WO2015190210A1 - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

Provided are: 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, cured product and printed wiring 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 capable of obtaining a cured product having better resolution, toughness, and heat resistance than before. The present invention relates to a composition, a dry film, a cured product, and a printed wiring board.

Currently, solder resist compositions for some consumer printed wiring boards and most industrial printed wiring boards are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density. A liquid development type solder resist composition that is finish-cured (mainly cured) by at least one of irradiation is used. Under such circumstances, from the viewpoint of environmental problems, alkali development type photo solder resist compositions using an aqueous alkali solution as a developing solution have become mainstream, and are used in large quantities in the production of actual printed wiring boards.

Conventionally, alkali-soluble resins, particularly epoxy acrylate-modified resins, are generally used for alkali development type photo solder resist compositions. For example, Patent Document 1 proposes a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound. Has been.

Japanese Patent Laid-Open No. 61-243869

Today, as the curable resin composition, phenol novolac type (cresol novolac type) epoxy acrylate resin and acrylic copolymer type resin are widely used in the alkali-soluble type. However, phenol novolac epoxy acrylate resins are not necessarily excellent in toughness, and acrylic copolymer resins are inferior in heat resistance. Thus, it has been difficult for conventional curable resin compositions to achieve both high toughness and heat resistance. On the other hand, in recent years, when semiconductor package components are mounted on a printed wiring board, the number of connected IOs and the size of the components are simultaneously reduced, and the wiring density is rapidly increased. In order to enable high-density wiring, a curable resin composition having high resolution is required.

Therefore, an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board that can obtain a cured product that is superior in resolution, toughness, and heat resistance than before. There is.

As a result of intensive studies to solve the above problems, the present inventors have made the resin used in the curable resin composition a resin having a specific structure, and set the particle size of the inorganic particles as the filler to a predetermined value. By making it below the value, it was found that the above problems could be solved, and the present invention was completed.

That is, the curable resin composition of the present invention comprises (A) the following formulas (1), (2),

An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a compound having the following.

The curable resin composition of the present invention may contain a resin having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group. The inorganic particles (B) having an average particle diameter of 200 nm or less are preferably silica. Moreover, it is preferable that (E) thermosetting resin is included. Furthermore, the (E) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.

The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention on a film.

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 capable of obtaining a cured product having excellent 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”) is (A) the following formulas (1), (2),

An amide-imide resin (hereinafter also referred to as “component (A)”) having at least one structure and an alkali-soluble functional group represented by: (B) inorganic particles having an average particle size of 200 nm or less (hereinafter referred to as “(B)”) (Also referred to as “component”), (C) a photopolymerization initiator (hereinafter also referred to as “(C) component”), (D) a compound having an unsaturated double bond (hereinafter referred to as “component (D)”) Included). By using a resin having the above structure as the resin component of the resin composition and using inorganic particles having an average particle size of 200 nm or less as a filler, a cured product having excellent resolution, toughness, and heat resistance is obtained. be able to.

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

Hereinafter, each component of the resin composition of this invention is demonstrated in detail.
<(A) component>
The component (A) of the resin composition of the present invention has the following formula (1) or (2),

It is an amide imide resin which has at least one structure represented by these, and an alkali-soluble functional group. When the resin composition of the present invention contains a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained. In particular, since the amidoimide resin having the structure represented by (1) is excellent in light transmittance, 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, the transmittance of light having a wavelength of 365 nm is 70% or more in the dry coating film 25 μm of the component (A). Is preferred.

The content of the structures of the formulas (1) and (2) in the component (A) of the resin composition of the present invention is preferably 10 to 70% by mass. By using such a resin, a cured product having excellent solvent solubility and excellent physical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained. The amount is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.

As the amideimide resin having the structure represented by the formula (1), in particular, the formula (3A) or (3B)

(In the formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group. A resin having a structure represented by a bond, an alkylene group such as CH ₂ or C (CH ₃ ) ₂ ) is preferable because it has excellent physical properties such as tensile strength and elongation and dimensional stability. In the resin composition of the present invention, from the viewpoint of solubility and mechanical properties, as the component (A), a resin having 10 to 100% by mass of the structure of the formulas (3A) and (3B) can be preferably used. More preferably, it is 20 to 80% by mass.

