TWI399396B - A hardened resin composition, a dry film using the same, and a printed wiring board - Google Patents

Description

Curable resin composition, dry film using the same, and printed wiring board

The present invention relates to a curable resin composition, and more particularly to a curable resin composition which can form a solder resist which exhibits low warpage and which is excellent in flame retardancy and flexibility. Further, the present invention relates to a dry film and a flame-retardant printed wiring board using the curable resin composition.

In the past, a printed wiring board and a flexible wiring board (hereinafter abbreviated as FPC) are required to be flame-retardant in order to be mounted on an electronic machine, and it is required to have a solder resist which is one of these. Flammability. Among them, the FPC is generally a film different from the printed wiring board of the glass epoxy substrate due to the formation of the polyimide substrate. However, since the solder resist to be applied is the same film thickness because of the printed wiring board and the FPC, the burden of the flame retardant of the solder resist is relatively large when the film is FPC.

Therefore, there have been various proposals for the flame retardancy of solder resists in the past. For example, Japanese Laid-Open Patent Publication No. 2007-10794 (Patent Document 1) proposes a flame-retardant photosensitive resin composition for FPC containing (a) a binder polymer and (b) a bromobenzene having a molecule. a polymerizable ethylenically unsaturated bonded photopolymerizable compound such as a halogenated aromatic ring or a (meth)acryl fluorenyl group, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and e) a phosphorus-containing compound having a phosphorus atom in the molecule. However, as a compound having a halogenated aromatic ring and a polymerizable unsaturated double bond, the use of a halogen compound is not preferable from the viewpoint of environmental load.

Therefore, the recent solder resist is replaced with a conventional green colorant ruthenium phthalocyanine green from the viewpoint of reducing environmental load, and a solder resist using an anthocyanin blue and a yellow colorant having no halogen atom. It is popular (for example, refer to Patent Document 2). Further, in order to clearly claim the halogen-free claim from the appearance, anthraquinone blue is used as a direct blue resist. However, although the solder resist is formed to protect the copper circuit, the other side has the role of making the copper circuit heat or moisture, electrical discoloration, or scratches, dirt, etc. on the copper circuit invisible (concealment). . In this regard, the solder resist is usually added with a coloring agent, and it is difficult to see the appearance defect due to the concentration of the solder. However, compared to the green color caused by the anthraquinone green, the blue solder resist ink or the green solder resist ink caused by the blue colorant and the yellow colorant is less concealed and has no It can be used as a function that can sufficiently realize a coloring agent which is difficult to see in appearance.

Further, in the printed circuit board of the film represented by FPC, there is a problem that warpage due to hardening shrinkage occurs when the solder resist is photocured or thermally cured.

However, aluminum hydroxide is a flame retardant filler, and it is known that when it is added to a resin composition, the more it is added, the more the composition becomes flame retardant. However, the shape of the aluminum hydroxide is not constant, and excessive addition causes a crack in the interface between the aluminum hydroxide and the resin as a starting point, and there is a problem that the bending resistance of the hardened film is lowered. Therefore, there is a demand for a printed wiring board having a flexural property, particularly a solder resist for an FPC board, which is limited in the amount of addition.

Further, in the method of preventing cracks at the interface between the organic substance and the inorganic substance, as in the case of a filler for an organic substance, a method of increasing the affinity of the inorganic particle is known, and a decane coupling agent treatment, a titanate, and the like have been conventionally performed. Aluminum chelation (alumichelate) treatment and the like. However, such an affinity-advancing method has little effect on aluminum hydroxide, and in the present state, the effect of improving the bending of the hardened film is hardly obtained.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2007-10794 (Scope of Patent Request)

[Patent Document 2] JP-A-2000-7974 (Scope of Patent Request)

The present invention has been made to solve the problems of the prior art as described above, and its main object is to provide a curable resin composition containing a halogen-free flame retardant which is low in warpage and can be formed. A curable resin composition of a solder resist layer having resistance to bending.

In addition, the object of the present invention is to provide a dry film which is low in warpage and excellent in flame retardancy and flexibility and a flame retardant film having such excellent characteristics by using the curable resin composition. Printed wiring board.

In order to achieve the above object, according to the present invention, there is provided a curable resin composition comprising (A) a carboxyl group-containing resin, (B) aluminum hydroxide, and (C) true spherical cerium oxide.

In the same manner, in addition to the above-mentioned respective components, the thermosetting resin having two or more cyclic ether groups and/or cyclic thioether groups in the molecule (D) may be further contained, and the thermosetting resin may be used. Composition. In other preferred embodiments, the (E) phosphorus-containing compound is further contained. In the other aspect, the photocurable thermosetting resin composition can be formed by further containing (F) a photopolymerization initiator and (G) a photopolymerizable monomer. In other preferred embodiments, the colorant (H) may be further contained. More preferably, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure or a carboxyl group-containing resin having a biphenyl aldehyde structure and an ethylenically unsaturated group, and further, in the above molecule The thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups is an epoxy resin having a biphenol aldehyde skeleton. Such a curable resin composition can be applied to the formation of a solder resist of a printed wiring board.

Further, according to the present invention, it is possible to provide a dry film obtained by applying the curable resin composition to a film, or to apply the curable resin composition or the curable resin composition to a carrier film. The dried film obtained by drying it is subjected to heat hardening and/or photohardening to obtain a cured product. Furthermore, according to the present invention, a printed wiring board having the above cured product can also be provided.

The curable resin composition of the present invention contains (A) a carboxyl group-containing resin, and contains (B) aluminum hydroxide and (C) true spherical ceria, and further preferably contains (E) phosphorus. The compound can be formed into a non-halogen composition to form a film having less environmental load, flame retardancy, and excellent in low warpage and flexibility. Therefore, by using the curable resin composition of the present invention, it is possible to provide a dry film which is low in warpage and excellent in flame retardancy and flexibility, and a printing of a flame retardant solder resist film having such excellent characteristics. Wiring board.

[Formation for implementing the invention]

As a result of intensive research in order to solve the above problems, the present inventors have found that, together with a carboxyl group-containing resin (A), a true spherical ceria (C) and hydrogen as a flame retardant filler are used. Alumina (B) maintains the flame retardancy of the curable resin composition and improves the bending resistance. In particular, since the true spherical cerium oxide does not have a surface which is the starting point of the crack of the hardened film, there is an effect that the bending resistance is directly increased. Further, the surface treatment by a decane coupling agent or the like has a very effective effect on cerium oxide, and the bending resistance can be greatly increased upward. This effect is an amazing effect that has never been considered before.

Hereinafter, each constituent component of the curable resin composition of the present invention will be described in detail.

In the case of the carboxyl group-containing resin (A) contained in the curable resin composition of the present invention, a known and customary resin compound containing a carboxyl group in the molecule can be used. Further, in the case of the alkali-developing resin composition, the carboxyl group-containing photosensitive resin (A') having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance. Further, it is preferred that the unsaturated group be derived from an acrylic acid or a methacrylic acid derivative. Further, when only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a photopolymerizable monomer having two or more ethylenically unsaturated groups in the molecule to be described later ( G).

