JP6799462B2 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board. Specifically, the present invention is a curable resin capable of obtaining a cured product having better resolution, toughness, and heat resistance than before. Concerning compositions, dry films, cured products and printed wiring boards.

Currently, the solder resist compositions of some consumer printed wiring boards and most industrial printed wiring boards are image-formed by developing after UV irradiation from the viewpoint of high accuracy and high density, and heat and light. A liquid-developable solder resist composition that is finish-cured (mainly cured) by at least one of irradiation is used. Under these circumstances, in consideration of environmental problems, an alkaline-developed photosolder resist composition using an alkaline aqueous solution as a developing solution has become the mainstream, and is widely used in the actual production of printed wiring boards.

Conventionally, an alkali-soluble resin, particularly an epoxy acrylate-modified resin, is generally used for an alkali-developed photosolder resist composition. 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 done.

JP-A-61-243869

Today, as the curable resin composition, a phenol novolac type (cresol novolac type) epoxy acrylate resin or an acrylic copolymer type resin is widely used as an alkali-soluble type. However, the phenol novolac type epoxy acrylate resin is not always excellent in toughness, and the acrylic copolymer type resin is inferior in heat resistance. As described above, it has been difficult to achieve both toughness and heat resistance with the conventional curable resin composition. On the other hand, in recent years, when mounting a semiconductor package component on a printed wiring board, the number of connected IOs and the miniaturization of the component are progressing at the same time, and the wiring density is rapidly increasing. 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 capable of obtaining a cured product having better resolution, toughness, and heat resistance than before. There is.

As a result of diligent 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 have a predetermined particle size of inorganic particles as a filler. We have found that the above problems can be solved by setting the value to less than or equal to the value, and have completed the present invention.

で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂と、（Ｂ）平均粒径が２００ｎｍ以下の無機粒子と、（Ｃ）光重合開始剤と、（Ｄ）不飽和二重結合を有する化合物と、を含むことを特徴とするものである。That is, the curable resin composition of the present invention has (A) the following formulas (1) and (2),

An amidoimide resin having at least one structure represented by (B) 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. It is characterized by containing a compound having.

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. Further, the inorganic particles (B) having an average particle size of 200 nm or less are preferably silica. Further, it is preferable to contain (E) a thermosetting resin. Further, the thermosetting resin (E) is preferably an epoxy resin having an alicyclic skeleton.

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

で表される少なくとも一方の構造およびアルカリ可溶性官能基を有するアミドイミド樹脂（以下、「（Ａ）成分」とも称す）と、（Ｂ）平均粒径が２００ｎｍ以下の無機粒子（以下、「（Ｂ）成分」とも称す）と、（Ｃ）光重合開始剤（以下、「（Ｃ）成分」とも称す）と、（Ｄ）不飽和二重結合を有する化合物と（以下、「（Ｄ）成分」とも称す）、を含む。樹脂組成物の樹脂成分として上記構造を有する樹脂を用い、かつ、充填剤として平均粒径が２００ｎｍ以下の無機粒子を用いることで、解像性、強靭性、耐熱性に優れた硬化物を得ることができる。[Curable resin composition]
The curable resin composition of the present invention (hereinafter, also referred to as “resin composition”) has (A) the following formulas (1) and (2),

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

Further, the resin composition of the present invention can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, or an aqueous ammonia solution, and it is not necessary to use a strongly alkaline developer for development. In addition, since it can be developed with 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 sodium carbonate solution (30 ° C., 1% by mass) of 0.05 g / L or more in 1 minute.

