Resin composition, solder resist, interlayer insulating material, dry film, cured product, and method for producing the cured product

Abstract

To provide a resin composition which achieves both stability and thermosetting property at the time of drying and storage, and is also excellent in adhesion, a solder resist, an interlayer insulation material, a dry film, and a cured product.SOLUTION: A resin composition contains (A) an alkali-soluble resin, (B) a thermosetting resin, and (C) a microcapsule type curing agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a solder resist, an interlayer insulating material, a dry film, a cured product, and a method for producing the cured product. [Background technology]

[0002] In printed wiring boards, solder resist is used as an insulating protective film for circuits. Conventionally, screen printing and photoresist have been known as methods for forming the solder resist pattern, but in recent years, photoresist has become the primary method in view of the increasing density and miniaturization of circuits on printed wiring boards.

[0003] Among these, solder resist is widely used, which forms a pattern through an exposure process using ultraviolet light and a development process using a developer, and then hardens by applying heat.In addition, due to environmental considerations, alkaline development using a dilute alkaline aqueous solution is the mainstream method for development.

[0004] Examples of alkali development type solder resists include solder resists using photosensitive resin compositions disclosed in Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2018-36574 [Patent Document 2] Patent No. 6817371 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the circuits of printed wiring boards have become increasingly dense and fine, increasing the need for more precise pattern formation. Generally, the above-mentioned alkali development type solder resist contains a thermosetting component and a thermosetting agent. However, if the thermosetting component reacts before being thermally cured after patterning, the curing will progress to the unexposed areas, causing defective pattern formation. Furthermore, if the alkali development type solder resist is a film type, there is a problem that poor adhesion will occur, causing defective lamination. In view of these problems, there is a demand for improving the stability during drying and the storage stability of the film, for example, by controlling the heating conditions in the process of applying and drying a liquid solder resist to a printed wiring board or in the drying process of removing the solvent in the dry film manufacturing process, and by preventing the reaction of the thermosetting component from progressing in the dried film until it is exposed to light. On the other hand, if the thermosetting property of the liquid solder resist is reduced in order to improve the stability during drying and storage as described above, poor curing during main curing and reduced adhesive strength to circuit components are likely to occur, making the liquid solder resist unreliable as a permanent protective film.

[0007] The solder resists disclosed in Patent Documents 1 and 2 have the above-mentioned problem that there is room for improvement in terms of achieving both stability during drying and storage and thermosetting properties.

[0008] In view of the above-mentioned problems of the conventional art, the present invention aims to provide a resin composition, a solder resist, an interlayer insulating material, a dry film, and a cured product that have both stability during drying and storage and thermosetting property, and also have excellent adhesive properties. [Means for solving the problem]

[0009] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned objects can be achieved by the following technical means, and have thus completed the present invention. That is, the present invention is as follows.

[0010] [1] (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, The alkali-soluble resin (A) has an aromatic ring in its main chain skeleton. Resin composition. [2] (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, The (C) microcapsule-type curing agent contains a reactive diluent. Resin composition. [3] (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, the alkali-soluble resin (A) has an aromatic ring in its main chain skeleton, The (C) microcapsule-type curing agent contains a reactive diluent. Resin composition. [4] The resin composition according to [2] or [3] above, wherein the reactive diluent has a monocyclic aromatic ring and is a monofunctional epoxy compound. 〔5〕 (D) a photopolymerization initiator; (E) a photosensitive monomer, Further including the above [1] to [ 4 ] The resin composition according to any one of the preceding items. [ 6 〕 The alkali-soluble resin (A) is a resin having a carboxy group, 5 ] The resin composition according to any one of the preceding items. [ 7 〕 The alkali-soluble resin (A) further has a reactive group other than a carboxy group, 6 ] The resin composition according to any one of the preceding items. [ 8 〕 The reactive group contains an ethylenically unsaturated double bond. 7The resin composition according to claim 1. [ 9 〕 The reactive group includes a (meth)acrylic group. 8 The resin composition according to claim 1.

[10] (F) The resin composition according to any one of [1] to [9], further comprising dicyandiamide.

[11] (G) The resin composition according to any one of [1] to

[10] above, further comprising a thermoplastic resin.

[12] (H) The resin composition according to any one of [1] to

[11] above, further comprising an adhesion aid.

[13] A solder resist comprising the resin composition according to any one of [1] to

[12] above.

[14] An interlayer insulating material comprising the resin composition according to any one of [1] to

[12] above.

[15] A support; a resin layer formed on the support; and The resin layer contains the resin composition according to any one of [1] to

[12] . Dry film.

[16] A cured product of the resin composition according to any one of [1] to

[12] above or the dry film according to

[15] above.

[17] a resin layer forming step of forming the resin composition according to any one of [1] to

[12] on a support; a photocuring step of exposing the resin layer to ultraviolet light and curing the exposed portion; a pattern formation step of developing the unexposed portion in the exposure step to form a pattern; a thermal curing step of heating after the pattern forming step; A method for producing a cured product comprising the steps of:

[18]

[18] The method for producing a cured product according to

[17] above, wherein the dry film according to

[15] above is transferred onto a support in the resin layer forming step. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition, a solder resist, an interlayer insulating material, a dry film, and a cured product that have both stability during drying and storage and thermosetting properties, and also have excellent adhesive properties. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0013] [Resin composition] The resin composition of the present embodiment is Component (A): an alkali-soluble resin having a carboxy group; Component (B): a thermosetting resin; Component (C): a microcapsule-type curing agent, Includes. According to this embodiment, a resin composition can be obtained which has both stability during drying and storage, thermosetting properties, and excellent adhesive properties.

[0014] (Component (A): alkali-soluble resin) The resin composition of the present embodiment contains an alkali-soluble resin (hereinafter, sometimes referred to as component (A)). As component (A), various known alkali-soluble resins can be used. In particular, alkali-soluble resins having a heteroatom in the substituent are preferred, and from the viewpoint of developability, alkali-soluble resins having a hydroxyl group or a carboxy group are preferred, and from the viewpoints of resolution and low contamination of the developer, alkali-soluble resins having a carboxy group are more preferred, and in particular, alkali-soluble resins further having a carboxy group and a reactive group other than a carboxy group are preferred from the viewpoints of heat resistance and strength of the cured product. The reactive group other than the carboxy group preferably has an ethylenically unsaturated double bond, which allows the reactive group to react with the photosensitive monomer (component (E)) described below to form a cured product with higher strength. The ethylenically unsaturated double bond is preferably derived from (meth)acrylic acid or a derivative thereof, that is, the reactive group preferably contains a (meth)acrylic group, from the viewpoint of good reactivity with the photosensitive monomer, component (E). (A) Alkali-soluble resins include, but are not limited to, the compounds (which may be either oligomers or polymers) shown in the following (1) to (13).

