JP2018189851A - Curable resin composition, dry film, cured product and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide means whereby, even when a thin film layer of a curable resin composition is put in an environment where it is exposed to high temperature, adhesion between the thin film layer and an adherend is prevented from deteriorating.SOLUTION: A composition contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an unsaturated double bond, (D) a thermosetting resin, (E) a heat curing accelerator with a melting point of 60°C or less, and (F) a solvent, where all the components of the composition are compatible with each other at room temperature.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a dry film, a cured product, and an electronic component.

  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 development type solder resist composition that is finish-cured (mainly cured) by at least one of irradiation is used. Under such circumstances, in consideration of environmental problems, an alkali development type solder resist composition using an aqueous alkali solution as a developing solution has become the mainstream, and is 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 the alkali development type solder resist composition. For example, Patent Document 1 proposes a solder resist composition comprising an alkali-soluble 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.

JP-A 61-243869

By the way, in the printed wiring board, in recent years, the transmission speed has been increased by increasing the number of connection terminals between the IC chip and the wiring board and increasing the density of the wiring, and it has been required to reduce the via size and form the fine wiring. Yes. Furthermore, in order to realize a multilayer structure with a thin substrate, it is required to further reduce the thickness of the interlayer insulating resin layer. However, with conventional curable resin compositions, it has been difficult to form a resin layer having a thin film and no defects.
On the other hand, the present inventors are exposed to high temperatures in a thin resin layer formed by using a conventional curable resin composition, for example, by forming a conductor on the resin layer by metal sputtering for forming fine wiring. As a result, it has been found that there is a problem that the adhesion with the conductor layer is deteriorated.
Therefore, the present invention is a curable resin composition that can easily form a thin film-free resin layer, and is also a cured product having excellent adhesion to an adherend even in high-temperature thermal history such as metal sputtering. An object is to provide a useful curable resin composition.

本発明の硬化性樹脂組成物において、前記（Ｄ）熱硬化性樹脂は、脂環骨格を有するエポキシ樹脂であることが好ましい。
本発明の硬化性樹脂組成物は、膜厚１０μm以下のパターン硬化物形成用であることが好ましい。
本発明のドライフィルムは、フィルム上に、前記硬化性樹脂組成物を塗布、乾燥してなる樹脂層を有することを特徴とするものである。
本発明の硬化物は、前記硬化性樹脂組成物または前記ドライフィルムの樹脂層を硬化されてなることを特徴とするものである。
本発明の電子部品は、前記硬化物を備えてなることを特徴とするものである。 The present invention includes (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an unsaturated double bond, (D) a thermosetting resin, and (E) a melting point of 60 ° C. A curable resin composition comprising the following thermosetting accelerator and (F) a solvent, wherein all components in the composition are mutually compatible at room temperature.
In the curable resin composition of the present invention, the blending amount of the (E) thermosetting accelerator is 0. 0 with respect to the total amount of the (A) alkali-soluble resin and the (D) thermosetting resin. It is preferable that it is 1-1.5 mass%.
In the curable resin composition of the present invention, the (A) alkali-soluble resin includes an amide-imide resin having at least one structure represented by the following formula (1) and the following formula (2) and an alkali-soluble functional group. It is preferable.

In the curable resin composition of the present invention, the (D) thermosetting resin is preferably an epoxy resin having an alicyclic skeleton.
The curable resin composition of the present invention is preferably for forming a patterned cured product having a thickness of 10 μm or less.
The dry film of the present invention has a resin layer formed by applying and drying the curable resin composition on the film.
The cured product of the present invention is obtained by curing the resin layer of the curable resin composition or the dry film.
The electronic component of the present invention is characterized by comprising the cured product.

  According to the curable resin composition of the present invention, a thin film-free resin layer can be easily formed, and the thin film resin layer comprising the curable resin composition is disposed in an environment exposed to high temperatures. Even in this case, since outgassing is suppressed, it is possible to prevent a decrease in adhesion between the thin film resin layer and the adherend.

The curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an unsaturated double bond, (D) a thermosetting resin, E) A composition comprising a thermosetting accelerator having a melting point of 60 ° C. or less and (F) a solvent, wherein all components in the composition are mutually compatible at room temperature.
Here, in the present invention, “all components are compatible with each other at room temperature (23 ° C.)” means that coarse particles of 5 μm or more are completely present in the curable resin composition obtained by mixing the components. When there is no. Whether or not they are compatible is determined by coating the entire surface using an applicator with a gap of 30 μm, and observing the range of 1 cm × 1 cm of the surface of the obtained coating film with an optical microscope at a magnification of 1000 times of 5 μm or more. This can be determined by examining the presence or absence of coarse particles.
In particular, the curable resin composition of the present invention preferably has no coarse particles of 1 μm or more, and the curable resin composition of the present invention has a pot life (pot life) of 24 hours or more. preferable. According to such a configuration, it is possible to stably produce a product having a resin layer that is thinner and has no defects.
Here, the “pot life (pot life)” as used in the present specification doubles the viscosity change (measured at 25 ± 1 ° C. using an E-type viscometer) after preparing the curable resin composition. Specifically, the first viscosity measurement data is recorded starting from the time when the preparation of all components of the curable resin composition is completed, and the viscosity is measured again after being left for a predetermined time. The time when it becomes twice the value.

1. Curable resin composition Hereinafter, each component and compounding of the curable resin composition according to the present invention will be described in detail.

1-1. Component 1-1-1. (A) Alkali-soluble resin The alkali-soluble resin is not particularly limited as long as it can be developed with an alkali developer, and known and commonly used resins can be used. For example, a resin having an alkali-soluble functional group such as a carboxyl group or a phenolic hydroxyl group can be used. Specifically, an alkali-soluble resin described later can be used.

1-1-1-1. Suitable alkali-soluble resins Among these, particularly preferred alkali-soluble resins include amidoimide resins having at least one structure represented by the following formula (1) and the following formula (2) and an alkali-soluble functional group. Hereinafter, the suitable amidoimide resin will be described in detail.

  When the curable 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. Furthermore, since the amide imide resin which has a structure represented by Formula (1) is excellent in the light transmittance, it can improve the resolution of a curable resin composition. In the curable resin composition of the present invention, the suitable amideimide resin preferably has transparency. For example, the transmittance of light having a wavelength of 365 nm is 70% in a dry coating film of 25 μm of the suitable amideimide resin. The above is preferable.

  As for content of the structure of Formula (1) and Formula (2) in the said suitable amide imide resin of the curable resin composition of this invention, 10-70 mass% is preferable. 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. Preferably it is 10-60 mass%, More preferably, it is 20-50 mass%.

｛式（３Ａ）および式（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。本発明の硬化性樹脂組成物においては、溶解性や機械物性の観点から、当該好適なアミドイミド樹脂における、式（３Ａ）および式（３Ｂ）の構造の含有量が１０〜１００質量％であ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。 As the amideimide resin having a structure represented by the formula (1), in particular, the formula (3A) or the formula (3B)

{In Formula (3A) and Formula (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, It is preferably an alkylene group such as a direct bond, CH ₂ or C (CH ₃ ) ₂ . }
A resin having a structure represented by the formula is preferable because of excellent physical properties such as tensile strength and elongation, and dimensional stability. In the curable resin composition of the present invention, from the viewpoint of solubility and mechanical properties, a resin having a structure content of formula (3A) and formula (3B) in the suitable amideimide resin is 10 to 100% by mass. Can be suitably used. More preferably, it is 20-80 mass%.

