KR20230107571A - Curable resin composition and dry film - Google Patents

Abstract

[Problem] Provision of a curable resin composition excellent in cleaning removability even when attached to a mixing container or tool used in the manufacturing process of solder resist ink and dried.
[Solution] The curable resin composition according to the present invention is a curable resin composition containing (A) a curable resin, (B) a filler, and (C) an organic solvent, and has a length of 20 mm x formed using the curable resin composition. It is characterized in that a completely dry coating film measuring 20 mm in width x 7 μm in thickness begins to dissolve in propylene glycol monomethyl ether acetate as a cleaning solvent within 20 seconds from the start of immersion in the cleaning solvent.

Description

Curable resin composition and dry film

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition excellent in cleaning removability. Moreover, this invention relates also to the dry film using this curable resin composition.

In general, solder resist ink is an insulating ink for the purpose of preventing solder adhesion to parts other than necessary and protecting circuits when soldering components to printed wiring boards of electronic devices, and is used in liquid form or dry film form. A curable resin composition used as a solder resist ink is composed of a curable resin as a main raw material and an organic solvent, a filler, and the like (see Patent Document 1, for example).

By the way, in the process of manufacturing solder resist ink, mixing is performed in a kiln, preliminary dispersion is performed by a mixing stirrer such as a dissolver, planetary mixer, and butterfly mixer, and kneading with a kneading machine such as a three-axis roll mill, a bead mill, and a blender evenly distributed Since it is an important task to uniformly disperse powder in a high-viscosity liquid using these mixing stirrers and kneaders, various mechanisms have been developed and used (see Patent Document 2, for example).

Here, since the solder resist ink forms a pattern by a chemical reaction, it is important to clean the tools to be used in order to prevent the mixing of compounds that cause changes in properties (see Patent Document 3, for example). However, it is considered that cleaning and removal of the solder resist ink in which the curing reaction has progressed is more difficult than general paint ink.

Japanese Unexamined Patent Publication No. 1-141904 Japanese Unexamined Patent Publication No. 2014-147883 Japanese Patent Publication No. 2012-522068

It is preferable that the mixing container or tool used in the manufacturing process of the solder resist ink is easy to clean and remove the attached and dried solder resist ink for repeated use. It is because it becomes the manufacturing cost of solder resist ink if cleaning removal takes time. Therefore, an object of the present invention is to provide a curable resin composition excellent in cleaning removability even when attached to a mixing container or tool used in the manufacturing process of solder resist ink and dried. Moreover, the objective of this invention is providing the dry film using this curable resin composition.

As a result of intensive research, the inventors of the present invention have found that, by adjusting the dissolution start time of a completely dry coating film of 20 mm in length x 20 mm in width x 7 μm in thickness formed using a curable resin composition in a specific cleaning solvent, solder resist The inventors have found that a curable resin composition excellent in washing removability can be obtained even when attached to a mixing container or tool used in the ink manufacturing process and dried, thereby completing the present invention.

That is, the curable resin composition according to the present invention is a curable resin composition containing (A) curable resin, (B) filler, and (C) organic solvent,

The dissolution start time of the completely dry coating film of 20 mm in length x 20 mm in width x 7 μm in thickness formed using the curable resin composition in propylene glycol monomethyl ether acetate as a cleaning solvent is the start of immersion in the cleaning solvent It is characterized in that within 20 seconds from.

In the aspect of the present invention, it is preferable that the time to complete dissolution of the completely dry coating film is within 40 seconds from the start of immersion in the cleaning solvent.

In the aspect of this invention, it is preferable that content of propylene glycol monomethyl ether acetate is 20 mass % or more in the said curable resin composition.

In the aspect of this invention, it is preferable that content of the said (B) filler is 45 mass % or less in the said curable resin composition.

In the aspect of this invention, it is preferable that said (A) curable resin contains carboxyl group-containing resin.

In the aspect of this invention, it is preferable that the weight average molecular weight of the said carboxyl group-containing resin is 6000 or less.

In the aspect of this invention, it is preferable that the said curable resin contains two or more types of carboxyl group-containing resin.

In the aspect of the present invention, it is preferably used for formation of a solder resist layer.

In an aspect of the present invention, it is preferably used for forming an interlayer insulating layer.

A dry film according to another aspect of the present invention includes a first film and a resin layer composed of a dry coating film of a curable resin composition formed on the first film,

The curable resin composition contains (A) a curable resin, (B) a filler, and (C) an organic solvent;

The dissolution initiation time of the completely dry film of 20 mm in length x 20 mm in width x 7 μm in thickness obtained from the dry film in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent It is characterized by being

ADVANTAGE OF THE INVENTION According to this invention, even when it adheres to the mixing container or tool used in the manufacturing process of a solder resist ink, and it dries, it can provide the curable resin composition excellent in wash-removability. Moreover, according to this invention, the dry film using this curable resin composition can be provided.

1 is a schematic diagram of an apparatus used for measuring the dissolution start time and dissolution completion time of a completely dry coating film in Examples.

[Curable Resin Composition]

The curable resin composition according to the present invention contains (A) curable resin, (B) filler, and (C) organic solvent. The curable resin composition according to the present invention only needs to satisfy the following physical properties, and may further contain a photopolymerization initiator, a coloring agent, an antifoaming agent, a leveling agent, and other components. Moreover, the said curable resin may contain any 1 type of a thermosetting resin, a carboxyl group-containing resin, and a photopolymerizable monomer, or a combination of multiple types may be sufficient as it. The curable resin composition according to the present invention satisfies the following physical properties, so that it has excellent cleaning removability even when adhering to a blending cylinder or tool used in the manufacturing process of solder resist ink and drying. This is presumed to be because the cleaning removability (solubility in cleaning solvent) of the dried composition (completely dried coating film) is mainly reflected in the dissolution start time in cleaning solvent.

