WO2011125604A1 - 硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 - Google Patents
硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 Download PDFInfo
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- WO2011125604A1 WO2011125604A1 PCT/JP2011/057612 JP2011057612W WO2011125604A1 WO 2011125604 A1 WO2011125604 A1 WO 2011125604A1 JP 2011057612 W JP2011057612 W JP 2011057612W WO 2011125604 A1 WO2011125604 A1 WO 2011125604A1
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- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
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- 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
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- 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
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- 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
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- 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
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
Definitions
- the present invention relates to a flame-retardant curable resin composition, and particularly to a curable resin composition capable of forming a coating film having low warpage and excellent flame retardancy.
- the present invention also relates to a dry film using such a curable resin composition and a printed wiring board having such a cured coating film.
- FPC printed wiring boards and flexible wiring boards
- the FPC since the FPC is usually made of a polyimide substrate, it is a thin film unlike a printed wiring board of a glass epoxy substrate.
- the coating film to be applied has the same film thickness on both the printed wiring board and the FPC, in the case of a thin-film FPC, the burden of flame retardancy on the coating film becomes relatively large.
- Patent Document 1 discloses (a) a binder polymer, (b) a halogenated aromatic ring such as a bromophenyl group, and a polymerizable ethylenic group such as a (meth) acryloyl group. Flame retardant for FPC containing a photopolymerizable compound having a saturated bond in the molecule, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus compound having a phosphorus atom in the molecule.
- a photosensitive resin composition has been proposed.
- halogen compound such as a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring
- FPCs equipped with light emitting diodes have demands for high reflectivity, bending resistance, and resolution.
- a solder resist that sufficiently satisfies the requirements cannot be obtained, for example, bending resistance and resolution are lowered.
- the present invention has been made to solve the above-described problems of the prior art, and its main purpose is to achieve halogen-free flame retardancy and to achieve high resolution and low warpage. It is providing the curable resin composition which can form a reflective white coating film layer. Furthermore, an object of the present invention is to provide a dry film and a cured coating film having low warpage and excellent flame retardancy, and a printed wiring having a flame retardant coating film having such excellent characteristics by using such a curable resin composition. To provide a board.
- a curable resin composition comprising a carboxyl group-containing resin, titanium oxide, and a phosphinic acid metal salt.
- the curable resin composition characterized by including a thermosetting resin further is provided.
- the carboxyl group-containing resin is a carboxylic acid resin having a urethane skeleton.
- coating and drying the said curable resin composition to a film is provided. Furthermore, according to this invention, the cured coating film obtained by heat-curing or photocuring or photocuring and thermosetting the dry film formed by apply
- the curable resin composition or the dry film obtained by applying and drying the curable resin composition on a film is cured by heat curing or photocuring or photocuring and thermosetting.
- a printed wiring board having a coating is also provided.
- the curable resin composition of the present invention since it contains a carboxyl group-containing resin, titanium oxide, and a phosphinic acid metal salt, it has a non-halogen composition with low environmental impact, excellent flame retardancy, and resolution. A coating film excellent in low warpage can be formed. Moreover, since the coating film formed here contains titanium oxide which is a white pigment, it has a high whiteness and is highly reflective and useful for a backlight of a liquid crystal panel.
- the curable resin composition containing a carboxyl group-containing resin, titanium oxide, and phosphinic acid metal salt has high whiteness and high reflectance.
- good resolution can be obtained by improving the developing resistance.
- the fact that such an effect can be obtained by using the combination of the three components is a surprising effect that is not expected from the prior art.
- each component of the curable resin composition of the present invention will be described in detail.
- carboxyl group-containing resin various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting a crosslinking reaction, adhesion and alkali developability can be used.
- a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance as a photosensitive composition for performing alkali development.
- the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
- the photosensitivity having a plurality of ethylenically unsaturated groups in the molecule described later. It is necessary to use a compound (photopolymerizable monomer) in combination.
- carboxyl group-containing resin examples include the following compounds (any of oligomers and polymers) are preferable.
- a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
- Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, polyethers Diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and optionally one alcoholic hydroxyl group A carboxyl group-containing urethane resin obtained by a polyaddition reaction with a compound having an acid.
- Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such
- Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
- bisphenol A type epoxy resin hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
- one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
- a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
- a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
- a dicarboxylic acid such as adipic acid, phthalic acid, hexahydrophthalic acid or the like is reacted with a bifunctional oxetane resin as described later, and the resulting primary hydroxyl group has phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride.
- a carboxyl group-containing polyester resin to which a dibasic acid anhydride such as
- An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
- one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and ⁇ -methylglycidyl (meth) acrylate
- a carboxyl group-containing photosensitive resin obtained by adding a compound having the following.
- (meth) acrylate is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
- the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
- the acid value of the carboxyl group-containing resin is desirably in the range of 20 to 120 mgKOH / g, more preferably in the range of 40 to 100 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 20 mgKOH / g, the adhesion of the coating film cannot be obtained, or alkali development becomes difficult in the case of the photocurable resin composition.
- the acid value exceeds 120 mgKOH / g the warp of the cured coating film becomes very large, and it is not suitable as the intended coating agent for FPC.
- a photocurable resin composition it is not preferable because it is dissolved and peeled off with a developer without distinction between an exposed portion and an unexposed portion, and it becomes difficult to draw a normal resist pattern.
- the preferred carboxyl group-containing resin those having an acid value of 20 to 60 mgKOH / g in the case of a thermosetting resin composition are preferable from the viewpoint of adhesion and low warpage. It is preferable to use a resin having an acid value of 60 to 120 mgKOH / g in combination with the resin.
- a urethane group-containing carboxyl group-containing polyurethane is preferable from the viewpoint of adhesion and low warpage, and as the high acid value resin, it is difficult to be a carboxyl group-containing resin having an aromatic ring. It is preferable from the viewpoints of flammability, heat resistance, and developability. If this relationship is reversed, in the case of a photocurable resin composition that requires development, poor development occurs, resulting in poor low warpage and bendability.
- Particularly preferred urethane resins are those using polyester polyol, polycarbonate diol, polyether and aliphatic and alicyclic isocyanates as raw materials.
