TWI415896B - A hardened resin composition, a dry film and a printed circuit board using the same - Google Patents

Abstract

The invention provides a curable resin composition, dry membrane and printed circuit board using the same, more particularly, the invention provide a curable resin composition and a dry membrane using the same, as well as a printed circuit board formed by a flame-resistant curable membrane such as a solder resisting membrane and the like formed by using the curable resin composition and the dry membrane, the curable resin composition has a halogen-free flame retardant, and can form a solder resisting layer with excellent flame resistance and insulating reliability and low warpage. The curable resin composition contains (A) a carboxyl-contained resin, (B) a phosphorus-containing compound and (C) layer-shaped composite hydroxide. a thermocuring resin composition comprises the above (A), (B) and (C), and (D) a thermocuring component with more than two ring-shaped ether group and/or ring-shaped sulfide group, and a photocuring thermocuring resin composition comprises the above (A), (B), (C) and (D), and (F) a photopolymerisable initiator and (G) a photopolymerisable monomer, preferably contains (E) aluminium hydroxide.

Description

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

The present invention relates to a curable resin composition, and particularly relates to a curable resin composition which can form a solder resist which is excellent in flame retardancy, low warpage, and insulation reliability. The present invention also relates to a dry film and a flame-retardant printed circuit board using the curable resin composition.

In the past, printed circuit boards and flexible circuit boards (hereinafter abbreviated as FPC) have been required to be mounted on electronic devices for flame retardancy, and these parts of the solder resist are also required to be flame retardant. Among them, the FPC is usually composed of a polyimide substrate, which is a film different from a printed circuit board of a glass epoxy substrate. However, since the solder resist to be applied has the same film thickness as the printed circuit board and the FPC, the burden of the flame retardancy of the solder resist is relatively large in the case of the FPC of the film.

Therefore, there have been various proposals for the incombustibility of solder resists from the past. For example, JP-A-2007-10794 (Patent Document 1) discloses a (a) binder polymer, (b) a halogenated aromatic ring having a bromophenyl group in the molecule, and a (meth) propylene. a polymerizable ethylenically unsaturated bonded photopolymerizable compound such as a mercapto group, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus-containing compound having a phosphorus atom in a molecule A flame retardant photosensitive resin composition for FPC. However, from the viewpoint of environmental load, it is not preferable to use a halogen compound such as a compound having a halogenated aromatic ring and a polymerizable unsaturated double bond.

Therefore, the recent solder resist replaces the ruthenium chloride cyanine green which is a green colorant from the viewpoint of reducing environmental load, and generally uses a solder resist which does not have a halogen atom and a blue color and a yellow colorant (for example, , refer to Patent Document 2). Further, in order to clearly recognize that halogen is not contained in appearance, it is also used as a blue solder resist as a blue solder blue. However, the solder resist is formed to protect the copper circuit, and on the other hand, one of the uses is to cause heat or moisture of the copper circuit, electrical discoloration, or scratches and dirt on the copper circuit to be unobserved (obscured). In this regard, a coloring agent is usually added to the solder resist, and the appearance of the colorant is made thick, so that the appearance defects are not easily found. However, compared with the green color of phthalocyanine, the blue solder resist ink formed by the blue solder resist ink or the blue colorant and the yellow colorant is weak in obscuration and cannot be sufficiently obtained. The appearance of a coloring agent that is not easily found in appearance.

Further, in the case of a printed circuit board of a film represented by FPC, the occurrence of warpage caused by hardening shrinkage is now a problem when the solder resist is photohardened or thermally hardened.

On the other hand, a method of achieving flame retardancy by halogen-free is widely known to use a phosphorus-containing compound. However, in the case where it is necessary to achieve a solder resist for a long-term electrically insulating printed circuit board, the phosphorus-containing compound, particularly a phosphate ester, may be inferior due to its poor hydrolysis resistance and particularly poor electrical resistance to mobility. The disadvantages of heavy use.

[Advanced technical literature] [Patent Literature]

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

[Patent Document 2] JP-A-2000-7974 (Application Patent Application)

The present invention has been made to solve the above-mentioned conventional problems, and its main object is to provide a curable resin composition containing a halogen-free flame retardant, which can form excellent flame retardancy, low warpage, and insulation. A curable resin composition of a resistive solder resist layer.

Further, an object of the present invention is to provide a printed circuit of a dry film which is excellent in low bending, flame retardancy and insulation reliability, and a flame retardant film having such excellent characteristics by using the curable resin composition. board.

In order to achieve the above object, according to the present invention, a curable resin composition containing (A) a carboxyl group-containing resin, (B) a phosphorus-containing compound, and (C) a layered double hydroxide can be provided.

In addition to the above-mentioned components, it can be used as a thermosetting resin by further containing (D) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in the molecule. Composition. Another suitable aspect is to further contain (E) aluminum hydroxide. Another suitable aspect is that it can be used as a photocurable thermosetting resin composition by further containing (F) a photopolymerization initiator and (G) a photopolymerizable monomer. Another suitable aspect is to further contain a colorant (H). 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. The thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule is an epoxy resin having a biphenol aldehyde skeleton, and the above layered double hydroxide (C) ) is a hydrotalcite. Such a hardening resin composition can be suitably used for the formation of a solder resist on a printed circuit board.

Moreover, according to the present invention, a dry film obtained by coating and drying the curable resin composition on a film or a coating of the curable resin composition or the curable resin composition on a carrier film is provided. The dried film is cured by heat hardening and/or photohardening. Further, according to the present invention, a printed circuit board having the above cured product is also provided.

The curable resin composition of the present invention contains (A) a carboxyl group-containing resin, (B) a phosphorus-containing compound, and (C) a layered double hydroxide, preferably by further containing (E) aluminum hydroxide. A film having a low environmental load and low flame retardancy, low bendability, and excellent insulation reliability is formed by a halogen-free composition. Therefore, by using the curable resin composition of the present invention, it is possible to provide a printed circuit board having a low-bending, flame-retardant and insulating reliability, and a flame-retardant solder resist film having such excellent characteristics.

The present invention is characterized in that a layered double hydroxide (C) and a phosphorus-containing compound (B) as a flame retardant are simultaneously used with respect to the carboxyl group-containing resin (A). It is considered that it is possible to use a layered double hydroxide (C) and a phosphorus-containing compound (G) in combination with an acid such as phosphoric acid of a phosphorus-containing compound, particularly a hydrolysis product of a phosphate ester, and a layered double hydroxide. The substance (C) acts as an antacid, and as a result, the occurrence of migration can be suppressed. Further, if the amount of the layered double hydroxide added is increased, the flame retardancy can be improved, and as a result, the amount of the phosphorus-containing compound can be reduced. However, it is considered that since the layered double hydroxide itself is an aqueous compound, an inert gas is generated due to the high temperature at the time of combustion, and the effect of making the fire become small is caused. As such, the layered double hydroxide is surprisingly effective in that it is unimaginable with respect to the flame retardant containing a phosphorus compound.

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

As 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 a 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 viewpoints of photocurability and development resistance. . Further, the unsaturated group is preferably one derived from an acrylic acid or a methacrylic acid derivative. When only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photohardenable, it is necessary to use a photopolymerization having two or more ethylenically unsaturated groups in the molecule, which will be described later. Sex monomer (G).