[Properties]

In the curable resin composition of the present invention, a completely dry coating film measuring 20 mm in length x 20 mm in width x 7 µm in thickness has an onset time of dissolution in propylene glycol monomethyl ether acetate as a cleaning solvent, from the start of immersion in the cleaning solvent to 20 Within seconds, preferably within 15 seconds, more preferably within 10 seconds, even more preferably within 9 seconds, and particularly preferably within 8 seconds.

Further, the time to complete dissolution of the completely dry coating film is preferably within 40 seconds from the start of immersion in the cleaning solvent, more preferably within 30 seconds, further preferably within 28 seconds, and particularly within 26 seconds. Preferably, it is most preferably within 25 seconds.

Regarding the formation of a completely dry coating film in the present invention, it is important that the contained solvent in the completely dry coating film is sufficiently volatilized. In this specification, the criterion for determining that the film is completely dry is a composition in a dry state prepared by heating at 80 ° C. for 3 hours, and room temperature (25 ° C.) It is assumed that the difference in volatilization rates between the compositions left under the condition is less than 10%. As a method for determining the difference in volatilization rate, the weight was measured using an electronic balance and calculated by the following formula (1). That is, it is determined that a completely dry coating film is formed when the above conditions are satisfied.

In the process of dissolving the completely dry coating film in the cleaning solvent, the smooth surface becomes uneven, and when the coating film is completely dissolved, the surface of the substrate is exposed. In the present invention, since the goal is to dissolve the surface of the coating film that is the most dry and difficult to clean, the criterion for dissolution is judged by the state of the surface of the coating film.

Hereinafter, each component constituting the curable resin composition according to the present invention is described.

[(A) curable resin]

Examples of the curable resin include a thermosetting resin that contributes to a thermosetting reaction by heating, a photocurable resin that contributes to a photocuring reaction by light irradiation, and a photocurable thermosetting resin that contributes to either reaction. The curable resin composition may contain only either one of the thermosetting resin and the photocurable resin, or may contain both.

The content of the curable resin is preferably 20 to 80% by mass, more preferably 25 to 75% by mass, still more preferably 50 to 70% by mass in terms of solid content in the curable resin composition. When content of curable resin is in the said range, a more excellent hardened|cured material can be obtained. Hereinafter, each curable resin is demonstrated.

[Thermosetting resin]

As the thermosetting resin, any known resin can be used. When the curable resin composition contains a thermosetting resin, the heat resistance of the cured coating film can be improved. Examples of the thermosetting resin include known and commonly used resins such as epoxy resins, isocyanate compounds, blocked isocyanate compounds, amino resins, polyfunctional oxetane compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, and episulfide resins. can be heard Among these, a preferable thermosetting resin is an epoxy resin. A thermosetting resin can be used individually by 1 type or in combination of 2 or more types.

Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, phenol novolak type epoxy resins, and cresol novolaks. type epoxy resins, bisphenol A novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and the like.

As commercially available epoxy resins, for example, jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Co., Ltd., YD-128, YDF-170, ZX-1059 manufactured by Nittetsu Chemical & Materials Co., Ltd. , ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Co., Ltd.

As the isocyanate compound, a polyisocyanate compound can be blended. As the polyisocyanate compound, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- aromatic polyisocyanates such as xylylene diisocyanate and 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; And the adduct form of the isocyanate compound mentioned above, the biuret form, the isocyanurate form, etc. are mentioned.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate blocking agent and the isocyanate compound which can react, the polyisocyanate compound etc. mentioned above are mentioned, for example. As an isocyanate blocking agent, it is a phenol type blocking agent, for example; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agent; mercaptan-based blocking agent; acid amide blocking agents; imide-based blocking agents; amine-based blocking agent; imidazole-based blocking agents; Immigration block system etc. are mentioned.

As an amino resin, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl] ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] ether, and 1,4- Bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl ) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as latex and their oligomers or copolymers, oxetane alcohols, novolac resins, poly(p-hydroxystyrene), cardotype bisphenols, calixarenes, calixresorcinalenes Or the etherified thing with resin which has a hydroxyl group, such as silsesquioxane, etc. are mentioned. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate are also exemplified.

When the content of the thermosetting resin includes a carboxyl group-containing resin described later in the composition, the number of functional groups of the thermosetting component that reacts per 1 mol of the carboxyl group contained in the carboxyl group-containing resin is preferably 0.5 to 2.5 mol, more preferably. 0.8 to 2.0 mol.

As the thermosetting component, it is preferable to include an alkali-soluble resin having an alkali-soluble group in view of imparting alkali developability to the composition. Examples of the alkali-soluble resin include carboxyl group-containing resin, a compound having two or more phenolic hydroxyl groups, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Among them, a carboxyl group-containing resin or a phenol resin is preferable because adhesion to the substrate is improved, and a carboxyl group-containing resin is more preferable because it is particularly excellent in developability. Hereinafter, carboxyl group-containing resin is demonstrated.

As the carboxyl group-containing resin, conventionally known various resins having a carboxyl group in the molecule can be used. The carboxyl group-containing resin may or may not have an ethylenically unsaturated double bond in the molecule. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. In this case, it corresponds to a photocurable thermosetting resin. In addition, when the curable composition of the present invention contains a carboxyl group-containing resin, it may be used not only for alkali development but also for alkali non-development. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule described later, that is, a photopolymerizable monomer. As a specific example of carboxyl group-containing resin, the following compounds (any of an oligomer and a polymer may be sufficient) are mentioned.