で表される少なくとも一方の構造と、アルカリ可溶性官能基と、を有するアミドイミド樹脂である。本発明の樹脂組成物が、シクロヘキサン環またはベンゼン環に直結したイミド結合を有する樹脂を含むことにより、強靭性および耐熱性に優れた硬化物を得ることができる。特に、（１）で表される構造を有するアミドイミド樹脂は、光の透過性に優れるため、樹脂組成物の解像性を向上させることができる。本発明の樹脂組成物においては、（Ａ）成分は、透明性を有することが好ましく、例えば、（Ａ）成分の乾燥塗膜２５μｍにおいて、波長３６５ｎｍの光の透過率は７０％以上であることが好ましい。Hereinafter, each component of the resin composition of the present invention will be described in detail.
<Ingredient (A)>
The component (A) of the resin composition of the present invention has the following formula (1) or (2),

It is an amidoimide resin having at least one structure represented by 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, the amidoimide resin having the structure represented by (1) is excellent in light transmission, 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, the transmittance of light having a wavelength of 365 nm is 70% or more in a dry coating film of the component (A) of 25 μm. Is preferable.

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. It is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass.

（式（３Ａ）および（３Ｂ）中、それぞれ、Ｒは１価の有機基であり、Ｈ、ＣＦ_３またはＣＨ_３であることが好ましく、Ｘは直接結合または２価の有機基であり、直接結合、ＣＨ_２またはＣ（ＣＨ_３）_２等のアルキレン基であることが好ましい。）で表される構造を有する樹脂が、引張強度や伸度等の物性および寸法安定性に優れるため好ましい。本発明の樹脂組成物においては、溶解性や機械物性の観点から、（Ａ）成分として、式（３Ａ）および（３Ｂ）の構造を１０〜１００質量％有する樹脂を好適に用いることができる。より好ましくは２０〜８０質量％である。Examples of the amidoimide resin having the structure represented by the formula (1) include the formula (3A) or (3B).

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

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

（式（４Ａ）および（４Ｂ）中、それぞれ、Ｒは１価の有機基であり、Ｈ、ＣＦ_３またはＣＨ_３であることが好ましく、Ｘは直接結合または２価の有機基であり、直接結合、ＣＨ_２またはＣ（ＣＨ_３）_２などのアルキレン基であることが好ましい。）で表される構造を有する樹脂が、引張強度や伸度等の機械的物性に優れる硬化物が得られることから好ましい。本発明の樹脂組成物においては、溶解性や機械物性の観点から、（Ａ）成分として、式（４Ａ）および（４Ｂ）の構造を１０〜１００質量％有する樹脂を好適に用いることができる。より好ましくは２０〜８０質量％である。Further, as the amidoimide resin having the structure represented by the formula (2), particularly, the formula (4A) or (4B)

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

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

The component (A) can be obtained by a known method. The amidoimide resin having the structure (1) can be obtained by using, for example, a diisocyanate compound having a biphenyl skeleton and cyclohexanepolycarboxylic 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'-diisocyanate-1,1'-biphenyl. , 4,4'-Diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diisocyanate-1,1'-biphenyl, 4,4'-diisocyanate- Examples thereof include 3,3'-ditrifluoromethyl-1,1'-biphenyl and 4,4'-diisocyanate-2,2'-ditrifluoromethyl-1,1'-biphenyl. 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.

Also, the amide-imide resin having the structure (2), for example, using a diisocyanate compound having a biphenyl skeleton, and TMA (trimellitic anhydride), a polycarboxylic acid anhydride having two acid anhydride groups Can be obtained.

Examples of the polycarboxylic dianhydride having two acid dianhydride groups include pyromellitic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, and 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 Dihydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianide Examples thereof include anhydrides and alkylene glycol bisanhydroxy trimellitates such as ethylene glycol bisuanhydrotrimelitate.

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. As the alkali-soluble functional group, a carboxyl group, a phenolic hydroxyl group, a sulfo group and the like are contained, and a carboxyl group is preferably contained.

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) in the above range, alkaline 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 dry 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, the developability and the storage stability are good. More preferably, it is 5,000 to 100,000.

Specific examples of the component (A) include Unidic V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon Kodoshi Paper Industry Co., Ltd.

