WO2010125721A1 - Photo-curable and heat-curable resin composition - Google Patents

Abstract

Disclosed are: a photo-curable and heat-curable resin composition which enables the formation of a cured coating film having excellent insulation reliability and chemical resistance and also having PCT resistance, HAST resistance and electroless gold plating resistance that are important for a solder resist for a semiconductor package; a dried film and a cured product of the composition; and a printed circuit board having, formed thereon, a cured coating film such (e.g., a solder resist) produced from the composition or the dried film. Specifically disclosed is a photo-curable and heat-curable resin composition which can be developed with a dilute aqueous alkaline solution. The resin composition comprises a carboxyl-group-containing resin (excluding a carboxyl-group-containing resin produced using an epoxy resin as a starting raw material), a photopolymerization initiator, and an amino resin having an alkoxymethyl group. The carboxyl-group-containing resin preferably contains no hydroxy group, and more preferably contains a photosensitive group. A preferred embodiment of the photo-curable and heat-curable resin composition additionally contains a heat-curable component, and preferably additionally contains a coloring agent.

Description

Photo-curable thermosetting resin composition

The present invention relates to a photocurable thermosetting resin composition that can be developed with a dilute alkaline aqueous solution, in particular, a solder resist composition that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a method using them The present invention relates to a printed wiring board having a cured film.

At present, some consumer printed wiring boards and most industrial printed wiring board solder resists are imaged by developing after irradiation with ultraviolet rays from the viewpoint of high accuracy and high density, and heat and / or light. Liquid development type solder resist that undergoes final curing (main curing) upon irradiation is used, and in consideration of environmental problems, alkali development type photo solder resists that use dilute alkaline aqueous solution as the developer are the mainstream, and actual printing It is used in large quantities in the production of wiring boards. In addition, solder resists are also required to have improved workability and high performance in response to the recent increase in the density of printed wiring boards as electronic devices become lighter, thinner and shorter.

However, the current alkali development type photo solder resist still has problems in terms of durability. That is, the alkali resistance, water resistance, heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type. This is because an alkali development type photo solder resist is mainly composed of a hydrophilic group, that is, a carboxyl group or a hydroxyl group in order to make alkali development possible. Decrease in adhesion and adhesion between the resist film and copper. As a result, acid resistance and alkali resistance as chemical resistance are weak. Especially in semiconductor packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package), PCT resistance (pressure) that should also be referred to as moisture and heat resistance. However, under such severe conditions, it is only a few hours to a few dozen hours. Further, in the HAST test (highly accelerated life test) in a state where a voltage is applied under humidification conditions, in most cases, a defect due to the occurrence of migration is confirmed within a few hours.

On the other hand, as a carboxyl group-containing resin used in a conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used. Japanese Patent Application Laid-Open No. 61-243869 (Patent Document 1) discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy. A solder resist composition comprising a compound has been reported. Japanese Patent Laid-Open No. 3-250012 (Patent Document 2) adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed.

In general epoxy acrylate modified resins, the epoxy resin used as a raw material already contains a large amount of chlorine ion impurities, and it is very difficult to remove this after the epoxy acrylate modification.

JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims)

The present invention has been made in view of the problems of the prior art as described above, and its main purpose is to have excellent insulation reliability and chemical resistance, and also important PCT resistance as a solder resist for semiconductor packages, The object is to provide a photocurable thermosetting resin composition capable of forming a cured film having HAST resistance and electroless gold plating resistance.
Furthermore, the object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable thermosetting resin composition, and a solder resist using the dry film and the cured product. An object of the present invention is to provide a printed wiring board on which a cured film such as the above is formed.

In order to achieve the above object, according to the present invention, a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin), a photopolymerization initiator, and an amino resin are included. A photocurable thermosetting resin composition that can be developed with a dilute alkaline aqueous solution is provided.

The carboxyl group-containing resin preferably does not contain a hydroxyl group, and preferably has a photosensitive group. In a preferred embodiment of the photocurable thermosetting resin composition of the present invention, the amino resin is an amino resin having an alkoxymethyl group, and further a thermosetting component, preferably a cyclic ether structure and / or a cyclic thioether. A solder resist containing a thermosetting component having a structure, preferably further containing a colorant.