[0015] (1): Water-soluble vinyl polymers containing hydroxyl groups. Commercially available products include, but are not limited to, the Kuraray Poval PVA series (manufactured by Kuraray Co., Ltd.).

[0016] (2): Examples include carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene.

[0017] (3): Examples include carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. When this carboxyl group-containing urethane resin is used as component (A), it is preferable that the main chain skeleton has an aromatic ring from the viewpoint of mechanical strength. In such a case, at least one of the diisocyanate, the carboxyl group-containing dialcohol compound, and the diol compound may have an aromatic ring.

[0018] (4) Examples include carboxyl group-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanate with (meth)acrylates of bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins, or their partially acid anhydride-modified products, and carboxyl group-containing dialcohol compounds and diol compounds.

[0019] (5): A carboxyl group-containing photosensitive urethane resin that is (meth)acrylated at the terminal by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin (3) or (4).

[0020] (6): Examples include carboxyl group-containing photosensitive urethane resins that are (meth)acrylated at the terminal by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (3) or (4).

[0021] (7) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl group present in the side chain.

[0022] (8) A carboxyl group-containing photosensitive resin is obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0023] (9) Examples include carboxyl group-containing polyester resins obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0024] (10): Examples of carboxyl group-containing resins include those obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl groups of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

[0025] (11): Examples include carboxyl group-containing photosensitive resins obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, and then reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0026] (12) A carboxyl group-containing photosensitive resin is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, which is then reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product, and then reacting the reaction product with a polybasic acid anhydride.

[0027] (13): A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (12) above.

[0028] In this specification, (meth)acrylate is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

[0029] The alkali-soluble resin (A) may be used alone or in combination of two or more. Among these, the alkali-soluble resins synthesized using the phenolic compounds described in (11) and (12) as starting materials are preferably used because the resins have excellent film adhesiveness and film formability due to increased mechanical strength due to the aromatic rings in the polymer main chain skeleton.

[0030] The acid value of the alkali-soluble resin (A) is preferably 20 to 200 mgKOH / g. From the viewpoint of sufficient alkali developability and prevention of dissolution of exposed areas, the acid value of the alkali-soluble resin (A) is preferably 20 to 200 mgKOH / g, more preferably 35 to 175 mgKOH / g, and even more preferably 50 to 150 mgKOH / g.

[0031] The weight average molecular weight of the alkali-soluble resin (A) varies depending on the resin skeleton, but is generally 2,000 to 150,000, preferably 3,000 to 120,000, and more preferably 5,000 to 100,000. When the weight-average molecular weight is 2,000 or more, the development resistance of the coating in the exposed area is improved and the resolution is excellent. On the other hand, when the weight-average molecular weight is 150,000 or less, the solubility of the unexposed area is good, the resolution is excellent, and storage stability also tends to be improved. The weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0032] The content of the alkali-soluble resin (A) in the resin composition of this embodiment is preferably 5 to 90% by mass, more preferably 7.5 to 85% by mass, and even more preferably 10 to 80% by mass, based on the total amount of the resin composition excluding the solvent. By adjusting the content to 5% by mass or more, preferably 10% by mass or more, the coating strength can be improved. Furthermore, by adjusting the content to 90% by mass or less, more preferably 80% by mass or less, the viscosity becomes appropriate, improving processability and providing sufficient resolution.

[0033] (Component (B): Thermosetting resin) The resin composition of the present embodiment contains a thermosetting resin (hereinafter, sometimes referred to as component (B)). There are no particular limitations on the component (B) as long as it is a thermosetting resin, and examples thereof include epoxy resins and oxetane compounds.

[0034] Examples of epoxy resins include, but are not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AC type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, tetrabromobiphenyl type epoxy resins, diphenyl ether type epoxy resins, benzophenone type epoxy resins, phenyl benzoate type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl sulfoxide type epoxy resins, diphenyl sulfone type epoxy resins, diphenyl disulfide type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, hydroquinone type epoxy resins, methylhydroquinone type epoxy resins, djibutane type epoxy resins, Examples of suitable epoxy resins include bifunctional epoxy resins such as perhydroquinone-type epoxy resins, resorcinol-type epoxy resins, methylresorcinol-type epoxy resins, and catechol-type epoxy resins; trifunctional epoxy resins such as N,N-diglycidylaminobenzene-type epoxy resins and triazine-type epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins and diaminobenzene-type epoxy resins; multifunctional epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, triphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthol aralkyl-type epoxy resins, and brominated phenol novolac-type epoxy resins; alicyclic epoxy resins; and epoxy resins modified with isocyanates or the like. These may be used alone or in combination of two or more.

[0035] The oxetane compound may be any compound having an oxetane ring, and is not limited to the following. Examples include 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., product name OXT-101), 3-ethyl-3-(phenoxymethyl)oxetane (manufactured by Toagosei Co., Ltd., product name OXT-211), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (manufactured by Toagosei Co., Ltd., product name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (manufactured by Toagosei Co., Ltd., product name OXT-121), and bis(3-ethyl-3-oxetanylmethyl)ether (manufactured by Toagosei Co., Ltd., product name OXT-221). Further examples include phenol novolac-type oxetane compounds. These compounds may be used alone or in combination of two or more. These oxetane compounds may be used in combination with the above-mentioned epoxy resins, or may be used alone.

[0036] Among these, bisphenol A type epoxy resins, heterocyclic epoxy resins, and mixtures thereof are preferred because of their excellent resistance to discoloration.

[0037] The content of the (B) thermosetting resin in the resin composition of this embodiment is preferably 3% by mass or more and 50% by mass or less, based on the total amount of the resin composition excluding the solvent. By making the content 3% by mass or more, storage stability in the film state is ensured, and properties such as adhesion between the cured product and the substrate, heat resistance, alkali resistance, and electrical insulation tend to be improved. By making the content 50% by mass or less, the amount of low-molecular-weight cyclic ether groups remaining in the dried coating film is small, and developability tends to be good. The content of the component (B) is more preferably 5 to 40 mass %, and even more preferably 10 to 30 mass %.