The resin composition of the present invention may contain a resin having a structure different from that of the component (A) and having an alkali-soluble functional group (hereinafter, also referred to as the component (A1)). By containing the component (A1), a dry film having good adhesion between the resin layer and the base material can be obtained. Therefore, the workability of the dry film is excellent. The fact that the structure is different from that of the component (A) means that the structures of the formulas (1) and (2) are not included. 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 using 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 a carboxyl group having a copolymerized structure of an unsaturated carboxylic acid. Containing resin, carboxyl group-containing resin using a phenol compound as a starting material, and carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule to the carboxyl group-containing resin. It is preferably at least one of the resins. Specific examples of the component (A1) are shown below.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Aliphatic compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An end carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the end of a urethane resin by a double addition 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 ( Meta) A carboxyl group-containing photosensitive urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.
(5) During the synthesis of the resin of (2) or (4) described above, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to the molecule such as hydroxyalkyl (meth) acrylate, and the terminal is added. (Meta) Acryloylated 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 isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing photosensitive urethane resin that is terminally (meth) acrylicized by adding a compound having.
(7) A (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are added to the hydroxyl groups existing in the side chain. A carboxyl group-containing photosensitive resin to which a basic acid anhydride is added. Here, the epoxy resin is preferably solid.
(8) A (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the generated hydroxyl groups. Carboxylic acid-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 obtained hydroxyl group is partially esterified with (meth) acrylic acid, and many of the remaining hydroxyl groups are present. A carboxyl group-containing photosensitive resin obtained by reacting with a basic acid anhydride.
(10) In addition to these resins (1) to (9), one epoxy group and one or more (meth) acryloyl groups are further added to the molecules such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin to which a compound is added.

The component (A1) is not limited to these, and one type or a plurality of types can be mixed and used. In addition, (meth) acrylate is a general term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions below.

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 or less, based on 100 parts by mass of the total of the component (A) and the component (A1). It is as follows. Within the above range, a cured product having good toughness and heat resistance can be obtained.

<Ingredient (B)>
The resin composition of the present invention contains (B) inorganic particles having an average particle size of 200 nm or less. The average particle size of the inorganic particles (B) is preferably 150 nm or less, and more preferably 100 nm or less. The reason for setting the average particle size of the inorganic particles to 200 nm or less is as follows. That is, usually, 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, but when the inorganic particles in the resin composition are exposed to light, the light scatters. The smaller the particle size, the less the scattering, but as a result of our studies, 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 turned out that it can be improved. Here, the average particle size is a value measured by a laser diffraction method. Examples of the measuring device by the laser diffraction method include Nikkiso Co., Ltd. (Nanotrac wave).

When measuring the average particle size of the inorganic particles in the cured product, first the surface of the cured product is etched by plasma treatment so that the inorganic particles can be seen, and the inorganic particles are observed with a SEM (scanning electron microscope). 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 work 5 times including other parts, and calculate the average value of the diameters of the inorganic particles. do it. For the plasma treatment, for example, MARCH PLASMA SYSTEM INC AP-1000 is used as an apparatus, POWER: 500 W, Pressure: 300 Torr, Gas: Ar, and the treatment time is 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, silitin, and silicoloid. Can be used. Among these, silica having a small coefficient of linear expansion can be preferably used. In addition, these inorganic particles may be used individually by 1 type and may use 2 or more types in combination.

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 the component (A1) is not contained, the component (A) is 100 parts by mass). It is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass. By setting the component (B) to 10 parts by mass or more, the effect of reducing the coefficient of linear expansion can be sufficiently obtained, while by setting the component (B) to 150 parts by mass or less, the resin composition of the present invention can be obtained. It is possible to prevent deterioration of workability at the time of application.

In the resin composition of the present invention, as described above, silica having a small coefficient of linear expansion can be preferably used as the component (B). In this case, the surface of silica is treated with a silane coupling agent. Is preferable. This is because it is possible to prevent precipitation and agglutination after being dispersed in the liquid, and as a result, the storage stability is excellent. Further, even when the resin composition is blended, it can be stably charged without agglutination, and further, the wettability between the resin and the particles of the obtained cured product can be improved.