As a specific example of the carboxyl group-containing resin (A), the compounds listed below (either an oligomer and a (poly) polymer) can be preferably used.

(1) a carboxyl group-containing copolymer obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene Resin.

(2) A divalent isocyanate such as an aliphatic diisocyanate, a divalent aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylol propionate or dimethylol butyrate. Alcohol compound, polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, and phenolic hydroxyl group A carboxyl group-containing urethane resin obtained by subjecting a diol compound such as an alcoholic hydroxyl group to a sequential addition reaction.

(3) A diisocyanate compound such as an aliphatic diisocyanate, a divalent aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester polyol. Amine group obtained by successive addition reaction of a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group At the end of the acid ester resin, an acid anhydride is reacted to form a terminal carboxyl group-containing urethane resin.

(4) making diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin, double Photosensitive carboxyl group-containing (meth) acrylate of a bifunctional epoxy resin such as a phenol epoxy resin or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound by sequential addition reaction A urethane resin.

(5) In the resin synthesis of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. A carboxyl group-containing urethane resin formed by terminal (meth) acrylate.

(6) In the synthesis of the resin of the above (2) or (4), one or more isocyanate groups and one or more molecules are added to the molecule such as a molar reaction product such as isophorone diisocyanate and pentaerythritol triacrylate. A compound of an acrylonitrile group, which is a terminal (meth) acrylated carboxyl group-containing urethane resin.

(7) reacting (meth)acrylic acid on a polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrogen in the hydroxyl group present in the side chain A photosensitive carboxyl group-containing resin obtained by addition of a 2-base acid anhydride such as phthalic anhydride.

(8) reacting (meth)acrylic acid on a polyfunctional epoxy resin which further oxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and makes 2 on the generated hydroxyl group. A photosensitive carboxyl group-containing resin formed by addition of a base acid anhydride.

(9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid on a 2-functional oxetane resin as described later and adding a 2-base acid anhydride to the produced first-order hydroxyl group .

(10) Further, the resin of the above (1) to (9) has one ring of a molecule such as a glycidyl (meth) acrylate or an α-methylepoxypropyl (meth) acrylate. A photosensitive carboxyl group-containing resin obtained by adding an oxy group to a compound of one or more (meth) acrylonitrile groups.

Among these carboxyl group-containing resins, preferred are (X) a carboxyl group-containing polyurethane resin, particularly an isocyanate group of an isocyanate group-containing component (diisocyanate) of the urethane resin. The polyfunctional epoxy resin used for the direct bonding to the benzene ring and (Y) for the synthesis of the aforementioned resin has a bisphenol A structure, a bisphenol F structure, a bisphenol structure, a biphenol aldehyde structure, and a bisxylenol structure. In particular, in the case of a compound having a biphenyl aldehyde structure and a hydride thereof, it is preferred because of low warpage and flexural resistance. Further, on the other hand, the modified product of the above (2), (3), (4), (5), (6) and the above (10) has a urethane in the main chain. Bonding, better for warping. Further, since the resin other than (1), (2) and (9) has a photosensitive group in the molecule, it is preferable because it has high photoreactivity.

In the present specification, the term "(meth)acrylate" acrylate, methacrylate, and the like is also the same in other similar expressions.

The carboxyl group-containing resin (A) is a crosslinking point at the time of heat curing because it has a large number of free carboxyl groups in the side chain of the main ‧ polymer. Further, when it is a photocurable resin composition, it can be developed by a dilute aqueous alkali solution.

Further, the acid value of the carboxyl group-containing resin (A) is preferably in the range of 30 to 200 mgKOH/g, more preferably 40 to 200 mgKOH/g, and particularly preferably in the range of 45 to 120 mgKOH/g. From the viewpoint of alkali developability, if the acid value of the carboxyl group-containing resin is less than 30 mgKOH/g, alkali imaging is difficult, and if it exceeds 200 mgKOH/g, the dissolution of the exposed portion progresses due to the developing solution. Therefore, the line width must be thinner than necessary, and the exposed portion and the unexposed portion are dissolved and peeled off by the developing liquid without any difference depending on the situation, resulting in difficulty in drawing the normal photoresist pattern.

Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the tack-removing property is poor, and the moisture resistance of the coating film after exposure is not good, and film reduction occurs during development, and the resolution is greatly weakened. On the other hand, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is also poor.

The amount of the carboxyl group-containing resin (A) as described above is 5 to 60% by mass, preferably 10 to 60% by mass, more preferably 20 to 60% by mass, particularly preferably 30 to 50% by mass based on the total composition. %. When the amount is less than the above range, the film strength may be lowered. On the other hand, when it is more than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered.

In the case of aluminum hydroxide (B), it is commercially available. Commercial products include, for example, HIGILITE series, HW, H21, H31, H32, H42M, and H43M manufactured by Showa Denko. In addition, in the case where the particle size of the aluminum hydroxide is fine, it is effective in the folding resistance, and it is used in a bead mill or the like in advance with a solvent or a resin to obtain a primary particle diameter, and is filtered by a sieve or the like to select 3 μm or more. More preferably, it is 1 μm or more, and it is preferable from the viewpoint of the flame retardancy and the flexibility of the hardened film obtained therefrom.

The amount of the aluminum hydroxide (B) to be added is preferably from 1 to 200 parts by mass, more preferably from 1 to 150 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). It is 10 to 100 parts by mass.

As the true spherical cerium oxide (C), commercially available true spherical cerium oxide having an average particle diameter of 0.25 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 3 μm, 5 μm or the like can be used as it is. In the case of commercial products, the company has a series of ADMATECHS SO series. Further, for the composition of the true spherical cerium oxide, a decane coupling agent or the like may be directly used, but a solvent, a decane coupling agent, and a true spherical cerium oxide may be used as a bead mill in advance. After the surface treatment, the decane coupling agent is dispersed to uniformly treat the surface of the cerium oxide, and further, particles having a particle size of 5 μm or more are selected by filtration or the like, and it is preferable from the viewpoint of flexibility.

The amount of the spheroidal cerium oxide (C) is preferably in the range of 1 to 200 parts by mass, preferably 1 to 150 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). It is preferably 5 to 100 parts by mass.

The composition of the present invention is composed of a thermosetting resin composition, and the thermosetting component (D) used for the purpose of improving the properties such as heat resistance and insulation reliability can be used in all cases. a compound having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group) in a molecule in which a carboxyl group of a resin of a carboxyl group is reacted, but a bifunctional or higher compound thereof The epoxy resin is preferable in terms of heat resistance and gold plating resistance, and in particular, an epoxy resin having a biphenyl aldehyde skeleton is preferred because of heat resistance, gold plating resistance, and flame retardancy. Examples of the epoxy resin having a biphenyl aldehyde skeleton include NC-3000L, NC-3000, NC-3000H, and NC-3100 manufactured by Nippon Kayaku Co., Ltd.