- a resin having a biphenyl novolac structure is preferable from the viewpoint of flame retardancy and heat resistance.
- a photoreactive group and a thermosetting reactive group exist independently. It is preferable because it has little curing shrinkage and is excellent in low warpage and folding resistance.
- the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated, and the storage stability of the composition may be inferior.
- the amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the total composition.
- the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable.
- the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.
- These carboxyl group-containing resins can be used without being limited to those listed above, and can be used by mixing one kind or plural kinds.
- titanium oxide used in the curable resin composition of the present invention a sulfuric acid method, a chlorine method, a rutile type, anatase type, a surface treatment with a hydrated metal oxide, or a surface treatment with an organic compound was performed. Titanium oxide or the like can be used. Among these titanium oxides, rutile type titanium oxide is more preferable. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase-type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the photocurable resin composition. On the other hand, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable coating film can be obtained.
- rutile type titanium oxide As the rutile type titanium oxide, a known rutile type can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd., CR-50, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used. Among these rutile titanium oxides, it is particularly preferable to use titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide from the viewpoints of dispersibility, storage stability, and flame retardancy.
- the compounding amount of such titanium oxide is 1 to 500 parts by mass, preferably 5 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the blending amount is less than 1 part by mass, the low warpage property and flame retardancy of the cured coating film cannot be obtained sufficiently, which is not preferable.
- the amount exceeds 500 parts by mass, it is difficult to obtain sufficient flexibility of the cured coating film, which is not preferable.
- the curable resin composition of the present invention is characterized by containing a phosphinic acid metal salt.
- a phosphinic acid metal salt By using a phosphinic acid metal salt, both the flexibility and flame retardancy of the cured coating film can be achieved. Moreover, since the phosphinic acid metal salt is not dissolved in the coating film but is dispersed, good resolution can be obtained.
- the phosphinic acid metal salt a compound represented by the following general formula (I) can be preferably used.
- R 1 and R 2 each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms
- M represents calcium, aluminum or zinc
- phosphinic acid metal salt having excellent heat resistance, it is possible to suppress the bleedout of the flame retardant in the heat press during mounting.
- phosphinic acid metal salts include Clariant's EXOLIT OP 1230, EXOLIT OP 930, and EXOLIT OP 935.
- the compounding amount of these metal phosphinates is desirably in the range of 1 to 100 parts by weight, preferably 3 to 80 parts by weight, more preferably 5 to 70 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. .
- thermosetting resin composition When the resin composition of the present invention is composed into a thermosetting resin composition or a photocurable thermosetting resin composition, the properties such as heat resistance and insulation reliability of the cured coating film are improved.
- thermosetting component capable of reacting with the carboxyl group of the carboxyl group-containing resin can be blended.
- thermosetting component for the curable resin composition of the present invention is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule. It is. Among them, a bifunctional epoxy resin is preferable, and diisocyanate and its bifunctional blocked isocyanate can also be used.
- thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule.
- a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound
- a compound having a plurality of oxetanyl groups in the molecule that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule
- the compound which has this, ie, an episulfide resin etc. are mentioned.
- Examples of the polyfunctional epoxy compound include jER (registered trademark) 828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron (registered trademark) 840, Epicron 850, Epicron 1050, Epicron 1050, and Toto, manufactured by DIC Corporation.
- Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N.
- E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd.
- Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd.
- Type A epoxy resin jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd.
- Glycidylamine type epoxy resin Glycidylamine type epoxy resin
- Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Araldide CY175, CY179 manufactured by Ciba Japan (all trade names)
- Alicyclic epoxy resin YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc.
- Xylenol type or biphenol type epoxy resins or mixtures thereof bisphenol S type epoxy resins such as Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name); Japan epoxy resin Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by KK; tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan Co., Ltd.
- bisphenol S type epoxy resins such as Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name)
- Japan epoxy resin Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by KK
- tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Japan Co., Ltd.
- CTBN modified epoxy resin e.g., Tohto Kasei Co. YR-102, YR-450, etc.
- CTBN modified epoxy resin e.g., Tohto Kasei Co. YR-102, YR-450, etc.
- These epoxy resins can be used alone or in combination of two or more.
- novolak-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins or mixtures thereof are preferable, and more preferable epoxy resins are epoxy resins having a biphenyl novolak skeleton, Flame retardancy can be improved.
- Examples of commercially available products include NC-3000L, NC-3000, NC-3000H, NC-3100 manufactured by Nippon Kayaku Co., Ltd.
- polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl)
- polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene
- Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
- the amount of the thermosetting component such as a compound having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. More preferably, it is in the range of 0.5 to 2.0 equivalents.
- the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.3, the crosslinking reaction with the carboxyl group-containing resin is reduced, so that heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.
- thermosetting component such as a compound having a plurality of cyclic (thio) ether groups in the molecule
- thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
- Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT (registered trademark) 3503N, U-CAT3502T (both dimethyl) Trade names of amine blocked isocyanate compounds), DBU, D
- thermosetting catalyst for epoxy resins or oxetane compounds or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used.
- the amount of these thermosetting catalysts to be blended is a normal quantitative ratio.
- the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the carboxyl group-containing resin. Part by mass.
- a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the curable resin composition of the present invention.
- Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule.
- the compound which has, ie, a blocked isocyanate compound, etc. are mentioned.
- polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
- aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
- alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
- adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.
- the blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.
- the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type.
- aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.
- Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
- isocyanate blocking agent for example, phenol blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxi
- the blocked isocyanate compounds may be commercially available, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062.
- the compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
- the compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 50 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. Proportion is appropriate. When the blending amount exceeds 50 parts by mass, storage stability is lowered, which is not preferable. Particularly preferred is the combined use with an epoxy resin having a biphenyl novolak skeleton, and the blending amount at that time is 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the curable resin composition of the present invention may be used in combination with a phosphorus compound other than the phosphinic acid metal salt for the purpose of further improving the flame retardancy.
- a phosphorus compound other than the phosphinic acid metal salt those conventionally known as organophosphorus flame retardants can be used.
- Examples of phosphorus compounds other than the particularly preferred phosphinic acid metal salts used in the present invention include (1) those having an acrylate group as a reactive group, (2) those having a phenolic hydroxyl group, (3) oligomers or polymers, and (4) Phenoxyphosphazene oligomer is mentioned.