Examples of the organic group contained in the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group and an isocyanate group. Can be mentioned. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

<Component (C)>
The resin composition of the present invention contains (C) a photopolymerization initiator. Examples of the photopolymerization initiator include an oxime ester type having a structure represented by the general formula (I), an α-aminoacetophenone type containing a structure represented by the general formula (II), and a general formula (III). It is preferable to contain one or more selected from the group consisting of an acylphosphine oxide system including the structure represented by the structure and a titanocene system having the structure represented by the general formula (IV).

In the 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, 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 may contain one or more oxygen atoms in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups. As the cycloalkyl group represented by R ¹ and R ² , a cycloalkyl group having 5 to 8 carbon atoms is preferable. As the alkanoyl group represented by R ¹ and R ² , an alkanoyl group having 2 to 20 carbon atoms is preferable. 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, a phenyl group and the like.

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

In general formula (III), R ⁷ and R ⁸ are each independently substituted with an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. Represents a 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, an aryl halide group, or a heterocyclic-containing aryl halide group.

（一般式（Ｖ）中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルで表し、ｎは０か１の整数である。）Specific examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6-. (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned. Examples of commercially available products include CGI-325 manufactured by BASF Japan, Irgacure OXE01, Irgacure OXE02, N-1919 manufactured by Adeka Corporation, NCI-831 and the like. A photopolymerization initiator having two oxime ester groups in the molecule and a photopolymerization initiator having a carbazole structure can also be preferably used. Specific examples thereof include an oxime ester compound represented by the following general formula (V).

(In the general formula (V), X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, 1 carbon atom). ~ 8 alkoxy groups, amino groups, alkylamino groups with 1 to 8 carbon atoms or dialkylamino groups substituted), naphthyl groups (alkyl groups with 1 to 17 carbon atoms, 1 to 8 carbon atoms) (Replaced with an alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), where Y and Z are hydrogen atoms and alkyl groups having 1 to 17 carbon atoms, respectively. , Alkyl 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, amino group, alkyl group having 1 to 8 carbon atoms Alkylamino having an alkylamino group or a dialkylamino group substituted), a naphthyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms). (Substituted with a group or dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents a bond or alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene having 1 to 10 carbon atoms. , Thiophen, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1.)

In particular, in the general formula (V), X and Y are methyl or ethyl groups, respectively, Z is methyl or phenyl, n is 0 and Ar is a bond or phenylene, naphthylene, thiophene or thienylene. Is preferable.

（一般式（ＶＩ）中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式（ＶＩＩ）で示される構造を表す。）

Moreover, as a preferable carbazole oxime ester compound, a compound represented by the following general formula (VI) 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 which may be 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 which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms. R ³ is substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, which may be linked by an oxygen atom or a sulfur atom and may be substituted with a phenyl group. May represent a benzyl group. R ⁴ represents a nitro group or an acyl group represented by X—C (= O) −. X is substituted with an alkyl group having 1 to 4 carbon atoms. It represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).)

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan), 4- (methylthiobenzoyl). -1-Methyl-1-morpholinoetan (Irgacure 907, trade name, manufactured by BASF Japan), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan, Inc.) and other commercially available compounds or solutions thereof can be used.

Specific examples of the acylphosphine oxide-based 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 and the like. Examples of commercially available products include Lucillin TPO manufactured by BASF and Irga Cure 819.

The titanocene-based photopolymerization initiator, bis (eta ^{5-2,4-cyclopentadiene-1-yl)} - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanium is Can be mentioned. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan Ltd.

Other photopolymerization initiators include, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, 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 , 4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone and other benzophenones; xanthones; Various peroxides such as 3,3'4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone; 1,7-bis (9-acrydinyl) heptane and the like can be mentioned.

