Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/44—Amides
  • C08G59/46—Amides together with other curing agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a photosensitive resin composition, a dry film, a cured product, and an electronic component.
• a liquid crystal display is composed of an optical attenuator, which is constructed by combining a liquid crystal whose polarization state changes by applying a voltage, and a polarizing filter, and a backlight unit installed behind the optical attenuator.
• an optical attenuator which is constructed by combining a liquid crystal whose polarization state changes by applying a voltage, and a polarizing filter, and a backlight unit installed behind the optical attenuator.
• backlight units that emit light uniformly over the entire surface have long been used, but by using a split drive method that divides the light emitting area depending on the brightness of the background, LEDs can be used only in areas where brightness is required.
• Technology is being developed to improve contrast by combining it with local dimming technology that lights up the display.
• the split drive method has been realized by using an edge-type LED backlight that uses a light guide plate to spread the light from LEDs arranged at the edge of the screen to the entire screen, and by mounting LEDs directly below the screen.
• products with the number of divisions ranging from several tens to around 100 have been commercialized. If the number of divisions is small, light leaks into areas that should originally be displayed darkly, causing a noticeable halo effect in which the contours of bright areas blur, making it impossible to obtain sufficient image beauty. Therefore, in recent years, from the viewpoint of improving contrast, a direct-type mini LED backlight has been proposed in which mini LEDs, the size of which has been reduced to about 1 mm or less, are arranged so as to cover a substrate.
• the glass substrate for the backlight is also suitable for, for example, 8th generation (2160 mm x 2460 mm). It's such a big thing. Therefore, when forming the above-mentioned mini-LED installation pattern using a white photosensitive resin composition having insulation properties and high reflectance, the area over which the white photosensitive resin composition is applied to the glass substrate also becomes large.
• the glass substrate itself has become thinner, from about 3 mm in the past to 0.7 mm or 0.5 mm, which is less than 1 mm. Due to this increased coating area and thinner glass, there was a problem in that the glass substrate was more likely to warp due to shrinkage of the white photosensitive resin composition due to heating during pattern formation and the subsequent reflow process. .
• the substrate is warped due to warping after the reflow process, resulting in problems such as not being able to support thinner and lighter displays. there were.
• it is required to maintain high reflectance after the reflow process but with conventional white photosensitive resin compositions, it is difficult to achieve both low warpage and high reflectance after the reflow process. there were.
• the present invention was made in view of the problems of the prior art, and its purpose is to provide a photosensitive resin composition that can achieve both low warpage and high reflectance after a reflow process, and a photosensitive resin composition using the same.
• Our goal is to provide dry films, cured products, and electronic components.
• the present inventors have made extensive studies to achieve the above objective. As a result, by using a composition containing a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and a bifunctional (meth)acrylate, it was possible to achieve both high reflectance and low warpage after the reflow process. The inventors have discovered that the above problems can be solved, and have completed the present invention.
• the photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, (B) a difunctional (meth)acrylate, and (C) It is characterized by containing a photopolymerization initiator, (D) an epoxy resin, (E) a white coloring agent, and (F) a carboxyl group-containing urethane resin that does not have an aromatic ring.
• (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• the diol having an aromatic ring is preferably a bisphenol A-based alkylene oxide adduct diol, and the (E) white coloring agent is preferably titanium oxide.
• the dry film of the present invention is characterized by being formed by drying the photosensitive resin composition of the present invention. Further, the cured product of the present invention is characterized in that it is obtained from the photosensitive resin composition of the present invention or the dry film of the present invention. Furthermore, the electronic component of the present invention is characterized by having a cured product.
• the present invention it is possible to provide a photosensitive resin composition that can achieve both low warpage and high reflectance after a reflow process, as well as dry films, cured products, and electronic components using the same.
• the photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, (B) a difunctional (meth)acrylate, and (F) It contains a carboxyl group-containing urethane resin that does not have an aromatic ring, thereby achieving both high reflectance and low warpage after the reflow process.
• the photosensitive resin composition of the present invention contains (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, as a carboxyl group-containing urethane resin effective for stress relaxation.
• Carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate is a urethane resin formed by a reaction between a polyisocyanate (a) of an aliphatic diisocyanate and a diol (b) having an aromatic ring. bond, but further has a urethane bond formed by a reaction involving polycarbonate polyol (c) and dimethylolalkanoic acid (d), and a carboxyl group introduced by the dimethylolalkanoic acid (d). It is preferable to have.
• a monohydroxyl compound (e) may be added as a reaction terminator (end-capping agent).
