JP2010250032A - Photosensitive flame-retardant composition and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive flame-retardant composition optimal for a protective layer of a printed board or the like by using together with a component having an ethylenically unsaturated double bond and a carboxyl group, a flame retardant that contains no halogen, has good solubility, that does not decrease characteristics inherent to a resin such as mechanical characteristics and molding processability when added to the resin, and does not cause whitening. <P>SOLUTION: The photosensitive flame-retardant composition contains: the component having the ethylenically unsaturated double bond and the carboxyl group; and the flame retardant having two 9,10-dihydro-9-oxa-10-oxid-10-phosphaphenanthrene moieties in one molecule. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is suitable as a solder resist or plating resist for printed wiring boards, particularly flexible printed wiring boards, and is also useful as an interlayer electrical insulating material, photosensitive optical waveguide, etc. It relates to a flammable composition.

  A protective layer called a coverlay or solder resist is formed on the printed wiring board for the purpose of protecting the wiring circuit during and after manufacturing, such as the soldering process performed when surface mounting electronic components during manufacturing. ing.

  For example, information devices such as mobile phones and digital cameras often use flexible printed wiring boards in addition to rigid wiring boards in order to increase functionality, reduce size, and reduce weight. Because flexible printed wiring boards are mainly used in the bent and connected areas of equipment, the photo solder resist used for them has a high degree of flexibility and fold resistance, and developability that can realize fine patterns. In addition, performance that satisfies solder heat resistance, substrate adhesion, insulation, and the like is required.

  In the field of electronic materials, flame retardancy is often required, and a flame retardant is often added to a resist forming composition. Conventionally, antimony oxides and halogen flame retardants have been used as flame retardants. However, antimony oxide is a toxic substance that causes poisoning, and when a halogen-based flame retardant is used, there is a problem that dioxins are generated during incineration. Therefore, it is desired to use a flame retardant containing no halogen or antimony.

  Examples of the flame retardant containing no halogen or antimony include inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide. However, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above compound, and as a result, the substrate adhesion, flexibility, and folding resistance required as a photo solder resist for flexible printed circuit boards are obtained. It will no longer be satisfactory.

  In addition to the above-mentioned problems of inorganic flame retardants, phosphorus-based flame retardants disclosed in Non-Patent Document 1 have low solubility in photosensitive components or solvents and high crystallinity. There existed a problem that the photosensitive flame-retardant composition became cloudy and the flame-retardant composition layer formed also whitened.

Journal of Polymer Science, Part A: Polymer Chemistry, 40, 359, 2001

  An object of the present invention is to provide a photosensitive flame retardant composition which does not contain halogen and antimony and is excellent in transparency.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
That is, the present invention contains a component (A) having an ethylenically unsaturated double bond and a carboxyl group, the component (A), and a flame retardant (B) represented by the following general formula [1]. The present invention relates to a photosensitive flame retardant composition.

General formula [1]

Wherein X ₁ and X ₂ are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted or unsubstituted phosphine group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, sulfonic acid Group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, or Represents a substituted carbonyl group, provided that X ₁ and X ₂ are not the same.
R _{1 to} R ₂₄ are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted or unsubstituted phosphine group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Aryl group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, sulfonic acid group, substituted or unsubstituted alkenyl group Represents a substituted or unsubstituted alkynyl group or a substituted carbonyl group X ₁ and R ₁ and X ₂ and R ₆ may each independently form a ring. )

The present invention also relates to a photosensitive flame retardant composition according to the invention R ₉ to R ₂₄ is a hydrogen atom.

The present invention also relates to a photosensitive flame retardant composition according to the invention either R ₁ to R ₈ is a hydrogen atom.

  The present invention also relates to the photosensitive flame retardant composition according to any one of the above inventions, wherein the component (A) having an ethylenically unsaturated double bond and a carboxyl group is a urethane resin. .

  The present invention also relates to the photosensitive flame retardant composition according to any one of the above inventions, further comprising an organic solvent.

  The present invention also relates to a photosensitive film characterized in that a photosensitive flame retardant composition layer formed from the photosensitive flame retardant composition described in the above invention is sandwiched between two peelable films. Relates to a flame retardant dry film.

  In the present invention, at least one surface of a printed wiring board on which a conductive circuit is formed is partially covered with a flame retardant composition layer formed from the photosensitive flame retardant composition described in the above invention. The present invention relates to a printed wiring board with a solder resist layer.

  The present invention also relates to the printed wiring board with a solder resist layer according to the invention, wherein the printed wiring board on which the conductive circuit is formed is a flexible printed wiring board on which the conductive circuit is formed.

  In addition, the present invention provides a photosensitive flame retardant formed by coating and drying the photosensitive flame retardant composition according to the above invention on the entire surface of at least one surface of a printed wiring board on which a conductive circuit is formed. It is characterized by partially irradiating the flammable composition layer with ultraviolet rays, removing the unexposed portion photosensitive flame retardant composition layer, and then thermally curing the remaining exposed portion flame retardant composition layer. The present invention relates to a method for producing a printed wiring board with a solder resist layer.

  In addition, the present invention peels off the peelable film covering one surface from the photosensitive flame retardant dry film described in the above invention, and the exposed photosensitive flame retardant composition layer is formed with a conductive circuit. After the other peelable film has been peeled off by partially irradiating with ultraviolet rays in a state where it is overlaid on the entire surface of at least one surface of the printed wiring board and is peeled off through another peelable film or other peelable film. After the exposed part photosensitive flame retardant composition layer is removed or the unexposed part photosensitive flame retardant composition layer is removed, the remaining exposed part flame retardant composition layer is thermally cured. It is related with the manufacturing method of the printed wiring board with a soldering resist layer.

  The flame retardant of the present invention can be non-halogenated and antimony-free, and does not cause pollution. Further, even when added to a curable resin, the curability is not adversely affected, and a flame retarding effect can be exhibited with a relatively small amount. In addition, the substituent of the conventionally known bis (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) bis (4-hydroxyphenyl) methane is changed to provide an asymmetric molecular type. By reducing the crystallinity, it is possible to improve the solubility in the resin composition and the solvent and to prevent whitening (crystallization) in the resin. By using this flame retardant, it is possible to provide a flame retardant resin composition that does not affect the original properties of the resin such as mechanical properties and molding processability when the resin is added.