- Phosphorus compound having acrylate group has a phosphorus element and is preferably a compound containing a plurality of (meth) acrylates in the molecule.
- Phosphorus element-containing acrylate has a phosphorus element and is preferably a compound containing a plurality of (meth) acrylates in the molecule.
- Examples thereof include compounds in which R 3 and R 4 are hydrogen atoms and R 5 is an acrylate derivative.
- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is used as a known and commonly used compound. It can be synthesized by a Michael addition reaction with a polyfunctional acrylate monomer.
- Examples of the known and commonly used acrylate monomers include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate.
- Polyhydric alcohols such as polyhydric acrylates such as these adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide additions of these phenols
- Polyacrylates such as products; and urethane acrylates of the above polyalcohols; Emissions diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.
- Phosphorus compound having a phenolic hydroxyl group The phosphorus compound having a phenolic hydroxyl group is highly hydrophobic and heat resistant, has no deterioration in electrical properties due to hydrolysis, and has high solder heat resistance. Also, as a suitable combination, by using an epoxy resin having a biphenyl skeleton or other epoxy resin as a thermosetting component, it reacts with the epoxy resin and is taken into the network, so that it does not bleed out after curing. Benefits are gained. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.
- Oligomers or Polymers Phosphorus compounds that are oligomers or polymers have the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleeding out after curing because of the large molecular weight.
- Commercial products include M-Ester-HP manufactured by Sanko Co., Ltd. and Byron 337 manufactured by Toyobo Co., Ltd.
- Phosphazene oligomer As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there is a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, tetramer, pentamer cyclic product, There are liquid and solid powders, both of which can be suitably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd.
- phosphorus compounds other than phosphinic acid metal salts can be used singly or in combination.
- the compounding amount of the phosphorus compound other than these phosphinic acid metal salts is suitably 150 parts by mass, particularly preferably 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the compounding amount of the phosphorus compound other than the phosphinic acid metal salt exceeds 150 parts by mass, the bleedout of the flame retardant and the bending characteristics of the cured coating film are deteriorated, which is not preferable.
- phosphorus compounds other than the above-mentioned phosphinic acid metal salts preferred are those having a reactive group, a phosphorus element-containing polymer, and a phosphazene oligomer.
- An element-containing acrylate compound is preferable from the viewpoint of bleeding out, and a phosphorus element-containing polyester polymer is preferable from the viewpoint of adhesion.
- phosphazene oligomer phenoxyphosphazene is preferable from the viewpoint of heat resistance, and further substituted phenoxyphosphazene having a substituent such as a cyano group or an alkyl group is preferable from the viewpoint of solubility.
- Aluminum hydroxide can be added to the curable resin composition of the present invention.
- the purpose of using aluminum hydroxide is not only to improve flame retardancy, but especially when it is made into a photocurable resin composition, the affinity and refractive index are close to that of a photosensitive resin, so that photocuring is efficient. In the point of progress
- the aluminum hydroxide used in the present invention a generally known aluminum hydroxide can be used.
- Commercially available products include Showa Denko's Heidilite series, HW, H21, H31, H32, H42M, H43M, and the like.
- the one where the particle size of aluminum hydroxide is fine is more effective for bending resistance, it is dispersed in advance to the primary particle size with a bead mill or the like together with a solvent or resin, and filtered to 3 ⁇ m or more, more preferably 1 ⁇ m. It is preferable to filter and select the above from the viewpoint of flame retardancy and bendability of the resulting cured film.
- the compounding amount of such aluminum hydroxide is 300 parts by mass, preferably 200 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 300 parts by mass, the bendability is deteriorated, which is not preferable.
- a photopolymerization initiator can be blended.
- Preferred initiators include one or more photopolymerizations selected from the group consisting of oxime ester photopolymerization initiators having an oxime ester group, ⁇ -aminoacetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators. Initiators can be used.
- oxime ester photopolymerization initiator commercially available products include CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, manufactured by Ciba Japan, N-1919, NCI-831 manufactured by ADEKA, and the like.
- numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.
- X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms),
- Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom, substituted with an alkyl group having 1 to 8 carbon atoms or a dialkylamino group.
- Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl
- X and Y are each a methyl group or an ethyl group
- Z is methyl or phenyl
- n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable.
- the blending amount of such an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photocurability is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when the amount exceeds 5 parts by mass, light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
- ⁇ -aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like.
- Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.
- acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
- Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.
- the blending amount of these ⁇ -aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5 to 10 parts by mass.
- examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the curable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds.
- a tertiary amine compound, a xanthone compound, etc. can be mentioned.
- benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- acetophenone compound examples include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
- anthraquinone compound examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
- thioxanthone compound examples include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
- ketal compound examples include acetophenone dimethyl ketal and benzyl dimethyl ketal.
- benzophenone compound examples include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
- the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc.
- 4,4′-dimethylaminobenzophenone Non-dimethylaminobenzophenone
- Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (die
- a dialkylamino group-containing coumarin compound ethyl 4-dimethylaminobenzoate (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), -Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Nippon Kayaku Co., Ltd.
- Kayacure DMBI 4-dimethylaminobenzoic acid 2 -Ethylhexyl (Esolol 507 manufactured by Van Dyk), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), and the like.
- thioxanthone compounds and tertiary amine compounds are preferred.
- the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability.
- thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
- the compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin.
- the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.
- a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
- dialkylaminobenzophenone compound 4,4′-diethylaminobenzophenone is preferable because of its low toxicity.
- the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself.
- a membrane can be provided.
- 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred.
- the blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.
- the compounding amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. If it exceeds 20 parts by mass, the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
- photopolymerization initiators can be used alone or as a mixture of two or more.
- the total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
- these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as needed to enhance surface photoreactivity, and changes the line shape and opening of the coating to vertical, tapered, or inversely tapered, as well as processing the line width and opening diameter Accuracy can be improved.
- acylphosphine oxide-based initiators are particularly preferable, and have the best light transmittance from the photobleaching performance, and have a phosphorus element to efficiently promote radical polymerization.
- the growth terminal is effective as a flame retardant imparting material because it has a structure containing phosphorus element.