In the resin composition of the present invention, as the component (A), an amidoimide resin containing 5 to 100 mol% of the structure of the formulas (3A) and (3B) is preferably used from the viewpoint of solubility and mechanical properties. Can do. The amount is more preferably 5 to 98 mol%, further preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.

Moreover, as an amide imide resin which has a structure represented by Formula (2), especially Formula (4A) or (4B)

(In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, It is preferable that the resin having a structure represented by a bond or an alkylene group such as CH ₂ or C (CH ₃ ) ₂ is a cured product having excellent mechanical properties such as tensile strength and elongation. To preferred. In the resin composition of the present invention, from the viewpoints of solubility and mechanical properties, as the component (A), a resin having a structure of formulas (4A) and (4B) of 10 to 100% by mass can be preferably used. More preferably, it is 20 to 80% by mass.

As the component (A) in the composition of the present invention, an amideimide resin containing 2 to 95 mol% of the structures of the formulas (4A) and (4B) can also be preferably used because it exhibits good mechanical properties. More preferably, it is 10 to 80 mol%.

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

Examples of the diisocyanate compound having a biphenyl skeleton include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl and 4,4′-diisocyanate-3,3′-diethyl-1,1′-biphenyl. 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate- Examples include 3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl, and the like. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.

Examples of the cyclohexane polycarboxylic acid anhydride include cyclohexane tricarboxylic acid anhydride and cyclohexane tetracarboxylic acid anhydride.

The amidoimide resin having the structure (2) can be obtained by using, for example, the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid hydrate having two acid anhydride groups.

Examples of polycarboxylic acid anhydrides having two acid anhydride groups include 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 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, 2, 3 Bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, ethylene glycol bisanhydro Examples include alkylene glycol bisan hydroxy trimellitate such as trimellitate.

The component (A) of the resin composition of the present invention has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By having an alkali-soluble functional group, it becomes a resin composition capable of alkali development. The alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, etc., and preferably contains a carboxyl group.

The acid value of the component (A) in 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 making the acid value of the component (A) within the above range, alkali development can be performed satisfactorily, and a normal cured product pattern can be formed. 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 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the moisture resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, developability and storage stability are good. More preferably, it is 5,000 to 100,000.

Specific examples of the component (A) include Unidic V-8000 series from DIC Corporation and SOXR-U from Nippon Kogyo Paper Industries.

The resin composition of the present invention may contain a resin having a different structure from the component (A) and having an alkali-soluble functional group (hereinafter also referred to as the component (A1)). By including the component (A1), a dry film having good adhesion between the resin layer and the substrate can be obtained. Therefore, the workability of the dry film is excellent. The difference between the component (A) and the structure means that it does not include the structures of the formulas (1) and (2). The alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A). As the component (A1), a carboxyl group-containing resin starting from an epoxy resin, a carboxyl group-containing resin having a urethane skeleton (also referred to as a carboxyl group-containing urethane resin), and a carboxyl group having a copolymer structure of an unsaturated carboxylic acid -Containing resins, carboxyl group-containing resins starting from phenolic compounds, and carboxyl group-containing resins obtained by adding compounds having one epoxy group and one or more (meth) acryloyl groups in the molecule to these carboxyl group-containing resins It is preferably at least one of resins. Specific examples of the component (A1) are shown below.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(5) During the synthesis of the resin described in (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing photosensitive urethane resin.
(6) During the synthesis of the resin of (2) or (4) described above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal and being terminally (meth) acrylated.
(7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl groups present in the side chain are added to 2 such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which a basic acid anhydride is added. Here, the epoxy resin is preferably solid.
(8) (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin. Here, the epoxy resin is preferably solid.
(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 novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polyvalent. A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
(10) In addition to these resins (1) to (9), one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound having the same.

The component (A1) is not limited to these, and can be used alone or in combination. In addition, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions hereinafter.

The acid value and weight average molecular weight of the component (A1) are in the same range as the acid value and weight average molecular weight of the component (A). The blending 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 with respect to 100 parts by mass in total of the component (A) and the component (A1). It is as follows. By setting it as said range, the hardened | cured material which has favorable toughness and heat resistance can be obtained.