• a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate is, for example, a polyisocyanate (a) of an aliphatic diisocyanate, a diol (b) having an aromatic ring, and a polycarbonate polyol (c). , dimethylolalkanoic acid (d), and monohydroxyl compound (e) may be mixed together and reacted, or polyisocyanate (a) of aliphatic diisocyanate and diol (b) having an aromatic ring may be reacted.
• a polycarbonate polyol (c) and a dimethylolalkanoic acid (d) may be reacted, and then a monohydroxyl compound (e) functioning as a reaction terminator may be reacted.
• a polycarbonate polyol (c), a diol having an aromatic ring (b), a dimethylolalkanoic acid (d), and a monohydroxyl compound (e) that functions as a reaction terminator may be mixed together to produce a fatty acid. It may be reacted with a polyisocyanate (a) of the group diisocyanate.
• the polyisocyanate (a) of the aliphatic diisocyanate various conventionally known polyisocyanates can be used, and the polyisocyanate is not limited to a specific compound.
• Specific examples of the aliphatic diisocyanate polyisocyanate (a) include diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. These polyisocyanates can be used alone or in combination of two or more. Among these, trimethylhexamethylene diisocyanate is preferred. When these diisocyanates are used, a cured product with excellent solder heat resistance can be obtained.
• bisphenol A type alkylene oxide adduct diol is preferred. Specific examples include ethylene oxide adducts, propylene oxide adducts, butylene oxide adducts of bisphenol A, and among these, propylene oxide adducts of bisphenol A are preferred from the viewpoint of improving soldering heat resistance.
• polycarbonate diol As the polycarbonate polyol (c), polycarbonate diol is preferred.
• polycarbonate diols include polycarbonate diol (c-1) containing repeating units derived from one or more linear aliphatic diols as constituent units, and polycarbonate diols (c-1) containing repeating units derived from one or more linear aliphatic diols; Examples include a polycarbonate diol (c-2) containing a repeating unit as a constituent unit, or a polycarbonate diol (c-3) containing a repeating unit derived from both of these diols as a constituent unit.
• polycarbonate diol (c-1) containing a repeating unit derived from a linear aliphatic diol as a constitutional unit include, for example, polycarbonate diol derived from 1,6-hexanediol, 1,5-pentanediol and 1,6-hexanediol, polycarbonate diol derived from 1,4-butanediol and 1,6-hexanediol, 3-methyl-1,5-pentanediol and 1,6-hexane Mention may be made of polycarbonate diols derived from diols.
• a specific example of the polycarbonate diol (c-2) containing a repeating unit derived from an alicyclic diol as a structural unit includes, for example, a polycarbonate diol derived from 1,4-cyclohexanedimethanol.
• polycarbonate diols (c-3) containing repeating units derived from both linear aliphatic diols and alicyclic diols include 1,6-hexane diol and 1,4 - Polycarbonate diols derived from cyclohexanedimethanol.
• Polycarbonate diols containing repeating units derived from linear aliphatic diols as structural units tend to have excellent low warpage and flexibility. Furthermore, polycarbonate diols containing repeating units derived from alicyclic diols as structural units tend to have high crystallinity and excellent tin plating resistance and soldering heat resistance. From the above viewpoint, it is recommended to use two or more types of these polycarbonate diols in combination, or to use polycarbonate diols containing repeating units derived from both linear aliphatic diols and alicyclic diols as constituent units. can.
• the copolymerization ratio of linear aliphatic diol and alicyclic diol should be 3:7 to 7 by mass. :3 polycarbonate diols are preferably used.
• the polycarbonate diol preferably has a number average molecular weight of 200 to 5,000, but the polycarbonate diol contains repeating units derived from linear aliphatic diols and alicyclic diols as constituent units, and When the copolymerization ratio of the alicyclic diol is 3:7 to 7:3 in terms of mass ratio, the number average molecular weight is preferably 400 to 2,000.
• Dimethylol alkanoic acid (d) is a dihydroxy aliphatic carboxylic acid having a carboxyl group, and specific examples thereof include dimethylol propionic acid, dimethylol butanoic acid, and the like. By using dimethylolalkanoic acid (d), carboxyl groups can be easily introduced into the urethane resin.
• the monohydroxyl compound (e) serves as an end-capping agent for polyurethane, and any compound having one hydroxyl group in the molecule may be used, such as aliphatic alcohol (e-1), monohydroxy mono(meth) ) acrylate compound (e-2), etc.
• aliphatic alcohol (e-1) include methanol, ethanol, propanol, isobutanol, etc.
• monohydroxy mono(meth)acrylate compound (e-2) include 2-hydroxyethyl Examples include acrylate.