As a specific example of the carboxyl group-containing resin (A), a compound (any of an oligomer and a polymer) as exemplified below can be suitably used.

(1) Copolymerization with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene by an unsaturated carboxylic acid such as (meth)acrylic acid The resulting carboxyl group-containing resin.

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group of dimethylolpropionic acid or dimethylolbutanoic acid. a diol compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a phenol A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound such as a hydroxyl group or an alcoholic hydroxyl group.

(3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate-based polyalcohol, a polyether-based polyalcohol or a polyester-based polyester An addition polymerization reaction of a diol compound such as a polyhydric alcohol, a polyolefin-based polyalcohol, an acrylic polyalcohol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group The terminal carboxy urethane resin is formed by reacting a terminal of a urethane resin with an acid anhydride.

(4) 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 Photosensitive carboxyl group formed by addition polymerization of a (meth) acrylate or a partial acid anhydride denatured product thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a resin or a biphenyl type epoxy resin A urethane resin.

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

(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 isophorone diisocyanate and pentaerythritol triacrylate. a methyl (meth) fluorenyl group-based compound and a terminal (meth) acrylated carboxyl group-containing urethane resin.

(7) reacting a polyfunctional (solid) epoxy resin as described later with (meth)acrylic acid to add a hydroxyl group present in the side chain to a dibasic acid anhydride such as anhydrous citric acid, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A photosensitive carboxyl group-containing resin.

(8) reacting a polyfunctional epoxy resin which epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin with (meth)acrylic acid, and sensitizing the generated hydroxyl group to a dibasic acid anhydride A resin containing a carboxyl group.

(9) A carboxyl group-containing polyester resin obtained by reacting a bifunctional oxetane resin described later with a dicarboxylic acid to form a dibasic acid anhydride to the produced first-order hydroxyl group.

(10) The resin of the above (1) to (9) further has a ring of a molecule such as a glycidyl (meth) acrylate or an α-methyl propyl propyl (meth) acrylate. A photosensitive carboxyl group-containing resin composed of an oxy group and a compound of one or more (meth) acrylonitrile groups.

Among these carboxyl group-containing resins, (X) a carboxyl group-containing polyurethane resin, particularly an isocyanate group having an isocyanate group component (including a diisocyanate) of a urethane resin and The polyfunctional epoxy resin used for the synthesis of the above resin is a bisphenol A structure, a bisphenol F structure, a biphenyl structure, a biphenol aldehyde structure, a bisphenol structure, and the like. In the case of a compound having a biphenyl aldehyde structure and a hydrogenated compound thereof, it is preferred that it has low bending and tortuosity. Further, on the other hand, the denatured products of the above (2), (3), (4), (5), (6) and the like (10) have a urethane bond in the main chain, It is better for bending. Further, the resin other than the above (1), (2), (3), and (9) preferably has a photoreactive group in the molecule and has high photoreactivity.

Further, in the present specification, (meth) acrylate means a general term for acrylate, methacrylate and a mixture thereof, and the other similar expressions are also the same.

The above-mentioned carboxyl group-containing resin (A) has a crosslinking point at the time of thermal curing because it has a large number of free carboxyl groups in the side chain of the main chain ‧ polymer. Moreover, in the case of a photocurable resin composition, it can be developed by a dilute alkali aqueous 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 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 development becomes difficult. On the other hand, if it exceeds 200 mgKOH/g, the exposure portion is caused by the developing solution. When the dissolution is performed, the line width is made thinner than necessary, and depending on the case, the exposed portion and the unexposed portion are indistinguishable from being dissolved and peeled off in the developing liquid, and the drawing of the normal photoresist pattern is difficult, which is not preferable.

Further, the weight average molecular weight of the carboxyl group-containing resin (A) differs depending on the resin skeleton, and is generally preferably 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 free performance is deteriorated, and the film is depleted when the moisture resistance of the coating film after exposure is deteriorated, and the resolution is remarkably deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the development property is remarkably deteriorated, and the storage stability is poor.

The amount of the carboxyl group-containing resin (A) is from 5 to 60% by mass, preferably from 10 to 60% by mass, more preferably from 20 to 60% by mass, particularly preferably 30, based on the total composition. ~ 50% by mass. When it is less than the above range, it is not preferable because the coating film strength is lowered. On the other hand, when it is more than the above range, it is not preferable because the viscosity of the composition is high and the coating property is lowered.

The curable resin composition of the present invention preferably contains the phosphorus-containing compound (B). As the phosphorus-containing compound, a conventionally known organic phosphorus-based flame retardant is preferred, and there are a phosphate ester and a condensed phosphate ester, a cyclic phosphazene compound, a phosphazene oligomer, a hypophosphite or the following general formula. (I) The compound represented.

[Chemical 1]

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

Commercial products of the compound represented by the above general 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 (B) which is particularly useful in the present invention may, for example, be (1) having an acrylate group or (2) having a phenolic hydroxyl group, (3) an oligomer or a polymer, or (4) phosphorus. The nitrile oligomer and (5) hypophosphite are used as reactive groups.

(1) Phosphorus-containing compound having an acrylate group

The acrylate having a phosphorus element is preferably a compound having a phosphorus element and having two or more (meth) acrylates in the molecule, and specifically, R ¹ and R ² in the above general formula (1) are hydrogen atoms. , R ³ is a compound of an acrylate derivative, generally by the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the well-known conventional multifunctional acrylate monomer The addition reaction is carried out for synthesis.

Examples of the above-mentioned conventionally known acrylate monomer include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol and trimethylolpropane; a polyvalent acrylate such as pentaerythritol, dipentaerythritol or hydroxyethyl isocyanurate or a polyvalent acrylate such as an ethylene oxide adduct, a propylene oxide adduct or a caprolactone adduct a polyvalent acrylate such as a phenoxy acrylate, a bisphenol A diacrylate, or an oxirane ethylene oxide adduct or a propylene oxide adduct; and the above polyols Rings of urethane acrylates, glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, trisethoxypropyl isocyanurate, etc. a polyvalent acrylate of oxypropyl ether; and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate.

(2) Phosphorus-containing compounds having phenolic hydroxyl groups

The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, and has no deterioration in electrical properties due to hydrolysis, and has high solder heat resistance. Further, a suitable combination is obtained by using an epoxy resin having a biphenyl skeleton or other epoxy resin as the component (D), and since it is incorporated into the network by reacting with the epoxy resin, it is possible to obtain no bleeding after hardening. -out) The advantage. Commercially available products are Sanko (share) HCA-HQ and the like.

(3) oligomer or polymer

The phosphorus-containing compound which is an oligomer or a polymer has no tortuosity due to the influence of the alkyl chain, and because of its large molecular weight, it is advantageous in that it does not bleed out after hardening. Commercially available products include M-Ester-HP manufactured by Sanguang Co., Ltd., and Vylon 337 containing phosphorus by Toyobo Co., Ltd.

(4) phosphazene oligomer

As a phosphazene oligomer, a phenoxyphosphazene compound is effective, a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, a tetramer, a pentamer ring, and a liquid Any shape or solid powder can be used as appropriate. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd. Among them, a phenoxyphosphazene oligomer substituted with a polar group such as an alkyl group or a hydroxyl group or a cyano group has high solubility in a carboxyl group-containing resin, and even if it is added in a large amount, there is no problem such as recrystallization. good.