In the thermosetting resin composition of the present invention, a thermosetting component having two or more cyclic (thio)ether groups in the molecule of the thermosetting component may be used, and two or more 3, 4 or 4 in the molecule may be used. The compound having one or two kinds of the cyclic ether group or the cyclic thioether group of the 5-membered ring may, for example, be a compound having two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D). -1) a compound having two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (D-2) having two or more thioether groups in the molecule A compound, that is, an episulfide resin (D-3) or the like.

Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Nippon Epoxy Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, and EPOTOHTOYD manufactured by Dongdu Chemical Co., Ltd. 011, YD-013, YD-127, YD-128, DER 317, DER 331, DER 661, DER 664 manufactured by Dow Chemical Co., Ltd., ARALDITE 6071, ARALDITE 6084, ARALDITEGY 250, ARALDITEGY 260, manufactured by Sumitomo Chemical Industries Co., Ltd. of Ciba Specialty Chemicals Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, AER 330, AER 331, AER 661, AER 664 (all are trade names) bisphenol A epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; Japan JER YL903 manufactured by Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOHTOYDB-400 manufactured by Tosho Kasei Co., Ltd., YDB-500, D. E. R. 542 manufactured by Dow Chemical Co., Ltd., ARALDITE 8011 manufactured by Ciba Specialty Chemicals Co., Ltd. Sumitepoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Industries, Ltd., A. E. R. 711, A. E. R. 714, manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin (both trade names); jER152, jER154, manufactured by Japan Epoxy Resin Co., Ltd., D. E. N. 431, D. E. N. 438, manufactured by DIC Corporation, manufactured by Dow Chemical Co., Ltd. EPICLONN-730, EPICLONN-770, EPICLONN-865, EPOTOHTOYDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., ARALDITEECN1235, ARALDITEECN1273, ARALDITEECN1299, ARALDITEXPY307, manufactured by Ciba Specialty Chemicals, EPPN-201, EOCN, manufactured by Nippon Kayaku Co., Ltd. -1025, EOCN-1020, EOCN-104S, RE-306, Sumiepoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, Ltd., A. E. R. ECN-235, ECN-299, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. ( A novolac type epoxy resin of the product name; EPICLON 830 manufactured by DIC Corporation; jER807 manufactured by Nippon Epoxy Co., Ltd., EPOOTOY DF-170, YDF-175, YDF-2004, and Ciba Specialty Chemicals, manufactured by Tosho Kasei Co., Ltd. Bisphenol P-type epoxy resin such as ARALDITEXPY306 (all trade names); hydrogenated bisphenol A epoxy resin such as EPOTOHTOST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; Oxygen resin company jER604, east EPOTOHTOYH-434 manufactured by Kasei Co., Ltd., ARALDITEMY 720 manufactured by Ciba Specialty Chemicals Co., Ltd., and Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxy propylamine type epoxy resin; manufactured by Ciba Specialty Chemicals Co., Ltd. Hydantoin type epoxy resin such as ARALDITECY-350 (trade name); CELLOXIDE 2021 manufactured by DAICEL Chemical Industry Co., Ltd., ARALDITECY175, CY179, etc. (all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd. Resin; YL-933 manufactured by Nippon Epoxy Co., Ltd., TEN, EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (all trade names), trihydroxyphenylmethane epoxy resin; Japan Epoxy Resin Co., Ltd. YL-6056, YX-4000, YL-6121 (all trade names), etc., bisphenol type or bisphenol type epoxy resin or a mixture of these; EBPS-200, Asahi Kasei Co., Ltd. Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink Chemicals Co., Ltd., and bisphenol A phenolic resin such as jER157S (trade name) manufactured by Nippon Epoxy Co., Ltd. Varnish type epoxy resin; day JER YL-931 manufactured by Epoxy Resin Co., Ltd., ARALDITE 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (all of which are trade names), tetraphenylolethane type epoxy resin; ARALDITEPT 810 manufactured by Ciba Specialty Chemicals Co., Ltd., manufactured by Nissan Chemical Industries Co., Ltd. Heterocyclic epoxy resin such as TEPIC (both trade names); diglycidyl phthalate resin such as BLEMMERDGT manufactured by Nippon Oil & Fats Co., Ltd.; tetraepoxypropyl tetrazide such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Ethylene-glycidyl xylenoylethane ethane resin; Ethanol Chemical Co., Ltd. ESN-190, ESN-360, DIC company HP-4032, EXA-4750, EXA-4700, etc. Base epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; and epoxy methacrylate of CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Copolymerization epoxy resin; copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, DAICEL Chemical Industry) PB-3600, etc.), CTBN modified epoxy resin (for example, Dongdu Huacheng Manufactured YR-102, YR-450, etc.) and the like, and the like, but not limited thereto. These epoxy resins may be used singly or in combination of two or more.

In the above polyfunctional oxetane compound (D-2), in addition to bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxo) Heterocyclic butyl methoxy) methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3) -oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate , (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or such oligomers or Examples of the polyfunctional oxetane such as a copolymer include oxetane and novolak resins, poly(p-hydroxystyrene), Cardo bisphenols, and calixarene. An etherified product derived from a resin having a hydroxyl group such as a resorcinol calixarene or a silsesquioxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may be mentioned.

The epoxidized resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A-type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the like. Further, an epoxy sulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom may be used in the same synthesis method.

The amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 1 equivalent to the carboxyl group of the carboxyl group-containing resin. 2.5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the carboxyl group remains on the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like may occur. Lower, so it is not good. On the other hand, when it exceeds 2.5 equivalents, a low molecular weight cyclic (thio)ether group remains on the dried coating film, and thus the strength and the like of the coating film are lowered, which is not preferable.

The curable resin composition of the present invention has a thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule, in order to further improve heat resistance and insulation reliability of the cured coating film. In addition, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, an amine resin such as a melamine resin, a melamine derivative, or a benzoguanamine resin, a cyclic carbonate compound, or a double horse may be used. A known thermosetting resin such as an imine, an oxazine compound, an oxazoline compound, or a carbodiimide resin.

In the case of a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, a compound having two or more isocyanate groups in one molecule is used, that is, a polyisocyanate compound or two or more molecules per molecule. A compound which blocks an isocyanate group, that is, a blocked isocyanate compound or the like.

As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, and naphthalene-1,5- Diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolyl dimer. Specific examples of the aliphatic polyisocyanate include tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl methyl double. (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, adducts, biuret bodies, and isocyanurate bodies of the above-mentioned isocyanate compounds can be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is protected by a reaction between an isocyanate group and a block agent, and is temporarily inactivated. Upon heating to a predetermined temperature, the blocker dissociates to form an isocyanate group.