Furthermore, according to this invention, the photocurable thermosetting dry film obtained by apply | coating and drying the said photocurable thermosetting resin composition on a carrier film, and the said photocurable thermosetting resin composition Alternatively, a cured product obtained by photocuring a dry film, preferably by photocuring in a pattern with a light source having a wavelength of 350 to 410 nm is provided.
Furthermore, according to the present invention, a print having a cured film obtained by photocuring the photocurable thermosetting resin composition or dry film into a pattern by direct drawing of ultraviolet rays and then thermosetting. A wiring board is also provided.

Since the photocurable thermosetting resin composition of the present invention uses a carboxyl group-containing resin that does not use an epoxy resin as a starting material as a component that can be developed with a dilute alkaline aqueous solution, the amount of halogen contained is significantly reduced. The electrical properties of the resulting cured coating are improved. An amino resin contained in combination with this, particularly an amino resin having an alkoxymethyl group, contributes to improving the hydrophobicity of the resulting cured coating film, and is particularly effective in resistance to gold plating. When used in combination with a carboxyl group-containing resin, it is very effective for further improving PCT resistance and HAST resistance. Therefore, by using the photo-curable thermosetting resin composition of the present invention, it has remarkably excellent insulation reliability and chemical resistance, and is also important as a solder resist for semiconductor packages. PCT resistance, HAST resistance, electroless A cured film having gold plating resistance can be formed.
Furthermore, the cured product obtained by the present invention can achieve significantly lower halogen as compared with a cured coating film obtained by a conventional solder resist, that is, it has an excellent advantage for further halogen-free requirements in the future. It is thought to have.

As described above, the photocurable thermosetting resin composition of the present invention is characterized by a carboxyl group-containing resin, a photopolymerization initiator, and an amino resin, particularly an amino resin having an alkoxymethyl group, which do not use an epoxy resin as a starting material. It is characterized by containing.
As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins can be used as long as the carboxyl group-containing resin does not use an epoxy resin as a starting material. Among them, a carboxyl having an ethylenically unsaturated double bond in the molecule. A group-containing photosensitive resin is preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, one or more ethylenically unsaturated groups are contained in the molecule as described later. It is necessary to use a compound having a photosensitivity (photosensitive monomer) in combination.

As specific examples of the carboxyl group-containing resin that can be used in the present invention, the following compounds (any of oligomers and polymers) are preferable.
(1) Bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, etc. Reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid and the like.

(2) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, molecules such as hydroxyalkyl (meth) acrylate A carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.

(5) During the synthesis of a carboxyl group-containing urethane resin by polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc. A carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.

(6) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(7) A functional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and the resulting primary hydroxyl group is reacted with phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A carboxyl group-containing polyester resin to which a dibasic acid anhydride such as an acid has been added is further added to one epoxy group and one or more (in one molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate). A carboxyl group-containing photosensitive resin obtained by adding a compound having a (meth) acryloyl group.

(8) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resins (1) to (7).
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin used in the present invention does not use an epoxy resin as a starting material, it has a feature that the chloride ion impurity content is very low. The chloride ion content of the carboxyl group-containing resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

Moreover, the carboxyl group-containing resin used in the present invention can easily obtain a resin containing no hydroxyl group. In general, the presence of a hydroxyl group has excellent characteristics such as improved adhesion by hydrogen bonding, but it is known to significantly reduce moisture resistance. Below, the outstanding point of the carboxyl group-containing resin of this invention compared with the epoxy acrylate modified resin currently used for the general solder resist is demonstrated.

A phenol novolak resin free from chlorine can be easily obtained. Resin that has no hydroxyl group in the range of double bond equivalent 300-550, acid value 40-120 mgKOH / g by partial acrylation of phenol resin modified with alkyl oxide and introduction of acid anhydride It is possible to obtain
On the other hand, when all epoxy groups of an epoxy resin synthesized from a similar phenol novolac resin are acrylated and acid anhydrides are introduced into all hydroxyl groups, the double bond equivalent is 400 to 500 and the acid value is greatly increased to 100 mgKOH / g. Thus, a coating film having developing resistance cannot be obtained even after exposure. Furthermore, since the acid concentration is high, the water resistance is poor, and the insulation reliability and PCT resistance are significantly reduced. That is, it is very difficult to completely eliminate the hydroxyl group from an epoxy acrylate resin derived from a similar phenol novolac type epoxy resin.