(5) hypophosphite

By using hypophosphite, the flame retardancy can be further improved without impairing the softness of the cured coating film. Further, by using a hypophosphite having excellent heat resistance, the bleeding of the flame retardant can be suppressed in the hot pressing at the time of mounting. Commercially available products include EXOLIT OP 930 and EXOLIT OP 935 manufactured by Clariant.

The compounding amount of the phosphorus-containing compound (B) as the flame retardant is preferably in the range of 0 to 200 parts by mass, particularly preferably 0 to 100% by mass based on 100 parts by mass of the carboxyl group-containing resin (A). Share. When the amount is sufficiently increased or more, the obtained toughness and the like of the cured film are deteriorated, which is not preferable.

As the layered double hydroxide of the above component (C), hydrotalcite and a compound such as hydrotalcite can be suitably used. Hydrotalcites and compounds such as hydrotalcite are one of the clay minerals produced in nature, for example, the base layer of positively charged [Mg _1-X Al _X (OH) ₂ ] ^X+ and the intermediate layer of load electricity [(CO ₃ ) _X/2 ‧ mH ₂ O] ^X-based layered inorganic compound. Many of the divalent or trivalent metals have the same layered structure as described above, and the general structural formula is as shown in the following formula (II).

[Chemical 2]

Wherein M ²⁺ is a divalent metal cation, M ³⁺ is a trivalent metal cation, A ^n- is an n-valent anion, and each element and the underside of the atomic group indicate the ratio of each element and the atomic group, X is 0<X≦0.33. m≧0, but it varies greatly with dehydration.

Specific examples of the layered double hydroxide (C) include indigirite Mg ₂ Al ₂ [(CO ₃ ) ₄ (OH) ₂ ]‧15H ₂ O, Fe ²⁺ ₄ Al ₂ [ (OH) ₁₂ CO ₃ ]‧3H ₂ O, Quintinite Mg ₄ Al ₂ (OH) ₁₂ CO ₃ ‧H ₂ O, Manasseite Mg ₆ Al ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, sjOegrenite Mg ₆ Fe ³⁺ ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Zaccagnaite Zn ₄ Al ₂ (CO ₃ )(OH) ₁₂ ‧3H ₂ O, hydroxycarbonite (Desautelsite) Mg ₆ Mn ³⁺ ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Hydrotalcite, Mg ₆ Al ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Pyroaurite Mg ₆ Fe ^{3 +} ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Reevesite Ni ₆ Fe ³⁺ ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Chromite (Stichtite) Mg ₆ Cr ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, Takovite Ni ₆ Al ₂ [(OH) ₁₆ CO ₃ ]‧4H ₂ O, and the like.

Further, commercially available hydrotalcites are exemplified by Kyowa Chemical Industry Co., Ltd.; ALCAMIZER, DHT-4A, KW-500, KW-1000, 堺Chem (share) STABIACE series HT-1, HT- 7, HT-P and so on.

Particularly preferred are synthetic hydrotalcites, and those having an average particle diameter of 2 μm or less, more preferably 1 μm or less are preferred.

The amount of the layered double hydroxide (C) is, for example, suitably from 5 to 100 parts by mass, preferably from 10 to 50 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount is more than the above range, it is not preferable because the viscosity and the shake of the composition become too high, the printability is lowered, and the cured product becomes brittle. On the other hand, if it is less than 5 parts by mass, it is not preferable because it may impair the ion-resistant movement effect.

The thermosetting component (D) used for the purpose of improving the properties such as heat resistance and insulation reliability, which is composed of the composition of the present invention and the thermosetting resin composition, can react with the carboxyl group of the carboxyl group-containing resin. A conventionally known compound having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter, abbreviated as a cyclic (thio)ether group) in the molecule can be used, and among them, a bifunctional one or more The epoxy resin is preferably from the viewpoint of heat resistance and gold plating resistance, and particularly an epoxy resin having a biphenyl aldehyde skeleton is preferred because it can improve 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. Alternatively, diisocyanates or their bifunctional blocked isocyanates may also be used.

Further, in the thermosetting resin composition of the present invention, a thermosetting component having two or more cyclic (thio)ether groups in the molecule as a thermosetting component is used as having 3, 4 or 4 in the molecule. Examples of the cyclic ether group or the cyclic thioether group of the 5-membered ring or a compound having two or more kinds of the two types of compounds include, for example, a compound having two or more epoxy groups in the molecule, that is, The functional epoxy compound (D-1) having 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, and EPICLON 2055 manufactured by DIC Corporation, and Dongdu Chemical Co., Ltd. EPOTOTE YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by The Dow Chemical Company, ARALDITE 6071, ARALDITE 6084, manufactured by Ciba Specialty Chemicals Co., Ltd. ARALDITE GY250, ARALDITE GY260, SUMIEPOXY ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, AER330, AER331, AER661, AER664, etc. by Asahi Kasei Industrial Co., Ltd. Name) bisphenol A type epoxy resin; jER YL903 manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTE YDB-400, YDB-500 manufactured by Dongdu Chemical Co., Ltd., manufactured by Dow Chemical Co., Ltd. DER542, ARALDITE 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., SUMIEPOXY ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries Co., Ltd., AER711, AER714, etc. (both trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. Oxygen resin; Japanese ring JER152 and jER154 manufactured by Resin Co., Ltd., DEN431 and DEN438 manufactured by Dow Chemical Co., Ltd., EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC Corporation, EPOTOTE YDCN-701 and YDCN manufactured by Dongdu Chemical Co., Ltd. -704, ARALDITE ECN1235, ARALDITE ECN1273, ARALDITE ECN1299, ARALDITE XPY307, manufactured by Ciba Specialty Chemicals Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Nippon Chemical Industry Co., Ltd. SUMIEPOXY ESCN-195X, ESCN-220, phenolic epoxy resin of AERECN-235, ECN-299, etc. (all are trade names) manufactured by Asahi Kasei Kogyo Co., Ltd.; EPICLON 830 made by DIC Corporation, Japan Epoxy Resin JER807 manufactured by the company, EPOTOTE YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., bisphenol F-type epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd. (all of which are trade names); Dongdu Chemical Company Hydrogenated bisphenol A epoxy resin such as EPOTOTE ST-2004, ST-2007, ST-3000 (trade name), jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOTE YH-434 manufactured by Dongdu Chemical Co., Ltd. ARALDITE MY720, manufactured by Bajing Chemical Co., Ltd., Sumitomo Chemical Industry Ethylene propyl urethane epoxy resin such as SUMIEPOXY ELM-120 (both trade names) manufactured by Seiko Co., Ltd.; and urethane urethane epoxy resin such as ARALDITE CY-350 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. ; Ceroxide 2021 manufactured by DAICEL Chemical Industry Co., Ltd., alicyclic epoxy resin manufactured by Ciba Specialty Chemicals Co., Ltd., ARALDITE CY175, CY179, etc. (all are trade names); YL-933, manufactured by Japan Epoxy Resin Co., Ltd., Dow Chemical Company's TEN, EPPN-501, EPPN-502 (all are trade names) trishydroxyphenylmethane epoxy resin; Japan Epoxy resin company YL-6056, YX-4000, YL-6121 (all商品 phenol type or biphenyl type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd. Name) bisphenol S type epoxy resin; bisphenol A phenolic epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; jER YL-931, Ciba Specialty Chemical Co., Ltd. Tetraphenylolethane type epoxy resin of ARALDITE 163 (all trade name) manufactured by Chemical Co., Ltd.; ARA made by Ciba Specialty Chemicals Co., Ltd. LDITE PT810, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (both trade names); a diepoxypropyl phthalate resin such as Blemmer DGT manufactured by Nippon Oil & Fats Co., Ltd.; ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Ethylene-based oxime phenolic phenol resin; Ethanol based on ESN-190, ESN-360, DIC, HP-4032, EXA-4750, EXA-4700, etc.; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by DIC Co., Ltd.; epoxy methacrylate copolymerized epoxy of CP-50S, CP-50M, etc. manufactured by Nippon Oil & Fats Co., Ltd. Resin; copolymerized epoxy resin having cyclohexylmaleimide and epoxypropyl methacrylate; epoxy-denatured polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN denatured epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more.

The polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-) Oxetanylmethoxy)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)methacrylic acid Ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or their oligomers Or a polyfunctional oxetane such as a copolymer, and examples thereof include oxetane and phenol resin, poly(p-hydroxystyrene), cardo type bisphenol, and calixarene. , calixresorcinarene, or an ether compound of a resin having a hydroxyl group such as silsesquioxane or the like. Other examples include copolymers of an oxetane ring-unsaturated monomer and an alkyl (meth)acrylate.

Examples of the episulfide resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule include bisphenol A-type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an anisole resin or the like in which an oxygen atom of an epoxy group of a novolac type epoxy resin is substituted with a sulfur atom can be used by 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, and the cyclic (thio)ether group is preferably 0.6. ～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 in the solder resist film, and heat resistance, alkali resistance, and electric resistance are caused. Insulation and the like are lowered, which is not preferable. On the other hand, when it is more than 2.5 equivalents, since the low molecular weight cyclic (thio)ether group remains on the dried coating film, the strength of the coating film or the like is lowered, which is not preferable.

In addition to the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule, the curable resin composition of the present invention is intended to further improve the heat resistance and the insulating reliability of the cured coating film. And 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, a benzoguanamine resin, a cyclic carbonate compound, or a double horse may be blended. A known thermosetting resin such as a methylene chloride, an oxazine compound, an oxazoline compound, or a carbamide resin.

The compound having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be a compound having two or more isocyanate groups in one molecule, 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-benzylidene diisocyanate, 2,6-benzylidene diisocyanate, and naphthalene-1,5-diisocyanate. , o-extended diisocyanate, m-extended diisocyanate and 2,4-benzylidene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene double (ring). Hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, an adduct of an isocyanate compound, a biuret and an isocyanurate body which have been mentioned above may be mentioned.

The blocked isocyanate-based isocyanate group contained in the blocked isocyanate compound is a group which is inactivated for a while by being protected by a reaction with a blocking agent. Upon heating to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound which can be reacted with the blocking agent include an isocyanurate type, a biuret type, and addition molding. 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 may be exemplified by the compounds exemplified above.

Examples of the isocyanate blocking agent include phenol blocking agents such as phenol, cresol, indophenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroguanamine, γ-butylide and a guanamine-blocking agent such as β-propionalamine; an active methylene blocking agent such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol, amyl alcohol, and B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycolic acid Alcohol-based blocking agents such as esters, diacetone alcohols, methyl lactate and ethyl lactate; guanidine oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, ethyl hydrazine oxime, cyclohexane hydrazine, etc. Blocking agent; thiol blocking agent such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid such as acetamide or benzoguanamine Amidoxime blocking agent; a quinone imine blocking agent such as succinimide succinate and succinimide; an amine blocking agent such as guanamine, aniline, butylamine or dibutylamine; imidazole, 2 -imidazole blocking agent such as ethyl imidazole; methyleneimine And an imine blocking agent such as propylimine.

The blocked isocyanate compound may also be a commercially available product, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, and Desmosum. 2170, Desmosum 2265 (above, manufactured by Sumitomo Bayer Carbamate 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 (made by Asahi Kasei Chemical Co., Ltd., trade name )Wait. However, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a blocking agent.

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

In the same manner, the compounding 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 100 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). The ratio of 2 to 70 parts by mass is appropriate. When the amount 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 mass parts, it is not preferable because the storage stability of the composition is lowered.

Further, examples of other thermosetting components include a melamine derivative and a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, a methylol urea compound, and the like. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated acetylene urea compound, and the alkoxymethylated urea compound may each be a methylol group The melamine compound, the methylol 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 for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or the like can be used. In particular, it is preferred to use a melamine derivative having a concentration of 0.2% or less of a human or environmentally friendly fumarine.

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, Mitsui Cyanamide (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, Sanwa Chemical Co., Ltd.). 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 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 - an imidazole derivative such as cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanamide, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as a benzylamine, a bisamine compound such as diammonium adipate or a ruthenium sebacate; a phosphorus compound such as triphenylphosphine; and the like, and a commercially available product includes, for example, four countries. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Industrial 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 methylamine, DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic hydrazine compounds and salts thereof). However, it is not limited thereto, and the thermosetting catalyst of the epoxy resin or the oxetane compound may promote the reaction of the epoxy group and/or the oxetanyl group with the carboxyl group, and may be used alone. It is also possible to mix two or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2 can also be used. 4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ iso-cyanuric acid adduct, 2,4-diamino-6-methyl An S-triazine derivative such as an acryloxyethyl-S-triazine ‧ isocyanuric acid addition product, etc., preferably a compound which can function as an adhesion imparting agent and the aforementioned thermosetting Use the catalyst together.

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

Aluminum hydroxide (E) can be directly used as a commercial product. Commercially available products include Higilite series, HW, H21, H31, H32, H42M, and H43M manufactured by Showa Denko. Further, since the particle size of the aluminum hydroxide is extremely effective in the folding resistance of the fine particle diameter, the solvent or the resin is used together as a bead in view of the flame retardancy and the tortuosity of the hardened film obtained therefrom. It is preferable to carry out dispersion processing, filtration, or the like until the primary particle diameter is polished, and it is preferably used by filtering 3 μm or more, more preferably 1 μm or more.

The amount of the aluminum hydroxide (E) to be added is preferably from 1 to 300 parts by mass, more preferably from 1 to 200 parts by mass, even more preferably 10 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). ~150 parts by mass.

The photopolymerization initiator (F) constituting the photocurable resin composition of the present invention may be selected from an oxime ester photopolymerization initiator having an oxime ester group, and an α-aminoacetophenone photopolymerization initiator. One or more kinds of photopolymerization initiators in the group of the catalyst and the mercaptophosphine oxide photopolymerization initiator.

The oxime ester photopolymerization initiator may, for example, CGI-325, Iragcure OXE01, Iragcure OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., ADEKA ARKLS NCI-831, and the like.

Further, a photopolymerization initiator having two oxime ester groups in the molecule may be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula (III).