In the case of the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent can be used. Examples of the isocyanate compound which can be reacted with the block agent include an isocyanurate type, a biuret type, and an adduct type. As the isocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenol-based blockers such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroinamide, and γ-butane An indoleamine block agent such as guanamine or β-propionalamine; an active methyl group blocker such as ethyl acetate and ethyl acetonide; methanol, ethanol, propanol, butanol, Pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, glycolic acid Alcohol blocker such as methyl ester, butyl glycolate, dipropyl copper alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime , anthraquinone blocker such as diethyl hydrazine monomethyl or cyclohexane hydrazine; butyl thiol, hexyl thiol, t-butyl thiol, thiophenol, methyl thiophenol, ethyl thiophenol, etc. a thiol-based block agent; an amide-based blocker such as decylamine or benzamide; a quinone imide blocker such as succinimide succinate or succinimide; , aniline, butylamine, dibutylamine, etc. Based blocking agent; imidazole, 2-ethylimidazole, etc. imidazole-based blocking agent; methylimine stretch and stretch propylene imine imine block, etc., and the like.

The blocked isocyanate compound may be a commercially available one, and may, for example, be Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosome 2170, Desmosome 2265 (above is Sumitomo Bayer Aurethane Co., Ltd., trade name), CORONATE 2512, CORONATE 2513, CORONATE 2520 (above, manufactured by Japan Polyurethane Industrial Co., Ltd., trade name), B-830, B -815, B-846, B-870, B-874, B-882 (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (manufactured by ASAHI KASEI CHEMICALS, trade name) Wait. Further, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a block agent.

The compound having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used alone or in combination of two or more.

The amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is from 1 to 100 parts by mass, more preferably from 2 parts by mass to 100 parts by mass of the carboxyl group-containing resin (A). The ratio of ~70 parts by mass is suitable. When the amount of the above-mentioned compounding is less than 1 part by mass, sufficient coating film toughness cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability of the composition may be lowered, which is not preferable.

Further, examples of the other thermosetting component include a melamine derivative and a benzoguanamine derivative. For example, there are a methylol melamine compound, a hydroxymethyl benzoguanamine compound, a methylol acetylene urea compound, a methylol urea compound, and the like. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated acetylene urea compound, and an alkoxymethylated urea compound may each have a methylol group The melamine compound, the hydroxymethyl benzoguanamine compound, the methylol acetylene urea compound, and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. In particular, it is preferably a melamine derivative having a concentration of 0.2% or less of a fumarin concentration excellent in the human body or the environment.

Examples of such commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, and 202. Same as 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above is Mitsui Cyanamid (share) system), NIKALAC Mx-750, the same Mx-032, the same Mx-270, the same Mx-280 , with Mx-290, with Mx-706, with Mx-708, with Mx-40, with Mx-31, with Ms-11, with Mw-30, with Mw-30HM, with Mw-390, with Mw-100LM Same as Mw-750LM (above is Sanhe Chemical (share) system). These thermosetting components may be used alone or in combination of two or more.

When the thermosetting component (D) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1- Imidazole derivatives such as cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethyl Amine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N - an amine compound such as dimethylbenzylamine, a hydrazine compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine; and a commercially available product, for example, four countries 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Kasei Kogyo Co., Ltd., U-CAT (registered trademark) 3503N and U-CAT3502T manufactured by SAN-APRO Co., Ltd. A trade name of a blocked isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, and U-CAT5002 (all of which are bicyclic hydrazine compounds and salts thereof). These are not particularly limited, and may be used alone as a thermosetting catalyst for an epoxy resin or an oxetane compound, or for a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group. Or use two or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4- can be used. Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ iso-cyanuric acid adduct, 2,4-diamino-6-methyl propylene oxime An S-triazine derivative such as an oxyethyl-S-triazine ‧ isocyanuric acid addition product, wherein a compound which acts as a adhesion imparting agent for this purpose is used in combination with the above-mentioned thermosetting catalyst good.

The amount of the thermosetting catalyst is preferably a ratio of a normal amount, and is, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0, per 100 parts by mass of the carboxyl group-containing resin (A). Parts by mass.

The curable resin composition of the present invention preferably contains a phosphorus-containing compound (E). In the case of a phosphorus-containing compound, it is preferably a conventionally known organic phosphorus-based flame retardant, which is a phosphate ester, a condensed phosphate ester, a cyclic phosphine nitride compound, a azophosphorus oligomer, a phosphonate or the following a compound of the formula (I).

【化1】

In the formula, R ¹ , R ² and R ³ each independently represent a substituent other than a halogen atom.

Commercially available products of the compound represented by the above formula (I) include HCA, SANKO-220, M-ESTER, and HCA-HQ (all of which are trade names of Sanguang Co., Ltd.).

The phosphorus-containing compound (E) which is particularly preferably used in the invention may, for example, be (1) having an acrylate group or (2) having a phenolic hydroxyl group, (3) an oligomer or a polymer, ( 4) an azophosphorus oligomer and (5) a phosphonate as a reactive group.

(1) Phosphorus-containing compound having an acrylate group

The acrylate having a phosphorus element is preferably a compound having two or more (meth) acrylates in the molecule, and specifically, R ¹ and R in the above general formula (1). A compound wherein ² is a hydrogen atom and R ³ is an acrylate derivative, generally by a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a conventionally known polyfunctional acrylate. The monomeric wheat can be added to the reaction to synthesize.

Examples of the above-mentioned conventionally known acrylate monomer include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexane diol and trimethylol Multivalents such as propane, pentaerythritol, dipentaerythritol, octahydroxyethyl isocyanurate or the like, or such ethylene oxide adducts, propylene oxide adducts or caprolactone adducts Acrylates; phenoxy acrylates, bisphenol A diacrylates, and phenolic ethylene oxide adducts or polyvalent acrylates such as propylene oxide adducts; and the above polyhydric alcohols Urethane acrylates, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triepoxypropyl isocyanuric acid a polyvalent acrylate of a glycidyl ether such as an isocyanurate; and a melamine acrylate; and/or a methacrylate corresponding to the above acrylate.

(2) Phosphorus-containing compounds having a phenolic hydroxyl group

The phosphorus-containing compound having a phenolic hydroxyl group is highly hydrophobic and heat-resistant, and the electrical properties due to hydrolysis are not lowered, and the solder has high heat resistance. Further, a preferred combination is obtained by introducing an epoxy resin having a biphenyl skeleton or another epoxy resin as the component (D) into the network by reacting with the epoxy resin, so that it can be bleed out after hardening. The advantages. In terms of commercial products, there are HCA-HQ manufactured by Sanguang Co., Ltd.

(3) oligomer or polymer

The phosphorus-containing compound of the oligomer or the polymer has a small decrease in the flexibility due to the influence of the alkyl chain, and has an advantage of being hardened and not bleed out due to the large molecular weight. In terms of commercial products, there are M-Ester-HP manufactured by Sanguang Co., Ltd., and phosphorus-containing VYLON 337 manufactured by Toyobo Co., Ltd.

(4) Phosphorus azo oligomers

In the case of the azophosphorus oligo compound, the phenoxy phosphine nitrogen compound is effective, and there are substituted or unsubstituted phenoxy azophosphorus oligo oligomers or a ring of 3, 4, and 5 It can be used as a liquid or solid powder. In the case of commercial products, there are FP-100, FP-300, FP-390, etc. manufactured by Fushimi Pharmaceutical Co., Ltd. Among them, a phenoxy phosphatidyl oligo group substituted with a polar group such as an alkyl group or a hydroxy group or a cyano group has high solubility in a carboxyl group-containing resin, and does not recrystallize even if it is added in a large amount. good.

