JP2006051469A - Method for producing dry resist photosensitive material and dry resist photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of stably producing a dry resist photosensitive material having a plurality of resist layers and without any quality defects, and to provide the dry resist photosensitive material. <P>SOLUTION: In the method for producing the dry resist photosensitive material, two or more kinds of coating liquids are applied onto a substrate and dried collectively by using a simultaneous multilayer coating apparatus to form the plurality of photosensitive layers simultaneously on the substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a dry resist photosensitive material and a dry resist photosensitive material, and more particularly, to a dry resist photosensitive material having a plurality of resist layers and having no quality failures such as reticulation, moisture absorption and swelling of the photosensitive layer. The present invention relates to a dry resist photosensitive material manufacturing method capable of manufacturing a photosensitive material stably and with high production efficiency, and a dry resist photosensitive material manufactured by the manufacturing method.

  In recent years, dry resist photosensitive materials are required to be able to write wiring patterns with higher accuracy.

  As dry resist photosensitive materials that can meet such requirements, multilayer dry resist photosensitive materials such as those having two or more layers such as a photosensitive layer and those having a cushion layer provided between a support and a photosensitive layer. There is.

  Even in a multilayer dry resist photosensitive material, a water-insoluble organic solvent-based coating solution is generally used as a coating solution for forming a photosensitive layer. However, it is necessary to use a coating solution having significantly different characteristics for each layer. Many.

Therefore, the multilayer dry resist photosensitive material has hitherto been applied to a coating layer and then dried to form one layer, and then the next coating solution is coated thereon and dried to obtain another layer. It was common to manufacture by the method of forming a layer (patent documents 1-5).
JP-A-10-111570 JP 03-017650 A JP 56-025732 A JP 56-136027 A JP-A-10-337524

  However, in the above method, there is a problem that the production efficiency is poor because the coating liquid is applied, dried and wound up for each layer, and the production line becomes large, and the space occupied by the production line and the investment amount are large. There was also a problem of increasing. Furthermore, foreign matters are mixed in during drying or winding, which may cause various quality failures. In addition, since a long time often elapses between the application of one coating solution and the application of another coating solution thereon, one photosensitive layer formed by applying the one coating solution is Absorbing moisture may cause problems such as reticulation and hygroscopic expansion, which are wrinkles due to the moisture absorption.

  The present invention has been made to solve the above-mentioned problems, and is a multilayer dry resist photosensitive material that is stable and free from quality failures such as reticulation, moisture absorption and swelling of the photosensitive layer. It is an object of the present invention to provide a dry resist photosensitive material manufacturing method and a dry resist photosensitive material that can be manufactured with high production efficiency.

  The invention described in claim 1 is a method for producing a dry resist photosensitive material in which two or more photosensitive layers are formed on a support, wherein two or more coating liquids are formed on the support using a simultaneous multilayer coating apparatus. The present invention relates to a method for producing a dry resist photosensitive material, in which the plurality of photosensitive layers are simultaneously formed by coating and drying at once.

  In the manufacturing method of the dry resist photosensitive material, since the plurality of photosensitive layers are formed at the same time, the manufacturing line is far more than in the case where coating, drying, and winding of the coating solution are repeated for each photosensitive layer. The production line occupies less space and requires less investment. Further, since the process length is shortened, the possibility of contamination by the coating liquid surface in the process is reduced, and therefore the burden of dust management in the process is reduced.

  In addition, since a plurality of coating liquids are applied at the same time, a coating film having a large film thickness can be formed at a time compared to the case where the coating liquid is applied one layer at a time and dried. Therefore, winding wrinkles can be reduced. In addition, when applying and drying the coating solution one layer at a time, the coating solution or the photosensitive layer may absorb moisture during the drying process, and reticulation may occur. Reticulation can be effectively prevented by forming a high film.

  According to a second aspect of the present invention, in the dry resist photosensitive material manufacturing method according to the first aspect, a die coater having two or more slots is used as the simultaneous multilayer coating apparatus. Regarding the method.

  According to a third aspect of the present invention, in the dry resist photosensitive material manufacturing method according to the first aspect, a die coater having one slide surface and one or more slots is used as the simultaneous multilayer coating apparatus. The present invention relates to a method for manufacturing a dry resist photosensitive material.

  The die coater according to claims 2 and 3 is an example of a simultaneous multilayer coating apparatus suitably used in the method for producing a dry resist photosensitive material of the present invention.

