WO2012173241A1 - 難燃性硬化性樹脂組成物、それを用いたドライフィルム及びプリント配線板 - Google Patents
難燃性硬化性樹脂組成物、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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- WO2012173241A1 WO2012173241A1 PCT/JP2012/065403 JP2012065403W WO2012173241A1 WO 2012173241 A1 WO2012173241 A1 WO 2012173241A1 JP 2012065403 W JP2012065403 W JP 2012065403W WO 2012173241 A1 WO2012173241 A1 WO 2012173241A1
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- resin composition
- curable resin
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- retardant
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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
-
- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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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- 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
-
- 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 more particularly to a flame retardant curable resin composition capable of forming a coating film excellent in dryness to touch, flexibility, low warpage and flame retardancy.
- the present invention also relates to a dry film using such a flame retardant curable resin composition, a flame retardant film obtained from the flame retardant curable resin composition, and a printed wiring board including the flame retardant film.
- FPC printed wiring boards and flexible wiring boards
- coating films cured coatings
- Flammability is required.
- 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 (a) a binder polymer, (b) a photopolymerization having in its molecule a halogenated aromatic ring such as a bromophenyl group and a polymerizable ethylenically unsaturated bond such as a (meth) acryloyl group.
- a flame retardant photosensitive resin composition for FPC containing a reactive compound, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus compound having a phosphorus atom in the molecule is proposed. Yes.
- an object of the present invention is to provide a flame retardant curable resin composition that is excellent in flame retardancy, excellent in flexibility of a cured coating, and capable of forming a cured coating without bleeding out of a flame retardant during high temperature pressing.
- the object of the present invention is to provide a flame-retardant dry film and cured product excellent in various properties as described above obtained by using such a flame-retardant curable resin composition, and the dry film and cured product.
- An object of the present invention is to provide a printed wiring board in which a flame-retardant cured film such as a solder resist is formed.
- the flame-retardant curable resin composition of the present invention contains (A) a carboxyl group-containing resin, (B) a flame retardant, (C) a block copolymer, and (D) a thermosetting component. It is characterized by.
- the flame retardant curable resin composition of the present invention preferably further contains a photopolymerization initiator and a photopolymerizable monomer.
- the (A) carboxyl group-containing resin has a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a bisxylenol structure, a biphenyl novolak structure, and a urethane structure.
- the flame retardant curable resin composition of the present invention has the (C) block copolymer represented by the following formula (I), ABA (I) (Wherein, A is a polymer unit having a glass transition point Tg of 0 ° C. or higher, and B is a polymer unit having a glass transition point Tg of less than 0 ° C.). .
- the (C) block copolymer has the formula (I) in which A represents polystyrene, polyglycidyl methacrylate, N-substituted polyacrylamide, or polymethyl. It is preferably a block copolymer that is methacrylate or its carboxylic acid-modified product or hydrophilic group-modified product, and B is polybutyl acrylate or polybutadiene.
- the flame-retardant curable resin composition of the present invention is preferably a solder resist.
- the dry film of the present invention is characterized in that the above-mentioned flame-retardant curable resin composition is applied to a film and dried.
- the flame retardant coating film of the present invention is obtained by heat-curing and / or photocuring the above-mentioned flame-retardant curable resin composition or dry film.
- the printed wiring board of the present invention comprises a flame retardant coating obtained by heat curing and / or photocuring the above flame retardant curable resin composition or dry film.
- a flame retardant curable resin composition that is excellent in dryness to touch, flexibility, low warpage, and flame retardancy, and can form a film with little flame retardant bleed out during high temperature pressing. be able to.
- the flame-retardant curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a flame retardant, (C) a block copolymer, and (D) a thermosetting component. To do. Since the flame-retardant curable resin composition of the present invention uses a block copolymer, it has flexibility and toughness without deteriorating the compatibility of resins, and has excellent bendability. A cured product with good dryness to the touch can be obtained.
- the flame-retardant curable resin composition of the present invention is suitable for a solder resist for flexible wiring boards in that a cured product having excellent flame retardancy and flexibility can be formed.
- each component of the curable resin composition of the present invention will be described in detail.
- (A) Carboxyl group-containing resin As said (A) carboxyl group containing resin, resin containing a well-known carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. Further, from the viewpoint of making the flame retardant curable resin composition of the present invention photocurable and developing resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group. Only a carboxyl group-containing resin having no polymerizable unsaturated double bond can be used as the component (A).
- the resin of component (A) does not have an ethylenically unsaturated bond
- a compound having at least one ethylenically unsaturated group in the molecule (photopolymerizable) Monomer) must be used in combination.
- the ethylenically unsaturated double bond those derived from acrylic acid, methacrylic acid or derivatives thereof 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, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
- carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- 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 (Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
- one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
- the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
- dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are reacted with a hydroxyl group present in the side chain by reacting a polyfunctional (solid) epoxy resin as described later.
- a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
- Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
- a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
- 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 the molecule such as glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above
- a photosensitive carboxyl group-containing resin obtained by adding a compound having a group.
- 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 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 20 mgKOH / g, the adhesion of the coating film may not be obtained, or when the photocurable resin composition is used, alkali development may be difficult.
- the weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, and more preferably 5,000 to 100,000.
- weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior.
- weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.
- the polyfunctional epoxy resin used for the synthesis of the resin is selected from the group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a bisxylenol structure, and a biphenyl novolak structure.
- a polyfunctional epoxy resin having a partial structure, a carboxyl group-containing resin that is a hydrogenated compound thereof, or a carboxyl group-containing resin having a urethane structure is preferable from the viewpoint of low warpage and bending resistance of the obtained cured product.
- a carboxyl group-containing resin having a biphenyl novolak structure is preferable from the viewpoint of flame retardancy.
- a carboxyl group-containing urethane resin obtained by using a diisocyanate in which an isocyanate group is not directly bonded to a benzene ring is used as a component having an isocyanate group (including a diisocyanate). Since there is no change, it is effective for concealment and has little UV absorption, it is preferable because it has excellent resolution when used as an alkali-developable composition.
- (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
- the blending amount of the carboxyl group-containing resin (A) as described above is 5 to 60% by mass, preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 30% by mass in the entire composition. 50% by mass.
- the amount is less than the above range, the coating 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.
- the flame-retardant curable resin composition of the present invention contains (B) a flame retardant.
- a flame retardant A conventionally well-known thing can be used as a flame retardant. From the viewpoint of the environment, a flame retardant containing no halogen is preferred. Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, hydrotalcites, and phosphorus-containing compounds. Moreover, a flame retardant may be used individually by 1 type, and may use 2 or more types together.
- Aluminum hydroxide may be untreated surface, using a silane coupling agent having a vinyl group or an epoxy group at its end, stearic acid, oleic acid, phosphoric acid ester, etc. Also good.
- Examples of commercially available aluminum hydroxide include Hydrite H42M, Hydrite H42S, Heidilite H42T, Heidilite H42ST-V, Showa Denko Co., Ltd., Nippon Light Metals B1403, B1403ST, B1403T, and the like.
- Magnesium hydroxide may be a natural product or a synthetic product, and may be untreated, a silane coupling agent having a vinyl group or an epoxy group at its terminal, stearic acid, You may use what was surface-treated with oleic acid, phosphoric acid ester, etc.
