TW201609869A - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

A curable resin composition that exhibits excellent resolution, toughness and heat resistance; a dry film; a cured product; and a printed wiring board. The curable resin composition contains (A) an amide-imide resin having an alkali-soluble functional group and at least one structure represented by formulae (1) and (2), (B) inorganic particles having an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond. The inorganic particles (B) having an average particle diameter of 200 nm or less are preferably silica, and the curable resin composition preferably contains (E) a thermosetting resin.

Description

Curable resin composition, dry film, hardened material and printed circuit board

The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board, and more specifically, a curable resin composition which can obtain a cured product which is superior in resolution, toughness, and heat resistance to the prior art. , dry film, hardened material and printed wiring board.

At present, some solder-based printed wiring boards and solder resist compositions of most industrial printed wiring boards are formed by image formation by ultraviolet light irradiation based on high-precision and high-density. A liquid-based development type solder resist composition which is subjected to modification hardening (formal hardening) in at least one of heat and light irradiation. Among them, based on environmental considerations, an alkali-developing type photoresist composition using an aqueous alkali solution as a developing liquid has become mainstream, and has been widely used in the manufacture of practical printed wiring boards.

In the past, an alkali-soluble resin, particularly an epoxy acrylate-modified resin, has been generally used in the alkali-developing type solder resist composition. For example, Patent Document 1 proposes a solder resist formed of a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound obtained by adding an acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monobasic acid. Composition.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

At present, as a curable resin composition, a phenol novolak type (cresol novolak type) epoxy acrylate resin or an acrylic copolymer type resin has been widely used in an alkali-soluble type. However, the phenol novolac type epoxy acrylate resin is not necessarily excellent in toughness, and the acryl-based copolymer resin has poor heat resistance. Therefore, the conventional curable resin composition is difficult to have both high toughness and heat resistance. On the other hand, in recent years, when a semiconductor package component is mounted on a printed wiring board, the increase in the number of connections IO is simultaneously performed with the small size of the component, and the wiring density is rapidly increased. In order to make high-density wiring possible, a curable resin composition having high resolution is required.

In view of the above, it is an object of the present invention to provide a curable resin composition, a dry film, a cured product, and a printed wiring board which are excellent in resolution, toughness, and heat resistance.

The present inventors have found that the resin used in the curable resin composition is a resin having a specific structure, and the particle diameter of the inorganic particles of the filler is made specific. Below the value, the above problems can be solved, and the present invention has finally been completed.

That is, the curable resin composition of the present invention is characterized by comprising (A), (B), (C), and (D): (A) having at least the following formulas (1) and (2) An amidoxime resin having a structure and an alkali-soluble functional group,

And (B) inorganic particles having an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond.

The curable resin composition of the present invention may further comprise a resin having an alkali-soluble functional group different from the (A) amidoximeimide resin. Further, the inorganic particles (B) having an average particle diameter of 200 nm or less are preferably vermiculite. Further, it is preferred to contain (E) a thermosetting resin. Further, the (E) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.

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

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

The printed wiring board of the present invention is characterized by comprising the cured product of the present invention.

According to the present invention, it is possible to provide a curable resin composition, a dry film, a cured product, and a printed wiring board which can obtain a cured product excellent in resolution, toughness, and heat resistance.

Hereinafter, embodiments of the present invention will be described in detail.

[Curable resin composition]

The curable resin composition of the present invention (hereinafter also referred to as "resin composition") includes (A), (B), (C), and (D): (A) has the following formula (1), (2) An amidoxime resin having at least one of the structures and an alkali-soluble functional group (hereinafter also referred to as "(A) component"),

(B) inorganic particles having an average particle diameter of 200 nm or less (hereinafter also referred to as "(B) component)", (C) photopolymerization initiator (hereinafter also referred to as "(C) component"), and ( D) A compound having an unsaturated double bond (hereinafter also referred to as "(D) component"). When a resin having the above-described structure is used as the resin component of the resin composition, and inorganic particles having an average particle diameter of 200 nm or less are used as the filler, a cured product excellent in resolution, toughness, and heat resistance can be obtained.

Further, the resin composition of the present invention can be imaged by a weakly alkaline aqueous solution such as an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate or an aqueous solution of ammonia, and it is not necessary to use a strong alkaline developing solution for development. Moreover, since it can be developed by a weak alkaline aqueous solution, the environmental load is small. The resin composition of the present invention has, for example, a solubility in an aqueous solution of sodium carbonate (30 ° C, 1% by mass) of 0.05 g/L or more in one minute.

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

<(A) component>

The component (A) of the resin composition of the present invention is an amidoxime resin having at least one structure represented by the following formula (1) or (2) and an alkali-soluble functional group:

When the resin composition of the present invention contains a resin having a quinone imine bond directly bonded to a cyclohexane ring or a benzene ring, a cured product excellent in toughness and heat resistance can be obtained. In particular, the amidoximeimide resin having the structure represented by (1) is excellent in light transmittance, so that the resolution of the resin composition can be improved. In the resin composition of the present invention, the component (A) preferably has transparency. For example, in 25 μm of the dried coating film of the component (A), the transmittance of light having a wavelength of 365 nm is preferably 70% or more.

The content of the structures of the formulae (1) and (2) in the component (A) of the resin composition of the present invention is preferably from 10 to 70% by mass. By using this resin, it is possible to obtain a cured product which is excellent in solvent solubility and excellent in physical properties such as heat resistance, tensile strength, and elongation, and dimensional stability. It is preferably from 10 to 60% by mass, more preferably from 20 to 50% by mass.