- the oxime ester-based initiator has good initiator efficiency and is effective for improving sensitivity in a small amount. Therefore, the volume change due to outgassing during heat treatment after resist film formation is small, and it is effective in reducing the warpage of the film, which is preferable. .
- Particularly preferred is a combination of both.
- the photosensitive compound having a plurality of ethylenically unsaturated groups in the molecule used when the curable resin composition of the present invention is photocurable is photocured by irradiation with active energy rays and contains the carboxyl group.
- the resin is insolubilized in an alkaline aqueous solution, or helps insolubilization.
- polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate can be used, specifically, Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaery
- an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin.
- a polyfunctional epoxy resin such as a cresol novolac type epoxy resin
- a hydroxy acrylate such as pentaerythritol triacrylate
- a diisocyanate such as isophorone diisocyanate
- the blending amount of the photosensitive compound having a plurality of ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. Is the ratio.
- the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable.
- the amount exceeds 100 parts by mass the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.
- polyfunctional acrylates such as pentaerythritol, dipentaerythritol, trimethylolpropane and other polyols that are molecularly extended with ethylene oxide, propylene oxide and caprolactone, and bifunctional polyethers, polyesters and polycarbonates.
- the urethane acrylate is preferred.
- the curable resin composition of the present invention can contain a colorant.
- a colorant conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. Specific examples include those with the following color index numbers (CI; issued by The Society of Dyers and Colorists). However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
- Red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
- Monoazo Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
- Disazo Pigment Red 37, 38, 41.
- Monoazo lakes Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
- Benzimidazolone series Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
- Perylene series Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
- Diketopyrrolopyrrole series Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
- Condensed azo series Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
- Anthraquinone series Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
- Kinacridone series Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
- Blue colorant include phthalocyanine and anthraquinone, and pigments are compounds classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
- the dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used.
- a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Green colorant examples include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.
- Yellow colorant examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
- Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
- Isoindolinone type Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
- Condensed azo series Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
- Benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
- Monoazo Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
- Disazo Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
- a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
- the blending ratio of the colorant as described above is not particularly limited, but is preferably 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. is there.
- a filler can be blended as necessary in order to increase the physical strength of the coating film.
- publicly known and commonly used inorganic or organic fillers can be used.
- barium sulfate, spherical silica, hydrotalcite and talc are preferably used.
- metal hydroxides such as metal oxides and magnesium hydroxide can be used as extender pigment fillers.
- the amount of these fillers is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. .
- the blending amount of the filler exceeds 500 parts by mass, the viscosity of the curable resin composition becomes high and the printability is lowered, or the cured product becomes brittle.
- the curable resin composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. .
- organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether a
- a radical scavenger that invalidates the generated radical and / or the generated peroxide is decomposed into a harmless substance and no new radical is generated.
- An antioxidant such as a peroxide decomposer can be added.
- antioxidants include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4-pi Lysyl) - sebacate, and the like amine compounds such as
- the radical scavenger may be commercially available, for example, ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (trade name, manufactured by ADEKA Corporation), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade name, manufactured by Ciba Japan Co., Ltd.) and the like.
- antioxidant that acts as a peroxide decomposer
- phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′.
- -Sulfur compounds such as thiodipropionate.
- the peroxide decomposing agent may be commercially available, for example, ADK STAB TPP (trade name, manufactured by ADEKA Corporation), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Registered trademark) TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and the like.
- Said antioxidant can be used individually by 1 type or in combination of 2 or more types.
- an ultraviolet absorber can be used in addition to the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays.
- ultraviolet absorber examples 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-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned.
- benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.
- benzotriazole derivative examples include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like.
- the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.
- Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (manufactured by Ciba Japan, trade name) and the like.
- Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, stabilization of the cured film obtained from the curable resin composition of this invention is possible. I can plan.
- the resin composition of the present invention is composed as a photocurable resin composition or a photocurable thermosetting resin composition
- N phenylglycines known and commonly used as chain transfer agents in order to improve sensitivity Phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole and the like can be used.
- chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzene
- Polyfunctional mercaptan compounds can be used and are not particularly limited.
- Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythri Poly (mercaptoacetate) s of polyhydric alcohols such as tetrakis (mercaptoacetate) and dipent
- Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.), Karenz (registered trademark) MT-PE1, Karenz MT-BD1, Karenz-NR1 (above, manufactured by Showa Denko KK) and the like can be mentioned.
- heterocyclic compound having a mercapto group acting as a chain transfer agent examples include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto.
- heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the photocurable resin composition or the photocurable thermosetting resin composition mercaptobenzothiazole, 3-mercapto-4- Methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, and 1-phenyl-5-mercapto-1H-tetrazole are preferred.
- chain transfer agents can be used alone or in combination of two or more.
- an adhesion promoter can be used in order to improve adhesion between layers or adhesion between a coating layer and a substrate.
- Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.) 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzo Examples include triazole, amino group-containing benzotriazole, and silane coupling agent.
- the curable resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite, silicones, fluorines, and polymers. Conventional additives such as an antifoaming agent and / or a leveling agent, silane coupling agents such as imidazole, thiazole, and triazole, antioxidants, rust inhibitors, and the like can be blended.
- thermal polymerization inhibitors known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite, silicones, fluorines, and polymers.
- Conventional additives such as an antifoaming agent and / or a leveling agent, silane coupling agents such as imidazole, thiazole, and triazole, antioxidants, rust inhibitors, and the like can be blended.
- the thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization with time of the 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, phenothiazine, Chloranil, naphthylamine, ⁇ -naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
- the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method,
- a tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. and performing volatile drying (temporary drying) at a temperature of about 60 to 100 ° C.
- a resin insulation layer can be formed by apply
- the entire surface may be exposed with a conveyor type photocuring apparatus that irradiates active energy rays.
- a contact type or a non-contact type exposure is selectively carried out by an active energy ray through a photomask having a pattern formed thereon or directly by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt.
- the resist pattern is formed by development with a sodium carbonate aqueous solution.
- thermosetting resin composition or a photo-curable thermosetting resin composition for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and the molecule A cured coating film that has excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties due to the reaction of thermosetting components having multiple cyclic ether groups and / or cyclic thioether groups. Can be formed.