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 , Triethanolamine and other tertiary amines, and can be used in combination with one or more of known and commonly used photosensitizers. 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 contained, the component (A) is 100 parts by mass). It is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.1 to 15 parts by mass. By setting the blending amount of the component (C) within the above range, radicals required for the reaction can be sufficiently generated, and light can be transmitted to a deep part, which causes problems such as brittleness of the cured product. It can be avoided. As the component (C), one type may be used alone, or two or more types may be used in combination.

<Ingredient (D)>
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 the resin composition of the present invention in an alkaline aqueous solution or assist in insolubilization. As such a compound, commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and 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. , N-methylol acrylamide, acrylamides such as N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; hexanediol, trimetyl propane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as their ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di. Polyvalent acrylates such as acrylates and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or urethane acrylates via diisocyanates, and the above acrylates. At least one of each methacrylate corresponding to the above can be mentioned.

Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate are added to 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-based resin can improve the photocurability without lowering the dryness to the touch. As the compound having an ethylenically unsaturated group in the molecule as described above, one kind may be used alone, or two or more kinds may be used in combination.

The blending ratio of the component (D) is preferably 1 to 60 parts by mass per 100 parts by mass of the total of the component (A) and the component (A1) (when the component (A1) is not included, 100 parts by mass of the component (A)). It is more preferably 5 to 50 parts by mass, and further preferably 10 to 40 parts by mass. By setting the blending amount of the component (D) within the above range, good photoreactivity can be obtained and heat resistance can be obtained at the same time.

<(E) Thermosetting resin>
The resin composition of the present invention preferably contains (E) a thermosetting resin (hereinafter, also referred to as “component (E)”) in order to further improve heat resistance. Examples of the thermosetting resin include two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, blocked isocyanate compounds, etc. in one molecule such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, and an episulfide resin. A compound having two or more isocyanate groups or a blocked isocyanate group, an amine resin such as a melamine resin or a benzoguanamine resin and a derivative thereof, and a known thermocurable resin such as bismaleimide, oxazine, a cyclocarbonate compound, and a carbodiimide resin. 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 solid or semi-solid. The polyfunctional epoxy resin includes bisphenol A type epoxy resin; brominated epoxy resin; novolak type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hidden in type epoxy resin; oil ring. Formula epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenel type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylol ethane type epoxy resin; heterocyclic epoxy Resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin ; Epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin and the like, but are not limited thereto. As the epoxy resin, bisphenol A type or bisphenol F type novolak type epoxy resin, bixyleneol type epoxy resin, biphenol type epoxy resin, biphenol novolak type (biphenyl aralkyl type) epoxy resin, naphthalene type epoxy resin or a mixture thereof is preferable. ..

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

As the component (E), a non-colored component is preferable from the viewpoint of resolution. As such a 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 it has an effect of improving the glass transition temperature 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 of the 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. By setting the blending amount of the component (E) within the above range, a composition having heat resistance and good developability and photoreactivity can be obtained.

When the resin composition of the present invention contains (E) a thermosetting resin, a thermosetting catalyst may be contained. 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 thereof include amine compounds such as 4-methyl-N and N-dimethylbenzylamine, hydrazine compounds such as adipate dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition to 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, and 2P4MHZ manufactured by Shikoku Kasei Kogyo Co., Ltd. (both are trade names of imidazole compounds), and U-CAT3503N and U manufactured by San Apro Co., Ltd. -CAT3502T (trade name of a blocked isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic amidine compounds and salts thereof) and the like can be mentioned. One of these may be used alone, or two or more thereof may be used in combination. 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 contained, the component (A) is 100 parts by mass). On the other hand, 0.1 to 10 parts by mass is preferable, and 0.1 to 5.0 parts by mass is more preferable.

Further, in the resin composition of the present invention, an organic solvent can be used for preparing the composition or for adjusting the viscosity for coating on 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 and 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; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha It is a system solvent or the like. As such an organic solvent, one type may be used alone, or two or more types may be used in combination.

