TW201732422A - Curable resin composition, dry film, cured article and printed wiring board - Google Patents

Abstract

To provide a curable resin composition capable of forming a cured article having low dielectric constant and low dielectric loss tangent and further a good pattern shape without halation and undercut, a dry film having a resin layer obtained from the composition, the cured article thereof and a printed wiring board having the cured article. There is provided a curable resin composition or the like containing (A) an alkali plastic resin, (B) an inorganic filler, (C) a photosetting compound having no hydroxyl group nor carboxyl group, (D) an adhesion giving agent and (E) a photoinitiator.

Description

Curable resin composition, dry film, cured product, and printed wiring board

The present invention relates to a curable resin composition, a cured product, and a printed wiring board, and more particularly to a hardening of a good pattern shape in which a hardened material can be formed with a low dielectric constant and a low dielectric tangent, and without halation and side etching. A curable resin composition of the material, a dry film having a resin layer obtained from the composition, a cured product thereof, and a printed wiring board having the cured product.

In general, in the printed wiring board, as a material for the interlayer insulating material or the solder resist ink material, a modified epoxy acrylate compound or an epoxy resin is widely used as a main component from the viewpoint of heat resistance or electrical insulating properties. And a resin composition containing an additive component such as a filler.

However, when the dielectric constant and the dielectric tangent of the cured product composed of the resin composition used in such a substrate material are communicated in a high frequency region, there is a problem in that the delay or loss of the electrical signal cannot be avoided.

On the other hand, in order to reduce the dielectric constant and dielectric tangent of the wiring board material, it has been necessary to sufficiently mix a filler having a small dielectric constant or dielectric tangent. For example, a large number of solder resist inks having a spherical porous filler having a dielectric constant or a dielectric tangent are proposed (refer to Patent Document 1).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] International Publication No. 2006/008995

However, the dielectric constant and dielectric tangent cannot be sufficiently reduced by simply mixing a large amount of inorganic filler. Moreover, in order to reduce the dielectric constant and the dielectric tangent and to mix a large amount of the inorganic filler, since a halo is generated on the cured product, the amount of light penetrating into the deep portion is reduced, and side etching is caused, and the pattern after hardening is generated. The shape will become an inverted cone as shown in Fig. 1(B), so there is also a problem that the adhesion is deteriorated.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a curable resin composition capable of forming a cured product having a low dielectric constant and a low dielectric tangent and having no good haze and side etching, and having a cured product having a good pattern shape. A dry film of the obtained resin layer, a cured product thereof, and a printed wiring board having the cured product.

In view of the above, the present inventors have found that the above problems can be solved by adding a photocurable compound having no hydroxyl group and a carboxyl group, and an adhesion imparting agent, and the present invention has been completed.

That is, the curable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an inorganic filler, (C) a photocurable compound having no hydroxyl group and a carboxyl group, and (D) adhesion imparting Agent, and (E) photopolymerization initiator.

The curable resin composition of the present invention is preferably an epoxy compound further containing a thermosetting component.

The curable resin composition of the present invention contains a carboxyl group-containing resin as the above-mentioned (A) alkali-soluble resin, and the ratio of the equivalent of the epoxy group contained in the epoxy compound to the equivalent weight of the carboxyl group contained in the carboxyl group-containing resin Below 1.0 is preferred.

In the curable resin composition of the present invention, the (C) photocurable compound having no hydroxyl group or carboxyl group is preferably a compound having a cyclic skeleton composed of a hydrocarbon.

In the curable resin composition of the present invention, the (C) photocurable compound having no hydroxyl group or carboxyl group is preferably a cyclic skeleton having at least two carbon numbers of 5 or more.

The curable resin composition of the present invention preferably further contains a wetting dispersant.

In the curable resin composition of the present invention, the wetting dispersing agent is preferably a decane coupling agent.

In the curable resin composition of the present invention, the (D) adhesion imparting agent is preferably an isocyanate compound.

The dry film of the present invention is characterized in that it has a resin layer obtained by applying the curable resin composition onto a film and drying it.

The cured product of the present invention is characterized in that the curable resin composition or the resin layer of the dry film is cured.

The printed wiring board of the present invention is characterized in that it has the above-mentioned cured product.

According to the present invention, it is possible to provide a curable resin composition capable of forming a cured product having a low dielectric constant and a low dielectric tangent and having no good haze and side etching, and having a cured product obtained from the composition. A dry film of a resin layer, a cured product thereof, and a printed wiring board having the cured product.

[Fig. 1] Fig. 1 is a schematic view showing a cross-sectional shape of a pattern formed of a cured coating film of a curable resin composition, and (A) is an ideal state for exhibiting a linearity such as a design width in a depth direction. (B) to show the side erosion state.

The curable resin composition of the present invention is characterized by comprising (A) an alkali-soluble resin, (B) an inorganic filler, and (C) a photocurable compound having no hydroxyl group or a carboxyl group (hereinafter, also referred to as "(C) The photocurable compound "), and (D) the adhesion imparting agent, and (E) the photopolymerization initiator. The detailed mechanism of action is not clear, but by cooperation (C) The photocurable compound unexpectedly enables the dielectric constant and the dielectric tangent, and the shape of the pattern becomes good. Further, by further blending the (D) adhesion imparting agent, the pattern shape is stabilized and it becomes difficult to become an inverted tapered structure.

Hereinafter, each component of the curable resin composition of the present invention will be described.

[(A) alkali soluble resin]

(A) The alkali-soluble resin is a resin containing an alkali-soluble group such as a carboxyl group and soluble in an alkali solution, and preferably a carboxyl group-containing resin. As the (A) alkali-soluble resin, a carboxyl group-containing resin is preferred. The carboxyl group-containing resin preferably has an ethylenically unsaturated bond in the molecule in addition to a carboxyl group from the viewpoint of photocurability or development resistance, and may not contain an ethylenically unsaturated double bond. Carboxyl resin. The ethylenically unsaturated double bond is preferably one derived from (meth)acrylic acid or such a derivative. (A) The alkali-soluble resin may be used singly or in combination of two or more.

Specific examples of the carboxyl group-containing resin include the compounds listed below (which may be any of an oligomer and a polymer).

(1) copolymerization with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene by an unsaturated carboxylic acid such as (meth)acrylic acid A carboxyl-containing resin is obtained. When the carboxyl group-containing resin has an aromatic ring, at least one of the unsaturated carboxylic acid and the unsaturated group-containing compound may have an aromatic ring.

