carboxyl group in the molecule, and at least one carbon-carbon double bond. The present inventors have found that the above-mentioned problems can be solved by a composition comprising a compound having a compound and a cured product thereof, and have completed the present invention.

That is, the present invention relates to the general formula (1):
R ¹ Si (OR ² ) ₃
(Wherein R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms having at least one thiol group, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). Hydrolysis of the group-containing alkoxysilane (a1) (except when all R ² are hydrogen atoms) and a condensation product (A) obtained by condensation (hereinafter referred to as component (A)), and in the molecule And a compound (B) having at least one carboxyl group and at least one carbon-carbon double bond (hereinafter referred to as component (B)) as essential components. A curable resin composition (hereinafter sometimes referred to as a resist resin composition); a method of forming a resist pattern, wherein the resist resin composition is printed on a substrate and then cured; Printing laminated resist obtained by the method for forming a preparative pattern; after etching the printed resist laminate, a printed wiring board obtained by further separating the printing resist.

  Since the resin composition for printing resist of the present invention can form a pattern by a printing method and can form a resist layer by ultraviolet curing, baking, drying steps are not required for curing, copper, aluminum, etc. are produced with high production efficiency. It is possible to provide a printed resist layer that has adhesion to the conductor, can withstand an etching process and an electrolytic plating process, and can be easily peeled later. Moreover, a printed wiring board can be provided by peeling a printing resist after etching the metal base material of this printing resist layer.

Component (A) used in the present invention has the general formula (1):
R ¹ Si (OR ² ) ₃
(Wherein R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms having at least one thiol group, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). It is a compound obtained by hydrolyzing and condensing group-containing alkoxysilanes (a1). Incidentally, R ² in the general formula (1) is the case of all hydrogen atoms, is obtained only by a condensation reaction without hydrolysis. Specific examples of the thiol group-containing alkoxysilanes (a1) (hereinafter referred to as component (a1)) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3- Mercaptopropyltributoxysilane, 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane 1,4-dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercapto Propyl tripropoxy Silane, 2-mercaptomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1, Examples include 2-dimercaptoethyltributoxysilane, and the exemplified compounds can be used alone or in appropriate combination. Among the exemplified compounds, 3-mercaptopropyltrimethoxysilane is particularly preferable because of high reactivity of hydrolysis reaction and easy availability.

  In addition to component (a1), trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Dialkyl dialkoxysilanes such as silane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Alkyltrialkoxysilanes such as rutriethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Metal alkoxides (a2) (hereinafter referred to as component (a2)) having no thiol group such as tetraalkoxytitaniums, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium and the like can be used. The component (a2) can be used either alone or in combination of two or more. Of these, the crosslink density of the component (A) can be adjusted by using trialkylalkoxysilanes, dialkyldialkoxysilanes, and tetraalkoxysilanes. By using alkyltrialkoxysilanes, the amount of thiol groups contained in component (A) can be adjusted.

When the component (a1) and the component (a2) are used in combination, [number of moles of thiol group contained in the component (a1)] / [total number of moles of the component (a1) and component (a2)] (molar ratio) is It is preferable that it is 0.2 or more. It is preferable in that the number of thiol groups contained in the component (A) contributing to active energy ray curability is sufficiently ensured by being 0.2 or more, and physical properties such as hardness of the cured product can be improved. .
Further, the [total number of moles of each alkoxy group contained in the component (a1) and the component (a2)] / [total number of moles of the component (a1) and the component (a2)] (molar ratio) is 2.5 or more. It is preferably 5 or less, and more preferably 2.7 or more and 3.2 or less. By setting the molar ratio within the range, a cured film having a high crosslinking density can be obtained while preventing gelation.

Component (A) used in the present invention can be obtained by condensing component (a1) alone or in combination with component (a2), condensing them after hydrolysis. By the hydrolysis reaction, the alkoxy group contained in component (a1) or component (a2) becomes a hydroxyl group, and alcohol is by-produced. The amount of water required for the hydrolysis reaction is [number of moles of water used in hydrolysis reaction] / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio). It is preferably 4 or more and 10 or less, more preferably 1. By making the molar ratio within this range, the number of alkoxy groups remaining without being hydrolyzed is reduced, and the amount of water to be removed in the condensation reaction (dehydration reaction) is reduced, thereby producing efficiently. Can do.
In the case where the component (A) is obtained only with the component (a1) in which R ² in the general formula (1) is all hydrogen atoms, only the condensation reaction is performed without hydrolysis, so that addition of water is not necessary. .

  In addition, when the component (a2) is used in combination with a tetraalkoxytitanium, a tetraalkoxyzirconium or the like, particularly a metal alkoxide having a high hydrolyzability and condensation reactivity, the hydrolysis and condensation reaction proceeds rapidly, and the system May gel. In this case, gelation can be avoided by adding the component (a2) after the hydrolysis reaction of the component (a1) has been completed and all water has been consumed.

  The catalyst used for the hydrolysis reaction is not particularly limited, and a known hydrolysis catalyst can be arbitrarily used. Examples of the hydrolysis catalyst include organic acids, inorganic acids, organic bases, and inorganic bases. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid (succinic acid), maleic acid, methylmalonic acid, adipic acid, and sebacic acid , Gallic acid, butyric acid, meritic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, Examples thereof include diazabicycloundecene, tetramethylammonium hydroxide, 1,8-diazabicyclo [5,4,0] -7-undecene and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these, formic acid is preferred because of its high catalytic activity and easy removal. The addition amount of the catalyst is preferably 0.1 to 25 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total of component (a1) and component (a2). If the amount is more than 25 parts by weight, the stability of the resulting resin composition for printing resist tends to decrease, and even if the catalyst can be removed in a subsequent step, the removal amount increases, which is disadvantageous in terms of production efficiency. It is. On the other hand, when the amount is less than 0.1 parts by weight, the reaction does not substantially proceed or the reaction time tends to be long. Although reaction temperature and time can be arbitrarily set according to the reactivity of a component (a1) or a component (a2), it is about 0-100 degreeC normally, Preferably it is about 20-60 degreeC, 1 minute-about 2 hours. The hydrolysis reaction can be performed in the presence or absence of a solvent. The type of the solvent is not particularly limited, and one or more arbitrary solvents can be selected and used, but it is preferable to use the same solvent as that used in the condensation reaction described later. When the reactivity of component (a1) or component (a2) is low, it is preferable to carry out without solvent.