- the heat treatment causes heat-free radical polymerization of the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state during exposure.
- heat treatment may be performed depending on the purpose and application.
- Examples of the base material include printed circuit boards and flexible printed circuit boards that are pre-formed on circuit, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) using other materials such as epoxy, fluorine, polyethylene, PPO, cyanate ester, etc., and other polyimide films, PET films , Glass substrates, ceramic substrates, wafer plates and the like.
- Volatile drying performed after the application of the curable resin composition of the present invention is performed by hot air circulation drying furnace, IR furnace, hot plate, convection oven, etc. Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.
- the obtained coating film is exposed (irradiated with active energy rays).
- the exposed portion (the portion irradiated by the active energy ray) is cured.
- the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
- the laser light source of the direct drawing machine either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
- Exposure for image formation depends thickness, etc., but generally 20 ⁇ 2000mJ / cm 2, preferably be in the range of 20 ⁇ 1500mJ / cm 2.
- the developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
- the curable resin composition of the present invention is a dry film having a coating layer formed by applying and drying a curable resin composition in advance on a film of polyethylene terephthalate or the like in addition to a method of directly applying the curable resin composition to a substrate in a liquid state. It can also be used in the form.
- the case where the curable resin composition of this invention is used as a dry film is shown below.
- the dry film has a structure in which a carrier film, a coating layer, and a peelable cover film used as necessary are laminated in this order.
- the coating layer is a layer obtained by applying and drying the curable resin composition on a carrier film or a cover film. After forming the coating film layer on the carrier film, a dry film can be obtained by laminating the cover film thereon or forming the coating film layer on the cover film and laminating this laminate on the carrier film.
- thermoplastic film such as a polyester film having a thickness of 2 to 150 ⁇ m is used.
- the coating layer is formed by uniformly applying a curable resin composition to a carrier film or a cover film with a thickness of 10 to 150 ⁇ m using a blade coater, a lip coater, a comma coater, a film coater or the like, and then drying.
- cover film a polyethylene film, a polypropylene film, or the like can be used.
- a protective film permanent protective film
- peel off the cover film stack the coating layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc.
- a coating layer is formed on the formed substrate. If the formed coating layer is exposed, developed, and heat-cured in the same manner as described above, a cured coating layer can be formed.
- the carrier film may be peeled off either before exposure or after exposure.
- Synthesis example 1 Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having a plurality of alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (T5650J manufactured by Asahi Kasei Chemicals Corporation) , 3600 g (4.5 mol) of number average molecular weight 800), 814 g (5.5 mol) of dimethylolbutanoic acid, and 118 g (1.6 mol) of n-butanol as a molecular weight regulator (reaction terminator) did.
- T5650J manufactured by Asahi Kasei Chemicals Corporation
- Synthesis example 2 In a reaction vessel equipped with a stirrer, a thermometer and a condenser, 2400 g of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (manufactured by Asahi Kasei Chemicals Corporation, T5650J, number average molecular weight 800) (3 mol), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound were added.
- polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol manufactured by Asahi Kasei Chemicals Corporation, T5650J, number average molecular weight 800
- Synthesis example 4 A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
- the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
- a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 g of the resulting novolac-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C.
- this resin solution is referred to as Varnish A-5.
- Preparation of aluminum hydroxide slurry 700 g of aluminum hydroxide (Hidelite 42M manufactured by Showa Denko KK), 280 g of Calbitoacetate as a solvent, and 20 g of BYK-110 (wet dispersant manufactured by Big Chemie Japan Co., Ltd.) were mixed and stirred. Dispersion treatment was performed using 5 ⁇ m zirconia beads. This was repeated three times to produce an aluminum hydroxide slurry that passed through a 3 ⁇ m filter.
- thermosetting resin composition of Example 1 the obtained substrate was cured by heating at 150 ° C. for 60 minutes.
- photocurable thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2 the resist was obtained with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) mounted on a metal halide lamp on the obtained substrate.
- the pattern was exposed, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern.
- This substrate was cured by heating at 150 ° C. for 60 minutes.
- the obtained evaluation substrate was subjected to 180 ° folding several times by goby folding, and the occurrence of cracks in the coating film at that time was observed visually and with a 200-fold optical microscope, and the number of times that cracks did not occur was determined. evaluated.
- ⁇ Low warpage> A sample prepared in the same manner as the sample for evaluation of flexibility (folding resistance) was cut into 50 mm ⁇ 50 mm ⁇ , and the average value was obtained by measuring the four corners, and evaluated according to the following criteria.
- the curable resin composition of each example and comparative example was applied to the entire surface of a polyimide film having a thickness of 12.5 ⁇ m or 25 ⁇ m (Kapton 50H, 100H manufactured by Toray DuPont Co., Ltd.) and dried at 80 ° C. for 20 minutes. And allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. About the thermosetting resin composition of Example 1, the obtained board
- thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2 a solder resist was applied at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) mounted on a metal halide lamp on this substrate. The entire surface was exposed, and a 1% Na 2 CO 3 aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and heat cured at 150 ° C. for 60 minutes to obtain an evaluation sample.
- This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. The evaluation is shown in Table 2 with the results of each of the above evaluation tests, in which the flame retardancy test passed is indicated as VTM-0 and the failure is indicated as combustion.
- the curable resin compositions of Examples 1 to 6 have sufficient low warpage, flexibility and resolution, and also have excellent flame retardancy. I understand that.
- the curable resin composition of Comparative Example 1 that does not contain titanium oxide and Comparative Example 2 that does not contain phosphinic acid metal salt it is extremely possible to achieve a balance between low warpage, resolution and flame retardancy. I find it difficult.
- Examples 7-11 Each photocurable thermosetting resin composition of Examples 2 to 6 shown in Table 1 prepared by adding no silicone antifoaming agent was diluted with methyl ethyl ketone and applied onto a carrier film. Then, it was dried by heating to form a curable resin composition layer having a thickness of 20 ⁇ m, and a cover film was laminated thereon to obtain dry films of Examples 7 to 11, respectively. This dry film was bonded to the test substrate used in the above-described test method using a laminator to produce a test substrate. About the obtained test board
- the curable resin composition of the present invention since it contains a carboxyl group-containing resin, titanium oxide, and a phosphinic acid metal salt, it has a non-halogen composition with low environmental impact, excellent flame retardancy, and resolution. A highly reflective white coating film layer excellent in low warpage can be formed. Therefore, such a curable resin composition and its dry film can be suitably used for forming a cured film such as a flame-retardant solder resist such as a printed wiring board or a flexible wiring board. Moreover, since the coating film formed here has high whiteness and high reflectance, it is particularly useful for backlights of liquid crystal panels.
