TWI689780B - Curable composition, dry film, cured product, printed wiring board and method of manufacturing printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a curable composition excellent in resolution and blackness of a cured product.

The solution of the present invention is a curable composition using its dry film, its cured product, and a printed wiring board provided with the cured product. The curable composition is a composition containing the following components: (A) containing a carboxyl group Resin, (B) photopolymerization initiator, (C) diluent, (D) polyfunctional epoxy compound having at least 2 epoxy groups in 1 molecule, (E) black colorant, and (F) other than black The coloring agent is characterized in that the dry coating film thickness has an absorbance of 1.5 or less per wavelength of 365 nm of 25 μm, an absorbance of 385 nm or less of 1.0, and an absorbance of 405 nm or less of 1.0.

Description

Curable composition, dry film, cured product, printed wiring board and method of manufacturing printed wiring board

The present invention relates to a method for manufacturing a curable composition, a dry film, a cured product, a printed wiring board, a dry film, a method for manufacturing a cured product, and a method for manufacturing a printed wiring board.

Generally speaking, in printed circuit boards used in electronic equipment, etc., when mounting electronic components, a solder resist is formed on the area on the substrate where the circuit pattern is formed excluding the connection hole. The resin composition is applied or cured by laminating a dry coating film on a dry film. This solder resist prevents solder from attaching to unnecessary parts and protects the conductors of the circuit.

In addition, the solder resist also has the function of shielding the circuit pattern from discoloration due to heat or moisture, or electrical discoloration, damage, dirt, etc., thereby preventing the deterioration of the appearance of the printed wiring board. Therefore, in order to improve the shielding property, a coloring agent is usually added to the resin composition or dry film used to form the solder resist (for example, refer to Patent Document 1).

In recent years, according to the miniaturization or high functionality of electronic equipment Requirements, printed circuit boards have also been developed to miniaturize circuit patterns, along with this, for solder resists have also been further developed into thin films. As a result, the shielding property of the solder resist decreases, and discoloration of the circuit as the underlying layer is seen through the solder resist, resulting in a problem of poor appearance. Therefore, in order to improve the shielding property, a dark black solder resist is required. In addition, from a design point of view, a black solder resist is required. In addition, carbon black has been used as a black colorant in the past.

As one of the pattern formation methods of the solder resist, although the photolithography method has been used in the past, when carbon black is blended in the solder resist ink in order to appear black, the carbon black will absorb from the ultraviolet region For a wide range of light up to the visible light region, the light transmittance will deteriorate, which will cause problems such as a reduction in resolution.

As a means for solving such a problem, Patent Document 2 describes a composition characterized by containing a black coloring agent and a coloring agent other than the black coloring agent. In addition, Patent Document 3 describes a composition characterized by combining a coloring agent other than a black coloring agent and blackening it. However, there is still room for improvement for the resolution system.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2009-258613

[Patent Document 2] Japanese Unexamined Patent Publication No. 2008-257045

[Patent Document 3] Japanese Patent Laid-Open No. 2010-091876

Therefore, an object of the present invention is to provide a curable composition excellent in resolution and blackness of a cured product, a dry film obtained by coating and drying the composition, a cured product of the composition or the dry film, and having the cured product Printed wiring board, method for manufacturing a dry film using the composition, method for manufacturing a cured product using the composition or the dry film, and method for manufacturing a printed wiring board using the composition or the dry film.

The inventors have made great efforts and found that it can be solved by blending a black colorant and a coloring agent other than black, and then making the dry coating film thickness absorbance at a specific wavelength of 25 μm into a specific range. The above-mentioned subject thus completes the present invention.

That is, the curable composition of the present invention is a composition containing the following components: (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) diluent, (D) 1 molecule has at least Two epoxy-based polyfunctional epoxy compounds, (E) black colorants, and (F) coloring agents other than black, characterized in that the film thickness of the dry coating film has an absorbance of 1.5 or less per wavelength of 365 nm at 25 μm. The absorbance at 385 nm is 1.0 or less, and the absorbance at 405 nm is 1.0 or less.

In the curable composition of the present invention, it is preferable that the coloring agent other than the aforementioned (F) black contains a purple coloring agent.

The curable composition of the present invention is preferably the aforementioned (F) black Other colorants contain orange colorants.

In the curable composition of the present invention, it is preferable that the coloring agent other than (F) black contains at least one of a red coloring agent, a blue coloring agent, and a yellow coloring agent.