The amidoxime imine resin having a structure represented by the formula (1), in particular, a resin having a structure represented by the formula (3A) or (3B), is excellent in physical properties such as tensile strength and elongation, and dimensional stability. Better:

(In the formulae (3A) and (3B), respectively, R is a monovalent organic group, and is preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, CH ₂ or C(CH ₃ ) _{2 is} an alkyl group). In the resin composition of the present invention, a resin having a structure of the formulas (3A) and (3B) of 10 to 100% by mass can be preferably used as the component (A) from the viewpoint of solubility and mechanical properties. More preferably 20 to 80% by mass.

In the resin composition of the present invention, as the component (A), an amidoxime having a structure of the formulas (3A) and (3B) of 5 to 100 mol% can be preferably used from the viewpoint of solubility and mechanical properties. Imine resin. It is preferably 5 to 98 mol%, more preferably 10 to 98 mol%, and most preferably 20 to 80 mol%.

Further, as the amidoximeimide resin having a structure represented by the formula (2), in particular, a resin having a structure represented by the formula (4A) or (4B),

(In the formulae (4A) and (4B), respectively, R is a monovalent organic group, and is preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, CH ₂ or C(CH ₃ ) ₂ or the like is preferably an alkyl group which is excellent in mechanical properties such as tensile strength and elongation. In the resin composition of the present invention, a resin having a structure of the formula (4A) and (4B) of 10 to 100% by mass can be preferably used as the component (A) from the viewpoint of solubility and mechanical properties. More preferably 20 to 80% by mass.

As the component (A) in the composition of the present invention, the amidoximeimide resin having a structure of 2 to 95 mol% of the formulas (4A) and (4B) can exhibit good mechanical properties. Good to use. More preferably 10 to 80 mol%.

The component (A) can be obtained by a conventional method. The amidoximeimine resin having the structure of (1) can be obtained, for example, by using a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic acid anhydride.

The diisocyanate compound having a biphenyl skeleton is exemplified by 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-diethyl Base-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-di Base-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-di-trifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2' -Di-trifluoromethyl-1,1'-biphenyl, and the like. Further, an aromatic polyisocyanate compound such as diphenylmethane diisocyanate or the like can also be used.

The cyclohexane polycarboxylic acid anhydride is exemplified by cyclohexane tricarboxylic anhydride, cyclohexane tetracarboxylic anhydride, and the like.

Moreover, the amidoxime imide resin having the configuration of (2) can be used. For example, it is obtained by the above-mentioned diisocyanate having a biphenyl skeleton and a polycarboxylic acid anhydride having two acid anhydride groups.

The polycarboxylic acid anhydride having two acid anhydride groups is exemplified by pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3',4 , 4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-2, 2',3,3'-tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-double ( 2,3-Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane Dihydride, 2,3-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)ether An alkanediol bishydroxybenzene trimellitate such as an anhydride or ethylene glycol dibenzoic anhydride.

The component (A) of the resin composition of the present invention further has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By a functional group having alkali solubility, it becomes a resin composition which can be developed by alkali. The functional group of the alkali-soluble one is a carboxyl group, a phenolic hydroxyl group, a sulfo group or the like, and preferably a carboxyl group.

The acid value of the component (A) of the resin composition of the present invention is preferably in the range of 20 to 120 mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g. By setting the acid value of the component (A) to the above range, it is possible to form a good alkali image and form a pattern of a normal cured product. The weight average molecular weight of the component (A) of the resin composition of the present invention varies depending on the resin skeleton, but is generally preferably from 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the non-contact property of the dried coating film, the moisture resistance of the coating film after exposure, and the solution Good sex. On the other hand, when the weight average molecular weight is 150,000 or less, the development property and storage stability are good. Better 5,000~100,000.

Further, specific examples of the component (A) are listed as UNDIC V-8000 series of DIC Corporation and SOXR-U of Nippon Paper Industry Co., Ltd.

The resin composition of the present invention may contain a resin having an alkali-soluble functional group (hereinafter also referred to as (A1) component) different from the component (A). By containing the component (A1), a dry film having good adhesion between the resin layer and the substrate is obtained. Therefore, the dry film is excellent in workability. The structure is different from the component (A) and means that the structures of the formulas (1) and (2) are not contained. The alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A). The component (A1) is preferably a carboxyl group-containing resin having an epoxy resin as a starting material, a carboxyl group-containing resin having a urethane skeleton (also referred to as a carboxyl group-containing urethane resin), and having no a carboxyl group-containing resin having a copolymerization structure of a saturated carboxylic acid, a carboxyl group-containing resin using a phenol compound as a starting material, and a carboxyl group-containing resin component having one carboxyl group and one or more (methyl group) Any one of a resin containing a carboxyl group and a resin containing a carboxyl group. Specific examples of the component (A1) are exemplified below.

(1) by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, a lower alkyl (meth)acrylate or an isobutylene. A resin containing a carboxyl group.

(2) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group-containing diol of dimethylolpropionic acid or dimethylolbutanoic acid Combined And polycarboxylate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, and phenolic hydroxyl group A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as an alcoholic hydroxyl group compound.

(3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarboxylate polyol, a polyether polyol, or a polyester compound Amine obtained by polyaddition reaction of a diol compound such as an alcohol, 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 terminal carboxyl group-containing urethane resin obtained by reacting a terminal of a urethane resin with an acid anhydride.

(4) by diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisxylenol type epoxy resin Photosensitive property of a carboxyl group-containing (meth) acrylate such as a bisphenol epoxy resin or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound by a polyaddition reaction A urethane resin.

(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 photosensitive urethane resin containing a carboxyl group.

(6) In the synthesis of the resin of the above (2) or (4), a molecule such as an isophorone diisocyanate and a pentaerythritol triacrylate having an isocyanate group and one or more (methyl group) is added to the molecule. Acetylene A photosensitive urethane resin containing a carboxyl group which is terminally (meth) acrylated.