<Others>
The resin composition of the present invention comprises (A) an amidoimide 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 photoreaction initiator, and (D) a compound having an unsaturated double bond, and other than that, there is no particular limitation. For example, in the resin composition of the present invention, if necessary, known and commonly used colorants (for example, white colorants such as titanium oxide, black colorants such as carbon black and titanium black, phthalocyanine blue, phthalocyanine green, and dysazo yellow). Etc.), thermal polymerization inhibitors, thickeners, defoaming agents, leveling agents, etc. can be added.

The resin composition of the present invention is suitable for forming an insulating cured film of a printed wiring board, more suitable for forming an insulating permanent film, and for forming a coverlay, a solder resist, and an interlayer insulating material. Optimal. The resin composition of the present invention can also be used for forming a solder dam or the like. The resin composition of the present invention may be a liquid type or a dry film type obtained by drying the liquid type resin composition. The liquid type resin composition may be a two-component type or the like 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. In the dry film of the present invention, the resin composition of the present invention is diluted with an organic solvent to adjust the viscosity to an appropriate level, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer coater, and a gravure are used. It can be obtained by applying it to a uniform thickness on a carrier film with a coater, a spray coater or the like, and usually drying it 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 the carrier film, but may be a cover film.

As the carrier film, a plastic film can be preferably used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a plastic film such as a polystyrene film are preferably used. The thickness of the carrier film is not particularly limited, but is generally selected as appropriate in 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 higher. The adhesive strength between the film and the cover film may be smaller.

The volatile drying performed after applying the resin composition of the present invention on the carrier film is performed in a hot air circulation type drying oven, IR furnace, hot plate, convection oven, etc. (using a dryer equipped with an air heating type heat source by steam). It can be carried out by using the method of bringing the hot air into countercurrent contact and the method of blowing the hot air from the nozzle onto the support).

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

[Printed circuit board]
The printed wiring board of the present invention comprises the cured product of the present invention. The printed wiring board of the present invention can be obtained by a method of directly applying the curable resin composition of the present invention onto the printed wiring board and a method of using the dry film of the present invention.

When the printed wiring board of the present invention is manufactured by the method of direct coating, the resin composition of the present invention is directly coated on the printed wiring board on which the circuit is formed, a coating film of the resin composition is formed, and then laser light or the like is used. The active energy rays of the above are directly irradiated according to the pattern, or are exposed by selectively irradiating the active energy rays through the photomask on which the pattern is formed, and the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. To do. Further, the resist pattern is irradiated with active energy rays at, for example, 500 to 2000 mJ / cm ² , and heated to a temperature of, for example, about 140 to 180 ° C. to be cured, thereby producing a printed wiring board having a cured product pattern. The resist pattern is irradiated with active energy rays in order to almost completely cure the component (D) or the like that did not react with the exposure when forming the image of the resist pattern.

When a dry film is used, the dry film of the present invention is laminated on a circuit-formed printed wiring board, a resin layer is laminated, and the carrier film is peeled off and developed in the same manner as described above. Then, the resin layer is irradiated with active energy rays and heated to, for example, a temperature of about 140 to 180 ° C. to be cured, thereby producing a printed wiring board having a pattern of the cured product. The pattern of the cured film may be formed by a photolithography method, a screen printing method, or the like.

The exposure machine used for irradiating the active energy beam may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and capable of irradiating ultraviolet rays in the range of 350 to 450 nm. Further, for example, a direct drawing device such as a direct imaging device that directly draws an image with active energy rays from CAD data from a computer can also be used. As the light source of the direct drawing device, a mercury short arc lamp, an LED, or a gas laser or a solid-state laser may be used as long as a laser beam having a maximum wavelength in the range of 350 to 410 nm is used. Exposure for image formation of the resist pattern varies depending thickness, etc., generally 20~1500mJ / cm ^2, preferably be in the range of 20~1200mJ / 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, etc. can be adopted. , Ammonia, amines and other alkaline aqueous solutions can be used.