- Kisuma 5A, Kisuma 5B, Kisuma 5E, Kisuma 5J, Kisuma 5P, Kisuma 5L, Albemarle Magnifin H5, Magnifin H7, Magnifin H10, etc. are mentioned.
- phosphorus-containing compound used as a flame retardant conventionally known compounds can be used as organic phosphorus flame retardants, for example, phosphate esters and condensed phosphate esters, cyclic phosphazene compounds, phosphazene oligomers, Examples thereof include phosphinic acid metal salts and compounds represented by the following general formula (II).
- R 1 , R 2 and R 3 each independently represent a substituent other than a halogen atom.
- R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 3 is a carbon atom optionally substituted by a hydrogen atom or a cyano group. It is preferably an alkyl group of 1 to 4, a 2,5-dihydroxyphenyl group, or a 3,5-di-t-butyl-4-hydroxyphenyl group, but is not limited thereto.
- Particularly preferred phosphorus-containing compounds used in the present invention include those having an acrylate group as a reactive group, those having a phenolic hydroxyl group, oligomers or polymers, phosphazene oligomers, phosphinates and the like.
- the compound whose R ⁇ 1 > and R ⁇ 2 > in the said general formula (II) is a hydrogen atom, and R ⁇ 3 > is a (meth) acrylate derivative is also preferable.
- Such a compound can be generally synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a known and commonly used polyfunctional (meth) acrylate monomer.
- glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxy.
- Polyhydric alcohols such as ethyl isocyanurate or polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts of these phenols or Polyhydric acrylates such as propylene oxide adducts; and urethane acrylates of the above polyalcohols Glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; and melamine acrylate and / or methacrylates corresponding to the acrylate It is done.
- polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts or caprolactone adduct
- a phosphorus-containing 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. Further, as an appropriate combination, when an epoxy resin is used among thermosetting resins, there is an advantage that it does not bleed out after curing because it reacts with the epoxy group and is taken into the network.
- Commercially available products include HCA-HQ manufactured by Sanko.
- the phosphorus-containing compound which is an oligomer or polymer, has the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleed-out after curing due to the large molecular weight.
- Commercially available products include M-Ester-HP manufactured by Sanko Co., Ltd. and phosphorus-containing Byron 337 manufactured by Toyobo Co., Ltd.
- a phenoxyphosphazene compound is effective, and there is a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, a tetramer, a pentamer, and a liquid or solid powder.
- any of them can be preferably used.
- Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical.
- phenoxyphosphazene oligomers substituted with alkyl groups or polar groups such as hydroxyl groups and cyano groups have high solubility in carboxyl group-containing resins, and there are no problems such as recrystallization even when added in large amounts. preferable.
- a phosphinic acid metal salt By using a phosphinic acid metal salt, flame retardancy can be improved without impairing the flexibility of the cured coating film. In addition, by using a phosphinic acid metal salt that is excellent in heat resistance, the bleedout of the flame retardant can be suppressed in the hot press during mounting.
- Commercially available products include EXOLIT OP 930 and EXOLIT OP 935 manufactured by Clariant.
- the blending amount of the flame retardant is preferably in the range of 1 to 200 parts by weight, particularly preferably 5 to 100 parts by weight with respect to 100 parts by weight of the (A) carboxyl group-containing resin.
- the heat resistance, bending characteristics and the like of the resulting cured film may be deteriorated, which is not preferable.
- the flame retardant curable resin composition of the present invention includes (C) a block copolymer.
- a block copolymer generally refers to a copolymer having a molecular structure in which two or more types of polymers having different properties are connected by covalent bonds to form a long chain.
- the block copolymer used in the present invention is preferably an ABA or ABA ′ type block copolymer.
- the central B is a soft block and has a low glass transition point Tg, preferably less than 0 ° C.
- both outer sides A to A ′ are hard blocks and have a high Tg.
- Tg is measured by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- a to A ′ are composed of polymer units having a Tg of 50 ° C.
- a to A ′ are preferably those having high compatibility with the (A) carboxyl group-containing resin, and B is compatible with the (A) carboxyl group-containing resin. Those having low solubility are preferred. In this way, it is considered that a specific structure in the matrix can be easily exhibited when a block copolymer in which the blocks at both ends are compatible with the matrix and the central block is incompatible with the matrix.
- the A or A ′ component is preferably polymethyl methacrylate (PMMA), polystyrene (PS), or the like, and the B component is preferably poly n-butyl acrylate (PBA) or polybutadiene (PB).
- PMMA polymethyl methacrylate
- PS polystyrene
- PB polybutadiene
- the block copolymer thus obtained has particularly good compatibility with the carboxyl group-containing resin and can also improve flexibility.
- the cured product using the block copolymer is superior in high-temperature press resistance compared to the cured product using the elastomer, and the bleed-out at the time of high-temperature pressing is higher than the cured product using the elastomer. It can be suppressed.
- Examples of the method for producing a block copolymer include the methods described in Japanese Patent Application Nos. 2005-515281 and 2007-516326.
- the acryl-type triblock copolymer manufactured using the living polymerization by Arkema for example is mentioned.
- SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate
- MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate
- MAM N type treated with carboxylic acid modification or hydrophilic group modification.
- MAM A type examples of SBM types include E41, E40, E21, and E20.
- MAM types include M51, M52, M53, and M22.
- MAM N types include 52N and 22N.
- MAM A types include SM4032XM10. It is done.
- the clarity produced by Kuraray Co., Ltd. is also a block copolymer derived from methyl methacrylate and butyl acrylate.
- the block copolymer used in the present invention is preferably a ternary or more block copolymer, and a block copolymer with precisely controlled molecular structure synthesized by a living polymerization method is effective for obtaining the effects of the present invention. And more preferable. This is considered to be because the block copolymer synthesized by the living polymerization method has a narrow molecular weight distribution, and the characteristics of each unit have been clarified.
- the molecular weight distribution of the block copolymer used is preferably 2.5 or less, more preferably 2.0 or less.
- the weight average molecular weight of the block copolymer is generally in the range of 20,000 to 400,000, more preferably 30,000 to 300,000.
- weight average molecular weight is less than 20,000, the intended effects of toughness and flexibility cannot be obtained, and the tackiness is inferior.
- weight average molecular weight exceeds 400,000, the viscosity of the curable resin composition becomes high, and the printability and developability are remarkably deteriorated.
- the blending amount of the block copolymer is preferably in the range of 1 to 50 parts by mass, more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If it is less than 1 part by mass, the effect is not expected, and if it is 50 parts by mass or more, the developability and applicability of the photocurable resin composition may be deteriorated, which is not preferable.
- the flame-retardant curable resin composition of the present invention includes (D) a thermosetting component used for the purpose of improving characteristics such as heat resistance and insulation reliability.
- a thermosetting component used for the purpose of improving characteristics such as heat resistance and insulation reliability.
- thermosetting components such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc.
- the thermosetting resin can be used.
- thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.
- cyclic (thio) ether groups cyclic thioether groups
- thermosetting components having a cyclic (thio) ether group there are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
- the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes a plurality of either one of the three-, four- or five-membered cyclic ether groups, or the 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
- thioether groups in the molecule examples thereof include compounds, that is, episulfide resins.
- polyfunctional epoxy compound examples include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330, A.I. E. R.
- Type or biphenol type epoxy resin or a mixture thereof bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical; TEPIC etc.
- bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .
- Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation
- tetraphenylolethane type epoxy resin such
- Examples include, but are not limited to, glycidyl methacrylate copolymer epoxy resins such as ⁇ 50S and CP-50M; and cyclohexyl maleimide / glycidyl methacrylate copolymer epoxy resins. These epoxy resins can be used alone or in combination of two or more. Among these, a biphenyl novolac type epoxy resin, a bixylenol type epoxy resin or a mixture thereof is particularly preferable from the viewpoint of low warpage and flame retardancy.
- 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 episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation and YSLV-120TE manufactured by Tohto Kasei Co., Ltd. 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 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 (A). More preferably, it is in the range of 0.5 to 2.0 equivalents.
- the amount of thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.3 equivalents, carboxyl groups remain in the cured film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. This is not preferable.
- the amount exceeds 2.5 equivalents the low molecular weight cyclic (thio) ether group remains in the dried coating film, which is not preferable because the strength of the cured coating film may be reduced.
- thermosetting component 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 and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
- Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
- 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.
- thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. 15.0 parts by mass.
- amino resin examples include amino resins such as melamine derivatives and benzoguanamine derivatives.
- examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
- the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
- the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
- a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
- Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, and the like. 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (made by Sanwa Chemical Co., Ltd.).
- the isocyanate compound a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used.
- the 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 inactivated. 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.
- an isocyanate compound used in order to synthesize combine a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example.
- aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.
- isocyanate blocking agent examples include phenolic 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, acetoxime
- the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
- Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B 846, B-870, B-874, B-882 (Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.
- the blending amount of the polyisocyanate compound or the blocked isocyanate compound is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is less than 1 part by mass, sufficient toughness of the coating film may not be obtained, which is not preferable.
- the amount exceeds 100 parts by mass the storage stability may decrease, which is not preferable.
- a urethanization catalyst can be added to the flame retardant curable resin composition of the present invention in order to accelerate the curing reaction between a hydroxyl group or a carboxyl group and an isocyanate group.
- the urethanization catalyst one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts should be used. Is preferred.
- tin catalyst examples include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.
- metal chloride examples include metal chlorides selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al.
- metal chlorides selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al.
- cobalt chloride, nickel chloride, ferric chloride, and the like. Can be mentioned.
- the metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al.
- metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al.
- cobalt acetylacetonate, nickel acetylacetonate, iron acetyl Examples include acetonate.
- the metal sulfate is a metal sulfate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include copper sulfate.
- Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′.
- N ′′, N ′′ -pentamethyldiethylenetriamine N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxy Chill) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ′′, N ′′ -tetramethyldiethylenetriamine, N, N, N′-trimethyl
- amine salt examples include organic acid salt amine salts such as DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).
- the blending amount of the urethanization catalyst is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- a photopolymerization initiator In order to make the flame-retardant curable resin composition of the present invention into a photocurable resin composition, a photopolymerization initiator can be blended.
- the photopolymerization initiator includes at least one selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. Photoinitiators are preferred.
- oxime ester photopolymerization initiators examples include CGI-325, Irgacure OXE01, Irgacure OXE02, ADEKA N-1919, and Adeka Arcles NCI-831 manufactured by BASF Japan.
- 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).
- 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 a C 1-8 alkyl group or a dialkylamino group.
- X and Y are each a methyl group or an ethyl group
- Z is methyl or phenyl
- n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene.
- the blending amount of the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is less than 0.01 parts by mass, the photocurability of the resin composition is insufficient, the coating film peels off, and the coating properties such as chemical resistance may deteriorate.
- it exceeds 5 parts by mass light absorption on the surface of the solder resist coating film becomes violent, 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 BASF Japan.
- acylphosphine oxide photopolymerization initiator examples 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. Examples of commercially available products include Lucilin TPO and Irgacure 819 manufactured by BASF Japan.
- the blending amount of the ⁇ -aminoacetophenone photopolymerization initiator and the acylphosphine oxide photopolymerization initiator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). . If it is less than 0.1 parts by mass, the photocurability of the resin composition will be insufficient, and the coating film may be peeled off, and the coating properties such as chemical resistance may be deteriorated. On the other hand, when it exceeds 30 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 15 parts by mass.
- Irgacure 389 and Irgacure 784 manufactured by BASF Japan can also be suitably used.
- the flame retardant curable resin composition of the present invention preferably uses an oxime ester photopolymerization initiator.
- the effect is that not only a sufficient sensitivity can be obtained even in a small amount, but also the shrinkage of the cured coating film can be suppressed because the volatilization of the photopolymerization initiator in the post-heating process at the time of thermosetting and mounting is small. Therefore, it is possible to greatly reduce the warpage.
- the use of an acylphosphine oxide-based photopolymerization initiator improves the deep curability during photoreaction, and further incorporates an initiator-derived phosphorus-containing compound component cleaved by light irradiation into the cured product network, thereby allowing the cured coating.
- the phosphorus concentration in the film can be effectively increased, and further flame retardancy can be improved.
- the flame-retardant curable resin composition of the present invention it is effective to use either an oxime ester photopolymerization initiator or an acylphosphine oxide photopolymerization initiator.
- the combination of oxime ester photopolymerization initiator and acylphosphine oxide photopolymerization initiator is more suitable from the viewpoints of balance of opening, improvement of processing accuracy, and further improvement of low warpage, bendability and flame retardancy. It is.
- photoinitiators and sensitizers that can be suitably used in the flame-retardant curable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, 3 A class 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
- Dialkylamino group-containing coumarin compounds ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylamino Ethyl benzoate (n-butoxy) (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate ( Examples include Van Dyk's Esol 507) and 4,4'-diethylaminobenzophenone (Hodogaya Chemical EAB).
- 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. It becomes possible to provide a solder resist film.
- 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
- the compounding 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 (A) carboxyl group-containing resin.
- amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained.
- the amount exceeds 20 parts by mass light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.
- thioxanthone compounds and tertiary amine compounds are preferred.
- a thioxanthone compound is contained from the viewpoint of deep part curability of the resin composition.
- thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.
- the blending amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability may be lowered and the cost of the product may be increased. More preferably, it is 10 parts by mass or less.
- photoinitiator aids and sensitizers may be used alone or as a mixture of two or more.
- the total amount of the above photopolymerization initiator, photoinitiator assistant, and sensitizer is 35 parts by mass with respect to 100 parts by mass of the carboxyl-containing resin (A) for a printed wiring board capable of alkali development.
- the following is preferable. When it exceeds 35 parts by mass, the deep-part curability of the flame-retardant curable resin composition tends to decrease due to light absorption.
- the photopolymerization initiator, photoinitiator assistant, and sensitizer as described above absorb a specific wavelength, so that 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 necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.
- a compound (photopolymerizable monomer) having one or more ethylenically unsaturated groups in the molecule can be used to form the flame retardant curable resin composition into a photocurable resin composition.
- the photopolymerizable monomer is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the (A) carboxyl group-containing resin in an alkaline aqueous solution.
- Examples of the compound used as the photopolymerizable monomer in the present invention include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. It is done.
- hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Multivalent acrylates such as a peroxide adduct, a propylene oxide adduct, or an ⁇ -caprolactone ad
- 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.
- An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photopolymerizable monomer.
- Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.
- polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts, and polyphenols such as ethylene oxide adducts or propylene oxide adducts of phenols are used.
- polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts
- polyphenols such as ethylene oxide adducts or propylene oxide adducts of phenols
- the compounding amount of the compound having one or more ethylenically unsaturated groups in the molecule used as the photopolymerizable monomer is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. More preferably, the proportion is 5 to 70 parts by mass.
- the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern development may be difficult due to alkali development after irradiation with active energy rays, which is not preferable.
- the amount exceeds 100 parts by mass the solubility in an aqueous alkali solution is lowered, and the coating film may become brittle.
- the curable resin composition of the present invention can contain a colorant.
- a colorant conventionally known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments 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 that the colorant does not contain a halogen from the viewpoint of reducing 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 type Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152,170, 172, 174, 176, 188, 198.
- Black colorant As the black colorant, a known and commonly used black colorant can be used. Examples of black colorants include carbon black pigments such as CIPigment black 6, 7, 9 and 18; graphite pigments such as CIPigment black 8, 10 and the like; CIPigment black 11, 12 and 27, pigment brown 35 and the like.
- Iron oxide pigments For example, iron oxide of KN-370 manufactured by Toda Kogyo Co., Ltd., 13M titanium black manufactured by Mitsubishi Materials Corporation, anthraquinone pigment expressed by CIPigment black 20, etc., CIPigment black 13, 25, 29, etc.
- Cobalt oxide pigments such as CIPigment black 15 and 28, copper oxide pigments such as CIPigment black 14 and 26, manganese pigments such as CIPigment black 14 and 26, antimony oxide pigments such as CIPigment black 23, and CIPigment black 30
- Nickel oxide pigments such as CIPigment black 31 and 32, perylene pigments represented by Pigment Black 1
- suitable pigments include aniline pigments, molybdenum sulfide and bismuth sulfide. These pigments are used alone or in appropriate combination. Particularly preferred is carbon black.
- carbon black manufactured by Mitsubishi Chemical Corporation, M-40, M-45, M-50, MA-8, MA-100, and perylene pigments are low among organic pigments. Effective for halogenation.
- White colorant As the white pigment, it is desirable to use titanium oxide, particularly rutile titanium oxide. 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 solder resist composition. In contrast, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable solder resist film can be obtained. As a rutile type titanium oxide, a well-known rutile type thing can be used.
- TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820, CR-50 manufactured by Ishihara Sangyo Co., Ltd., CR-60, CR-90, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used.
- a colorant such as purple, orange or brown 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 the colorant excluding titanium oxide is preferably 0.01 to 10 parts by weight, particularly 100 parts by weight of the (A) carboxyl group-containing resin. A ratio of 0.1 to 5 parts by mass is preferable. On the other hand, the amount of titanium oxide is preferably 1 to 300 parts by mass, particularly preferably 10 to 150 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the flame retardant curable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength and the like of the obtained cured product.
- a filler publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used.
- aluminum hydroxide, magnesium hydroxide, boehmite and the like can also be used.
- NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano-silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin.
- XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names)
- Hanose-Chemie NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) can also be used. . These may be used alone or in combination of two or more.
- the blending amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Part.
- the blending amount of the filler exceeds 500 parts by mass, the viscosity of the curable resin composition becomes high and the printability may be lowered, or the cured product may become brittle.
- Binder polymer Conventionally known binder polymers can be used in the flame-retardant curable resin composition of the present invention for the purpose of improving the flexibility and dryness of the cured product obtained.
- the binder polymer cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable.
- the cellulose polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., the polyester polymer based on the Byron series manufactured by Toyobo Co., Ltd., and the phenoxy resin based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.
- the amount of the binder polymer added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the blending amount of the binder polymer exceeds 50 parts by mass, the alkali developability of the curable resin composition is inferior, and the pot life that can be developed may be shortened.
- the flame-retardant curable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the resulting cured product and improving the brittleness of the cured product.
- the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers.
- resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
- epoxy-containing polybutadiene elastomers acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used.
- One type of elastomer may be used alone, or a mixture of two or more types may be used.
- an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate.
- the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.
- the flame retardant curable resin composition of the present invention prevents oxidation.
- An antioxidant can be added.
- the radical scavenger may be commercially available, for example, ADK STAB 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 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Japan, TINUVIN 5100 Japan Name).
- antioxidant acting as a peroxide decomposer examples include 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 (manufactured by ADEKA, trade name), Mark AO-412S (manufactured by ADEKA, trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., product) Name).
- ADK STAB TPP manufactured by ADEKA, trade name
- Mark AO-412S manufactured by ADEKA, trade name
- Sumilizer TPS manufactured by Sumitomo Chemical Co., Ltd., product
- the above antioxidants may be used alone or in combination of two or more.
- the flame retardant curable resin composition of the present invention is not limited to the above-mentioned antioxidants in order to take measures against stabilization of ultraviolet rays.
- Absorbents can be used.
- the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.
- benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone
- specific 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;
- specific examples of benzotriazole derivatives include 2- (2'- Hydroxy-5'-t-butylphenyl) benzotriazole, -(2'-hydroxy-5'-methylphenyl) enzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro
- 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 (above, manufactured by BASF Japan Ltd., trade name).
- Said ultraviolet absorber may be used individually by 1 type, and can also be used in combination of 2 or more type.
- the flame retardant curable resin composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite.
- thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite.
- conventional thickeners such as silicone, fluorine, polymer, etc., and / or leveling agents, silane coupling agents such as imidazole, thiazole and triazole, rust preventives, etc.
- silane coupling agents such as imidazole, thiazole and triazole, rust preventives, etc.
- Such known and commonly used additives can be blended.
- the thermal polymerization inhibitor can be used to prevent unintentional thermal polymerization or temporal polymerization of the flame retardant curable resin composition.
- thermal polymerization inhibitors 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, and phenothiazine, nitroso compound, chelate of nitroso compound
- the flame retardant curable resin composition of the present invention is an organic solvent for the synthesis of the above-mentioned (A) carboxyl group-containing resin and preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. Can be used.
- 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
- the flame-retardant curable resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer made of the curable resin composition formed on the carrier film. it can.
- the flame retardant curable resin composition of the present invention is diluted with the organic solvent to adjust to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater,
- a film can be obtained by applying a uniform thickness on a carrier film with a transfer roll coater, gravure coater, spray coater or the like and drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
- a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
- a peelable cover film is laminated on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to do.
- the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film What is necessary is just to have a smaller adhesive force between the membrane and the cover film.
- the flame-retardant curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, flow coating method, roll coating method, bar coater method, screen on the substrate.
- 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.degree.
- the flame retardant curable resin composition layer is brought into contact with the substrate by a laminator or the like. After the lamination, the resin insulating layer can be formed by peeling off the carrier film.
- Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, 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 substrate, ceramic substrate, wafer plate and the like.
- Volatile drying performed after the application of the flame-retardant curable resin composition of the present invention is performed using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (using a steam-heated air source).
- This method can be carried out using a method in which the hot air in the machine is brought into countercurrent contact and a method in which the hot air is blown onto the support from the nozzle.
- the flame retardant curable resin composition of the present invention is heated to a temperature of, for example, about 140 to 180 ° C. and thermally cured, whereby (A) the carboxyl group of the carboxyl group-containing resin and (D) the thermosetting
- the components react to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.