｛式（４Ａ）および式（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。
本発明の硬化性樹脂組成物においては、溶解性や機械物性の観点から、当該好適なアミドイミド樹脂における、式（４Ａ）および式（４Ｂ）の構造の含有量が１０〜１００質量％であ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。 Moreover, as an amide imide resin which has a structure represented by Formula (2), especially Formula (4A) or Formula (4B)

{In Formula (4A) and Formula (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, An alkylene group such as a direct bond, CH ₂ or C (CH ₃ ) ₂ is preferred. }
Is preferable because a cured product having excellent mechanical properties such as tensile strength and elongation can be obtained.
In the curable resin composition of the present invention, from the viewpoints of solubility and mechanical properties, a resin having a structure content of formula (4A) and formula (4B) in the preferred amideimide resin is 10 to 100% by mass. Can be suitably used. More preferably, it is 20-80 mass%.

  The suitable amidoimide resin can be obtained by a known method.

  The acid value of the suitable amidoimide resin 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 suitable amidoimide resin within the above range, good alkali development is possible, and a pattern of a normal cured product can be formed. The weight average molecular weight of the suitable amidoimide resin 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 5,000-100,000. Here, the weight average molecular weight in this specification is a value measured by GPC.

  In addition, as a specific example of the suitable amide imide resin, SOXR-U manufactured by Nippon Kogyo Paper Industry Co., Ltd. may be mentioned.

  Such a suitable alkali-soluble amideimide resin can be used by mixing one kind or plural kinds.

1-1-1-2. Other Alkali-Soluble Resins The curable resin composition of the present invention has, as an alkali-soluble resin component, a resin having another alkali-soluble functional group (hereinafter referred to as "(" A1) component ") can also be used. That the structure is different from the suitable alkali-soluble amideimide resin means that it does not include the structures of the formulas (1) and (2).
The component (A1) is not particularly limited as long as it is a resin having an alkali-soluble functional group such as a carboxyl group or a phenolic hydroxyl group, and a publicly known one can be used. Starting with a carboxyl group-containing resin as a starting material, a carboxyl group-containing resin having a urethane skeleton (hereinafter also referred to as “carboxyl group-containing urethane resin”), a carboxyl group-containing resin having a copolymer structure of unsaturated carboxylic acid, and a phenol compound It is at least one of a carboxyl group-containing resin as a raw material and a 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 preferable. Specific examples of the component (A1) are shown below.

(A1-1) Carboxy group-containing obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene resin.
(A1-2) 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 and polycarbonate polyols, poly Carboxyl group-containing urethane by polyaddition reaction of diol compounds such as ether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups resin.
(A1-3) 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 terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by polyaddition reaction of a diol compound such as an A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(A1-4) 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 anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(A1-5) During the synthesis of the above-mentioned resin (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added. A carboxyl group-containing photosensitive urethane resin that is terminally (meth) acrylated.
(A1-6) During the synthesis of the above-mentioned resin (2) or (4), an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., one isocyanate group and one or more (meth) in the molecule A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having an acryloyl group and then terminal (meth) acrylated.
(A1-7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl group present in the side chain is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which is added a dibasic acid anhydride. Here, the epoxy resin is preferably solid.
(A1-8) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. A carboxyl group-containing photosensitive resin. Here, the epoxy resin is preferably solid.
(A1-9) 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 A carboxyl group-containing photosensitive resin obtained by reacting with a polybasic acid anhydride.
(A1-10) In addition to these resins (A1-1) to (A1-9), one epoxy group and one or more at least one molecule in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate A carboxyl group-containing photosensitive resin obtained by adding a compound having a (meth) acryloyl group.

  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 preferred amidoimide resin.

The alkali-soluble resin as described above preferably contains a mixture of the suitable alkali-soluble amideimide resin and the component (A1). By mixing and containing in this way, a dry film having good adhesion between the resin layer and the substrate can be obtained. As a result, excellent workability of the dry film can be obtained.
Here, it is preferable that the compounding ratio of the said amideimide resin and (A1) component is 5-50 mass% with respect to 100 mass parts of total amounts of an amideimide resin and (A1) component, More preferably, it is 10-30. % By mass. By setting it as said range, the hardened | cured material which has favorable toughness and heat resistance can be obtained.