Hereinafter, the resin composition of the present invention will be described in detail with reference to 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 formulations shown in Tables 1 to 4 below. The obtained resin composition was entirely coated on a patterned copper foil substrate for evaluation by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Then, the obtained evaluation substrate was exposed to a resist pattern at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. was 90 at a spray pressure of 0.2 MPa. Developed for seconds. After forming the resist pattern of the cured product, it was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure of 1000 mJ / cm ² , and then heated at 180 ° C. for 60 minutes to cure. As the amidimide resin (A-1), other resins (A1-1), and (A1-2), those synthesized according to the following synthesis method were used. The obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, coefficient of linear expansion 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. The optimum exposure amount was determined by the following procedure.

<Optimal exposure>
The 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 bafflor-polished, washed with water, dried, the obtained resin composition was applied by a screen printing method, and dried in a hot air circulation type drying oven at 80 ° C. for 30 minutes. After drying, it was exposed using a high-pressure mercury lamp exposure device through a photomask (Step Tablet No. 2 manufactured by Eastman Kodak Co., Ltd.). The irradiated material was used as a test piece, and after developing for 60 seconds with a developing solution having a spray pressure of 2 kg / cm ² (1 mass% sodium carbonate aqueous solution at 30 ° C.), the number of stages 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 defined as the appropriate exposure amount.

<Synthesis of Amidimide Resin (A-1) (Synthesis Example 1)>
848.8 g of GBL (gamma butyrolactone), 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4'-diisocyanate-3,3'" in a flask equipped with a stirrer, a thermometer and a condenser. -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) Add 29.7 g (0.15 mol) of acid-3,4-anhydrous), raise the temperature to 80 ° C while paying attention to heat generation while stirring, dissolve and react at this temperature for 1 hour, and further. After raising the temperature 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 gas, and the inside of the system became a brown transparent liquid. A solution of a polyamide-imide resin (A1) having a viscosity of 7 Pa · s at 25 ° C. and a resin solid content of 17% and a solution acid value of 5.3 (KOH mg / g) (resin composition in which the resin is dissolved in γ-butyrolactone). Got The solid acid value of the resin was 31.2 (KOHmg / g). Moreover, as a result of the measurement of gel permeation chromatography (GPC), the weight average molecular weight was 34,000. The polyamide-imide resin (A-1) is a resin having the structures of the above formulas (1) and (2) and a carboxyl group.

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

<Synthesis of other resin (A1-2) (Synthesis example 3)>
An autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirrer, and a novolac type 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 added dropwise, and the mixture was reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Then, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, and the non-volatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A propylene oxide reaction solution of the novolak type cresol resin was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

Next, 293.0 g of the alkylene oxide reaction solution of the obtained novolak 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 added to a stirrer, a thermometer and air. It was charged into a reactor equipped with a blowing tube, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 g of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 g of the obtained novolak-type 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. With stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added, and the mixture was reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mgKOH / g and a non-volatile content of 71% was obtained. Hereinafter, the obtained resin will be referred to as another resin (A1-2).

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

<Tensile strength / elongation (toughness)>
A 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 was obtained by using an autograph AG-X manufactured by Shimadzu Corporation at 1 mm / min. A tensile test was performed at speed. The obtained results are also shown in Tables 1 to 4. When the breaking point stress and elongation are large, the toughness is excellent.
A: Breaking point stress 80N / mm ² or more / elongation 3% or more B: Breaking point stress 50N / mm ² or more and less than 80N / mm ² / elongation 2% or more and less than 3% C: Breaking point stress 50N / mm less than ² / elongation Less than 2%