[0038] (Component (C): Microcapsule-type hardener) The resin composition of the present embodiment contains a microcapsule-type curing agent (hereinafter, sometimes referred to as component (C)). From the viewpoint of solvent resistance, (C) the microcapsule-type curing agent is preferably one containing the later-described (C1) reactive diluent as a constituent element. Here, the microcapsule-type curing agent is a curing agent having at least a core containing a curing agent component and a shell covering the core, and also includes a masterbatch-type curing agent containing an epoxy resin. Furthermore, the phrase "containing a reactive diluent as a component" means that the reactive diluent is contained in at least one component of the epoxy resin, such as the core or shell, which are components of the microcapsule-type curing agent, or, in the case of a masterbatch-type curing agent, the dispersed component. From the standpoint of resistance to water and organic solvents in particular, it is preferable that the reactive diluent is contained in at least the shell. This suppresses elution of the core component in the medium temperature range, improving application in film form, and allows the core component to diffuse in the high-temperature range, i.e., in a high-fluidity environment, resulting in a highly uniform cured product.

[0039] Since component (C) is in microcapsule form, the resin composition of this embodiment has excellent stability when dried and during storage, and since the core can contain a highly reactive component, it is possible to achieve both stability and thermosetting properties.

[0040] The core constituting the (C) microcapsule-type curing agent may be any curing agent used to cure the (B) thermosetting resin, and is not particularly limited. Examples include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, catalyst-based curing agents, and modified products thereof. These may be used alone or in combination of two or more. From the viewpoint of storage stability, amine adducts are preferred among amine-based curing agents.

[0041] The particle size of the core constituting the (C) microcapsule-type curing agent is, in terms of the average particle size defined as the median diameter, preferably more than 0.3 μm and not more than 12 μm, more preferably 1.0 μm or more and 10 μm or less, and even more preferably 1.5 μm or more and 5.0 μm or less. Here, the average particle size refers to the Stokes diameter measured by laser diffraction / light scattering. An average particle size of 12 μm or less tends to make it possible to obtain a homogeneous cured product, while a particle size of more than 0.3 μm tends to make it possible to suppress aggregation between particles.

[0042] (C) The shell that constitutes the microcapsule-type curing agent has a wavenumber of 1630 to 1680 cm -1 and a bonding group that absorbs infrared radiation at wavenumbers of 1680 to 1725 cm -1 and a bonding group that absorbs infrared radiation at wavenumbers of 1730 to 1755 cm -1 and a bonding group capable of absorbing infrared rays, at least on the surface. This tends to reduce the rate of aggregation of curing agent particles, and to provide a resin composition excellent in thermosetting property and storage stability.

[0043] When the (C) microcapsule-type curing agent is a masterbatch type, any known epoxy resin can be appropriately used as the dispersed epoxy resin, and examples thereof include the epoxy resins exemplified above as the (B) thermosetting resin.

[0044] ((C1) Reactive diluent) From the viewpoint of solvent resistance, component (C), the microcapsule-type curing agent, preferably contains (C1), a reactive diluent, which is a compound having a reactive functional group that can be incorporated into the cured structure, such as an epoxy group.

[0045] (C1) The reactive diluent is not limited to the following, but examples thereof include epoxy compounds that can reduce viscosity without impairing reactivity. In this specification, the term (C1) reactive diluent refers to a compound that excludes the epoxy resins exemplified above as the (B) thermosetting resin and has a viscosity at 25°C of 1 mPa·s or more and less than 3 Pa·s. In the resin composition of the present embodiment, the reactive diluent (C1) is preferably an epoxy compound, from the viewpoint of its compatibility with the thermosetting resin (B) and its incorporation into the cured structure after the thermosetting reaction.

[0046] The epoxy compound used as the (C1) reactive diluent is not limited to the following, but examples thereof include the following epoxy compounds having no aromatic ring and epoxy compounds having an aromatic ring.

[0047] Examples of monofunctional epoxy compounds having no aromatic ring include compounds such as n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether. Examples of monofunctional epoxy compounds having an aromatic ring include styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, and compounds such as SY-OPG (trade name) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. Examples of bifunctional epoxy compounds having no aromatic ring include 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, vinylcyclohexene dioxide, and compounds such as Mitsubishi Chemical Corporation (trade name: YX-8000) and Sakamoto Yakuhin Kogyo Co., Ltd. (trade name: SR-8EGS). Examples of bifunctional epoxy compounds having one or more aromatic rings include hexahydrophthalic acid diglycidyl ether, resorcinol diglycidyl ether, tert-butylhydroquinone diglycidyl ether, diglycidyl ether of polyoxyalkylene bisphenol A, N,N-diglycidylaniline, and N,N-diglycidyl-o-toluidine. Examples of trifunctional epoxy compounds include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline.

[0048] In the resin composition of this embodiment, the reactive diluent (C1) preferably has an aromatic ring from the viewpoint of enhancing solvent resistance, and more preferably the reactive diluent (C1) is an epoxy compound having the aromatic ring, the aromatic ring being monocyclic and monofunctional, from the viewpoint of further enhancing the solvent resistance of the microcapsule-type curing agent (C). Furthermore, it is even more preferable that the monofunctional group is an epoxy group, from the viewpoint of exhibiting sufficient mechanical strength by being incorporated into the cured product after the reaction. Furthermore, it is more preferable that the number of carbon atoms in each substituent on the aromatic ring is 3 or less from the viewpoint of improving penetration into the capsule membrane and solvent resistance, which will be described later.

[0049] The mechanism by which the reactive diluent (C1) has a monocyclic aromatic ring and is a monofunctional epoxy compound as described above improves solvent resistance is thought to be as follows, although it is not intended to be limiting. When the reactive diluent (C1) has an aromatic ring, the aromatic rings of the reactive diluent incorporated into the shell exhibit a stacking effect to form a network, which increases the cohesive strength of the shell. This allows for the construction of a shell that is resistant to swelling in solvents, thereby improving the solvent resistance of the microcapsule-type curing agent (C). Furthermore, the reactive diluent (C1) has a monocyclic and monofunctional aromatic ring, which reduces steric hindrance, allowing it to easily penetrate into the shell and form a denser, wider stacking network of aromatic rings. Here, each substituent on the aromatic ring has 3 or less carbon atoms, which further reduces steric hindrance, enhances penetration into the shell, and further improves solvent resistance. The above-mentioned mechanism significantly improves solvent resistance compared to conventional microcapsule-type curing agents that do not contain reactive diluents. Furthermore, the number of applicable solvents increases, broadening the range of materials available for the resin composition, such as component (A) or component (B) and the thermoplastic resin (F) described below, making it easier to impart desired physical properties to the resin composition.