1-1-2. (B) Photopolymerization initiator The curable resin composition of the present invention contains (B) a photopolymerization initiator (hereinafter also referred to as “component (B)”). Here, (B) component may be used individually by 1 type, and may be used in combination of 2 or more type. As the photopolymerization initiator (B), any known and commonly used photopolymerization initiator can be used without particular limitation. In particular, an oxime ester-based compound having a structure represented by the general formula (I), a general formula (II) Selected from the group consisting of an α-aminoacetophenone system having a structure represented by formula (II), an acylphosphine oxide system having a structure represented by formula (III), and a titanocene system having a structure represented by formula (IV). It is preferable to contain 1 type, or 2 or more types.

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 the general formula (II), R ³ and R ⁴ each independently represent 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 be bonded to form a cyclic alkyl ether group.

In 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 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, a phenyl group (an alkyl group having 1 to 17 carbon atoms, or 1 to 1 carbon atoms). 8 alkoxy groups, amino groups, substituted with alkylamino groups having 1 to 8 carbon atoms or dialkylamino groups, naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 to 8 carbon atoms) Represents an alkoxy group, an amino group, an alkylamino group having a C1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, a C1-17 alkyl group, C1-C8 alkoxy group, halogen group, phenyl group, phenyl group (having C1-C17 alkyl group, C1-C8 alkoxy group, amino group, C1-C8 alkyl group An alkylamino group having an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, or an alkyl group having 1 to 8 carbon atoms, substituted with an alkylamino group or a dialkylamino group) Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, It is represented by 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 which may be substituted with 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 and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group. R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (VII), which may be substituted with an alkyl group having 1 to 4 carbon atoms.

  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 Commercially available compounds such as -morpholinyl) phenyl] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or solutions 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, bis (2,6-dimethoxybenzoyl). ) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Irgacure TPO manufactured by BASF, Omnirad 819 manufactured by IGM Resins, and the like.

  Examples of the titanocene-based photopolymerization initiator include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. It is done. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

  Other known and commonly used photopolymerization initiators include, for example, 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 Acetophenones such as 1,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone di Ketals such as tilketal and benzyldimethyl ketal; benzophenones such as benzophenone; xanthones; various peroxides such as 3,3′4,4′-tetra- (tert-butylperoxycarbonyl) benzophenone; 1,7-bis (9-acridinyl) heptane and the like.

  In the curable 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 such as known and commonly used photosensitizers can be used in combination. Furthermore, 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.

1-1-3. (C) Compound having an unsaturated double bond The curable resin composition of the present invention contains (C) a compound having an unsaturated double bond (hereinafter also referred to as “component (C)”). The component (C) can be photocured by irradiation with an active energy ray 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 , N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, N-dimethylaminoethyl acrylate, N Aminoalkyl acrylates such as N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, 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.

1-1-4. (D) Thermosetting resin The curable resin composition of the present invention contains (D) a thermosetting resin (hereinafter also referred to as “component (D)”) in order to further improve heat resistance. 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. .

  Among these, an epoxy resin having an alicyclic skeleton is preferable from the viewpoint of improving resolution, and an epoxy resin having an aromatic ring skeleton (for example, naphthalene skeleton) is preferable from the viewpoint of improving heat resistance.

Examples of the epoxy resin having an alicyclic skeleton include an epoxy resin having a dicyclopentadiene skeleton. The epoxy resin having the alicyclic skeleton can be expected to have an effect of improving the glass transition temperature as compared with the epoxy resin having the chain skeleton.
Examples of the epoxy resin having an aromatic ring skeleton include an epoxy resin having a naphthalene skeleton. In the epoxy resin having a naphthalene skeleton, naphthalene has a planar structure, can reduce a linear expansion coefficient, and can further improve heat resistance. 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.

  One type of thermosetting resin as described above may be used alone, or two or more types may be used in combination.

