CN112888748A - Resin composition, cured film, printed wiring board with cured film, and method for producing same - Google Patents

Resin composition, cured film, printed wiring board with cured film, and method for producing same Download PDF

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Publication number
CN112888748A
CN112888748A CN201980068811.6A CN201980068811A CN112888748A CN 112888748 A CN112888748 A CN 112888748A CN 201980068811 A CN201980068811 A CN 201980068811A CN 112888748 A CN112888748 A CN 112888748A
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resin composition
group
cured film
resin
composition according
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CN112888748B (en
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松永宏树
木户雅善
小木曽哲哉
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
    • 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
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)

Abstract

The resin composition comprises (a) a binder resin, (b) a thermosetting resin, and (c) a flame retardant. (a) The binder resin is a polymer having a urethane bond in the molecule, and may further have a carboxyl group and/or lightA polymerizable functional group. (c) The flame retardant is an organic phosphorus compound represented by the following general formula. In the formula, R2And R5Each independently is an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted anthracenyl group; r1、R3、R4And R6Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group.

Description

Resin composition, cured film, printed wiring board with cured film, and method for producing same
Technical Field
The present invention relates to a resin composition, a cured film obtained by curing the resin composition, and a printed wiring board provided with the cured film.
Background
An insulating cured film is formed on a circuit of a printed wiring board using an insulating thermosetting resin or an ultraviolet curable resin for maintaining insulation reliability. Flame retardancy is sometimes required for an insulating cured film, and a non-halogen flame retardant is used from the viewpoint of environmental load (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-21243
Disclosure of Invention
Problems to be solved by the invention
In order to provide sufficient flame retardancy to the insulating cured film on the printed wiring board, a large amount of a flame retardant needs to be added, which may cause a decrease in strength and heat resistance of the cured film. Further, when a liquid flame retardant is used, bleeding may occur, and when a flame retardant such as a metal phosphinate or aluminum hydroxide is used, the flame retardant may be eluted or detached by chemical solution treatment after alkali development and curing. Further, if a large amount of a flame retardant is added to improve flame retardancy, flexibility of the cured film may be reduced.
The purpose of the present invention is to provide a cured film having excellent flame retardancy, being less likely to cause defects such as bleeding, and having excellent flexibility, and a resin composition for forming the cured film.
Means for solving the problems
The resin composition of the present invention comprises (a) a binder resin, (b) a thermosetting resin, and (c) a flame retardant. (a) The binder resin is a polymer having a urethane bond in the molecule, and may further have a carboxyl group and/or a photopolymerizable functional group. The acid value of the binder resin may be 5 to 200 mgKOH/g. (b) The thermosetting resin is, for example, a polyfunctional epoxy resin.
(c) The flame retardant is an organic phosphorus compound (spiro diphosphonate compound) shown in the following general formula.
Figure BDA0003026234890000021
In the formula, R2And R5Each independently is a phenyl group optionally having a substituent, a naphthyl group optionally having a substituent, or an anthracenyl group optionally having a substituent. R1、R3、R4And R6Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted anthracenyl group.
The resin composition may further contain (d) a compound having an ethylenically unsaturated group (photocurable compound), (e) a photopolymerization initiator, and (f) a colorant, in addition to the above-described component (a), (b), and (c). The content of the component (c) in the resin composition may be about 10 to 30 parts by weight based on 100 parts by weight of the total solid content.
The resin composition is applied to a substrate, and a solvent is dried as necessary to form a coating film (insulating film). The insulating film is photo-cured and/or thermally cured to obtain a cured film. For example, a printed wiring board with a cured film can be formed by applying the resin composition to the surface of a printed wiring board to form a coating film, irradiating at least a part of the surface of the coating film with active light to perform photocuring, developing with alkali or the like as necessary, and then heating and thermally curing the photocured coating film. The printed wiring board may be a flexible printed wiring board using a flexible film base material such as a polyimide film.
ADVANTAGEOUS EFFECTS OF INVENTION
The cured film formed from the resin composition has excellent flame retardancy, is less likely to cause troubles such as bleeding of the flame retardant, and has excellent flexibility.
Detailed Description
The resin composition of the present invention comprises (a) a binder resin, (b) a thermosetting resin, and (c) an organophosphorus compound. Since the resin composition has a thermosetting resin, the resin composition has thermosetting properties. (a) The binder resin may have reactivity with the thermosetting resin.
(a) The binder resin may have a photocurable functional group such as an ethylenically unsaturated group. By including a binder resin having photocurability in the resin composition, the resin composition has both thermosetting properties and photocurability (photosensitivity). The resin composition may further contain (d) a compound having an ethylenically unsaturated group (photocurable compound). The resin composition may further contain (e) a photopolymerization initiator.
The resin composition may further contain (f) a colorant. By containing the colorant, the insulating film obtained from the resin composition can be colored as desired.
< adhesive resin >
The binder resin is a polymer that is soluble in an organic solvent and has a weight average molecular weight of 1000 or more and 1000000 or less in terms of polyethylene glycol. The weight average molecular weight of the binder resin is more preferably 2000 to 200000, still more preferably 3000 to 100000, and particularly preferably 4000 to 50000. If the weight average molecular weight of the binder resin is within the above range, a cured film excellent in heat resistance and flexibility can be easily obtained.