(1) Carboxyl group-containing resin (lower alkyl ( As the meth)acrylate, methyl (meth)acrylate and the like are exemplified).

(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-based polyols and polyether-based polyols , Polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of diol compounds such as compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) Bifunctional epoxy resins such as diisocyanate, 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, and biphenol type epoxy resin A carboxyl group-containing photosensitive urethane resin by a polyaddition reaction of a (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) During the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added, and the terminal (meth)acrylic carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin of (2) or (3) above, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., having one isocyanate group and one or more (meth)acryloyl groups in the molecule, A carboxyl group-containing photosensitive urethane resin obtained by adding a compound and carrying out terminal (meth)acrylation.

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

(7) Carboxyl group-containing photosensitive resin obtained by further reacting (meth)acrylic acid with a multifunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the generated hydroxyl group. .

(8) Dibasic bases such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like to primary hydroxyl groups generated by reacting dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid with bifunctional oxetane resins. A polyester resin containing a carboxyl group to which an acid anhydride was added.

(9) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and unsaturated compounds such as (meth)acrylic acid A carboxyl group obtained by reacting a group-containing monocarboxylic acid with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with respect to the alcoholic hydroxyl group of the obtained reaction product. Contains photosensitive resin.

(10) A monocarboxylic acid containing an unsaturated group is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and a polybasic acid anhydride is added to the reaction product obtained Carboxyl group-containing photosensitive resin obtained by making it react.

(11) A monocarboxylic acid containing an unsaturated group is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a polybasic acid anhydride is added to the reaction product obtained Carboxyl group-containing photosensitive resin obtained by making it react.

(12) A carboxyl group-containing photosensitive resin formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) above.

As carboxyl group-containing resin, you may use carboxyl group-containing copolymer resin. As a carboxyl group-containing copolymer resin, the resin of (1) and the copolymer resin in (12) are mentioned. As the resin of (12), for example, in addition to the carboxyl group-containing resin obtained by copolymerization of (meth)acrylic acid and methyl (meth)acrylate, glycidyl methacrylate or 3,4-epoxycyclohexylmethyl (meth) Carboxyl group-containing photosensitive resin formed by adding (meth)acrylate having an alicyclic epoxy group, such as an acrylate, is mentioned.

In addition, in this specification, (meth)acrylate is a term which collectively names acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The carboxyl group-containing resin that can be used in the present invention is not limited to those listed above. In addition, the carboxyl group-containing resin enumerated above may be used individually by 1 type, and may mix and use multiple types.

In the present invention, considering the developability when using a weak alkali developer such as sodium carbonate aqueous solution and the drawing ability of the resist pattern, the acid value of the carboxyl group-containing resin is preferably in the range of 30 to 150 mgKOH/g, and 50 to 120 It is more preferable that it is the range of mgKOH/g. The higher the acid value of the carboxyl group-containing resin, the better the developability, but since the dissolution of the exposed portion by the developing solution proceeds, the exposed portion and the unexposed portion may be dissolved and peeled off with the developer without distinction.

The weight average molecular weight of the carboxyl group-containing resin is preferably 6,000 or less, and preferably 2,000 or more. By using a carboxyl group-containing resin having a weight average molecular weight of 6,000 or less, the solubility of the completely dried coating film in a dissolving solvent can be improved, and the washing removability can be improved. In addition, resolution and touch-drying performance can be improved by using a carboxyl group-containing resin having a weight average molecular weight of 2,000 or more. A weight average molecular weight can be measured by gel permeation chromatography (GPC).

The content of the carboxyl group-containing resin is preferably 20 to 80% by mass, more preferably 20 to 75% by mass, still more preferably 20 to 50% by mass in terms of solid content in the curable resin composition. The intensity|strength of a cured coating film can be improved by setting it as 20 mass % or more. Moreover, by setting it as 80 mass % or less, the viscosity of curable resin composition becomes suitable and processability improves.

[Photocurable Resin]

The photocurable resin is a compound having an ethylenically unsaturated group, and includes polymers, oligomers, monomers, and the like, and a mixture thereof may be used. By including a photocurable resin, the strength of a cured film can be improved. Photocurable resin can be used individually by 1 type or in combination of 2 or more types.

As the compound having an ethylenically unsaturated group, known and usual photopolymerizable oligomers, photopolymerizable monomers and the like can be used. Among these, it is preferable to use a photopolymerizable monomer from the viewpoint of providing more crosslinkability and curability of the cured coating film.

The photopolymerizable oligomer is an oligomer having an ethylenically unsaturated double bond. Examples of photopolymerizable oligomers include unsaturated polyester oligomers and (meth)acrylate oligomers. As the (meth)acrylate-based oligomer, epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol type epoxy (meth)acrylate, and urethane (meth) Acrylate, epoxyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. are mentioned.

The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond. Examples of such a photopolymerizable monomer include alkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate and cyclohexyl (meth)acrylate; Hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; mono- or di(meth)acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and trishydroxyethyl isocyanurate, or polyhydric (meth)acrylates of ethylene oxide or propylene oxide adducts thereof ; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols, such as phenoxyethyl (meth)acrylate and polyethoxy di(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine (meth)acrylate. A photopolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

The content of the photocurable resin is preferably 3 to 20% by mass, more preferably 5 to 15% by mass in terms of solid content in the curable resin composition. When the content of the photopolymerizable monomer is 3% by mass or more, photocurability is good, and pattern formation is easy in alkali development after active energy ray irradiation. On the other hand, in the case of 20% by mass or less, halation is less likely to occur and good resolution is easily obtained.