[0050] (C) Commercially available products can also be used as the microcapsule-type curing agent. Examples of commercially available products that contain a reactive diluent include, but are not limited to, Novacure LSA-H2104 (manufactured by Asahi Kasei Corporation, containing phenyl glycidyl ether as a reactive diluent). Furthermore, Novacure series products (manufactured by Asahi Kasei Corporation), such as Novacure HX-3742, HX-3088, HXA3792, HXA9322HP, and HXA9382HP, which do not contain a reactive diluent, can also be used. Microcapsule-type curing agents containing a reactive diluent made using these products are also included in the present invention.

[0051] When the microcapsule-type curing agent (C) is a masterbatch, the content of the reactive diluent (C1) in the microcapsule-type curing agent (C) is preferably 3% by mass or more, more preferably 4% by mass or more, even more preferably 5% by mass or more, and even more preferably 6% by mass or more in order to provide sufficient solvent resistance. Furthermore, the content is preferably 15% by mass or less, more preferably 13% by mass or less, even more preferably 12% by mass or less, and even more preferably 11% by mass or less in order to prevent excessive viscosity reduction, deterioration of storage stability, and reduction in mechanical strength of the cured product. When the reactive diluent (C1) is added during the production of the resin composition of this embodiment, the content of the reactive diluent (C1) based on the total amount of the resin composition excluding the solvent is preferably 0.005% by mass or more from the viewpoint of imparting solvent resistance, and is preferably 2% by mass or less, more preferably 1% by mass or less from the viewpoint of storage stability.

[0052] In the resin composition of this embodiment, the content of component (C) is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, and even more preferably 0.05 mass% or more, based on the total amount of the resin composition excluding the solvent, from the viewpoint of curability. Also, from the viewpoint of coating film uniformity, it is preferably 14 mass% or less, more preferably 13 mass% or less, and even more preferably 12 mass% or less.

[0053] The microcapsule-type curing agent (C) described above also functions as a curing accelerator when used in combination with the other curing agents (F) described below. That is, it complements the curing effect of the other curing agents (F) and allows the resin composition of this embodiment to exhibit better thermosetting properties.

[0054] (Component (D) Photopolymerization initiator) The resin composition of the present embodiment may contain (D) a photopolymerization initiator (hereinafter sometimes referred to as component (D)). When the epoxy resin composition of the present embodiment contains component (D), the resin composition of the present embodiment can be photocured.

[0055] The component (D) is not particularly limited as long as it generates an active species such as an acid, a base, or a radical upon irradiation with light. Examples of the component (D) include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis-(2,6-dimethoxybenzoyl). )-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan Ltd., IRGACURE 819), and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Ltd., CAROCUR Monoacylphosphine oxides such as TPO; hydroxyacetophenones such as 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers;Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (BASF Japan Ltd., IRGACURE369), 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone;

[0056] Examples of the component (D) include thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; and anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone. Nons; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzoic acid esters such as ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (BASF Japan Ltd., IRGACURE OXE-02); titanocenes such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. These may be used alone or in combination of two or more.

[0057] As the (D) photopolymerization initiator, acylphosphine oxide-based photopolymerization initiators such as bisacylphosphine oxides and monoacylphosphine oxides, acetophenones, and oxime esters are preferred because they have excellent deep curing properties and surface curing properties.

[0058] The content of the (D) photopolymerization initiator in the resin composition of this embodiment is preferably 0.01 to 30 parts by mass, calculated as solid content, per 100 parts by mass of the (A) alkali-soluble resin. By incorporating the (D) photopolymerization initiator in this range, the resin composition of this embodiment exhibits sufficient photocurability on copper and also improves resolution. The content is more preferably 0.05 to 20 parts by mass, and even more preferably 0.1 to 10 parts by mass.

[0059] (Component (E): Photosensitive monomer) The resin composition of the present embodiment may further contain (E) a photosensitive monomer (hereinafter sometimes referred to as component (E)). By including the photosensitive monomer (E) in the epoxy resin composition of the present embodiment, it is possible to improve the photocurability without reducing the dryness to touch.

[0060] As the (E) photosensitive monomer, any known monomer having a photopolymerizable functional group can be used as appropriate, and various (meth)acrylate compounds are preferably used. Examples of the (E) photosensitive monomer include, but are not limited to, di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric (meth)acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or ethylene oxide adducts or propylene oxide adducts thereof; polyhydric (meth)acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Examples of the epoxy (meth)acrylate compound include acrylates; polyhydric (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylates; epoxy (meth)acrylate resins obtained by reacting a polyfunctional epoxy resin such as a cresol novolac epoxy resin with (meth)acrylic acid; and epoxy urethane (meth)acrylate compounds obtained by reacting a half urethane compound of a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate with the hydroxyl group of an epoxy (meth)acrylate resin. These may be used alone or in combination of two or more.

[0061] The content of the (E) photosensitive monomer in the resin composition of this embodiment is preferably 5 to 100 parts by mass, more preferably 7.5 to 85 parts by mass, and even more preferably 10 to 70 parts by mass, relative to 100 parts by mass of the (A) alkali-soluble resin, calculated as solid content. When the content of the (E) photosensitive monomer is within this range, the photocurability of the resulting resin composition can be prevented from decreasing, and a normal resist pattern can be easily formed by alkaline development after irradiation with active energy rays. Furthermore, the solubility in an alkaline aqueous solution can be prevented from decreasing, and the cured coating film can be prevented from becoming brittle. Furthermore, contamination of the developer during the development step can be further prevented.

[0062] (Component (F): Other hardeners) The resin composition of this embodiment may further contain (F) another curing agent (hereinafter sometimes referred to as component (F)). Component (F) is a component excluding the above-mentioned components (A) to (E) and the later-described components (G) to (H). By including component (F) in the resin composition of this embodiment, it becomes possible to impart various functions derived from the curing agent to the cured product. Component (F) is not particularly limited, and examples thereof include amine compounds, acid anhydrides, phenolic hydroxyl group-containing compounds, amide compounds, and carboxylic acid compounds.

[0063] Examples of the amine compound include, but are not limited to, aliphatic amine compounds such as trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, and dimethylaminohexanol.

[0064] Examples of the amine compound include alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N',N"-tris(dimethylaminopropyl)hexachloro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N'-dimethylpiperazine, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU).