The binder resin is a urethane polymer having at least 1 urethane bond in the molecule. By using a urethane polymer as the binder resin and an organic phosphorus compound described later as the flame retardant (c), excellent flame retardancy can be imparted without lowering the flexibility of the insulating cured film. Urethane-based polymers are obtained, for example, by the reaction of a diol with a diisocyanate.
The diisocyanate compound may be any of an alicyclic diisocyanate compound and an aliphatic diisocyanate compound. The diisocyanate compound may be a reaction product formed with a compound having two or more functional groups capable of reacting with an isocyanate group, and may be, for example, a urethane compound having an isocyanate group at an end.
The diisocyanate compound may be any of aromatic isocyanate, alicyclic isocyanate, and aliphatic isocyanate and alicyclic diisocyanate. The diisocyanate compound may be a reactant formed with a compound having two or more functional groups capable of reacting with an isocyanate group of the diisocyanate compound, and may be, for example, a urethane compound having an isocyanate group at an end. Among them, when an alicyclic diisocyanate or an aliphatic diisocyanate is used, the resin composition tends to have excellent photosensitivity. Examples of the alicyclic diisocyanate include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the diol include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol; polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random copolymers of tetramethylene glycol and neopentyl glycol; a polyester diol obtained by reacting a polyhydric alcohol with a polybasic acid; a polycarbonate diol having a carbonate skeleton; polycaprolactone diol obtained by subjecting lactones such as γ -butyrolactone, e-caprolactone and δ -valerolactone to a ring-opening addition reaction; bisphenol A, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, hydrogenated bisphenol A, ethylene oxide adducts of hydrogenated bisphenol A, propylene oxide adducts of hydrogenated bisphenol A, and the like. Two or more kinds of diols may be used in combination. Among the above, when a long-chain diol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyalkylene glycol, polyester glycol, polycarbonate glycol, or polycaprolactone glycol is used, the elastic modulus of the cured film tends to be lowered, and the flexibility tends to be improved.
The binder resin may have a carboxyl group in the molecule. Since the carboxyl group is present, the binder resin reacts with the component (b) described below, and thus the heat resistance and chemical resistance of the cured film tend to be improved. When used in the form of a photosensitive resin composition, the binder resin has a carboxyl group, so that the solubility in an alkali developing solution is improved, and thus a fine pattern can be formed by development in a short time. The acid value of the binder resin is preferably 5 to 200mgKOH/g, more preferably 15 to 100 mgKOH/g. By providing the binder resin with an appropriate acid value, the crosslinked structure with the component (b) is densely formed, and therefore, the heat resistance, insulation reliability, and chemical resistance of the cured film can be improved.
The polymer having a carboxyl group in the molecule can be obtained, for example, by using a compound having 2 hydroxyl groups and 1 carboxyl group in the molecule as a diol component for forming the urethane-based polymer. Examples of the diol compound having 2 hydroxyl groups and 1 carboxyl group include aliphatic diols such as 2, 2-bis (hydroxymethyl) propionic acid, 2-bis (2-hydroxyethyl) propionic acid, 2-bis (3-hydroxypropyl) propionic acid, 2, 3-dihydroxy-2-methylpropionic acid, 2-bis (hydroxymethyl) butyric acid, 2-bis (2-hydroxyethyl) butyric acid, 2-bis (3-hydroxypropyl) butyric acid, 2, 3-dihydroxybutyric acid, 2, 4-dihydroxy-3, 3-dimethylbutyric acid, and 2, 3-dihydroxyhexadecanoic acid; aromatic diols such as 2, 3-dihydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, and 3, 5-dihydroxybenzoic acid.
The binder resin may have an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "(meth) acryloyl group" means acryloyl group or methacryloyl group.
The photocurable film may be formed from the resin composition as long as the binder resin has a photocurable functional group such as a (meth) acryloyl group. When the resin composition contains the component (d) described later, the binder resin having a photocurable functional group also reacts with the component (d), and therefore the crosslinking density of the photocurable film is increased, and the heat resistance and chemical resistance tend to be improved. Since the photocrosslinking density is increased, elution of the flame retardant into a developer or the like tends to be suppressed.
The polymer having a (meth) acryloyl group in a molecule can be obtained, for example, by using a compound containing a hydroxyl group and at least 1 (meth) acryloyl group in a molecule and/or a compound containing an isocyanate group and at least 1 (meth) acryloyl group in a molecule in addition to a diol component and a diisocyanate component for forming a urethane polymer.
Examples of the compound having a hydroxyl group and a (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, o-phenylphenol glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, 2-hydroxy-phenyl) ethyl (meth) acrylate, and the like, N-methylolacrylamide, 3, 5-dimethyl-4-hydroxybenzylacrylamide and the like. Examples of the compound having an isocyanate group and a (meth) acryloyl group in a molecule include 2- (meth) acryloyloxyethyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate, and 2- (2-methacryloyloxyethyloxy) ethyl isocyanate.