  According to a fourth aspect of the present invention, in the dry resist photosensitive material manufacturing method according to any one of the first to third aspects, of the two layers formed adjacent to each other, an upper layer farther from the support is formed. The present invention relates to a method for producing a dry resist photosensitive material in which the surface tension σ1 of the upper layer coating solution is smaller than the surface tension σ2 of the lower layer coating solution that forms a lower layer closer to the support layer.

  According to the manufacturing method of the dry resist photosensitive material, it is possible to suitably prevent the occurrence of coating splash in which the upper layer coating solution is repelled by the lower layer coating solution.

  According to a fifth aspect of the present invention, in the dry resist photosensitive material manufacturing method according to any one of the first to fourth aspects, of the two layers formed adjacent to each other, an upper layer farther from the support is formed. The present invention relates to a method for producing a dry resist photosensitive material in which the specific gravity g1 of the coating liquid to be applied is equal to or lower than the specific gravity g2 of the coating liquid for forming a lower layer closer to the support layer.

  According to the manufacturing method of the dry resist photosensitive material, it is possible to effectively prevent the mixing of the coating liquid in which the coating liquids of the upper layer and the lower layer are mixed.

  According to a sixth aspect of the present invention, in the dry resist photosensitive material manufacturing method according to any one of the first to fifth aspects, of the two layers formed adjacent to each other, an upper layer farther from the support is formed. The present invention relates to a method for producing a dry resist photosensitive material in which the viscosity η1 of the upper layer coating solution is equal to or lower than the viscosity η2 of the lower layer coating solution that forms a lower layer closer to the support layer.

  Also by the manufacturing method of the dry resist photosensitive material, it is possible to effectively prevent the mixing of the coating liquid in which the coating liquids of the upper layer and the lower layer are mixed.

  A seventh aspect of the present invention relates to a dry resist photosensitive material manufactured by the method of manufacturing a dry resist photosensitive material according to any one of the first to sixth aspects.

  In the dry resist photosensitive material, due to the reasons described in claims 1 to 6, there are still quality failures such as reticulation, mixing of the upper layer coating solution with the lower layer coating solution, and coating flipping. Further, since the space occupied by the production line and the investment amount are small, it can be produced at low cost.

  As described above, according to the present invention, a dry resist photosensitive material having a plurality of resist layers, which is free from a quality failure such as reticulation, moisture absorption and swelling of the photosensitive layer, is stable and high. Provided are a dry resist photosensitive material manufacturing method and a dry resist photosensitive material that can be manufactured with production efficiency.

1. Form of Dry Resist Photosensitive Material As a dry resist photosensitive material manufactured by the dry resist photosensitive material manufacturing method according to the present invention, for example, as shown in FIG. There is a two-layer dry resist photosensitive material 20 on which an upper layer 6 is formed. In addition, it is preferable to stick the protective film 10 on the surface of the upper layer 6 and protect the upper layer from oxygen in the air until the start of use. FIG. 1A shows a two-layer dry resist photosensitive material in which a protective film 10 is stuck on the surface of the upper layer 6.

  An example of the lower layer 4 is a low-sensitivity layer, and an example of the upper layer is a high-sensitivity layer that is more sensitive to laser light than the low-sensitivity layer.

  In the dry resist photosensitive material, as shown in FIG. 2 (A), the upper layer 6 side is bonded to the electroless copper plating layer 32 of the copper-clad substrate 30, and as shown in FIG. It exposes by irradiating a laser beam from the body 2 side. Moreover, in what adhered the protective film 10 to the surface of the upper layer 6, after peeling the protective film 10, the upper layer 6 side is bonded to the copper bonding board | substrate 30, and it exposes. In FIG. 2, reference numeral 36 denotes a substrate of the copper-clad substrate 30, 34 denotes a copper vapor deposition layer, and 38 denotes a through hole.

2. Form of Simultaneous Multilayer Coating Device FIGS. 3 and 4 show examples of the simultaneous multilayer coating device used in the method for producing a dry resist photosensitive material according to the present invention.

  In FIG. 3, a simultaneous multilayer coating apparatus 100 shown in FIG. 3A and a simultaneous multilayer coating apparatus 102 shown in FIG. 3B are examples of the simultaneous multilayer coating apparatus used for manufacturing the two-layer dry resist photosensitive material 20.

  The simultaneous multilayer coating apparatus 100 is an example of a die coater having two slots, and includes a transport drum 40 that wraps and transports the support 2, and a die 42 that is disposed so as to face the transport drum 40. .

  The die 42 is formed in a substantially wedge shape and is disposed so that the thickness thereof decreases toward the drum 40.