Hereinafter, the present invention will be described in detail. Examples of the method for producing the component (A) having an ethylenically unsaturated double bond and a carboxyl group according to the present invention include the following synthetic methods including those conventionally known.
It can be obtained by esterifying acrylic acid with an epoxy resin and then adding an acid anhydride to the generated hydroxyl group.
Also, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid and a copolymerized vinyl monomer are radically polymerized to synthesize a carboxyl group-containing acrylic prepolymer, and then an unsaturated group-containing epoxy compound is esterified with the carboxyl group in the above. It can be obtained by adding an acid anhydride to the generated hydroxyl group.
Also, a diisocyanate compound, a polyol compound, and a carboxylic acid compound having two hydroxyl groups are reacted to synthesize a carboxyl group-containing urethane prepolymer, and then one epoxy in the molecule for a part of the carboxyl groups in the above. It can be obtained by reacting an epoxy group in a (meth) acrylate having a group or an oxetane group.
Also, a polyol compound and a polybasic acid anhydride having two acid anhydride groups in the molecule are reacted to synthesize a carboxyl group-containing polyester polyol having an ester bond derived from half esterification in the main chain, This was reacted with diisocyanate to obtain a carboxyl group-containing urethane prepolymer. Furthermore, it is produced by reacting a part of carboxyl groups in this urethane prepolymer with (meth) acrylate having one epoxy group or oxetane group in the molecule.
In addition, a polyol compound, a diisocyanate compound and a carboxylic acid compound having two hydroxyl groups in the molecule are reacted to synthesize a carboxyl group-containing urethane prepolymer, and then 1 in the molecule relative to the carboxyl group in the molecule. After making a hydroxyl group-containing urethane prepolymer by reacting an epoxy group or oxetane group in a (meth) acrylate having one epoxy group or oxetane group, the hydroxyl group in the above and one acid anhydride group are It can be obtained by reacting with an acid anhydride group in the polybasic acid anhydride.
The component (A) having an ethylenically unsaturated double bond and a carboxyl group is preferably one having a urethane bond from the viewpoint of flexibility.

  The acid value of the component (A) having an ethylenically unsaturated double bond and a carboxyl group of the present invention is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g. When the acid value is less than 10 mgKOH / g, sufficient developability cannot be obtained. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. Moreover, when an acid value exceeds 200 mgKOH / g, the solubility of the coating film with respect to a developing solution becomes high, and even the part which wants to make it photocure and leave as a pattern is developed, and there exists a possibility that the shape of a pattern may deteriorate. The acid value is measured by potentiometric titration according to JIS K 2501.

  The ethylenically unsaturated group equivalent of the component (A) having an ethylenically unsaturated double bond and a carboxyl group of the present invention is preferably 200 to 3000 g / eq, more preferably 300 to 2000 g / eq. is there. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity is excessive, the film is dissolved at the time of development, and the portion desired to be removed is cured and a good pattern shape may not be obtained. If the ethylenically unsaturated group equivalent exceeds 3000 g / eq, the photosensitivity is inferior and the portion to be cured is not sufficiently cured, and the pattern is dissolved during development, and a good pattern shape may not be obtained. In addition, the ethylenically unsaturated group equivalent is the molecular weight of the resin divided by the number of ethylenically unsaturated groups per molecule, and the molecular weight of the resin relative to one ethylenically unsaturated group, that is, in the resin Represents the reciprocal of the ethylenically unsaturated group concentration.

  It is preferable that the weight average molecular weights of the component (A) which has an ethylenically unsaturated double bond and a carboxyl group of this invention are 1000-100000, More preferably, it is 3000-60000. When the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. Moreover, when it makes a coating film, tack is strong in the state before hardening, and workability | operativity, such as sticking to a photomask or a base material, will deteriorate significantly. On the other hand, when the weight average molecular weight exceeds 100,000, the soldering heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling during coating may be deteriorated. The weight average molecular weight (Mw) is measured using a standard polystyrene calibration curve by GPC (gel permeation chromatography). The measurement conditions for GPC are as follows. Two measuring machines “HPC-8020” (manufactured by Tosoh), column “LF-604” (manufactured by Showa Denko: GPC column for rapid analysis: 6 mm ID × 150 mm size) connected in series, solvent: tetrahydrofuran, flow rate 0.6 ml / min Column temperature 40 ° C.

  Next, the flame retardant (B) of the present invention will be described. The flame retardant of the present invention has a structure represented by the general formula [1]. By including two 9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene moieties known to exhibit a flame-retardant effect in one molecule, non-halogen and antimony-free are achieved, and a small amount The flame retardant effect can be exhibited by the addition of. In addition, by changing the substituent of the conventionally known bis (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) bis (4-hydroxyphenyl) methane, The molecular type can be reduced, and stacking between molecules can be reduced. Thereby, the crystallinity of a flame retardant is reduced, the solubility with respect to a resin composition or a solvent can be improved, and whitening (crystallization) in a resin can be prevented.

X ₁ and X ₂ in the general formula [1] in the present invention are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted Unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted or unsubstituted phosphine group, substituted or Unsubstituted aryloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, Sulfonic acid group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl Represented by a group or a substituted carbonyl group. However, X ₁ and X ₂ are not the same.

In X ₁ and X ₂ , the substituted or unsubstituted amino group is preferably a substituted amino group having 1 to 40 carbon atoms, for example, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propyl Amino group, dipropylamino group, butylamino group, dibutylamino group, benzylamino group, dibenzylamino group, (m-tolyl) amino group, (p-tolyl) amino group, phenylmethylamino group, phenylamino group, Diphenylamino group, di-m-tolylamino group, di-p-tolylamino group, di-p-pyridylamino group, di-m-pyridylamino group, phenylthiophenylamino group, diphenylthioamino group, difuranylamino group, di-p- Biphenylylamino group, di (4-methylbiphenyl) amino group, naphthylphenyla Mino group, dinaphthylamino group, phenyl-p-biphenylamino group, bis [4- (α, α'-dimethylbenzyl) phenyl] amino group, formylamino group, acetylamino group, propionylamino group, butyrylamino group, iso Butyrylamino group, benzoylamino group, isocyanate group, aziridinyl group, 2-methylaziridinyl group, maleimide group, acetamide group, propionamide group, butyramide group, carbamic acid methyl ester group, carbamic acid ethyl ester group, carbamic acid Examples include a phenyl ester group, a diglycidylamino group, and a bis (3-ethyloxetane-3-ylmethyl) amino group.