<(B) component>
The resin composition of the present invention includes (B) inorganic particles having an average particle size of 200 nm or less. (B) The average particle diameter of the inorganic particles is preferably 150 nm or less, and more preferably 100 nm or less. The reason why the average particle size of the inorganic particles is 200 nm or less is as follows. That is, normally, an ultraviolet wavelength having a wavelength of 450 nm or less is used for exposure of the resin composition. 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 exposed to light, the light is scattered. As the particle size is smaller, the scattering is reduced. However, as a result of the study by the present inventors, the resolution is greatly improved by setting the particle size of the inorganic particles to 200 nm or less, which is about half the wavelength of ultraviolet rays for exposure. It was found that it can be improved. Here, the average particle diameter is a value measured by a laser diffraction method. Nikkiso Co., Ltd. (Nanotrac wave) etc. are mentioned as a measuring apparatus by a laser diffraction method.

When measuring the average particle size of the inorganic particles in the cured product, the surface of the cured product is first etched by plasma treatment so that the inorganic particles can be seen, and the inorganic particles are observed with a scanning electron microscope (SEM). To do. To obtain the average particle size of the inorganic particles, measure the diameter of the observed inorganic particles in the range of 1 μm ² , perform the operation five times including other points, and calculate the average value of the inorganic particle diameters. do it. In the plasma treatment, for example, a MARCH PLASMA SYSTEM INC AP-1000 is used as an apparatus, and POWER: 500 W, Pressure: 300 Torr, Gas: Ar, and a treatment time of 10 minutes.

Examples of the inorganic particles include known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicin, and silicocolloid. Can be used. Among these, silica having a small linear expansion coefficient can be suitably used. In addition, these inorganic particles may be used individually by 1 type, and may be used in combination of 2 or more type.

The blending amount of the component (B) in the resin composition of the present invention is 100 parts by mass in total of the component (A) and the component (A1) (when not including the component (A1), 100 parts by mass of the component (A)). The amount is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass. (B) By making a component 10 mass parts or more, the reduction effect of a linear expansion coefficient can fully be acquired, On the other hand, the resin composition of this invention is made by making (B) component 150 mass parts or less. It is possible to prevent deterioration in workability during application.

In the resin composition of the present invention, as described above, silica having a small linear expansion coefficient can be suitably used as the component (B). In this case, the surface of the silica is treated with a silane coupling agent. Are preferred. This is because precipitation and aggregation can be prevented after being dispersed in the liquid, and as a result, the storage stability is excellent. In addition, it is possible to stably add the resin composition without agglomeration, and to improve the wettability between the resin and the particles of the obtained cured product.

Examples of the organic group contained in the silane coupling agent include vinyl, epoxy, styryl, methacryloxy, acryloxy, amino, ureido, chloropropyl, mercapto, polysulfide, and isocyanate groups. Can be mentioned. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.

<(C) component>
The resin composition of the present invention contains (C) a photopolymerization initiator. (C) As the photopolymerization initiator, an oxime ester system including a structure represented by the general formula (I), an α-aminoacetophenone system including a structure represented by the general formula (II), and a general formula (III) It is preferable to contain 1 type (s) or 2 or more types selected from the group which consists of the acylphosphine oxide type | system | group containing the structure represented, and the titanocene type | system | group of the structure represented by general formula (IV).

In general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl 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, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms and may contain one or more oxygen atoms in the alkyl chain. 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 benzoyl 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 and a phenyl group.

In general formula (II), R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number 1 to 6 alkyl groups may be represented, or two may combine to form a cyclic alkyl ether group.

In the general formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Group, or a carbonyl group having 1 to 20 carbon atoms (except when both are carbonyl groups having 1 to 20 carbon atoms).

In general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.

Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be suitably used. Specific examples include oxime ester compounds represented by the following general formula (V).

(In the general 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 (an alkyl group having 1 to 17 carbon atoms, a carbon number of 1 Substituted with an alkoxy group having 8 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms) Substituted with an alkoxy group, an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are a hydrogen atom and an alkyl group having 1 to 17 carbon atoms, respectively. An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms). Alkylamino group substituted by alkylamino group or dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene Thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)

In particular, in general formula (V), X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that

Moreover, the compound which can be represented by the following general formula (VI) as a preferable carbazole oxime ester compound can also be mentioned.

(In the general formula (VI), R ¹ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group. R ³ may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, which may be substituted with a phenyl group. R ⁴ represents a benzyl group or an acyl group represented by X—C (═O) —, wherein X is substituted with an alkyl group having 1 to 4 carbon atoms. Aryl group or thienyl group , A morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).

Specific examples of the α-aminoacetophenone photopolymerization initiator include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.), 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a commercially available compound or a solution thereof can be used.

Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). ) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO and Irgacure 819 manufactured by BASF.

As the titanocene photopolymerization initiator, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is used. Can be mentioned. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

Examples of other photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2 Thioxanthones such as 1,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketone Ketones such as benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones; various peroxides such as 3,3′4,4′-tetra- (tert-butylperoxycarbonyl) benzophenone; 1,7- And bis (9-acridinyl) heptane.

In the resin composition of the present invention, in addition to the above photopolymerization initiator, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine In addition, one or more known photosensitizers such as tertiary amines such as triethanolamine can be used in combination. Further, when a deeper photocuring depth is required, a 3-substituted coumarin dye, a leuco dye, or the like can be used in combination as a curing aid, if necessary.

In the resin composition of the present invention, the blending ratio of the component (C) is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). The amount is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass. By setting the blending amount of the component (C) within the above range, radicals necessary for the reaction can be sufficiently generated, and light can be transmitted to the deep part, so that the cured product becomes brittle. It can be avoided. In addition, (C) component may be used individually by 1 type, and may be used in combination of 2 or more type.

<(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 active energy rays to insolubilize or assist insolubilization of the resin composition of the present invention in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylolacrylamide and N, N-dimethylaminopropylacrylamide; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate, or their ethylene oxide adducts, propylene oxide adducts Or polyvalent acrylates such as ε-caprolactone adduct; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adduct or propylene oxide adduct of these phenols; glycerin diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyacid acrylates of sidyl ether; not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, And at least one of the methacrylates corresponding to the acrylate.

Furthermore, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property. A compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more.

The blending ratio of the component (D) is preferably 1 to 60 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). The amount is more preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass. (D) By making the compounding quantity of a component into the said range, favorable photoreactivity can be acquired and it can have heat resistance.

<(E) Thermosetting resin>
In order to further improve the heat resistance, the resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter also referred to as “component (E)”). Examples of thermosetting resins include polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. in one molecule such as two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, block isocyanate compounds, etc. Compounds having two or more isocyanate groups or blocked isocyanate groups, amine resins such as melamine resins and benzoguanamine resins and derivatives thereof, known thermosetting resins such as bismaleimide, oxazine, cyclocarbonate compounds and carbodiimide resins Can be mentioned.

As the epoxy resin, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid or may be solid or semi-solid. Polyfunctional epoxy resins include: bisphenol A type epoxy resins; brominated epoxy resins; novolac type epoxy resins; bisphenol F type epoxy resins; hydrogenated bisphenol A type epoxy resins; glycidyl amine type epoxy resins; Epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; Resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl meta Acrylate copolymer based epoxy resins; polybutadiene rubber derivative epoxy modified; copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, but CTBN modified epoxy resins, but is not limited thereto. The epoxy resin is preferably a bisphenol A type or bisphenol F type novolak type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolak type (biphenylaralkyl type) epoxy resin, a naphthalene type epoxy resin or a mixture thereof. .

In particular, an epoxy resin having a naphthalene skeleton is preferable as the thermosetting resin. This is because naphthalene has a planar structure, can reduce the coefficient of linear expansion, and can further improve heat resistance. In addition, these thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available epoxy resins having a naphthalene skeleton include ESN-190 and ESN-360 manufactured by Nippon Steel Chemical, EPICRON HP-4032 and EPICRON HP-4032D manufactured by DIC.

As the component (E), an uncolored component is preferable from the viewpoint of resolution. As such component (E), a thermosetting resin having an alicyclic skeleton is preferable, for example, a dicyclopentadiene skeleton-containing thermosetting resin is preferable, and a dicyclopentadiene skeleton-containing epoxy resin is particularly preferable. Further, a thermosetting resin having an alicyclic skeleton is preferable because an effect of improving the glass transition temperature is obtained as compared with an epoxy resin having a chain skeleton.

The blending ratio of the component (E) is preferably 10 to 100 parts by mass per 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). More preferably, it is 10 to 80 parts by mass. (E) By making the compounding quantity of a component into the said range, the composition which has heat resistance and has both favorable developability and photoreactivity can be obtained.

When the resin composition of the present invention contains (E) a thermosetting resin, a thermosetting catalyst may be included. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide, and phosphorus compounds such as triphenylphosphine. Besides these, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used.