  The hydrolysis reaction may be carried out by using [component (a1) and component (a1) and component (a1) and component (a1)] in combination with [component (a1) and component (a1)]. The total number of moles of hydroxyl groups contained in a2) / [total number of moles of each alkoxy group contained in component (a1) and component (a2)] (molar ratio) is allowed to proceed so as to be 0.5 or more. Preferably, adjusting to 0.8 or more is more preferable. The condensation reaction following the hydrolysis reaction proceeds not only between the hydroxyl groups generated by the hydrolysis but also between the hydroxyl groups and the remaining alkoxy groups, so that all the alkoxy groups need not necessarily be hydrolyzed to hydroxyl groups. . If hydrolysis is allowed to proceed until the molar ratio is about 0.5, it becomes easier to obtain a printing resist resin composition in a more stable manner.

  In the condensation reaction, water is by-produced between the hydroxyl groups, and alcohol is by-produced between the hydroxyl groups and the alkoxy group to vitrify. A conventionally known dehydration condensation catalyst can be arbitrarily used for the condensation reaction. Examples of the dehydration condensation catalyst include those exemplified for the hydrolysis catalyst. As mentioned above, formic acid is preferred because of its high catalytic activity and easy removal. The reaction temperature and time can be arbitrarily set according to the reactivity of the component (a1) or component (a2), but are usually about 40 to 150 ° C., preferably 60 to 100 ° C., about 30 minutes to 12 hours. .

  Condensation reaction is carried out by the above method. [Total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [Total number of moles of alkoxy groups contained in component (a1) and component (a2)] (molar ratio ) Is preferably 0.3 or less, and more preferably 0.2 or less. By setting the molar ratio within the above range, it is possible to prevent unreacted hydroxyl groups and alkoxy groups from undergoing a condensation reaction and gelation during storage of the resist resin composition, thereby obtaining a product having higher storage stability. Further, the condensation reaction is prevented after curing, and no volatile matter is generated, and the occurrence of cracks in the resulting printed resist layer is reduced.

  The condensation reaction is preferably performed by diluting the solvent so that the concentration of component (a1) (or both when component (a2) is used in combination) is about 2 to 80% by weight. It is more preferable. It is preferable to use a solvent having a boiling point higher than that of water and alcohol generated by the condensation reaction because these can be distilled off from the reaction system. As the solvent, one or more arbitrary solvents can be selected and used, but those having a low boiling point are preferable because they can be easily distilled off later in the reaction system.

  It is preferable to remove the solvent used after completion of the condensation reaction because a drying step is not required before the pattern forming step using the finally obtained resin composition for a printing resist. Further, in the case of pattern formation by printing, a certain degree of viscosity may be required, which is also desirable in this respect.

  After completion of the condensation reaction, it is preferable to remove the used catalyst because the stability of the finally obtained resist resin composition is improved. The removal method can be appropriately selected from various known methods depending on the catalyst used. For example, when formic acid is used, it can be easily removed by a method such as heating to above the boiling point or depressurization after completion of the condensation reaction, and formic acid is also preferred in this respect.

  The component (B) used in the present invention is not particularly limited as long as it is a compound having at least one carboxyl group and at least one carbon-carbon double bond in the molecule, but the carboxyl group equivalent is 50 to 2000 g. / mol, preferably 70 to 600 g / mol. When the amount is 50 g / mol or more, the polarity is kept low, the etching resistance of the resulting resist cured product is improved, and when the amount is 2000 g / mol or less, the resist cured product can be easily peeled off with an alkali solution. Adhesion can be further improved. Examples of such component (B) include commercially available unsaturated carboxylic acids, partial ester compounds of a compound having one hydroxyl group and one carbon-carbon double bond in the molecule and a polyvalent carboxylic acid, A partially esterified product of a compound having only one each of an epoxy group and a carbon-carbon double bond and a polyvalent carboxylic acid can be mentioned.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid, 2-butenoic acid, 3-butenoic acid, 4-pentenoic acid, 3-pentenoic acid, 2-pentenoic acid, 5-hexenoic acid, 4-hexenoic acid, 3- Carboxylic acid having a linear unsaturated hydrocarbon group such as hexenoic acid, 2-hexenoic acid, monomethyl maleate, monoethyl maleate, crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gadoleic acid vaccenate , Eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid , Boseopentaenoic acid, eicosapentaenoic acid, ozbond acid, sardine acid, tetracosapentaenoic acid , Docosahexaenoic acid, nisic acid, abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenic acid, methylene succinic acid, allylmalonic acid, isopropylidene succinate Examples include acid, 2,4-hexadienic acid, acetylenedicarboxylic acid, and aconitic acid. Polycaprolactone mono (meth) acrylate and the like can also be used. Among these, acrylic acid, methacrylic acid, and 3-butenoic acid have low molecular weight and good absorbability to the silicone rubber blanket. Therefore, it is preferable that a larger amount is held in the blanket in terms of excellent transferability and high definition.

In the case of using a partial ester compound of a compound having one hydroxyl group and one carbon-carbon double bond and a polyvalent carboxylic acid in the molecule, its production method is known, for example, dibasic acid, three It can be obtained by reacting an acid anhydride such as a basic acid with a compound having one hydroxyl group and one carbon-carbon double bond in the molecule by heating, if necessary, using a catalyst. In the case of this reaction, it is desirable to keep the monoesterified product. Specific examples of the acid anhydride include succinic acid, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, nadic acid, methyl nadic acid, dodecyl succinic acid, chlorendic acid, benzophenone tetracarboxylic acid, ethylene glycol Bis (anhydrotrimate), polyazelenic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, 3-propyltetrahydrophthalic acid 4-propyltetrahydrophthalic acid, 3-butyltetrahydrophthalic acid, 4-butyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid 4 Examples of anhydrides corresponding to polyvalent carboxylic acids such as ethylhexahydrophthalic acid, 3-propylhexahydrophthalic acid, 4-propylhexahydrophthalic acid, 3-butylhexahydrophthalic acid, and 4-butylhexahydrophthalic acid be able to. These acid anhydrides can be used alone or in combination of two or more.
Specific examples of the compound having one hydroxyl group and one carbon-carbon double bond in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Examples include butyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, a reaction product with acryloyloxyethyl hexahydrophthalic acid, and the like. These can be used alone or in combination of two or more.