1-1-5. (E) Thermosetting accelerator The curable resin composition of the present invention has (E) a melting point of 60 ° C. or lower (preferably a normal temperature (23 ° C. or higher) because of excellent pot life) ( (Hereinafter also referred to as “component (E)”). Here, the “melting point” in the present specification can be determined by measuring the value of the melted endothermic peak by raising the temperature from 0 ° C. to 5 deg.C / min using a differential scanning calorimeter (DSC). Here, as the thermosetting accelerator, imidazole derivatives such as 2-ethyl-4-methylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; benzyldimethylamine, diethylenetriamine, triethylenetetramine, Examples include amine compounds such as isophoronediamine and mensendiamine; hydrazine compound phosphorus compounds and the like. Besides these, guanamine and S-triazine derivatives can also be used.

  Commercially available thermosetting accelerators include, for example, 1.2DMZ, 2E4MZ, 2E4MZ-CN, 1B2MZ, 1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd., Fujicure 7000, Fujicure 7001, Fujicure 7002, Fujicure 7004, Suncure 7004 manufactured by T & K TOKA. Examples include DBU and DBN manufactured by the company. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Particularly suitable thermosetting accelerators are components having an imidazole skeleton. The reason is that the curing reaction at room temperature is difficult to proceed, so that the pot life of the composition is as long as 24 hours or longer, and the reaction is easy to proceed when heat treatment is performed and the workability is excellent.

1-1-6. (F) Solvent Furthermore, the curable resin composition of this invention contains a solvent for the preparation of a composition, or the viscosity adjustment for apply | coating to a board | substrate or a carrier film. Examples of such solvents (organic solvents) 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.

1-1-7. Optional components The curable resin composition of the present invention may be prepared by using a known and commonly used nanofiller, a known and commonly used colorant (for example, a white colorant such as titanium oxide, a black colorant such as carbon black and titanium black, Phthalocyanine blue, phthalocyanine green, disazo yellow, etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like can be added.

1-2. Formulation 1-2-1. Component (B) / Component (A) The blending ratio of component (B) is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 20 parts by mass per 100 parts by mass of component (A). More preferably, it is 0.1-15 mass parts. By setting the blending amount of the component (B) 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.

1-2-2. Component (C) / Component (A) The blending ratio of component (C) is preferably 1 to 60 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 10 to 100 parts by weight per 100 parts by weight of component (A). 40 parts by mass. (C) By making the compounding quantity of a component into the said range, favorable photoreactivity can be acquired and it can have heat resistance.

1-2-3. Component (D) / Component (A) The blending ratio of component (D) is preferably 10 to 100 parts by weight, more preferably 10 to 80 parts by weight per 100 parts by weight of component (A). By setting the blending amount of component (D) within the above range, a composition having heat resistance and having both good developability and photoreactivity can be obtained.

1-2-4. (E) Component / (A) component + (D) component The blending ratio of the thermosetting accelerator is 0.1 to 1.5% by mass with respect to the total amount of the (A) component and the (D) component. Is preferred. Thus, since the thermosetting accelerator according to the present invention is dispersed in a liquid state in the composition, the amount of component (E) added may be small and unreacted residue is small. Therefore, generation of outgas is suppressed in the sputtering process in the subsequent process, and the adhesion is excellent.

2. Method of using curable resin composition (application)
The curable resin composition of the present invention is suitable for forming an insulating cured film of a printed wiring board, and forms a permanent insulating film such as a cover lay, a solder resist, an interlayer insulating material, and an insulating material for forming a rewiring layer. It is further suitable for use. Here, the resin composition of the present invention is particularly suitable for forming a cured product pattern of a thin film having a film thickness of 10 μm or less (the lower limit is not particularly limited, for example, 2 μm). In addition, the curable resin composition of this invention can also be used for formation of a solder dam etc. The curable 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 resin composition may be a two-component type from the viewpoint of storage stability, but may be a one-component type. Hereinafter, a dry film is explained in full detail as one usage aspect of curable resin composition.