Examples of commercially available thermosetting catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. In the resin composition of the present invention, the blending amount of the thermosetting catalyst is 100 parts by mass in total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). On the other hand, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass.

Furthermore, the resin composition of the present invention can use an organic solvent for the preparation of the composition or for adjusting the viscosity for application to a substrate or a carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propanol Ethylene glycol, or propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

<Others>
The resin composition of the present invention comprises (A) an amide-imide resin having at least one structure represented by the above formula (1) or (2) and an alkali-soluble functional group, and (B) an inorganic having an average particle size of 200 nm or less. It is characterized by containing particles, (C) a photoinitiator, and (D) a compound having an unsaturated double bond, and there is no particular limitation for the rest. For example, in the resin composition of the present invention, a known and commonly used colorant (for example, a white colorant such as titanium oxide, a black colorant such as carbon black or titanium black, phthalocyanine blue, phthalocyanine green, or disazo yellow is used as necessary. Etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like can be added.

The resin composition of the present invention is suitable for forming an insulating cured film on a printed wiring board, more preferably for forming an insulating permanent film, and for forming a coverlay, solder resist, and interlayer insulating material. Is optimal. In addition, the resin composition of this invention can also be used for formation of a solder dam etc. The resin composition of the present invention may be a liquid type or a dry film type obtained by drying a liquid type resin composition. The liquid resin composition may be a two-component type from the viewpoint of storage stability, but may be a one-component type.

[Dry film]
The dry film of the present invention has a resin layer obtained by applying the resin composition of the present invention on a film (hereinafter also referred to as “carrier film”) and then drying it. The dry film of the present invention is prepared by diluting the resin composition of the present invention with an organic solvent so as to have an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It can be obtained by applying a uniform thickness on a carrier film with a coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but in general, the film thickness after drying may be appropriately set in the range of 5 to 150 μm, preferably 10 to 60 μm. The film is not limited to a carrier film but may be a cover film.

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

After applying the resin composition of the present invention on the carrier film, a peelable cover film may be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

Volatile drying performed after the resin composition of the present invention is applied on a carrier film is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with an air heating heat source using steam). And a method of spraying the hot air against the support from a nozzle).

[Cured product]
The cured product of the present invention is a product obtained by curing the resin composition of the present invention and a product obtained by curing the resin layer of the dry film of the present invention. The cured product of the present invention is obtained by applying an active energy ray to the coating film obtained after applying the resin composition of the present invention and evaporating and drying the solvent, or by irradiating the active film with an active energy ray. It can be obtained by curing an exposed portion which is a portion irradiated with active energy rays.

[Printed wiring board]
The printed wiring board of the present invention comprises the cured product of the present invention. The printed wiring board of this invention can be obtained by the method of apply | coating the curable resin composition of this invention directly on a printed wiring board, and the method of using the dry film of this invention.

When the printed wiring board of the present invention is produced by the direct coating method, the resin composition of the present invention is directly coated on the printed wiring board on which a circuit is formed, and after forming a coating film of the resin composition, laser light, etc. Directly irradiate the active energy rays according to the pattern or selectively irradiate the active energy rays through the photomask on which the pattern is formed, and develop the unexposed area with a dilute alkaline aqueous solution to form a resist pattern. To do. Further, the printed wiring board having the cured product pattern is manufactured by irradiating the resist pattern with active energy rays at, for example, 500 to 2000 mJ / cm ² and curing it by heating to a temperature of about 140 to 180 ° C., for example. Irradiation of the active energy ray to the resist pattern is performed in order to almost completely cure the component (D) that did not react by exposure when forming an image of the resist pattern.

When using a dry film, after laminating the dry film of the present invention on a printed wiring board on which a circuit is formed and laminating a resin layer, the carrier film is peeled off and developed in the same manner as described above. Thereafter, the resin layer is irradiated with active energy rays and heated to a temperature of about 140 to 180 ° C. for curing to produce a printed wiring board having a cured product pattern. The cured film pattern may be formed by a photolithography method or a screen printing method.

As an exposure apparatus used for irradiation of active energy rays, any apparatus capable of irradiating ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. Furthermore, for example, a direct drawing apparatus such as a direct imaging apparatus that directly draws an image with active energy rays by CAD data from a computer can be used. As a light source for the direct drawing apparatus, either a mercury short arc lamp, an LED, or a laser beam having a maximum wavelength in the range of 350 to 410 nm may be used. The exposure amount for forming the image of the resist pattern varies depending on the film thickness and the like, but can be generally in the range of 20 to 1500 mJ / cm ² , preferably 20 to 1200 mJ / cm ² .