- the exposed portion (active energy ray) is obtained by performing exposure (irradiation of active energy rays) on the coating film obtained after coating and volatile drying of the solvent.
- the portion irradiated by (3) is cured.
- a contact type or non-contact type
- exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3).
- a resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution).
- 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 ⁇ 800mJ / cm 2, preferably be in the range of 20 ⁇ 600mJ / 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.
- A-2 Preparation of resin corresponding to carboxyl group-containing resin (7)
- the varnish is hereinafter referred to as A-2.
- the obtained propylene oxide adduct solution 718.0 g, 4-methoxyphenol 0.36 g, toluene 459.6 g, acrylic acid 28.8 g, and methanesulfonic acid 12.1 g were charged into a 2 L glass flask, and the temperature was 100 to 110 ° C.
- generated by reaction was distilling 7.2g of water as an azeotrope with toluene. Then, it cooled to room temperature and neutralized with 51.8 g of 15% potassium hydroxide aqueous solution. Further, the acrylate resin solution was purified by washing once with 5% saline and three times with pure water. The resin content in the solution was 36.1%.
- Varnish B-3 To 15 g of MAM type block copolymer M53 (manufactured by Arkema), 50 g of carbitol acetate was added, stirred, and dissolved by heating at 85 ° C. This is named Varnish B-3. To 15 g of MAM type block copolymer M22 (manufactured by Arkema), 50 g of carbitol acetate was added, stirred, and dissolved by heating at 85 ° C. This is named Varnish B-4.
- Varnish B-5 50 g of carbitol acetate was added to 15 g of MAM N type block copolymer M22N (manufactured by Arkema) modified with a hydrophilic group, stirred and heated to 85 ° C. to dissolve. This is named Varnish B-6.
- Examples 1 to 10 Comparative Examples 1 to 3
- the above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and flame-retardant cured.
- a functional resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained flame-retardant curable resin composition was evaluated by the particle size measurement by the Grindometer by Eriksen.
- ⁇ Tackiness> The flame retardant curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were applied on the entire surface of a copper solid substrate by screen printing and dried at 80 ° C. for 30 minutes. Check the dryness of the dry paint film. ⁇ : No stickiness. ⁇ : Slightly sticky ⁇ : Sticky.
- 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 by goblet folding several times, and the occurrence of cracks in the coating film at that time was observed visually and with a 200-fold optical microscope until cracks were generated.
- the number of bendings was measured to evaluate flexibility.
- A The number of bendings is 5 or more.
- ⁇ The number of bending is 3 to 4 times.
- ⁇ The number of folding times is 1 to 2 times.
- X The number of times of bending is zero.
- ⁇ 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.
- thermosetting resin composition of Example 1 and Comparative Example 1 was subjected to pattern printing on a patterned polyimide film substrate, dried at 80 ° C. for 30 minutes, allowed to cool to room temperature, and then heated at 150 ° C. for 60 minutes. And cured.
- the entire surface was applied by screen printing onto a patterned polyimide film substrate, and then dried at 80 ° C. for 30 minutes, to room temperature. Allowed to cool.
- the obtained substrate is exposed to the resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm 2. Development was performed for 60 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The resulting printed circuit board (evaluation board) was carried out for 60 minutes vacuum press at 0.99 ° C. giving a load of 20 kgf / cm 2 with scissors SUS plate with a cushion material. The opening part of the board
- the flame-retardant curable resin composition of each Example and Comparative Example was screen printed on a polyimide film having a thickness of 25 ⁇ m and 12.5 ⁇ m (manufactured by Toray DuPont, Kapton 100H (25 ⁇ m), Kapton 50H (12.5 ⁇ m)). The whole surface was applied, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. About the thermosetting resin composition of Example 1 and Comparative Example 1, the obtained board
- the obtained double-sided substrate was used with an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp at an optimum exposure amount.
- the entire surface of the solder resist was exposed, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was developed for 60 seconds under a spray pressure of 2 kg / cm 2 , 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 together with the results of each evaluation test in which the flame retardance test pass is indicated as VTM-0 and the failure is indicated as combustion.
- Examples 11 to 19 A flame retardant curable resin composition prepared by adding the flame retardant curable resin composition shown in Examples 2 to 10 shown in Table 1 without a silicone antifoaming agent was diluted with methyl ethyl ketone, and a carrier film (PET ) And dried by heating to form a photosensitive resin composition layer having a thickness of 20 ⁇ m, and a cover film (PP) was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned copper foil substrate using a laminator to prepare a test substrate. In the same manner as the test method and the evaluation method described above, an evaluation test of each characteristic was performed.
- Example 11 The dry film having the composition of Example 2 is Example 11, the composition of Example 3 is Example 12, the composition of Example 4 is Example 13, the composition of Example 5 is Example 14, and the composition of Example 6
- the compositions of Example 15 and Example 7 correspond to Example 16
- the composition of Example 8 corresponds to Example 17
- the composition of Example 9 corresponds to Example 18, and the composition of Example 10 corresponds to Example 19, respectively.
- the results are shown in Table 3 below.
- the flame-retardant curable resin compositions of Examples 1 to 19 have good touch drying properties, flexibility, low warpage, high temperature press resistance, and It can be seen that it also has excellent flame retardancy.
- the flame retardancy is sufficient, but Comparative Examples 1 and 2 are inferior to the touch dryness and low warpage.
- Comparative Example 4 was found to be inferior in finger touch drying and high-temperature press resistance.