Moreover, urethane resin can also synthesize | combine easily the resin which does not contain a hydroxyl group by match | combining the equivalent of a hydroxyl group and an isocyanate group. A preferred resin is an isocyanate compound not using phosgene as a starting material and a carboxyl group-containing resin having a halogen content of 0 to 30 ppm synthesized from a raw material not using epihalohydrin, and more preferably synthesized so as not to theoretically contain a hydroxyl group. Resin.
From such a viewpoint, the carboxyl group-containing resins (1) to (5) shown as specific examples above can be particularly preferably used.

In addition, as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, a 3,4-epoxy is used with respect to the carboxyl group-containing resin (6) obtained by copolymerization with the unsaturated group-containing compound shown above. A carboxyl group-containing photosensitive resin obtained by reacting cyclohexylmethyl (meth) acrylate also has a small amount of halogen since it uses an alicyclic epoxy, and can be suitably used.

On the other hand, the carboxyl group-containing resin (6) is obtained by reacting glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, or copolymerizing glycidyl methacrylate as an unsaturated group-containing compound. There is a concern that the amount of chlorine will increase the amount of chlorine. Moreover, epoxy acrylate can also be used as a diol compound in the synthesis | combination of a urethane resin. Although a halogen component is contained, it can be used from the viewpoint that the amount of halogen can be controlled.

Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

The weight-average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally within 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 of the dried coating film may be inferior, the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. . On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The blending amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the total composition. When the amount is less than the above range, the coating strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high and the coating property and the like deteriorate, which is not preferable.

The photopolymerization initiator is one or more selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A photopolymerization initiator can be used.

Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02, Adeka N-1919, and Adeka Arcles NCI-831 manufactured by Ciba Japan. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon atom having 1 carbon atom), substituted with an alkyl group having a C 1-8 alkyl group or a dialkylamino group. Alkyl groups having 8 to 8 alkoxy groups, halogen groups, phenyl groups, phenyl groups (alkyl groups having 1 to 17 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, amino groups, alkyl groups having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, Represents thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.

In particular, in the above formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is preferably phenylene, naphthylene, thiophene or thienylene.

The blending amount of such an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane resin. When it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.

Specific examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

Specific examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.

In addition, photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. A tertiary amine compound, a xanthone compound, etc. can be mentioned.

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, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

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

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4- Dialkylamino group-containing coumarin compounds such as methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) , -Dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylaminobenzoic acid Examples include 2-ethylhexyl acid (Esolol 507 manufactured by Van Dyk), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, a thioxanthone compound is preferably included from the viewpoint of deep curability. Of these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.

The amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing urethane resin. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The compounding amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane resin. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing urethane resin having the biphenyl novolac structure. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases, and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

The amino resin having an alkoxymethyl group used in the photocurable thermosetting resin composition of the present invention not only functions as a crosslinking agent component in the composition of the present invention, but also for improving the hydrophobicity of the resulting solder resist. It is considered to work excellently. In particular, it was effective in gold plating resistance, and when used in combination with a carboxyl group-containing resin not using an epoxy resin as a starting material, it was further effective in PCT resistance and HAST resistance.

Examples of amino resins include melamine derivatives and benzoguanamine derivatives, and in particular, melamine derivatives having an alkoxymethyl group and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are the methylol groups of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (above, manufactured by Sanwa Chemical Co., Ltd.).
The amino resin as a thermosetting component as described above can be used alone or in combination of two or more.

The compounding amount of such an amino resin is preferably 5 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount of the amino resin is less than 5 parts by mass, the intended effect of the present invention is not confirmed. On the other hand, when the amount exceeds 50 parts by mass, the tackiness of the dried coating film may be deteriorated or the development may be poor. Therefore, it is not preferable.

In the photocurable thermosetting resin composition of the present invention, other thermosetting components other than the amino resin can be added in order to impart heat resistance. Examples of the thermosetting component used in the present invention include known and commonly used thermosetting resins such as blocked isocyanate compounds, maleimides, benzoxazines, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins. Can be used. Among these, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule.