[0065] Furthermore, examples of the amine compound include aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylylenediamine, pyridine, picoline, α-methylbenzylmethylamine, and imidazole.

[0066] Furthermore, examples of the amine compound include modified amine compounds such as epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, amine imides, boron trifluoride-piperidine complexes, and boron trifluoride-monoethylamine complexes.

[0067] Examples of the acid anhydride include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0068] Examples of the phenolic hydroxyl group-containing compound include, but are not limited to, polyhydric phenol compounds such as phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol adduct resin, phenol aralkyl resin (Xyloc resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked via bismethylene groups), and alkoxy group-containing aromatic ring-modified novolac resin (a polyhydric phenol compound in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0069] The amide-based compound is not limited to the following, but examples thereof include dicyandiamide and polyamidoamine. Examples of the polyamidoamine include those obtained by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0070] The carboxylic acid compound is not limited to the following, but examples thereof include carboxylic acid compounds such as carboxylic acid-terminated polyesters and maleic acid-modified polypropylene glycol.

[0071] These (F) other curing agents may be used alone or in combination of two or more. Component (F) is preferably an amine compound, and dicyandiamide is particularly preferred from the viewpoints of workability, curability, and long-term stability.

[0072] In the resin composition of this embodiment, the content of component (F) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the resin composition excluding the solvent, from the viewpoint of curability. Also, from the viewpoint of ensuring the stability of the film state, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0073] (Component (G): Thermoplastic resin) The resin composition of the present embodiment may further contain a (G) thermoplastic resin (hereinafter sometimes referred to as component (G)). By including the (G) thermoplastic resin in the resin composition of this embodiment, when the resin composition is cast or applied to a predetermined thickness on a printed wiring board and dried to form a coating film or a dry film, cracks and breaks can be prevented and the shape can be maintained.

[0074] (G) Thermoplastic resins include, but are not limited to, phenoxy resins, polyvinyl butyral resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyethersulfone resins, polyphenylene ether resins, polysulfone resins, and elastomers having functional groups such as carboxyl groups, hydroxyl groups, vinyl groups, and amino groups. These may be used alone or in combination of two or more. The thermoplastic resin used in the resin composition of the present embodiment is also called a film-forming polymer or a binder polymer.

[0075] As the (G) thermoplastic resin, a phenoxy resin is preferred because of its excellent long-term reliability. Here, "long-term reliability" refers to the fact that when applied as an insulating protective film for a printed wiring board, the desired insulating performance, adhesive performance, etc. do not easily deteriorate over time. Examples of phenoxy resins include, but are not limited to, bisphenol A phenoxy resins, bisphenol F phenoxy resins, bisphenol A-bisphenol F mixed phenoxy resins, bisphenol A-biphenyl mixed phenoxy resins, bisphenol A-bisphenol S mixed phenoxy resins, fluorene ring-containing phenoxy resins, and caprolactone-modified bisphenol A phenoxy resins.

[0076] The number average molecular weight of the (G) thermoplastic resin is preferably 9,000 or more and 23,000 or less, more preferably 9,500 or more and 21,000 or less, and even more preferably 10,000 or more and 20,000 or less. Here, the number average molecular weight is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC), and is the average value calculated for the range of polystyrene-equivalent molecular weights of 728 or more. By setting the number average molecular weight of the (G) thermoplastic resin to 9,000 or more, it is possible to prevent the (G) thermoplastic resin from slipping through the crosslinked structure of the cured product, and to prevent a decrease in the cohesive strength of the cured product, which is preferable because it prevents a decrease in long-term reliability. On the other hand, when the number average molecular weight is 23,000 or less, the resist film obtained from the resin composition of the present embodiment can maintain high adhesion to the printed wiring board as the adherend, and can suppress the occurrence of localized curing defects during adhesion, prevent the occurrence of corrosion of wiring and electrodes, and obtain high insulation reliability, which is preferable.

[0077] The content of the thermoplastic resin (G) in the resin composition of this embodiment, based on the total amount of the resin composition excluding the solvent, is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of preventing cracks after forming the resin composition of this embodiment into a film. Also, from the viewpoint of the handleability of the varnish and the ease of film production, it is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0078] (Component (H): Adhesion aid) The resin composition of the present embodiment may further contain (H) an adhesion aid (hereinafter, sometimes referred to as component (H)). As the adhesion aid, any known substance that has a polar functional group capable of forming a complex with a metal and that is incorporated into a curing system can be used. From the viewpoint of improving the physical properties of the cured product, such as heat resistance, guanamine and its derivatives, and melamine and its derivatives are particularly preferred.

[0079] The content of the adhesion aid (H) in the resin composition of this embodiment, based on the total amount of the resin composition excluding the solvent, is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, from the viewpoint of improving adhesiveness during thermal curing. Also, from the viewpoint of ensuring thermal stability in a film state, it is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0080] (solvent) The resin composition of the present embodiment may further contain a solvent. By containing a solvent, it becomes possible to prepare the resin composition and adjust its viscosity and coatability. The solvent is not particularly limited, and known solvents can be used. Examples of the solvent include, but are not limited to, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, octane, and decane; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether. Examples of suitable solvents include glycol ethers such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, and propylene carbonate; alcohols such as methanol, ethanol, isopropanol, and n-butanol; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and petroleum solvents such as petroleum ether, petroleum naphtha, mineral spirits, and solvent naphtha. These may be used alone or in combination of two or more.

[0081] The content of the solvent in the resin composition of the present embodiment is not particularly limited, and can be adjusted appropriately depending on the viscosity, solubility, film coatability, etc. of the resin used.

[0082] (Other additives) In addition to the above-described components (A) to (H), the resin composition of the present embodiment may further contain additives such as organic fillers, inorganic fillers, colorants, antifoaming agents, flow control agents, thickeners, release agents, wetting agents, flame retardants, surfactants, and resins, as needed.

[0083] The organic filler functions as a shock absorber, capable of mitigating stress generated by impact. Examples of organic fillers include, but are not limited to, organic fine particles of acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), silicone-modified resin, and copolymers containing these as components. From the viewpoint of improving adhesiveness, preferred organic microparticles include, for example, alkyl (meth)acrylate-butadiene-styrene copolymer, alkyl (meth)acrylate-silicone copolymer, silicone-(meth)acrylic copolymer, a complex of silicone and (meth)acrylic acid, a complex of alkyl (meth)acrylate-butadiene-styrene and silicone, and a complex of alkyl (meth)acrylate and silicone. The organic filler may also be organic fine particles having a core-shell structure, with the core and shell layers having different compositions. Examples of core-shell organic fine particles include particles having a silicone-acrylic rubber core to which an acrylic resin is grafted, and particles having an acrylic resin grafted to an acrylic copolymer. These organic fillers may be used alone or in combination of two or more.