(7) reacting a polyfunctional epoxy resin having a bifunctional or higher functional group to be described later with (meth)acrylic acid, and adding phthalic anhydride or tetrahydrophthalic anhydride to the hydroxyl group present in the side chain. A photosensitive resin containing a carboxyl group formed by a dibasic acid anhydride such as hexahydrophthalic anhydride. Here, the epoxy resin is preferably in a solid state.

(8) Further, a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin described later with epichlorohydrin is reacted with (meth)acrylic acid, and a divalent anhydride is added to the produced hydroxyl group. A photosensitive resin containing a carboxyl group. Here, the epoxy resin is preferably in a solid state.

(9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as a novolac, and the obtained hydroxyl group is partially esterified with (meth)acrylic acid to make the remaining A photosensitive resin containing a carboxyl group formed by reacting a hydroxyl group with a polybasic acid anhydride.

(10) The resin of (1) to (9) further has an epoxy group in a molecule such as glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate. A photosensitive resin containing a carboxyl group, which is a compound of one or more (meth)acrylonitrile groups.

The component (A1) is not limited to the use of these, and may be used in combination of one type or plural types. Further, the term "(meth)acrylate" is a generic term for a mixture of acrylate, methacrylate, and the like, and the same performance is similar for the following.

The acid value and weight average molecular weight of the component (A1) are (A) The acid value and the weight average molecular weight are in the same range. The amount of the component (A1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less based on 100 parts by mass of the total of the component (A) and the component (A1). By achieving the above range, a cured product having good toughness and heat resistance can be obtained.

<(B) component>

The resin composition of the present invention contains (B) inorganic particles having an average particle diameter of 200 nm or less. The average particle diameter of the inorganic particles (B) is preferably 150 nm or less, more preferably 100 nm or less. The reason why the average particle diameter of the inorganic particles is 200 nm or less is as follows. That is, in general, the exposure of the resin composition uses an ultraviolet wavelength having a wavelength of 450 nm or less. In order to improve the resolution of the resin composition, it is necessary to suppress the scattering of light. However, when the inorganic particles in the resin composition are irradiated, the light is scattered. The smaller the particle size, the less the particle size is scattered. As a result of the review by the inventors of the present invention, it has been found that the resolution of the inorganic particles can be greatly improved by setting the particle diameter of the inorganic particles to about 200 nm or less of about one-half of the ultraviolet wavelength for exposure. Here, the average particle diameter is a value measured by a laser diffraction method. A measuring device using a laser diffraction method is exemplified by a Nanotrac wave or the like.

When the average particle diameter of the inorganic particles in the cured product is measured, the surface of the cured product is first treated with a plasma and etched to obtain an inorganic particle, and the inorganic particles are observed by SEM (scanning electron microscope). When the average particle diameter of the inorganic particles was obtained, the diameter of the observed inorganic particles was measured in the range of 1 μm ² , and the other portions were also subjected to the operation five times to calculate the average value of the diameters of the inorganic particles. The plasma treatment system uses, for example, MARCH PLASMA SYSTEM INC AP-1000 as a device, and is set to power: 500 W, pressure: 300 Torr, gas: Ar, and treatment time: 10 minutes.

As the inorganic particles, for example, vermiculite, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Boehmite, mica powder, hydrotalcite, Sillitin (silica material), Sillikolloid (for example) can be used. Conventional inorganic fillers such as alumina clay). Among these, it is preferable to use a vermiculite having a small coefficient of linear expansion. In addition, these inorganic particles may be used alone or in combination of two or more.

The blending amount of the component (B) in the resin composition of the present invention is 100 parts by mass based on the total of the components (A) and (A1) (100 parts by mass of the component (A) when the component (A1) is not contained) It is preferably from 10 to 150 parts by mass, more preferably from 30 to 120 parts by mass. By setting the component (B) to 10 parts by mass or more, the effect of reducing the linear expansion coefficient can be sufficiently obtained. On the other hand, by setting the component (B) to 150 parts by mass or less, application of the resin of the present invention can be prevented. The workability at the time of the composition deteriorates.

In the resin composition of the present invention, as described above, a vermiculite having a small coefficient of linear expansion can be preferably used as the component (B). In this case, the vermiculite is preferably a surface treated with a decane coupling agent. The reason is that precipitation or aggregation can be prevented after dispersion in a liquid, and as a result, excellent storage stability is obtained. Further, when the resin composition is blended, it can be stably placed without being agglomerated, and further, the wettability of the resin and the particles of the obtained cured product can be improved.

The organic group contained in the decane coupling agent is exemplified by, for example, a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, or the like. Amine, ureido, chloropropyl, decyl, polythioether, isocyanate, and the like. The decane coupling agent may be used alone or in combination of two or more.

<(C) component>

The resin composition of the present invention contains (C) a photopolymerization initiator. (C) The photopolymerization initiator is preferably an α-aminoacetophenone system containing an oxime ester system having a structure represented by the formula (I) and a structure represented by the formula (II). One or two or more selected from the group consisting of a sulfhydryl phosphine oxide having a structure represented by the formula (III) and a titanocene having a structure represented by the formula (IV).

In the formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkano group or a benzamidine group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkano group or a benzyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom and the like.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and the alkyl chain may have one or more oxygen atoms. Further, it may be substituted with one or more hydroxyl groups. The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms. The alkanoyl group represented by R ¹ and R ² is preferably an alkanoyl group having 2 to 20 carbon atoms. The benzinyl group represented by R ¹ and R ² may have a substituent, and the substituent is exemplified by an alkyl group having 1 to 6 carbon atoms, a phenyl group or the like.