There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on their structures. In addition, a stronger three-dimensional cross-linking network is formed by performing a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group, particularly an epoxy group, in the composition, resulting in chemical resistance, solder heat resistance and electroless gold. A solder resist having plating resistance can be formed. At that time, it is known that a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group) generates a hydroxyl group, which generally improves adhesion to a substrate or a support. It is thought that there is an effect. However, there is a concern that the formation of a hydroxyl group improves hydrophilicity and deteriorates later insulation reliability and PCT resistance. Therefore, in the present invention, a stronger three-dimensional crosslinking is achieved by reacting an amino resin further having an alkoxymethyl group with a hydroxyl group generated by a thermosetting reaction between a carboxyl group and a cyclic (thio) ether group (for example, an epoxy group). We created a reaction system that forms a network and improves hydrophobicity. That is, the hydroxyl group produced by the thermosetting reaction of a carboxyl group and a cyclic (thio) ether group (for example, epoxy group) is reacted with an amino resin having an alkoxymethyl group to control the amount of the hydroxyl group, thereby achieving both water resistance and adhesion. Can be improved. At this time, by using a thermosetting catalyst described later together, the carboxyl group of the carboxyl group-containing resin is first reacted with the cyclic (thio) ether group (for example, epoxy group) of the thermosetting component, and the resulting hydroxyl group is alkoxymethylated. A two-stage curing method in which an amino resin having a group is reacted and cured is more effective in improving the characteristics.

Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. A compound having a plurality of epoxy groups in the molecule, i.e., a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, i.e., a polyfunctional oxetane compound, a plurality of compounds in the molecule Examples thereof include compounds having a thioether group, that is, episulfide resins.

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epotote YDF-170, YDF-175, YDF-175 manufactured by Toto Kasei 2004, Bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as Epoxy Resin's jER157S (trade name); Tetraphenylolethane type such as Japan Epoxy Resin's jERYL-931, Ciba Japan's Araldide 163, etc. (all trade names) Epoxy resin; Aral made by Ciba Japan Heterocyclic epoxy resins such as id PT810, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resins such as Bremer DGT manufactured by NOF Corporation; tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Irethane resin; Naphthalene group-containing epoxy resins such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by DIC; HP-7200 and HP-7200H manufactured by DIC Epoxy resin having a dicyclopentadiene skeleton such as CP-50S, CP-50M glycidyl methacrylate copolymer epoxy resin such as Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resin (For example, manufactured by Toto Kasei R-102, YR-450, etc.), epoxy-modified polybutadiene rubber derivatives (Daicel Chemical Industries, Ltd. PB-3600 etc.) and the like, but not limited thereto.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, 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) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably 1 equivalent to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. Is in the range of 0.8 to 2.0 equivalents. When the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

When using a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

The compounding amount of these thermosetting catalysts is sufficient in a normal quantitative ratio, and is preferably, for example, with respect to 100 parts by mass of a carboxyl group-containing resin or a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. Is 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

The photocurable thermosetting resin composition of the present invention contains a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule in order to improve the curability of the composition and the toughness of the resulting cured film. Can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is done.

The blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Company), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.). Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The proportion of parts is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability falls and it is not preferable.

A urethanization catalyst can be added to the photo-curable thermosetting resin composition of the present invention in order to promote curing of hydroxyl groups, carboxyl groups and isocyanate groups. As the urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and / or amine salts. .

Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

The metal chloride is a metal chloride made of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Can be mentioned.

The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.

Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N′- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxy Chill) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N ′, N ″, N ″ -tetramethyldiethylenetriamine, N, N, N′-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imi Sol, 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′-amino) Propyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxyethyl) ) Amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N , N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′ , N'-bis (2-hydroxypropyl) amine, melamine or / and benzoguanamine.

Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5,4,0] undecene-7).

The compounding amount of the urethanization catalyst is sufficient in an ordinary quantitative ratio. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts per 100 parts by mass of the carboxyl group-containing resin. 0 parts by mass.

The photocurable thermosetting resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Indexes (CI; issued by The Society of Dyers and Colorists) are listed.
Monoazo: 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.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: 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.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include 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 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: 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: 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.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, for the purpose of adjusting the color tone, a colorant such as purple, orange, brown, or black may be added.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

The blending ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. It is enough.