The binder resin may have 2 or more photocurable functional groups in 1 molecule. For example, in the polymerization of a urethane polymer, if a compound having 1 hydroxyl group and 1 (meth) acryloyl group in 1 molecule is used in addition to a diol and a diisocyanate and the ratio thereof is increased, a urethane di (meth) acrylate having (meth) acryloyl groups at both ends of a polymer chain can be obtained.
The content of the component (a) in the resin composition is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, and even more preferably 30 to 60 parts by weight, based on 100 parts by weight of the total solid content, from the viewpoint of improving adhesion between a cured film formed from the resin composition and a substrate material such as a polyimide film.
< b) thermosetting resin >
The thermosetting resin is a compound having at least 1 thermosetting functional group in a molecule. Examples of the thermosetting resin include epoxy resins, oxetane resins, isocyanate resins, blocked isocyanate resins, bismaleimide resins, diallyl nadimide resins, polyester resins (for example, unsaturated polyester resins), diallyl phthalate resins, silicone resins, vinyl ester resins, melamine resins, polybismaleimide triazine resins (BT resins), cyanate ester resins (for example, cyanate ester resins), urea resins, guanamine resins, sulfonamide resins, aniline resins, polyurea resins, thiocarbamate resins, polymethine resins, episulfide resins, ene-thiol resins, and benzoxazine resins. A polyfunctional epoxy resin having 2 or more epoxy groups in 1 molecule is preferable because it can impart heat resistance to the cured film and can impart adhesiveness to a conductor such as a metal foil or a circuit board.
Examples of the polyfunctional epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, biphenyl type epoxy resin, phenoxy type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, and amine type epoxy resin. The epoxy resin may be a modified epoxy resin based on urethane, rubber, chelate, dimer acid, or the like. As the component (b), a commercially available epoxy resin can be used as it is.
From the viewpoint of heat resistance and chemical resistance of the cured film, the epoxy equivalent (mass (g) of the compound containing 1 equivalent of epoxy group) of the epoxy resin is preferably 2000 or less, and more preferably 1500 or less. The epoxy resin preferably has a weight average molecular weight of about 150 to 2000, more preferably about 200 to 1500.
The content of the component (b) in the resin composition is preferably 1 to 70 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 10 to 20 parts by weight, based on 100 parts by weight of the total solid content, from the viewpoint of improving the heat resistance and chemical resistance of a cured film formed from the resin composition.
The resin composition may contain a curing agent and/or a curing accelerator for thermosetting resins. Examples of the curing agent include phenol resins such as phenol novolac resin, cresol novolac resin, and naphthalene-type phenol resin; amino resins, urea resins, melamine, dicyandiamide, and the like. Examples of the curing accelerator include phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, triethanolamine and tetraethanolamine; borate compounds such as 1, 8-diazabicyclo [5,4,0] -7-undecenium tetraphenylborate; imidazoles such as imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2, 4-dimethylimidazole, and 2-phenyl-4-methylimidazole; imidazolines such as 2-methylimidazoline, 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2, 4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline; oxazine imidazoles such as 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, and 2, 4-diamino-6 [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine.
< flame retardant >
The resin composition contains an organophosphorus compound (spiro diphosphonate compound) represented by the following general formula as a flame retardant.
Figure BDA0003026234890000071
In the formula, R2And R5Each independently is a phenyl group optionally having a substituent, a naphthyl group optionally having a substituent, or an anthracenyl group optionally having a substituent. R1、R3、R4And R6Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted anthracenyl group.
The above-mentioned organophosphorus compound can be produced, for example, by the method described in Japanese patent laid-open publication No. 2004-35480.
By using a urethane polymer as a binder resin and a spiro diphosphonate compound as a flame retardant, an insulating film exhibiting excellent flame retardancy can be obtained by adding a small amount of the flame retardant. Since the amount of the flame retardant to be added is small, the decrease in heat resistance and film strength associated with the addition of the flame retardant can be suppressed. The reason why the flame retardancy is improved by the combination of the binder resin and the flame retardant is considered to be that the thermal decomposition behavior of the polymer and the flame retardant is matched. For example, it can be considered that: since free radicals generated by thermal decomposition of the polymer are trapped in the flame retardant, it is a main reason that the chain reaction can be stopped at the initial stage of combustion, which contributes to improvement of flame retardancy.
When the resin composition is used as a photosensitive resin composition, the use of a spiro diphosphonate compound as a flame retardant makes it difficult for the flame retardancy and adhesion of a photocurable film to change before and after alkali development, and the bleeding of the flame retardant to occur. The reason why the change in characteristics before and after the alkali development is small is as follows: the flame retardant is an organic phosphorus compound, so that the flame retardant has high compatibility with the binder resin; the flame retardant is solid at room temperature and is difficult to dissolve in an alkali developing solution.
In general, a cured film containing a flame retardant tends to have a lower flexibility and a lower bending resistance as the content of the flame retardant increases, but in the combination of the urethane polymer as the component (a) and the spiro diphosphonate flame retardant as the component (c), the flexibility is less likely to decrease even without adding a flame retardant. Therefore, the resin composition of the present invention can also be suitably used for forming an insulating protective film of a flexible printed circuit board for a foldable device.