In the formula (II), R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Alternatively, two bonds may be bonded to form a cyclic alkyl ether group.

In the formula (III), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group which may be substituted by a halogen atom, an alkyl group or an alkoxy group. Or a carbonyl group having 1 to 20 carbon atoms (except when the two are carbonyl groups having 1 to 20 carbon atoms).

In the formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group or a halogenated aryl group containing a hetero ring.

Specific examples of the oxime ester photopolymerization initiator are 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoguanidinopurine)], ethyl ketone, 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) and the like. Commercially available products are CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Corporation of Japan, N-1919 manufactured by Adeka Co., Ltd., NCI-831, and the like. It is also preferred to use a photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure. Specifically, it is an oxime ester compound represented by the following general formula (V).

(In the formula (V), X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (alkyl group having 1 to 17 carbon atoms, carbon number) 1 to 8 alkoxy group, amine group, alkylamino group having a carbon number of 1 to 8 or a dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, carbon number 1) Alkoxy group of ~8, an amine group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, and Y and Z respectively represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, Alkoxy group having 1 to 8 carbon atoms, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, and an alkane having 1 to 8 carbon atoms) Alkylamino or dialkylamino substituted), naphthyl (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amine group, alkyl group having 1 to 8 carbon atoms Alkylamino or dialkylamino substituted), mercapto, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond, or an alkylene group having a carbon number of 1 to 10, a vinyl group, and a stretch Phenyl, biphenyl, exopyridyl, anthranyl, thienyl, decyl, thienyl, furanyl, 2,5-pyrrole-diyl, 4,4'-stilbene ) two bases, 4, 2'- Two ethylene group, n is an integer of 0 or 1).

In particular, in the general formula (V), X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is preferably a bond, or a phenyl group, an anthranyl group, a thienyl group or Thienylene.

Further, preferred examples of the oxazolidinate compound include compounds represented by the following formula (VI).

(In the formula (VI), R ¹ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents a carbon number. An alkyl group of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted by an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and R ³ represents an oxygen atom or a sulfur atom. An alkyl group having 1 to 20 carbon atoms which may be substituted by a phenyl group, a benzyl group which may be substituted by an alkoxy group having 1 to 4 carbon atoms, R ⁴ represents a nitro group, or represented by XC(=O)- The fluorenyl group, X represents an aryl group, a thienyl group, a morpholinyl group, a thiophenyl group or a structure represented by the following formula (VII) which may be substituted with an alkyl group having 1 to 4 carbon atoms.

As a specific example of the α-aminoacetophenone photopolymerization initiator, (4-morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, Japan) can be used. Manufactured by BASF), 4-(methylthiobenzamide) 1-methyl-1-morpholine ethane (Irgacure 907, trade name, manufactured by BASF Japan), 2-(dimethylamino)-2-[(4-methylphenyl)methyl] A commercially available compound such as 1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379, trade name, manufactured by BASF Corporation of Japan) or a solution thereof.

Specific examples of the fluorenylphosphine oxide-based photopolymerization initiator are 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene). - phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are listed as Lucirin TPO, Irgacure 819, and the like manufactured by BASF Corporation.

The titanocene photopolymerization initiator is exemplified by bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl). -Phenyl) titanium. Commercially available products are Irgacure 784 manufactured by BASF Corporation of Japan.

Other photopolymerization initiators are exemplified by benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether; acetophenone, 2, 2 Acetophenones such as dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl Anthraquinones such as hydrazine, 2-ethylhydrazine, 2-tert-butylhydrazine, 1-chloroindole, 2-pentylhydrazine, etc.; 2,4-dimethylthioxanthone, 2,4 - thioxanthone such as diethyl thioxanthone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone; acetophenone dimethyl acetal, benzyl dimethyl acetal, etc. Aldehydes; benzophenones such as benzophenone; xanthone; 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone and other peroxides Class; 1,7-bis(9-acridinyl)heptane and the like.

The resin composition of the present invention may be combined with, for example, N,N-dimethylaminobenzoic acid ethyl ester, N,N-di, in addition to the above photopolymerization initiator. One or a combination of two or more kinds of conventional light sensitizers, such as isoamyl methylaminobenzoate, amyl 4-dimethylaminobenzoate, triethylamine, triethanolamine, and the like . Further, when deeper light hardening depth is required, a 3-substituted coumarin dye, a leuco dye, or the like may be used as a curing aid as needed.

In the resin composition of the present invention, the blending ratio of the component (C) is 100 parts by mass of the component (A) per 100 parts by mass of the component (A) and the component (A1). It is preferably from 0.05 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, even more preferably from 0.1 to 15 parts by mass. When the amount of the component (C) is in the above range, radicals required for the reaction can be sufficiently generated, and since light can be transmitted to the deep portion, problems such as embrittlement of the cured product can be avoided. Further, the component (C) may be used singly or in combination of two or more.

<(D) component>

The resin composition of the present invention contains (D) a compound having an unsaturated double bond. The component (D) can be photocured by irradiation with an active energy ray, and the resin composition of the present invention can be insolubilized in an aqueous alkali solution or contribute to insolubilization. As the compound, conventionally used polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (A) can be used. The acrylate or urethane (meth) acrylate may specifically be hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethyl Diacrylates of diols such as diols, polyethylene glycols, and propylene glycol; N,N-dimethyl propylene Acrylamides such as decylamine, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminoethyl acrylate, N,N-acrylic acid Aminoalkyl acrylates such as dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and para-hydroxyethyl isocyanurate or the like a polyvalent acrylate such as an alkane adduct, a propylene oxide adduct or an ε-caprolactone adduct; a phenoxy acrylate, a bisphenol A diacrylate, and an epoxy of the phenol Multivalent acrylates such as ethane adducts or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl A polyvalent acrylate of a glycidyl ether such as cyanurate; not limited to the above, a polyhydric alcohol such as a polyether polyol, a polycarbonate diol, a hydroxyl terminated polybutadiene or a polyester polyol; Esterification, or acrylates and melamine acrylates obtained by acylation of diisocyanates with urethanes, And at least any one of the methacrylates corresponding to the above acrylate.

Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak epoxy resin with acrylic acid, or a hydroxyl group such as an epoxy acrylate resin and a hydroxyl group such as pentaerythritol triacrylate may be mentioned. An epoxy urethane acrylate compound obtained by reacting a carbamide of a diisocyanate such as acrylate or isophorone diisocyanate. These epoxy acrylate-based resins can improve the photocurability without lowering the dryness of the touch. The compound having an ethylenically unsaturated group in the above-mentioned molecule may be used alone or in combination of two or more.

(D) component ratio, in (A) and (A1) When it is 100 parts by mass or less (100 parts by mass of the component (A)), it is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass. Share. By setting the amount of the component (D) to the above range, good photoreactivity can be obtained and heat resistance can be obtained at the same time.

<(E) Thermosetting resin>

In order to further improve heat resistance, the resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter also referred to as "(E) component"). The thermosetting resin is exemplified by, for example, a polyfunctional epoxy compound, a polyfunctional oxetane compound, or a cyclothiopropane resin, and has two or more cyclic ether groups and/or a cyclic thioether group or a polyisocyanate compound. a compound having two or more isocyanate groups, a protected isocyanate group, an amine compound such as a melamine resin or a benzoquinone resin, a derivative thereof, a bismaleimide, an oxazine, or the like in one molecule such as a protected isocyanate compound. A conventional thermosetting resin such as a cyclic carbonate compound or a carbodiimide resin.

As the epoxy resin, a conventionally used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin can be in the form of a liquid or a solid or even a semi-solid. The polyfunctional epoxy resin is exemplified by bisphenol A type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine type Epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trishydroxyphenylmethane type epoxy resin; bisphenol type or biphenol type epoxy resin or a mixture thereof Bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetrahydroxyphenylethane type epoxy resin; heterocyclic ring Oxygen resin; diglycidyl phthalate resin; tetraglycidyl phthalic acid ethane resin; epoxy resin containing naphthyl group; epoxy resin having dicyclopentadiene skeleton; methyl group Glycidyl acrylate copolymerized epoxy resin; copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative; CTBN modified ring Oxygen resin or the like, but is not limited to these. The epoxy resin is preferably a bisphenol A type or a bisphenol F type novolak type epoxy resin, a bisphenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolac type (biphenyl aralkyl group). Type) epoxy resin, naphthalene epoxy resin or a mixture of these.

In particular, the thermosetting resin is preferably an epoxy resin having a naphthalene skeleton. Since naphthalene is a planar structure, the coefficient of linear expansion can be lowered to further improve heat resistance. In addition, these thermosetting resins may be used alone or in combination of two or more. Commercial products of an epoxy resin having a naphthalene skeleton are exemplified by ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., EPICRON HP-4032 manufactured by DIC Corporation, EPICRON HP-4032D, and the like.

From the viewpoint of resolution, the component (E) is preferably a colorless one. The component (E) is preferably a thermosetting resin having an alicyclic skeleton. For example, it is preferably a thermosetting resin containing a dicyclopentadiene skeleton, and preferably an epoxy group containing a dicyclopentadiene skeleton. Resin. Further, the thermosetting resin having an alicyclic skeleton is preferable because it can obtain an effect of improving the glass transition temperature more than the epoxy resin of the chain skeleton.

The blending ratio of the component (E) is 100 parts by mass of the component (A) per 100 parts by mass of the component (A) and the component (A1). The portion) is preferably from 10 to 100 parts by mass, more preferably from 10 to 80 parts by mass. By setting the amount of the component (E) to the above range, a composition having heat resistance and having good developability and photoreactivity can be obtained.

When the resin composition of the present invention contains (E) a thermosetting resin, it may contain a thermosetting catalyst. The thermosetting catalysts are exemplified by imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl- Imidazole derivatives such as 2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-(dimethyl Amine compounds such as amino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An anthracene compound such as diammonium adipate or diterpene sebacate; a phosphorus compound such as triphenylphosphine. Further, in addition to these, ruthenium, acetyl hydrazine, benzoquinone, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl may also be used. -2,4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ isocyanuric acid adduct, 2,4-diamino-6- An S-triazine derivative such as an acryloyloxyethyl-S-triazine ‧ isocyanuric acid addition product.

Commercially available thermosetting catalysts are, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industrial Co., Ltd., and U-CAT manufactured by SAN-APRO Co., Ltd. 3503N, U-CAT 3502T (both trade names of protected isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and salts thereof). These may be used alone or in combination of two or more. In the resin composition of the present invention, the amount of the thermosetting catalyst is adjusted to 100 in total with respect to the components (A) and (A1). The mass part (100 parts by mass of the component (A) when the component (A1) is not contained) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass.

Further, in the resin composition of the present invention, an organic solvent may be used in order to prepare a composition or to adjust the viscosity to be applied to a substrate or a carrier film. The organic solvent may, for example, be a ketone, an aromatic hydrocarbon, a glycol ether, a glycol ether acetate, an ester, an alcohol, an aliphatic hydrocarbon or a petroleum solvent. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; fibrin, methyl cellosolve, butyl cellosolve, Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, acetic acid Esters such as butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; An aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain, or solvent petroleum brain. These organic solvents may be used alone or in combination of two or more.