2-1. Dry Film The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention onto 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 curable resin composition of the present invention with an organic solvent and adjusting the viscosity to 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. It can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, what is necessary is just to set suitably in the range of 3-100 micrometers in the film thickness after drying, Preferably it is 5-40 micrometers. 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. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After coating and drying the curable resin composition of the present invention on a carrier film, a film that can be peeled off from the surface of the coating film (hereinafter referred to as the following) for the purpose of preventing dust from adhering to the coating film surface. (Also referred to as “cover film”). As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. When peeling the cover film, the adhesive force between the coating film and the carrier film As long as the adhesive force between the coating film and the cover film is smaller.

  The drying treatment performed after the curable resin composition of the present invention is applied on the carrier film can be performed using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like.

3. Cured product The cured product of the present invention is obtained by curing the curable resin composition of the present invention and by curing the resin layer of the dry film of the present invention. The cured product of the present invention is active against a coating film obtained after applying the curable resin composition of the present invention and evaporating and drying the solvent, or against a resin film obtained by laminating a dry film. It can be obtained by irradiating with energy rays and then developing, followed by curing by active energy rays or heating, if necessary.

4). Electronic component The electronic component of the present invention comprises the cured product of the present invention, and examples thereof include a printed wiring board. This printed wiring board can be obtained by a method of directly applying the curable resin composition of the present invention on a printed wiring substrate and a method of using the dry film of the present invention.

When producing a printed wiring board by a direct coating method, the curable resin composition of the present invention is directly coated on a printed wiring substrate formed with a circuit, dried to form a dry coating film, 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 was formed, and develop the unexposed area with an alkaline aqueous solution to form a patterned resin layer To do. Further, the pattern resin layer is irradiated with active energy rays at, for example, 500 to 2,000 mJ / cm ² , or heated to a temperature of about 140 to 180 ° C. to be cured, thereby having a cured product pattern. Manufactures printed wiring boards. The pattern resin layer is irradiated with active energy rays in order to almost completely cure the component (C) that has not reacted by exposure when forming an image of the pattern resin layer.
In addition, as a method of direct application, in addition to the above-described photolithography method, a screen printing method, an ink jet printing method, or the like may be used.

  When manufacturing using a dry film, after laminating the dry film of the present invention on a printed wiring substrate on which a circuit has been formed and laminating a resin layer, after exposure as described above, the carrier film is peeled off and developed. Then, a pattern resin layer is formed. Thereafter, the pattern resin layer is irradiated with, for example, active energy rays or cured by heating to a temperature of about 140 to 180 ° C., thereby producing a printed wiring board having a patterned resin layer of a cured product.

Here, as an exposure apparatus used for irradiation with active energy rays, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, or the like is installed and can irradiate ultraviolet rays in the range of 350 to 450 nm. Furthermore, for example, a direct drawing apparatus such as a direct imaging apparatus that directly draws an image with an active energy ray 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. Exposure for image formation of the pattern the resin layer varies depending thickness, etc., generally 20~1,500mJ / cm ^2, preferably be in the range of 20~1,200mJ / 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.