[0084] The inorganic filler can improve the physical strength of the resin composition of this embodiment, and therefore the printed wiring board has excellent long-term reliability. Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, zinc oxide, zirconium oxide, antimony oxide, aluminum oxide (alumina), fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate, zinc sulfide, and calcium sulfate; sulfites such as calcium sulfite; titanates such as potassium titanate and lead titanate; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. Among these, for example, titanium oxide is preferred as an inorganic filler contained in a resin composition applied to a light-emitting diode mounting substrate from the viewpoint of white appearance and reflectance. The shape of the inorganic filler is not particularly limited, and may be, for example, amorphous, spherical, or scaly, and there is no particular limit to whether the inorganic filler is surface-treated or not. These inorganic fillers may be used alone or in combination of two or more.

[0085] Examples of colorants include, but are not limited to, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, leucocrystal violet, carbon black, naphthalene black, and solvent blue. These colorants may be used alone or in combination of two or more.

[0086] Examples of the antifoaming agent include silicone-based antifoaming agents and non-silicone-based antifoaming agents. Examples of the silicone-based antifoaming agent include KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the non-silicone-based antifoaming agent include FOAMKILLER NSI-0.00 (manufactured by Aoki Oil & Fat Industries Co., Ltd.). These colorants may be used alone or in combination of two or more.

[0087] Examples of flow control agents include, but are not limited to, organic silane compounds such as silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-n-butoxide and zirconium tetraacetylacetonate.

[0088] Examples of thickeners include, but are not limited to, animal-based thickeners such as gelatin; plant-based thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylic thickeners, modified polyacrylic thickeners, polyether thickeners, urethane-modified polyether thickeners, and carboxymethyl cellulose.

[0089] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic release agents made of a copolymer of glycidyl (meth)acrylate and a linear alkyl (meth)acrylate ester having 16 to 22 carbon atoms.

[0090] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.

[0091] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0092] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzenesulfonates and alkylpolyoxyethylenesulfates, cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as alkyldimethylamine oxides and alkylcarboxybetaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

[0093] Examples of resins include, but are not limited to, polyester resin, polyurethane resin, acrylic resin, polyether resin, melamine resin, and modified epoxy resins such as urethane-modified epoxy resin, rubber-modified epoxy resin, and alkyd-modified epoxy resin.

[0094] In addition, for the purpose of imparting desired physical properties within a range that does not deviate from the effects of the present invention, antioxidants, thermal polymerization inhibitors, ultraviolet absorbers, antistatic agents, antiaging agents, antibacterial and antifungal agents, leveling agents, thixotropy-imparting agents, photoinitiator assistants, sensitizers, radical polymerization inhibitors, curing accelerators, surface treatment agents, dispersants, dispersion assistants, surface modifiers, stabilizers, fluorescent materials, and the like may be added.

[0095] [Method for producing resin composition] The resin composition of this embodiment can be obtained by mixing the above-mentioned components (A) to (C), and, if necessary, components (D) to (H), a solvent, other additives, and the like. The mixing method is not particularly limited, and the mixture can be obtained, for example, by thoroughly mixing the various components described above until they become uniform using a mixing roll such as a three-roll mill, a ball mill, or a sand mill, a dissolver, a planetary mixer, a kneader, an extruder, or the like.

[0096] [Use of resin composition] The resin composition of this embodiment is suitable for use in forming a solder resist and as an interlayer insulating material. A solder resist and an interlayer insulating material containing the resin composition of this embodiment have high stability when dried and during storage, and are excellent in curability and adhesiveness. The resin composition of the present embodiment may be used as is to form a solder resist or an interlayer insulating material, or may be used in a liquid form by adding a solvent or the like, or may be made into a dry film as described below.

[0097] [Dry film] The dry film of the present embodiment has a support and a resin layer formed on the support, and the resin layer contains the resin composition of the present embodiment. The dry film may have a protective layer on the surface of the resin layer opposite to the support, if necessary. By using the resin composition of this embodiment to form a dry film, the inclusion of dirt and dust can be suppressed, and a resist film with a uniform thickness can be easily formed on a printed wiring board using a laminator or the like.

[0098] (Support) The support is made of a material that does not change in quality or deform due to heat under the temperature conditions during the drying process of the organic solvent in the resin layer. Examples of such a support include, but are not limited to, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films may be stretched as required.

[0099] (protective layer) The protective layer is preferably made of a material capable of sufficiently maintaining the smoothness of the surface of the resin layer, and examples of such a protective layer include, but are not limited to, polyethylene film, polypropylene film, polyethylene terephthalate film treated for easy peeling, and oriented polypropylene film.

[0100] [Method for manufacturing dry film] The dry film of this embodiment can be produced by sequentially laminating a support, a resin layer, and, if necessary, a protective layer. As a method for laminating the support, the resin layer, and the protective layer, a known method can be adopted. For example, the resin composition of the present embodiment is first prepared and applied to a support in a uniform thickness using a known method such as an applicator or a bar coater, followed by drying to form a resin composition layer on the support. Subsequently, if necessary, a protective layer is laminated on the formed resin composition layer, thereby producing a dry film.

[0101] The drying method for obtaining a dry film is not particularly limited, and may involve heating in an oven or the like, or hot air blowing, etc. The drying temperature may be constant or may involve a temperature gradient, for example, at a temperature of 50 to 180°C for 1 to 30 minutes. From the viewpoint of exhibiting excellent film storage stability, the drying temperature is preferably 150°C or less, and the drying time at a high temperature range of 120 to 180°C is preferably 10 minutes or less, and more preferably 5 minutes or less. Furthermore, when drying a solvent with a boiling point of 150°C or higher, vapor pressure can be utilized to dry the film at a medium temperature range of 80 to 120°C for 15 to 30 minutes. Drying at a medium temperature range is preferable to drying at a high temperature of 150°C or higher for a short period of time, from the viewpoint of superior stability of the dried film.