The content of the component (c) in the resin composition is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total solid content. The spirocyclic diphosphonate-based compound is less in amount and more likely to exhibit a flame retardant effect even when compared with an inorganic phosphorus-based compound. Therefore, the content of the component (c) in the resin composition may be 20 parts by weight or less or 15 parts by weight or less. The amount of phosphorus contained in the total solid content of the resin composition is preferably 0.5 to 10 wt%, more preferably 1 to 7 wt%, and still more preferably 1.5 to 5 wt%. The content of the phosphorus atom may be 4% by weight or less or 3% by weight or less.
[ photo-curable Compound ]
The resin composition may contain a photocurable compound. The resin composition has photosensitivity by containing the photocurable compound. (a) When the binder resin has a photocurable functional group, the photocurable compound also reacts with the component (a), and therefore the crosslinking density of the photocurable film is increased, and the heat resistance and chemical resistance tend to be improved.
The photocurable compound has at least 1 photocurable functional group. The photocurable functional group is preferably an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group. (d) Component (c) preferably has 2 or more photocurable functional groups in 1 molecule.
From the viewpoint of increasing the crosslinking density of the photocurable film, a material having a lower molecular weight than that of the component (a) can be used as the component (d). (d) The weight average molecular weight of the component (b) is preferably 2000 or less, more preferably 1500 or less, and still more preferably less than 1000. (d) The equivalent weight of the functional group of the component (mass (g) of the compound containing 1 equivalent of the ethylenically unsaturated group) is preferably 1000 or less, more preferably 750 or less, and still more preferably 500 or less.
Examples of the polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups in 1 molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1- (meth) acryloyloxy-3- (meth) acryloyloxypropyl, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2, 4-diethyl-1, 5-pentanediol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 3-methyl-1, 5-pentanediol di (meth) acrylate, 2, 4-diethyl-1, 5-pentanediol di (meth) acrylate, 1, 4-cyclohexanedimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 4' -isopropylidenediphenol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxy-diethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, 2, 4-diethyl-pentanediol di (meth) acrylate, 2, 4-isopropylidene diphenol di (meth) acrylate, and mixtures thereof, Difunctional (meth) acrylates such as 2, 2-bis [4- ((meth) acryloyloxy-polyethoxy) phenyl ] propane, 2-hydrogenated bis [4- ((meth) acryloyloxy-polyethoxy) phenyl ] propane, 2-bis [4- ((meth) acryloyloxy-polypropoxy) phenyl ] propane, bisphenol F EO-modified (n ═ 2 to 50) di (meth) acrylate, bisphenol a EO-modified (n ═ 2 to 50) di (meth) acrylate, and bisphenol S EO-modified (n ═ 2 to 50) di (meth) acrylate; trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, isocyanuric acid tri (ethane (meth) acrylate), 1,3, 5-tri (meth) acryloyl hexahydro-s-triazine, and the like; tetrafunctional or higher (meth) acrylates such as tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol poly (meth) acrylate. Among the above, bisphenol a EO-modified (n-2 to 50) di (meth) acrylate is preferable because the solubility of the photosensitive resin composition in an aqueous developer such as an aqueous alkali solution is improved and the development time can be shortened.
When the resin composition contains the component (d), the content thereof is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total solid content of the resin composition.
< f photo-polymerization initiator >
(a) When the component (b) has a photopolymerizable functional group and/or when the resin composition contains the component (d), the resin composition preferably contains the photopolymerization initiator (e). The photopolymerization initiator is a compound that absorbs light energy such as UV (ultraviolet light) to activate the photopolymerization initiator and initiates/accelerates the reaction of radical polymerizable groups. By adding a photopolymerization initiator to the resin composition, the resin composition can be used as a photosensitive resin composition.
Examples of the photo radical polymerization initiator include self-cleavage type photo radical polymerization initiators such as benzoin-based compounds, acetophenones, aminoketones, oxime esters, acylphosphine oxide-based compounds, and azo-based compounds; and hydrogen abstraction type photo-radical polymerization initiators such as benzophenones, benzoin ethers, benzil ketals, dibenzosuberenones, anthraquinones, xanthenones, thioxanthones, halogenated acetophenones, dialkoxyphenones, hydroxyacetophenones, halogenated bisimidazoles, halotriazines, etc.
The content of the component (e) in the resin composition may be appropriately set. The content of the component (e) is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and still more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total of the components (a) and (d), from the viewpoint of improving photosensitivity and preventing overexposure.
< (f) colorant
By adding (f) a colorant to the resin composition, the insulating film formed of the resin composition can be colored arbitrarily. The colorant is any one of a dye or a pigment. Examples of the colorant include a blue colorant, a red colorant, a yellow colorant, an orange colorant, and a violet colorant. Insulating films of various colors can be formed by combining a plurality of coloring agents. For example, a black colorant can also be produced by combining a blue pigment, an orange pigment, and a violet pigment.