≪Preparation example≫
<Raw material>
{Component A} Alkali-soluble resin A1: Carboxyl group-containing resin synthesized in the following synthesis example (solid content 65%)
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 reacted 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. As a result of measurement by gel permeation chromatography (GPC), the weight average molecular weight was 8,000.
A2: Carboxyl group-containing resin synthesized in the following synthesis example (solid content: 71%)
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 added dropwise 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. Thus, a resin solution of a carboxyl group-containing photosensitive resin having a solid content acid value of 88 mgKOH / g, a solid content of 71%, and a weight average molecular weight of 2,000 was obtained.
A3: Carboxyl group-containing amidoimide resin synthesized in the following synthesis example (solid content: 17%)
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. Thus, a solution of a carboxyl group-containing amidoimide resin having a 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 dissolved in γ-butyrolactone) Composition) was obtained. This resin was a carboxyl group-containing amidoimide resin having the structures of the formulas (1) and (2) of the present invention. The solid content acid value of the resin was 31.2 (KOH mg / g), and the weight average molecular weight was 34,000.
A4: Carboxyl group-containing amidoimide resin SOXR-U (20% solids) (manufactured by Nippon Kogyo Paper Industries Co., Ltd.), which is a carboxyl group-containing amidoimide resin having the structure of the formula (2) of the present invention.
{Component B} Photopolymerization initiator B1: Irgacure TPO manufactured by BASF
B2: BASF Irgacure 784
B3: BASF Irgacure OXE02
{Component C} Compound having an unsaturated double bond C1: Dipentaerythritol hexaacrylate C2: Dicyclopentadiene diacrylate {Component D} Thermosetting resin D1: Naphthalene skeleton-containing epoxy resin HP4032 (150 eq) (manufactured by DIC)
D2: Naphthol-modified epoxy resin NC7000 (230 eq) (manufactured by Nippon Kayaku Co., Ltd.)
D3: Siloxane type resin SE-01GL (167 eq) (manufactured by Nagase ChemteX Corporation)
D4: Dicyclopentadiene skeleton epoxy resin HP-7200H (280 eq) (manufactured by DIC)
D5: Triazine skeleton epoxy resin TEPIC-S (100 eq) (manufactured by Nissan Chemical Co., Ltd.)
{Component E} Thermosetting accelerator E1: 2E4MZ Melting point 40 ° C. (Shikoku Chemicals)
E2: 1B2MZ Melting point 40 ° C (Shikoku Chemicals)
E3: Fuji Cure 7000 Melting point 38 ° C (T & K TOKA)
E4: Melamine melting point 354 ° C
E5: Dicyandiamide 210 ° C
E6: 2P4MZ Melting point 180 ° C (Shikoku Chemicals)
E7: Triethylenetetramine, melting point 12 ° C
{Component F} Solvent F1: MEK (methyl ethyl ketone)
F2: PMA (propylene glycol monomethyl ether acetate)
{Other ingredients}
Inorganic particles 1: Silica inorganic particles having an average particle diameter of 100 nm 2: Silica pigment having an average particle diameter of 1 μm: Phthalocyanine blue (PB-15: 4) (dispersed to an average particle diameter of 100 nm or less)

<Preparation of Resin Compositions According to Examples and Comparative Examples>
Based on the component compositions shown in Tables 1 to 4, each component was blended, premixed with a stirrer, and then kneaded and dispersed to prepare resin compositions according to Examples and Comparative Examples. In addition, the compounding quantity in a table | surface shows a mass part.