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Abstract
Description
一方、発光ダイオード(LED)を搭載するFPCにおいては、高反射率、耐折り曲げ性、解像性についての要求がある。しかし、高反射率を追求すると耐折り曲げ性、解像性が低下するなど、要求を充分に満たすソルダーレジストは得られない。
さらに本発明の目的は、かかる硬化性樹脂組成物を用いることによって、低反りで難燃性に優れたドライフィルム及び硬化塗膜、並びにこのような優れた特性の難燃性皮膜を有するプリント配線板を提供することにある。
本発明によれば、さらに熱硬化性樹脂を含むことを特徴とする硬化性樹脂組成物が提供される。
また、本発明によれば、上記カルボキシル基含有樹脂が、ウレタン骨格を有するカルボン酸樹脂であることを特徴とする硬化性樹脂組成物が提供される。
さらに本発明によれば、上記硬化性樹脂組成物又は上記硬化性樹脂組成物をフィルムに塗布乾燥してなるドライフィルムを、熱硬化又は光硬化あるいは光硬化及び熱硬化して得られる硬化塗膜が提供される。
また、ここで形成される塗膜は、白色顔料である酸化チタンを含有するため、白色度が高く、高反射率で液晶パネルのバックライト等に有用である。
以下、本発明の硬化性樹脂組成物の各構成成分について詳しく説明する。
(1)(メタ)アクリル酸等の不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。
また、上記カルボキシル基含有樹脂の酸価は、20~120mgKOH/gの範囲が望ましく、より好ましくは40~100mgKOH/gの範囲である。カルボキシル基含有樹脂の酸価が20mgKOH/g未満であると、塗膜の密着性が得られなかったり、光硬化性樹脂組成物の場合にはアルカリ現像が困難となる。
一方、酸価が120mgKOH/gを超えた場合には、硬化塗膜の反りが非常に大きくなり、目的としているFPC用のコーティング剤として不適当である。また、光硬化性樹脂組成物の場合には、露光部と未露光部の区別なく現像液で溶解剥離してしまい、正常なレジストパターンの描画が困難となるので好ましくない。好ましいカルボキシル基含有樹脂としては、熱硬化性樹脂組成物の場合には酸価が20~60mgKOH/gのものが、密着性と低反りの観点から好ましく、さらに現像性を付与する場合は、それら樹脂に酸価60~120mgKOH/gの樹脂を併用することが好ましい。
この関係が逆であると、現像を必要とする光硬化性樹脂組成物の場合には、現像不良が発生したり、低反りや折り曲げ性が劣る結果となる。
特に好ましいウレタン樹脂としては、ポリエステルポリオール、ポリカーボネートジオール、ポリエーテルと脂肪族及び脂環式イソシアネートを原料としたものが好ましい。また、芳香族環を有するカルボキシル基含有樹脂としては、ビフェニルノボラック構造を有するものが難燃性、耐熱性の観点から好ましい。
これらカルボキシル基含有樹脂は、前記列挙したものに限らず使用することができ、1種類でも複数種混合しても使用することができる
ブロック剤と反応し得るイソシアネート化合物としては、イソシアヌレート型、ビウレット型、アダクト型等が挙げられる。このイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート又は脂環式ポリイソシアネートが用いられる。芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネートの具体例としては、先に例示したような化合物が挙げられる。
リン元素含有アクリレートは、リン元素を有しており、分子中に複数の(メタ)アクリレートを含む化合物が良く、具体的には、前記一般式(II)におけるR3とR4が水素原子であり、R5がアクリレート誘導体である化合物が挙げられ、一般に、9,10-ジヒドロ-9-オキサ-10-フォスファフェナンスレン-10-オキサイドと公知慣用の多官能アクリレートモノマーとのマイケル付加反応により合成することができる。
このフェノール性水酸基を有するリン化合物は、疎水性、耐熱性が高く、加水分解による電気特性の低下が無く、はんだ耐熱性が高い。また、好適な組み合わせとして、熱硬化性成分としてビフェニル骨格を有するエポキシ樹脂やその他のエポキシ樹脂を使用することによって、エポキシ樹脂と反応し、ネットワークに取り込まれるので、硬化後にブリードアウトすることが無いという利点が得られる。市販品としては、三光(株)製HCA-HQなどがある。
オリゴマーもしくはポリマーであるリン化合物は、アルキル鎖の影響により折り曲げ性の低下が少なく、また分子量が大きいため硬化後のブリードアウトが無いという利点が得られる。市販品としては、三光(株)製M-Ester-HP、東洋紡(株)製バイロン337などがある。
フォスファゼンオリゴマーとしてはフェノキシフォスファゼン化合物が有効であり、置換もしくは無置換フェノキシフォスファゼンオリゴマー又は3量体、4量体、5量体の環状物があり、液状や固体粉末のものがあるがいずれも好適に使用することができる。市販品としては、(株)伏見製薬所製FP-100、FP-300、FP-390などがある。
このような光重合開始剤、光開始助剤、及び増感剤の総量は、前記カルボキシル基含有樹脂100質量部に対して35質量部以下であることが好ましい。35質量部を超えると、これらの光吸収により深部硬化性が低下する傾向にある。
赤色着色剤としてはモノアゾ系、ジズアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがあり、具体的には以下のものが挙げられる。
モノアゾ系:Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269。
ジスアゾ系:Pigment Red 37, 38, 41。
モノアゾレーキ系:Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1,68。
ベンズイミダゾロン系:Pigment Red 171、Pigment Red 175、Pigment Red 176、Pigment Red 185、Pigment Red 208。
ぺリレン系:Solvent Red 135、Solvent Red 179、Pigment Red 123、Pigment Red 149、Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224。
ジケトピロロピロール系:Pigment Red 254、Pigment Red 255、Pigment Red 264、Pigment Red 270、Pigment Red 272。
縮合アゾ系:Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。
アンスラキノン系:Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。
キナクリドン系:Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209。
青色着色剤としてはフタロシアニン系、アントラキノン系があり、顔料系はピグメント(Pigment)に分類されている化合物、具体的には:Pigment Blue 15、Pigment Blue 15:1、Pigment Blue 15:2、Pigment Blue 15:3、Pigment Blue 15:4、Pigment Blue 15:6、Pigment Blue 16、Pigment Blue 60。