When a partially esterified product of a compound having only one epoxy group and one carbon-carbon double bond and a polycarboxylic acid is used, a method for producing this compound is known, for example, an epoxy group and a carbon-carbon double bond. Can be obtained by heating and reacting an ethylenically unsaturated compound having only one each with an acid anhydride such as dibasic acid or tribasic acid, if necessary. In this reaction, it is desirable to stop by monoesterification.
Specific examples of the partially esterified product of a compound having only one epoxy group and one carbon-carbon double bond and a polycarboxylic acid include glycidyl such as glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate. And (meth) acrylates, (3,4-epoxycyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid epoxycyclohexyl derivatives. These can be used alone or in combination of two or more. Moreover, what corresponds to the said acid anhydride can be used as polyhydric carboxylic acid.

In the present invention, if necessary, a compound (C) having no carboxyl group and having at least two carbon-carbon double bonds (hereinafter referred to as component (C)) can be used. The component (C) is not particularly limited as long as it is a compound having no carboxyl group and having at least two carbon-carbon double bonds. Component (C) includes allyl compounds and (meth) acrylates.
As the allyl compound in component (C), diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether, Compounds containing two allyl groups, such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, propylene glycol diallyl ether, dipropylene glycol diallyl ether, tripropylene glycol diallyl ether, triallyl isocyanurate, pentaerythritol tri Allyl ether, pentaerythritol tet Allyl ether, a compound containing three or more allyl groups, such as trimethylolpropane triallyl ether. These compounds can be used either alone or in combination.

  Examples of (meth) acrylates in component (C) include nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tris. (Meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like. These compounds can be used either alone or in combination.

Since component (C) is intended to crosslink component (A), the functional group having a carbon-carbon double bond is preferred over the reaction between the functional group having a carbon-carbon double bond and a thiol group. It is preferable to use one having low radical polymerizability so as not to cause inconvenience of polymerizing each other. From this viewpoint, the allyl compound is preferable, and among them, triallyl isocyanurate, diallyl phthalate, and pentaerythritol triallyl ether are preferable.

Such a component (C) is available as a commercial item. For example, a copolymer comprising methylallylsiloxane and dimethylsiloxane, a copolymer comprising epichlorohydrin and allyl glycidyl ether (Daiso Co., Ltd .: trade name “Epichromer”, Nippon Zeon Co., Ltd .: trade name “Gechron”, etc. ), Allyl group-terminated polyisobutylene polymer (Kaneka Co., Ltd .: trade name “Epion”), urethane acrylate (produced by Arakawa Chemical Industries, Ltd .: trade name “Beam Set 550B”), and the like. These commercially available products are preferred in that they have low radical polymerizability, can ensure the viscosity of the resist resin composition, and can improve the flexibility of the cured product. These commercially available products can be used alone or in combination of two or more.

  Here, since the polymerization reaction between the components (B) and (C) can occur simultaneously with the ene = thiol reaction, the carbon-carbon double bond in (B) and (C) with respect to the thiol group in (A) The ratio (molar ratio) is preferably 1 or more.

  From the above viewpoint, the proportion of components (A) and (B) used in preparing the active energy ray-curable resin composition for printing resist of the present invention is [carbon-carbon double bond contained in component (B)]. The number of moles] / [number of moles of thiol groups contained in component (A)] (molar ratio) is preferably 0.9 to 100. When it exceeds 100, since the amount of the component (A) to be used is too small, the desired effect of the present invention tends to be hardly obtained. Moreover, when it is less than 0.9, a thiol group remains and a malodor may be generated by the decomposition | disassembly. Moreover, since the carboxyl group equivalent in this composition becomes high, there exists a tendency for the effect desired by this invention to become difficult to be acquired.

  When using the component (C), it is preferably blended in an amount of 50% by weight or less based on the total amount of the component (B). When it exceeds 50% by weight, the crosslink density of the cured product is excessively increased, so that alkali solubility tends to decrease. In addition, when the component (C) is used in combination, the use ratio of the component (A), the component (B) and the component (C) is [the carbon-carbon double bond contained in the component (B) and the component (C). Number of moles] / [number of moles of thiol groups contained in component (A)] (molar ratio) is preferably 0.9-100. When the molar ratio exceeds 100, the amount of the component (A) to be used is too small, and the desired effect of the present invention tends to be hardly obtained. Moreover, when it is less than 0.9, a thiol group remains and a malodor may be generated by the decomposition | disassembly. Moreover, since the molar ratio of the carboxyl group is too small, the desired effect of the present invention tends to be difficult to obtain.

  It does not specifically limit as a polymerization initiator which can be used for the active energy ray curable resin composition for printing resists of this invention, A conventionally well-known photocation initiator, photoradical initiator, etc. can be selected arbitrarily. Examples of the photocationic initiator include sulfonium salts, iodonium salts, metallocene compounds, benzoin tosylate, and the like, which are compounds that generate an acid upon irradiation with ultraviolet rays. -6974, UVI-6990 (both trade names manufactured by Union Carbide, USA), Irgacure 264 (Ciba Japan Co., Ltd.), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), and the like. The usage-amount of a photocationic polymerization initiator is normally about 10 weight part or less with respect to 100 weight part of this composition, Preferably it is 1-5 weight part. Examples of the photo radical initiator include Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (Ciba Japan Co., Ltd.), benzophenone, and the like, and about 15 parts by weight or less, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the composition. 15 parts by weight. When there is a concern about a decrease in the weather resistance of the resulting cured product, it is better not to use a photoinitiator or a photosensitizer, especially when used for an optical member that requires high weather resistance and transparency. .

  Moreover, in order to improve the storage stability during storage of the active energy ray-curable resin composition for printing resist, a compound that suppresses the ene-thiol reaction can be blended. Examples of such compounds include triphenylphosphine and triphenyl phosphite. Of these, triphenyl phosphite is preferable because it has a high inhibitory effect on the ene-thiol reaction, is liquid at room temperature, and is easy to handle. The amount of the compound to be blended in the resin composition for printing resist is preferably about 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition. By using in such a range, it is possible to reduce the amount of residual thiol groups that cause a decrease in physical properties of the resulting cured product while suppressing a sufficient ene-thiol reaction.