(2) Two different kinds of aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc. Cyanate ester, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol, a polyester polyol, or a polyolefin polyol A carboxyl group-containing amine obtained by addition polymerization of a diol compound such as an alcohol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group Carbamate resin. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of a diisocyanate, a carboxyl group-containing diol compound, and a diol compound may have an aromatic ring.

(3) a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester system. An amine obtained by addition polymerization of a diol compound such as a polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group A carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the end of the urethane resin. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate compound, the diol compound, and the acid anhydride may have an aromatic ring.

(4) From diisocyanate, with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biguanide epoxy resin, double a carboxyl group-containing aminocarboxylic acid obtained by addition polymerization of a (meth) acrylate or a partial acid anhydride denature thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a phenol type epoxy resin Ester resin. The carboxyl group-containing urethane resin is When an aromatic ring is present, at least one of a diisocyanate, a (meth) acrylate of a bifunctional epoxy resin, or a partial acid anhydride denatured product, a carboxyl group-containing diol compound, and a diol compound may have an aromatic ring.

(5) In the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. a terminal (meth) acrylated carboxyl group-containing urethane resin. When the carboxyl group-containing urethane resin has an aromatic ring, the compound having one hydroxyl group and one or more (meth) acrylonitrile groups in the molecule may have an aromatic ring.

(6) In the synthesis of the resin of the above (2) or (4), a molar reactant such as isophorone diisocyanate or pentaerythritol triacrylate is added, and one isocyanate group and one or more molecules are added to the molecule. A (meth)acryloyl group-containing compound, which is a terminal (meth)acrylated carboxyl group-containing urethane resin. When the carboxyl group-containing urethane resin has an aromatic ring, the compound having one isocyanate group and one or more (meth) acrylonitrile groups in the molecule may have an aromatic ring.

(7) reacting a polyfunctional epoxy resin with (meth)acrylic acid, and adding a dibasic acid anhydride such as anhydrous citric acid, tetrahydroanhydroiodinic acid or hexahydrohydrous citric acid to the hydroxyl group present in the side chain. Carboxyl containing resin. When the carboxyl group-containing resin has an aromatic ring, at least one of the polyfunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.

(8) reacting a polyfunctional epoxy resin which further epoxidizes a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and (meth)acrylic acid A carboxyl group-containing resin obtained by adding a hydroxyl group to a dibasic acid anhydride. When the carboxyl group-containing resin has an aromatic ring, at least one of the bifunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxycyclobutane resin with a dicarboxylic acid to form a dibasic acid anhydride on the produced first-order hydroxyl group. When the carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxycyclobutane resin, the dicarboxylic acid, and the dibasic acid anhydride may have an aromatic ring.

(10) reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and reacting with an unsaturated group-containing monocarboxylic acid to obtain The carboxyl group-containing resin obtained by reacting the reaction product with a polybasic acid anhydride.

(11) reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propylene carbonate, and reacting with an unsaturated group-containing monocarboxylic acid, A carboxyl group-containing resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(12) an epoxy compound having a plurality of epoxy groups in one molecule, and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenylethyl alcohol. Reaction of an unsaturated group-containing monocarboxylic acid such as methyl)acrylic acid to obtain an alcoholic hydroxyl group of the obtained reaction product with anhydrous maleic acid, tetrahydroanhydrous decanoic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid, and A carboxyl group-containing resin obtained by reacting a polybasic acid such as a diacid. When the carboxyl group-containing polyester resin has an aromatic ring, the epoxy compound, at least one compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, at least one containing an unsaturated monocarboxylic acid and a polybasic acid anhydride The species has an aromatic ring.

(13) Adding a resin such as epoxypropyl (meth) acrylate or α-methyl propyl propyl (meth) acrylate to the resin in any one of the above (1) to (12) in a molecule A carboxyl group-containing resin having a compound having one epoxy group and one or more (meth) acrylonitrile groups. When the carboxyl group-containing resin has an aromatic ring, the compound having one epoxy group and one or more (meth) acrylonitrile groups in the molecule may have an aromatic ring.

(14) a copolymer of a compound having one epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, and reacting with an unsaturated monocarboxylic acid to form a second-order hydroxyl group and A carboxyl group-containing resin obtained by reacting a saturated or unsaturated polybasic acid anhydride. When the carboxyl group-containing resin has an aromatic ring, at least one of the copolymer, the unsaturated monocarboxylic acid, and the unsaturated polybasic acid anhydride may have an aromatic ring.

(15) reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, and reacting the resulting carboxylic acid with a compound having one epoxy group and an unsaturated double bond in one molecule to obtain a hydroxyl group and Carboxyl resin. When the carboxyl group-containing resin has an aromatic ring, at least one of a hydroxyl group-containing polymer, a polybasic acid anhydride, and a compound having one epoxy group and an unsaturated double bond in one molecule may have an aromatic ring.

Further, in this (meth) acrylate type, acrylate, methacrylate, and the like are collectively referred to, and the same is true for other similar expressions.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone ‧ polymer, it can be developed with a diluted aqueous alkali solution.

Further, in order to make the solder of the cured product excellent in heat resistance, it is preferable to use a carboxyl group-containing resin having an aromatic ring.

The carboxyl group-containing resin is preferably such that it does not substantially have a hydroxyl group in its structure. Examples of the carboxyl group-containing resin having substantially no hydroxyl group include the carboxyl group-containing resins of the above (1), (10) and (11). The carboxyl group-containing resin can lower the dielectric constant and dielectric tangent of the cured product by substantially having no hydroxyl group.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, preferably 40 to 180 mgKOH/g. When it is in the range of 20 to 200 mgKOH/g, the peeling property and the printability of the dried coating film formed using the aqueous alkali solution are good, and it is less likely to hang during drying.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. When it is in this range, the non-stick property is good, and the coating film after exposure is excellent in moisture resistance, and film formation is less likely to occur at the time of development. Moreover, when it is in the range of the weight average molecular weight, the printability and the heat resistance of the coating film become favorable. It is preferably 5,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography.

[(B) Inorganic filler]

The curable resin composition of the present invention contains (B) an inorganic filler. (B) The inorganic filler is used to increase the physical strength of the cured product obtained by the lift. (B) The inorganic filler is not particularly limited, and conventionally known inorganic fillers such as cerium oxide, nubous alumina, aluminum hydroxide, and glass can be used. Powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, titanium oxide, non-fibrous glass, hydrotalcite, slag wool, earthworm Inorganic pigments such as aluminum acid, calcium citrate, and zinc. (B) The inorganic filler may be used singly or in combination of two or more. Further, the (B) inorganic filler may be subjected to surface treatment.