  Inside the die 42, a first slot 44 </ b> A and a second slot 46 </ b> A are provided toward the end surface facing the drum 40. The first slot 44 </ b> A and the second slot 46 </ b> A are formed in parallel to each other, and open at the end surface on the side facing the drum 40. A lower layer coating solution for forming the lower layer 4 is discharged from the first slot 44A, and an upper layer coating solution for forming the upper layer 6 is discharged from the second slot 46A.

  The coating liquid supply flow path 44B and the coating liquid supply flow path 46B communicate with the root portions of the first slot 44A and the second slot 46A, respectively. The coating liquid is supplied to the first slot 44A and the second slot 46A through the coating liquid supply flow path 44B and the coating liquid supply flow path 46B, respectively.

  If the support 2 is wound around the drum 40 and rotated in the direction of arrow a, and the lower layer coating liquid is supplied to the coating liquid supply channel 44B and the upper layer coating solution is supplied to the coating solution supply channel 46B, the lower layer coating solution is The upper layer coating liquid is discharged from the first slot 44A onto the support 2, and the upper layer coating liquid is discharged from the second slot 46A and laminated on the lower layer coating liquid. If this is dried by an appropriate method, a two-layer dry resist photosensitive material 20 having a lower layer 4 formed on the support 2 and an upper layer 6 formed thereon is formed.

  The simultaneous multilayer coating apparatus 102 is an example of a die coater having one slide surface and one or more slots, and is arranged so as to face the conveyance drum 50 and the conveyance drum 50 around which the support 2 is wound and conveyed. And a die 52 provided.

  The die 52 is formed in a substantially wedge shape, and is disposed so that the thickness decreases toward the drum 50.

  Inside the die 52, a first slot 54 </ b> A that opens at an end surface facing the drum 50, a slide surface 58 that extends obliquely downward from above to the opening of the slot 54 </ b> A, and an opening in the middle of the slide surface 58. A second slot 56A. At the base of the first slot 54A and the second slot 56A, there are provided a coating liquid supply channel 54A and a coating solution supply channel 56B for supplying the coating liquid to the first slot 54A and the second slot 56A, respectively.

  If the support body 2 is wound around the drum 50 and rotated in the direction of arrow a, and the lower layer coating liquid is supplied to the coating liquid supply channel 54B and the upper layer coating liquid is supplied to the coating solution supply channel 56B, the lower layer coating solution is It is discharged onto the support 2 from the first slot 54A. On the other hand, the upper layer forming liquid is discharged from the second slot 56A to the slide surface 58 and laminated on the lower layer coating liquid. If this is dried by an appropriate method, a two-layer dry resist photosensitive material 20 having a lower layer 4 formed on the support 2 and an upper layer 6 formed thereon is formed.

3. 3. Description of Each Layer of Dry Resist Photosensitive Material 3-1 Lower Layer Examples of main components of the lower layer 4 include a binder, a polymerizable compound, and a photopolymerizable initiator. In addition to the above, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a color former, a colorant, and the like can be blended in the lower layer. Further, adhesion promoters to the substrate surface and other auxiliary agents (for example, pigments, conductive agents) Particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal cross-linking agents, surface tension modifiers, chain transfer agents, etc.). By appropriately blending these components, the properties of the lower layer 4 such as sensitivity, bakeout property, film physical properties and the like can be adjusted in relation to the upper layer 6 described later.

  Hereinafter, each component mix | blended with the lower layer 4 is explained in full detail.

A. As the binder, a polymer that is swellable or soluble in an alkaline aqueous solution is used.

  Examples of such a polymer include acidic group-containing polymers having acidic groups such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain.

  Examples of acidic group-containing polymers include vinyl copolymer resins, polyurethane resins, polyamide resins, epoxy resins and the like having carboxyl groups. Among these, solubility in solvents, alkaline developer A carboxyl group-containing vinyl copolymer resin is most preferred from the viewpoints of solubility in water, ease of synthesis, and ease of adjustment of film properties.

  Examples of the carboxyl group-containing vinyl copolymer resin include a homopolymer of a carboxyl group-containing vinyl monomer having a carboxyl group, and a copolymer of the carboxyl group-containing vinyl monomer and other copolymer monomers.

A-1 Carboxyl group-containing vinyl monomer Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, An acrylic acid dimer, an addition reaction product of a monomer having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono (meth) acrylate and the like. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

A-2 Copolymer monomer The copolymer monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine) , Vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, mono (2-acryloyloxyethyl ester) phosphate, Monophosphate (1- Chill-2-acryloyloxyethyl ester), functional groups (e.g., a urethane group, a urea group, a sulfonamide group, a phenol group and a vinyl monomer and the like having an imide group).