In the curable composition of the present invention, it is preferable that the aforementioned (B) photopolymerization initiator contains an oxime ester-based photopolymerization initiator.

In the curable composition of the present invention, the oxime ester-based photopolymerization initiator is preferably a dimer oxime ester-based photopolymerization initiator.

The dry film of the present invention is characterized by having a resin layer obtained by coating and drying the curable composition on the film.

The cured product of the present invention is characterized in that at least one of the curable composition and the resin layer of the dry film is cured.

The printed wiring board of the present invention is characterized by having the above-mentioned cured product.

The method for producing a dry film of the present invention is characterized by using the aforementioned curable composition.

The method for producing a cured product of the present invention is characterized by using the aforementioned curable composition.

The method for manufacturing a printed wiring board of the present invention is characterized by using at least any one of the curable composition and the dry film.

According to the present invention, it is possible to provide a curable composition excellent in resolution and blackness of a cured product, and a tree obtained by coating and drying the composition A dry film of a fat layer, a cured product of the composition or the resin layer of the dry film, a printed wiring board having the cured product, and a method of manufacturing a printed wiring board using the composition.

[Figure 1] This is a photograph showing a cross section of a 50 μm line portion formed by exposure development of the curable composition of Example 2.

[Figure 2] This is a photographic view showing a cross section of a 50 μm line portion formed by exposure development of the curable composition of Comparative Example 2.

The curable composition of the present invention is a composition containing the following components: (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) diluent, (D) 1 molecule has at least 2 rings Oxygen-based multifunctional epoxy compound, (E) black colorant, and (F) coloring agent other than black, characterized in that the thickness of the dry coating film has an absorbance of 1.5 or less per wavelength of 365 nm at 25 μm, and an absorbance of 385 nm It is 1.0 or less and the absorbance at a wavelength of 405 nm is 1.0 or less.

In the curable composition of the present invention, it is important to satisfy the above three absorbance systems. By satisfying the above-mentioned absorbance, in the case of exposure, especially LDI (Laser Direct Imaging) exposure, it can be hardened to the deep part to form a fine pattern. Although the detailed mechanism is not clear, it is speculated that the reason is that if the wavelength of the irradiation is discussed, the The case is that the irradiated wavelength is about 350~420nm, and the peak wavelength is the range of I line (365nm), h line (405nm), or 370~400nm according to the light source. Therefore, the peak wavelength is 350~ The light transmittance in the range of 420nm becomes important. The absorbance of the film thickness of the dry coating film per 25 μm wavelength of 365 nm is preferably 1.0 to 1.5. In the case of 1.0 or more, the peak width is not easily generated. In addition, the absorbance of the film thickness of the dry coating film per 25 μm at a wavelength of 385 nm is preferably 0.5 to 1.0. In the case of 0.5 or more, it is not easy for the peak top to be too wide. The absorbance of the film thickness of the dry coating film per 25 μm wavelength of 405 nm is preferably 0 to 1.0.

Although the method of adjusting to the above-mentioned absorbance is not particularly limited, it is preferably adjusted by the types or blending ratios of (E) black colorants and (F) coloring agents other than black. It can also be adjusted by (B) the type or blending ratio of the photopolymerization initiator. The absorbance system can be measured using an ultraviolet-visible spectrophotometer.

(F) A coloring agent other than black, from the viewpoint of resolution, as the coloring agent other than black (F), it is preferable to contain at least one kind of purple coloring agent, orange coloring agent, and red coloring agent, more preferably At least one of the purple colorant and the orange colorant is more preferably a purple colorant and an orange colorant. From the viewpoint of blackness, it is preferable that the coloring agent other than black (F) contains at least one of a purple coloring agent and a blue coloring agent, and more preferably contains a purple coloring agent. Moreover, when a blue coloring agent is contained, it is more preferable to further contain a yellow coloring agent. From the viewpoint of resolution and blackness, it is particularly preferable that the coloring agent other than (F) black contains a purple colorant, an orange colorant, a blue colorant, and a yellow colorant.

Hereinafter, each component will be described in detail.

[(A) Carboxyl group-containing resin]

(A) A carboxyl group-containing resin, especially a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule, as a photosensitive composition for alkali development, from the viewpoint of photocurability or development resistance It is better. However, the unsaturated double bond is preferably acrylic acid or methacrylic acid, or derivatives derived from these.