Further, as the (B) inorganic filler, a compound such as a perovskite type, that is, calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, or the like may be used. A composite oxide of a main component. By using a perovskite type compound, a cured product having good dielectric properties can be obtained.

As the inorganic filler (B), since the cured product is easily made into a low dielectric constant and a low dielectric tangent, cerium oxide is preferred. As the cerium oxide, it is more preferable to highly fill the spherical cerium oxide.

The shape of the spherical ceria is not limited to a true one as long as it is spherical. As the suitable spherical cerium oxide, for example, the true sphericity measured by the following operation is 0.8 or more, but it is not limited thereto.

The true sphericity is measured as follows. The photograph was taken by SEM, and the value calculated from (true sphericity) = {4π × (area) ÷ (peripheral length) ² } was calculated from the area of the observed particles and the peripheral length. Specifically, an average value of 100 particles was measured using an image processing apparatus.

(B) The amount of inorganic filler blended in solid content conversion The amount is preferably 1 to 1000 parts by mass, more preferably 10 to 500 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin.

[(C) Photocurable compound having no hydroxyl group or carboxyl group]

The curable resin composition of the present invention contains (C) a photocurable compound having no hydroxyl group or a carboxyl group (hereinafter also referred to as "(C) photocurable compound").

The (C) photocurable compound is not particularly limited as long as it is a compound which is cured by irradiation with an active energy ray and exhibits electrical insulating properties and does not have any of a hydroxyl group and a carboxyl group. (C) The photocurable compound is preferably one or more ethylenically unsaturated bonds in the molecule, and preferably has a (meth) acrylonitrile group. (C) The photocurable compound may be used alone or in combination of two or more.

Dipentaerythritol hexa(meth)acrylate (DPHA), which is often used as a photocurable compound, is usually a mixture with a compound having a hydroxyl group, dipentaerythritol penta (meth) acrylate, but as (C) photocurability. The compound is preferably a mixture with a compound having a hydroxyl group such as DPHA.

As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer and a photopolymerizable vinyl monomer which are conventionally used may be used as long as they do not contain a hydroxyl group or a carboxyl group. Among them, examples of the photopolymerizable oligomer include an unsaturated polyester oligomer and a (meth)acrylate oligomer. Examples of the (meth) acrylate-based oligomer include urethane (meth) acrylate, polyester (meth) acrylate, and polyether (A). Acrylate, polybutadiene denatured (meth) acrylate, and the like.

Examples of the photopolymerizable vinyl monomer include a styrene derivative such as styrene, chlorostyrene or α-methylstyrene; and ethylene such as vinyl acetate, vinyl butyrate or vinyl benzoate. Base esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n- Vinyl ethers such as octadecyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, etc.; acrylamide, methacrylamide, N-methoxymethyl propylene (Methyl) acrylamides such as decylamine, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, etc.; triallyl isocyanurate, decanoate Allyl compound of propyl ester, diallyl isononate, etc.; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydroindenyl (meth) acrylate Esters of (meth)acrylic acid; alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate ; ethylene glycol di(methyl) Oleate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tris(A) Alkyl polyol poly(meth) acrylate such as acrylate; diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, ethoxylated trishydroxyl Polyoxyalkylene glycol poly(meth)acrylates such as propane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate; hydroxy hydroxypivalate neopentyl glycol diester Poly(meth) acrylates such as acrylates; ginseng [(meth) propylene oxiranyl ethyl) isomeric cyanurate A cyanuric acid type poly(meth) acrylate or the like.

(C) The photocurable compound is preferably a compound having a cyclic skeleton composed of a hydrocarbon. Here, examples of the cyclic skeleton include a cyclic aliphatic skeleton, an aromatic skeleton, and a condensed polycyclic skeleton. (C) The photocurable compound is preferably a cyclic skeleton having at least two or more carbon atoms of 5 or more, and preferably two or more aromatic skeletons. Since the annular skeleton, in particular, the more aromatic skeletons, the development resistance is improved, so that the pattern shape is good. Here, at least two or more means that the biphenyl skeleton or the bisphenol skeleton may have two or more cyclic skeletons independently, or may be, for example, a dicyclopentadiene skeleton, an anthracene skeleton, a naphthalene skeleton or an anthracene skeleton. Two or more condensed condensed polycyclic rings having a cyclic skeleton. The condensed polycyclic ring may be not only a condensed polycyclic ring of the same kind of ring, but also a ring of a different kind, for example, a condensed polycyclic ring of a five-membered ring and a six-membered ring. Among them, a biphenyl skeleton, a bisphenol skeleton, a dicyclopentadiene skeleton, an anthracene skeleton, and a novolac type phenol skeleton are preferred.

Examples of the compound having a cyclic skeleton composed of a hydrocarbon include vinylcyclohexyl ether, isodecyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (A). Acrylate, 9,9-bis[4-(2-(methyl)acryloxyethoxy)phenyl]anthracene, dimethylol-tricyclodecane di(meth)acrylate, etc. . Further, a photocurable compound having a hydroxyl group such as an epoxy group (meth) acrylate may be contained within a range not inhibiting the effects of the present invention.

(C) The amount of the photocurable compound is preferably 0.5 to 200 parts by mass, and preferably 1 to 100 parts by mass, based on 100 parts by mass of the alkali-soluble resin in terms of solid content.

The curable resin composition of the present invention may contain (C) a photocurable compound other than the photocurable compound, within the range not impairing the effects of the present invention.

[(D) Adhesion imparting agent]

The (D) adhesion imparting agent is preferably an adhesion imparting agent such as an imidazole-based, thiazole-based, triazole-based or isocyanate-based adhesive, and is imparted with an isocyanate-based adhesiveness from the viewpoint of the cross-sectional shape of the pattern. The agent is preferred.

As the isocyanate-based adhesion imparting agent, a known isocyanate compound such as a monoisocyanate compound having one isocyanate group or a polyisocyanate having two or more isocyanate groups can be used. In the present invention, it is preferred to block the isocyanate compound from the viewpoint of improving workability due to excellent storage stability.

As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate can be used.

The aromatic polyisocyanate may, for example, be 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate or naphthalene-1,5. - Diisocyanate, o-extended diisocyanate, m-extended diisocyanate, diphenylmethylene diisocyanate and 2,4-methylphenyl dimer.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, and 4,4-methylene bis ( Cyclohexyl isocyanate) and isophorone diisocyanate.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, an adduct of an isocyanate compound, a diurea, and an isocyanurate as exemplified above can be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by the reaction with the blocking agent and is inactivated for a while. Upon heating to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound which can be reacted with the terminal blocking agent include the above-mentioned polyisocyanate compound.