• the carboxyl group-containing urethane resin derived from (A) a diol having an aromatic ring and an aliphatic diisocyanate (A) (a) polyisocyanate, (b) bisphenol A-based alkylene oxide adduct diol,
• a carboxyl group-containing urethane resin obtained by reacting c) polycarbonate diol and (d) dimethylolalkanoic acid
• warping can be further suppressed by using it in combination with a bifunctional (meth)acrylate ( It is preferable because it has a low warpage effect.
• the weight average molecular weight of the carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate is preferably 500 to 100,000, more preferably 8,000 to 50,000.
• the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography.
• the acid value of the carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate is preferably in the range of 5 to 150 mgKOH/g, more preferably 10 to 100 mgKOH/g. If the acid value is less than 5 mgKOH/g, the reactivity with the thermosetting component may decrease and heat resistance may be impaired. On the other hand, if the acid value exceeds 150 mgKOH/g, the properties of the cured film as a resist such as alkali resistance and electrical properties may deteriorate. Note that the acid value of the resin is a value measured in accordance with JIS K5407.
• the blending amount of (A) the carboxyl group-containing urethane resin derived from the diol having an aromatic ring and an aliphatic diisocyanate is as follows: F) Total amount of carboxyl group-containing urethane resin having no aromatic ring: 100 parts by mass (if the photosensitive resin composition of the present invention contains (G) other carboxyl group-containing resin described below, component (A), Preferably 3 parts by mass to 50 parts by mass, more preferably 5 parts by mass to 30 parts by mass, even more preferably 5 parts by mass to 100 parts by mass of the total amount including component (F) and component (G). It is 15 parts by mass.
• Ratio of the amount of (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate to (F) a carboxyl group-containing urethane resin having no aromatic ring (F)/(A) is preferably 1.0 to 32.3, more preferably 2.3 to 20.0.
• the photosensitive resin composition of the present invention contains a difunctional (meth)acrylate. Since the (meth)acrylate has an ethylenically unsaturated group, it is photocured by irradiation with active energy rays and helps insolubilize the photosensitive resin composition of the present invention in an alkaline aqueous solution. (Meth)acrylate
• the (B) difunctional (meth)acrylate of the present invention is difunctional and therefore forms a crosslinked structure, and especially when used in combination with component (A), it increases the flexibility and hardness of the cured coating film. It satisfies the contradictory physical properties of improving .
• the blending amount of (B) bifunctional (meth)acrylate is preferably 15 parts by mass. ⁇ 100 parts by weight, more preferably 30 parts to 100 parts by weight.
• the blending amount of trifunctional or higher-functional (meth)acrylate is 40 parts by mass to 80 parts by mass when the total amount of (meth)acrylates contained in the photosensitive resin composition of the present invention is 100 parts by mass.
• Warping can be suppressed even if the Warpage can be suppressed if the tetrafunctional or higher-functional (meth)acrylate is 5 parts by mass or less when the total amount of (meth)acrylates contained in the photosensitive resin composition of the present invention is 100 parts by mass.
• the total amount of (meth)acrylate contained in the photosensitive resin composition of the invention is 100 parts by mass, it is preferably less than 1 part by mass.
• Difunctional (meth)acrylates include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and Polyhydric alcohols such as pentaerythritol, tris-hydroxyethyl isocyanurate, or diacrylates such as ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and these Diacrylates such as ethylene oxide adducts or propylene oxide adducts of phenols; diacrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglyl
• epoxy diacrylate resins are produced by reacting diacrylic acid with polyfunctional epoxy resins such as cresol novolac type epoxy resins, and hydroxy acrylates such as pentaerythritol triacrylate and isophorone diisocyanates are added to the hydroxyl groups of the epoxy diacrylate resins.
• polyfunctional epoxy resins such as cresol novolac type epoxy resins
• hydroxy acrylates such as pentaerythritol triacrylate and isophorone diisocyanates are added to the hydroxyl groups of the epoxy diacrylate resins.
• examples include epoxyurethane diacrylate compounds obtained by reacting diisocyanate with half-urethane compounds.
• Such an epoxy diacrylate resin can improve photocurability without reducing dryness to the touch.
• the amount of bifunctional (meth)acrylate is (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) a carboxyl group-containing resin having no aromatic ring.
• Total amount of urethane resin 100 parts by mass (if the photosensitive resin composition of the present invention contains other carboxyl group-containing resin (G) described below, component (A), component (F), and component (G) are also added)
• a suitable proportion is 5 to 100 parts by weight, more preferably 5 to 70 parts by weight, based on the total amount (100 parts by weight).
• the amount is 5 parts by mass or more, photocurability is improved and pattern formation is improved by alkaline development after irradiation with active energy rays, which is preferable.
• the amount is 100 parts by mass or less, the solubility in an alkaline aqueous solution is good and the coating film is less likely to become brittle, which is preferable.