As a specific example of (A) a carboxyl group-containing resin, the compounds listed below (preferably any of oligomers and polymers) are preferable.

(1) Obtained from copolymers of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene The carboxyl-containing resin.

(2) With diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, and carboxyl group containing dimethylol propionic acid, dimethylol butyric acid, etc. Alcohol compounds and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diol, with phenol A carboxyl group-containing urethane resin obtained by the addition polymerization reaction of a diol compound such as an alcoholic hydroxyl group and an alcoholic hydroxyl group compound and a compound having one alcoholic hydroxyl group as needed.

(3) With diisocyanate, and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin , Biphenol epoxy resin, etc. The carboxyl group-containing photosensitive urethane resin obtained by the polyaddition reaction of the (meth)acrylate of the bifunctional epoxy resin or its partial anhydride modifier, carboxyl group-containing diol compound, and diol compound.

(4) In the synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl group in the molecule of hydroxyalkyl (meth)acrylate, etc. is added, Carboxyl group-containing photosensitive urethane resin subjected to terminal (meth)acrylation.

(5) In the synthesis of the resin of (2) or (3) above, the mole reaction products such as isophorone diisocyanate and pentaerythritol triacrylate have one isocyanate group and one or more (methyl ) Acrylate compound, a carboxyl group-containing photosensitive urethane resin subjected to terminal (meth)acrylation.

(6) A carboxyl group-containing photosensitive resin in which a bifunctional or more polyfunctional (solid) epoxy resin and (meth)acrylic acid are reacted to add a dibasic anhydride to a hydroxyl group present in a side chain. Hereinafter, this is called carboxylic acid-modified epoxy acrylate. In addition, as specific examples of the multifunctional epoxy resin, for example, those described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2011-213828 can be cited.

(7) A polyfunctional epoxy resin which further epoxidizes the hydroxyl group of a bifunctional (solid) epoxy resin with (chloro)acrylic acid and (meth)acrylic acid with epichlorohydrin is added to the resulting hydroxyl group to add the content of the dibasic anhydride Carboxyl photosensitive resin.

(8) The difunctional oxetane resin is reacted with dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, etc. The carboxyl group-containing polyester resin of binary acid anhydrides such as the first-grade hydroxyl addition phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

(9) Use bisphenol A, bisphenol F, bisphenol S, novolac phenol resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensates of dihydroxynaphthalene and aldehydes, etc. A compound having a plurality of phenolic hydroxyl groups in one molecule reacts with an alkylene oxide such as ethylene oxide, propylene oxide, etc. to react the resulting reaction product with an unsaturated group-containing monocarboxylic acid to make the resulting A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

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

(11) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group and (meth)acrylic acid in one molecule such as p-hydroxyphenylethanol The monocarboxylic acid containing unsaturated group is reacted to make the alcoholic hydroxyl group of the reaction product obtained with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydride.

(12) The resins of (1) to (11) above are further added with 1 in one molecule of epoxypropyl (meth)acrylate, α-methylepoxypropyl (meth)acrylate, etc. A carboxyl group-containing photosensitive resin composed of a compound of one epoxy group and one or more (meth)acryloyl groups.

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

In the curable composition of the present invention, (A) a carboxyl group-containing resin, preferably a resin obtained by combining the above (6) and (12), specifically, preferably a carboxylic acid-modified epoxy acrylate , (A1) carboxyl group-containing photosensitive resin obtained by reacting with a compound having an epoxy group and a radical polymerizable unsaturated group.

As described above, the carboxyl group-containing resin has a large number of carboxyl groups in the main chain/polymer side chain, so that development by dilute alkaline aqueous solution is possible.

In addition, the acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, and more preferably in the range of 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20 mgKOH/g or more, the adhesion of the coating film becomes good, and the alkali development becomes good. On the other hand, in the case where the acid value is 200 mgKOH/g or less, since the dissolution of the exposed portion due to the developer can be suppressed, the line can be suppressed from being too thin, or the exposed portion can be distinguished from the unexposed portion depending on the situation By dissolving and peeling with the developer, the resist pattern can be drawn well.

In addition, although the weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, it is preferably in the range of 2,000 to 150,000, and further in the range of 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the non-stick performance is good, the moisture resistance of the coating film after exposure is good, and the film reduction during development is suppressed to suppress the solution Decrease in resolution. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good, and the storage stability is also excellent.