Examples of the isocyanate blocking agent include phenolic terminal blocking agents such as phenol, cresol, indophenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroinamide, and γ-butyl An internal amide-based blocking agent such as decylamine and β-propionalamine; an active methylene-based blocking agent such as ethyl acetate and ethyl acetonylacetate; methanol, ethanol, propanol and butanol , pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, glycolic acid Alcohol-based blocking agent for ester, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, a thiol-based blocking agent such as cyclohexane hydrazine or the like; a thiol-based blocking agent such as butyl thiol, hexyl thiol, t-butyl thiol, thiophenol, methyl thiophenol or ethyl thiophenol; An acid amide amine blocking agent such as guanamine or benzamide; a quinone imine blocking agent such as succinimide succinate and succinimide; guanamine, aniline, butylamine, An amine-based blocking agent such as dibutylamine; an imidazole-based blocking agent such as imidazole or 2-ethylimidazole; an imide-based blocking agent such as methyleneimine and propylimine; dimethyl A pyrazole-based blocking agent such as pyrazole; a maleate-based blocking agent such as diethyl maleic acid.

As the blocked isocyanate compound, for example, Sumidule (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS can be cited. -2078, TPLS-2117, Desmosome 2170, Desmosome 2265 (all manufactured by Sumitomo Bayer®), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all are Japanese polyurethanes) Industrial (share) system), B-830, B-815, B-846, B-870, B-874, B-882 (all are Mitsui Takeda Chemical Co., Ltd.), Duranate SBN-70D, TPA-B80E , 17B-60PX, E402-B80T (all are manufactured by Asahi Kasei Chemicals Co., Ltd.), TRIXENE BI 7982, 7950, 7951, 7960, 7961, (Baxeneden Chemicals Limited), which also uses Duranate SBN-70D TRIXENE BI 7982 is preferred. Further, Sumidule BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a terminal blocking agent.

These isocyanate compounds may be used singly or in combination of two or more.

(D) The amount of the adhesion imparting agent is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin in terms of solid content. If the amount is in the range of the aforementioned parts by mass Inside, a sufficient cross-sectional shape of the pattern can be obtained and good adhesion is obtained. It is preferably 0.1 to 20 parts by mass.

[(E) Photopolymerization initiator]

The curable resin composition of the present invention contains (E) a photopolymerization initiator. As the (E) photopolymerization initiator, any photopolymerization initiator which is known as a photopolymerization initiator or a photoradical generator can be used.

The (E) photopolymerization initiator may, for example, be bis-(2,6-dichlorobenzylidene)phenylphosphine oxide or bis-(2,6-dichlorobenzylidene)-2. 5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-1 -naphthylphosphine oxide, bis-(2,6-dimethoxybenzylidene)phenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4- Trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethyl a bis-decylphosphine oxide such as benzhydryl)-phenylphosphine oxide (manufactured by BASF JAPAN, IRGACURE 819); 2,6-dimethoxybenzylphosphonium diphenylphosphine oxide, 2, 6-Dichlorobenzyl hydrazinodiphenylphosphine oxide, 2,4,6-trimethylbenzyl phenylphosphonic acid methyl ester, 2-methylbenzyl phenyldiphenylphosphine oxide, trimethyl Monodecylphosphine oxides such as isopropyl phenyl phenylphosphonate and 2,4,6-trimethylbenzyl hydrazino diphenylphosphine oxide (manufactured by BASF JAPAN, DAROCUR TPO) 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2- -1- {4- [4- (2-hydroxy-2- Hydroxyacetophenones such as benzyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one Benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and other benzoin; benzoin alkyl ether; benzophenone , p-methylbenzophenone, mischrone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, etc. Benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-di Chloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2- Dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1- Acetophenones such as [4-(4-ythyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthone; hydrazine, chloranil, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, 2-pentyl hydrazine, 2- Anthracene or the like; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; ethyl-4-dimethylamino benzoate, 2-(two a benzoic acid ester such as methylamino)ethylbenzoate or ethyl p-dimethylbenzoate; 1,2-octanedione, 1-[4-(phenylthio)-,2- (O-benzylindolyl)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl]-, 1-(0-B Anthraquinone esters; bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)benzene Titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2- Titanocenes such as (1-pyrrol-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitroindole, butyl acylate, fennel ate ethyl ether, azobisisobutyl Nitrile, tetramethylthiuram disulfide, and the like. The photopolymerization initiator may be used singly or in combination of two or more.

In the above, acetophenone (hereinafter referred to as "acetophenone photopolymerization initiator") and ferrocene (hereinafter referred to as "titanocene photopolymerization initiator"), and A mercaptophosphine oxide photopolymerization initiator such as a bis-decylphosphine oxide-based mercaptophosphine oxide is preferred. When an acetophenone-based photopolymerization initiator is blended, it is preferred because it is less likely to cause hardening inhibition due to oxygen. When a titanocene-based photopolymerization initiator is blended, it is preferable because deep curing property can be obtained and the pattern shape is good. When a fluorenylphosphine oxide photopolymerization initiator is blended, it is preferable because it has less viscosity and excellent discoloration suppression effect.

(E) The amount of the photopolymerization initiator is preferably 0.01 to 50 parts by mass, and preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the (A) alkali-soluble resin.

(wetting dispersant)

As the wetting dispersing agent, those having an effect of assisting in dispersing an organic or inorganic filler can be generally used. As such a wet dispersing agent, a compound having a polar group such as a carboxyl group, a hydroxyl group, an acid ester or the like, or a polymer compound such as an acid-containing compound such as a phosphate ester or a copolymer containing an acid group or a hydroxyl group-containing polymer can be used. Carboxylic acid esters, polyoxyalkylene oxides, salts of long-chain polyamine guanamines and acid esters, and the like. The wetting dispersing agent may be used singly or in combination of two or more. use.

Such a wetting dispersant is preferably a coupling agent. As the coupling agent, for example, a decane-based coupling agent, an organic decazane compound, a titanate-based coupling agent, a zirconium-based coupling agent, an aluminum-based coupling agent, or the like can be used. In particular, in the present invention, a decane-based coupling agent is suitably used.

Examples of such a decane-based coupling agent include a vinyl decane-based coupling agent, an amino decane-based coupling agent, an epoxy decane-based coupling agent, a mercapto decane-based coupling agent, and a (meth) acrylonitrile-based decane-based coupling agent. A decane-based coupling agent.

Among the above decane-based coupling agents, a (meth)acrylic decane coupling agent, a vinyl decane coupling agent, and an epoxy decane coupling agent are also preferred.