In X ₁ and X ₂ , the substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 40 carbon atoms, more preferably a substituted alkyl group having 1 to 20 carbon atoms, for example, methyl An unsubstituted linear group such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group or the like In addition to branched alkyl group, ethoxyethyl group, ethoxymethyl group, methoxymethyl group, methoxyethyl group, 2-phenylisopropyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α, α -Methylphenylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group, 3-methyloxetane-3-ylmethyl Group, 3-ethyloxetane-3-ylmethyl group, 2-isocyanatoethyl group, 2-aziridinylethyl group, 2- (tert-butylcarbodiimide) ethyl group, 2- (cyclohexylcarbodiimide) ethyl group, maleimidomethyl group , Hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 9-hydroxynonyl group, 1-hydroxylethyl group and the like.

In X ₁ and X ₂ , the substituted or unsubstituted cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 4 to 8 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo A heptyl group, a cyclooctyl group, an adamantyl group, etc. are mentioned.

In X ₁ and X ₂ , the substituted or unsubstituted alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 10 carbon atoms. For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, n-pentaoxy group, n-heptaoxy group, n-octyloxy group, t -Octyloxy group, benzyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, 3-methyloxetane-3-ylmethyloxy group, 3-ethyloxetane-3-ylmethyloxy group, 2-isocyanatoethyloxy Group, 2-aziridinylethyloxy group, 2-benzocyclobutenylethyloxy group, Droxymethyloxy group, 2-hydroxyethyloxy group, 3-hydroxypropyloxy group, 4-hydroxybutyloxy group, 5-hydroxypentyloxy group, 9-hydroxynonyloxy group, 2-hydroxy-2methylpropyloxy group , Prop-2-nyloxy group, 1-methylprop-2-nyloxy group, but-2-yloxy group, 3-phenylprop-2-nyloxy group, prop-2-nyloxy group, 1-methylprop-2-nyloxy group Group, but-2-ynyloxy group, pent-2-yloxy group, 3-phenylprop-2-ynyloxy group, propynyloxy group, 2-phenylethynyl group, acrylic acid group, 1-methylacrylic acid group, 1,2- Dimethylacrylic acid group, 1-phenylacrylic acid group, 4,5-dihydrooxazolylmethyl Such as alkoxy groups.

In X ₁ and X ₂ , the substituted or unsubstituted silyloxy group is preferably a substituted or unsubstituted silyloxy group having 0 to 50 carbon atoms, more preferably a substituted or unsubstituted group having 0 to 20 carbon atoms. For example, silyloxy group, methylsilyloxy group, dimethylsilyloxy group, trimethylsilyloxy group, triethylsilyloxy group, tributylsilyloxy group, trimethoxysilyloxy group, triethoxysilyloxy group, phenylsilyloxy Group, diphenylsilyloxy group, triphenylsilyloxy group, dimethylphenylsilyloxy group, diphenylmethylsilyloxy group, diphenylmethoxysilyloxy group, diphenylethoxysilyloxy group, dimethyl-tert-butylsilylo group And a xyl group.

In X ₁ and X ₂ , the substituted or unsubstituted silyl group is preferably a substituted or unsubstituted silyl group having 0 to 50 carbon atoms, more preferably a substituted or unsubstituted group having 0 to 20 carbon atoms. For example, silyl group, methylsilyl group, dimethylsilyl group, trimethylsilyl group, triethylsilyl group, tributylsilyl group, trimethoxysilyl group, triethoxysilyl group, phenylsilyl group, diphenylsilyl group, triphenylsilyl Group, dimethylphenylsilyl group, diphenylmethylsilyl group, diphenylmethoxysilyl group, diphenylethoxysilyl group, dimethyl-tert-butylsilyl group and the like.

In X ₁ and X ₂ , the substituted or unsubstituted phosphineoxy group includes a dimethylphosphineoxy group, a diphenylphosphineoxy group, a ditolylphosphineoxy group, a dinaphthylphosphineoxy group, a substituted or unsubstituted phosphine oxideoxy group. Dimethylphosphine oxideoxy group, diphenylphosphine oxideoxy group, ditolylphosphine oxideoxy group, dinaphthylphosphine oxideoxy group, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, etc. Can be mentioned.

In X ₁ and X ₂ , the substituted or unsubstituted phosphine group includes a dimethylphosphine group, a diphenylphosphine group, a ditolylphosphine group, a dinaphthylphosphine group, and the substituted or unsubstituted phosphine oxide group includes a dimethylphosphine oxide group. , Diphenylphosphine oxide group, ditolylphosphine oxide group, dinaphthylphosphine oxide group, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, and the like.

In X ₁ and X ₂ , the substituted or unsubstituted aryloxy group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 40 carbon atoms, more preferably 6 carbon atoms. Substituted or unsubstituted monocyclic or condensed polycyclic aromatic groups having ˜18, for example, phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, p-biphenyloxy group, m-biphenyloxy group 2-anthryloxy group, 9-anthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, 2-fluorenyloxy group, 3-flurane Olenyloxy group, 9-fluorenyloxy group, 1-pyrenyloxy group, 2-pyrenyloxy group, 3-perylenyloxy group, o-tolyloxy group, m-to Ryloxy group, p-tolyloxy group, 4-methylbiphenyloxy group, terphenyloxy group, 4-methyl-1-naphthyloxy group, 4-tert-butyl-1-naphthyloxy group, 4-naphthyl-1-naphthyloxy Group, 6-phenyl-2-naphthyloxy group, 10-phenyl-9-anthryloxy group, spirofluorenyloxy group, 2-benzocyclobutenyloxy group and the like.