<other>

The resin composition of the present invention is characterized by comprising (A) an amidoximeimide resin having at least one of the structures represented by the above formula (1) or (2) and an alkali-soluble functional group, and (B) an average particle diameter of The inorganic particles of 200 nm or less, (C) the photoreaction initiator, and (D) the compound having an unsaturated double bond are not particularly limited. For example, a conventionally used coloring agent (for example, a white coloring agent such as titanium oxide or carbon) may be added to the resin composition of the present invention as needed. Black colorants such as black and titanium black, phthalocyanine blue, phthalocyanine green, disazo yellow, etc., thermal polymerization inhibitors, tackifiers, antifoaming agents, leveling agents, and the like.

The resin composition of the present invention is preferably used for forming an insulating cured film of a printed wiring board, and is preferably used for forming an insulating permanent film, and is preferably used as a protective layer, a solder resist, or an interlayer insulating material. Further, the resin composition of the present invention can also be used for the formation of a flux barrier. The resin composition of the present invention may be in the form of a liquid or a dry film type obtained by drying a liquid resin composition. The liquid resin composition may be a two-liquid type or the like based on the viewpoint of preservation stability, or may be a one-liquid type.

[dry film]

The dry film of the present invention has a resin layer obtained by applying the resin composition of the present invention to a film (hereinafter also referred to as "carrier film") and then drying. The dry film of the present invention utilizes an organic solvent to dilute and adjust the resin composition of the present invention to a moderate viscosity, and to use a corner washer, a blade coater, a lip coater, a bar coater, and a squeeze. An applicator, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc., are coated on the carrier film to have a uniform thickness, and are usually dried at a temperature of 50 to 130 ° C for 1 to 30. Obtained in minutes. The coating film thickness is not particularly limited, but is usually set to be in the range of 5 to 150 μm, preferably 10 to 60 μm, in terms of film thickness after drying. The film is not limited to the carrier film, and may be a protective film.

As the carrier film, a plastic film can be suitably used, and a polyester film such as polyethylene terephthalate or the like, a polyimide film, or a polyamidimide is preferably used. Plastic film such as film, polypropylene film, and polystyrene film. The thickness of the carrier film is not particularly limited, and is generally selected in the range of 10 to 150 μm.

After the resin composition of the present invention is applied onto a carrier film, the protective film which can be peeled off from the surface layer of the film can be further used for the purpose of preventing dust from adhering to the surface of the coating film or the like. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used as long as the adhesion force of the film and the protective film is smaller than the adhesion force between the film and the carrier film when the protective film is peeled off. Yes.

The resin composition of the present invention is applied to a carrier film and then evaporated and dried by using a hot air circulating drying furnace, an IR furnace, a heating plate, a convection oven, or the like (using a heat source having a heating method using steam, drying is performed). The method of hot air convection contact in the machine and the method of blowing the nozzle from the support are performed.

[hardened material]

The cured product of the present invention is obtained by curing the resin composition of the present invention and curing the resin layer of the dry film of the present invention. The cured product of the present invention can be exposed to the active energy ray by exposing the coating film obtained by applying the resin composition of the present invention to a solvent obtained by volatilizing and drying the solvent, or by irradiating the dry film with an active energy ray. Part of the exposed portion is hardened and obtained.

[Printed wiring board]

The printed wiring board of the present invention includes the cured product of the present invention. The printed wiring board of the present invention can be directly obtained by using the curable resin composition of the present invention The method of coating on a printed wiring board is obtained by the method of using the dry film of this invention.

When the printed wiring board of the present invention is produced by direct coating, the resin composition of the present invention can be directly applied onto a printed circuit board on which a circuit is formed to form a coating film of a resin composition, and then directly through the pattern. The active energy ray such as laser light is irradiated, or the active energy ray is selectively irradiated through a mask formed with a pattern, and the unexposed portion is developed with a dilute alkali aqueous solution to form a resist pattern. Further, the resist pattern is irradiated with, for example, an active energy ray of 500 to 2000 mJ/cm ² and heated to a temperature of, for example, about 140 to 180 ° C to be cured, whereby a printed wiring board having a pattern of a cured product is produced. Further, the irradiation of the active energy ray to the resist pattern is performed to substantially completely perform the hardening reaction of the unreacted component (D) or the like under exposure during the formation of the image of the resist pattern.

When a dry film is used, the dry film of the present invention is bonded to a laminated resin layer on a printed wiring board on which a circuit is formed, and after exposure as described above, the carrier film is peeled off and developed. Subsequently, the resin layer is irradiated with an active energy ray and heated to a temperature of, for example, about 140 to 180 ° C to be cured, whereby a printed wiring board having a pattern of a cured product is produced. Further, the formation of the pattern of the cured film can be formed by a photolithography method, or can be formed by a screen printing method or the like.

The exposure machine used for the irradiation of the active energy ray may be equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, etc., and may be irradiated with ultraviolet rays in the range of 350 to 450 nm. A direct rendering device for direct rendering devices that render images from direct CAD data using CAD data from a computer. As the light source of the direct drawing device, any one of a gas laser and a solid laser can be used as long as a mercury short-arc lamp, an LED, and a laser beam having a maximum wavelength of 350 to 410 nm are used. The exposure amount for image formation of the resist pattern varies depending on the film thickness, etc., but is generally in the range of 20 to 1500 mJ/cm ² , preferably 20 to 1200 mJ/cm ² .

The developing method may be a dipping method, a rinsing method, a spraying method, a brushing method, or the like, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine or the like may be used. An aqueous alkali solution is used as a developing solution.

Example

Hereinafter, the resin composition of the present invention will be described in detail using examples.