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  These copolymerization monomers may be used alone or in combination of two or more.

A-3 Production Method of Carboxyl Group-Containing Vinyl Copolymer Resin The carboxyl group-containing vinyl copolymer resin can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a solution polymerization method in which the monomer is dissolved in a suitable solvent, a radical polymerization initiator is added to the monomer, and polymerization is performed in solution. In addition, emulsion polymerization or the like in which the monomer is dispersed in an aqueous medium and a radical polymerization initiator is added therein to initiate polymerization can be performed.

  There is no restriction | limiting in particular in the suitable solvent used by the said solution polymerization method, According to the monomer to be used, the solubility of the produced | generated copolymer, etc., it can select suitably, For example, methanol, ethanol, propanol, isopropanol 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include azo such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Compounds, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

A-3 Characteristics of the carboxyl group-containing vinyl copolymer resin There is no particular limitation on the content of the carboxyl group-containing vinyl monomer of the carboxyl group-containing vinyl copolymer resin, and it can be appropriately selected according to the purpose. 5 to 50 mol% is preferable, 10 to 40 mol% is more preferable, and 15 to 35 mol% is particularly preferable.

  If the content is 5 mol% or more, sufficient limit formation with respect to an alkaline developer is obtained, and if it is 50 mol% or less, the developer resistance of the cured portion (image portion) is sufficient.

  There is no restriction | limiting in particular in the molecular weight of the binder which has the said carboxyl group, Although it can select suitably according to the objective, For example, as a mass mean molecular weight, 2,000-300,000 are preferable, 4,000-150, 000 is more preferable.

  If the mass average molecular weight is 2,000 or more, sufficient film strength is obtained and stable production is easy, and if it is 300,000 or less, good developability is obtained.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. Examples of the case where two or more binders are used in combination include, for example, a combination of two or more binders composed of different copolymer components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 and the like can be used.

  There is no restriction | limiting in particular in content of the said binder in the said photosensitive layer, Although it can select suitably according to the objective, For example, 10-90 mass% is preferable, 20-80 mass% is more preferable, 40-80 Mass% is particularly preferred.

  When the content is less than 10% by mass, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be deteriorated. Stability and strength of the cured film (tent film) may be reduced. The content may be the total content of the binder and the polymer binder used in combination as necessary.

  There is no restriction | limiting in particular in the acid value of the said binder, Although it can select suitably according to the objective, For example, 70-250 (mgKOH / g) is preferable, 90-200 (mgKOH / g) is more preferable, 100 -180 (mg KOH / g) is particularly preferred.

  If the acid value is 70 (mgKOH / g) or more, sufficient developability and resolution can be obtained. On the other hand, if the acid value is 250 (mgKOH / g) or less, both the developer resistance and adhesion of the pattern are good. Therefore, if the acid value is within the above range, a permanent pattern such as a wiring pattern can be obtained with high definition.

B. Polymerizable compound The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a monomer or oligomer having at least one of a urethane group and an aryl group. Moreover, it is preferable that these have 2 or more types of polymeric groups.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

B-1 Urethane Group-Containing Monomer The urethane group-containing monomer is not particularly limited as long as it has a urethane group, and can be appropriately selected according to the purpose. For example, JP-B-48-41708 and JP-A-51-51 -37193, Japanese Patent Publication No. 5-50737, Japanese Patent Publication No. 7-7208, Japanese Patent Application Laid-Open No. 2001-154346, Japanese Patent Application Laid-Open No. 2001-356476, and the like. Examples include adducts of a polyisocyanate compound having a group and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having two or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, A diisocyanate such as 3,3′dimethyl-4,4′-diphenyl diisocyanate; a polyaddition product of the diisocyanate with a bifunctional alcohol (in this case, both ends are isocyanate groups); a burette or isocyanurate of the diisocyanate; Trimer; the diisocyanate or diisocyanates and trimethylolpropane, pe Taerisurutoru, polyfunctional alcohols such as glycerin, or the like adducts of other functional alcohol obtained of such these ethylene oxide adducts and the like.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  The urethane group-containing monomer may be a compound having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, or tri (meth) acrylate of ethylene oxide-modified isocyanuric acid. Can be mentioned.