The decane-based coupling agent is composed of an organic substance (organic group) and hydrazine, and is generally XnR'(n-1)Si-R"-Y (X=hydroxyl group, alkoxy group, etc., Y=vinyl group, epoxy group). a compound represented by a styrene group, a styrene group, a methacryloxy group, an acryloxy group, an amine group, a urea group, a chloropropyl group, a decyl group, a polythioether group, an isocyanate group, etc. Since there are two or more different reactive groups in the molecule, it is usually used as an intermediary for bonding an organic material which is very difficult to bond with an inorganic material, and is used for strength improvement of a composite material, modification of a resin, surface modification, and the like.

Specific examples of the decane-based coupling agent are as follows.

For example, N-γ-(aminoethyl)-γ-aminopropyltriethoxydecane, N-γ-(aminoethyl)-γ-aminopropyltrimethoxydecane, γ -Aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ- Aminopropylmethyldiethoxydecane, γ-aminopropylmethyldimethoxydecane, γ-aminopropylphenyldiethoxydecane, 2-amino-1-methylidene Triethoxy decane, N-methyl-γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane, N-butyl-γ-amino Propylmethyldiethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-N-β-(amine Benzyl)-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxy Propylmethyldimethoxydecane (3-glycidoxypropylmethyldimethoxydecane), β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ- Mercaptopropyltrimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-isocyanatopropyltriethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, ethylene Base (2-methoxyethoxy)decane, methacryloxypropyltrimethoxydecane, γ-polyoxyethylenepropyltrimethoxydecane, 3-propene oxime Trimethoxy Silane, etc., wherein Yi Yi 3- glycidoxypropyl methyl dimethoxysilane Silane, 3- (meth) Bing Xixi trimethoxysilane Silane preferred.

Examples of commercially available decane-based coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, and KBM-1403. , KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM -573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all are trade names; Shin-Etsu is a system of oxygen). These may be used singly or in combination of two or more.

The amount of the wetting dispersant is preferably 0.01 to 20 parts by mass, and preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the alkali-soluble resin in terms of solid content.

(thermosetting component)

The photocurable resin composition of the present invention may contain a thermosetting component. By further thermosetting the resin composition after light curing, the properties of the cured product such as heat resistance and insulation reliability can be improved. As the thermosetting component, for example, an amine-based resin, a melamine resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, an epoxy compound, and a polyfunctional oxygen ring can be used. A known thermosetting resin such as an alkane compound or an episulfide resin. In the present invention, an epoxy compound and an oxycyclobutane compound can be suitably used, and these can also be used in combination.

As the epoxy compound, a known compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is also preferable. For example, a monoepoxy compound such as a monoepoxy compound such as butyl glycidyl ether, phenylepoxypropyl ether or propylene propyl (meth)acrylate, or a bisphenol A type epoxy may be mentioned. Resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyepoxypropyl Ether, phenyl-1,3-diepoxypropyl ether, biphenyl-4,4'-diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, ethylene glycol or Propylene glycol epoxide Propyl ether, sorbitol polyepoxypropyl ether, ginseng (2,3-epoxypropyl)isocyanate, triepoxypropyl ginseng (2-hydroxyethyl)isocyanuric acid The ester or the like is a compound having two or more epoxy groups in one molecule. These may be used alone or in combination of two or more kinds in combination with the required characteristics.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, and Nippon Steel Chemicals (shares) Epotote YD-011, YD-013, YD-127, YD-128, Dow Chemical Japan (shares) DER317, DER331, DER661, DER664, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all are trade names) of bisphenol A manufactured by Asahi Kasei E Materials Co., Ltd. Type epoxy resin; JERYL903 made by Mitsubishi Chemical Co., Ltd., Epiclon 152, Epiclon 165 made by DIC, Epotote YDB-400, YDB-500, Dow Chemical Japan (share) DER542, Sumi-Epoxy ESB-400, ESB-700, Sumitomo Chemical Co., Ltd., AER711, AER714, etc. (all are trade names) brominated epoxy resin; Mitsubishi Chemical Co., Ltd. jER152, jER154, Dow Chemical Japan (stock) DEN431, DEN438, DIC (share) Epiclon N-730, Epiclon N-770 EpiclonN-865, Nippon Steel Chemical living EPPN- gold (shares) made of Epotote YDCN-701, YDCN-704, Nippon Kayaku (shares) of the system 201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei E material (stock) AERECN -235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. , YDCN-704A, DIC (share) Epiclon N-680, N-690, N-695 (all are trade names) and other phenolic epoxy resin; DIC (share) Epiclon 830, Mitsubishi Chemical (share) system JER807, bisphenol F-type epoxy resin of Epotote YDF-170, YDF-175, YDF-2004, etc. (all are trade names) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; Nippon Steel & Sumitomo Chemical Co., Ltd. Epotote ST-2004, ST-2007, ST-3000 (trade name), etc. Hydrogenated bisphenol A epoxy resin; Mitsubishi Chemical Co., Ltd. jER604, Nippon Steel & Sumitomo Chemical Co., Ltd. Epotote YH-434 Sumitomo Chemical Co., Ltd. Sumi-Epoxy ELM-120 (all are trade names) epoxy propylamine epoxy resin; B-urea urea-type epoxy resin; (shares) Dell's Ceroxide 2021, etc. (all are trade names) alicyclic epoxy resin; Mitsubishi Chemical Corporation's YL-933, Dow Chemical Day TEN, EPPN-501, EPPN-502, etc. (all are trade names) of trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL- made by Mitsubishi Chemical Corporation Bisphenol or bisphenol epoxy resin such as 6121 (both are trade names) or a mixture of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA, DIC Bisphenol S type epoxy resin such as EXA-1514 (trade name); manufactured by Mitsubishi Chemical Corporation Bisphenol A novolac type epoxy resin such as jER157S (trade name); Tetraphenylolethane type epoxy resin such as jERYL-931 (all are trade names) manufactured by Mitsubishi Chemical Corporation; Nissan Chemical Industry ( Heterocyclic epoxy resin such as TEPIC (both trade names); diepoxypropyl phthalate resin such as Blenmer DGT made by Nippon Oil Co., Ltd.; Nippon Steel & Sumitomo Chemical Co., Ltd. ) a tetra-epoxypropyl xylene decyl ethane resin such as ZX-1063; ESN-190, ESN-360, DIC (manufacturing) HP-4032, EXA-4750, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. The naphthalene group of EXA-4700 or the like contains an epoxy resin; an epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by DIC; and CP-50S and CP-made by Nippon Oil Co., Ltd. 50M epoxy methacrylate copolymerized epoxy resin; and copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; CTBN modified epoxy resin (for example, new Nippon Steel is a chemical company (YR-102, YR-450, etc.), etc., but it is not limited to this. Among these, a bisphenol A type epoxy resin, a heterocyclic epoxy resin, or a mixture of these is preferable because it is excellent in discoloration resistance.