As a developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be adopted, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate An aqueous alkali solution such as ammonia or amines can be used.

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>
Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. The obtained resin composition was applied on the entire surface of a patterned copper foil substrate for evaluation by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, the obtained evaluation substrate is exposed to a resist pattern with an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied under a spray pressure of 0.2 MPa. Developed for seconds. After forming the resist pattern of the cured product, it was cured by UV irradiation at 180 ° C. for 60 minutes after irradiation with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm ² . The amide imide resin (A-1), other resins (A1-1), and (A1-2) were synthesized according to 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 size of the inorganic particles in Tables 1 to 4 is a value measured by a laser diffraction method. In addition, the optimal exposure amount was calculated | required in the following procedures.

<Optimum exposure amount>
Resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Tables 1 to 4 below. Next, the copper-clad laminated substrate was polished with buffalo, washed with water and dried, and the obtained resin composition was applied by a screen printing method and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2). The irradiated piece was used as a test piece, and after developing for 60 seconds with a developer having a spray pressure of 2 kg / cm ² (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 10 was determined as the appropriate exposure amount.

<Synthesis of Amidoimide Resin (A-1) (Synthesis Example 1)>
A flask equipped with a stirrer, a thermometer and a condenser was charged with 888.8 g of GBL (gamma-butyrolactone), 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4′-diisocyanate-3,3 ′). -Dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol), TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1,3,4-tricarboxylic acid) Acid-3,4-anhydride) 29.7 g (0.15 mol) was added, the temperature was raised to 80 ° C. while paying attention to heat generation while stirring, and the mixture was dissolved and reacted at this temperature for 1 hour. After heating up to 160 ° C. over 2 hours, the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown transparent liquid. Solution of polyamideimide resin (A1) having a resin solid content of 17% with a viscosity of 7 Pa · s at 25 ° C. and a solution acid value of 5.3 (KOHmg / g) (resin composition in which the resin is dissolved in γ-butyrolactone) Got. The solid content acid value of the resin was 31.2 (KOH mg / g). Moreover, it was the weight average molecular weight 34,000 as a result of the measurement of a gel permeation chromatography (GPC). The polyamideimide resin (A-1) is a resin having a structure of the above formulas (1) and (2) and a carboxyl group.

<Synthesis of Other Resin (A1-1) (Synthesis Example 2)>
Orthocresol novolak type epoxy resin [DICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged, and the reaction was performed at 110 ° C. for 4 hours. After cooling, a cresol novolak-type carboxyl group-containing resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. The obtained resin is referred to as other resin (A1-1).

<Synthesis of Other Resin (A1-2) (Synthesis Example 3)>
A novolac cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

Next, 293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged 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. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, the obtained resin is referred to as other resin (A1-2).

<Resolution>
The pattern of the cured film of the prepared evaluation board | substrate was observed with the scanning electron microscope (SEM) of 1,000 times, and the following evaluation criteria evaluated. The obtained results are also shown in Tables 1 to 4.
AA: A line and space of 10 μm or less can be formed.
A: Line and space of 15 μm or less can be formed.
B: Line and space of 25 μm or less can be formed.
C: Line and space 25 μm cannot be formed.

<Tensile strength / elongation (toughness)>
Cured coatings (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 described above were applied at 1 mm / min with an autograph AG-X manufactured by Shimadzu Corporation. Tensile tests were performed at speed. The obtained results are also shown in Tables 1 to 4. When the stress at break and elongation are large, the toughness is excellent.
A: Stress at break 80 N / mm ² or more / elongation 3% or more B: Stress at break 50 N / mm ² or more, less than 80 N / mm ² / elongation 2% or more and less than 3% C: Stress at break 50 less than N / mm ² / elongation Less than 2%