Examples of the Blue colorant include c.i. pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60; solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 as a dye system. In addition to the above, a phthalocyanine compound substituted or not substituted with a metal may be used as the blue colorant.
Examples of Orange colorants include c.i. pigment Orange 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, and 73.
Examples of the Violet colorant include c.i. pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50; solvent Violet 13, 36.
(f) The content of the component (b) may be appropriately set depending on the kind of the colorant and the color of the insulating film, and may be, for example, about 1 to 10 parts by weight, 2 to 7 parts by weight or 3 to 5 parts by weight, based on 100 parts by weight of the total solid content of the resin composition.
< other ingredients >
The resin composition may contain a solvent in addition to the components (a) to (f). The solvent is not particularly limited as long as it can dissolve a resin component such as a binder polymer, and a polar organic solvent such as a sulfoxide, a formamide, an acetamide, a pyrrolidone, an acetate, an ether, hexamethylphosphoramide, or γ -butyrolactone can be suitably used. These polar organic solvents may be used in combination with aromatic hydrocarbons such as xylene and toluene.
The resin composition may contain various additives such as a defoaming agent, a leveling agent, an adhesion imparting agent, a stabilizer, and a filler, if necessary. Examples of the defoaming agent and the leveling agent include acrylic compounds, vinyl compounds, and silicone compounds.
< preparation of resin composition >
The resin composition is prepared by mixing the above-mentioned respective components. The above-mentioned components may be subjected to pulverization, dispersion, defoaming, or the like before and/or after mixing, as necessary. The pulverization/dispersion may be carried out using a kneading apparatus such as a bead mill, a ball mill, or a three-roll mill.
< formation of insulating film >
The insulating film can be formed by applying a resin composition (solution) on a substrate and drying the solvent as necessary. As the substrate, for example, a printed circuit board can be used. By forming an insulating film on the metal wiring of the printed circuit board, insulation reliability is improved. The printed wiring board may be a flexible printed wiring board using a flexible substrate such as a polyimide film.
The resin composition may be applied to the substrate by screen printing, curtain coating, reverse roll, spray coating, spin coating using a spinner, or the like. The thickness of the coating film may be adjusted so that the thickness after drying is about 5 to 100 μm, preferably 10 to 100 μm. When drying is performed by heating, the drying temperature is preferably 120 ℃ or less, and more preferably 40 to 100 ℃ from the viewpoint of suppressing the thermosetting reaction.
The dried coating film can be directly used as an insulating film. From the viewpoint of improving the heat resistance and chemical resistance of the insulating film, it is preferable to perform curing by heat curing and/or photo curing. When a thermosetting film is formed, the component (b) may be cured by heat treatment of the coating film. (a) When the component (b) has a carboxyl group, the crosslinking density is increased by the reaction between the component (a) and the component (b). From the viewpoint of sufficiently performing heat curing and suppressing oxidation of the metal wiring by heat, the curing temperature (maximum temperature at the time of heat curing) is preferably 100 to 250 ℃ or less, more preferably 120 to 200 ℃, and further preferably 130 to 180 ℃.
When a photocurable film is formed, the coating film may be exposed. In the exposure, an exposed portion is selectively cured by disposing a negative photomask on the coating film and irradiating the coating film with active light such as ultraviolet light, visible light, or electron beam. Next, development is performed by spraying, stirring, dipping, or the like, whereby the non-exposed portion is dissolved, thereby forming a pattern cured film.
As the developer, an aqueous alkali solution is generally used. (a) When the component (a) has a carboxyl group and a photocurable functional group, the component (a) is alkali-soluble in an unexposed coating film, and the component (a) is not alkali-soluble in an exposed coating film because of photocuring. Therefore, if a photomask is disposed for exposure and developed using an alkali developer, unexposed portions are dissolved in the developer, and thus a pattern cured film is formed. As described above, the spiro diphosphonate flame retardant of component (c) is not easily eluted in an alkali developing solution, and therefore, the characteristics of the cured film, such as flame retardancy and adhesion, can be maintained even when alkali developing is performed.
Examples of the alkaline compound of the developer include alkali metals, alkaline earth metals, ammonium ions, hydroxides, carbonates, bicarbonates, and amine compounds. Specific examples of the base compound include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N-dimethylethanolamine, triethanolamine, triisopropanolamine, and triisopropanolamine.
The developing solution may contain an organic solvent having miscibility with water, such as methanol, ethanol, N-propanol, isopropanol, N-methyl-2-pyrrolidone, and the like. The alkali concentration of the developer is usually 0.01 to 20 wt%, preferably 0.02 to 10 wt%, and the temperature of the developer is usually 0 to 80 ℃, preferably 10 to 60 ℃. The developed pattern cured film (relief pattern) is preferably washed with a washing liquid such as water or an acidic aqueous solution.