Moreover, a solvent can be mix | blended with the active energy ray curable resin composition for printing resists of this invention as needed. A conventionally known solvent can be arbitrarily used as the solvent. However, since a volatile component should not be generated after the pattern is formed, it is preferable to use a solvent that easily volatilizes so that it can be volatilized easily before the pattern is formed. When coating and using the resin composition for printing resists, it may be diluted with a solvent to obtain a desired viscosity. The viscosity of the active energy ray-curable resin composition for printing resist may be appropriately set depending on the printing method and application, but is usually 0.5 Pa · S to 5000 Pa · S, preferably 2 Pa · S to 1000 Pa · S. . If the viscosity is less than 0.5 Pa · S, the pattern may not be printed accurately due to bleeding, and if the viscosity exceeds 5000 Pa · S, the pattern may not flow efficiently.
Further, when forming a pattern, bubbles may be generated due to volatilization of the solvent after formation, and the pattern may be disturbed. Therefore, the components (A), (B) and (C) in the resin composition for printing resist ) Is preferably 90% by weight or more, and more preferably 95% by weight or more. The total concentration may be calculated from the total concentration of component (A), component (B) and component (C) and the amount of solvent added during the preparation of the resin composition for printing resist. Heating may be performed at a temperature equal to or higher than the boiling point of the solvent contained in the resin composition for about 2 hours, and the weight may be determined by a change in weight before and after heating. In addition, when using a solvent in the case of a synthesis | combination of a component (A), you may volatilize a solvent so that nonvolatile content may become 90 weight% or more after completion | finish of reaction. Moreover, after preparing the fat composition for printing resists, the used solvent can be volatilized and the total density | concentration of a component (A), a component (B), and a component (C) can also be raised.

  Moreover, the active energy ray-curable resin composition for a printing resist of the present invention, as yet another aspect, hydrolyzes the component (a1) and the optional component (a2) in the presence of a catalyst, ) And (C). Conditions such as reaction temperature, reaction time, and solvent type are all the same as in the case of the component (A).

  Furthermore, in the active energy ray-curable resin composition for printing resist of the present invention, the component (a1) and / or a hydrolyzate thereof (D) (however, excluding the condensate) are used depending on the application [hereinafter, combined Component (D)]. As the component (D), the component (a1) used in the synthesis of the component (A) may be used as it is, its hydrolyzate may be used, or these may be used in combination. By using a component (D), there exists an advantage which can improve adhesiveness more. It is preferable to contain 0.1-20 weight part of compounding quantities of a component (D) in 100 weight part of active energy ray-curable resin compositions for printing resists in conversion of solid content. The content of 0.1 parts by weight or more is preferable because the effect of improving the adhesion of the resin composition for printing resist to the substrate becomes sufficient. In addition, when the content is 20 parts by weight or less, the volatile content when the component (D) undergoes hydrolysis and condensation reaction is reduced, so that the resin composition for printing resist can be thickened or the obtained cured product is brittle. It is preferable because it is difficult to become. As such a component (D), 3-mercaptopropyltrimethoxysilane is particularly preferable in terms of the effect of improving the adhesion.

  Further, the active energy ray-curable resin composition for printing resist of the present invention includes the component (a2) and / or a hydrolyzate thereof (excluding the condensate) (E) according to the use (resist etc.). (Hereinafter referred to as component (E) together). As the component (E), the component (a2) used in the synthesis of the component (A) can be used as it is, its hydrolyzate can be used, or these can be used in combination. By using the resin composition for printing resist containing the component (E), the refractive index of the obtained cured product can be adjusted. When the resin composition for printing resist is used as a coating agent having a high refractive index, alkoxytitaniums and alkoxyzirconiums are suitable as the component (E). It is preferable that the compounding quantity of a component (E) is about 0.1-20 weight part with respect to 100 weight part of active energy ray-curable resin compositions in conversion of solid content. It is preferable to set the amount to 0.1 parts by weight or more and 20 parts by weight or less because generation of foaming and cracks during curing can be suppressed.

  In addition, the active energy ray-curable resin composition for printing resist of the present invention has a polymer component (F) (hereinafter referred to as “component”) in which an ethylenically unsaturated group-containing monomer is polymerized in order to improve transferability during printing. F)) can be blended. By blending the component (F), transferability can be improved. The polymer component (F) is not particularly limited as long as it is soluble in the component (B) and the component (C). The weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of the component (F) is about 1000 to 50000, preferably about 5000 to 20000. If the weight average molecular weight is 1000 or less, the effect of improving the viscosity may be lowered, and if the weight average molecular weight is 50000 or more, the components (B) and (C) may not be dissolved.

Such component (F) is not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid 2 − (meth) acrylic acid alkyl esters such as ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid cyclohexyl, or (meth) acrylic acid cycloalkyl esters, (meth) acrylic acid ethylene glycol methyl ether, (meta ) (Meth) acrylic acid polyethylene glycol alkyl ether, (meth) acrylic acid polyethylene glycol alkyl ether, (meth) acrylic acid aminomethyl, (meth) acrylic acid N − methylaminomethyl, (Meth) acrylic acid N, N − aminoalkyl (meth) acrylates such as diethylaminoethyl, glycidyl (meth) acrylate, oligoethylene oxide (meth) acrylate, oligopropylene oxide (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, (meth) Methoxypolyethylene glycol acrylate, methacrylic acid, acrylic acid, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylamino (Meth) acrylate polymer obtained by homopolymerization or copolymerization of ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc., (meth) A polymer in which styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, etc. are used in combination with the monomer component of the acrylate polymer, and further, the unsaturated component is not limited to the monomer component or polymer as long as the weight average molecular weight is satisfied. Any homopolymer or copolymer of a monomer containing a hydrocarbon group may be used. These (F) components may be used alone or in combination of two or more.

It is preferable that the compounding quantity of a component (F) is about 0.1-70 weight part with respect to 100 weight part of active energy ray-curable resin compositions in conversion of solid content. It is preferable that the content be 0.1 parts by weight or more and 20 parts by weight or less because the viscosity of the active energy ray-curable resin composition is increased and transferability is improved. If the amount is 70 parts by weight or more, the amount of the active energy ray-curable resin composition to be used is too small, so that the desired effect of the present invention tends to be hardly obtained.

  Furthermore, the active energy ray-curable resin composition for printing resists of the present invention has a plasticizer, a weathering agent, an antioxidant, a heat, and the like within a range that does not impair the effects of the present invention. Stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, fillers, and the like may be blended.

For example, in the active energy ray-curable resin composition for a printing resist of the present invention, a silica filler for increasing the viscosity can be dispersed according to the use.