B-2 Aryl Group-Containing Monomer The aryl group-containing monomer is not particularly limited as long as it has an aryl group, and can be appropriately selected according to the purpose. For example, a polyhydric alcohol compound having an aryl group, Examples thereof include esters or amides of unsaturated carboxylic acids with at least one of a polyvalent amine compound and a polyvalent amino alcohol compound.

  Examples of the polyhydric alcohol compound, polyamine compound or polyhydric amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1,5-dihydroxy-1, 2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2,3,5,6-tetra Methyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4- Diol, 1,1′-bi-2-naphthol, dihydroxynaphthalene, 1,1′-methylene-di-2-naphth 1,2,4-benzenetriol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methyl hydroquinone, methylene-2,4,6-trihydroxybenzoate, phloroglicinol, pyrogallol, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α -(1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino-4-hydroxyphenylsulfone and the like can be mentioned. In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as xylylene bis (meth) acrylamide, novolac epoxy resin and bisphenol A diglycidyl ether, phthalic acid, trimellitic acid, etc. Esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, cationically polymerizable divinyl ethers (for example, bisphenol A divinyl ether), epoxy as a polymerizable monomer Compound (for example, novolac type epoxy resin, bisphenol A diglycidyl ether, etc.), vinyl ester (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, etc.), styrene Compounds such as divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like.

  Specific examples of the aryl group-containing monomer include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 2,2-bis [4-((meth) acrylic). Oxyethoxy) phenyl] propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethoxy groups substituted with one phenolic OH group ( For example, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaetoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, phenol 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (for example, 2,2-bis (4 -((Meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypenta) Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl) Lopan, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, or the like, or a polyether moiety of these compounds contains both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule A compound having a bisphenol skeleton and a urethane group (for example, a compound described in WO01 / 98832 or a commercially available product, manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-200, BPE-500, BPE-1000) Compound. These compounds may be compounds obtained by changing the part derived from the bisphenol A skeleton to bisphenol F or bisphenol S.

  Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Examples thereof include compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.).

B-3 Other polymerizable monomers In the pattern forming method of the present invention, a polymerizable monomer other than the monomer containing the urethane group and the aryl group-containing monomer is used in a range not deteriorating the characteristics as the pattern forming material. May be.

  Examples of the polymerizable monomer other than the monomer containing a urethane group and the monomer containing an aromatic ring include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) And an ester of an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-bentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate A di (meth) acrylate of an alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, a compound described in WO01 / 98832), at least one of ethylene oxide and propylene oxide Trimethylolpropane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate Examples include relate and xylenol di (meth) acrylate.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate, penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1, Preference is given to 5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate added with ethylene oxide, and the like.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonic acid ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester (isocrotonic acid ester) of the isocrotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, and diethylenetriamine bis (meth) acrylamide.

  In addition to the above, as the polymerizable monomer, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, Polyester acrylate and polyester (meth) acrylate as described in JP-B-6183, JP-B-49-43191 and JP-B-52-30490. Rate oligomers, epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether and the like) and polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting (meth) acrylic acid, Japan Adhesion Association Vol. 20, No. 7, 300-308 Photocurable monomers and oligomers and allyl esters described in page (1984) (eg diallyl phthalate, diallyl adipate, malonic acid) Allyl, diallylamide (eg, diallylacetamide), cationically polymerizable divinyl ethers (eg, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol) Divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol di) Glycidyl ether, diethylene glycol diglycidyl ether, dipropylene group Recall diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, etc.), epoxy compounds, oxetanes (for example, compounds described in WO01 / 22165), N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β- And compounds having two or more different ethylenically unsaturated double bonds, such as methacryloxyethyl) acrylamide and allyl methacrylate.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  These polyfunctional monomers or oligomers may be used alone or in combination of two or more.

  If necessary, the polymerizable monomer may be used in combination with a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule.

  Examples of the monofunctional monomer include the compounds exemplified as the raw material of the binder, and the dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) described in JP-A-6-236031. Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., compounds described in Japanese Patent No. 2744443, WO00 / 52529, Japanese Patent No. 2548016, etc. Is mentioned.

B-4 Content of Polymerizable Compound The content of the polymerizable compound in the lower layer 2 is, for example, preferably 5 to 90% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass. If the content is 5% by mass or more, the tent strength of the film is sufficient, and if it is 90% by mass or less, it is possible to prevent deterioration of edge fusion during storage (bleed out from the roll end). .

  Moreover, 5-100 mass% is preferable, as for content of the polyfunctional monomer which has 2 or more of the said polymeric groups in a polymeric compound, 20-100 mass% is more preferable, and 40-100 mass% is especially preferable.

C photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable, and may be an activator that generates some kind of action with a photoexcited sensitizer and generates an active radical, depending on the type of monomer. The photopolymerization initiator may include a component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm). It is preferable to contain at least one kind.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxides, thio compounds, Examples include ketone compounds, aromatic onium salts, and metallocenes. Among these, halogenated hydrocarbons having a triazine skeleton, oxime derivatives, ketone compounds, hexaarylbiimidazoles from the viewpoints of sensitivity and storage stability of the photosensitive layer, and adhesion between the photosensitive layer and the printed wiring board forming substrate. System compounds are preferred.

  Examples of the hexaarylbiimidazole include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-methoxyphenyl) biimidazole, 2,2'-bis (4-methoxyphenyl) -4 , 4 ', , 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-Trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, compounds described in WO00 / 52529, and the like.

  The biimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960); Org. It can be easily synthesized by the method disclosed in Chem, 36 (16) 2262 (1971).

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And compounds described in the book.

3-2 Upper Layer Examples of the main component of the upper layer 6 include a binder, a polymerizable compound, and a photopolymerizable initiator. All of the binder, the polymerizable compound, and the photopolymerizable initiator are as described in the lower layer.

3-3 Support The support 2 is preferably one that can be peeled off from the lower layer after the exposure, and transmits the laser light used at the time of exposure, and more preferably has a smooth surface. Specifically, it is preferably a colorless and transparent synthetic resin film, but it may be a colored transparent film or a translucent film.

  Examples of the synthetic resin used for the support 2 include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, and poly (meth) acrylic acid ester. Polymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulosic film, Various plastic films, such as a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  The thickness of the support is, for example, preferably from 2 to 150 μm, more preferably from 5 to 100 μm, particularly preferably from 8 to 50 μm, but those outside the above range can also be selected depending on the purpose.

  The pattern forming material may form a protective film on the photosensitive layer.

3-5 Protective Film Examples of the protective film 10 include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.

  The thickness of the protective film 10 is, for example, preferably 5 to 100 μm, more preferably 8 to 50 μm, and particularly preferably 10 to 30 μm, but is not limited to the above range.

  When the protective film 10 is used, the relationship of adhesive force A> adhesive force B is established between the adhesive force A between the lower layer 4 and the support 2 and the adhesive force B between the upper layer 6 and the protective film 10. It is preferable.

  Examples of the combination of the support 2 and the protective film 10 (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. It is done. Moreover, the above-mentioned relationship of adhesive force can be satisfy | filled by surface-treating at least any one of the support body 2 and the protective film 10.

  The surface treatment of the support 2 may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

  Moreover, 0.3-1.4 are preferable and the static friction coefficient of the support body 2 and the protective film 10 has more preferable 0.5-1.2.

  When the coefficient of static friction is 0.3 or more, excessive slip does not occur, and no winding deviation occurs when the dry resist photosensitive material 20 or the dry resist photosensitive material 22 is wound in a roll shape. If the static friction coefficient is 1.4 or less, it is not so difficult to wind the dry resist photosensitive material 20 or the dry resist photosensitive material 22 in a roll shape.

1. Example 1, Example 2, Comparative Examples 1-3
[Composition of lower layer coating solution]
The composition of the lower layer coating solution is as follows.
a. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8, mass average molecular weight: 90000, Tg: 70 ° C. 15 parts by mass b. Dodeca polypropylene glycol diacrylate 6.5 mass parts c. Tetraethylene glycol dimethacrylate 1.5 parts by mass d. 4,4'-bis (diethylamino) benzophenone 0.04 parts by mass e. Benzophenone: 1.0 part by mass f. 4-toluenesulfonamide 0.5 parts by mass g. Malachite green oxalate 0.02 parts by mass h. 1,2,4-triazole... 0.01 parts by mass i. Leuco crystal violet 0.2 mass part j. Tribromophenyl sulfone: 0.1 part by mass k. Fluorine oligomer: 0.1 part by mass l. Methyl ethyl ketone: 15 parts by mass m. Propylene glycol monomethyl ether ... 10 parts by mass n. Cyclohexanone: 5 parts by mass.