In X ₁ and X ₂ , the substituted or unsubstituted aryl group is preferably a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 40 carbon atoms, more preferably 6 to 6 carbon atoms. A substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 18 such as phenyl group, 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-methylbiphenyl group, terphenyl group, 4-methyl-1-naphthyl group, 4-tert-butyl Ru-1-naphthyl group, 4-naphthyl-1-naphthyl group, 6-phenyl-2-naphthyl group, 10-phenyl-9-anthryl group, spirofluorenyl group, 4-malemidylphenyl group, 2- A benzocyclobutenyl group etc. are mentioned.

In X ₁ and X ₂ , the substituted or unsubstituted heterocyclic oxy group is preferably a 5- or 6-membered heterocyclic oxy group containing O, N or S as a hetero atom, or a condensed polycyclic heterocyclic group. A ring oxy group is mentioned. The heterocyclic oxy group is preferably a heterocyclic oxy group having 4 to 40 carbon atoms, more preferably a heterocyclic oxy group having 4 to 20 carbon atoms, such as a thienyloxy group, a furyloxy group, Pyridyloxy group, pyridinyloxy group, pyrazinyloxy group, pyrimidinyloxy group, pyridazinyloxy group, triazinyloxy group, indolinyloxy group, quinolyloxy group, quinoxalyloxy group, acridinyloxy group, pyrrolyloxy group, Pyranyloxy group, thiopyranyloxy group, dioxanyloxy group, piperidinyloxy group, morpholinyloxy group, piperazinyloxy group, carbazolyloxy group, oxazolyloxy group, oxadiazolyloxy group , Benzoxazolyloxy group, thiazolyloxy group, thiadiazolyl Si group, benzothiazolyloxy group, triazolyloxy group, imidazolyloxy group, imidazopyridyloxy group, benzoimidazolyloxy group, pranyloxy group, morpholyloxy group, piperidyloxy group, piperazinyloxy group, benzofuryloxy group, A 2-benzothienyloxy group, an indolyloxy group, an acridinyloxy group, a phenanthroyloxy group, and the like can be given.

In X ₁ and X ₂ , the substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group containing O, N, S as a hetero atom, or a condensed polycyclic heterocyclic group Is mentioned. The heterocyclic group is preferably a heterocyclic group having 4 to 40 carbon atoms, more preferably a heterocyclic group having 4 to 20 carbon atoms, such as a thienyl group, a furyl group, a pyridyl group, a pyridinyl group. , Pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group, indolinyl group, quinolyl group, quinoxalyl group, acridinyl group, pyrrolyl group, pyranyl group, thiopyranyl group, dioxanyl group, piperidinyl group, morpholinyl group, piperazinyl group, carbazolyl group, oxazolyl Group, oxadiazolyl group, benzoxazolyl group, thiazolyl group, thiadiazolyl group, benzothiazolyl group, triazolyl group, imidazolyl group, imidazolpyridyl group, benzoimidazolyl group, pranyl group, morpholyl group, piperidyl group, piperazinyl group, benzofuryl Group, 2-benzothienyl group, indolyl group, acridinyl group, and phenanthrolyl group.

In X ₁ and X ₂ , the substituted or unsubstituted alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 10 carbon atoms. For example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, t-butylthio group, n-pentylthio group, n-heptylthio group, n-octylthio group, t- An octylthio group, a benzylthio group, an adamantylthio group, etc. are mentioned.

In X ₁ and X ₂ , the substituted or unsubstituted arylthio group is preferably an arylthio group having a condensed polycyclic aromatic group having a substituted or unsubstituted monocycle having 6 to 40 carbon atoms, and more preferably Is an arylthio group having a substituted or unsubstituted monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a p-biphenylthio group, m-biphenylthio group, 2-anthrylthio group, 9-anthrylthio group, 2-phenanthrylthio group, 3-phenanthrylthio group, 9-phenanthrylthio group, 2-fluorenylthio group, 3-fluorenylthio group, 9-fluorenylthio group Group, 1-pyrenylthio group, 2-pyrenylthio group, 3-perylenylthio group, o-tolylthio Group, m-tolylthio group, p-tolylthio group, 4-methylbiphenylthio group, terphenylthio group, 4-methyl-1-naphthylthio group, 4-tert-butyl-1-naphthylthio group, 4-naphthyl-1- group A naphthylthio group, a 6-phenyl-2-naphthyl group, a 10-phenyl-9-anthrylthio group, a spirofluorenylthio group and the like can be mentioned.

In X ₁ and X ₂ , the substituted or unsubstituted alkenyl group is preferably an alkenyl group having 1 to 40 carbon atoms, more preferably a substituted alkenyl group having 1 to 20 carbon atoms. Examples include 2-nyl group, 1-methylprop-2-nyl group, but-2-enyl group, 3-phenylprop-2-nyl group, and hex-4-nyl group.

In X ₁ and X ₂ , the substituted or unsubstituted alkynyl group is preferably an alkynyl group having 1 to 40 carbon atoms, more preferably a substituted alkynyl group having 1 to 20 carbon atoms. 2-nyl group, 1-methylprop-2-nyl group, but-2-ynyl group, pent-2-yl group, 3-phenylprop-2-nyl group, prop-1-nyl group, 2-phenylethynyl group Etc.

In X ₁ and X ₂ , the substituted carbonyl group includes carboxylic acid group, methoxycarbonyl group, phenoxycarbonyl group, dimethylaminocarbonyl group, diphenylaminocarbonyl group, ditolylaminocarbonyl group, methylcarbonyl group, ethylcarbonyl group, phenyl Carbonyl group, tolylcarbonyl group, propenonyl group, buten-2-one-1-nonyl group, 2-methylbut-2-one-1-nonyl group, 3-phenylprop-2-one-1-nonyl group, Examples include 2-butenyloxycarbonyl group.

In the general formula [1] in the present invention, R _{1 to} R ₂₄ are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted Or an unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyloxy group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphineoxy group, a substituted or unsubstituted phosphine group, a substituted Or an unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group Sulfonic acid group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl Or it is represented by a substituted carbonyl group.