The silica filler added for this purpose is not particularly limited, but those having a specific surface area of 50 to 400 m ² / g and a primary average particle diameter of 7 to 40 nm are preferable. As the silica particles, any silica produced by a so-called pyrolysis method (fumed) or a sol-gel method can be suitably used. Further, from the viewpoint of improving dispersibility, the surface of the silica particles is preferably hydrophobized with a surface treating agent, and in particular, the surface treated with dimethyldichlorosilane is preferred. As a compounding quantity of a silica particle, 0.1-5 weight part with respect to 100 weight part of active energy ray curable resin compositions for printing resists of this invention in conversion of solid content, Furthermore, 1-3 weight part. A range is preferred. When the amount is less than 0.1 part by weight, the effect of increasing the viscosity does not appear so much. When the amount exceeds 5 parts by weight, the physical properties of the cured product tend to be lowered.

Specific examples of hydrophilic fumed silica include AEROSIL90, AEROSIL130, AEROSIL150, AEROSIL200, AEROSIL300, AEROSIL380, and AEROSIL manufactured by Nippon Aerosil Co., Ltd.
OX50, AEROSIL EG50, AEROSIL TT600, Leoroseal QS-09, QS-10L, QS-10, QS-102, CP-102, QS-20L, QS-20, QS-25C, QS-30 manufactured by Tokuyama Corporation QS-30C, QS-40 and the like. As a specific example of hydrophobic fumed silica, AEROSIL manufactured by Nippon Aerosil Co., Ltd.
R972, AEROSIL R974, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL
R816, AEROSIL R7200, AEROSIL R8200, AEROSIL R9200, AEROSIL RY50, AEROSIL NY50, AEROSIL
RY200, AEROSIL RY200S, AEROSIL RX50, AEROSIL NAX50, AEROSIL RX200, AEROSIL RX300, AEROSIL
R504, AEROSIL DT4, Reorosil MT-10, MT-10C, DM-10, DM-10C, DM-20S, DM-30, DM-30S, KS-20S, KS-20SC, HM- manufactured by Tokuyama Corporation 20L, HM-30S, PM-20L, etc. are mentioned.

The silica filler can be dispersed using various dispersion mixing means such as a three roll mill, a two roll mill, a sand mill, an attritor, a ball mill, a kneader, a propeller mixer, an ultrasonic stirrer, and a cutter mill. In order to improve the dispersion of the filler during dispersion, a dispersion aid can be appropriately added. Since the dispersion aid has an effect of helping dispersion and preventing reaggregation after dispersion, a photocurable composition having a uniform composition and excellent storage stability can be obtained.

The active energy ray-curable resin composition for printing resist of the present invention is a resist pattern formed by applying a resin composition for printing resist on a substrate in a desired shape (pattern) in advance by a printing method and then curing by light irradiation. It is suitable for the method. By using this, it is possible to efficiently produce a printed resist laminate in which a target resist pattern is formed by a printing method.

The substrate used for pattern formation of the present invention includes conductive polymers such as PEDOT, polypyrrole and polyaniline, metal oxides such as ITO, ZTO, indium oxide, tin oxide and zinc oxide, inorganic materials such as glass and silicon, aluminum , Metal materials such as stainless steel, copper, polyethylene terephthalate resin, polyester resin, polyimide resin, epoxy resin, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl chloride resin In addition to resin materials such as polyvinylidene chloride resin, polystyrene resin, polymethyl methacrylate resin, nylon resin, polycarbonate resin, polynorbornene resin, and triacetyl cellulose resin, paper or the like can be used. You may improve the adhesiveness of the resin composition for printing resists by processing the surface of these base materials by an oxidation process, an acid process, a plasma process, a discharge process, etc. Since the resin composition for printing resist is usually on the surface of the substrate, the thickness of the substrate can be arbitrarily set. Moreover, you may provide the resin layer etc. which do not participate in a photoreaction between the resin composition for printing resists, and a board | substrate. Among these, glass, metal silicon, and polyethylene terephthalate resin are preferable. In addition, it is preferable that the base material is a substrate, a film, or a sheet because application of the resin composition for printing resist becomes easy.

Although it does not specifically limit as a printing method used for this invention, For example, letterpress reverse transfer printing, screen printing, gravure printing, gravure offset printing, letterpress offset printing is mentioned, for example.

The irradiation amount of the active energy ray is not particularly limited, and may be appropriately determined according to the type of compound used in the active energy ray-curable resin composition for printing resist, the film thickness, etc. What is necessary is just to irradiate so that an integrated light quantity may be about 50-10000 mJ / cm < ² >. Moreover, when coating or filling with a thick film, it is preferable to improve photocurability by adding a photoreaction initiator or a photosensitizer to the composition as described above.

Active energy rays used for curing include high energy ionizing radiation and ultraviolet rays. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. The irradiation time of the active energy ray is not particularly limited, and known conditions can be employed. When the active energy ray-curable resin composition for a printing resist contains a solvent, the method for volatilizing the solvent may be appropriately determined according to the type, amount, film thickness, etc. of the solvent, but about 40 to 150 ° C. It is preferably heated to 60 to 100 ° C., and the conditions are about 5 seconds to 2 hours under normal pressure or reduced pressure.

In the case of performing heat curing, the curing temperature and the heating time are appropriately determined in consideration of the type of component (B) and component (C) used, the type of solvent, the thickness of the cured product, and the like. That's fine. Usually, it is preferable to set it as the conditions for about 1 minute-about 24 hours at about 20-150 degreeC. Moreover, after completion | finish of hardening, about 100 degreeC-300 degreeC, Preferably it is 120 degreeC or more and less than 250 degreeC, It heats for about 1 minute-about 6 hours, and removes a residual solvent completely and also advances hardening reaction. The cured film thus obtained is characterized by excellent heat resistance and chemical resistance due to the effect of silica complexation. Curing may be performed either by active energy ray curing or heat curing alone or in combination. When used together, the order is not particularly limited, but the physical properties of the cured product can be further improved by further heating the cured product usually obtained by ultraviolet irradiation. The heating method may be appropriately determined, but the heating is performed at about 40 to 300 ° C., preferably 100 to 250 ° C., and the conditions are about 1 minute to 6 hours.