[Composition of upper layer coating solution]
The composition of the upper layer coating solution is as follows.
a. Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 40 / 26.7 / 4.5 / 28.8, mass average molecular weight: 90000, Tg: 50 ° C. 15 parts by mass b. Polypropylene glycol diacrylate 6.5 mass parts c. Tetraethylene glycol dimethacrylate 1.5 parts by mass d. 4,4'-bis (diethylamino) benzophenone 0.4 parts by mass e. Benzophenone: 3.0 parts by mass f. 4-toluenesulfonamide 0.5 parts by mass g. Malachite green oxalate 0.02 parts by mass h. 1,2,4-triazole... 0.01 parts by mass i. Leuco crystal violet 0.2 mass part j. Tribromophenyl sulfone: 0.1 part by mass k. Fluorine oligomer: 0.1 part by mass l. Methyl ethyl ketone: 15 parts by mass m. Propylene glycol monomethyl ether ... 10 parts by mass n. Cyclohexanone: 5 parts by mass.

  In FIG. 3, the die coater 100 shown in FIG. 3A is used, a PET film having a thickness of 16 μm is used as the support 2, the lower layer coating solution is supplied to the first slot 44 A, and the upper layer coating solution is supplied to the second slot 46 A. It was applied to No. 2 and visually checked for the presence and extent of the reticulation phenomenon. The results are shown in Table 1. The thicknesses of the lower layer coating solution and the upper layer coating solution in Table 1 are dry film thicknesses (the same applies hereinafter).

表１において、○は、レチキュレーションの発生が認められなかったことを示し、△は、レチキュレーションの発生が認められたものの、品質上許容できるぎりぎりのレベルであったことを示し、×は、品質上許容できない程度のレチキュレーションの発生が認められたことを示す。

In Table 1, ◯ indicates that no reticulation was observed, △ indicates that reticulation was observed, but was at a level that was acceptable in terms of quality, and × Indicates that reticulation that is unacceptable in terms of quality was observed.

  The physical properties of the upper layer coating solution and the lower layer coating solution were as shown in Table 2.

表１から明らかなように、下層形成液と上層形成液とを同時重層塗布して支持体上の塗膜の厚さを大きくすることにより、得られたドライレジスト感光材料を巻取るときの皺の発生を低減させることができる。

As is apparent from Table 1, the lower layer forming solution and the upper layer forming solution are simultaneously applied in multiple layers to increase the thickness of the coating film on the support. Can be reduced.

  In addition, as shown in Comparative Examples 1 to 3, reticulation tends to occur when only one layer of the coating liquid is applied on the support, but as shown in Examples 1 and 2, the lower layer forming liquid and the upper layer forming When the liquid is applied simultaneously in multiple layers, reticulation is unlikely to occur even if the coating thickness as a whole is the same as in Comparative Examples 1 to 3.

2. Example 3, Reference Examples 1 and 2
The presence and extent of coating repellency failure when the surface tensions of the upper layer forming solution and the lower layer forming solution used in Examples 1 and 2 and Comparative Examples 1 to 3 were adjusted as shown in Table 3 were visually evaluated. The results are shown in Table 3. Moreover, the coating thickness of the lower layer was 15 μm, and the coating thickness of the upper layer was 5 μm. The specific gravity and viscosity are as shown in Table 2.

表３において、○は、塗布面に塗布ハジキが認められなかったことを、×は、塗布ハジキが明瞭に認められたことを示す。

In Table 3, o indicates that no application repelling was observed on the coated surface, and x indicates that application repelling was clearly recognized.

  As apparent from Table 3, in Example 3 where the surface tension σ1 of the upper layer coating solution was smaller than the surface tension σ2 of the lower layer coating solution, no occurrence of coating repellency was observed on the surface of the dry resist photosensitive material 20, In Reference Example 1 and Reference Example 2 in which the surface tension σ1 of the upper layer coating solution is equal to or larger than the surface tension σ2 of the lower layer coating solution, occurrence of coating repellency was recognized to the extent that it causes a quality problem.

3. Examples 4 and 5, Reference Examples 3 and 4
The occurrence of layer mixing between coating solutions when the specific gravity of the upper layer forming solution and the lower layer forming solution used in Examples 1 and 2 and Comparative Examples 1 to 3 was adjusted as shown in Table 4 was visually evaluated. The results are shown in Table 4.

表４において、○は、塗布液の層混合が認められなかったことを示し、△は、塗布液の層混合が一部認められたことを示す。

In Table 4, “◯” indicates that layer mixing of the coating solution was not observed, and “Δ” indicates that layer mixing of the coating solution was partially recognized.

  The surface tension, viscosity, and dry film thickness of the lower layer coating solution and the upper layer coating solution are as shown in Table 5.