In R _{1 to} R ₂₄ , a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted silyloxy group, substituted or An unsubstituted silyl group, a substituted or unsubstituted phosphineoxy group, a substituted or unsubstituted phosphine group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic oxy group, The substituted or unsubstituted heterocyclic group, the substituted or unsubstituted alkylthio group, the substituted or unsubstituted arylthio group, the substituted or unsubstituted alkenyl group, the substituted or unsubstituted alkynyl group, and the substituted carbonyl group are as described above. A substituted or unsubstituted amino group represented by X ₁ and X ₂ ; Is an unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted Or an unsubstituted phosphine group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylthio group , Substituted or unsubstituted arylthio group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, and substituted carbonyl group.

X ₁ and R ₁ and X ₂ and R ₆ may each independently form a ring.

Preferable examples when X ₁ and R ₁ and X ₂ and R ₆ form a ring include the following substituent groups.

In the formula, R ₂₅ and R ₂₆ each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

In R ₂₅ and R ₂₆ , the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group are the substituted or unsubstituted alkyl group represented by the aforementioned X ₁ and X ₂ , and substituted or unsubstituted. It is synonymous with a substituted aryl group.

In general formula [1], it is preferable that _one of X ₁ and X ₂ is a hydrogen atom in view of the availability of raw materials and the difficulty of synthesis.

In general formula [1], R _{9 to} R ₂₄ are preferably a hydrogen atom, and more preferably R _{1 to} R ₈ are also a hydrogen atom, from the viewpoint of availability of raw materials and synthesis difficulty.

  Typical examples of the compound represented by the general formula [1] which is the flame retardant of the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.

Table 1

  The compound group represented by the general formula [1] can be obtained by a known method. For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- A 10-oxide derivative and a benzophenone derivative can be used as starting materials to be obtained through a one-step or two-step reaction. (See Journal of Polymer Science, Part A: Polymer Chemistry, 40, 359, 2001)

Reaction formula 1

Reaction formula 2

Reaction formula 3

  The compound obtained above is isolated and purified from the reaction mixture according to conventional isolation methods such as extraction, distillation, column purification, recrystallization, reprecipitation, washing, filtration and drying. .

  It is also preferable that the photosensitive flame retardant resin composition of the present invention contains a photopolymerization initiator (C). The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating radical polymerization by photoexcitation. For example, a monocarbonyl compound, dicarbonyl compound, acetophenone compound, benzoin ether compound, acylphosphine oxide compound, aminocarbonyl A compound etc. can be used.

Although there is no restriction | limiting in the usage-amount of a photoinitiator (C), It adds in 1-20 weight part with respect to 100 weight part of component (A) which has an ethylenically unsaturated double bond and a carboxyl group. Is preferred. Moreover, a well-known organic amine can also be added as a sensitizer.

  The photosensitive flame retardant resin composition of the present invention preferably further contains an ethylenically unsaturated group-containing compound (D).

The ethylenically unsaturated group-containing compound (D) is used for the purpose of adjusting the photosensitivity of the photosensitive flame retardant resin composition, and has an ethylenically unsaturated double bond in the molecule. In the present invention, a photosensitive compound other than the “component (A) having an ethylenically unsaturated double bond and a carboxyl group” can be used as the ethylenically unsaturated group-containing compound (D).
The ethylenically unsaturated group-containing compound (D) has an ethylenically unsaturated double bond in the molecule and “component (A) having an ethylenically unsaturated double bond and a carboxyl group” of the present invention. Although not particularly limited as long as it is not included in the regulations, for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkylene glycol ester, a compound having a carboxyl group and an ethylenically unsaturated group [however, Excluding compounds included in the definition of component (A) having an ethylenically unsaturated double bond and a carboxyl group], (meth) acrylate compounds having a hydroxyl group, nitrogen-containing (meth) acrylate compounds, and the like.

  The ethylenically unsaturated group-containing compound (D) is preferably used in an amount of 0.1 to 300 parts by weight with respect to 100 parts by weight of the component (A) having an ethylenically unsaturated double bond and a carboxyl group. It is more preferable to use 0.5 to 200 parts by weight, and it is even more preferable to use 5 to 100 parts by weight. If the amount is less than 0.1 parts by weight, the photosensitivity of the photosensitive flame retardant resin composition may be insufficient. If the amount exceeds 300 parts by weight, the flexibility may be insufficient.

  The photosensitive flame retardant resin composition of the present invention may further contain a thermosetting compound (E) and a thermosetting aid (F).

  The thermosetting compound (E) has two or more functional groups capable of reacting with the functional group (carboxyl group and hydroxyl group) contained in the component (A) having an ethylenically unsaturated double bond and a carboxyl group. There is no particular limitation.

  Examples of the compound having at least two functional groups capable of reacting with a hydroxyl group in the thermosetting compound (E) include polyisocyanate compounds, amino resins, phenol resins, and polyfunctional polycarboxylic acid anhydrides.

  Among the thermosetting compounds (E), compounds having at least two functional groups capable of reacting with carboxyl groups include compounds having two or more epoxy groups or oxetane groups, polyfunctional vinyl ether compounds, and high molecular weight polycarbodiimides. And aziridine compounds. Among these, a compound having two or more epoxy groups or oxetane groups is particularly preferable in view of the curing speed and the durability of the cured product.

  These thermosetting compounds (E) may be used alone or in combination. The amount of the thermosetting compound (E) used may be determined in consideration of the use of the photosensitive flame retardant resin composition, and is not particularly limited. However, the ethylenically unsaturated double bond and the carboxyl group are not limited. 0.1 to 100 parts by weight is preferable, and 0.5 to 80 parts by weight is more preferable with respect to 100 parts by weight of the component (A). Thereby, since the crosslinking density of the cured film formed from the photosensitive flame retardant resin composition can be adjusted moderately, various physical properties of the cured film can be further improved. When the usage-amount of a thermosetting compound (E) is less than 0.1 weight part, there exists a possibility that the crosslinking density of a cured film may become low and cohesion force and durability may become insufficient. On the other hand, if the amount used exceeds 100 parts by weight, the crosslink density of the cured film becomes excessive and the flexibility of the cured product may be reduced.