Abstract
Description
さらに本発明の目的は、このような難燃性硬化性樹脂組成物を用いることによって得られる上記のような諸特性に優れた難燃性のドライフィルム及び硬化物、並びに該ドライフィルムや硬化物によりソルダーレジスト等の難燃性の硬化被膜が形成されてなるプリント配線板を提供することにある。
A-B-A (I)
(式中、Aはガラス転移点Tgが0℃以上のポリマー単位であり、Bはガラス転移点Tgが0℃未満のポリマー単位である。)で表されるブロック共重合体であることが好ましい。
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。
上記(A)カルボキシル基含有樹脂としては、公知のカルボキシル基を含む樹脂を用いることができる。カルボキシル基の存在により、樹脂組成物をアルカリ現像性とすることができる。また、本発明の難燃性硬化性樹脂組成物を光硬化性にすることや耐現像性の観点から、カルボキシル基の他に、分子内にエチレン性不飽和結合を有することが好ましいが、エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを(A)成分として用いることもできる。(A)成分の樹脂がエチレン性不飽和結合を有さない場合は、組成物を光硬化性とするためには、分子中に1個以上のエチレン性不飽和基を有する化合物(光重合性モノマー)を併用する必要がある。エチレン性不飽和二重結合としては、アクリル酸もしくはメタアクリル酸又はそれらの誘導体由来のものが好ましい。
また、上記カルボキシル基含有樹脂の酸価は、20~200mgKOH/gの範囲が望ましく、より好ましくは40~150mgKOH/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とした場合にはアルカリ現像が困難となることがある。一方、酸価が200mgKOH/gを超えた場合には、現像液による露光部の溶解が進むために、必要以上にラインが痩せたり、場合によっては、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ことがあるので好ましくない。
特にカルボキシル基含有樹脂としてビフェニルノボラック構造を有する場合、難燃性の観点から好ましい。
また、ウレタン構造を有するカルボキシル基含有樹脂の中でも、イソシアネート基を有する成分(ジイソシアネートも含む)として、イソシアネート基が直接ベンゼン環に結合していないジイソシアネートを用いて得られるカルボキシル基含有ウレタン樹脂が、黄変がなく、隠蔽性に有効で、かつ紫外線吸収が少ないため、アルカリ現像性組成物とした際に解像性に優れる特徴があり、好ましい。
尚、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレート及びそれらの混合物を総称する用語であり、他の類似の表現についても同様である。
本発明の難燃性硬化性樹脂組成物は、(B)難燃剤を含む。難燃剤としては慣用公知のものを使用できる。環境に対する観点から、ハロゲンを含まない難燃剤が好ましい。難燃剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、ハイドロタルサイト類、リン含有化合物などが挙げられる。また、難燃剤は1種を単独で用いてもよく、2種以上を併用してもよい。
式中、R1、R2及びR3は、それぞれ独立に、ハロゲン原子以外の置換基を示す。
本発明の難燃性硬化性樹脂組成物には、(C)ブロック共重合体が含まれる。ブロック共重合体とは一般的に性質の異なる二種類以上のポリマーが、共有結合で繋がり長い連鎖になった分子構造の共重合体を呼ぶ。
また、ABAあるいはABA’型ブロック共重合体のうち、AないしA’がTgが50℃以上のポリマー単位からなり、BがTgが-20℃以下であるポリマー単位からなるブロック共重合体がさらに好ましい。
また、ABAあるいはABA’型ブロック共重合体のうち、AないしA’が上記(A)カルボキシル基含有樹脂との相溶性が高いものが好ましく、Bが上記(A)カルボキシル基含有樹脂との相溶性が低いものが好ましい。このように、両端のブロックがマトリックスに相溶であり、中央のブロックがマトリックスに不相溶であるブロック共重合体とすると、マトリックス中において特異的な構造を示しやすくなると考えられる。
また、株式会社クラレ製のクラリティもメタクリル酸メチルとアクリル酸ブチルより誘導されるブロック共重合体である。
本発明の難燃性硬化性樹脂組成物は、耐熱性、絶縁信頼性等の特性を向上させる目的で用いられる(D)熱硬化性成分を含む。(D)熱硬化性成分としては、イソシアネート化合物、ブロックイソシアネート化合物、アミノ樹脂、マレイミド化合物、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、多官能エポキシ化合物、多官能オキセタン化合物、エピスルフィド樹脂などの公知慣用の熱硬化性樹脂が使用できる。これらの中でも好ましい熱硬化性成分は、1分子中に複数の環状エーテル基及び/又は環状チオエーテル基(以下、環状(チオ)エーテル基と略称する)を有する熱硬化性成分である。これら環状(チオ)エーテル基を有する熱硬化性成分は、市販されている種類が多く、その構造によって多様な特性を付与することができる。
本発明の難燃性硬化性樹脂組成物を光硬化性樹脂組成物に組成するために、光重合開始剤を配合することができる。光重合開始剤としては、オキシムエステル基を有するオキシムエステル系光重合開始剤、α-アミノアセトフェノン系光重合開始剤、およびアシルホスフィンオキサイド系光重合開始剤からなる群から選択される1種以上の光重合開始剤が好ましい。
(式中、Xは、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている)を表し、Y、Zはそれぞれ、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、ハロゲン基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている)、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Arは、炭素数1~10のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、2,5-ピロール-ジイル、4,4’-スチルベン-ジイル、4,2’-スチレン-ジイルを表し、nは0又は1の整数である。)
また、アシルホスフィンオキサイド系光重合開始剤の使用は、光反応時の深部硬化性を向上させ、更に光照射により開裂した開始剤由来リン含有化合物成分が硬化物ネットワークに組み込まれることにより、硬化塗膜中のリン濃度を効果的に高めることができ、更なる難燃性の向上を可能とする。
その他、本発明の難燃性硬化性樹脂組成物に好適に用いることができる光開始助剤及び増感剤としては、ベンゾイン化合物、アセトフェノン化合物、アントラキノン化合物、チオキサントン化合物、ケタール化合物、ベンゾフェノン化合物、3級アミン化合物、及びキサントン化合物などを挙げることができる。
本発明において、難燃性硬化性樹脂組成物を光硬化性樹脂組成物に組成するために分子中に1個以上のエチレン性不飽和基を有する化合物(光重合性モノマー)を用いることができる。光重合性モノマーは、活性エネルギー線照射により、光硬化して、前記(A)カルボキシル基含有樹脂を、アルカリ水溶液に不溶化、又は不溶化を助けるものである。
本発明の硬化性樹脂組成物は、着色剤を配合することができる。着色剤としては、赤、青、緑、黄、黒、白などの慣用公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。具体的には、下記のようなカラーインデックス(C.I.;ザ ソサイエティ オブ ダイヤーズ アンド カラリスツ(The Society of Dyers and Colourists)発行)番号が付されているものを挙げることができる。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しない着色剤であることが好ましい。
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。
黒色着色剤としては、公知慣用の黒色着色剤を使用することができる。黒色着色剤としては、C.I.Pigmentblack6、7、9および18等に示されるカーボンブラック系の顔料、C.I.Pigment black 8、10等に示される黒鉛系の顔料、C.I.Pigment black 11、12および27,Pigment Brown35等で示される酸化鉄系の顔料:例えば戸田工業社製KN-370の酸化鉄、三菱マテリアル社製13Mのチタンブラック、C.I.Pigment black 20等で示されるアンスラキノン系の顔料、C.I.Pigment black13、25および29等で示される酸化コバルト系の顔料、C.I.Pigmentblack 15および28等で示される酸化銅系の顔料、C.I.Pigment black 14および26等で示されるマンガン系の顔料、C.I.Pigment black23等で示される酸化アンチモン系の顔料、C.I.Pigment black 30等で示される酸化ニッケル系の顔料、C.I.Pigmentblack 31、32で示されるペリレン系の顔料、Pigment Black 1で示されるアニリン系の顔料および硫化モリブデンや硫化ビスマスも好適な顔料として例示できる。これらの顔料は、単独で、または適宜組合せて使用される。特に好ましいのは、カーボンブラックであり例えば、三菱化学社製のカーボンブラック、M-40、M-45、M-50、MA-8、MA-100、またペリレン系の顔料は有機顔料の中でも低ハロゲン化に有効である。