<Linear expansion coefficient and glass transition point (heat resistance)>
A cured 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 described above while applying a load of 10 g with TMA6100 manufactured by Seiko Instruments Inc. A tensile test was performed in a temperature range of 0 ° C. to 260 ° C. at a constant rate of temperature increase. The linear expansion coefficient (CTE) was calculated from the amount of elongation of the cured film with respect to temperature. Moreover, the glass transition point (Tg) was obtained from the inflection point. The obtained results are also shown in Tables 1 to 4. When Tg is high and CTE is low, the heat resistance is excellent.
A: Tg 180 ° C. or more / CTE less than 40 ppm B: Tg 150 ° C. or more, less than 180 ° C./CTE less than 50 ppm, 40 ppm or more C: Tg 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 an applicator with a gap of 60 μm, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thus, a dry film having a resin layer was produced. The resin layer on the obtained PET film was cut into a size of 10 cm square and bent so as to form a diagonal line. When bent, it was confirmed whether the resin layer was present in a stable film form on PET.
A: It is bent in the same manner as PET and does not peel off from PET.
B: Although it does not peel from PET, the bent part is cracked.
C: The bent part is broken and peeled off from the PET.

<Developability>
The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied to a copper foil substrate, and after drying, a dry coating film was formed so that the area of the coating film was 10 cm × 10 cm and the thickness was 50 μm. . 3 L of a 1% by mass sodium hydroxide aqueous solution was placed in a beaker and heated to 30 ° C. to prepare a developer. Further, the weight of the substrate on which the dry coating film was formed was measured. Then, the substrate was immersed in the developer, and the substrate was shaken for 1 minute and taken out. Thereafter, the substrate was immediately washed with water, dried, and then weighed again. From the change in weight of the substrate, developability, that is, (change in weight of substrate: g) / (volume of developer: L) was calculated and evaluated. It can be seen that the higher the developability value, the faster the development speed. In the case of a composition containing a general polyimide resin (TECHMIGHT E2020, manufactured by Air Water Co., Ltd.), the developability is 0.01 g / L or less, which is almost insoluble.

Amidoimide resin (A-1): Resin synthesized in Synthesis Example 1 (resin solid content: 17%)
Amidoimide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kogyo Paper Industries Co., Ltd.), corresponding to other carboxyl group-containing amidoimide resins having the structure of the above formula (2) (A1 -1): carboxyl group-containing resin synthesized in Synthesis Example 2 (solid content 65%)
Other resin (A1-2): carboxyl group-containing resin synthesized in Synthesis Example 3 (solid content: 71%)
Inorganic particles 1: Silica inorganic particles having an average particle size of 100 nm 2: Silica inorganic particles having an average particle size of 50 nm 3: Barium sulfate inorganic particles having an average particle size of 100 nm 4: Silica photopolymerization initiator having an average particle size of 1 μm 1: manufactured by BASF TPO
Photopolymerization initiator 2: IRG-369 manufactured by BASF
Photopolymerization initiator 3: IRG-OXE02 manufactured by BASF
Compound having unsaturated double bond 1: Dipentaerythritol hexaacrylate Compound having unsaturated double bond 2: Dicyclopentadiene diacrylate thermosetting resin 1: Naphthalene skeleton-containing epoxy resin HP4032 (150 eq) (manufactured by DIC)
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 dicyclopentadiene skeleton (made by Nippon Kayaku Co., Ltd.)
Thermosetting resin 5: dicyclopentadiene skeleton epoxy resin HP-7200H (280 eq) (manufactured by DIC)
Thermosetting catalyst 1: Melamine thermosetting catalyst 2: Dicyandiamide

From Tables 1 to 4, it can be seen that the resin composition of the present invention can obtain a cured product having excellent resolution, heat resistance, and toughness. Moreover, it turns out that the dry film obtained from the resin composition of this invention is excellent in workability | operativity.

Claims (10)

1. (A) The following formulas (1), (2),
   

   

   

   An amide-imide resin having at least one structure represented by: and an alkali-soluble functional group; (B) inorganic particles having an average particle size of 200 nm or less; (C) a photopolymerization initiator; and (D) an unsaturated double bond. And a curable resin composition comprising:
2. The curable resin composition according to claim 1, comprising a resin having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group.
3. The curable resin composition according to claim 1, wherein the inorganic particles (B) having an average particle diameter of 200 nm or less are silica.
4. (E) The curable resin composition of Claim 1 containing a thermosetting resin.
5. The curable resin composition according to claim 4, wherein the (E) thermosetting resin is an epoxy resin having an alicyclic skeleton.
6. A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to any one of claims 1 to 5 on a film.
7. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5.
8. A cured product obtained by curing the resin layer of the dry film according to claim 6.
9. A printed wiring board comprising the cured product according to claim 7.
10. A printed wiring board comprising the cured product according to claim 8.