[0102] [Cured product and method for producing the cured product] The cured product of this embodiment is a cured product of the resin composition of this embodiment and the dry film of this embodiment. The cured product of this embodiment can be produced by curing the resin composition of this embodiment or the resin layer of the dry film. The method for producing a cured product includes a resin layer formation step of forming a resin composition on a support, a photocuring step of exposing the resin layer to ultraviolet light and curing the exposed areas, a pattern formation step of developing the unexposed areas in the exposure step to form a pattern, and a thermal curing step of heating after the pattern formation step. In the resin layer forming step, a dry film may be transferred onto a predetermined support.

[0103] Examples of the curing method include, but are not limited to, a photocuring method, a heat curing method, and a method using both photocuring and heat curing. From the viewpoint of facilitating the formation of a high-density, high-precision resist pattern, the method using both photocuring and heat curing is preferred. Specifically, the resin composition of this embodiment is applied to a printed wiring board, and the solvent is evaporated and dried to obtain a resin layer. Alternatively, in the case of a dry film, the resin layer is obtained by transferring the dry film to a predetermined support using a laminator or the like, and then the exposed portions are exposed to light to harden the exposed portions. Specifically, the exposed portions are selectively photocured by passing the exposed portions through a patterned photomask or by directly drawing a pattern using a laser direct exposure machine. Subsequently, the unexposed portions are developed with an alkaline aqueous solution to form a resist pattern. Further heating for thermal curing (post-cure) can form a cured product with excellent insulating properties, high adhesion, high strength, long-term reliability, and the like.

[0104] The exposure device used for the light irradiation is not particularly limited as long as it is a device that irradiates ultraviolet rays in the range of 350 to 450 nm, but for example, various mercury lamps such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and mercury short arc lamps, and direct imaging devices such as direct imaging devices that directly draw patterns with a laser based on computer CAD data may be used. The exposure dose for pattern formation varies depending on the film thickness, etc., but is generally 20 to 1000 mJ / cm. 2 , preferably 20 to 800 mJ / cm 2 The range may be:

[0105] The developing method is not limited to the following, but examples thereof include a dipping method, a shower method, a spray method, and a brush method. The developer is not limited to the following, but examples thereof include aqueous alkaline solutions of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, and the like.

[0106] The heat curing method is not particularly limited, and may be heating in an oven or the like, or may be using hot air blowing or a far-infrared oven. The curing temperature and time can be set appropriately depending on the composition of the resin composition used and the heating equipment. For example, in the case of using an oven or hot air blowing, the curing time is set at a temperature of 100 to 180°C for 30 to 90 minutes. [Example]

[0107] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. In the following, "parts" and "%" are by mass unless otherwise specified.

[0108] [Ingredients] The components (A) to (G) and solvent components used in the examples and comparative examples are shown in Tables 1 to 3 below. (Component (A): alkali-soluble resin) (A-1) 8KQ-2001 (manufactured by Taisei Fine Chemical Co., Ltd., main chain structure: acrylic polymer, reactive group: methacrylic group, acid value: 128, weight average molecular weight: 20,000, solid content: 66%) (A-2) CCR-1171H (manufactured by Nippon Kayaku Co., Ltd., main chain structure: cresol novolac, reactive group: acrylic group, acid value: 100, weight average molecular weight: 6500, solid content: 40%)

[0109] (Component (B): Thermosetting resin) jER828 (Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent: 186 g / eq)

[0110] (Component (C): Microcapsule-type hardener) (C-1) LSA-H2104 (Asahi Kasei Corporation, a microcapsule-type hardener masterbatch containing a solid core and phenyl glycidyl ether (10%) as a reactive diluent) (C-2) Curing agent of Example 1 described in Japanese Patent No. 5558118

[0111] (Component (D) Photopolymerization initiator) HCPK (1-hydroxycyclohexyl phenyl ketone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0112] (Component (E): Photosensitive monomer) DPHA (Fujifilm Wako Pure Chemical Industries, Ltd., dipentaerythritol hexaacrylate)

[0113] (Component (F): Other hardeners) 2E4MZ (manufactured by Shikoku Kasei Co., Ltd.) Dicyandiamide (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0114] (Component (G): Thermoplastic resin) PKHB (InChem, phenoxy resin, number average molecular weight of 14600 for polystyrene equivalent molecular weights of 728 or more)

[0115] (Component (H): Adhesion aid) Melamine (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0116] [Preparation of resin composition and production of dry film] Resin compositions were prepared by mixing the components (A) to (H) in the amounts shown in Examples 1 to 8 and Comparative Examples 1 to 4 in Tables 1 to 3 below. This resin composition was applied to a polyethylene terephthalate film (thickness: 50 μm) as a support so that the dry film thickness was 40 μm, and then heated and dried for 5 minutes in an oven preheated to 120° C. Thereafter, the surface opposite the support was protected with a polyethylene terephthalate film that had been treated to be easily peeled, to obtain a film-type epoxy resin composition. These were used as dry films of Examples 1 to 8 and Comparative Examples 1 to 4.

[0117] [Methods for measuring and evaluating characteristics] (Film storage stability) Using the resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2, film-type epoxy resin compositions were produced in the same manner as described above (production of resin compositions and dry films). Thereafter, the film-type epoxy resin composition was stored in an incubator at 25°C for 7 days. The FT-IR spectrum of the film-type epoxy resin composition before and after storage was measured using a Fourier transform infrared spectrophotometer (FT / IR-6600, manufactured by JASCO Corporation). The 2920cm methylene group-derived epoxy resin and phenoxy resin show no change in strength due to heat drying. -1 Based on the absorption P1 around 915 cm -1 The intensity ratio P2 / P1 to the nearby absorption P2 was compared before and after storage, and the epoxy consumption rate was calculated using the following formula. In the formula below, P10 and P20 are strengths after storage. Epoxy consumption rate = 100 - (P2 / P1) / (P20 / P10) x 100 The epoxy consumption rate after storage was evaluated according to the following criteria. Epoxy consumption rate <25% ◎ 25%≦Epoxy consumption rate<30% 〇 30%≦Epoxy consumption rate ×

[0118] (Film adhesion) Using the epoxy resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2, film-type epoxy resin compositions were produced in the same manner as described above (production of resin compositions and dry films). After peeling off the easily peelable polyethylene terephthalate film, a film-type epoxy resin composition cut to a width of 25 mm and a length of 5 mm was placed at a predetermined position on the copper plate, and another copper plate was placed on top of it and fixed in place, and the film-type epoxy resin composition was then left to stand in an oven at 60°C for 10 minutes, thereby adhering the film-type epoxy resin composition to the copper plate. After returning to room temperature, the polyethylene terephthalate film support was peeled off from the film-type epoxy resin composition, and the area of ​​the film-type epoxy resin composition stuck to the copper plate was evaluated. The ratio of the area of ​​the adhesive to the original area of ​​the copper plate was evaluated according to the following criteria. Area ratio < 90% × 90% or less area ratio 〇