These epoxy compounds may be used alone or in combination of two or more.

Next, the description will be given regarding the oxycyclobutane compound. As the general formula (I) below: Specific examples of the oxycyclobutane compound containing an oxycyclobutane ring represented by the formula (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) may, for example, be 3-ethyl-3-hydroxyl group. Methyloxetane (manufactured by Toagos Corporation, trade name: OXT-101), 3-ethyl-3-(phenoxymethyl)oxycyclobutane (manufactured by East Asia Synthetic Co., Ltd., trade name OXT) -211), 3-ethyl-3-(2-ethylhexyloxymethyl)oxycyclobutane (manufactured by Toago Corporation, trade name: OXT-212), 1,4-double {[(3) -ethyl-3-oxocyclobutanyl)methoxy]methyl}benzene (manufactured by Toagos Corporation, trade name OXT-121), bis(3-ethyl-3-oxocyclobutane A) Ethyl ether (manufactured by East Asia Synthetic Co., Ltd., trade name: OXT-221). Further, an oxycyclobutane compound such as a phenol novolac type may be mentioned. These oxycyclobutane compounds may be used in combination with the above epoxy compounds, or may be used singly.

The thermosetting component is preferably a compound having a cyclic skeleton composed of a hydrocarbon, and an epoxy compound having a cyclic skeleton composed of a hydrocarbon is preferred. Here, the example of the cyclic skeleton is the same as the above (C) photocuring component. The cyclic skeleton is preferably a cyclic skeleton having at least two or more carbon atoms of 5 or more. Among them, a biphenyl skeleton, a bisphenol skeleton, a dicyclopentadiene skeleton, and an anthracene skeleton are preferred.

The amount of the thermosetting component is 0.5 to 100 by mass based on 100 parts by mass of the (A) alkali-soluble resin in terms of solid content. The amount is preferably from 1 to 50 parts by mass.

When the curable resin composition of the present invention contains the carboxyl group-containing resin as the (A) alkali-soluble resin, the ratio of the equivalent of the epoxy group contained in the epoxy compound to the equivalent weight of the carboxyl group contained in the carboxyl group-containing resin is 1.0. The following is preferable, preferably 0.7 or less, more preferably 0.5 or less. When the equivalent ratio is 1.0 or less, the ratio of the hydroxyl groups in the cured product is small, and the dielectric constant can be lowered, and in particular, the dielectric tangent can be lowered.

(Organic solvents)

Further, the curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity of the substrate or the carrier film. As the organic solvent, ketones such as methyl ethyl ketone or cyclohexanone; aromatic hydrocarbons such as toluene, hydrazine, and tetramethylbenzene; 赛路苏, methyl 赛路苏, and butyl race road can be used. Sue, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, Glycol ethers such as tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, 赛路苏 acetate, butyl racelus acetate, carbitol acetate, butyl An ester of carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propyl carbonate, etc.; an aliphatic hydrocarbon such as octane or decane; petroleum ether; A well-known organic solvent such as a petroleum solvent such as petroleum brain or solvent naphtha. These organic solvents may be used singly or in combination of two or more.

Further, the curable resin composition of the present invention can also be formulated Other additives that are well known in the art of electronic materials. Examples of other additives include a hardener, a hardening catalyst, an antioxidant, a heat stabilizer, a thermal polymerization inhibitor, an ultraviolet absorber, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, and an antibacterial agent. Mold, defoamer, leveling agent, thickener, shake imparting agent, coloring agent, photoinitiating aid, sensitizer, hardening accelerator, release agent, surface treatment agent, dispersant, dispersion aid Agent, surface modifier, stabilizer, phosphor, etc.

The curable resin composition of the present invention can be used after being dried, or can be used as a liquid. When it is used as a liquid, it may be one-liquid or two-liquid or more.

The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention and drying it on a carrier film. When the dry film is formed, the curable resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate viscosity, and then a comma coater, a blade coater, or a blade coater. a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A gravure coater, a spray coater, or the like is applied to the carrier film to a uniform thickness. Thereafter, the applied composition is usually dried by drying at a temperature of 50 to 130 ° C for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited. Generally, the film thickness after drying is suitably selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film can be used, and for example, A polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like. The thickness of the carrier film is not particularly limited, and is generally suitably selected within the range of 10 to 150 μm.

After the resin layer composed of the curable resin composition of the present invention is formed on the carrier film, it is preferable to laminate the film on the surface of the film to prevent adhesion of dust or the like on the surface of the film. As the peelable cover film, for example, a polyethylene film or a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. The cover film may be smaller than the adhesive force of the resin layer and the carrier film when the cover film is peeled off.

Further, in the present invention, the resin layer may be formed by applying the curable resin composition of the invention to the protective film and drying it, and laminating the carrier film on the surface thereof. In the present invention, when a dry film is produced, any of a carrier film and a protective film can be used as the film to which the curable resin composition of the present invention is applied.

In addition, the resin layer obtained by applying the curable resin composition of the present invention and evaporating and drying the solvent is exposed to light (light irradiation), and the exposed portion (portion irradiated with light) is cured. Specifically, the contact pattern or the non-contact method is used to expose the photomask by the selective active energy, or the direct pattern exposure by the laser direct exposure machine, by the dilute alkali aqueous solution. (For example, a 0.3 to 3 mass% aqueous sodium carbonate solution) develops an unexposed portion to form a photoresist pattern. When the curable resin composition of the present invention contains a thermosetting component, it is heated to a temperature of about 100 to 180 ° C by heat hardening (post-hardening) to form heat resistance, chemical resistance, moisture absorption resistance, Hardening, electrical properties, etc. Film (hardened).

Further, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the above organic solvent, and is applied to a substrate by a dip coating method, a shower coating method, a roll coating method, a bar coating method, or a screen printing method. After coating by a method such as a printing method or a curtain coating method, the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a non-stick resin layer. Further, when the composition is applied onto a carrier film or a protective film, dried, and wound into a film to form a film, the resin layer and the substrate of the composition of the present invention are laminated by a laminator or the like. After bonding and bonding to the substrate, the resin layer can be formed on the substrate by peeling off the carrier film.