<Examples 1 to 25 and Comparative Examples 1 to 3>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the following Tables 1 to 4. The obtained resin composition was entirely coated on the copper foil substrate for evaluation of the pattern by screen printing, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature. Subsequently, the obtained evaluation substrate was exposed to a resist pattern with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C for 90 seconds under a pressing pressure of 0.2 MPa. After forming a resist pattern of the cured product, the UV irradiation furnace was irradiated with ultraviolet rays under the conditions of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 180 ° C for 60 minutes to be hardened. Further, the amidoxime imide resin (A-1) and the other resins (A1-1) and (A1-2) were synthesized by the following synthesis method. The obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, linear expansion coefficient, and glass transition point. The average particle diameter of the inorganic particles in Tables 1 to 4 is a value obtained by a laser diffraction method. Moreover, the optimum exposure amount is obtained in the following order.

<Optimum exposure>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the following Tables 1 to 4. Next, the laminated substrate to which copper was applied was subjected to a buff roll polishing, washed with water, dried, and the obtained resin composition was applied by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, it was exposed through a reticle (manufactured by Eastman Kodak Co., Ltd., Step Tablet No. 2) using a high pressure mercury lamp exposure apparatus. The irradiated person was set as a test piece, and development liquid was irradiated at a pressure of 2 kg/cm ² (1% by mass aqueous sodium carbonate solution at 30° C.) for 60 seconds, and the number of remaining coating films was visually determined. The exposure amount in which the number of the remaining coating film is 10 segments is set as an appropriate exposure amount.

Synthesis of amidoxime imine resin (A-1) (Synthesis Example 1)

Feeding GBL (γ-butyrolactone) 848.8g with MDI (diphenylmethane diisocyanate) 57.5g (0.23 mol), DMBPDI (4,4'- in the flask with stirring device, thermometer and condenser) Diisocyanate-3,3'-dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol) and TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1, 3,4-tricarboxylic acid-3,4-anhydride) 29.7 g (0.15 mol), while stirring, the temperature was raised to 80 ° C under heat, dissolved and reacted at this temperature for 1 hour, and further heated to 160 ° C in 2 hours, and reacted at this temperature for 5 hours. . The reaction is carried out together with the foaming of carbon dioxide gas, and the system becomes a transparent liquid of brown color. A solution of a polyamidoquinone imide resin (A1) having a resin solid content of 17% and a solution acid value of 5.3 (KOH mg/g) at a viscosity of 7 Pa ‧ at 25 ° C was obtained (resin was dissolved in γ-butyrolactone) Resin composition). Further, the acid value of the solid content of the resin was 31.2 (KOH mg/g). Further, as a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight was 34,000. The polyamidimide resin (A-1) is a resin having the structures of the above formulas (1) and (2) and a carboxyl group.

<Synthesis of Other Resin (A1-1) (Synthesis Example 2)>

An ortho-cresol novolac type epoxy resin was fed into 600 g of diethylene glycol monoethyl ether acetate [EPICLON N-695, manufactured by DIC Corporation, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6] 1070 g (glycidyl group (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol) and hydroquinone 1.5 g, and the mixture was heated and stirred to 100 ° C to dissolve uniformly. Next, 4.3 g of triphenylphosphine was fed, and the mixture was heated to 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours. 415 g of an aromatic hydrocarbon (Solvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic anhydride were fed into the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours, and after cooling, A cresol novolak type carboxyl group-containing resin solution having a solid content of 89 mg KOH/g and a solid content of 65% was obtained. The obtained resin is referred to as another resin (A1-1).

<Synthesis of Other Resin (A1-2) (Synthesis Example 3)>

A novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4) 119.4 was fed to an autoclave equipped with a thermometer, a nitrogen gas introduction device, an alkylene oxide introduction device, and a stirring device. g, 1.19 g of potassium hydroxide and 119.4 g of toluene, the system was replaced with nitrogen while stirring, and heated to heat. Subsequently, 63.8 g of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 132 ° C for 0 to 4.8 kg/cm ² for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain a propylene oxide of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Reaction solution. This phenolic hydroxyl group is added to an average of 1.08 moles of alkylene oxide per one equivalent.

Next, 293.0 g of the alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were fed into a mixer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min, and reacted at 110 ° C for 12 hours while stirring. Water formed by the reaction was distilled off as 12.40 g of water as an azeotropic mixture with toluene. Subsequently, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by water washing. Subsequently, the mixture was distilled off with 118.1 g of diethylene glycol monoethyl ether acetate as an evaporator, and a novolac type acrylate resin solution was obtained. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min, and slowly added while stirring. 60.8 g of tetrahydrophthalic anhydride was reacted at 95 to 101 ° C for 6 hours. obtain A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mg KOH/g of a solid matter and 71% of a nonvolatile matter. Hereinafter, the obtained resin was made into another resin (A1-2).

<Resolvability>

The pattern of the cured film of the evaluation substrate produced by a scanning electron microscope (SEM) of 1,000 times was observed and evaluated by the following evaluation criteria. The results obtained are also shown in Tables 1 to 4.

AA: Lines and spaces of 10 μm or less can be formed.

A: Lines and spaces of 15 μm or less can be formed.

B: Lines and spaces of 25 μm or less can be formed.

C: Lines and spaces of 25 μm could not be formed.

<tensile strength ‧ elongation (strong toughness)>

The cured film (10 mm × 40 mm) obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as above, and Autograph AG-X manufactured by Shimadzu Corporation, at a speed of 1 mm/min. A tensile test was performed. The results obtained are also shown in Tables 1 to 4. When the stress at break point and elongation are large, the toughness is excellent.