• (C) Photopolymerization initiator In the photosensitive resin composition of the present invention, a known and commonly used photopolymerization initiator (C) can be used.
• the photopolymerization initiator may be used alone or in combination of two or more types, but one having a photobleaching effect is preferable.
• the photobleaching effect is when a photopolymerization initiator absorbs light and generates radicals, which cleaves and breaks the conjugated bonds in the molecules, which reduces the absorbance in the ultraviolet region and prevents ultraviolet light from passing inside. It is to disappear.
• Preferred examples of the photopolymerization initiator (C) having a photobleaching effect include monoacylphosphine oxide photopolymerization initiators and bisacylphosphine oxide photopolymerization initiators.
• monoacylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• Examples include trimethylbenzoyl phenylphosphinic acid methyl ester, 2-methylbenzoyl diphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester. Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is easily available.
• bisacylphosphine oxide photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, ,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2, 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-tri
• the amount of the photopolymerization initiator is the sum of (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) a carboxyl group-containing urethane resin having no aromatic ring.
• Amount 100 parts by mass (if the photosensitive resin composition of the present invention contains (G) another carboxyl group-containing resin described below, the total amount including components (A), (F), and (G)): 100 parts by mass
• the amount is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight. If the blending amount is within the above range, the photocurability of the coating film will be good, and pattern formation after exposure and development will also be good.
• Epoxy resin In the photosensitive resin composition of the present invention, a known and commonly used epoxy resin (D) can be used to improve the heat resistance of the cured product. (D) The epoxy resin may be used alone or as a mixture of two or more.
• epoxy resins include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, and phenol Novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group containing Examples include epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin, ⁇ -caprolactone-modified epoxy resin, etc. . Further, in order to impart flame retardancy, a material having a halogen such as chlorine or bromine or an atom such as phosphorus introduced into its structure may be used.
• the blending amount of (D) epoxy resin in the photosensitive resin composition of the present invention is as follows: (A) carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate; and (F) an epoxy resin having an aromatic ring. 100 parts by mass of the total amount of carboxyl group-containing urethane resin (in the case where the photosensitive resin composition of the present invention contains other carboxyl group-containing resin (G) described below, component (A), component (F), and component (G)) It is desirable that the proportion is 5 to 150 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the total amount including components (). If the amount is within the above range, the solder heat resistance of the cured coating film of the photosensitive resin composition will be good, and various properties, especially electrical insulation, will also be improved when used as an insulating protective film for printed wiring boards. Becomes good.
• (E) Colorant exhibiting white color is used to whiten the cured coating film, and includes titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, and lead white. , zinc sulfide, lead titanate, barium titanate, and the like.
• the (E) white coloring agent of the present invention it is preferable to use titanium oxide because it has a high effect of suppressing discoloration due to heat.
• titanium oxide manufactured by the sulfuric acid method or chlorine method rutile-type titanium oxide, anatase-type titanium oxide, or titanium oxide that has been surface-treated with a hydrous metal oxide or an organic compound can be used. can.
• rutile titanium oxide is preferred.
• Anatase titanium oxide is often used because it has higher whiteness than rutile titanium oxide.
• anatase titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the curable resin composition.
• rutile type titanium oxide has slightly inferior whiteness compared to anatase type titanium oxide, it has almost no photoactivity, so it is possible to obtain a stable solder resist film.
• known rutile-type titanium oxides can be used as the rutile-type titanium oxide.
• TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industries Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd. CR-50, CR-60, CR-90, KR-270, KR-310, KR-380 manufactured by Titanium Kogyo Co., Ltd., etc. can be used.
• rutile-type titanium oxides it is particularly preferable to use titanium oxide whose surface has been treated with hydrated alumina or aluminum hydroxide from the viewpoint of dispersibility in the composition and storage stability.
• the blending amount of (E) the colorant exhibiting white color is determined by the amount of (A) the carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) the aromatic ring.
• 100 parts by mass of the carboxyl group-containing urethane resin if the photosensitive resin composition of the present invention contains another carboxyl group-containing resin (G), which will be described later
• the (A) component, the (F) component The amount is preferably in the range of 50 to 500 parts by weight, preferably 100 to 450 parts by weight, and more preferably 150 to 450 parts by weight, based on 100 parts by weight of the total amount including component (G).
• the photosensitive resin composition of the present invention can suppress discoloration due to heat and can obtain a coating film with high reflectance.
• the carboxyl group-containing urethane resin having no aromatic ring preferably contains a compound having a non-aromatic isocyanate group, a compound having two or more alcoholic hydroxyl groups in one molecule, and a compound having two or more alcoholic hydroxyl groups in one molecule.