[(B) Filler]

As a filler, all known fillers can be used. Examples of the filler include silica such as amorphous silica, crystalline silica, fused silica, and spherical silica, talc, boehmite, hydrotalcite, slaked lime, calcium hydroxide, calcium carbonate, calcium sulfate, potassium carbonate, magnesium carbonate, clay, and mica powder. , aluminum oxide, aluminum hydroxide, barium sulfate, copper sulfide, alumina, zinc oxide, iron, zinc sulfide, zirconium oxide, chromium oxide, cadmium oxide, cadmium sulfide, and copper oxide. Among these, from a dispersible viewpoint, silica and barium sulfate are preferable. A filler may be used individually by 1 type, and may use 2 or more types together. By containing a filler, heat resistance can be improved or fluctuations at the time of application|coating can be reduced. In addition, from the viewpoint of lowering gloss, aluminum silicate containing SiO ₂ and Al ₂ O ₃ as main components may be used.

The presence or absence of surface treatment of the filler is not particularly limited, but it may be surface treated to enhance dispersibility. Aggregation can be suppressed by using the surface-treated filler. The surface treatment method of the filler is not particularly limited, and a known and usual method may be used, but it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. desirable.

The average particle diameter of the filler can preferably be used in a filler of 10 μm or less, but from the viewpoint of dispersibility, it is more preferably 0.1 to 5.0 μm, still more preferably 0.2 to 3.0 μm. The average particle diameter of a filler is an average particle diameter (D ₅₀ ) including not only the particle diameter of primary particles but also the particle diameter of secondary particles (aggregates), and is a value of D ₅₀ measured by a laser diffraction method. As a measuring device by the laser diffraction method, Microtrac MT3300EXII manufactured by Microtrac Bell Co., Ltd. is exemplified. In addition, the value of each particle diameter of the above-mentioned filler shall mean the value measured by carrying out the above-mentioned filler before adjusting (preliminary stirring, kneading|mixing) curable resin composition.

Depending on the mode of use, the filler may be blended with other components in a powdery or solid state, or may be blended with other components after mixing with a solvent or dispersant to form a slurry. In addition, in content of a filler mentioned later, it shall mean the value in a powdery or solid state.

The content of the filler in the curable resin composition is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and more preferably 5% by mass or more. , More preferably, it is 10 mass % or more, More preferably, it is 20 mass % or more. When the content of the filler is within the above range, the washing removability of the completely dry coating film can be improved while the cured product has high strength.

[(C) organic solvent]

The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or film. As an organic solvent, 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 Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Diethyl Ether, Tripropylene Glycol Monomethyl Ether glycol ethers such as; Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol esters such as monomethyl ether acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and common organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. Among these, when the curable resin composition in the present invention uses a porous material such as amorphous silica, it is easy to absorb oil on the surface of the silica during curing or drying, and as a result, the glossiness of the formed cured coating film is lowered. is preferred, and propylene glycol monomethyl ether acetate is more preferred. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent is not particularly limited, and can be appropriately set according to the target viscosity so as to facilitate preparation of the curable resin composition.

In the present invention, the content of propylene glycol monomethyl ether acetate is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, in the curable resin composition. Further, preferably it is 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less. In the present invention, the content of propylene glycol monomethyl ether acetate in the curable resin composition is not only the amount of propylene glycol monomethyl ether acetate blended as an organic solvent (C), but also other components (above (A) curable resin and (B) ) It is a value including the amount of propylene glycol monomethyl ether acetate in liquid components used for preparation of fillers, etc.). When the content of propylene glycol monomethyl ether acetate is within the above range, the washing removability of the completely dried coating film can be improved.

The curable resin composition of the present invention may further contain the following optional components.

[Photoinitiator]

A photoinitiator is for reacting carboxyl group-containing resin or a photopolymerizable monomer by exposure. As the photopolymerization initiator, all known ones can be used. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and 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, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-( bisacylphosphine oxides such as 2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, p monoacylphosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate, 1-hydroxy-cyclohexylphenyl 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 hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, 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; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H Oxime esters, such as -carbazol-3-yl]-,1-(O-acetyl oxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyloin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned.

Commercially available products of the alkylphenone-based photopolymerization initiator include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins. Moreover, as a commercial item of an acylphosphine oxide type photoinitiator, Omnirad 819 by IGM Resins, etc. are mentioned. Commercially available products of the oxime ester photopolymerization initiator include Irgacure OXE01 and OXE02 manufactured by BASF Japan Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., Adeka Akles NCI-831 and NCI-831E, and TR manufactured by Changzhou Tronly New Electronic Materials. -PBG-304 etc. are mentioned.

In addition, Japanese Unexamined Patent Publication No. 2004-359639, Japanese Unexamined Patent Publication No. 2005-097141, Japanese Unexamined Patent Publication No. 2005-220097, Japanese Unexamined Patent Publication No. 2006-160634, Japanese Unexamined Patent Publication No. 2008-094770 No., Japanese Patent Publication No. 2008-509967, Japanese Patent Publication No. 2009-040762, and carbazole oxime ester compounds described in Japanese Unexamined Patent Publication No. 2011-80036, etc. are mentioned.

The content of the photopolymerization initiator is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass in terms of solid content in the curable resin composition. When content of a photoinitiator is 0.1 mass % or more, the photocurability of curable resin composition becomes favorable, and coating film characteristics, such as chemical resistance, also become favorable. On the other hand, in the case of 10% by mass or less, the light absorption on the surface of the resist film (cured coating film) becomes good, and the deep curability is less likely to decrease.