[0119] (Adhesiveness) Using the epoxy resin compositions of Examples 3 to 8 and Comparative Example 2, film-type epoxy resin compositions were produced in the same manner as described above (production of resin compositions and dry films). Using the obtained film-type epoxy resin composition, test pieces were prepared in accordance with JIS K6850. The adherend used was a cold-rolled copper plate conforming to JIS C3141 and measuring 25 mm in width, 100 mm in length, and 1.6 mm in thickness. An uncured test piece, which was made by sandwiching a film-type epoxy resin composition between two copper plates, was placed in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Corporation, which has a stable internal temperature of 150°C, and heated for 1 hour to obtain a test piece for measuring shear adhesive strength. The mixture was left in a room temperature environment and cooled to room temperature. After cooling to room temperature, the maximum load at which the adhesive surface of the test piece breaks and the test piece separates was measured using a Shimadzu Corporation "AGX-5kNX" with a load cell of 5kN and a speed of 5mm / min. The maximum load at which the test piece separates is divided by the adhesive area to determine the shear adhesive strength.

[0120] [Examples 1 to Reference example 2], [Comparative Example 1] The components were mixed in the proportions shown in Table 1 below, and resin compositions and dry films were prepared by the methods described above. The properties of the prepared resin compositions were measured by the above-mentioned methods.

[0121] [Table 1]

[0122] As shown in Table 1, Examples 1 to 3 using a microcapsule-type curing agent Reference example It was found that Example 2 had good film storage stability and film adhesion compared to Comparative Example 1. In particular, Example 1, which used a microcapsule-type curing agent containing a reactive diluent, had a high film storage stability and film adhesion compared to Comparative Example 1. Reference example Compared to 2, it was found to have better film storage stability.

[0123] Example 3 , Reference Example 4, Example 5 ~8], [Comparative Example 2] The components were mixed in the proportions shown in Table 2 below, and resin compositions and dry films were prepared by the methods described above. The properties of the prepared resin compositions were measured by the above-mentioned methods.

[0124] [Table 2]

[0125] As shown in Table 2, even in the photocurable compounding systems containing the components (D) and (E), the results were similar to those in Examples 3 to 5, which used the microcapsule-type curing agent (C). Reference example It was found that Example 4 had good film storage stability and film adhesion compared to Comparative Example 2. In particular, Example 3, which used a microcapsule-type curing agent containing a reactive diluent, had a high film storage stability and film adhesion compared to Comparative Example 2. Reference example It was found that the film storage stability was superior to that of 4. From Examples 5 and 6, it was found that the above-mentioned tendency was not only observed for (A-1) but also for (A-2) component having an aromatic ring in the main chain skeleton, and furthermore, a significant increase in adhesive strength was confirmed. Furthermore, from Examples 7 and 8, it was found that by further adding dicyandiamide as component (F), it was possible to further improve adhesive strength while maintaining excellent storage stability and adhesiveness.

[0126] [Examples 5-6], [Comparative Examples 3-4] The components were blended in the proportions shown in Table 3 below, and resin compositions and dry films were prepared by the methods described above. After preparing the dry film, 250mJ / cm2 was applied to the coating. 2 The exposure was carried out. The exposure device used was the "HMW-201KB" (5kW ultra-high pressure mercury lamp) manufactured by Oak Manufacturing Co., Ltd. The properties of the prepared resin compositions after exposure were evaluated by the methods described above in (Film adhesion) and (Adhesion).

[0127] [Table 3]

[0128] As shown in Table 3 above, it was found that even in the films that had undergone the exposure process, Examples 5 and 6, which used a microcapsule-type curing agent, achieved both high levels of film attachability and adhesiveness. [Industrial Applicability]

[0129] The resin composition of the present invention has industrial applicability in applications such as various solder resist materials and dry films for forming resist patterns on printed wiring boards and the like.

Claims

1. (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, The alkali-soluble resin (A) has an aromatic ring in its main chain skeleton. Resin composition.

2. (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, The (C) microcapsule-type curing agent contains a reactive diluent. Resin composition.

3. (A) an alkali-soluble resin; (B) a thermosetting resin; (C) a microcapsule-type curing agent; Including, the alkali-soluble resin (A) has an aromatic ring in its main chain skeleton, The (C) microcapsule-type curing agent contains a reactive diluent. Resin composition.

4. the reactive diluent has a monocyclic aromatic ring and is a monofunctional epoxy compound; The resin composition according to claim 2 or 3.

5. (D) a photopolymerization initiator; (E) a photosensitive monomer, The resin composition according to claim 1 , further comprising:

6. The alkali-soluble resin (A) is a resin having a carboxy group. The resin composition according to any one of claims 1 to 5.

7. The alkali-soluble resin (A) further has a reactive group other than a carboxy group. The resin composition according to any one of claims 1 to 6.

8. the reactive group comprises an ethylenically unsaturated double bond; The resin composition according to claim 7.

9. The reactive group comprises a (meth)acrylic group. The resin composition according to claim 8.

10. (F) further containing dicyandiamide; The resin composition according to any one of claims 1 to 9.

11. (G) further containing a thermoplastic resin, The resin composition according to any one of claims 1 to 10.

12. (H) further containing an adhesion aid, The resin composition according to any one of claims 1 to 11.

13. A solder resist comprising the resin composition according to claim 1 .

14. An interlayer insulating material comprising the resin composition according to any one of claims 1 to 12.

15. A support; a resin layer formed on the support; and The resin layer contains the resin composition according to any one of claims 1 to 12. Dry film.

16. A cured product of the resin composition according to any one of claims 1 to 12 or the dry film according to claim 15.

17. a resin layer forming step of forming the resin composition according to any one of claims 1 to 12 on a support; a photocuring step of exposing the resin layer to ultraviolet light and curing the exposed portion; a pattern formation step of developing the unexposed portion in the exposure step to form a pattern; a thermal curing step of heating after the pattern forming step; A method for producing a cured product comprising the steps of:

18. In the resin layer forming step, the dry film according to claim 15 is transferred onto a support. A method for producing the cured product according to claim 17.

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