In the above pattern formation, in the case where the cured portion of the active energy ray-curable resin composition for printed resist after curing by light irradiation or the like, or when developing and dissolving the uncured portion, as a solvent for the developer, For example, N-methylpyrrolidone, methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Isoamyl acetate, ethyl lactate, methyl-ethyl ketone, acetone, cyclohexanone, N, N-dimethylformamide, acetonitrile, al Potassium aqueous solution etc. are mentioned. You may use these individually or in combination of 2 or more types. Further, basic substances such as trimethylamine and triethylamine and surfactants may be added to these solvents.

As the alkaline aqueous solution, for example, an aqueous solution of an inorganic salt such as sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate, or an aqueous solution of an organic salt such as hydroxytetramethylammonium or hydroxytetraethylammonium can be used. You may use these individually or in combination of 2 or more types.

The laminate on which the resist pattern thus obtained is formed is transparent, and the curing shrinkage before and after pattern formation is about 0.1 to 5%.

A patterned printed wiring board can be obtained by etching the laminate on which the resist pattern is formed with an etching solution. This may be used as it is, or the resist pattern may be peeled off.

The etching solution is not particularly limited, and examples thereof include ferric chloride, cupric chloride, persulfates, and an aqueous solution of hydrogen peroxide / sulfuric acid.

The means for stripping the resist pattern is not particularly limited, and for example, those corresponding to the solvent for the developer can be used. Among these, alkaline aqueous solutions such as an aqueous sodium hydroxide solution and an aqueous hydroxytetramethylammonium solution are particularly preferable.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In each example, parts and% are based on weight unless otherwise specified.

Production Example 1 (Production of condensate (A-1))
In a reactor equipped with a stirrer, a condenser, a water separator, a thermometer, and a nitrogen inlet, 3400 parts of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-803”), ion 936 parts of exchanged water ([number of moles of water used for hydrolysis reaction] / [number of moles of alkoxy group contained in component (a1)] (molar ratio) = 1.0), 17.0 parts of 95% formic acid were charged. The hydrolysis reaction was performed at room temperature for 30 minutes. During the reaction, the temperature increased by a maximum of 35 ° C. due to exotherm. After the reaction, 5670 parts of toluene was charged and heated. When the temperature was raised to 71 ° C., methanol generated by hydrolysis and a part of toluene began to be distilled off. The temperature was raised to 75 ° C. over 2 hours, and the water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. and 20 kPa to distill off a part of the remaining toluene, methanol, water, and formic acid. The concentration was 99.0%. The concentration of the thiol group in the condensate (A-1) was 7.41 mmol / g.

Production Example 2 (Production of condensate (A-2))
In the same reactor as in Production Example 1, 2500 parts of 3-mercaptopropyltrimethoxysilane, 347 parts of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name “KBM-11”) (in [component (a1)) Number of moles of thiol group contained] / [total number of moles of component (a1) and component (a2)] = 0.83, [total number of moles of alkoxy groups contained in component (a1) and component (a2)] / [Total number of moles of component (a1) and component (a2)] = 3), 824 parts of ion-exchanged water ([number of moles of water used in hydrolysis reaction] / [included in component (a1) and component (a2) The total number of moles of each alkoxy group] (molar ratio) = 1.0) and 14 parts of 95% formic acid were charged and subjected to a hydrolysis reaction at room temperature for 30 minutes. During the reaction, the temperature increased by 32 ° C. due to exotherm. After the reaction, 3000 parts of toluene was charged and heated. When the temperature was raised to 71 ° C., part of methanol and toluene generated by hydrolysis began to be distilled off. The temperature was raised to 75 ° C. over 1 hour, and the water was distilled off by condensation reaction. After further reacting at 75 ° C. for 1 hour, the pressure was reduced at 70 ° C. and 20 kPa to distill off a part of the remaining toluene, methanol, water, and formic acid. Furthermore, pressure reduction was carried out at 70 degreeC and 0.7 kPa, and toluene was distilled off, and 1820 parts of condensates (A-2) were obtained. The concentration was 98.7%. Moreover, the density | concentration of the thiol group of a condensate (A-2) was 7.00 mmol / g.

Example 1 (Production of active energy ray-curable resin composition for printing resist)
With respect to 28.8 parts of the condensate (A-1) obtained in Production Example 1, acryloyloxyethyl hexahydrophthalic acid (manufactured by Kyoeisha Oil Chemical Co., Ltd.) as a component (B): trade name “Light Acrylate HOA- "HH", carbon-carbon double bond concentration 3.6 mmol / g, carboxylic acid number 281.96, hereinafter referred to as HOA-HH) 120.4 parts ([carbon-carbon 2 contained in component (B) Mole number of heavy bond] / [Mole number of thiol group contained in component (A)] (molar ratio) = 2.00), hydroxycyclohexyl phenyl ketone (Ciba Japan Co., Ltd.) as a photocuring catalyst 0.75 part of “Irgacure 184” (hereinafter referred to as “Irg184”), ethylene glycol dimethyl ether (Nippon Emulsifier Co., Ltd .: trade name “DMG”) as a solvent for dissolving Irg184 The following DMG hereinafter) blended with 1.5 parts was printed resist actinic radiation-curable resin composition of the carboxyl group equivalent 354.67g / mol.

Example 2 (Production of active energy ray-curable resin composition for printing resist)
With respect to 43.0 parts of the condensate (A-2) obtained in Production Example 2, 158 parts of HOA-HH as component (B) ([number of moles of carbon-carbon double bonds contained in component (B)] / [Mole number of thiol group contained in component (A)] (molar ratio) = 2.00), 1.0 part of Irg184 as a photocuring catalyst, 2.0 parts of DMG as a solvent for dissolving Irg184, An active energy ray-curable resin composition for printing resist having a carboxyl group equivalent of 364.57 g / mol was obtained.

Example 3 (Production of active energy ray-curable resin composition for printing resist)
100 parts HOA-HH as component (B) and triallyl isocyanurate (hereinafter TAIC, manufactured by Nippon Kasei Co., Ltd.) as component (B) with respect to 34.2 parts of condensate (A-2) obtained in Production Example 2 : Trade name “TAIC”, concentration of carbon-carbon double bond is 12.0 mmol / g) 12.5 parts (([number of moles of carbon-carbon double bond contained in component (B)] + [component (C) The number of moles of carbon-carbon double bonds contained in (C)] / [The number of moles of thiol groups contained in component (A)] (molar ratio) = 2.01), Irg184 as 0 as the photocuring catalyst .75 parts and 1.5 parts of DMG as a solvent for dissolving Irg184 were blended to obtain an active energy ray-curable resin composition for a carboxyl group equivalent of 421.39 g / mol printing resist.