[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, or a phenyl group (via an alkyl group having 1 to 17 carbon atoms and a carbon number of 1 to 8) Alkoxy group, amine group, alkylamino group or dialkylamine group having an alkyl group having 1 to 8 carbon atoms, naphthyl group (alkyl group having 1 to 17 carbon atoms, carbon number 1 to 8) An alkoxy group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group (via an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, and an alkyl group having 1 to 8 carbon atoms) a substituted alkylamino or dialkylamino group, a naphthyl group (via 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. ,biphenylalkenyl,extended pyridyl, —naphthyl, thiophene, anthracenyl, thiophene, extended furan, 2,5-pyrrole-diyl, 4,4′-fluorene-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 preferably a phenylene group, a naphthyl group, a thiophene group or a thiophene group.

The α-aminoacetophenone photopolymerization initiator is specifically 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-benzyl 2--2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. Commercially available products include Iragcure 907, Iragcure 369, Iragcure 379, and the like manufactured by Ciba Specialty Chemicals.

The mercaptophosphine oxide photopolymerization initiator may specifically be 2,4,6-trimethylbenzylidenediphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene). - 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 Iragcure 819 manufactured by Ciba Specialty Chemicals.

Among the above photopolymerization initiators, a mercaptophosphine oxide-based initiator is preferred because of its photobleaching property, and its light permeability is most excellent and it has an effect on flame retardancy. Further, the oxime ester-based starter is excellent in efficiency as a starter, and the sensitivity is improved in a small amount, and the amount of exhaust gas during heat treatment after the formation of the photoresist film is small, and the bending of the film is effectively reduced, which is preferable. The ideal is to use both together.

The amount of the photopolymerization initiator (F) is preferably from 0.01 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, per 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 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 is more than 30 parts by mass, the light absorption on the surface of the solder resist coating film of the photopolymerization initiator (F) is intense, and the deep hardenability tends to be lowered, which is not preferable.

In the case of the oxime ester-based photopolymerization initiator having the group represented by the above formula (III), the compounding amount thereof is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). The mass fraction is more preferably in the range of 0.01 to 5 parts by mass.

Other photopolymerization initiators, photoinitiating aids, and sensitizers which can be suitably used as the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, hydrazine compounds, thioxanthone compounds, and A ketal compound, a diphenyl ketone compound, a xanthone 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 acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone. 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-diisopropylthiophene. Tons of 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-benzyl fluorenyl diphenyl sulfide, 4-benzyl fluorenyl 4'-methyl diphenyl sulfide, and 4-benzyl hydrazine. Base-4'-ethyldiphenyl sulfide, 4-benzylindolyl-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminodiphenyl ketone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.). , 4,4'-diethylaminodiphenyl ketone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminodiphenyl ketone, 7-(diethylamino)-4-methyl- A dialkylamine group such as 2H-1-benzopipen-2-one (7-(diethylamino)-4-methylhumifrolin) contains a xanthan compound, 4-dimethylamine Ethyl benzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylamino benzoic acid (n-butyl) Oxy)ethyl ester (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylamino benzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2 Ethylhexyl ester (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. The composition of the present invention is preferably a thioxanthone compound from the viewpoint of deep hardenability, wherein 2,4-dimethyl ketone, 2,4-diethylthioxanthone, 2-chlorothiazide A thioxanthone compound such as a ketone or a 2,4-diisopropylthioxanthone is preferred.

The amount of the thioxanthone compound 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, and the cost of the product is indirectly increased, which is not preferable.

The tertiary amine compound is preferably a compound having a dialkylaminophenyl structure, wherein the dialkylaminodiphenyl ketone compound and the dialkylamine-containing humectin compound having a maximum absorption wavelength of 350 to 410 nm It is especially good. The dialkylaminodiphenyl ketone compound preferably has a low toxicity of 4,4'-diethylaminodiphenyl ketone. The dialkylamine group having a maximum absorption wavelength of 350 to 410 nm contains a xanthanin compound, and the maximum absorption wavelength is in the ultraviolet field, and the coloring is small, and the colorless and transparent photosensitive composition fundamentally uses a coloring pigment to reflect the coloring pigment. The provision of a color solder mask film of the self color is made possible. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-one is preferred because it exhibits excellent sensitization with respect to laser light having a wavelength of 400 to 410 nm. .

The amount of the 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 formed by the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered.

In order to enhance the sensitivity, the photocurable resin composition of the present invention may be a conventionally used N-phenylglycine, phenoxynonanoic acid, thiophenoxynonanoic acid, thiol thiazole or the like as a chain transfer agent. Specific examples of the chain transfer agent include chain-locking transfer of 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 mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3- Mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(extended ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan, Propanethiol, butyl mercaptan, pentyl mercaptan, 1-octyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

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

In particular, it is a heterocyclic compound having a mercapto group which is a chain-locking agent which does not impair the developability of the photocurable resin composition, and is a mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2 Preferably, 4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain-locking agents may be used alone or in combination of two or more.

These photopolymerization initiators, photoinitiating aids, sensitizers, and chain-locking agents may be used singly or as a mixture of two or more types.

The total amount of the photopolymerization initiator, the photo-starting aid, the sensitizer, and the chain-locking agent is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, there is a tendency that the light is absorbed and the deep hardenability is lowered.

The photopolymerizable monomer (G) used for the composition of the present invention to form a photocurable resin composition is photocured by irradiation with an active energy ray, and the photocurable resin composition of the present invention is insolubilized. An aqueous alkali solution or a person who helps it to dissolve. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol; a polyvalent acrylate such as a polyhydric alcohol such as hydroxyethyl isocyanurate or an ethylene oxide adduct or a propylene oxide adduct thereof; phenoxy acrylate, bisphenol A a polyvalent acrylate such as an acrylate or an oxirane ethylene oxide adduct or a propylene oxide adduct; glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trihydroxyl a polyvalent acrylate of a glycidyl ether such as methyl propane triepoxypropyl ether or triethoxypropyl isocyanurate; and a melamine acrylate, and/or a methyl group corresponding to the above acrylate Acrylates, etc.

Further, an epoxy acrylate resin which reacts a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, or a hydroxy acrylic acid such as pentaerythritol triacrylate which is a hydroxyl group of the epoxy acrylate resin may be mentioned. An epoxy urethane acrylate compound obtained by reacting an ester with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve the 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). More preferably, it is a ratio of 5 to 70 parts by mass. When the amount is less than 5 parts by mass, the photocurability is lowered, and formation of a pattern by alkali image development after irradiation with an active energy ray is difficult, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes 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, the color index (C.I.; The Society of Dyers and Colourists) number is attached as follows. However, it is preferable to reduce the environmental load and the influence on the human body without containing halogen.

Red colorant:

Red colorants are monoazo, disazo, monoazo lake, benzimidazolone, anthraquinone, pyrrolopyrrolone (diketopyrrolopyrrole), condensed azo, hydrazine Specific examples of the oxime system and the quinacridone system include the following.

Monoazo systems: 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.

Bisazo: 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.

Pyrrolopyrroledione: 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.

Quinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

The blue colorants are phthalocyanine and lanthanide, and the pigments are compounds classified into pigments, 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 the dye system 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, Solvent Blue 70 and so on. In addition to the above, a phthalocyanine compound substituted with or without a metal may also be used.

Green colorant:

The green colorant is similarly phthalocyanine, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a phthalocyanine compound which may be substituted with or without a metal may also be used.

Yellow colorant:

Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, and an anthraquinone type, and specific examples thereof include the following.

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

Isoindolinone series: 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.