Next, the thermosetting aid (F) will be described. In the present invention, the heat curing aid (F) represents a compound that contributes directly or catalytically to the curing reaction during heat curing.
A thermosetting adjuvant (F) is suitably selected by the kind of thermosetting compound (E) to be used.

  In the present invention, when an epoxy compound is used as the thermosetting compound (E), the use of dicyandiamide, carboxylic acid hydrazide, imidazoles, or diazabicyclo compounds as the thermosetting aid (F) is more efficient. It is preferable because the curing reaction proceeds and the coating film has excellent resistance.

  In the present invention, the thermosetting aid (F) is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A) having an ethylenically unsaturated double bond and a carboxyl group. It is preferable to use it, and the inside of the range of 0.5-8 weight part is still more preferable. If the amount used is less than 0.1 parts by weight, the cohesive strength and durability of the cured product may be insufficient. On the other hand, when the amount used is more than 10 parts by weight, an excessive thermosetting auxiliary agent remains in the cured product, which may deteriorate various physical properties of the cured product, such as bleeding and deterioration of insulating properties.

  The photosensitive flame retardant resin composition of the present invention may contain the following resins as necessary. Specific examples include acrylic resins, polyester resins, urethane resins, urea resins, urethane urea resins, epoxy resins, polyamide resins, and polyimide resins. From the viewpoint of developability, those containing a carboxyl group are preferred, and those having excellent compatibility with the component (A) having an ethylenically unsaturated double bond and a carboxyl group are preferred.

  In addition, the photosensitive flame retardant resin composition of the present invention is an optional component as long as the object of the present invention is not impaired, and further includes a solvent, a dye, a pigment, an antioxidant, a polymerization inhibitor, a leveling agent, a humectant, Viscosity modifiers, antiseptics, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic wave shielding agents, fillers, and the like can be added.

  Since the photosensitive flame retardant resin composition of the present invention is characterized by excellent alkali developability when used as a protective layer for a printed wiring board, a coating film forming process including photocuring, alkali development, and post-cure is used. It can be suitably used for the intended use. Furthermore, since it is excellent in coating-film resistance and is excellent in flexibility at the same time, it can be suitably used particularly for solder resist inks for flexible printed wiring boards and photosensitive coverlay films.

  In the photosensitive flame retardant resin composition of the present invention, metals, ceramics, glass, plastics, wood, slate and the like can be used as a substrate, and are not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

  The photosensitive flame retardant resin composition of the present invention is applied to a carrier film such as a plastic film to a uniform thickness by a known coating device such as a comma coater, a blade coater, a roll coater, a die coater, a lip coater, By heating and drying, the solvent is volatilized and a dry film can be obtained. In that case, in order to protect the surface, it is preferable to bond together a protective film. Although there is no restriction | limiting in particular in the thickness of the said dry film, Usually, it selects suitably in the range of 10-100 micrometers.

The photosensitive flame retardant resin composition of the present invention can be cured by irradiation with active energy rays to obtain a cured product. The active energy ray means an electromagnetic wave having a wavelength capable of reacting a photopolymerization initiator or an ethylenically unsaturated group in the photosensitive flame retardant resin composition, and includes electron beam, ultraviolet ray, radiation, γ ray and the like. As an irradiation device, for example, as an ultraviolet irradiation device, as a light source, for example, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a xenon lamp, a semiconductor laser, an Ar laser, a carbon arc lamp, a tungsten lamp And pulse UV lamps. Examples of the electron beam irradiation apparatus include a thermionic emission gun, a field emission gun, and the like. Dose, although in the case of ultraviolet can be suitably set within a range of 5~2000mJ / cm ^2, a range of administrative steps likely 50~1000mJ / cm ² is more preferable.
In the case of an electron beam, 20 to 2000 KeV is preferable. Further, it is possible to use ultraviolet rays or electron beams and heat by infrared rays, far infrared rays, hot air, high frequency heating, or the like.

  The method of using the photosensitive flame retardant resin composition of the present invention is, for example, forming a flame retardant resin composition as a protective layer on a conductive circuit formed on an insulating layer such as a polyimide film or a glass epoxy substrate, After forming a desired pattern on the protective layer through a known exposure / development process, a cured layer is formed by heating at 100 ° C. to 200 ° C. for about 30 minutes to 2 hours as a post cure. In addition, in order to improve solder heat resistance and the like, it is possible to further irradiate active energy rays after the post cure. The flame-retardant resin composition of the present invention is preferably used for applications such as printed wiring boards, but for flexible printed circuit boards that require flexibility and the like because of its excellent adhesion and flexibility. More preferably, it is used.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

Prior to Examples, the synthesis of a compound used as a flame retardant of the present invention and the synthesis of a urethane resin solution used in producing a flame retardant resin composition will be described.

Synthesis example 1
Synthesis Method of Compound 1 4-Hydroxybenzophenone (5.00 g), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter HCA) (32.6 g) was placed in a 100 ml flask, and nitrogen was added. The mixture was stirred at 190 ° C. for 3 hours under an atmosphere. After cooling the reaction solution, 80 ml of methanol was added and stirred for 1 hour. The precipitated white solid was collected by suction filtration, and stirred in 300 ml of methanol. After 1 hour, the white solid was collected by suction filtration and dried in vacuo overnight to give compound 1. (12.0 g) was obtained. EI-MS (PolarisQ manufactured by Thermo Electron) m / z = 613 (molecular weight: 613).

Synthesis Examples 2-31
In the synthesis example 1 described above, the compounds shown in Table 2 were synthesized by changing the 4-hydroxybenzophenone and HCA used to benzophenone derivatives and HCA derivatives corresponding to the respective compounds.

  About the structure of the compound which is the flame retardant of this invention obtained by the synthesis examples 1-31, it identified by the EI-MS spectrum. Table 2 shows the measurement results of the synthesized compounds, the benzophenone derivatives and HCA derivatives used, and the mass spectra of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 2

Synthesis Example 32
Synthesis Method of Compound 3 4-Chlorobenzophenone (5.00 g) and HCA (29.9 g) were placed in a 100 ml flask and stirred at 190 ° C. for 6 hours under a nitrogen atmosphere. After cooling the reaction solution, 80 ml of THF was added and stirred for 1 hour. The precipitated solid was collected by suction filtration, stirred in 300 ml of THF. After 1 hour, the white solid was collected by suction filtration and dried overnight in vacuo to give Intermediate 1 (8.0 g) shown below. EI-MS m / z = 629 631 633 (molecular weight: 631).