In combination with the photopolymerization initiator described above, a photoinitiation aid or a sensitizer may be used. Examples of photoinitiation aids or sensitizers include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. In particular, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone It is preferable to use By containing the thioxanthone compound, deep curability can be improved. Although these compounds can be used as a photoinitiator in some cases, it is preferable to use them in combination with a photopolymerization initiator. In addition, a photoinitiation adjuvant or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

In addition, since these photoinitiators, photoinitiation adjuvants, and sensitizers absorb a specific wavelength, their sensitivity is lowered in some cases and may function as ultraviolet absorbers. However, these are not used only for the purpose of improving the sensitivity of the resin composition. Absorbs light of a specific wavelength as needed, enhances the photoreactivity of the surface, changes the line shape and aperture of the resist pattern to vertical, tapered, or reverse-tapered, and improves the accuracy of line width and aperture diameter can make it

[coloring agent]

A colorant can be blended with the curable resin composition of the present invention. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. From the viewpoint of reducing environmental load and having little effect on the human body, It is preferable that it is a colorant which does not contain a halogen.

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. and those assigned the same color-index (C.I.; published by The Society of Dyersand Colourists) number.

As the monoazo red colorant, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146 , 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 and the like. Moreover, Pigment Red 37, 38, 41 etc. are mentioned as a disazo type red coloring agent. In addition, as a monoazo lake-based red colorant, Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53: 1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68 and the like. Moreover, Pigment Red 171, 175, 176, 185, 208 etc. are mentioned as a benzimidazolone system red coloring agent. Moreover, Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224 etc. are mentioned as a perylene red colorant. Moreover, Pigment Red 254, 255, 264, 270, 272 etc. are mentioned as a diketopyrrolopyrrole type red coloring agent. Moreover, Pigment Red 220, 144, 166, 214, 220, 221, 242 etc. are mentioned as a condensed azo red colorant. Moreover, Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207 etc. are mentioned as anthraquinone system red colorant. Moreover, Pigment Red 122, 202, 206, 207, 209 etc. are mentioned as a quinacridone system red colorant.

Examples of blue colorants include phthalocyanine-based and anthraquinone-based, and pigment-based compounds classified as pigments. For example, Pigment Blue 15, 15:1, 15:2, 15:3, 15 :4, 15:6, 16, 60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 or the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the anthraquinone yellow colorant include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, etc. are mentioned. Pigment Yellow 110, 109, 139, 179, 185 etc. are mentioned as an isoindolinone system yellow colorant. Pigment Yellow 93, 94, 95, 128, 155, 166, 180 etc. are mentioned as a condensed azo yellow colorant. Pigment Yellow 120, 151, 154, 156, 175, 181 etc. are mentioned as a benzimidazolone system yellow colorant. Further, as the monoazo yellow colorant, Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104 , 105, 111, 116, 167, 168, 169, 182, 183 and the like. Further, as the disazo yellow colorant, Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, etc. can be heard

In addition, a colorant such as purple, orange, brown, black, or white may be added. Specifically, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63 , 64, 71, 73, Pigment Brown 23, 25, carbon black, titanium oxide and the like.

The content of the coloring agent is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 1.5% by mass in terms of solid content in the curable resin composition.

[Other Added Ingredients]

In the curable resin composition of the present invention, if necessary, a photoinitiation aid, a thermosetting catalyst, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion accelerator, a block copolymer, a chain transfer agent, and a polymerization inhibitor at least one of antifoaming agents and leveling agents, such as anti-freeze agents, antioxidants, rust inhibitors, thickeners such as finely divided silica, organic bentonite and montmorillonite, silicone-based, fluorine-based and polymer-based, imidazole-based, thiazole-based, Components such as silane coupling agents such as triazoles, flame retardants such as phosphinic acid salts, phosphoric acid ester derivatives, and phosphorus compounds such as phosphazene compounds may be further blended. Those known in the field of electronic materials can be used.

[Preparation method]

In preparation of the curable resin composition of the present invention, after weighing and blending each component, it is preliminarily stirred with a stirrer. Then, it can prepare by dispersing each component with a kneading machine as needed and kneading.

As said kneading machine, a bead mill, a ball mill, a sand mill, a 3-axis roll mill, a 2-axis roll mill etc. are mentioned, for example. Dispersion conditions such as the type of beads and particle size of the bead mill can be appropriately set according to the target viscosity, but examples of the type of beads include zirconia beads and alumina beads. As a particle diameter of a bead, the range of (phi) 0.015-2.0 mm is mentioned, for example. Among these, the range of (phi) 0.3 - 1.5 mm is more preferable. The filling rate of the beads is 50 to 95%, and it is preferable that the number of revolutions of the rotor is 800 to 1300 rpm. Moreover, as a target viscosity, it is preferable that the viscosity of the composition at the time of injection|throwing-in of a bead mill is 200 dPa*s or less from the viewpoint of improving dispersibility and making a cured coating film more low gloss. On the other hand, as a lower limit, 50 dPa·s or more is preferable. The viscosity in the present invention is 50 ° C., 100 rpm, 30 seconds in accordance with the viscosity measurement method by a 10-cone-plate rotational viscometer of JIS Z 8803: 2011, using 3 ° × R9.7 as a cone rotor. It is a value measured with a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.).

On the other hand, dispersion conditions, such as the rotation ratio of each roll of a 3-axis roll mill, can also be appropriately set according to the target viscosity.

Further, in order to further improve the dispersibility, first, after weighing and blending the slurry of the raw materials using a kneading machine such as a bead mill or a three-roll mill, you may pre-stir with a stirrer. When forming a slurry of raw materials, it is preferable to knead by a bead mill or the like after weighing and blending a wet dispersant such as a silane coupling agent. Then, you may prepare by dispersing each component containing what was slurried with the kneading machine as in the said illustration, and kneading by a bead mill etc.