染料系としては、Solvent Blue 35、Solvent Blue 63、Solvent Blue 68、Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97、Solvent Blue 122、Solvent Blue 136、Solvent Blue 67、Solvent Blue 70等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系があり、具体的にはPigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green 20、Solvent Green 28等を使用することができる。上記以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。
黄色着色剤としてはモノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等があり、具体的には以下のものが挙げられる。
アントラキノン系:Solvent Yellow 163、Pigment Yellow 24、Pigment Yellow 108、Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。
イソインドリノン系:Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。
縮合アゾ系:Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。
ベンズイミダゾロン系:Pigment Yellow 120、Pigment Yellow 151、Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。
モノアゾ系:Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183。
ジスアゾ系:Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198。
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、C.I.ピグメントオレンジ1、C.I.ピグメントオレンジ5、C.I.ピグメントオレンジ13、C.I.ピグメントオレンジ14、C.I.ピグメントオレンジ16、C.I.ピグメントオレンジ17、C.I.ピグメントオレンジ24、C.I.ピグメントオレンジ34、C.I.ピグメントオレンジ36、C.I.ピグメントオレンジ38、C.I.ピグメントオレンジ40、C.I.ピグメントオレンジ43、C.I.ピグメントオレンジ46、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ51、C.I.ピグメントオレンジ61、C.I.ピグメントオレンジ63、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ71、C.I.ピグメントオレンジ73、C.I.ピグメントブラウン23、C.I.ピグメントブラウン25、C.I.ピグメントブラック1、C.I.ピグメントブラック7等がある。
上記の酸化防止剤は、1種を単独で又は2種以上を組み合わせて用いることができる。
画像形成のための露光量は膜厚等によって異なるが、一般には20~2000mJ/cm2、好ましくは20~1500mJ/cm2の範囲内とすることができる。
撹拌装置、温度計、コンデンサーを備えた反応容器に、アルコール性ヒドロキシル基を複数有する化合物として1,5-ペンタンジオールと1,6-ヘキサンジオールから誘導されるポリカーボネートジオール(旭化成ケミカルズ(株)製T5650J、数平均分子量800)を3600g(4.5モル)、ジメチロールブタン酸を814g(5.5モル)、及び分子量調整剤(反応停止剤)としてn-ブタノール118g(1.6モル)を投入した。次に、芳香環を有しないイソシアネート化合物としてトリメチルヘキサメチレンジイソシアネート2009g(10.8モル)を投入し、撹拌しながら60℃まで加熱して停止し、反応容器内の温度が低下し始めた時点で再度加熱して80℃で撹拌を続け、赤外線吸収スペクトルでイソシアネート基の吸収スペクトル(2280cm-1)が消失したことを確認して反応を終了した。次いで、固形分が60wt%となるようにカルビトールアセテートを添加し、希釈剤を含有する粘稠液体のカルボキシル基含有樹脂を得た。得られたカルボキシル基含有ポリウレタンの固形分の酸価は49.8mgKOH/gであった。以下、この反応生成物の樹脂溶液をワニスA-1とする。
撹拌装置、温度計、コンデンサーを備えた反応容器に、1,5-ペンタンジオールと1,6-ヘキサンジオールから誘導されるポリカーボネートジオール(旭化成ケミカルズ(株)製、T5650J、数平均分子量800)を2400g(3モル)、ジメチロールプロピオン酸を603g(4.5モル)、及びモノヒドロキシル化合物として2-ヒドロキシエチルアクリレートを238g(2.6モル)投入した。次いで、ポリイソシアネートとしてイソホロンジイソシアネート1887g(8.5モル)を投入し、撹拌しながら60℃まで加熱して停止し、反応容器内の温度が低下し始めた時点で再度加熱して80℃で撹拌を続け、赤外線吸収スペクトルでイソシアネート基の吸収スペクトル(2280cm-1)が消失したことを確認して反応を終了した。固形分が50質量%となるようにカルビトールアセテートを添加した。得られたカルボキシル基含有樹脂の固形分の酸価は50mgKOH/gであった。以下、この反応生成物の樹脂溶液をワニスA-2とする。
ジエチレングリコールモノエチルエーテルアセテート600gにオルソクレゾールノボラック型エポキシ樹脂(DIC社製、EPICLON N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070g、アクリル酸360g、及びハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン4.3gを仕込み、110℃に加熱して2時間反応後、120℃に昇温してさらに12時間反応を行った。得られた反応液に芳香族系炭化水素(ソルベッソ150)415g、テトラヒドロ無水フタル酸456.0gを仕込み、110℃で4時間反応を行い、冷却後、固形分酸価89mgKOH/g、固形分65%の樹脂溶液を得た。以下、この樹脂溶液をワニスA-3とする。
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和高分子(株)製、商品名「ショーノールCRG951」、OH当量:119.4)119.4g、水酸化カリウム1.19g及びトルエン119.4gを仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド63.8gを徐々に滴下し、125~132℃、0~4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56gを添加混合して水酸化カリウムを中和し、不揮発分62.1%、水酸基価が182.2g/eq.であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基1当量当りアルキレンオキシドが平均1.08モル付加しているものであった。得られたノボラック型クレゾール樹脂のアルキレンオキシド反応溶液293.0g、アクリル酸43.2g、メタンスルホン酸11.53g、メチルハイドロキノン0.18g及びトルエン252.9gを、撹拌機、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、110℃で12時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、12.6gの水が留出した。その後、室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35gで中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート118.1gで置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次に、得られたノボラック型アクリレート樹脂溶液332.5g及びトリフェニルホスフィン1.22gを、撹拌器、温度計及び空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物60.8gを徐々に加え、95~101℃で6時間反応させた。固形物の酸価88mgKOH/g、不揮発分71%のカルボキシル基含有感光性樹脂を得た。以下、この樹脂溶液をワニスA-4とする。