Example 4 (Production of active energy ray-curable resin composition for printing resist)
With respect to 37.2 parts of the condensate (A-2) obtained in Production Example 2, 96.5 parts of HOA-HH as component (B) and 12.1 parts of TAIC as component (C) ((in [Component (B) Mole number of carbon-carbon double bond contained] + [mole number of carbon-carbon double bond contained in component (C)] / [mole number of thiol group contained in component (A)] (molar ratio ) = 2.01), 0.75 parts of Irg184 as a photocuring catalyst, 1.5 parts of DMG as a solvent for dissolving Irg184, and a silica filler for adjusting the viscosity (hereinafter DM-20S, manufactured by Tokuyama Corporation): An active energy ray-curable resin composition for a printing resist having a carboxyl group equivalent of 431.26 g / mol was obtained by dispersing 3.5 parts of a trade name “Leolosil DM-20S” using a disper.

Example 5 (Production of active energy ray-curable resin composition for printing resist)
With respect to 19.2 parts of the condensate (A-2) obtained in Production Example 2, methacrylic acid (hereinafter MAA, manufactured by Mitsubishi Rayon Co., Ltd .: trade name “methacrylic acid”, carbon-carbon two The concentration of the heavy bonds is 11.6 mmol / g) 17.1 parts, and 4.2 parts of TAIC as the component (C) (([number of moles of carbon-carbon double bonds contained in component (B)] + [component ( C) The number of moles of carbon-carbon double bonds contained in C)] / [number of moles of thiol groups contained in component (A)] (molar ratio) = 2.00) 20 parts, DMG 0.4 part as a solvent for dissolving Irg 184, and dispersion of silica filler 1.4 parts for viscosity adjustment using a disper, the active energy ray for printing resist having a carboxyl group equivalent of 214.27 g / mol Curable resin composition And the.

Example 6 (Production of active energy ray-curable resin composition for printing resist)
With respect to 15.6 parts of the condensate (A-2) obtained in Production Example 2, 18.2 parts of MAA and 8.6 parts of HOA-HH as component (B), and 5.0 parts of TAIC (([ The number of moles of carbon-carbon double bonds contained in component (B)] + [the number of moles of carbon-carbon double bonds contained in component (C)]) / [mol of thiol groups contained in component (A) Number] (molar ratio) = 3.00), 0.21 part of Irg184 as a photocuring catalyst, 0.42 part of DMG as a solvent for dissolving Irg184, and 1.7 parts of silica filler for disperse viscosity adjustment. By using and dispersing, an active energy ray-curable resin composition for printing resist having a carboxyl group equivalent of 205.18 g / mol was obtained.

Example 7 (Production of active energy ray-curable resin composition for printing resist)
With respect to 15.6 parts of the condensate (A-2) obtained in Production Example 2, 18.2 parts of MAA and 8.6 parts of HOA-HH as component (B), and 5.0 parts of TAIC (([ The number of moles of carbon-carbon double bonds contained in component (B)] + [the number of moles of carbon-carbon double bonds contained in component (C)]) / [mol of thiol groups contained in component (A) Number] (molar ratio) = 3.00), 26.0 parts of beam set 255D (hereinafter referred to as BS255D, manufactured by Arakawa Chemical Co., Ltd .: trade name “Beam Set 255D”) as component (F), as a photocuring catalyst A printing resist having a carboxyl group equivalent of 314.76 g / mol by blending 0.21 part of Irg184 and 0.42 part of DMG as a solvent for dissolving Irg184 and dispersing 2.6 parts of silica filler using a disper for viscosity adjustment. for It was sexual energy ray curable resin composition.

Comparative Example 1 (Production of active energy ray-curable resin composition for printing resist)
For 100 parts of component (B) HOA-HH, 1.0 part of Irg184 as a photo-curing catalyst, 2.0 parts of DMG as a solvent for dissolving Irg184, and a printing resist having a carboxyl group equivalent of 290.42 g / mol An active energy ray-curable resin composition was obtained.

Comparative Example 2 (Production of active energy ray-curable resin composition for printing resist)
With respect to 44.0 parts of the condensate (A-1) obtained in Production Example 1, component (B) was not used, and 23.7 parts of TAIC ([carbon contained in component (C) — Number of moles of carbon double bond] / [number of moles of thiol group contained in component (A)] (molar ratio) = 1.00), 1.0 part of Irg184 as a photocuring catalyst, solvent for dissolving Irg184 As an active energy ray-curable resin composition for a printing resist having a carboxyl group equivalent of 0 g / mol.

Comparative Example 3 (Production of active energy ray-curable resin composition for printing resist)
Pentaerythritol tetrakis as thiol component instead of component (A)
(3-mercaptobutyrate) (manufactured by Showa Denko KK: trade name “Karenz MT PE1”, hereinafter referred to as PE1) 38.7 parts, HOA-HH 160 parts as component (B) (in [component (B) The number of moles of carbon-carbon double bonds contained] / [number of moles of thiol groups contained in component (A)] (molar ratio) = 2.00), 1.0 part of Irg184 as a photocuring catalyst, Irg184 As a solvent for dissolving A, 2.0 parts of DMG was blended to prepare an active energy ray-curable resin composition for a printing resist having a carboxyl group equivalent of 355.31 g / mol.

Table 1 shows the compositions of the active energy ray-curable resin compositions for printing resists of Examples 1 to 7 and Comparative Examples 1 to 3 described above.


The symbols in Table 1 are as follows.
HOA-HH: acryloyloxyethyl hexahydrophthalic acid (Kyoeisha Yushi Chemical Co., Ltd. trade name “Light Acrylate HOA-HH”)
PE1: pentaerythritol tetrakis (3-mercaptobutyrate) (trade name “Karenz MT PE1”, Showa Denko KK)
TAIC: triallyl isocyanurate (Nippon Kasei Co., Ltd. product name: “TAIC”)
Irg184: Hydroxycyclohexyl phenyl ketone (Ciba Japan Co., Ltd. trade name “Irgacure 184”)
DMG: Ethylene glycol dimethyl ether (Nippon Emulsifier Co., Ltd. trade name “DMG”)
MMA: Methacrylic acid (Mitsubishi Rayon Co., Ltd.)
BS255D: Beam Set 255D (Arakawa Chemical Co., Ltd. trade name “Beam Set 255D”)

(Pattern formation)
The active energy ray-curable resin composition for printing resists obtained in Examples 1 to 7 and Comparative Examples 1 to 3 was coated on a copper foil or aluminum foil to a film thickness of 10 μm, and an ultraviolet irradiation device (USHIO ( The resist layer was obtained by irradiating ultraviolet rays with a detector of 254 nm using a trade name “UV-152”) so that the integrated light quantity becomes 500 mJ / cm ² .