[Usage]

The curable resin composition according to the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board, such as a solder resist layer, a cover lay, or an interlayer insulating layer, and is particularly useful for forming a solder resist layer. In addition, since the curable resin composition of the present invention can form a cured product having excellent film strength even if it is a thin film, it is suitable for use in printed wiring boards requiring thinning, such as package substrates (printed wiring boards used for semiconductor packages). It can be used suitably also for formation of a pattern layer. Moreover, the hardened|cured material obtained from the curable resin composition of this invention can be used suitably for a flexible printed wiring board at the point which is excellent in flexibility.

In addition, the curable resin composition of the present invention can be used not only for forming a pattern layer of a cured coating film, but also for a use without forming a pattern layer, for example, a mold application (sealing application).

[Dry Film]

Curable resin composition of this invention can also be made into the form of the dry film provided with the 1st film and the resin layer which consists of a dry coating film of the said curable resin composition formed on this 1st film. The completely dry coating film of 20 mm in length x 20 mm in width x 7 μm in thickness obtained from the dry film of the present invention is characterized by satisfying the same physical properties as those described in [Physical properties] of the [curable resin composition] above. .

The first film in the present invention is laminated by heating or the like so that the resin layer side comprising the curable resin layer formed on a dry film on a base material such as a substrate is in contact with each other and when integrally molded, at least adhered to the resin layer. say that In the case of dry film formation, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, A film can be obtained by applying a uniform thickness on the first film with a spray coater or the like and drying at a temperature of 50 to 130° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but is generally appropriately selected from the range of 1 to 150 µm, preferably 5 to 60 µm, as the film thickness after drying.

As the first film, any known film may be used without particular limitation, and examples thereof include polyester films such as polyethylene terephthalate and polyethylene naphthalate, thermoplastic resins such as polyimide films, polyamideimide films, polypropylene films, and polystyrene films. A film containing may be suitably used. Among these, from viewpoints of heat resistance, mechanical strength, handleability, etc., a polyester film is preferable. Moreover, a laminated body of these films can also be used as a 1st film.

Moreover, it is preferable that the above thermoplastic resin film is a film stretched in the uniaxial direction or biaxial direction from a viewpoint of improving mechanical strength.

The thickness of the first film is not particularly limited, but may be, for example, 10 μm to 150 μm.

After the resin layer of the curable resin composition of the present invention is formed on the first film, a second peelable film is laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is desirable to do The second film in the present invention refers to the curable resin layer formed on a dry film on a base material such as a substrate when laminated by heating or the like so that the resin layer side is in contact with each other and molded integrally, from the curable resin layer before lamination. it says peeled As the second film that can be peeled, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used. What is necessary is just to have the adhesive force of a resin layer and a 2nd film smaller.

Although the thickness of the 2nd film is not specifically limited, For example, it can be 10 micrometers - 150 micrometers.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, "part" and "%" below are all based on mass unless otherwise specified.

(Synthesis of Curable Resin Solution A-1 (Containing Carboxyl Group))

In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 119.4 g of novolak type cresol resin (manufactured by Aika Kogyo Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4), potassium hydroxide 1.19 g and 119.4 g of toluene were introduced, the inside of the system was substituted with nitrogen while stirring, and the temperature was raised with heating. Then, 63.8 g of propylene oxide was 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. got a solution. This was an average of 1.08 moles of alkylene oxide added per 1 equivalent of phenolic hydroxyl group.

Subsequently, 293.0 g of the obtained alkylene oxide reaction solution of the novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing pipe. Then, air was blown in at a rate of 10 ml/min and reacted at 110°C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 g of water flowed out. Then, it cooled to room temperature, and neutralized the obtained reaction solution with 35.35 g of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of propylene glycol monomethyl ether acetate (hereinafter referred to as “PMA”) with an evaporator to obtain a novolak-type acrylate resin solution. Then, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were put into a reactor equipped with a stirrer, a thermometer and an air blowing tube, air was blown in at a rate of 10 ml/min, and stirring, 60.8 g of tetrahydrophthalic anhydride was added little by little, and it was made to react at 95-101 degreeC for 6 hours, and curable resin solution A-1 was obtained. The solid content of obtained curable resin solution A-1 was 65%, the acid value of 88 mgKOH/g of a solid, and the weight average molecular weight were about 2,500 (polystyrene conversion).

(Synthesis of Curable Resin Solution A-2)

In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were added, the temperature was maintained at 40 ° C. or less, 228 parts of 25% sodium hydroxide aqueous solution was added, and after the addition was completed, 50 It reacted for 10 hours at ℃. After completion of the reaction, the mixture was cooled to 40° C., and neutralized to pH 4 with a 37.5% phosphoric acid solution while maintaining the temperature below 40° C. After that, it was allowed to stand and the water layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water and solvent were removed under reduced pressure at a temperature of 50°C or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. When a part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were added, and uniformly dissolved at 50°C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50°C or lower. After that, 8 parts of oxalic acid were added and reacted at 100°C for 10 hours. After completion of the reaction, distillate was removed at 180°C under reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A. In addition, in an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 130 parts of the novolak resin A, 2.6 parts of a 50% sodium hydroxide aqueous solution, toluene / methyl isobutyl ketone (mass ratio = 2/ 1) 100 parts were charged, the inside of the system was purged with nitrogen while stirring, then the temperature was raised by heating, and 45 parts of ethylene oxide was introduced little by little at 150°C and 8 kg/cm 2 to react. The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg/cm 2 , then cooled to room temperature. 3.3 parts of 36% aqueous hydrochloric acid solution was added and mixed to this reaction solution, and sodium hydroxide was neutralized. This neutralization reaction product was diluted with toluene, washed with water three times, and solvent removed with an evaporator to obtain an ethylene oxide adduct of novolac resin A having a hydroxyl value of 175 g/eq. This was obtained by adding an average of 1 mol of ethylene oxide per 1 equivalent of phenolic hydroxyl group. 175 parts of ethylene oxide adduct of novolac resin A thus obtained, 75 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, 130 parts of toluene A reactor equipped with a stirrer, a thermometer, and an air blowing tube , stirred while blowing in air, heated to 115°C, and reacted for another 4 hours while distilling off water generated by the reaction as an azeotropic mixture with toluene, and then cooled to room temperature. After washing the obtained reaction solution with water using 5% NaCl aqueous solution and removing toluene by distillation under reduced pressure, PMA was added to obtain curable resin solution A-2. Solid content of obtained curable resin solution A-2 was 70%, and the weight average molecular weight was about 5,500 (polystyrene conversion).