The insulating film may be further subjected to heat-based thermosetting after photocuring. The coating film after photocuring has thermosetting properties because thermosetting functional groups such as epoxy groups of the component (b) remain unreacted. By heating, the carboxyl group of the component (a) reacts with the epoxy group of the component (b), and the like, a crosslinked network of the binder resin and the thermosetting resin is formed, and the heat resistance of the cured film is improved. As described above, the curing temperature is preferably 100 to 250 ℃, more preferably 120 to 200 ℃, and further preferably 130 to 180 ℃ from the viewpoint of sufficiently performing heat curing and suppressing oxidation of the metal wiring due to heat.
The cured film obtained from the resin composition has excellent heat resistance and flame retardancy, and thus can be suitably used as a surface protective material for a printed circuit board. Further, the cured film is excellent in flexibility, and therefore, it can be suitably used as a cured film for a flexible printed circuit board provided with a metal wiring on a flexible film such as a polyimide film.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[ Synthesis examples ]
In the following synthesis examples, a polymer having a carboxyl group in the molecule was polymerized. The properties of the polymers obtained in synthesis examples 1 and 2 were evaluated by the following methods.
< concentration of solid content >
Measured according to JIS K5601-1-2. The drying conditions were set at 170 ℃ for 1 hour.
< weight average molecular weight >
The measurement was performed by Gel Permeation Chromatography (GPC) under the following conditions.
The using device comprises the following steps: tosoh HLC-8220GPC equivalent device
Column: tosoh TSK gel Super AWM-H (6.0mm I.D.. times.15 cm). times.2 roots
Protection of the column: tosoh TSK guard column Super AW-H
Eluent: 30mM LiBr +20mM H3PO4 in DMF
Flow rate: 0.6mL/min
Column temperature: 40 deg.C
Detection conditions are as follows: RI: polarity (+), sensitivity (0.5sec)
Sample concentration: about 5mg/mL
Molecular weight standards: PEG (polyethylene glycol)
< acid value >
Measured according to JIS K5601-2-1.
(Synthesis example 1)
40.00g of 1, 2-bis (2-methoxyethoxy) ethane (methyltriglyme) and 20.62g of norbornene diisocyanate (0.100 mol) were put into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen gas inlet as a polymerization solvent, and heated to 80 ℃ under stirring and dissolved in a nitrogen gas flow. To this solution, 50.00g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei corporation, trade name: PCDL T5652, weight average molecular weight: 2000), 3.70g (0.025 mol) of 2, 2-bis (hydroxymethyl) butyric acid, and 13.02g (0.100 mol) of 2-hydroxyethyl methacrylate were dissolved in 40.00g of methyltriglyme for 1 hour. This solution was heated and stirred at 80 ℃ for 5 hours to obtain a solution of a urethane polymer (a1) having a carboxyl group in the molecule and a methacryloyl group at the end. The solid content concentration of the solution was 52%, the weight average molecular weight of the polymer was 8600, and the acid value was 18 mgKOH/g.
(Synthesis example 2)
100.0g of methyltriglyme as a polymerization solvent was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen gas inlet tube, and the temperature was raised to 80 ℃ while stirring under a nitrogen gas flow. 12.0g (0.14 mol) of methacrylic acid, 28.0g (0.16 mol) of benzyl methacrylate, 60.0g (0.42 mol) of butyl methacrylate, and 0.5g of azobisisobutyronitrile as a radical polymerization initiator, which had been previously mixed at room temperature, were added dropwise from a dropping funnel over 3 hours while maintaining the temperature at 80 ℃. After the completion of the dropwise addition, the reaction solution was heated to 90 ℃ with stirring, and stirred for a further 2 hours while keeping the temperature of the reaction solution at 90 ℃ to obtain a solution of an acrylic polymer (a2) having a carboxyl group in the molecule. The solution had a solid content of 50%, the weight-average molecular weight of the polymer was 48000, and the acid value was 78 mgKOH/g.
[ preparation of resin composition ]
The compositions (in parts by weight) having the compositions shown in table 1 were dissolved in methyl triglyme, stirred by a stirrer, and then dispersed by a three-roll mill. Thereafter, defoaming was performed by a defoaming device to prepare a uniform solution. The amount of methyltriglyme as the solvent (including the total amount of the solvent contained in the polymer solution of the above synthesis example) was 30 parts by weight. In addition to the components shown in Table 1, 1.0 part by weight of a photopolymerization initiator (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime, "Irgacure OXE 02", manufactured by BASF Co.) and 0.1 part by weight of a butadiene-based antifoaming agent ("FLOELEN AC-2000", manufactured by Kyoeisha chemical Co., Ltd.) were added to each resin composition.
[ formation and evaluation of cured film ]
< formation of cured film on polyimide film >
A resin composition was applied to a polyimide film (product of KANEKA, Inc. 'APICAL 25 NPI') having a thickness of 25 μm so as to have a final dry thickness of 20 μm by screen printing, dried at 80 ℃ for 20 minutes, and irradiated with a cumulative exposure of 100mJ/cm2Is exposed to ultraviolet rays. Then, at a rate of 1.0kgf/mm2Spraying 1.0 wt% sodium carbonate aqueous solution at 30 ℃ for 60 secondsAnd (5) line development. After the development, the film was thoroughly washed with pure water and then heated in an oven at 140 ℃ for 60 minutes to form a cured film on the polyimide film (after the development).