The resin composition thus obtained was evaluated for compatibility, film-forming property, outgas generation amount, wiring adhesion, pot life, and breaking strength.
(Compatibility)
On the copper foil, the resin compositions according to Examples and Comparative Examples were applied to the entire surface using an applicator with a gap of 30 μm, and a 1 cm × 1 cm square range of the obtained coating film surface was magnified 1000 times with an optical microscope. The particle size of coarse particles (the largest particles) was measured, and the compatibility (whether or not they were compatible) was evaluated at room temperature (23 ° C.). Here, “compatible” means a case where there are no coarse particles of 5 μm or more.
(Film forming property)
On the PET film, the resin compositions according to Examples and Comparative Examples were applied on the entire surface using an applicator with a gap of 30 μm, and dried at 80 ° C. for 30 minutes to produce a dry film having a dry coating film. The range of 1 cm × 1 cm □ on the film surface was observed with an optical microscope at a magnification of 1000 times, and the film forming property was evaluated by the presence or absence of defects such as pinholes. The evaluation criteria are as follows.
○: No defects such as pinholes ×: Defects such as pinholes (outgas generation amount)
Preparation of Evaluation Board On the copper foil, the resin compositions according to Examples and Comparative Examples were applied over the entire surface using an applicator with a gap of 30 μm, dried at 80 ° C. for 30 minutes, and then an exposure apparatus equipped with a high-pressure mercury lamp. The entire surface was exposed to light, and developed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. and a spray pressure of 0.2 MPa for 60 seconds. Furthermore, after irradiating with ultraviolet rays under the condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, the substrate was heated and cured at 180 ° C. for 60 minutes to prepare an evaluation substrate having a cured resin layer on the copper foil.
Evaluation Method About the obtained evaluation substrate, as a test piece, a predetermined amount of the cured resin layer is peeled off, outgas generated at 200 ° C. for 60 minutes is extracted using a heat desorption apparatus, and n-Dodecane is obtained by GC / MS. The amount (%) of outgas generated per 1 mg was quantified and evaluated.
(Wiring adhesion)
Production of Evaluation Substrate Similar to the production of the substrate used in the evaluation of the amount of outgas generated, a substrate having a cured resin layer with a film thickness of 10 μm on a copper foil was produced, and a sputtering apparatus was formed on the resin layer of this substrate. After forming a seed metal layer of Ti 50 nm and Cu 200 nm using, a metal layer for wiring was formed in a solid shape to a thickness of 20 μm by electrolytic copper plating, and an evaluation substrate was produced.
Evaluation Method For the obtained evaluation substrate, the formed wiring metal layer was cut into a width of 1 cm and peeled off at an angle of 90 ° to measure the adhesion (based on JIS C6481) and evaluated.
(Pot life)
The viscosity immediately after the preparation of the composition is defined as the initial viscosity, and the time during which the composition viscosity is twice the initial viscosity is defined as the pot life (pot life), and the resin composition according to the examples and comparative examples is used for the pot. Life was measured and evaluated. The evaluation criteria are as follows. The viscosity was measured at 25 ± 1 ° C. using an E-type viscometer.
○: Pot life is 24 hours or more ×: Pot life is less than 24 hours (breaking strength)
Preparation of Evaluation Substrate An evaluation substrate having a cured resin layer with a thickness of 10 μm on a copper foil was prepared in the same manner as the preparation of the substrate used in the evaluation of the amount of outgas generated.
Evaluation method About the obtained evaluation board | substrate, the cured resin layer was peeled as a test piece, and breaking strength was measured and evaluated about this test piece based on JISK7127. The evaluation criteria are as follows.
◎: 80 MPa or more ○: 40 MPa or more, less than 80 MPa Δ: less than 40 MPa

These evaluation results are also shown in Tables 1 to 4.
As is apparent from the results shown in Tables 1 to 4, all the components in the composition are compatible with each other at room temperature (less than 5 μm). It was found that it can be formed. Moreover, a thin film resin layer made of the resin composition of this example is formed at 200 ° C.
Even when placed in a high temperature environment, it has been found that outgassing is suppressed, and therefore, the adhesion between the thin film resin layer and the wiring is excellent.

Claims (8)

(A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an unsaturated double bond, (D) a thermosetting resin, and (E) a thermosetting having a melting point of 60 ° C. or lower. A curable resin composition comprising an accelerator and (F) a solvent, wherein all components in the composition are compatible with each other at room temperature. The blending amount of the (E) thermosetting accelerator is 0.1 to 1.5% by mass with respect to the total amount of the (A) alkali-soluble resin and the (D) thermosetting resin. The curable resin composition according to claim 1. The curable resin composition according to claim 1 or 2, wherein the (A) alkali-soluble resin contains an amide-imide resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group. .

The curable resin composition according to any one of claims 1 to 3, wherein the (D) thermosetting resin is an epoxy resin having an alicyclic skeleton. The curable resin composition according to any one of claims 1 to 4, which is used for forming a pattern cured product having a thickness of 10 µm or less. A dry film comprising a resin layer formed by applying and drying the curable resin composition according to any one of claims 1 to 5 on a film. Hardened | cured material formed by hardening | curing the resin layer of the curable resin composition as described in any one of Claims 1-5, or the dry film of Claim 6. An electronic component comprising the cured product according to claim 7.