Examples of the substrate include a phenol paper, an epoxy paper, and an epoxy glass cloth, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed by copper or the like. High utilization of glass polyimine, glass cloth/epoxy non-woven fabric, glass cloth/epoxy paper, epoxy synthetic fiber, fluorocarbon resin, polyethylene, polyphenylene ether, polyphenylene ether, cyanate ester, etc. The frequency circuit is made of copper-clad laminate or the like, and is a copper-clad laminate of all grades (FR-4, etc.), and other such as a metal substrate, a polyimide film, a PET film, or polyethylene naphthalate ( PEN) film, glass substrate, ceramic substrate, wafer board, and the like.

The above-mentioned volatilization drying or thermosetting may be carried out by using a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven or the like (using a heat source having a heating method of air by steam to bring the hot air in the dryer into contact with each other in a countercurrent manner) Implemented by blowing the nozzle toward the support).

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like may be mounted, and a device that irradiates ultraviolet rays in a range of 350 to 450 nm may be used. A drawing device (for example, a laser direct imaging device that draws an image with direct laser light by CAD data from a computer) is used. As the light source or laser source of the direct drawing machine, the maximum wavelength can be in the range of 350~410nm. The exposure amount for forming an image differs depending on the film thickness and the like, but it can be generally 20 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

As the development method, a dipping method, a rinsing method, a spraying method, a brushing method, or the like can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate or sodium citrate can be used. An aqueous solution of an alkali such as ammonia or an amine.

The curable resin composition of the present invention is preferably used as a printed wiring board in order to form a cured film on a printed wiring board, and is preferably used for forming a permanent film, and is preferably formed into a permanent insulating film or solder resist ink. The user of the interlayer insulating layer or the cover film. In particular, it is suitable for forming a solder resist ink, that is, as a solder resist ink composition. Further, the curable resin composition of the present invention can also be used to form a solder dam.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples.

(Synthesis Example 1 (alkali-soluble resin A-1) of alkali-soluble resin)

In an autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 parts of a phenol novolak type phenol resin (trade name "Shonol CRG951", OH equivalent: 119.4), and potassium hydroxide were placed. 1.19 parts and 119.4 parts of toluene were stirred and simultaneously subjected to nitrogen substitution in the system, and heated to increase the temperature. Next, 63.8 parts of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain a propylene oxide phenol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Reaction solution. This is an average of 1.08 moles of alkylene oxide per 1 equivalent of phenolic hydroxyl groups.

Next, 293.0 parts of the alkylene oxide reaction solution of the phenolic cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were placed in a mixer, a thermometer, and an air blowing tube. The reactor was blown with air at a rate of 10 ml/branch, and stirred while reacting at 110 ° C for 12 hours. The water formed by the reaction was distilled off into 12.6 parts of water as an azeotropic mixture with toluene. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, followed by washing with water. Thereafter, toluene was replaced with 118.1 parts of diethylene glycol monoethyl ether acetate using an evaporator, and distilled to obtain a novolac type acrylate resin solution.

Next, 332.5 parts of the obtained phenolic acrylate resin solution and 1.22 parts of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and the air was blown at a rate of 10 ml/min. Add 60.8 parts of tetrahydrophthalic anhydride, reverse at 95~101 °C It should be 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid content of 88 mg KOH/g, a carboxylic acid equivalent (solid content) 638, a nonvolatile content of 71%, and a Mw of about 10,000 was obtained. This resin solution is referred to as an alkali-soluble resin solution A-1.

(Synthesis Example 2 (alkali-soluble resin A-2) of alkali-soluble resin)

600 g of p-ethylene glycol monoethyl ether acetate was placed in an o-cresol novolac type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average The number of functional groups was 7.6] 1070 g (number of epoxy groups (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone, and the mixture was heated and stirred to 100 ° C to be uniformly dissolved.

Next, 4.3 g of triphenylphosphine was placed, and the mixture was heated to 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours. Into the obtained reaction liquid, 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydroanhydrous ruthenic acid were placed, and the mixture was reacted at 110 ° C for 4 hours, and cooled to obtain a photosensitive carboxyl group-containing resin solution. . This resin solution is referred to as an alkali-soluble resin solution A-2. The solid content of the alkali-soluble resin solution A-2 was 65%, and the acid value of the solid content was 89 mgKOH/g.

(Synthesis Example 3 (alkali-soluble resin A-3) of alkali-soluble resin)

Cyclomer ACA Z250 (solid content acid value: 65 gKOH/g, solid content: 46%) manufactured by Dell Corporation was used. This is referred to as an alkali-soluble resin solution A-3.

(Synthesis Example 4 (alkali-soluble resin A-4) of alkali-soluble resin)

In a 2000 ml flask equipped with a stirrer and a cooling tube, 431 g of dipropylene glycol monomethyl ether was placed, and the mixture was heated to 90 ° C under a nitrogen stream. The mixture was dissolved in 104.2 g of styrene, 296.6 g of methacrylic acid, and dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.: V-601) 23.9 g, dropped into the flask in 4 hours.

Thereby, an alkali-soluble resin A-4 which is a non-photosensitive carboxyl group-containing resin was obtained. The solid content of the resin A-4 was 140 mgKOH/g, and the solid content was 50% by mass.

(Photocurable compound C-1 having no hydroxyl group or carboxyl group)

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 106 parts of a novolac type phenol resin (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106) and 2.6 parts of a 50% sodium hydroxide aqueous solution were placed. 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1), stirred and nitrogen-substituted in the system, followed by heating and heating, and slowly introducing 60 parts of propylene oxide at 150 ° C and 8 kg / cm ² Its reaction. The reaction system was continued until about 4 hours after the measurement pressure became 0.0 kg/cm ² , and then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added, and sodium hydroxide was neutralized. The neutralization reaction product was diluted with toluene, washed with water three times, and desolventized using an evaporator to obtain an alkylene oxide adduct of a phenolic phenol resin having a hydroxyl equivalent of 164 g/eq. This is an average of 1 mole of alkylene oxide added per 1 equivalent of hydroxyl groups.

164 parts of an alkylene oxide adduct of the obtained novolac type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.05 parts of hydroquinone monomethyl ether, and 100 parts of toluene were placed in a mixer and a thermometer. Air was blown into the reactor of the tube, air was blown while stirring, and reacted at 110 ° C for 6 hours. After the water formed by the reaction was distilled off as an azeotropic mixture with toluene, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a methacrylate resin solution of a phenolic type PO having a nonvolatile content of 75%. This is referred to as (C) photocurable compound C-1.

Each component was blended according to the mixing shown in the following table, and after preliminary mixing using a stirrer, the mixture was dispersed by a three-roll mill, and kneaded to prepare a composition. Moreover, the amount of the ingredients in the table represents the parts by mass.