(5) phosphonate

By using a phosphonate, the flame retardancy can be further improved without impairing the softness of the hardened coating film. Further, by using a phosphonate having excellent heat resistance, it is possible to suppress bleed out of the flame retardant during hot pressing at the time of mounting. As for the commercial item, EXOLIT OP 930, EXOLIT OP 935, etc. by Clariant Co., Ltd. are mentioned.

The amount of the phosphorus-containing compound (E) of the flame retardant is preferably in the range of 0 to 200 parts by mass, particularly preferably 0 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). . If it is more closely matched with this, the bending characteristics and the like of the obtained hardened film are not deteriorated.

In the photopolymerization initiator (F) constituting the photocurable resin composition of the present invention, photopolymerization of an oxime ester photopolymerization initiator having an oxime ester group and α-aminoacetophenone photopolymerization can be used. One or more kinds of photopolymerization initiators selected from the group consisting of a starting agent and a mercaptophosphine oxide photopolymerization initiator.

Examples of the oxime ester photopolymerization initiator include CGI-325, IRUGACURE OXE01, IRUGACURE OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., and ADEKA ARKLS NCI-831.

Further, a photopolymerization initiator having two oxime ester groups in the molecule can be used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula can be mentioned.

[Chemical 2]

(wherein, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group (an alkyl group having 1 to 17 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms) a group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and a naphthyl group (an alkyl group having 1 to 17 carbon atoms and an alkyl group having 1 to 8 carbon atoms) An oxy group, an amine group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, and Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 Alkoxy group of ～8, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) a substituted alkylamino or dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) Substituted by an alkylamino or dialkylamino group, a mercapto group, a pyridyl group, a benzofuranyl group, a benzothienyl group, and Ar represents an alkylene group having a carbon number of 1 to 10, a vinyl group, and a phenylene group. , biphenyl, exopyridyl, naphthyl, thiophene, thiophene, thienylene, furanyl, 2,5-pyrrole -diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1.

In particular, in the above formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, and Ar is a stretching phenyl group, a stretching naphthyl group, a thiophene or a thienyl group ( Thienylene) is good.

The α-aminoacetophenone photopolymerization initiator is specifically 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1. , 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. As a commercial item, IRUGACURE907, IRUGACURE369, IRUGACURE379, etc. by Ciba Specialty Chemicals company are mentioned.

Specific examples of the mercaptophosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis(2,4,6-trimethyl). Benzobenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF Corporation and IRUGACURE 819 manufactured by Ciba Specialty Chemicals.

Among the above photopolymerization initiators, a particularly preferred mercaptophosphine oxide-based initiator is preferred in terms of photobleachability, and has an effect on flame retardancy. Further, the oxime ester-based initiator has a good initial agent efficiency, and a small amount has an effect on sensitivity improvement. Therefore, there is less exhaust gas during heat treatment after formation of the photoresist film, and there is a decrease in warpage of the film. The effect is better. Especially good for both.

The amount of the photopolymerization initiator (F) to be used is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the photopolymerization initiator (F) is less than 0.01 parts by mass, the photocurability on the copper is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the light absorption on the surface of the solder resist coating film of the photopolymerization initiator (F) becomes intense, and the deep hardenability tends to be lowered, which is not preferable.

Further, when it is an oxime ester-based photopolymerization initiator having a group represented by the above formula (II), the amount of the carboxyl group-containing resin (A) is preferably from 0.01 to 20 in terms of 100 parts by mass. The mass part is more preferably in the range of 0.01 to 5 parts by mass.

Other examples of the photopolymerization initiator, photoinitiator, and sensitizer which can be used in the photocurable resin composition of the present invention include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantate. A ketone compound, a ketal compound, a diphenyl ketone compound, an oxonone compound, a tertiary amine compound, and the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1 , 1-dichloroacetophenone.

Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine.

Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthene. ketone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the diphenyl ketone compound include diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, and 4-benzene. Mercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminodiphenyl ketone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.). Dialkylaminodiphenyl ketone, 7-(diethylamino)-4-methyl-2H, etc., 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) a dialkylamino group-containing coumarin compound, 4-dimethylamine, such as 1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) Kean acid ethyl ester (KAYACURE EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (Quantacure DMB manufactured by International Biosynthetics Co., Ltd.), 4-dimethylamino benzoic acid (n-butoxy group) Ethyl (Quantacure BEA, manufactured by International Biosynthetics Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (KAYACURE DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2-ethyl Hexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, it is preferable to use a thioxanthone compound from the viewpoint of deep hardenability, and more preferably 2,4-dimethylthioxanthone or 2,4-diethylthioxanthone. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred.

The amount of the thioxanthone compound to be used is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, which is related to the cost of the product, which is not preferable.

In the case of the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, wherein a dialkylaminodiphenyl ketone compound and a dialkylamine group-containing fragrance having a maximum absorption wavelength of 350 to 410 nm are preferred. Soybean compounds are particularly preferred. In the case of the dialkylaminodiphenyl ketone compound, 4,4'-diethylaminodiphenyl ketone is preferred as low toxicity. The coumarin compound containing a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm has a small color absorption due to the maximum absorption wavelength in the ultraviolet region, and the colorless and transparent photosensitive composition can provide a coloring pigment more than the original one. A color resist film that reflects the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the above-mentioned tertiary amine compound is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. On the other hand, when it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film is severe due to the tertiary amine compound, and the deep hardenability tends to be lowered.

In the photocurable resin composition of the present invention, in order to improve the sensitivity, conventionally known N-phenylamino acetic acid, phenoxyacetic acid, thiophenoxyacetic acid, thiol thiazole, or the like can be used. Chain transfer agent. Specific examples of the chain transfer agent include a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; a chain transfer agent having a hydroxyl group such as ethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3- Mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan , propane thiol, butane thiol, heptane thiol, 1-octane thiol, cycloheptane thiol, cyclohexane thiol, thio glycerol, 4,4-thiobisbenzene thiol ( Thiobestzenzenthiol) et al.

Further, as the heterocyclic compound having a mercapto group acting as a chain transfer agent, for example, mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4-methyl- 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butylidene, N-methoxy-2 - mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-mercapto-4-butylidene, N-ethyl-2- Mercapto-4-butyrolactam, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2-mercapto-4- Butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalinamide, N-ethyl-2-mercapto -5-valeroinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentalinamide, N-(2-ethoxy)ethyl-2-mercapto-5-pentyl Indoleamine and 2-mercapto-6-caprolactam and the like.

In particular, in the case of a heterocyclic compound having a mercapto group as a chain transfer agent without impairing the developability of the photocurable resin composition, mercaptobenzothiazole and 3-mercapto-4-methyl-4H-1 are used. 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used alone or in combination of two or more.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more.

The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 mass parts, the deep hardenability tends to fall by this light absorption.