• Examples include carboxyl group-containing urethane resins obtained by reacting a compound having one alcoholic hydroxyl group with a compound having one alcoholic hydroxyl group.
• Carboxyl group-containing urethane resin that does not have an aromatic ring is a diol (b) that has an aromatic ring or a polycarbonate diol (c-2) that contains repeating units derived from an alicyclic diol as a constituent unit.
• polycarbonate diol (c-3) which contains repeating units derived from both linear aliphatic diols and alicyclic diols as constituent units, but otherwise has (A) an aromatic ring. It can be synthesized in the same manner as carboxyl group-containing urethane resins derived from diols and aliphatic diisocyanates. Examples of the compound having a non-aromatic isocyanate group include polyisocyanates having no aromatic ring, and specifically, polyisocyanate (a) of the above-mentioned aliphatic diisocyanate.
• polyisocyanate is not limited to polyisocyanate (a) which is an aliphatic diisocyanate as long as it does not have an aromatic ring, and examples thereof include isophorone diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, and cyclohexane-1,4-dimethylene diisocyanate.
• Polyisocyanates such as methylene diisocyanate can also be used.
• the compound having two or more alcoholic hydroxyl groups in one molecule polycarbonate diol, a carboxyl group, and a compound having two or more alcoholic hydroxyl groups are preferable.
• polycarbonate diol polycarbonate diol (c-1) containing as a constituent unit a repeating unit derived from one or more types of linear aliphatic diol is preferred, and specific examples are as described above.
• the compound having a carboxyl group and two or more alcoholic hydroxyl groups dimethylolalkanoic acid (d) is preferable, and specific examples thereof are as described above.
• the compound having one alcoholic hydroxyl group in one molecule the above-mentioned monohydroxyl compound (e) is preferable, and specific examples are as described above.
• a carboxyl group-containing urethane resin that does not have an aromatic ring a polycarbonate that contains a polyisocyanate that does not have an aromatic ring and a repeating unit derived from one or more linear aliphatic diols as a constituent unit.
• a carboxyl group-containing urethane resin obtained by reacting diol (c-1), dimethylolalkanoic acid (d), and monohydroxyl compound (e) discoloration due to heat can be suppressed, This is preferable because it has the effect of obtaining a coating film with higher reflectance.
• the blending amount of (F) a carboxyl group-containing urethane resin that does not have an aromatic ring is the same as that of (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate.
• the photosensitive resin composition of the present invention includes (G) another carboxyl group-containing resin, (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) a carboxyl group-containing urethane resin having an aromatic ring.
• Carboxyl group-containing resins other than carboxyl group-containing urethane resins may also be included.
• the blending amount of (G) other carboxyl group-containing resin in the photosensitive resin composition of the present invention is (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) an aromatic ring.
• the amount is 50 parts by mass or less, preferably 20 parts by mass or less, in 100 parts by mass of the total amount including the carboxyl group-containing urethane resin without the carboxyl group-containing resin and (G) other carboxyl group-containing resin. If the amount is within this range, the effects due to (G) other carboxyl group-containing resins can also be obtained without impairing the effects of the photosensitive resin composition of the present invention.
• (G) As the other carboxyl group-containing resin, known and commonly used carboxyl group-containing resins can be used, but by using them together with the carboxyl group-containing urethane resins of components (A) and (F), The following carboxyl group-containing resins are preferred because they can suppress discoloration and provide a cured coating film with high reflectance.
• a carboxyl group-containing resin either an oligomer or a polymer. Note that lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.
• thermosetting catalyst in the photosensitive resin composition of the present invention, can be blended in order to accelerate the thermosetting reaction and further improve properties such as adhesion, chemical resistance, and heat resistance.
• thermosetting catalysts include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
• 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N -Amine compounds such as -dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
• commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all brand names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U manufactured by San-Apro Co., Ltd.
• -CAT registered trademark
• U-CAT3502T all are trade names of dimethylamine blocked isocyanate compounds
• DBU DBU
• DBN DBN
• U-CATSA102 U-CAT5002
• U-CAT5002 all are bicyclic amidine compounds and their salts
• thermosetting catalyst for epoxy resins or oxetane compounds, or any catalyst that promotes the reaction between epoxy groups and/or oxetanyl groups and carboxyl groups, and may be used alone or in combination of two or more.
• thermosetting catalysts can be used alone or in combination of two or more, and the amount blended is sufficient in a usual quantitative ratio, for example, from (A) diol having an aromatic ring and aliphatic diisocyanate.
• the total amount of the derived carboxyl group-containing urethane resin and (F) the carboxyl group-containing urethane resin having no aromatic ring is 100 parts by mass (the photosensitive resin composition of the present invention does not contain (G) other carboxyl group-containing resin). is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the total amount including component (A), component (F), and component (G). It is 0 parts by mass.