Intermediate 1

  Intermediate 1 (5.00 g), diphenylamine (2.01 g), copper powder (0.2 g), potassium carbonate (10.0 g), 1,3-dimethyl-2-imidazolidinone (obtained in a 100 ml flask) 50 mL) and stirred at 150 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution was cooled, poured into 500 ml of distilled water, and stirred for 1 hour. The precipitated solid was collected by suction filtration. The obtained solid was purified by column chromatography to obtain compound 3 (2.56 g). EI-MS m / z = 764 (molecular weight: 764).

Synthesis Examples 33 to 37
In the above synthesis example 32, the compounds shown in Table 3 were synthesized by changing the 4-chlorobenzophenone and diphenylamine used to benzophenone derivatives and amine derivatives corresponding to the respective compounds.

  About the structure of the compound which is the flame retardant of this invention obtained by the synthesis examples 32-37, it identified by the EI-MS spectrum. Table 3 shows the measurement results of the synthesized compounds, the benzophenone derivatives and amine derivatives used, and the mass spectra of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 3

Synthesis Example 38
Synthesis Method of Compound 8 4-Hydroxybenzophenone (5.00 g), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter HCA) (32.6 g) was placed in a 100 ml flask, and nitrogen was added. The mixture was stirred at 190 ° C. for 3 hours under an atmosphere. After cooling the reaction solution, 80 ml of methanol was added and stirred for 1 hour. The precipitated white solid was collected by suction filtration, and stirred in 300 ml of methanol. After 1 hour, the white solid was collected by suction filtration and dried in vacuo overnight to give compound 1. (12.0 g) was obtained. EI-MS (PolarisQ manufactured by Thermo Electron) m / z = 613 (molecular weight: 613).

Compound 1 (5.00 g), bromoethane (1.33 g), potassium hydroxide (1.4 g), and ethanol (100 mL) were placed in a 100 ml flask and stirred at 25 ° C. for 2 days under a nitrogen atmosphere. After completion of the reaction, the mixture was poured into 400 ml of distilled water and stirred for 1 hour. The precipitated solid was collected by suction filtration. The obtained solid was purified by column chromatography to obtain Compound 8 (4.51 g). EI-MS m / z = 641 (molecular weight: 641).

Synthesis Examples 39 to 59
In the above synthesis example 38, the compounds shown in Table 4 were synthesized by changing the 4-hydroxybenzophenone and bromoethane used to benzophenone derivatives and halides corresponding to the respective compounds.

  About the structure of the compound which is the flame retardant of this invention obtained by the synthesis examples 38-59, it identified by EI-MS spectrum. Table 4 shows the measurement results of the synthesized compounds, the benzophenone derivatives and halides used, and the mass spectra of the compounds. The compound numbers are the same as those described in Table 1 in this specification.

Table 4

[Example of production of component having ethylenically unsaturated double bond and carboxyl group]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, PTG850 sn (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, weight average molecular weight = about 850, hydroxyl value = 129 mgKOH / g ) 55 parts, dimethylol butanoic acid (Nippon Kasei Co., Ltd.) 178 parts, and 375 parts of cyclohexanone as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and uniformly dissolved. Subsequently, 267 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 10,000, a molecular weight distribution of 2.03, and an actually measured acid value of resin solids of 138 mgKOH / g.
Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 85 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed, and cyclohexanone was further added to adjust the solid content to 50.0% to obtain a urethane resin (A-2) solution. The ethylenically unsaturated group equivalent of the resin solid content by this design was 1156 g / eq, the weight average molecular weight in terms of polystyrene was 12800, the molecular weight distribution was 2.25, and the acid value of the resin solid content by actual measurement was 68 mgKOH / g. .

[Example 1]
100 parts of urethane (A) solution having an ethylenically unsaturated double bond and a carboxyl group obtained in the resin production example, Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd .: 2) as a photopolymerization initiator (C) -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane) 1.0 part, also DETX-S (manufactured by Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone) 0.3 part Aronix M-310 (manufactured by Toagosei Co., Ltd .: trimethylolpropane PO-modified triacrylate) as the ethylenically unsaturated group-containing compound (D), HP7200 (Dainippon Ink Chemical Co., Ltd.) as the thermosetting component (E) Company: 20.0 parts dicyclopentadiene type epoxy), DICY7 (Ajinomoto Fine Techno Co., Ltd.) as thermosetting aid (F) Company: Dicyandiamide) 0.8 parts, Additive R812 (Nippon Aerosil Co., Ltd .: hydrophobic silica fine particles) 15.0 parts, Blue paste (blue pigment / base resin (phenolic resin) / solvent (carbitol acetate) = 28/12/60) 1.0 part, 30.0 parts of compound 2 as a flame retardant (B) were blended and kneaded with three rolls to prepare the photosensitive flame retardant resin composition of the present invention. .

[Examples 2 to 59]
A photosensitive flame retardant resin composition was prepared by the same formulation as in Example 1 except that the compound 2 of Example 1 was changed to the compounds shown in Table 5.

[Comparative Examples 1 and 2]
A photosensitive flame retardant resin composition was prepared by the same formulation as in Example 1 except that Compound 2 in Example 1 was changed to Compound X, which is a known compound, and Compound Y shown below.

Compound X

Compound Y

[Create sample A]
The obtained photosensitive flame retardant resin composition was applied onto Kapton 100H (manufactured by Toray DuPont Co., Ltd .: polyimide film (25 μm thickness)) so that the dry film thickness was 20 μm, and a hot air dryer at 80 ° C. For 30 minutes and then cooled to room temperature. This is irradiated with an integrated light amount of 400 mJ / cm ² using an ultraviolet exposure device (USHIO INC .: “UVC-2534 / 1MNLC3-AA08”, 120 W / cm metal halide lamp, 1 light), and a hot air dryer at 150 ° C. For 1 hour. The obtained cured product was cooled to room temperature. This is designated as sample A.