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

For the purpose of adjusting the color tone, a coloring agent such as purple, clear color, brown color, or black may be added.

Specific examples include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CIPigment Orange 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16. CIPigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 46, CIPigment Orange 49, CIPigment Orange 51. CIPigment Orange 61, CIPigment Orange 63, CIPigment Orange 64, CIPigment Orange 71, CIPigment Orange 73, CIPigment Brown 23, CIPigment Brown 25, CIPigment Black 1, CIPigment Black 7, and the like.

The blending ratio of the coloring agent (H) is not particularly limited, and is preferably from 0 to 10 parts by mass, particularly preferably from 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). full.

The curable resin composition of the present invention may be blended with a filler as needed in order to increase the physical strength of the coating film and the like. As such a filler, conventionally known inorganic or organic fillers may be used. In addition to the previously described aluminum hydroxide and hydrotalcite, true spherical cerium oxide, barium sulfate, cerium oxide, talc, magnesium hydroxide may also be used. , bauxite, alumina, titanium oxide, etc., these may be used alone or in combination of two or more.

The amount of the filler 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 is high, the printability is lowered, and the cured product is brittle, which is not preferable.

The curable resin composition of the present invention may be a conventionally known binder polymer for the purpose of improving flexibility and dryness. The binder polymer is preferably a cellulose-based, polyester-based or phenoxy resin-based polymer. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., polyester polymers such as Vylon series manufactured by Toyobo Co., Ltd., and phenoxy resin-based polymers. Phenoxy resins of bisphenol A, bisphenol F and their hydrogenation compounds 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, and particularly preferably 5 to 30 parts by mass, based on 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 alkali developability of the curable resin composition is deteriorated, and the time required for development can be shortened, which is not preferable.

The curable resin composition of the present invention may be an adhesion promoter in order to improve interlayer adhesion or adhesion of the photosensitive resin layer to the substrate. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl-1. -Phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, Tetrazole, benzotriazole, carboxybenzotriazole, and amine group contain benzotriazole, decane coupling agent, and the like.

In general, since most of the polymer materials start to oxidize, the oxidative degradation of the chain is caused, and the function of the polymer material is lowered. The curable resin composition of the present invention can be added to prevent oxidation (1). The radical scavenger which is free of radicals or/and (2) an antioxidant such as a peroxide decomposing agent which decomposes the generated peroxide in a harmless substance and does not generate a new radical.

As the antioxidant which operates as a radical scavenger, specific examples thereof include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6- Di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-parade (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-2,4,6-(1H,3H,5H)trione Anthraquinone compounds such as phenolic, menaquinone, and benzoquinone, and amines such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate and phenothiazine Compounds, etc.

The radical scavenger may also be a commercially available product, and examples thereof include Adeka Stab AO-30, Adeka Stab AO-330, Adeka Stab AO-20, Adeka Stab LA-77, Adeka Stab LA-57, and Adeka Stab LA-67. Adeka Stab LA-68, Adeka Stab LA-87 (above, manufactured by Asahi Kasei Corporation, trade name), IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals, trade name).

Specific examples of the antioxidant to be used as a peroxide decomposer include a phosphorus compound such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, and hydrazine. A sulfur-based compound such as octadecyl 3,3'-thiopropionate.

The peroxide decomposing agent may be a commercially available product, and examples thereof include Adeka Stab TPP (product name manufactured by Asahi Kasei Co., Ltd.), Mark AO-412S (product name manufactured by Adeka Argus Chemicals Co., Ltd.), and Sumilizer TPS (Sumitomo Chemical Co., Ltd.). System, product name, etc.

The above-mentioned antioxidants may be used alone or in combination of two or more.

In addition, in the curable resin composition of the present invention, the ultraviolet curable agent can be used in addition to the above-mentioned antioxidant, in order to prevent the deterioration of the ultraviolet rays.

Examples of the ultraviolet absorber include a diphenyl ketone derivative, a benzyl ester derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a benzoic acid ester derivative, and an o-amine benzyl ester derivative. , dibenzylbenzylmethane derivatives, and the like. Specific examples of the diphenyl ketone derivative include 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-n-octaethoxydiphenyl ketone, and 2,2'-dihydroxy- 4-methoxybenzophenone and 2,4-dihydroxydiphenyl ketone. Specific examples of the benzoic acid ester derivative include 2-ethylhexyl sulphate, phenyl sulphate, pt-butylphenyl sulphate, and 2,4-di-t-butylphenyl-3. , 5-di-t-butyl-4-hydroxybenzyl ester and hexamethyl-3,5-di-t-butyl-4-hydroxybenzyl ester, and the like. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methylphenyl group. 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 also be a commercially available product, and examples thereof include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, Ciba Specialty Chemicals Co., Ltd., trade name).

The above-mentioned ultraviolet absorbers can be used singly or in combination of two or more kinds, and the molded article obtained from the curable resin composition of the present invention can be stabilized by using the above-mentioned antioxidant together.

Further, in the curable resin composition of the present invention, an organic solvent can be used in order to adjust the synthesis or composition of the carboxyl group-containing resin (A) or to adjust the viscosity for application to the substrate or the carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, hydrazine, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve; Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, C An alcohol such as an alcohol, ethylene glycol or propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, petroleum brain, hydrogenated petroleum brain or solvent oil. The organic solvent may be used singly or in combination of two or more.

The curable resin composition of the present invention may further contain a conventionally known thermal polymerization inhibiting agent, a conventionally known tackifier such as fine powder of cerium oxide, organic bentonite, montmorillonite, or the like, a polyfluorene-based system, a fluorine-based compound, and the like. A well-known conventional additive such as a defoaming agent and/or a leveling agent such as a polymer, a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, an antioxidant, or a rust preventive agent.

The aforementioned thermal polymerization inhibiting agent can be used to prevent thermal polymerization or temporal polymerization of the aforementioned polymerizable compound. The thermal polymerization inhibiting agent may, for example, be 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, benzenetriol, 2-hydroxydiphenyl ketone, 4- Methoxy-2-hydroxydiphenyl ketone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2 , 2'-methylenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-o-toluidine, methylene blue, copper and organic chelating agents The reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al are chelated.

The curable resin composition of the present invention may be in the form of a dry film having a carrier film (support) and a layer composed 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 the viscosity to a suitable viscosity, and is formed by a corner washer, a knife coater, a lip coater, and a bar coater. Machine, squeegee coater, reverse coater, transfer roll coating, gravure coater, sprayer, etc. are coated on the carrier film to a uniform thickness, usually 50-130 ° C The film was obtained after drying for 1 to 30 minutes at a temperature. The coating film thickness is not particularly limited, and generally, the film thickness after drying can be suitably selected from the range of 10 to 150 μm, preferably 20 to 60 μm.

The carrier film may be a plastic film, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film or the like is preferably used. . The thickness of the carrier film is not particularly limited, and is generally suitably selected in the range of 10 to 150 μm.

Further, in order to prevent the dust from adhering to the surface of the film or the like after the film formation on the carrier film, it is preferable to laminate the peelable cover film on the surface of the film.

The peelable cover film can be, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like, as long as the adhesive film and the carrier film are bonded to the film and the cover film. Then the force is still small.