• an organic solvent is used to easily dissolve or disperse each component (A) to (F) and (G), or to adjust the viscosity to a suitable level for coating. can do.
• organic solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, Methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, ace
• the photosensitive resin composition of the present invention may contain a known and commonly used mercapto compound or adhesion promoter, if necessary, in order to improve adhesion to a base material such as polyimide.
• mercapto compounds include 2-mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1,2,4-triazole, and 3-mercapto.
• Examples include mercapto group-containing silane coupling agents such as -propyltrimethoxysilane.
• adhesion promoter examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and vinyltriazine. These may be used alone or in combination of two or more.
• the blending amount is 100 parts by mass (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) a carboxyl group-containing urethane resin having no aromatic ring.
• the photosensitive resin composition of the invention contains (G) another carboxyl group-containing resin, 10 parts by mass per 100 parts by mass of the total amount including components (A), (F), and (G).
• the following ranges are appropriate. When the amount of these compounds is within the above range, these compounds do not react more than necessary with the epoxy groups of the epoxy resin (D) necessary for the crosslinking reaction, and the crosslinking density does not decrease.
• the curable resin composition of the present invention contains ( 1) A radical scavenger that nullifies the generated radicals and/or (2) An oxidizing agent such as a peroxide decomposer that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. Inhibitors can be added.
• the radical scavenger may be commercially available, for example, Adekastab (registered trademark) AO-30, Adekastab AO-330, Adekastab AO-20, Adekastab LA-77, Adekastab LA-57, Adekastab LA-67, Adekastab LA-68, ADEKA STAB LA-87 (all manufactured by ADEKA Co., Ltd.), Irganox (registered trademark) 1010, Irganox 1035, Irganox 1076, Irganox 1135, Tinuvin (registered trademark) 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Examples include Tinuvin 292 and Tinuvin 5100 (both manufactured by BASF Japan Co., Ltd.).
• antioxidants that act as peroxide decomposers include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralaurylthiopropionate, dilaurylthiodipropionate, and distearyl 3,3'-thiodipropionate.
• sulfur-based compounds such as pionate.
• the peroxide decomposer may be a commercially available one, such as ADEKA STAB TPP (manufactured by ADEKA Co., Ltd.), ADEKA STAB AO-412S (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) TPS (Sumitomo Chemical Co., Ltd.). ) etc.
• One kind of antioxidant can be used alone or two or more kinds can be used in combination.
• an ultraviolet absorber can be used in addition to an antioxidant.
• ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
• benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. , 4-dihydroxybenzophenone and the like.
• benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
• benzotriazole derivatives include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)enzotriazole, 2-(2'- Hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, Examples include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole.
• triazine derivatives examples include hydroxyphenyltriazine, bisethylhexyloxyphenolmethoxyphenyltriazine, and the like.
• the ultraviolet absorber may be a commercially available product, such as Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Examples include Tinuvin 479 (both manufactured by BASF Japan Co., Ltd.).
• the photosensitive resin composition of the present invention may further contain at least one filler selected from the group consisting of inorganic fillers and organic fillers, if necessary, for the purpose of improving properties such as adhesion, hardness, and heat resistance. It can contain.
• inorganic fillers include barium sulfate, calcium carbonate, silicon oxide, amorphous silica, talc, clay, hydrotalcite, mica powder, etc.
• organic fillers include silicon powder, nylon powder, fluorine powder, etc. .
• silica is particularly excellent in low hygroscopicity and low volume expansion.
• the silica may be fused or crystalline, and may be a mixture thereof, but silica surface-treated with a coupling agent or the like is particularly preferred since it can improve electrical insulation. It is desirable that the filler has an average particle size of 25 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 3 ⁇ m or less.
• the blending amount of these inorganic and/or organic fillers is determined between (A) a carboxyl group-containing urethane resin derived from a diol having an aromatic ring and an aliphatic diisocyanate, and (F) a carboxyl group-containing urethane resin having no aromatic ring.
• Total amount 100 parts by mass (if the photosensitive resin composition of the present invention contains (G) another carboxyl group-containing resin, the total amount including components (A), (F), and (G)): 100 parts by mass 150 parts by weight or less per part), preferably 50 parts by weight or less.
• the amount of the filler is in the above ratio, the cured coating film will have good bending durability.
• additives other than the above-mentioned components may be added to the photosensitive resin composition of the present invention as long as the effects of the present invention are not impaired.
• Additives include known and commonly used thickeners such as organic bentonite and montmorillonite, antifoaming agents and/or leveling agents such as silicone-based, fluorine-based, and polymer-based agents, and fibers such as glass fiber, carbon fiber, and boron nitride fiber. Examples include reinforcing materials.