In the same manner as described above, the resin composition was applied to the polyimide film, dried and exposed, and then heated in an oven at 140 ℃ for 60 minutes without performing development, thereby forming a cured film on the polyimide film (before development).
< flame retardancy >
Flame retardancy test was carried out as follows using a polyimide film having a cured film formed thereon (before and after development) as a sample in accordance with the flame retardancy UL94 standard.
The polyimide film with the cured film was cut into a width of 50mm × a length of 200mm, a reticle was drawn on a central portion (a portion of 125 mm) in the longitudinal direction, the cured film side was wound into a cylindrical shape so as to be outward, and an adhesive tape was attached so that an overlapping portion (a portion of 75mm in the longitudinal direction) above the reticle and an upper portion thereof were free from a gap, thereby producing a cylinder for a flame retardancy test.
The upper part of the sample was held by a clip and fixed vertically, the flame of the burner was ignited by approaching the lower part of the sample for 3 seconds, the flame of the burner was removed after 3 seconds, and the flame of the sample was measured and the combustion disappeared after several seconds. The test was repeated 2 times for 1 sample, and the case where the flame was stopped within 10 seconds after the sample was moved from the flame of the burner and the flame was self-extinguished without reaching the mark line was regarded as OK for 2 times; the number of times 1 out of 2 was recorded as NG when the flame did not extinguish within 10 seconds or when the flame rose and burned to the marked line. The test was conducted on 5 samples and evaluated according to the following criteria.
A: 5 are all OK
B: 1-4 of the 5 are OK
C: 5 are all NG
< adhesion >
The polyimide films on which the cured films (before and after development) were formed were used as samples, and the adhesiveness of the cured films was evaluated by the checkered tape method according to JIS K5400. The tape peeling test was repeated 5 times for 1 sample, and the residual area ratio (residual film ratio) of the cured film in the sample after the test was evaluated according to the following criteria.
A: no peeling was observed (residual area ratio 100%)
B: peeling was observed, but the residual area ratio was 95% or more
C: the residual area ratio is more than 80% and less than 95
D: the residual area rate is less than 80 percent
The polyimide film on which the cured film (after development) was formed was cut into a size of 5mm × 100mm, bent 180 ° so that the cured film was positioned outside, and a load of 100g was applied to the bent portion for 3 seconds. After the load was removed, the bent portion was observed with an optical microscope to evaluate the presence or absence of cracks. This operation was carried out until cracks occurred in the cured film, and evaluation was carried out according to the following criteria.
A: no crack even if bent 10 times
B: cracks are generated when the sheet is bent for 2 to 9 times
C: cracks were generated when bent 1 time
< stickiness >
In the same manner as described above, the resin composition was applied to the polyimide film, and the polyimide film was dried at 80 ℃ for 20 minutes to form a coating film (B-stage film). The state of peeling was observed by stacking 2 films so that the coating films were in contact with each other, and evaluated by the following criteria.
A: the coating films were not adhered to each other, and no adhering mark was left on the coating films
B: the coating films have traces left after being adhered and peeled from each other, or the coating films are adhered to each other completely and cannot be peeled from each other
< bleed >
A copper foil of a flexible copper-clad laminate obtained by laminating a polyimide film (APICAL 25NPI, manufactured by KANEKA) having a thickness of 25 μm and an electrolytic copper foil having a thickness of 12 μm with a polyimide adhesive was etched into a comb pattern having a line width/pitch of 100 μm/100 μm, and the copper foil was immersed in a 10 volume% sulfuric acid aqueous solution for 1 minute to perform surface treatment of the copper foil, followed by cleaning with pure water to produce a flexible printed wiring board. The resin composition was applied to the wiring-forming surface of the flexible printed wiring board by screen printing so that the final dry thickness reached 20 μm, and drying, exposure, development, washing and heating were carried out in the same manner as described above to obtain a flexible printed wiring board with a cured film. The terminals of the wiring of this sample were connected to a power supply, and after applying a dc current of 100V for 1000 hours in an environment tester at 85 ℃ and 85% RH, the sample was visually observed and evaluated by the following criteria.
A: no abnormality such as swelling or bleeding was observed on the surface of the test piece and the copper wiring
B: abnormalities such as swelling and bleeding were observed on the surface of the test piece and/or the copper wiring
[ evaluation results ]
The compositions (compounding ratio and P atom content relative to the total solid content) and the evaluation results of the resin compositions of examples and comparative examples are shown in table 1. In table 1, the hatched items indicate that the evaluation is not performed. The details of each component are as follows.