[Evaluation of adhesion]
According to JIS K5400, 100 grids of 1 mm × 1 mm were made for sample A, and a peeling test was performed using cello tape (registered trademark). The peeled state of the grid was observed and evaluated according to the following criteria.
○: No peeling.
X: 20% or less of the grid is peeled off.

[Evaluation of flexibility]
Sample A was folded 180 degrees, and then the same part was folded 180 degrees on the opposite side. The state of the coating film at that time was judged according to the following criteria.
○: No cracks are observed on the film surface.
X: The film is broken, and cracks are clearly seen on the film surface.

[Evaluation of solder heat resistance]
Sample A was immersed in a 260 ° C. solder bath (JIS C 6481) for 10 seconds as one cycle, and the number of times swelling and peeling occurred in the coating film was measured and judged according to the following criteria.
○: No swelling or peeling occurs in the coating film for 5 cycles or more.
Δ: Swelling or peeling occurs in the coating film in 2 to 5 cycles.
X: Swelling or peeling occurred in the coating film in one cycle.

[Flame retardance evaluation]
Sample A was tested according to the UL94 flame retardant test and evaluated according to the following criteria.
VTM-0 ... equivalent to UL VTM-0.
HB ... UL HB equivalent × ... Does not extinguish by 100 mm or complete combustion in UL HB test. The high flame retardancy is in the order of VTM-0>HB> ×.

[Evaluation of developability]
On the PET film, the photosensitive flame retardant resin compositions obtained in Examples 1 to 59 and Comparative Examples 1 and 2 were applied so that the film thickness after drying was 20 μm, and dried with hot air at 80 ° C. Dry for 20 minutes. The dried coating film was brought into close contact with a copper-clad laminate (the copper surface was roughened by etching) by vacuum lamination (60 ° C., 0.2 MPA = 2 kg / cm ² ). Subsequently, a negative film having a resist pattern [φ200 μm hole] was brought into close contact with the PET film, and irradiated with ultraviolet rays (400 mJ / cm ² ) using an ultraviolet exposure device (EXM-1201F, short arc lamp manufactured by Oak Seisakusho). Next, the PET film was peeled off and developed with a 1% aqueous sodium carbonate solution at a spray pressure of ² kg / cm ² for 60 seconds. Thereafter, heat curing was performed with a hot air dryer at 150 ° C. for 1 hour to prepare Sample B. Φ200μm hole was observed with a magnifying glass, the resist layer was developed and the diameter of the exposed copper surface (the hole was opened) was measured, and the resolution was judged according to the following criteria .
○: Diameter of 150 μm or more and less than 200 μm.
Δ: Diameter of 100 μm or more and less than 150 μm.
X: Diameter less than 100 μm.

<Evaluation results>
The evaluation results are shown in Table 5.

Table 5

As is apparent from Table 5, the photosensitive flame retardant resin composition of the present invention is excellent in substrate adhesion, flexibility, solder heat resistance, flame retardancy, developability, and flexibility and bendability. Therefore, it can be seen that it can be suitably used for a printed wiring board or the like.

Claims (10)

A photosensitivity comprising a component (A) having an ethylenically unsaturated double bond and a carboxyl group, the component (A) and a flame retardant (B) represented by the following general formula [1] Flame retardant composition.

Wherein X ₁ and X ₂ are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted or unsubstituted phosphine group, substituted or unsubstituted aryloxy Group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, sulfonic acid Group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, or Represents a substituted carbonyl group, provided that X ₁ and X ₂ are not the same.
R _{1 to} R ₂₄ are each independently a hydrogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted silyloxy group, substituted or unsubstituted silyl group, substituted or unsubstituted phosphineoxy group, substituted or unsubstituted phosphine group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Aryl group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, sulfonic acid group, substituted or unsubstituted alkenyl group Represents a substituted or unsubstituted alkynyl group or a substituted carbonyl group X ₁ and R ₁ and X ₂ and R ₆ may each independently form a ring. ) The photosensitive flame retardant composition according to claim 1, wherein R _{9 to} R ₂₄ are hydrogen atoms. The photosensitive flame retardant composition according to claim 1, wherein R _{1 to} R ₈ are hydrogen atoms. The photosensitive flame retardant composition according to claim 1, wherein the component (A) having an ethylenically unsaturated double bond and a carboxyl group is a urethane resin.
  The photosensitive flame retardant composition according to claim 1, further comprising an organic solvent.   A photosensitive flame retardant dry film, wherein a photosensitive flame retardant composition layer formed from the photosensitive flame retardant composition according to claim 5 is sandwiched between two peelable films. .   At least one surface of a printed wiring board on which a conductive circuit is formed is partially covered with a flame retardant composition layer formed from the photosensitive flame retardant composition according to claim 5. A printed wiring board with a solder resist layer.   8. The printed wiring board with a solder resist layer according to claim 7, wherein the printed wiring board on which the conductive circuit is formed is a flexible printed wiring board on which the conductive circuit is formed.   The photosensitive flame retardant composition according to claim 5 is coated and dried on the entire surface of at least one surface of the printed wiring board on which the conductive circuit is formed. A printed wiring with a solder resist layer, wherein the exposed exposed portion flame retardant composition layer is thermally cured after partially irradiating ultraviolet rays to remove the unexposed portion photosensitive flame retardant composition layer A manufacturing method of a board.   A peelable film covering one surface is peeled off from the photosensitive flame retardant dry film according to claim 6, and the exposed photosensitive flame retardant composition layer is formed on at least a printed wiring board on which a conductive circuit is formed. Overlaid on the entire surface of one side, through the other peelable film or with the other peelable film peeled off, partially irradiated with ultraviolet rays, and after peeling off the other peelable film, the unexposed area photosensitive flame retardant After removing the photosensitive composition layer or removing the unexposed area photosensitive flame retardant composition layer, the remaining exposed area flame retardant composition layer is thermally cured, with a solder resist layer A method for manufacturing a printed wiring board.