The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation with active energy rays, and the carboxyl group-containing resin is converted into an alkaline aqueous solution. Insolubilize or help insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

The compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. It is. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

The photo-curable thermosetting resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers. The amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.

In the photocurable thermosetting resin composition of the present invention, a binder polymer can be used for the purpose of improving the touch drying property and the handling property. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

The photocurable thermosetting resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving the brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. In addition, resins in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

Furthermore, the photocurable thermosetting resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. can do.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of the present invention includes In order to prevent oxidation, (1) radical scavengers that invalidate the generated radicals and / or (2) peroxidation that decomposes the generated peroxides into harmless substances and prevents the generation of new radicals. Antioxidants such as product decomposing agents can be added.

Specific examples of the antioxidant that acts as a radical scavenger 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-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6, - tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, TINUVIN 5100 Japan) Product name).

Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In general, the polymer material absorbs light, which causes decomposition / degradation. Therefore, the photo-curing thermosetting resin composition of the present invention has the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. In addition to the agent, an ultraviolet absorber can be used.

Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) 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, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, The molded product obtained from the photocurable thermosetting resin composition of this invention by using together with the said antioxidant. Can be stabilized.

In the photocurable thermosetting resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. . Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclope Tanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

Further, the polyfunctional mercaptan-based compound is not particularly limited. For example, fat such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc. Aromatic thiols such as aromatic thiols, xylylene dimercaptan, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate) ), Trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaeri Poly (mercaptoacetate) s of polyhydric alcohols such as litholhexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3 -Mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Poly (3-mercaptopropionate) s of polyhydric alcohols such as pionate) and dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryloxy) ) Butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-merta And poly (mercaptobutyrate) such as ptobutyrate).

Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5 Lerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2, 1,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

In the photocurable thermosetting resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents and the like.

The photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. Also, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, etc. Known and commonly used additives can be blended.

The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying) at a temperature of about 60 to 100 ° C. Thereafter, the contact pattern (or non-contact pattern) is selectively exposed to active energy rays through a photomask having a pattern formed thereon, or directly exposed to a pattern using a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0). And a resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution. Further, for example, a thermosetting component having a carboxyl group of the carboxyl group-containing resin and a plurality of cyclic ether groups and / or cyclic thioether groups in the molecule by heating to a temperature of about 140 to 180 ° C. and thermosetting. In addition, the amino resin having an alkoxymethyl group reacts with the hydroxyl group generated by the reaction to form a stronger three-dimensional crosslinked network, and the hydrophobicity is improved, so that the heat resistance, chemical resistance, A cured coating film excellent in various properties such as moisture absorption resistance, adhesion, and electrical characteristics can be formed.

Examples of the base material include printed circuit boards and flexible printed circuit boards that are pre-formed with a circuit, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin. , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

Volatile drying performed after applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle.

As described above, after applying the photocurable thermosetting resin composition of the present invention and evaporating and drying, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 200 mJ / cm ² , preferably 5 to 100 mJ / cm ² , more preferably 5 to 50 mJ / cm ² . As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any apparatus may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

The photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable photocurable thermosetting resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
For the solder resist layer, the alkali-developable photo-curable thermosetting resin composition is uniformly applied to a carrier film or cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and dried. Formed.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis example 1
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the obtained novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolak acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.

Synthesis example 2
In a 5-liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 1,245 g of polycaprolactone diol (PLACEL208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g as polyisocyanate, 777 g of isophorone diisocyanate as polyisocyanate, 119 g of 2-hydroxyethyl acrylate as hydroxyl group-containing (meth) acrylate, p-methoxyphenol and di-t-butyl-hydroxytoluene each of 0 .5 g was added. The mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The volatile content was adjusted to 50% by mass using carbitol acetate. A resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as varnish A-2.

Synthesis example 3
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Japan) 21.4 g of oil and fat Co., Ltd., trade name: Perbutyl O) was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Placcel FM1: manufactured by Daicel Chemical Industries, Ltd.) were added as a polymerization initiator. (4-t-butylcyclohexyl) peroxydicarbonate (trade name: Parroyl TCP, manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise with 31.4 hours over 3 hours, and further aged for 6 hours to contain a carboxyl group. A copolymer resin was obtained. The reaction was performed under a nitrogen atmosphere.
Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd., trade name: Cyclomer A200) and dimethylbenzylamine 3 as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. .6 g, 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor was added, and the mixture was heated to 100 ° C. and stirred to carry out epoxy ring-opening addition reaction. After 16 hours, a resin solution having a solid content acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, this is referred to as varnish A-3.