(Synthesis of curable resin solution A-3 (containing carboxyl group))

In a four-necked flask equipped with a stirrer and a reflux condenser, 220 g of cresol novolak type epoxy resin (manufactured by DIC Co., Ltd., EPICLON N-695, epoxy equivalent: 220) was put, and diethylene glycol monoethyl ether acetate (carbitol acetate ) was added and dissolved by heating. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95-105 degreeC, 72 g of acrylic acid was dripped little by little, and it was made to react for 16 hours. The reaction product was cooled to 80 to 90°C, 106 g of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours and taken out after cooling. The resin solution of curable resin solution A-3 obtained in this way was obtained. As for the solid content of obtained curable resin solution A-3, 65% and the acid value of solid content were 100 mgKOH/g and the weight average molecular weight were about 8,000 (polystyrene conversion).

(Synthesis of curable resin solution A-4 (containing carboxyl group))

In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110° C., and 174.0 parts by mass of methacrylic acid and ε-caprolactone modified methacrylic acid (average molecular weight) were added. 314) 174.0 parts by mass, 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether (DPM), and t-butylperoxy 2-ethylhexanoate as a polymerization catalyst (manufactured by Nichiyu Co., Ltd., A mixture of 12.0 parts by mass of perbutyl O) was added dropwise over 3 hours, and further stirred at 110°C for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling this resin solution, 289.0 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Co., Ltd., Cyclomer M100), 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether Addition, the temperature was raised to 100 ° C., and ring-opening addition reaction of the epoxy group was performed by stirring, and curable resin solution A-4 was obtained. As for the solid content of obtained curable resin solution A-4, 79.8 mgKOH/g and the weight average molecular weight of 46 mass % and the acid value of solid content were about 18,000 (polystyrene conversion).

(Preparation of silica slurry without surface treatment)

Dispersion treatment was performed using 700 g of spherical silica (made by Admatech Co., Ltd.), 300 g of PMA as a solvent, and 0.7 µm zirconia beads in a bead mill. This was repeated three times and filtered with a 3 µm filter to prepare a silica slurry having an average particle diameter of 0.7 µm. Solid content of the obtained silica slurry was 70 mass %.

(Preparation of silica slurry with surface treatment)

Using the silica slurry (in PMA, solid content: 70% by mass) having an average particle diameter of 0.7 μm obtained above, 4% by mass of methacrylsilane (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added to the silica , and treated with a bead mill for 10 minutes to obtain a silica slurry surface-treated with methacrylsilane. Solid content of the obtained silica slurry was 70 mass %.

(Preparation of barium sulfate slurry)

700 g of barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle diameter of 0.3 μm, 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a wet dispersing agent were mixed and stirred, and 0.7 Dispersion treatment was performed using μm zirconia beads. This was repeated three times and filtered through a 3 µm filter to prepare a barium sulfate slurry having an average particle diameter of 0.3 µm. Solid content of the obtained barium sulfate slurry was 70 mass %.

[Examples 1 to 6, Comparative Examples 1 to 3]

(Preparation of Curable Resin Composition)

Each component was mix|blended according to the formulation shown in following Table 1, and it disperse|distributed with the stirrer, and curable resin composition was prepared, respectively. The compounding quantity in a table|surface shows a mass part. Evaluation was performed as follows using the adjusted curable resin composition.

The compounding quantity in Table 1 shows parts by mass.

Details of each component in Table 1 are as follows.

※1: Curable resin solution A-1 synthesized above (containing carboxyl group)

※2: Curable resin solution A-2 synthesized above

※3: Curable resin solution A-3 synthesized above (containing carboxyl group)

※4: Curable resin solution A-4 synthesized above (containing carboxyl group)

※5: Carbitol acetate cut product of epoxy resin (manufactured by DIC Co., Ltd., HP-7200L)

※6: Silica slurry without surface treatment synthesized above

※7: Silica slurry with surface treatment synthesized above

※8: The barium sulfate slurry synthesized above

※9: PMA

※10: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins, Omnirad 907)

※11: Black colorant (manufactured by Mitsubishi Chemical Co., Ltd., MA-100)

※12: White colorant (Thai Bake CR-58, manufactured by Ishihara Sangyo Co., Ltd.)

*13: Acrylate-based leveling agent (BYK-350, manufactured by Big Chemie Japan)

*14: Acrylate-based leveling agent (BYK-361N, manufactured by Big Chemie Japan)

※15: Polymerization inhibitor (QS-30, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

In addition, "content of PMA in curable resin composition" of ※ 16 is not only the amount of PMA blended as the above (C) organic solvent, but also the liquid used for preparing the above (A) curable resin and (B) filler (slurry) It is a value including the amount of PMA in the component.