<1> JER828US, manufactured by Mitsubishi chemical corporation; bisphenol A type epoxy resin (average molecular weight 370, epoxy equivalent 190)
<2> manufactured by Hitachi chemical Co., Ltd. "FANCRYL FA-321M"; EO-modified bisphenol A dimethacrylate (average molecular weight 804)
<3> FIREGUARD FCX-210 manufactured by Imperial corporation; spiro diphosphonate-based flame retardants
<4> Exolit OP-935 manufactured by CLARIANT Inc.; phosphinic acid metal salt flame retardant
<5> SPB-100L available from Otsuka chemical Co., Ltd.; phosphazene flame retardants
<6> APYRAL AOH60 manufactured by NABALTEC Inc.; aluminum hydroxide-based flame retardant
<7> CR-733S, manufactured by Dayagi chemical industries, Ltd.; phosphoric ester flame retardant
<8> Black pigment obtained by mixing the following blue pigment, orange pigment and violet pigment in a weight ratio of 1:1:1
Blue pigment: pigment Blue 15:4 manufactured by BASF corporation
Orange pigment: pigment Orange 43 manufactured by Clariant corporation
A violet pigment: pigment Violet 19 manufactured by CLARIANT
[ Table 1]
Figure BDA0003026234890000191
In reference examples 1 and 2 in which no flame retardant was added, the folding endurance was good, but the flame retardancy was insufficient. In comparative example 4 using a phosphazene flame retardant, comparative example 5 using an aluminum hydroxide flame retardant, and comparative example 6 using a phosphate flame retardant, no improvement in flame retardancy was observed. In addition, in comparative examples 4 and 6 in which a liquid flame retardant was used, the viscosity was deteriorated.
In comparative examples 1 to 3 using a phosphinic acid metal salt flame retardant, the flame retardancy was poor when the amount of the flame retardant used was small, and the folding endurance tended to decrease when the amount of the flame retardant added was increased. In addition, in these comparative examples, flame retardancy and adhesiveness tended to decrease after alkali development. This is considered to be because: elution and detachment of the flame retardant occur by alkali development.
Examples 1 and 2 using the spiro diphosphonate-based flame retardant were excellent in flame retardancy. In addition, from the comparison of example 1 with comparative examples 1 to 6, it is clear that: the flame retardancy of the spirocyclic diphosphonate flame retardant can be improved by adding a small amount of the spirocyclic diphosphonate flame retardant. This is considered to be because: the radical trapping mechanism of the flame retardant effectively acts on the free radicals generated at the start of combustion.
In examples 1 and 2, the cured films exhibited high adhesion, and no decrease in adhesion or heat resistance occurred after the alkali development. In examples 1 and 2, the same good folding endurance as in reference example 1 containing no flame retardant was exhibited, and the reduction in folding endurance due to the addition of the flame retardant did not occur.
In comparative examples 7 and 8 in which an acrylic polymer was used as a binder resin and a spiro diphosphonate-based flame retardant was added, flame retardancy, adhesion and tackiness were good in the same manner as in examples 1 and 2. However, in comparative examples 7 and 8, the folding endurance was reduced as the amount of the flame retardant added was increased.
From the above results, it can be seen that: when a spiro diphosphonate flame retardant is added to a resin composition containing a urethane binder, a cured film having excellent flame retardancy and adhesion and also excellent flexibility can be specifically formed.

Claims (14)

1. A resin composition which is a curable resin composition comprising (a) a binder resin, (b) a thermosetting resin and (c) a flame retardant,
the binder resin (a) is a polymer having a urethane bond in the molecule,
the flame retardant (c) is an organic phosphorus compound represented by the following general formula,
Figure FDA0003026234880000011
in the formula, R2And R5Each independently is an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted anthracenyl group; r1、R3、R4And R6Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted anthracenyl group.
2. The resin composition according to claim 1, wherein the (a) binder resin has a carboxyl group in a molecule.
3. The resin composition according to claim 2, wherein the (a) binder resin has an acid value of 5 to 200 mgKOH/g.
4. The resin composition according to any one of claims 1 to 3, wherein the (a) binder resin has an ethylenically unsaturated group in a molecule.
5. The resin composition according to any one of claims 1 to 4, further comprising (d) a compound having an ethylenically unsaturated group.
6. The resin composition according to claim 4 or 5, further comprising (e) a photopolymerization initiator.
7. The resin composition according to any one of claims 1 to 6, further comprising (f) a colorant.
8. The resin composition according to any one of claims 1 to 7, wherein the (b) thermosetting resin is a polyfunctional epoxy resin.
9. The resin composition according to any one of claims 1 to 8, wherein the content of the (c) flame retardant is 10 to 30 parts by weight relative to 100 parts by weight of the total solid content.
10. A cured film formed from a cured product of the resin composition according to any one of claims 1 to 9.
11. A printed wiring board with a cured film, comprising the cured film according to claim 10 on a printed wiring board.
12. The cured film-bearing printed circuit board according to claim 11, wherein the printed circuit board has flexibility.
13. A method for producing a printed wiring board with a cured film, comprising applying the resin composition according to any one of claims 1 to 9 to a metal wiring formation surface of a printed wiring board to form a coating film, and curing the coating film by heating and/or exposure to light.
14. A method for producing a printed wiring board with a cured film, comprising applying the resin composition according to any one of claims 1 to 9 to a metal wiring forming surface of a printed wiring board to form a coating film,
at least a part of the surface of the coating film is irradiated with active light to be photo-cured,
developing with an alkali, and dissolving and removing the coating film that is not cured, thereby forming a patterned cured film.
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