The photopolymerizable monomer (G) used in the photocurable resin composition of the present invention is photocured by irradiation with an active energy ray, and the photocurable resin composition of the present invention is insoluble. In the case of an aqueous alkali solution, or to help insolubilize. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexane diol, trimethylolpropane, pentaerythritol, and a polyvalent acrylate such as pentaerythritol, a hydroxyethyl isocyanurate or the like, or an oxyethylene adduct such as an oxyethylene adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, an ethylene oxide adduct of such a phenol, or a polyvalent acrylate such as a propylene oxide adduct; glycerol diepoxypropyl ether, glycerol triepoxypropyl a polyvalent acrylate of a glycopropyl ether such as an ether, trimethylolpropane triepoxypropyl ether or tricoxypropyl isocyanurate; and melamine acrylate, and/or corresponding Each of the methacrylates of the above acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid on a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a pentaerythritol three on the hydroxyl group of the epoxy acrylate resin may be mentioned. An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate such as acrylate with a halfurethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve photocurability without lowering the dryness of the touch.

The amount of the photopolymerizable monomer (G) having two or more ethylenically unsaturated groups in the molecule is preferably 100 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). It is a ratio of 5 to 70 parts by mass. When the amount of the collocation is less than 5 parts by mass, the photocurability is lowered, and it is difficult to form a pattern by alkali imaging after irradiation with an active energy ray. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered to make the coating film brittle, which is not preferable.

The curable resin composition of the present invention can be blended with a coloring agent (H). As the coloring agent (H), a conventionally known coloring agent such as red, blue, green, or yellow may be used, and any of a pigment, a dye, and a coloring matter may be used. Specifically, a color index (C.I.; The Society of Dyers and Colourists issued) number as follows may be mentioned. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferred that halogen is not contained.

Red coloring agent: red coloring agent, such as monoazo, diazo, monoazo, benzimidazolone, anthracene, diketopyrrolopyrrole, condensed azo, hydrazine The lanthanide, the quinacridone system, etc., specifically, the following are mentioned.

Monoazo system: 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.

Diazo system: Pigment Red 37, 38, 41.

Monoazo lake system: 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.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

The system is: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone is: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant: For blue colorants, there are anthracyclines, anthraquinones, and pigments are classified as Pigment compounds, specifically: Pigment Blue 15, Pigment Blue 15: 1. Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

For dye systems, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67 are available. , Solvent Blue 70, etc. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

Green colorant: For green colorant, there are similarly anthracycline, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20 can be used. , Solvent Green 28, etc. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used.

The yellow coloring agent: a yellow coloring agent is a monoazo type, a diazo type, a condensed azo type, a benzimidazolone type, an isoindrone type, an anthraquinone type, etc., Specifically, the following are mentioned. Listed.

Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: 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.

Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, for the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown, or black may be added.

Specifically, for example, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI color orange 1, CI color orange 5, CI color orange 13, CI color orange 14, CI color orange 16, CI color orange 17, CI color orange 24, CI color orange 34, CI color orange 36, CI color orange 38, CI Color Orange 40, CI Color Orange 43, CI Color Orange 46, CI Color Orange 49, CI Color Orange 51, CI Color Orange 61, CI Color Orange 63, CI Color Orange 64, CI color orange 71, CI color orange 73, CI color brown 23, CI color brown 25, CI color black 1, CI color black 7 and so on.

The ratio of the above-mentioned coloring agent (H) is not particularly limited, and it is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). To be full.

In order to enhance the physical strength and the like of the coating film, the curable resin composition of the present invention may be blended with a filler as needed. As such a filler, a well-known conventional inorganic or organic filler may be used. In addition to the aluminum hydroxide and the true spherical cerium oxide previously exemplified, barium sulfate, cerium oxide, talc, and magnesite may also be used. , magnesium hydroxide, boehite, alumina, titanium oxide, etc., which may be used alone or in combination of two or more.

The amount of the fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the filler is more than 300 parts by mass, the viscosity of the curable resin composition becomes high, the printability is lowered, and the cured product becomes brittle.

In the curable resin composition of the present invention, a conventionally known binder polymer can be used for the purpose of improving flexibility and dryness. In terms of the binder polymer, a cellulose-based, polyester-based or phenoxy resin-based polymer is preferred. Examples of the cellulose-based polymer include Cellulose Acetate Butyrate (CAB) and Cellulose Acetate Propionate (CAP) series manufactured by Eastman Co., Ltd., and polyester-based polymers, preferably VYLON series manufactured by Toyobo Co., Ltd., and phenoxy resin system. In terms of polymer, bisphenol A, bisphenol F and phenoxy resins of such hydrides are preferred. The amount of the binder polymer to be added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, even more preferably 5 to 30 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). . When the amount of the binder polymer is more than 50 parts by mass, the alkalinity of the curable resin composition is poor, and the start time of development can be shortened.

In the curable resin composition of the present invention, in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate, an adhesion promoter may be used. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl- 1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole , tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like.

In general, when a large amount of a polymer material starts to oxidize, that is, a chain oxidative degradation occurs next, and the function of the polymer material is lowered, the curable resin composition of the present invention can be added to prevent oxidation (1). a radical scavenger which can invalidate generated radicals and/or (2) an antioxidant which decomposes the generated peroxide into a harmless substance and does not generate a new radical peroxide decomposing agent .

The antioxidant acting as a radical scavenger, and specific examples thereof include hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, and hydroquinone. Monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methyl-bis(4-methyl-6-t-butylphenol), 1,1,3 - ginseng (2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t- Butyl-4-hydroxybenzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4, a benzoquinone compound such as 6-(1H, 3H, 5H)trione or the like, a benzoquinone compound such as methyl benzoquinone or benzoquinone, or bis(2,2,6,6-tetramethyl-4-piperidine) An amine compound such as a sebacate or a phenothiazine.

The radical scavenger may be a commercially available one, and may, for example, be ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above is manufactured by Asahi Kasei Corporation, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above) It is a product of Ciba Specialty Chemicals Co., Ltd., trade name, etc.

Examples of the antioxidant of the peroxide decomposer include a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, and dilauryl thiodipropionate. A sulfur-based compound such as an ester or a distearyl 3,3'-thiodipropionate.

The peroxide decomposing agent may be, for example, ADK STAB TPP (manufactured by Asahi Kasei Co., Ltd., trade name), Mark AO-412S (made by Adeka ARGUS Chemical Co., Ltd., trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., Product name).

These antioxidants may be used alone or in combination of two or more.

In general, since the polymer material absorbs light and causes decomposition and deterioration, the curable resin composition of the present invention can be used in addition to the above-mentioned antioxidant, in addition to the above-mentioned antioxidant. .

Examples of the ultraviolet absorber include a diphenyl ketone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamic acid ester derivative, and an ortho-amine benzoate. An acid ester derivative, a benzhydrylmethane derivative or the like. Specific examples of the diphenyl ketone derivative include 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-n-octyloxydiphenyl ketone, and 2,2'-di Hydroxy-4-methoxybenzophenone and 2,4-dihydroxydiphenyl ketone and the like. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, and 2,4-di-t-. Butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methyl group. Phenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 ',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'- Hydroxy-3',5'-di-t-pentylphenyl)benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

The ultraviolet absorber may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (The above is a product name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

The ultraviolet ray absorbing agent may be used singly or in combination of two or more kinds thereof, and it is intended to stabilize the molded article obtained from the curable resin composition of the present invention by use in combination with the above-mentioned antioxidant.