• a known and commonly used thermal polymerization inhibitor such as an imidazole type, a thiazole type, or a triazole type, a dispersant, an antifoaming agent, a plasticizer, a foaming agent, a flame retardant, an antistatic agent, Antiaging agents, antibacterial and antifungal agents, etc. can be added.
• a silane coupling agent such as an imidazole type, a thiazole type, or a triazole type
• a dispersant such as an imidazole type, a thiazole type, or a triazole type
• an antifoaming agent such as an imidazole type, a thiazole type, or a triazole type
• a dispersant such as an imidazole type, a thiazole type, or a triazole type
• an antifoaming agent such as an imidazole type, a thiazole type, or a triazole type
• a thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of a polymerizable compound.
• the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, chloranil, Naphthylamine, ⁇ -naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4- Examples include toluidine, methylene blue, a reaction product of copper with an organic chelating agent, methyl salicylate, phenothiazine, a nitroso compound, and a chelate of a nitroso compound with Al.
• the photosensitive resin composition having the above composition can be obtained by dissolving or dispersing each of the above-mentioned components or, if necessary, the components described below using a mixer, such as a disper, kneader, three-roll mill, bead mill, etc. It can be obtained by At that time, a solvent inert to epoxy groups and phenolic hydroxyl groups may be used. As such an inert solvent, the above-mentioned organic solvents are preferable.
• the photosensitive resin composition of the present invention can be applied to printed circuit boards by various conventionally known methods such as curtain coating, roll coating, spray coating, and dip coating, as well as by various methods such as dry film or prepreg. It can be used in any form and purpose. Various solvents can be used depending on the method and purpose of use, and in some cases, not only good solvents but also poor solvents may be used.
• the photosensitive resin composition of the present invention can be adjusted to have a viscosity suitable for the coating method using, for example, the organic solvent, and applied onto a substrate by dip coating, flow coating, roll coating, bar coater, screen printing, etc.
• a tack-free coating film can be formed by coating by a method such as a curtain coating method and drying (temporary drying) by volatilizing the organic solvent contained in the composition at a temperature of about 60 to 100°C. Then, using a contact method (or non-contact method), the pattern is selectively exposed to active energy rays through a patterned photomask or directly pattern-exposed using a laser direct exposure machine, and the unexposed areas are developed with a dilute alkaline aqueous solution to form a resist pattern.
• the cyclic (thio)ether group of the thermosetting component of A white cured coating film is formed which achieves a high level of flexibility and high reflectance in a well-balanced manner, and which exhibits little decline in reflectance over time.
• Examples of the above-mentioned base materials include glass substrates, printed wiring boards with circuits formed in advance, flexible printed wiring boards, paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/ Copper-clad laminates of all grades (FR-4, etc.) using composite materials such as nonwoven fabric - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. , polyimide film, PET film, ceramic substrate, wafer plate, etc. can be used.
• Volatile drying or thermal curing (post-curing) performed after applying the photosensitive resin composition of the present invention may be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (equipped with an air heating type heat source using steam). This can be carried out using a method in which the hot air in the dryer is brought into countercurrent contact using a dryer, or a method in which the hot air is blown onto the support from a nozzle.
• the exposure machines used for the above-mentioned active energy ray irradiation include direct writing equipment (for example, laser direct imaging equipment that draws images directly with a laser using CAD data from a computer), exposure machines equipped with metal halide lamps, and (ultra) high-pressure mercury lamps.
• direct writing equipment for example, laser direct imaging equipment that draws images directly with a laser using CAD data from a computer
• exposure machines equipped with metal halide lamps and (ultra) high-pressure mercury lamps.
• An exposure machine equipped with a mercury short arc lamp, an exposure machine equipped with a mercury short arc lamp, or a direct writing device using an ultraviolet lamp such as an (ultra) high-pressure mercury lamp can be used.
• the active energy ray either a gas laser or a solid laser may be used as long as a laser beam having a maximum wavelength in the range of 350 to 450 nm is used.
• the exposure amount varies depending on the film thickness, etc., but can generally be in the range of 5 to 800 mJ/cm 2 , preferably 5 to 500 mJ/cm 2 .
• the direct drawing device for example, one manufactured by Nippon Orbotech Co., Ltd. or the like can be used, and any device that oscillates a laser beam with a maximum wavelength of 350 to 450 nm may be used.
• the above development method may be a dipping method, a shower method, a spray method, a brush method, etc.
• the developer may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc.
• Alkaline aqueous solutions such as ammonia and amines can be used.