<Coefficient of linear expansion / 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 above was applied with a load of 10 g by TMA6100 manufactured by Seiko Instruments Inc. A tensile test was performed in a temperature range of 0 ° C. to 260 ° C. at a constant temperature rise rate. The coefficient of linear expansion (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, heat resistance is excellent.
A: Tg 180 ° C or more / less than CTE 40ppm B: Tg 150 ° C or more and less than 180 ° C / CTE less than 50ppm 40ppm or more C: Tg less than 150 ° C / CTE 50ppm 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 having a gap of 60 μm, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Then, 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 existed in the form of a stable film on PET.
A: It is bent in the same way as PET and does not come off from PET.
B: It does not come off from PET, but the bent part breaks.
C: The bent part cracks and peels off from 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. .. A 3 L 1% by mass sodium hydroxide aqueous solution was placed in a beaker and heated to 30 ° C. to prepare a developing solution. In addition, the weight of the substrate on which the dry coating film was formed was measured. Then, the substrate was immersed in a developing solution and shaken for 1 minute to take out. Immediately after that, the substrate was washed with water, dried, and then weighed again. The developability, that is, (change in weight of substrate: g) / (volume of developer: L) was calculated and evaluated from the change in weight of the substrate. 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 Inc.), the developability is 0.01 g / L or less, which is almost insoluble.

Amidimide resin (A-1): Resin synthesized in Synthesis Example 1 (resin solid content 17%)
Amidimide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kodoshi Kogyo Co., Ltd.), which corresponds to a carboxyl group-containing amidimide resin having the structure of the above formula (2) and another resin (A1). -1): Carboxylic group-containing resin synthesized in Synthesis Example 2 (solid content 65%)
Other resin (A1-2): Carboxylic group-containing resin synthesized in Synthesis Example 3 (solid content 71%)
Inorganic particles 1: Silica inorganic particles with an average particle size of 100 nm 2: Silica inorganic particles with an average particle size of 50 nm 3: Barium sulfate inorganic particles with an average particle size of 100 nm 4: Silica photopolymerization initiator with an average particle size of 1 μm 1: Made by BASF TPO
Photopolymerization Initiator 2: BASF IRG-369
Photopolymerization Initiator 3: IRG-OXE02 manufactured by BASF
Compound with unsaturated double bond 1: Dipentaerythritol hexaacrylate Compound with unsaturated double bond 2: Dicyclopentadiene diacrylate Thermosetting resin 1: Naphthalene skeleton-containing epoxy resin HP4032 (150eq) (manufactured by DIC)
Thermosetting resin 2: Naphthol-modified epoxy resin NC7000 (230eq) (manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 3: Biphenyl aralkyl type epoxy resin NC3000 (275eq) (manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 4: Dicyclopentadiene skeleton-containing epoxy resin XD-1000 (250eq) (manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 5: Dicyclopentadiene skeleton epoxy resin HP-7200H (280eq) (manufactured by DIC Corporation)
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. Further, it can be seen that the dry film obtained from the resin composition of the present invention is excellent in workability.

Claims (10)

(A) The following equations (1), (2),

An amidoimide resin 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 as a filler , (C) a photopolymerization initiator, and (D) unsaturated. A curable resin composition containing a compound having a saturated double bond .
When the blending amount of the (B) inorganic particles contains 100 parts by mass of the (A) amidimide resin (however, the resin (A1) having a structure different from that of the (A) amidimide resin and having an alkali-soluble functional group) is contained. It is 30 to 150 parts by mass with respect to the total of 100 parts by mass of the component (A) and the component (A1).
A curable resin composition, wherein a 50 μm dry coating film obtained from the curable resin composition can be developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. The curable resin composition according to claim 1, which contains a resin (A1) having a structure different from that of the (A) amidoimide resin and having an alkali-soluble functional group. (B) The curable resin composition according to claim 1, wherein the inorganic particles having an average particle size of 200 nm or less are silica. (E) The curable resin composition according to claim 1, which comprises a thermosetting resin. The curable resin composition according to claim 4, wherein the thermosetting resin (E) is an epoxy resin having an alicyclic skeleton. A dry film according to any one of claims 1 to 5, wherein the curable resin composition has a resin layer obtained by coating and drying on a film. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5. A cured product according to claim 6, wherein the resin layer of the dry film is cured. A printed wiring board comprising the cured product according to claim 7. A printed wiring board comprising the cured product according to claim 8.