Further, in the curable resin composition of the present invention, an organic solvent can be used for the adjustment of the synthesis or composition of the carboxyl group-containing resin (A) or the viscosity adjustment for coating on a substrate or a carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethoxyethanol, methyl ethoxyethanol, and butyl b. Oxyethanol, diethylene glycol ethyl ether, methyl diglycol ether, butyl diglycol ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl Glycol ethers such as ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate Esters such as alcohols; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum systems such as petroleum ether, petroleum light oil, hydrogenated petroleum light oil, and solvent light oil. Solvents, etc. Such an organic solvent may be used singly or in combination of two or more.

The curable resin composition of the present invention may be blended with a conventionally known thermal polymerization inhibitor, fine powder of cerium oxide, organic clay, montmorillonite, or the like, a conventionally known tackifier, an anthrone, a fluorine system, or the like. A well-known and conventional additive such as a defoaming agent and/or a leveling agent such as a polymer, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, an antioxidant, and a rust preventive agent.

The aforementioned thermal polymerization inhibiting agent can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. Examples of the thermal polymerization inhibiting agent include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butyl catechol, benzenetriol, and 2-hydroxydiphenyl. Ketone, 4-methoxy-2-hydroxydiphenyl ketone, copper chloride (CuCl), phenothiazine, tetrachlorophenyl hydrazine, naphthylamine, β-naphthol, 2,6-di-t- Butyl-4-cresol, 2,2'-methyl bis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, trinitrophenol, 4- Toluidine, methyl blue, copper and organic chelating agent reactants, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al chelate.

The curable resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer formed of the curable resin composition formed on the carrier film.

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 a suitable viscosity, and is used as a comma coater or a blade coater. , a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater A coater, a gravure coater, and a spray coater are coated on the carrier film to have a uniform thickness, and are usually dried at a temperature of 50 to 130 ° C for 1 to 30 minutes to obtain a coating film. The coating film thickness is not particularly limited, but the film thickness after drying is generally 10 to 150 μm, preferably 20 to 60 μm.

For carrying the film, a plastic film is used, in which a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like is used. The plastic film is preferred. The thickness of the carrier film is not particularly limited, and generally, it can be appropriately selected in the range of 10 to 150 μm.

After the film is formed on the carrier film, it is preferable to laminate a peelable coating film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

For the peelable coated film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the coated film is peeled off, if the film and the coated film have a lower adhesion force than the film and The adhesive force carrying the film can be.

The curable resin composition of the present invention is adjusted to have a viscosity suitable for the coating method, for example, by a dip coating method, a cast coating method, a roll coating method, or a bar coating on a substrate. Coating by a method such as a method, a screen printing method, a curtain coating method, etc., and the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a tack-free one. Coating film. In addition, when the composition is applied onto a carrier film, dried, and wound into a dry film as a film, the curable resin composition layer is brought into contact with the substrate by a laminator or the like. After the substrate is applied, the carrier film is peeled off to form a resin insulating layer.

When it is a photocurable resin composition, it can be selectively exposed by an active energy ray or by laser through a contact type (or non-contact method) through a patterned photomask. The direct exposure machine directly exposes the pattern, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a photoresist pattern. When the composition further contains the thermosetting component (D), it is thermally cured by, for example, heating to a temperature of about 140 to 180 ° C, and has two or more cyclic ether groups and/or cyclic sulfides in the molecule. The thermosetting component (D) reacts with the carboxyl group of the carboxyl group-containing resin (A) to form excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Hardened film. Further, even if the thermosetting component (D) is not contained, by the heat treatment, the ethylenic unsaturated bond remaining in an unreacted state during the exposure is subjected to thermal radical polymerization, and the coating film characteristics can be improved. Purpose ‧ Use for heat treatment (thermal hardening).

In addition to the above-mentioned substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth are also used. / Non-woven epoxy, glass cloth / paper epoxy, synthetic 繊 epoxide, fluorine ‧ polyethylene ‧ PPO ‧ cyanate ester and other grades (FR-4, etc.) copper-clad laminates, other polyimine Film, PET film, glass substrate, ceramic substrate, wafer board, etc.

The volatilization drying performed after applying the curable resin composition of the present invention may be a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (using a heat source having a method of heating air by means of steam, This can be carried out by means of a method in which the hot air in the dryer is in contact with each other and a method of blowing the support from the nozzle.

In the case of a photocurable resin composition, the coating film obtained after coating and volatilizing the solvent is exposed (exposure by active energy rays) to expose the exposed portion (the portion irradiated by the active energy ray) )hardening.

In the above-mentioned exposure machine for active energy ray irradiation, a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in the range of 350 to 450 nm may be used. A direct rendering device (eg, a direct laser imaging device that directly renders an image based on laser data from a computer) can be used. For laser light sources that directly depict the machine, if laser light with a maximum wavelength of 350 to 410 nm is used, it can be either a gas laser or a solid laser. The amount of exposure for image formation varies depending on the film thickness, etc., but is generally 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

In the aspect of the development method, it may be a dipping method, a leaching method, a spraying method, a painting method, or the like, and in the case of a developing liquid, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, cesium may be used. An aqueous solution of an alkali such as sodium, ammonia or an amine.

[Examples]

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are all based on quality without any special restrictions.

Synthesis example

(A-1) Synthesis of a resin corresponding to the carboxyl group-containing resin (5): in a reaction vessel equipped with a stirring device, a thermometer, and a capacitor, 1,5-heptanediol and 1,6-hexene are charged. Alkylene glycol-derived polycarbonate diol (made by ASAHI KASEI CHEMICALS, TJ5650J, number average molecular weight 800) 2400g (3 moles), dimethyl propyl propionate 603g (4.5 moles) and as a single 2-hydroxyethyl acrylate of the hydroxy compound 238 g (2.6 mol). Next, 1887 g (8.5 mTorr) of isophorone diisocyanate as a polyisocyanate was put, and it heated after stirring to 60 degreeC with stirring, and it was set to it, and it heat-re-heats at the temperature of a reaction container, and stirring at 80 degreeC, and infrared- The absorption spectrum confirmed that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group disappeared, and the reaction was terminated. Diethylene glycol diethyl ether acetate was added to separate the solid formation into 50% by mass. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH/g.

(A-2) Photosensitive carboxyl group-containing resin corresponding to the carboxyl group-containing resin (7): a photosensitive carboxyl group-containing resin having a photosensitive group and a polyfunctional epoxy having a biphenyl aldehyde structure--Japan Chemical The resin solution of ZCR-1601H (solid content: 65%; acid value of resin: 98 mgKOH/g) was A-2.