* 1: Resin solution of the above-mentioned alkali-soluble resin A-1* 2: Resin solution of the above-mentioned alkali-soluble resin A-2*3: Resin solution of the above-mentioned alkali-soluble resin A-3* 4 : Resin solution of the above-mentioned alkali-soluble resin A-4* 5: Shine Chemical Industry Co., Ltd. decane coupling agent KBE-503, 3-methacryloxypropyltriethoxydecane* 6: Total Rongshe Chemical Co., Ltd. Polyflow No.90 * 7: CIPigment Blue 15:3 * 8: CIPigment Yellow 147 * 9: Irgacure 379, 2-(dimethylamino)-2-[4, manufactured by BASF JAPAN -Methylphenyl)methyl]-1-[4-(4-ythyl)phenyl]-1-butanone* 10: manufactured by Yueyang Jinmaotai Technology Co., Ltd. *11: Melamine produced by Nissan Chemical Industry Co., Ltd. * 12: KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. * 13: SO-E2, spherical cerium oxide manufactured by Admatechs Co., Ltd. * 14: Photohardening synthesized above Resin solution of compound C-1* 15: A-BPEF, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene*, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Rongshe Chemical (strand) light acrylate DCP-A, dimethylol-tricyclodecane diacrylate* 17: AMP-20GY, phenoxy polyethylene glycol acrylate*, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. : Osaka Organic Chemical Industry Co., Ltd. Biscoat # 540, bisphenol A diglycidyl ether acrylic acid adduct * 19: Co., Ltd. epoxide ester M-600A, 2-hydroxy-3 -Phenoxypropyl acrylate* 20: 4HBA, 4-hydroxybutyl acrylate manufactured by Nippon Kasei Co., Ltd. * 21: NC-3000H, biphenyl phenolic epoxy compound, card made from Nippon Kayaku Co., Ltd. Bile alcohol acetate dissolved product, solid content 75% * 22: TRIXENE BI7982, adhesiveness imparting agent (blocking isocyanate) manufactured by Baxenden Chemicals Co., Ltd. * 23: carbitol acetate

The curable resin composition of each of the obtained examples and comparative examples was evaluated based on the following. The results are shown in the above table.

<Evaluation of dielectric constant and dielectric tangent> (production of test piece)

The curable resin composition obtained in the examples and the comparative examples was appropriately diluted with methyl ethyl ketone, and then applied to a PET film by using a coater so that the film thickness after drying was 20 μm (Toray) On a system, FB-50: 16 μm), a dry film was obtained after drying at 80 ° C for 30 minutes. Using a vacuum laminator (MVLP-500, manufactured by KK), the obtained dry film was laminated under the conditions of a pressure of 0.8 MPa, 70 ° C, 1 minute, and a vacuum of 133.3 Pa. On an electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) having a thickness of 9 μm. The dry film laminated on the copper foil was subjected to solid exposure at an optimum exposure amount using an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp) to peel off the PET film. On the exposed dry film, the dry film was again thermally laminated, and then subjected to substantial exposure at an optimum exposure amount. A dry film layer having a thickness of 400 μm was formed on the copper foil by repeating lamination and exposure 20 times. The copper foil on which the dry film layer was formed was irradiated with ultraviolet rays in a UV transfer furnace under the conditions of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 160 ° C for 60 minutes to harden the dry film layer. Next, the copper foil with the dry film layer is etched to remove the copper foil by using an etching solution consisting of 340 g/l of a second copper chloride and a free hydrochloric acid concentration of 51.3 g/l, and is sufficiently washed with water and dried to obtain a thickness. A test piece composed of a 400 μm cured film.

(evaluation method)

The dielectric constant and dielectric tangent of the test piece thus produced at 1 GHz were measured and evaluated using an RF impedance/material analyzer (Agilent E4991A, manufactured by Agilent Technologies, Inc.). The evaluation criteria are as follows.

<section shape>

The curable resin composition of each of the examples and the comparative examples was completely coated on a copper substrate by screen printing, and dried at 80 ° C for 30 minutes. The negative film of L/S=50/500 was used for exposure at an optimum exposure amount, and the image was obtained by performing a 60-second development using a 1% Na ₂ CO ₃ aqueous solution at 30 ° C under a spray pressure of 2 kg/cm ² . . After the development, the relief shape was observed with an optical microscope, and evaluation was performed as follows. The results obtained are shown in Table 1 above.

◎: None of the thin line patterns can be found to be distorted, thickened, and side etched (the difference between the top and bottom dimensions).

○: Some of the thin line patterns were found to be distorted, thickened, and side etched (the difference between the top and bottom dimensions).

△: Any one of the distortion, thickening, and side etching (the difference in size between the top and the bottom) of the fine line pattern was found.

×: A defect of a thin line pattern was found.

As shown in the above table, it is understood that the curable resin composition of the present invention can be obtained to form a low dielectric constant and a low dielectric tangent, and is dull A curable resin composition of a cured product having a good pattern shape of halo and side etching.

Claims (11)

A curable resin composition comprising (A) an alkali-soluble resin, (B) an inorganic filler, (C) a photocurable compound having no hydroxyl group and a carboxyl group, (D) an adhesion imparting agent, and (E) Photopolymerization initiator. The curable resin composition of claim 1, which further comprises an epoxy compound as a thermosetting component. The curable resin composition according to claim 1 or 2, which comprises a carboxyl group-containing resin as the above (A) alkali-soluble resin, and an epoxy group equivalent of the epoxy compound is included in the carboxyl group-containing resin. The ratio of the equivalent weight of the carboxyl group is 1.0 or less. The curable resin composition according to any one of claims 1 to 3, wherein the (C) photocurable compound having no hydroxyl group or a carboxyl group is a compound having a cyclic skeleton composed of a hydrocarbon. The curable resin composition according to any one of claims 1 to 4, wherein the (C) photocurable compound having no hydroxyl group or a carboxyl group has at least two or more cyclic skeletons having 5 or more carbon atoms. The curable resin composition according to any one of claims 1 to 5, which further comprises a wetting dispersant. The curable resin composition of claim 6, wherein the wetting dispersant is a decane coupling agent. The curable resin composition according to any one of claims 1 to 7, which The above (D) adhesion imparting agent is an isocyanate compound. A dry film comprising a resin layer obtained by applying a curable resin composition according to any one of claims 1 to 8 to a film and drying the film. A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 8, or a resin layer of the dry film of claim 9. A printed wiring board characterized by having a cured product as claimed in claim 10.