表４に示すように、上層塗布液の比重ｇ１が下層塗布液の比重ｇ２と均しいかまたは小さい実施例４および５においてはドライレジスト感光材料２０の表面に塗布液の層混合は認められなかったが、上層塗布液の表面張力σ１が下層塗布液の表面張力σ２よりも大きな参考例３および参考例４においては、表面の一部に塗布液の層混合の発生が認められた。

As shown in Table 4, in Examples 4 and 5 where the specific gravity g1 of the upper layer coating solution is equal to or smaller than the specific gravity g2 of the lower layer coating solution, no layer mixing of the coating solution is observed on the surface of the dry resist photosensitive material 20. However, in Reference Example 3 and Reference Example 4 in which the surface tension σ1 of the upper layer coating liquid was larger than the surface tension σ2 of the lower layer coating liquid, generation of layer mixing of the coating liquid was observed on a part of the surface.

4). Examples 6-11, Reference Examples 5-8
The occurrence of layer mixing between the coating liquids when the viscosity of the upper layer forming liquid and the lower layer forming liquid used in Examples 1 and 2 and Comparative Examples 1 to 3 was adjusted as shown in Table 6 was visually evaluated. The results are shown in Table 6.

表６において、○は、塗布液の層混合が認められなかったことを示し、△は、塗布液の層混合が一部認められたことを、×は、塗布液の層混合が多く見られたことを示す。

In Table 6, “◯” indicates that layer mixing of the coating solution was not observed, “Δ” indicates that part of layer mixing of the coating solution was observed, and “×” indicates that layer mixing of the coating solution was frequently observed. It shows that.

  The surface tension, specific gravity, and dry film thickness of the lower layer coating solution and the upper layer coating solution are as shown in Table 7.

表６に示すように、上層塗布液の粘度η１が下層塗布液の粘度η２よりも小さい実施例６〜１１においてはドライレジスト感光材料２０の表面に塗布液の層混合は認められなかったが、上層塗布液の粘度η１が下層塗布液の粘度η２と等しいかまたは大きな参考例５〜８においては、塗布液の層混合の発生が明らかに認められた。

As shown in Table 6, in Examples 6 to 11 in which the viscosity η1 of the upper layer coating solution was smaller than the viscosity η2 of the lower layer coating solution, layer mixing of the coating solution was not observed on the surface of the dry resist photosensitive material 20, In Reference Examples 5 to 8 in which the viscosity η1 of the upper layer coating solution was equal to or larger than the viscosity η2 of the lower layer coating solution, the occurrence of layer mixing of the coating solution was clearly observed.

FIG. 1 is a cross-sectional view showing an example of a two-layer dry resist photosensitive material. FIG. 2 is a cross-sectional view showing a state where the dry resist photosensitive material shown in FIG. 1 is attached to a substrate. FIG. 3 is an explanatory diagram showing a two-layer simultaneous multilayer coating apparatus.

Explanation of symbols

2 Support 4 Lower layer 6 Upper layer 100 Simultaneous multilayer coating device 102 Simultaneous multilayer coating device

Claims (7)

A method for producing a dry resist photosensitive material in which a plurality of photosensitive layers are formed on a support,
A method for producing a dry resist photosensitive material, wherein the plurality of photosensitive layers are simultaneously formed by simultaneously applying and drying two or more kinds of coating solutions on a support using a simultaneous multilayer coating apparatus. .   2. The method for producing a dry resist photosensitive material according to claim 1, wherein a die coater having two or more slots is used as the simultaneous multilayer coating apparatus.   2. The method of producing a dry resist photosensitive material according to claim 1, wherein a die coater having one slide surface and one or more slots is used as the simultaneous multilayer coating apparatus.   The surface tension σ1 of the upper layer coating liquid that forms the upper layer farther from the support among the two layers formed adjacent to each other is smaller than the surface tension σ2 of the lower layer coating liquid that forms the lower layer closer to the support layer. The method for producing a dry resist photosensitive material according to any one of 1 to 3.   The specific gravity g1 of the upper coating solution that forms the upper layer farther from the support among the two layers formed adjacent to each other is less than the specific gravity g2 of the lower coating solution that forms the lower layer closer to the support layer. 5. The method for producing a dry resist photosensitive material according to any one of 4 above.   Among the two layers formed adjacent to each other, the viscosity η1 of the rising coating solution that forms the upper layer farther from the support is equal to or lower than the viscosity η2 of the lower coating solution that forms the lower layer closer to the support layer. 6. The method for producing a dry resist photosensitive material according to any one of 5 above.   A dry resist photosensitive material produced by the method for producing a dry resist photosensitive material according to claim 1.

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