Comparative Synthesis Example 1
Orthocresol novolak epoxy resin (produced by DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings)) to 600 g of diethylene glycol monoethyl ether acetate : 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, this is referred to as varnish R-1.

Comparative Synthesis Example 2
Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2200 parts, dimethylolpropionic acid 134 parts, acrylic acid 648.5 parts, methylhydroquinone 4.6 parts Then, 1131 parts of carbitol acetate and 484.9 parts of solvent naphtha were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., and allowed to react for about 32 hours to obtain a reaction product having an acid value of 0.5 mg KOH / g. Next, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent naphtha were added to this, heated to 95 ° C., reacted for about 6 hours, cooled, and solid acid value A resin solution of a carboxyl group-containing photosensitive resin having 40 mg KOH / g and a nonvolatile content of 65% was obtained. Hereinafter, this is referred to as varnish R-2.

Comparative Synthesis Example 3
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH is further added. The reaction was carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil / water separation, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were charged, heated to 90 ° C., stirred and reacted. The mixture was dissolved. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained. Hereinafter, this is referred to as varnish R-3.

Examples 1 and 2 and Comparative Examples 1 to 3
Using the resin solutions obtained in each of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, and then kneaded with a three-roll mill. A photocurable thermosetting resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in terms of chloride ion impurity content (total of chloride and bromide) by using a flask combustion treatment ion chromatograph method based on the JPCA standard. The results are also shown in Table 1.

As is apparent from the results shown in Table 1 above, the photocurable thermosetting resin compositions of Examples 1 and 2 using carboxyl group-containing resins (A-1, A-2) that do not use an epoxy resin as a starting material. Compared with the photocurable thermosetting resin compositions of Comparative Examples 1 to 3 using a carboxyl group-containing photosensitive resin (R-1, R-2, R-3) starting from an epoxy resin. It was revealed that the amount of halogen was extremely small.

Examples 3 to 11 and Comparative Examples 4 to 6
Using the resin solution of the above synthesis example, blended in the proportions (parts by mass) shown in Table 2 together with various components shown in Table 2 below, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

<Remarks>
* 1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Japan)
* 2: 2,4-diethylthioxanthone (KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd.)
* 3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1,1- (O-acetyloxime)
(Irgacure OXE 02: manufactured by Ciba Japan)
* 4: Adeka Arcles NCI-831 (manufactured by ADEKA Corporation)
* 5: Epoxidized polybutadiene resin (PB3600: manufactured by Daicel Chemical Industries, Ltd.)
* 6: Bixylenol type epoxy resin (YX-4000: manufactured by Japan Epoxy Resin Co., Ltd.)
* 7: Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
* 8: Methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd.)
* 9: C.I. I. Pigment Blue 15: 3
* 10: C.I. I. Pigment Yellow147
* 11: 2-mercaptobenzothiazole * 12: Antioxidant (Ciba Japan)
* 13: B-30 (manufactured by Sakai Chemical Co., Ltd.)
* 14: Hydrotalcite (Kyowa Chemical Industry Co., Ltd.)
* 15: Diethylene glycol monoethyl ether acetate * 16: Dipentaerystol hexaacrylate

Performance evaluation:
<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 18 μm was subjected to a copper surface roughening treatment (MEC etch bond CZ-8100 manufactured by MEC Co., Ltd.), washed with water, dried, and then subjected to photocurable thermosetting resin compositions of the above examples and comparative examples. The product was applied to the entire surface by a screen printing method, and dried for 60 minutes in an 80 ° C. hot air circulation drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and remains after developing (30 ° C., 0.2 MPa, 1 wt% sodium carbonate aqueous solution) for 60 seconds. When the step tablet pattern is 7 steps, the optimum exposure was set.