The curable resin composition of the present invention can be subjected to a dip coating method, a flow coating method, a roll coating method, a bar coating method, or a web on a substrate by, for example, adjusting the viscosity of a suitable coating method before the organic solvent. Coating is carried out by a method such as a plate printing method or a curtain coating method, 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 non-tacky coating film. In addition, when the composition is coated on a carrier film and dried, the dry film is taken up as a film, and the curable resin composition layer is brought into contact with the substrate by a laminator or the like, and then bonded to the substrate. The resin insulating layer is formed by peeling off the carrier film.

In the case of a photocurable resin composition, thereafter, it is contacted (or non-contacted) through a patterned photomask, selectively exposed by an active energy ray or by a laser direct exposure machine. Direct pattern exposure, 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 containing the thermosetting component (D) is further contained, for example, it is heated and cured at a temperature of about 140 to 180 ° C to have two or more carboxyl groups and molecules in the carboxyl group-containing resin (A). The cyclic ether group and/or the thermosetting component (D) of the cyclic thioether group are reacted to form various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. Hardened film. Further, even in the case where the thermosetting component (D) is not contained, the ethylenic unsaturated bond remaining in the unreacted state at the time of exposure is thermally radically polymerized by heat treatment, for the purpose of lifting the coating. The film properties can also be heat treated (thermosetting) depending on the purpose.

The above substrate may be used in addition to a printed circuit board or a flexible printed circuit board in which a circuit has been previously formed, such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven ring. All grades of FR, etc. As the laminate, other examples include a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer plate.

The volatilization and drying of the curable resin composition of the present invention may be carried out by using a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, or the like (a heat source using a vapor-heated air method) The hot air in the dryer is brought into contact with the countercurrent and the manner in which the nozzle is attached to the support.

In the case of the photocurable resin composition, the exposed portion (the portion irradiated with the active energy ray) is hardened by exposure (exposure to the active energy ray) to the coating film obtained by coating and volatilizing the solvent. .

The exposure machine used for the active energy ray irradiation may be a device that is equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, etc., and is irradiated with ultraviolet rays in the range of 350 to 450 nm, and may be directly drawn. Device (for example, a laser direct imaging device that uses a CAD image of a computer to directly depict a laser image). The laser light source of the direct drawing machine can be any one of a gas laser and a solid laser as long as it uses a laser beam having a maximum wavelength of 350 to 410 nm. The amount of exposure for forming an image differs depending on the film thickness and the like, and is generally 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

The above development method can be formed by a dipping method, a shower method, a spraying method, a brushing method, etc., and a developing solution can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia. An aqueous solution of an alkali such as an amine.

[Examples]

The following examples and comparative examples are specifically described with reference to the present invention, but the present invention is not limited by the following examples in nature. The “parts” and “%” referred to in the following terms are all based on quality without any special restrictions.

Synthesis Example 1 (A-1) Synthesis of the resin as described above for the carboxyl group-containing resin (2):

A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol is introduced into a reaction vessel equipped with a stirring device, a thermometer, and a condenser as a compound having two or more alcoholic hydroxyl groups. (Asahi Kasei Chemicals Co., Ltd., TJ5650J, number average molecular weight 800) 3600g (4.5 moles), dimethylol butyrate 814g (5.5 moles), and n-butanol as a molecular weight regulator (reaction stop) 118g (1.6 m). Next, 2009g (10.8 mol) of trimethylhexamethylene diisocyanate which is an isocyanate compound which does not have an aromatic ring is put, and it heats it to 60 degreeC after stirring, and stops, and reheats in the temperature in a reaction container began to fall. Stirring was continued at 80 ° C, and it was confirmed by infrared absorption spectrum that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group disappeared, and the reaction was terminated. Thereafter, carbitol acetate was added to make the solid content 60% by weight, and a carboxyl group-containing resin having a viscous liquid of a diluent was obtained. The acid value of the solid content of the obtained carboxyl group-containing polyurethane was 49.8 mgKOH/g.

Synthesis Example 2 (A-2) Synthesis of the resin as described above for the carboxyl group-containing resin (5):

A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol is supplied to a reaction vessel equipped with a stirring device, a thermometer, and a condenser (Taiwan Chemical Co., Ltd., TJ5650J, number average) Molecular weight 800) 2400 g (3 mol), dimethylglycolic acid 603 g (4.5 mol), and 2-hydroxyethyl acrylate as a monohydroxy compound 238 g (2.6 mol). Next, 1887 g (8.5 m) of isophorone diisocyanate of polyisocyanate was charged, and the mixture was stirred and heated to 60 ° C, and then stopped. When the temperature in the reaction vessel began to decrease, it was again heated and stirred at 80 ° C to absorb infrared rays. After the spectrum confirmed that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group disappeared, the reaction was terminated. The carbitol acetate was added to make the solid content 50% by mass. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH/g.

Synthesis Example 3 (A-3) Synthesis of the resin as described above for the carboxyl group-containing resin (4):

In a separable flask, RE310S (2-functional bisphenol A type epoxy resin, epoxy equivalent: 184 g/eq) manufactured by Nippon Chemical Co., Ltd. as a bisphenol A type epoxy compound was placed in an amount of 368.0 g, and acrylic acid (molecular weight). : 72.06) 142.7 g, 2.94 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibiting agent, and 1.53 g of triphenylphosphine as a reaction catalyst, at a temperature of 98 ° C The reaction was carried out so that the acid value of the reaction liquid was 0.5 mgKOH/g or less to obtain an epoxy carboxylate compound (a) (theoretical molecular weight: 510.7). Next, 588.2 g of carbitol acetate and 105.5 g of dimethylolpropionic acid (b) (molecular weight: 134.16) were added as a reaction solvent to the reaction liquid, and the temperature was raised to 45 °C. To the solution, the reaction temperature was not more than 65 ° C, and 264.7 g of isophorone diisocyanate (c) (molecular weight: 222.28) was slowly dropped. After the completion of the dropwise addition, the temperature was raised to 80 ° C, and the reaction was carried out for 6 hours by the absorption absorption measurement in the vicinity of 2250 cm ^-1 by infrared absorption spectrometry, and further reacted at 98 ° C for 2 hours to obtain an aqueous alkali solution. Soluble urethane resin 60% by weight resin solution. The acid value was measured and found to be 28.9 mgKOH/g (solid content acid value: 48.1 mgKOH/g).

(A-4) The resin which is the carboxyl group-containing resin (7):

In the above-mentioned carboxyl group-containing resin (7), a photosensitive carboxyl group-containing resin (manufactured by Nippon Kayaku Co., Ltd.) using a polyfunctional epoxy having a photosensitive group-based biphenol aldehyde structure (solid fraction: 65%) The acid value of the resin was 98 mgKOH/g)].

Modulation of aluminum hydroxide slurry:

700 g of aluminum hydroxide (Higilite 42M manufactured by Showa Denko Co., Ltd.), 280 g of carbitol acetate as a solvent, and BYK-110 of 20 g were mixed and stirred, and 0.5 μm of zirconium dioxide was used in the bead mill. The beads are subjected to dispersion treatment. This was repeated 3 times to prepare an aluminum hydroxide slurry (E-1) which passed through a 3 μm filter.