<Preparation of completely dry coating film (Examples 1 to 6 and Comparative Examples 1 to 3)>

The curable resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were applied by screen printing on a copper plate serving as a base material, left at room temperature (25°C) for 4 months, and dried to obtain a size of 20 mm in length x 20 mm in width. A coating film having a film thickness of 7 µm was prepared. Since the obtained coating film was within 10% of the volatilization rate calculated by the said formula (1), it was judged that a completely dry coating film was formed. In addition, the film thickness of the completely dry coating film was measured using a laser microscope (VR-3200 manufactured by Keyence Corporation).

<Preparation of completely dry coating film (Example 7)>

The curable resin composition of Example 6 was applied onto the polyethylene terephthalate film as the first film using an applicator, dried at 80° C. for 10 minutes, and dry provided with a resin layer containing a dry coating film of the curable resin composition. got the film After that, lamination was performed on a copper plate serving as a base material using a vacuum laminator, and after peeling off the first film, it was left to dry for 4 months at room temperature (25°C) to have a length of 20 mm × width of 20 mm × film thickness of 7 μm. A coating film was prepared. Since the obtained coating film was within 10% of the volatilization rate difference calculated by the said Formula (1), it was judged that a completely dry coating film was formed. In addition, the film thickness of the completely dry coating film was measured using a laser microscope (VR-3200 manufactured by Keyence Corporation).

(dissolution start time and dissolution completion time)

The apparatus shown in Fig. 1 was used to measure the dissolution start time and dissolution completion time of the completely dry coating film. Specifically, 70 ml of PMA as a cleaning solvent (5) and a stirrer (6) were placed in a 100 ml beaker (2) and placed in a water bath set at 25°C. The temperature of the cleaning solvent was stabilized by stirring the cleaning solvent using an agitator 7 (manufactured by As One Co., Ltd., M-3, 500 rpm). Subsequently, the copper plate 1 coated with the completely dry coating film 3 prepared above was arranged so that the depth of immersion was 20 mm from the surface of the cleaning solvent, and was immersed perpendicularly to the surface of the cleaning solvent. Using a laser level (manufactured by TJM Design Co., Ltd., ZEROS-KJC), a line of laser (visible light semiconductor laser, wavelength 635 nm, line width 2 mm, light output 2.5 mW or less) was applied to the completely dry coating film on the immersed copper plate. was incident horizontally, and a part of the completely dried coating film was examined in the flow direction of the cleaning solvent. Dissolution start time was when the bright line on the copper plate of the base generated by dissolution of the completely dry coating film was confirmed in an area of 2 mm x 1 mm in the entire irradiation area (2 mm x 20 mm) of the laser beam 4. On the other hand, when the bright line on the copper plate of the base generated by dissolution of the completely dry coating film was confirmed in a region of 2 mm × 19 mm in the area of 2 mm × 20 mm before irradiation of the laser beam, the dissolution completion time was taken. In addition, the bright line may be confirmed at any location in the entire irradiation portion of the laser beam. The measurement limit of the dissolution time was up to 120 seconds. Therefore, when dissolution was not started or completed even after 120 seconds had elapsed, it was indicated by x in Table 2, respectively.

(Confirmation of cleaning removability)

The surface of the completely dry coating film of the copper plate coated with the completely dry coating film prepared above was wiped with a clean wash impregnated with PMA as a cleaning solvent, and visually evaluated according to the following criteria.

○: The completely dry coating film could be completely removed from the copper plate.

(triangle|delta): A part of the completely dry coating film was able to be removed from the copper plate.

x: The completely dry coating film could not be removed from the copper plate.

As is apparent from Table 2, it is understood that the curable resin compositions of Examples 1 to 6 and the dry film of Example 7 are excellent in wash removability of completely dry coating films. On the other hand, the completely dry coating films of Comparative Examples 1 to 3 did not complete dissolution even after 120 seconds from the start of immersion in PMA as a cleaning solvent, indicating poor cleaning removability.

1: copper plate
2: 100ml beaker
3: completely dry coating
4: laser light
5: cleaning solvent
6: Agitator
7: Agitator

Claims (9)

A curable resin composition containing (A) a curable resin, (B) a filler, and (C) an organic solvent,
The dissolution start time of the completely dry coating film of 20 mm in length x 20 mm in width x 7 μm in thickness formed using the curable resin composition in propylene glycol monomethyl ether acetate as a cleaning solvent is the start of immersion in the cleaning solvent Characterized in that within 20 seconds from, curable resin composition. According to claim 1,
The curable resin composition, wherein the time to complete dissolution of the completely dry coating film is within 40 seconds from the start of immersion in the cleaning solvent. According to claim 1 or 2,
Curable resin composition whose content of propylene glycol monomethyl ether acetate is 20 mass % or more in the said curable resin composition. According to any one of claims 1 to 3,
Curable resin composition in which content of the said (B) filler is 45 mass % or less in the said curable resin composition. According to any one of claims 1 to 4,
Curable resin composition in which said (A) curable resin contains carboxyl group-containing resin. According to any one of claims 1 to 5,
Curable resin composition whose weight average molecular weight of the said carboxyl group-containing resin is 6000 or less. According to any one of claims 1 to 6,
Curable resin composition used for formation of a solder resist layer. According to any one of claims 1 to 6,
A curable resin composition used for forming an interlayer insulating layer. A dry film comprising a first film and a resin layer comprising a dry coating film of a curable resin composition formed on the first film,
The curable resin composition contains (A) a curable resin, (B) a filler, and (C) an organic solvent;
The dissolution initiation time of the completely dry film of 20 mm in length x 20 mm in width x 7 μm in thickness obtained from the dry film in propylene glycol monomethyl ether acetate as a cleaning solvent is within 20 seconds from the start of immersion in the cleaning solvent Characterized in that, a dry film.

Images