A: Break point stress 80N/mm ² or more / elongation 3% or more

B: break point stress 50N/mm ² or more and less than 80N/mm ² / elongation 2% or more and less than 3%

C: The stress at the break point is less than 50N/mm ² / the elongation is less than 2%

<Linear expansion coefficient ‧ Glass transition point (heat resistance)>

A Tg 6100 manufactured by Seiko Instruments Co., Ltd. was applied to a hardened film having a size of 3 mm × 10 mm obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as above, while applying a load of 10 g. The tensile test was carried out at a temperature rising rate ranging from 0 ° C to 260 ° C. The coefficient of linear expansion (CTE) was calculated from the amount of elongation of the cured film with respect to temperature. Also, a glass transition point (Tg) was obtained from the bending point. The results obtained are also shown in Tables 1 to 4. Tg is high, and when CTE is low, heat resistance is excellent.

A: Tg 180 ° C or more / CTE less than 40 ppm

B: Tg above 150 ° C, less than 180 ° C / CTE less than 50 ppm and above 40ppm

C: Tg is less than 150 ° C / CTE 50 ppm or more

<Dry film workability>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied onto a polyethylene terephthalate (PET) film having a thickness of 38 μm using a cloth having a gap of 60 μm, and dried at 80 ° C for 30 minutes. The film was cooled to room temperature to prepare a dry film having a resin layer. The resin layer on the obtained PET film was cut into a size of 10 cm square to be bent in a diagonal manner. When the bending was confirmed, whether or not the resin layer was stably present on the PET in the form of a film.

A: The same bending as PET, not peeled off from PET.

B: Although not peeled off from the PET, the bent portion was broken.

C: The bent portion was broken and peeled off from the PET.

<Development>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied onto a copper foil substrate, and after drying, a dried coating film was formed so that the coating film area was 10 cm × 10 cm and the thickness was 50 μm. 3 L of a 1% by mass aqueous sodium hydroxide solution was poured into a beaker, and the mixture was heated to 30 ° C to prepare a developing solution. Further, the weight of the substrate on which the dried coating film was formed was measured. Next, the substrate was immersed in a developing solution and shaken for 1 minute to be taken out. Subsequently, the substrate was washed immediately, and dried, and the weight was measured again. The developability was calculated from the change in the weight of the substrate, that is, (the weight change of the substrate: g) / (the volume of the developing liquid: L) and evaluated. It can be seen that the higher the value of imaging, the faster the imaging speed. In addition, when the composition of the general polyimine resin (manufactured by AIR WATER Co., Ltd., TECHMIGHT E2020) is contained, the development property is 0.01 g/L or less, and it is almost insoluble.

Amidoxime resin (A-1): resin synthesized in Synthesis Example 1 (resin solid content 17%)

Amidoxime resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Japan Kogami Paper Co., Ltd.), which corresponds to the above formula (2) Carboxyl-containing amidoxime imide resin

Other resin (A1-1): a carboxyl group-containing resin synthesized in Synthesis Example 2 (solid content: 65%)

Other resin (A1-2): a carboxyl group-containing resin synthesized in Synthesis Example 3 (solid content: 71%)

Inorganic Particle 1: Meteorite with an average particle diameter of 100 nm

Inorganic Particle 2: Meteorite with an average particle diameter of 50 nm

Inorganic particles 3: barium sulfate having an average particle diameter of 100 nm

Inorganic particles 4: vermiculite with an average particle diameter of 1 μm

Photopolymerization initiator 1: TPO manufactured by BASF

Photopolymerization initiator 2: IRG-369 manufactured by BASF

Photopolymerization initiator 3: IRG-OXE02 manufactured by BASF

Compound 1 with unsaturated double bond: dipentaerythritol hexaacrylate

Compound 2 with an unsaturated double bond: dicyclopentadiene diacrylate

Thermosetting resin 1: epoxy resin HP4032 (150 eq) containing a naphthalene skeleton (manufactured by DIC Corporation)

Thermosetting Resin 2: Naphthol modified epoxy resin NC7000 (230 eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting Resin 3: Biphenyl aralkyl type epoxy resin NC3000 (275 eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting Resin 4: Epoxy Resin XD-1000 (250 eq) containing a dicyclopentadiene skeleton (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting Resin 5: Dicyclopentadiene skeleton epoxy resin HP-7200H (280 eq) (manufactured by DIC Corporation)

Thermal curing catalyst 1: melamine

Thermal curing catalyst 2: dicyandiamide

As is apparent from Tables 1 to 4, the resin composition of the present invention can obtain a cured product excellent in resolution, heat resistance and toughness. Further, it is understood that the dry film obtained from the resin composition of the present invention has excellent workability.

Claims (10)

A curable resin composition comprising (A), (B), (C), and (D): (A) having at least one structure represented by the following formulas (1) and (2) and alkali solubility Functional amino amidoximine resin, And (B) inorganic particles having an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond. The curable resin composition of claim 1, which comprises a resin having a structure different from that of the above (A) amidoximeimide resin and having an alkali-soluble functional group. The curable resin composition of the first aspect of the invention, wherein the (B) inorganic particle-based vermiculite having an average particle diameter of 200 nm or less. The curable resin composition of claim 1, wherein (E) a thermosetting resin is contained. The curable resin composition of claim 4, wherein the (E) thermosetting resin has an alicyclic skeleton epoxy resin. a dry film characterized by having the scope as claimed in the patent The resin layer obtained by applying the curable resin composition of any one of the items 1 to 5 to a film and drying it. A cured product which is characterized in that the curable resin composition according to any one of claims 1 to 5 is cured. A cured product characterized by curing a resin layer of a dry film of claim 6 of the patent application. A printed wiring board comprising the cured product of claim 7 of the patent application. A printed wiring board comprising the cured product of claim 8 of the patent application.