水酸化アルミニウム(昭和電工(株)製ハイジライト42M)700gと、溶剤としてカルビトーアセテート280g、BYK-110(ビックケミー・ジャパン(株)製湿潤分散剤)20gを混合攪拌し、ビーズミルにて0.5μmのジルコニアビーズを用い分散処理を行った。これを3回繰り返して3μmのフィルターを通した水酸化アルミニウムスラリーを作製した。
前記各合成例の樹脂溶液を用い、表1に示す種々の成分とともに表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、硬化性樹脂組成物を調製した。ここで、得られた各硬化性樹脂組成物の分散度をエリクセン社製グラインドメータによる粒度測定にて評価したところ、15μm以下であった。
<最適露光量>
上記実施例2~6及び比較例1、2の光硬化性熱硬化性樹脂組成物を、銅厚35μmの回路パターン基板をバフロール研磨後、水洗し、乾燥してからスクリーン印刷法により全面に塗布し、80℃の熱風循環式乾燥炉で30分間乾燥させた。乾燥後、メタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いてステップタブレット(Kodak No.2)を介して露光し、現像(30℃、0.2MPa、1wt%Na2CO3水溶液)を60秒で行った際残存するステップタブレットのパターンが6段の時を最適露光量とした。
実施例2~6及び比較例1,2の光硬化性熱硬化性樹脂組成物を、銅べた基板上にスクリーン印刷で前面塗布し、80℃で30分乾燥させた。L/S(ライン/スペース)=80/400μmのネガフィルムを用いて最適露光量で露光し、上記条件で現像する。現像後、80μmのラインが残っているかどうかを確認した。
○:銅べた基板上に80μmのラインが残っている。
×:銅べた基板上に80μmのラインが残っていない。
上記各実施例及び比較例の硬化性樹脂組成物を、25μm厚のポリイミドフィルム(東レ・デュポン(株)製カプトン100H)にスクリーン印刷で全面塗布し、80℃で30分乾燥し、室温まで放冷した。実施例1の熱硬化性樹脂組成物については、得られた基板を150℃で60分加熱して硬化した。実施例2~6及び比較例1、2の光硬化性熱硬化性樹脂組成物については、得られた基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でレジストパターンを露光し、30℃の1wt%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、レジストパターンを得、この基板を、150℃で60分加熱して硬化した。
得られた評価基板に対してハゼ折りにより180°折り曲げを数回繰り返して行い、その際の塗膜におけるクラック発生状況を目視及び200倍の光学顕微鏡で観察し、クラックが発生しなかった回数を評価した。
可撓性(耐折性)の評価用サンプルと同様に作製したサンプルを50mm×50mm□に切り出し、4角の反りを測定して平均値を求め、以下の基準で評価した。
○:反りが1mm未満であるもの。
△:反りが1mm以上、4mm未満であるもの。
×:反りが4mm以上であるもの。
各実施例及び比較例の硬化性樹脂組成物を、12.5μm又は25μm厚のポリイミドフィルム(東レ・デュポン(株)製カプトン50H、100H)にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷した。さらに裏面を同様にスクリーン印刷で全面塗布し、80℃で20分乾燥して室温まで放冷し両面塗布基板を得た。実施例1の熱硬化性樹脂組成物については、得られた基板を150℃で60分加熱して硬化し、試験片とした。実施例2~6及び比較例1、2の光硬化性熱硬化性樹脂組成物については、この基板にメタルハライドランプ搭載の露光装置(HMW-680-GW20)を用いて最適露光量でソルダーレジストを全面露光し、30℃の1%Na2CO3水溶液をスプレー圧0.2MPaの条件で60秒間現像を行い、150℃で60分間熱硬化を行い評価サンプルとした。この難燃性評価用サンプルついて、UL94規格に準拠した薄材垂直燃焼試験を行った。評価は難燃性試験合格をVTM-0、不合格を燃焼と表した
前記各評価試験の結果を表2にまとめて示す
表1に示す実施例2~6の各光硬化性熱硬化性樹脂組成物をシリコーン系消泡剤を配合せずに調製した各硬化性樹脂組成物をメチルエチルケトンで希釈し、キャリアフィルム上に塗布し、加熱乾燥して、厚さ20μmの硬化性樹脂組成物層を形成し、その上にカバーフィルムを貼り合わせて、それぞれ実施例7~11のドライフィルムを得た。このドライフィルムを、前述した試験方法に用いた試験基板にラミネーターを用いて張り合わせ、試験基板を作製した。得られた試験基板について、前述した評価方法と同様にして各特性の評価試験を行った。結果を表3に示す。
Claims (5)
- カルボキシル基含有樹脂、
酸化チタン、及び
ホスフィン酸金属塩
を含有することを特徴とする硬化性樹脂組成物。 - 前記カルボキシル基含有樹脂がポリウレタンであることを特徴とする請求項1に記載の硬化性樹脂組成物。
- 請求項1又は2に記載の硬化性樹脂組成物をフィルムに塗布乾燥してなるドライフィルム。
- 請求項1又は2に記載の硬化性樹脂組成物又は該硬化性樹脂組成物をフィルムに塗布乾燥してなるドライフィルムを、熱硬化又は光硬化あるいは光硬化及び熱硬化して得られる硬化塗膜。
- 請求項1又は2に記載の硬化性樹脂組成物又は該硬化性樹脂組成物をフィルムに塗布乾燥してなるドライフィルムを、熱硬化又は光硬化あるいは光硬化及び熱硬化して得られる硬化塗膜を有するプリント配線板。
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CN201180015939.XA CN102822284B (zh) | 2010-03-31 | 2011-03-28 | 固化性树脂组合物、使用其的干膜以及印刷电路板 |
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CN102822284A (zh) | 2012-12-12 |
CN102822284B (zh) | 2017-02-22 |
KR20120132538A (ko) | 2012-12-05 |
JP5820568B2 (ja) | 2015-11-24 |
JP2011213828A (ja) | 2011-10-27 |
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