Modulation of cerium oxide slurry:

700 g of true spherical ceria (SO-E2 manufactured by Admatech Co., Ltd.), 295 g of carbitol acetate as a solvent, and 5 g of a vinyl decane coupling agent as a decane coupling agent were mixed and stirred in the above-mentioned bead mill. Disperse treatment. This was repeated 3 times to prepare a cerium oxide slurry filtered through a 3 μm filter.

Examples 1 to 9, Comparative Examples 1, 2

Using the resin solution of the above-mentioned synthesis example, the various components shown in Table 1 were blended with the ratio (parts by mass) shown in Table 1, and the mixture was prepared by mixing in a mixer, and then kneaded in three roll mills to obtain a hardenability. Resin composition. Here, when the degree of dispersion of the obtained curable resin composition was evaluated by particle size measurement by a Grind Meter manufactured by Erichsen Co., Ltd., it was 15 μm or less.

Performance evaluation:

<Optimum exposure amount>

The photocurable thermosetting resin composition of the above Examples 2 to 9 and Comparative Examples 1 and 2 was subjected to buff roll polishing on a circuit pattern substrate having a copper thickness of 35 μm, followed by water washing and drying. The printing method was carried out by a plate printing method, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out by a stage exposure machine (Kodak No. 2) using an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20 manufactured by ORC Co., Ltd.), and development was carried out (30 ° C, 0.2 MPa, The 1 wt% Na ₂ CO ₃ aqueous solution) is the most suitable exposure amount when the pattern of the stage exposure machine remaining at 90 seconds is 6 stages.

Characteristic test:

The compositions of the above Examples 1 to 9 and Comparative Examples 1 and 2 were completely coated on the patterned polyimide film substrate by screen printing, dried at 80 ° C for 30 minutes, and left to cool. Room temperature. The substrate obtained by the thermosetting resin composition of Example 1 was cured by heating at 150 ° C for 60 minutes. With respect to the photocurable thermosetting resin compositions of Examples 2 to 9 and Comparative Examples 1 and 2, an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp was used for the obtained substrate to expose exposure at an optimum exposure amount. In the flux pattern, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist pattern. The substrate was heated at 150 ° C for 60 minutes and then hardened. The obtained printed circuit board (evaluation substrate) was evaluated as follows.

<flux heat resistance>

The evaluation substrate of the rosin-based flux was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with denatured alcohol, and then the expansion and peeling of the photoresist layer were visually evaluated. The criterion for determination is as follows.

○: No peeling was observed after immersion for 10 seconds.

△: No peeling was observed after immersion for 5 seconds.

X: After immersion for 5 seconds, there was swelling and peeling in the photoresist layer.

<electroless gold plating resistance>

Using an electroless nickel plating bath and an electroless gold plating bath of a commercially available product, plating was carried out under the conditions of nickel 3 μm and gold 0.03 μm, and it was visually evaluated whether or not the photoresist layer was peeled off or not after the tape was peeled off. Infiltration. The criterion for determination is as follows.

○: No infiltration or peeling was observed.

△: Some micro-infiltration was observed after plating, and peeling was also observed after the tape was peeled off.

×: Peeling after plating.

<low bending property>

In place of the above-mentioned polyimide film substrate, a cured film produced on Kapton 200H (polyamide film manufactured by Toray Dupont Co., Ltd., thickness: 25 μm) was cut out at 50 × 50 mm, and the bending of the four corners was measured. The average value was obtained and evaluated according to the following criteria.

○: Those who are less than 1 mm in bending

△: The bending is 1 mm or more, and the thickness is less than 4 mm.

×: The bending is 4 mm or more.

<Electrical characteristics>

The evaluation substrate was fabricated under the above conditions using a comb-type electrode pattern of a line pattern with a line width and a line width of 50/50 μm, and the comb-shaped electrode was humidified at 110 ° C and 85% RH. Under the conditions, a bias voltage of DC50V was applied to confirm the presence or absence of movement after 200 hours. The criterion for determination is as follows.

○: No confirmation change at all

△: Only a few changers

×: Generate a mover

<flammability>

Substituting the above polyimine film substrate on a 50 μm thick polyimide film (Kapton 200H), a 25 μm thick polyimide film (Kapton 100H), and a 12.5 μm thick polyimide film (Kapton 50H) The compositions of the respective examples and comparative examples were completely coated by screen printing, dried at 80 ° C for 20 minutes, and then left to cool to room temperature. Further, the entire surface was coated by a screen printing method on the back surface, and dried at 80 ° C for 20 minutes, and then allowed to cool to room temperature to obtain a double-coated substrate. The thermosetting resin composition of Example 1 was obtained by heating the obtained double-coated substrate at 150 ° C for 60 minutes. With respect to the photocurable thermosetting resin compositions of Examples 2 to 9 and Comparative Examples 1 and 2, an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp was used for the obtained double-coated substrate to optimize exposure. The solder resist was subjected to full exposure, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds, and heat-cured at 150 ° C for 60 minutes to obtain an evaluation sample. For the sample for evaluation of flame retardancy, a vertical burning test of a thin material based on the UL94 standard was carried out. The evaluation is based on the UL94 specification and is indicated as VTM-0 or VTM-1.

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

Examples 10-15

The composition shown in the examples 2, 3, and 6 to 9 shown in Table 1 was prepared by using methyl ethyl ketone as a flame retardant photocurable resin composition prepared by mixing a polyfluorene-based antifoaming agent. After dilution, the carrier film was coated and dried by heating to form a photosensitive resin composition layer having a thickness of 20 μm, and a cover film was bonded thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the copper foil substrate on which the pattern was formed using a laminator. The substrate was exposed to a solder resist pattern using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and the carrier film was peeled off, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed at 0.2 °. The condition of MPa was developed for 90 seconds to obtain a photoresist pattern. Thereafter, the film was heat-cured by a hot air dryer at 150 ° C for 60 minutes to prepare a test substrate. With respect to the obtained test substrate having the cured film, the evaluation test of each characteristic was carried out by using the same test method and evaluation method as described above.

The results of the above respective evaluation tests were compiled and shown in Table 3.

Claims (12)

A curable resin composition comprising (A) a carboxyl group-containing resin, (B) a phosphorus-containing compound, and (C) a layered double hydroxide. The curable resin composition according to the first aspect of the invention, further comprising (D) a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group in the molecule. The curable resin composition according to claim 1, which further contains (E) aluminum hydroxide. The curable resin composition according to 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 biphenyl novolac structure and an ethylenically unsaturated group. The sclerosing resin composition according to the first aspect of the invention, wherein the layered double hydroxide (C) is a compound represented by the following general structural formula (II) [Chemical Formula 1] (wherein M ²⁺ represents a divalent metal cation, M ³⁺ represents a trivalent metal cation, A ^n- represents an n-valent anion, and each element and the underside of the radical represent a ratio of each element and atomic group, X It is 0 < X ≦ 0.33, m ≧ 0). The curable resin composition according to 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 skeleton Epoxy resin. The curable resin composition according to any one of claims 1 to 8, which is used for forming a solder resist. A dry film obtained by coating and drying a curable resin composition according to any one of claims 1 to 8 on a film. A cured product obtained by coating and drying a curable resin composition according to any one of claims 1 to 8 on a substrate, or the curable resin. The dried coating film obtained by coating and drying a dry film on a film is thermally cured and/or photohardened. A printed circuit board characterized by having the cured product according to the eleventh aspect of the aforementioned patent application.