<Developability>
The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 μm, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% sodium carbonate aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Maximum development life>
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 20 minutes from 20 to 80 minutes, and allowed to cool to room temperature. . The substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

<Tackiness>
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and the film was pressure-bonded with ORW HMW-GW20 under reduced pressure conditions for 1 minute, and then the sticking state of the film when the negative film was peeled was evaluated according to the following criteria.
○: When peeling off the film, there is no resistance at all and no mark is left on the coating film.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

Characteristic test:
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds. Obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 130 ° C. for 60 minutes and then at 150 ° C. for 30 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Acid resistance>
The evaluation substrate was immersed in a 10 wt% HCl aqueous solution at room temperature for 30 minutes, and the infiltration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off

<Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the penetration and the dissolution of the coating film were visually confirmed, and further, peeling by tape beer was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 5μm and gold 0.05μm, and tape peeling is used to check for resist layer peeling and plating penetration. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<PCT resistance>
The evaluation substrate on which the solder resist cured coating film was formed was treated for 168 hours under the conditions of 121 ° C., saturation, and 0.2 MPa using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Corporation), and the state of the coating film Evaluated. Judgment criteria are as follows.
○: No swelling, peeling, discoloration, or dissolution △: Some swelling, peeling, discoloration, or dissolution ×: Many swelling, peeling, discoloration, or dissolution

<HAST characteristics>
A solder resist cured coating film was formed on a BT substrate on which comb-type electrodes (line / space = 20 μm / 20 μm) were formed, and an evaluation substrate was prepared. This evaluation board | substrate was put into the high temperature / humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 12V was charged, and the in-chamber HAST test was done for 168 hours. The insulation resistance value in the tank when 168 hours passed was evaluated according to the following criteria.
○: 108Ω or more △: 106-108Ω
×: 106Ω or less

<Evaluation as a photosensitive resin composition capable of storing one liquid at room temperature>
Example 6 and Comparative Example 4 shown in Table 2 were allowed to stand at room temperature for 10 days, and the thickening rate and the maximum development life were confirmed. As a result, in Example 6, the thickening rate was 106%, whereas in Comparative Example 4, the thickening rate was 228%. In addition, the maximum development life after 10 days at room temperature was not changed in Example 6 in 60 minutes, whereas in Comparative Example 4, it was shortened to 20 minutes. This shows that Example 6 using an amino resin is a composition that is stable even when stored at room temperature in one liquid, and is a one-pack type that can be stored at room temperature, which was very difficult with conventional epoxy resin systems. This result is considered to have the potential as a photosensitive resin composition.

Examples 12 to 17 and Comparative Examples 7 to 9
Each composition of Examples 4, 7, 8, 9, 10, and 11 and Comparative Examples 4, 5, and 6 prepared at the blending ratio shown in Table 2 was diluted with methyl ethyl ketone, applied onto a PET film, and 80 ° C. And dried for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Further, a cover film was laminated thereon to produce a dry film, which were designated as Examples 12 to 17 and Comparative Examples 7 to 9, respectively.

<Dry film evaluation>
The cover film is peeled off from the dry film obtained as described above, the film is thermally laminated on the patterned copper foil substrate, and then, under the same conditions as the substrate used for the coating film property evaluation of the above example. Exposed. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 90 seconds under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 130 ° C. for 60 minutes and then at 150 ° C. for 30 minutes. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 4.

As is apparent from the results shown in Tables 3 and 4, the photo-curable thermosetting resin composition of the present invention has electroless gold plating resistance, PCT resistance, HAST characteristics (required for a solder resist for semiconductor packages) ( It was confirmed that the composition was useful as a photo-curable thermosetting resin composition having electrical characteristics.

Claims (5)

1. A carboxyl group-containing resin having a photosensitive group (excluding a carboxyl group-containing resin starting from an epoxy resin),
   A photocurable thermosetting resin composition that can be developed with a dilute aqueous alkali solution, comprising a photopolymerization initiator and an amino resin.
2. The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin does not contain a hydroxyl group.
3. A photocurable thermosetting dry film obtained by applying and drying the photocurable thermosetting resin composition according to claim 1 or 2 on a film.
4. Curing obtained by photocuring a photocurable thermosetting resin composition according to claim 1 or 2, or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film. object.
5. The photocurable thermosetting resin composition according to claim 1 or 2 or a dry film obtained by applying and drying the photocurable thermosetting resin composition on a film is patterned by direct drawing of ultraviolet rays. A printed wiring board having a cured film obtained by photocuring into a shape and then thermosetting.