• the photosensitive resin composition of the present invention can be formed by applying the photosensitive resin composition to a film (first film) such as polyethylene terephthalate in advance and drying it. It can also be used in the form of a dry film with layers. The case where the photosensitive resin composition of the present invention is used as a dry film is shown below.
• the dry film has a structure in which a first film, a resin layer, and an optionally peelable second film are laminated in this order.
• This resin layer is, for example, a layer obtained by applying a photosensitive resin composition to the first film or the second film and drying it. After forming a resin layer on the first film, a second film is laminated thereon, or a resin layer is formed on the second film and this laminate is laminated on the first film to form a dry film. can get.
• thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
• the resin layer is formed by uniformly applying a photosensitive resin composition to the first film or the second film to a thickness of 10 to 150 ⁇ m using a blade coater, lip coater, comma coater, film coater, etc. and drying it.
• a polyethylene film, a polypropylene film, etc. can be used, but it is preferable that the adhesive force with the resin layer is smaller than that of the first film.
• a protective film permanent protective film
• the second film is peeled off, the resin layer and the base material on which the circuit is formed are stacked, and the circuit is pasted using a laminator or the like.
• a resin layer is formed on the base material.
• a cured coating film can be formed by exposing, developing, and heating and curing the formed resin layer in the same manner as described above.
• the first film may be peeled off either before or after exposure.
• This carboxyl group-containing resin solution has a solid content acid value of 120 mgKOH/g, a solid content of 50%, and a molecular weight of 20,000. Furthermore, the mass average molecular weight of the obtained carboxyl group-containing resin is based on the pump LC-6AD manufactured by Shimadzu Corporation and the column Shodex (registered trademark) KF-804, KF-803, KF-802 manufactured by Showa Denko Co., Ltd. It was measured by high performance liquid chromatography connected in triplicate.
• Rosin-based flux was applied to each evaluation board obtained above, and the board was immersed in a solder bath preset at 260° C. for 10 seconds. Next, after cleaning the flux with denatured alcohol, blistering and peeling of the cured coating film was visually evaluated.
• the evaluation criteria for heat resistance were as follows. ⁇ : There was no blistering or peeling in the cured coating film. ⁇ : There was blistering and peeling in the cured coating film.
• the reflectance at 450 nm of the cured coating film formed on each of the evaluation substrates obtained above was measured using a spectrophotometer (manufactured by Konica Minolta, Inc., model number: CM-5). The evaluation results are shown in the "after curing" row in Table 1.
• the evaluation criteria for reflectance were as follows. ⁇ : Reflectance was 90% or more. ⁇ : Reflectance was 86% or more and less than 90%. ⁇ : Reflectance was less than 86%.
• the above evaluation substrate was subjected to a reflow process once using a reflow apparatus (NIS-20-82C manufactured by Atec Techtron Co., Ltd.) at a maximum temperature of 260° C. for 10 seconds. Thereafter, the reflectance was measured and evaluated using the same criteria as in the above evaluation. The evaluation results are shown in the "after reflow" row in Table 1.
• each photosensitive resin composition was applied onto a copper foil having a thickness of 18 ⁇ m to form a coating film having a thickness of 30 ⁇ m after drying. After that, after drying for 30 minutes in a hot air circulation drying oven at 80°C, a solid image was printed with an exposure dose of 900 mJ/cm 2 using an exposure device equipped with a metal halide lamp (HMW-680-GW20: manufactured by Oak Seisakusho Co., Ltd.). It was exposed to light and developed (30° C., 0.2 MPa, 1 wt% Na 2 CO 3 aqueous solution) for 60 seconds.
• HMW-680-GW20 metal halide lamp
• the resulting coating film formed on the copper foil was cut into 5 cm x 5 cm pieces along with the copper foil, heated and cured at 150° C. for 60 minutes in a hot air circulation drying oven, and then returned to room temperature.
• a sample 5 x 5 cm piece of cured coating film with copper foil (hereinafter referred to as a sample) on a workbench for 1 hour.
• the heights of the four ends of the sample from the surface of the workbench were measured with a ruler and totaled.
• a similar test was conducted three times for each sample, and the average value of the three tests was determined.
• the evaluation results are shown in the "after curing" row in Table 1.
• the evaluation criteria for warpage were as follows.
• ⁇ Total height was 40 mm or more and less than 60 mm. ⁇ : The total height was 60 mm or more. Further, the above-mentioned evaluation substrate was subjected to a reflow process once using a reflow apparatus (NIS-20-82C manufactured by Atec Techtron) at a maximum temperature of 260° C. for 10 seconds. Thereafter, the reflectance was measured and evaluated using the same criteria as in the above evaluation. The evaluation results are shown in the "after reflow" row in Table 1.

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