白色顔料としては、酸化チタン、特に、ルチル型酸化チタンを用いるのが望ましい。アナターゼ型酸化チタンは、ルチル型と比較して白色度が高いためによく使用される。しかしながら、アナターゼ型酸化チタンは、光触媒活性を有するために、ソルダーレジスト組成物中の樹脂の変色を引き起こすことがある。これに対し、ルチル型酸化チタンは、白色度はアナターゼ型と比較して若干劣るものの、光活性を殆ど有さないために、安定したソルダーレジスト膜を得ることができる。ルチル型酸化チタンとしては、公知のルチル型のものを使用することができる。具体的には、富士チタン工業社製TR-600、TR-700、TR-750、TR-840、石原産業社製R-550、R-580、R-630、R-820、CR-50、CR-60、CR-90、チタン工業社製KR-270、KR-310、KR-380等を使用することができる。
具体的に例示すれば、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet13、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等がある。
本発明の難燃性硬化性樹脂組成物は、得られる硬化物の物理的強度等を上げるために、必要に応じて、フィラーを配合することができる。このようなフィラーとしては、公知慣用の無機又は有機フィラーが使用できるが、特に硫酸バリウム、球状シリカ、タルクが好ましく用いられる。また、難燃性を付与する目的で、水酸化アルミニウム、水酸化マグネシウム、ベーマイトなども使用することができる。さらに、1個以上のエチレン性不飽和基を有する化合物や前記多官能エポキシ樹脂にナノシリカを分散したHanse-Chemie社製のNANOCRYL(商品名) XP 0396、XP 0596、XP 0733、XP 0746、XP 0765、XP 0768、XP 0953、XP 0954、XP 1045(何れも製品グレード名)や、Hanse-Chemie社製のNANOPOX(商品名) XP 0516、XP 0525、XP 0314(何れも製品グレード名)も使用できる。これらを単独で又は2種以上配合することができる。
本発明の難燃性硬化性樹脂組成物には得られる硬化物の可撓性、指触乾燥性の向上を目的に慣用公知のバインダーポリマーを使用することができる。バインダーポリマーとしてはセルロース系、ポリエステル系、フェノキシ樹脂系ポリマーが好ましい。セルロース系ポリマーとしてはイーストマン社製セルロースアセテートブチレート(CAB)、セルロースアセテートプロピオネート(CAP)シリーズが挙げられ、ポリエステル系ポリマーとしては東洋紡社製バイロンシリーズ、フェノキシ樹脂系ポリマーとしてはビスフェノールA、ビスフェノールFおよびそれらの水添化合物のフェノキシ樹脂が好ましい。
本発明の難燃性硬化性樹脂組成物は、得られる硬化物に対する柔軟性の付与、硬化物の脆さの改善などを目的にエラストマーを配合することができる。エラストマーとしては、例えばポリエステル系エラストマー、ポリウレタン系エラストマー、ポリエステルウレタン系エラストマー、ポリアミド系エラストマー、ポリエステルアミド系エラストマー、アクリル系エラストマー、オレフィン系エラストマーが挙げられる。また、種々の骨格を有するエポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン-アクリロニトリルゴムで変性した樹脂なども使用できる。更にはエポキシ含有ポリブタジエン系エラストマー、アクリル含有ポリブタジエン系エラストマー、水酸基含有ポリブタジエン系エラストマー、水酸基含有イソプレン系エラストマー等も使用することができる。エラストマーは、1種を単独で用いてもよく、2種類以上の混合物として使用してもよい。
本発明の難燃性硬化性樹脂組成物には層間の密着性、又は感光性樹脂層と基材との密着性を向上させるために密着促進剤を用いることができる。密着促進剤としては、例えば、ベンズイミダゾール、ベンズオキサゾール、ベンズチアゾール、2-メルカプトベンズイミダゾール、2-メルカプトベンズオキサゾール、2-メルカプトベンズチアゾール、3-モルホリノメチル-1-フェニル-トリアゾール-2-チオン、5-アミノ-3-モルホリノメチル-チアゾール-2-チオン、2-メルカプト-5-メチルチオ-チアジアゾール、トリアゾール、テトラゾール、ベンゾトリアゾール、カルボキシベンゾトリアゾール、アミノ基含有ベンゾトリアゾール、シランカップリング剤などがある。
高分子材料の多くは、一度酸化が始まると、次々と連鎖的に酸化劣化が起き、高分子素材の機能低下をもたらすことから、本発明の難燃性硬化性樹脂組成物には酸化を防ぐために(1)発生したラジカルを無効化するようなラジカル補足剤または/及び(2)発生した過酸化物を無害な物質に分解し、新たなラジカルが発生しないようにする過酸化物分解剤などの酸化防止剤を添加することができる。
高分子材料は光を吸収し、それにより分解・劣化を起こすことから、本発明の難燃性硬化性樹脂組成物は紫外線に対する安定化対策を行うために、上記酸化防止剤の他に、紫外線吸収剤を使用することができる。
紫外線吸収剤としてはベンゾフェノン誘導体、ベンゾエート誘導体、ベンゾトリアゾール誘導体、トリアジン誘導体、ベンゾチアゾール誘導体、シンナメート誘導体、アントラニレート誘導体、ジベンゾイルメタン誘導体などが挙げられる。具体的なベンゾフェノン誘導体の例としては2-ヒドロキシ-4-メトキシ-ベンゾフェノン2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-n-オクトキシベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン及び2,4-ジヒドロキシベンゾフェノンなど;具体的なベンゾエート誘導体の例としては2-エチルヘキシルサリチレート、フェニルサリチレート、p-t-ブチルフェニルサリチレート、2,4-ジ-t-ブチルフェニル-3,5-ジ-t-ブチル-4-ヒドロキシベンゾエート及びヘキサデシル-3,5-ジ-t-ブチル-4-ヒドロキシベンゾエートなど;具体的なベンゾトリアゾール誘導体の例としては2-(2’-ヒドロキシ-5’-t-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)エンゾトリアゾール、2-(2’-ヒドロキシ-3’-t-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-t-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール及び2-(2’-ヒドロキシ-3’,5’-ジ-t-アミルフェニル)ベンゾトリアゾール;具体的なトリアジン誘導体の例としてはヒドロキシフェニルトリアジン、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジンなどが挙げられる。
上記の紫外線吸収剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いることもできる。上記酸化防止剤と併用することで本発明の硬化性樹脂組成物より得られる成形物の安定化が図れる。
本発明の難燃性硬化性樹脂組成物は、さらに必要に応じて、ハイドロキノン、ハイドロキノンモノメチルエーテル、t-ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び/又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤、防錆剤などのような公知慣用の添加剤類を配合することができる。
さらに、本発明の難燃性硬化性樹脂組成物は、上記(A)カルボキシル基含有樹脂の合成や組成物の調製のため、又は基板やキャリアフィルムに塗布するための粘度調整のため、有機溶剤を使用することができる。
ドライフィルム化に際しては、本発明の難燃性硬化性樹脂組成物を前記有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~130℃の温度で1~30分間乾燥して膜を得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で、10~150μm、好ましくは20~60μmの範囲で適宜選択される。
剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。
[A-1:前記カルボキシル基含有樹脂(5)に該当する樹脂の合成]
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(旭化成ケミカルズ社製、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。得られたワニスを以下、A-1と称する。
前記カルボキシル基含有樹脂(7)に該当し、感光性基含有でビフェニルノボラック構造の多官能エポキシを使用した感光性カルボキシル基含有樹脂[日本化薬社製ZCR-1601H(固形分65%、樹脂としての酸価は98mgKOH/g)]を用いた。ワニスを以下、A-2と称する。
1Lオートクレーブに、オルソクレゾールと4,4’-ビス(クロロメチル)ビフェニルの縮合反応により得られるビフェニルアラルキル樹脂(水酸基当量232g/eq、平均核体数3.1)313.2g、水酸化カリウム3.13g、トルエン344.1gを仕込み130℃まで昇温しながら攪拌し溶解した。次にプロピレンオキサイド87.8gを徐々に滴下し、125~130℃、0.15~0.40MPaで10時間反応させた。その後、室温まで冷却し、反応溶液に85%リン酸を4.11g添加して水酸化カリウムを中和した。水酸基当量296g/eq、樹脂分54.8%のプロピレンオキサイド付加物溶液を得た。