Examples 1-7, adhesiveness to aluminum foil of resist layer obtained from active energy ray curable resin composition for printing resist obtained in Comparative Examples 1-3, alkali solubility, etching resistance, based on silicone rubber blanket Table 2 shows the test results of the transferability to the material.

The copper and aluminum adhesion shown in Table 2 was evaluated by measuring 10 × 10 squares on the resist layer, applying cellophane tape (CT-24 manufactured by Nichiban Co., Ltd.), and pulling it upward. The evaluation criteria are as follows.
1: No peeling at all.
2: Peeling is hardly observed, but material destruction is slightly observed.
3: Peeling is observed.

The alkali solubility shown in Table 2 was evaluated by immersing the resist layer in a 1.0% aqueous sodium hydroxide solution for 1 minute. The etching resistance is evaluated by immersing the resist layer in a 40% FeCl ₃ aqueous solution for 1 minute. The evaluation criteria are as follows.
1: The resist layer is completely dissolved.
2: Part of the resist layer does not dissolve.
3: The resist layer does not dissolve at all.

The transferability shown in Table 2 is an evaluation of how the varnish is transferred from the silicone rubber blanket to the copper substrate. The evaluation criteria are as follows.
1: The varnish is completely transferred to the substrate 2: The varnish is almost transferred to the substrate 3: The varnish is transferred to the substrate, but about half of the varnish remains in the silicone rubber blanket 4: The varnish is silicone Almost remains in the rubber blanket

Example 8 (resist patterning by printing)
The active energy ray-curable resin composition obtained in Example 4 was gravure-printed on a copper-plated polyimide film with a silicone rubber blanket (stripe pattern with a line width of 200 μm and a line interval of 300 μm), and integrated light intensity was detected with a 254 nm detector. Was irradiated with ultraviolet rays so as to be 500 mJ / cm ² , a laminate having a stripe etching resist pattern was obtained. This laminated body is a polyimide in which copper is etched with 40% aqueous ferric chloride solution and the resist pattern is peeled off with 2% aqueous sodium hydroxide solution to form a copper stripe pattern with a line width of 200 μm and a line interval of 300 μm. A film was obtained.

Example 9 (resist patterning by printing)
As in Example 8, the active energy ray-curable resin composition obtained in Example 5 was gravure-printed on a copper-plated polyimide film with a silicone rubber blanket (stripe pattern having a line width of 200 μm and a line interval of 300 μm), and 254 nm. When an ultraviolet ray was irradiated with the detector of No. 1 so that the integrated light quantity became 500 mJ / cm ² , a laminate having a stripe etching resist pattern was obtained. This laminated body is a polyimide in which copper is etched with 40% aqueous ferric chloride solution and the resist pattern is peeled off with 2% aqueous sodium hydroxide solution to form a copper stripe pattern with a line width of 200 μm and a line interval of 300 μm. A film was obtained.

Example 10 (resist patterning by printing)
As in Example 8, the active energy ray-curable resin composition obtained in Example 6 was gravure-printed on a copper-plated polyimide film with a silicone rubber blanket (stripe pattern having a line width of 200 μm and a line interval of 300 μm), and 254 nm. When an ultraviolet ray was irradiated with the detector of No. 1 so that the integrated light quantity became 500 mJ / cm ² , a laminate having a stripe etching resist pattern was obtained. This laminated body is a polyimide in which copper is etched with 40% aqueous ferric chloride solution and the resist pattern is peeled off with 2% aqueous sodium hydroxide solution to form a copper stripe pattern with a line width of 200 μm and a line interval of 300 μm. Got the film

Example 11 (resist patterning by printing)
Similarly to Example 8, the active energy ray-curable resin composition obtained in Example 7 was gravure-printed on a copper-plated polyimide film with a silicone rubber blanket (stripe pattern having a line width of 200 μm and a line interval of 300 μm), and 254 nm. When an ultraviolet ray was irradiated with the detector of No. 1 so that the integrated light quantity became 500 mJ / cm ² , a laminate having a stripe etching resist pattern was obtained. This laminated body is a polyimide in which copper is etched with 40% aqueous ferric chloride solution and the resist pattern is peeled off with 2% aqueous sodium hydroxide solution to form a copper stripe pattern with a line width of 200 μm and a line interval of 300 μm. Got the film

Examples 8 to 11 show that after curing, the conductor adhesion, etching resistance, and alkali solubility are excellent, a substrate with a resist pattern by printing can be obtained, and a circuit pattern can be formed on the substrate by etching and resist peeling. . Accordingly, the active energy ray-curable resin composition for resist of the present invention can be suitably used as a resist layer used in the printed wiring board, the lead frame, and the LCD industry.

Claims (7)

General formula (1):
R ¹ Si (OR ² ) ₃
(Wherein R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms having at least one thiol group, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). The group-containing alkoxysilane (a1) is hydrolyzed (except when R ² is all hydrogen atoms) and condensed (A), and at least one carboxyl group in the molecule and at least An active energy ray-curable resin composition for a printing resist, comprising a compound (B) having one carbon-carbon double bond. The active energy ray-curable resin composition for a printing resist according to claim 1, wherein the condensate (A) contains a metal alkoxide (a2) having no thiol group as a constituent component. The active energy ray-curable resin composition for a printing resist according to claim 1 or 2, comprising a compound (C) having no carboxyl group and having at least two carbon-carbon double bonds as a constituent component. The active energy ray-curable resin composition for a resist according to any one of claims 1 to 3, comprising a polymer (F) obtained by polymerizing an ethylenically unsaturated group-containing monomer having a weight average molecular weight of 1,000 to 50,000 as a constituent component. A method for forming a resist pattern, comprising: printing the active energy ray-curable resin composition for resist according to any one of claims 1 to 4 on a substrate and then curing the composition. The printing resist laminated body obtained by the formation method of the resist pattern of Claim 5. A printed wiring board obtained by etching the printed resist laminate according to claim 6 and further peeling the printed resist.