Preparation of aluminum hydroxide slurry: 700 g of aluminum hydroxide (HIGILITE 42M manufactured by Showa Electric Co., Ltd.) and 280 g of diethylene glycol diethyl ether acetate as solvent, and 20 g of BYK-110 were mixed and stirred, and 0.5 on a bead mill. The πm zirconia beads are subjected to dispersion treatment. This was repeated 3 times, and a 3 μm filter was passed to prepare an aluminum hydroxide slurry (B-1).

Preparation of a cerium oxide slurry: 700 g of true spherical cerium oxide (SO-E2 manufactured by ADMATECHS Co., Ltd.), 295 g of diethylene glycol diethyl ether acetate as a solvent, and vinyl decane coupling as a decane coupling agent In the case of 5 g of the agent, dispersion treatment was carried out in a bead mill in the same manner as above. This was repeated 3 times, and filtered through a 3 μm filter to prepare a cerium oxide slurry (C-1).

Similarly, 700 g of true spherical ceria (SO-C5 manufactured by ADMATECHS Co., Ltd.) was dispersed in the same manner as the above-described ceria slurry, and a ceria slurry (C-2) was prepared by passing through a filter of 5 μm.

Examples 1 to 9 and Comparative Examples 1 to 4

Using the resin solution of the above-mentioned synthesis example, it was mixed with the various components shown in Table 1 in the ratio (parts by mass) shown in Table 1, and after preliminary mixing in a mixer, a 3-roll mill was used for kneading. A solder resist hardening resin composition is prepared. Here, the degree of dispersion of the obtained curable resin composition was evaluated by particle size measurement by a particle size measuring instrument manufactured by Eriksen Co., Ltd., and was 15 μm or less.

Performance evaluation: <Optimum exposure amount>

The circuit pattern substrate having a copper thickness of 35 μm was polished by a buff roll, and then washed and washed with water to apply the thermosetting ‧ light of the above Examples 2 to 9 and Comparative Examples 1 to 4 by screen printing The curable resin composition was dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20 manufactured by ORC Co., Ltd.) was used, and exposure was performed via a step tablet (Kodak No. 2) to perform 90-second imaging. When the pattern of the ladder plate remaining at 90 ° C, 0.2 MPa, and 1 wt% Na ₂ CO ₃ aqueous solution was 6 stages, it was an optimum exposure amount.

Characteristic test: <Solder heat resistance>

The evaluation substrate on which the rosin-based flux was applied was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with a modified alcohol, and then the swelling and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows.

○: immersed once in 10 seconds, and there was no peeling.

△: 1 time immersion in 5 seconds, no peeling.

×: The film was immersed once for 5 seconds, and the photoresist layer was swollen and peeled off.

<flammability>

The composition of each of the examples and the comparative examples was completely screen-printed on a 12.5 μm or 25 μm thick polyimide film (Kapton 100H, 50H manufactured by DuPont-Toray Co., Ltd.), and dried at 80 ° C for 20 minutes. Allow to cool to room temperature. Further, the inside was uniformly coated by screen printing in the same manner, and after drying at 80 ° C for 20 minutes, it was left to cool to room temperature to obtain a substrate coated on both sides. The substrate of Example 1 was thermally cured at 150 ° C for 60 minutes as an evaluation sample. On the other hand, in the substrates of Examples 2 to 9 and Comparative Examples 1 to 4, the exposure agent (HMW-680-GW20) equipped with a metal halide lamp was used to expose the solder resist at an optimum exposure amount, and 1 wt% Na ₂ CO at 30 ° C was used. _{3 The} aqueous solution was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds, and heat-hardened at 150 ° C for 60 minutes to obtain an evaluation sample. This sample for flame retardancy evaluation was subjected to a thin vertical burning test in accordance with the UL94 specification. The evaluation is based on the UL94 specification and is shown as VTM-0 or NG (VTM-0 indicates unfulfilled).

<Flexibility (Folding Resistance)>

The compositions of the respective examples and comparative examples were screen-printed on a 25 μm-thick polyimide film (Kapton 100H manufactured by DuPont-Toray Co., Ltd.), dried at 80 ° C for 30 minutes, and then left to cool. Warm up. The substrate of Example 1 was thermally cured at 150 ° C for 60 minutes as an evaluation sample. On the other hand, in the substrates of Examples 2 to 9 and Comparative Examples 1 to 4, the exposure agent (HMW-680-GW20) equipped with a metal halide lamp was used to expose the solder resist at an optimum exposure amount, and 1 wt% Na ₂ CO at 30 ° C was used. _{3 The} aqueous solution was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds, and heat-hardened at 150 ° C for 60 minutes to obtain an evaluation sample.

The obtained evaluation sample was repeatedly subjected to 180° bending by seam folding, and the occurrence of cracks in the cover layup was observed by visual observation and optical microscopy (magnification × 200), and the crack was evaluated. The number of times that did not occur.

The results of the above various evaluation tests are shown in Table 2.

Examples 10-17

The composition shown in Examples 2 to 9 shown in Table 1 was prepared by diluting a flame retardant photocurable resin composition prepared without using an anthrone-based antifoaming agent with methyl ethyl ketone, and applying it to The carrier film was dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm, and the coated film was bonded thereon to obtain a dry film. Thereafter, the coated film was peeled off, and the film was bonded to the copper foil substrate on which the pattern was formed, using a laminator. On this substrate, an exposure device (HMW-680-GW20) equipped with a metal halide lamp was used to expose the solder resist pattern at an optimum exposure amount, and after peeling off the carrier film, 1 wt% Na ₂ CO _{3 at} 30 ° C was used. The aqueous solution was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist pattern. Thereafter, the mixture was heat-cured at 60 ° C in a hot air dryer for 60 minutes to prepare a test substrate. The obtained test substrate having a hardened film was carried out in the same manner as the above-described test method and evaluation method, and an evaluation test of each characteristic was performed.

The results of the above various evaluation tests are shown in Table 3.

Claims (11)

A curable resin composition characterized by (A) a carboxyl group-containing resin, (B) aluminum hydroxide, and (C) true spherical cerium oxide. The curable resin composition according to claim 1, which further comprises (D) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in the molecule. The curable resin composition of claim 1, which further comprises (E) a compound containing phosphorus. The curable resin composition of claim 1, which further comprises (F) a photopolymerization initiator and (G) a photopolymerizable monomer. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) has a biphenol novolak structure and an ethylenically unsaturated group. The curable resin composition of claim 2, wherein the thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule has a biphenol aldehyde varnish Skeleton epoxy resin. The curable resin composition according to any one of claims 1 to 7, which is a solder resist. A dry film obtained by coating and drying a curable resin composition according to any one of claims 1 to 7 on a film. A cured product obtained by applying a dried coating film obtained by drying a curable resin composition according to any one of claims 1 to 7 to a substrate, or coating the above-mentioned curable resin composition A dry film obtained by drying a film on a film, and a dried coating film obtained by laminating the film, is obtained by thermal curing and/or photohardening. A printed wiring board characterized by having the cured product of claim 10 of the aforementioned patent application.