MAMタイプのブロック共重合体M51(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-1とする。
MAMタイプのブロック共重合体M52(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-2とする。
MAMタイプのブロック共重合体M53(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-3とする。
MAMタイプのブロック共重合体M22(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-4とする。
親水基変性処理されたMAM Nタイプのブロック共重合体M52N(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-5とする。
親水基変性処理されたMAM Nタイプのブロック共重合体M22N(アルケマ社製)15gにカルビトールアセテート50gを加え、攪拌し、85℃にて加熱することにより溶解させた。これをワニスB-6とする。
三菱レイヨン社製BR-87(主成分:ポリメチルメタアクリレート、Mw:25,000)15gにカルビトールアセテート50gを加え、攪拌し、100℃にて加熱することにより溶解させた。これをワニスC-1とする。
根上工業社製AS-3000E(主成分:ポリブチルアクリレート、Mw:650,000、固形分30%)を用いた。これをワニスC-2とする。
上記の樹脂溶液(ワニス)を、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、難燃性硬化性樹脂組成物を調製した。ここで、得られた各難燃性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。
*2:大塚化学社製SPE-100
*3:クラリアント社製エクソリットOP935
*4:昭和電工社製ハイジライトH-42M
*5:ビフェノールノボラック型エポキシ樹脂のカルビトールアセテート溶液(固形分75%)日本化薬社製NC-3000-H-CA75
*6:旭化成ケミカルズ社製TPA-B80E
*7:BASFジャパン社製TPO
*8:BASFジャパン社製OXE-02
*9:東亞合成社製 M-350
*10:日本化薬社製UX-2201
*11:C.I.Pigment Blue 15:3
*12:C.I.Pigment Yellow147
*13:ジエチレングリコールモノエチルエーテールアセテート
*14:宇部興産社製 カルボキシル基末端ブタジエンニトリルゴム
*15:石原産業社製 二酸化チタン CR97
*16:三菱化学社製 カーボンブラック M-50
<最適露光量>
上記実施例2~10及び比較例2~4の難燃性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。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1~10及び比較例1~4の難燃性硬化性樹脂組成物を銅べた基板上にスクリーン印刷で全面塗布し、80℃で30分乾燥させた。乾燥塗膜の指触乾燥性を確認する。
○:べたつきがないもの。
△:僅かにべたつきがあるもの。
×:べたつきがあるもの。
上記各実施例及び比較例の難燃性硬化性樹脂組成物を、25μm厚のポリイミドフィルム(東レ・デュポン社製カプトン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、比較例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2~10及び比較例2~4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、クラックが発生するまでに行った折り曲げ回数を測定し、可撓性を評価した。
◎:折り曲げ回数が5回以上であるもの。
○:折り曲げ回数が3~4回であるもの。
△:折り曲げ回数が1~2回であるもの。
×:折り曲げ回数が0回であるもの。
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。
実施例1、比較例1の熱硬化性樹脂組成物をパターン形成されたポリイミドフィルム基板上にパターン印刷を行い、80℃で30分乾燥し、室温まで放冷したのち150℃で60分加熱して硬化した。実施例2~10及び比較例2~4の光硬化性熱硬化性樹脂組成物については、パターン形成されたポリイミドフィルム基板上にスクリーン印刷で全面塗布した後80℃で30分乾燥し、室温まで放冷した。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2kg/cm2の条件で60秒間現像を行い、レジストパターンを得た。この基板を、150℃で60分加熱して硬化した。得られたプリント基板(評価基板)をクッション材ではさみSUS板を用いて20kgf/cm2の加重を与え150℃で60分真空プレスを行った。プレス後の基板の開口部を目視および200倍の光学顕微鏡で観察しブリードアウトの確認を行い以下の基準で評価した。
○:開口部にブリードアウトなし。
×:開口部にブリードアウトあり。
各実施例及び比較例の難燃性硬化性樹脂組成物を、25μm、12.5μm厚のポリイミドフィルム(東レデュポン社製、カプトン100H(25μm)、カプトン50H(12.5μm))にスクリーン印刷で全面塗布し、80℃で30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30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及び比較例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2~10及び比較例2~4の光硬化性熱硬化性樹脂組成物については、得られた両面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1wt%Na2CO3水溶液をスプレー圧2kg/cm2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2~10に示す難燃性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難燃性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(PET)上に塗布し、加熱乾燥して、厚さ20μmの感光性樹脂組成物層を形成し、その上にカバーフィルム(PP)を貼り合わせてドライフィルムを得た。その後、カバーフィルムを剥がし、パターン形成された銅箔基板に、ラミネーターを用いフィルムを貼り合わせ、試験基板を作製した。前述した試験方法及び評価方法と同様にして、各特性の評価試験を行なった。なお、実施例2の組成によるドライフィルムが実施例11、実施例3の組成が実施例12、実施例4の組成が実施例13、実施例5の組成が実施例14、実施例6の組成が実施例15、実施例7の組成が実施例16、実施例8の組成が実施例17、実施例9の組成が実施例18、実施例10の組成が実施例19にそれぞれ対応する。結果を下記表3に記す。
Claims (8)
- (A)カルボキシル基含有樹脂、
(B)難燃剤、
(C)ブロック共重合体、および、
(D)熱硬化性成分、
を含有することを特徴とする難燃性硬化性樹脂組成物。 - さらに、光重合開始剤、及び、光重合性モノマーを含有する請求項1記載の難燃性硬化性樹脂組成物。
- 前記(A)カルボキシル基含有樹脂が、ビスフェノールA構造、ビスフェノールF構造、ビフェノール構造、ビフェノールノボラック構造、ビスキシレノール構造、ビフェニルノボラック構造およびウレタン構造からなる群から選ばれる部分構造を有するカルボキシル基含有樹脂である請求項1または2記載の難燃性硬化性樹脂組成物。
- 前記(C)ブロック共重合体が、下記式(I)、
A-B-A (I)
(式中、Aはガラス転移点Tgが0℃以上のポリマー単位であり、Bはガラス転移点Tgが0℃未満のポリマー単位である。)
で表されるブロック共重合体である請求項1または2記載の難燃性硬化性樹脂組成物。 - ソルダーレジストである請求項1または2記載の難燃性硬化性樹脂組成物。
- 請求項1または2記載の難燃性硬化性樹脂組成物をフィルムに塗布乾燥してなることを特徴とするドライフィルム。
- 請求項1または2記載の難燃性硬化性樹脂組成物、または、請求項6に記載のドライフィルムを熱硬化及び/又は光硬化して得られることを特徴とする難燃性被膜。
- 請求項1または2記載の難燃性硬化性樹脂組成物又は請求項6に記載のドライフィルムを熱硬化及び/又は光硬化して得られる難燃性被膜を備えることを特徴とするプリント配線板。
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KR20140023323A (ko) | 2014-02-26 |
JP5865369B2 (ja) | 2016-02-17 |
CN103619960B (zh) | 2016-11-16 |
KR101907714B1 (ko) | 2018-10-12 |
CN103619960A (zh) | 2014-03-05 |
JPWO2012173241A1 (ja) | 2015-02-23 |
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