The curable composition of the present invention may contain one (A) carboxyl group-containing resin alone or two or more kinds. In the case where the curable composition of the present invention contains two or more kinds of (A) carboxyl group-containing resin, for example, it is preferable to contain the above-mentioned (A1) carboxyl group-containing photosensitive resin.

In addition, the curable composition of the present invention may contain (A) a carboxyl group-containing resin as described above (A1) a carboxyl group-containing photosensitive resin and a carboxyl group-containing acrylic copolymer that does not have an alicyclic skeleton. Examples of the carboxyl group-containing acrylic copolymer having no alicyclic skeleton include (1) styrene copolymerized carboxyl group-containing resins listed as specific examples of the above (A) carboxyl group-containing resins. As the blending ratio in the case of blending a carboxyl group-containing acrylic copolymer having no alicyclic skeleton, when (A) the entire carboxyl group-containing resin is 100 parts by mass, for example, 10 to 95 parts by mass, preferably 10~80 parts by mass.

[(B) Photopolymerization initiator]

The curable composition of the present invention contains (B) a photopolymerization initiator. Examples of the (B) photopolymerization initiator system include a diphenyl ketone system, an acetophenone system, an acetophenone system, a benzoin ether system, a benzyl ketal system, an acylphosphine oxide system, and an oxime ether system. , Oxime esters, titanocene, and other well-known and commonly used compounds.

As the (B) photopolymerization initiator, an oxime ester-based photopolymerization initiator including the structural part represented by the general formula (I) shown below is preferable. The aforementioned oxime ester-based photopolymerization initiator is more preferably a dimer of oxime ester-based photopolymerization. Initial agent. In addition, the oxime ester-based photopolymerization initiator is preferably a carbazole structure, and more preferably a dimer oxime ester-based photopolymerization initiator having a carbazole structure. In addition, examples of the Acetophenone-based photopolymerization initiator system include an α-Acetophenone-based photopolymerization initiator including a structural part represented by the following general formula (II). Examples of the acylphosphine oxide-based photopolymerization initiator system include an acylphosphine oxide-based photopolymerization initiator including a structural part represented by the following general formula (III). Examples of the titanocene-based photopolymerization initiator system include a titanocene-based photopolymerization initiator represented by the following general formula (IV).

In the general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R ² represents phenyl, alkyl, cycloalkyl, alkyl acetyl or benzoyl.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent group include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms in the alkyl chain. Furthermore, it may be substituted with one or more hydroxyl groups.

The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 2 to 20 carbon atoms.

The benzoyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent system include an alkyl group having 1 to 6 carbon atoms and a phenyl group.

In general formula (II), R ³ and R ⁴ each independently represent an alkyl or aralkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Alternatively, two bonds may be bonded to form a cyclic alkyl ether group.

In general formula (III), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group or a halogen atom, and an aryl group substituted with an alkyl group or an alkoxy group, Or a carbonyl group having 1 to 20 carbon atoms (however, it is excluded that both sides are carbonyl groups having 1 to 20 carbon atoms).

In general formula (IV), R ⁹ and R ¹⁰ independently represent a halogen atom, an aryl group, a halogenated aryl group, and a heterocyclic-containing halogenated aryl group.

-9-酮、以及乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)及以下述一般式(I-2)所表示之化合物等之具有咔唑骨架的肟酯系化合物等。 Examples of the oxime ester-based photopolymerization initiator system containing a structural part represented by general formula (I) include: 1,2-octanedione-1-[4-(phenylthio)-2-(O- (Benzoyl oxime)], a compound represented by the following formula (I-1), 2-(acetyl oximino methyl) sulfur

-9-ketone, and acetone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetamide) And oxime ester compounds having a carbazole skeleton and the like represented by the following general formula (I-2).

In general formula (I-2), R ¹¹ is synonymous with R ¹ in general formula (I), and R ¹² and R ¹⁴ are each independently synonymous with R ² in general formula (I). R ¹³ represents a hydrogen atom, a halogen atom, a C 1-12 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, a C 2-12 alkyl group, a carbon number 2 Alkoxycarbonyl group of ~12 (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain ) Or phenoxy carboxyl.

Such an oxime ester-based photopolymerization initiator can improve the sensitivity of the curable composition of the present invention for exposure to direct imaging, and is excellent in resolution, which is preferable. In addition, the oxime ester-based photopolymerization initiator is particularly preferably a dimer.

The dimer oxime ester-based photopolymerization initiator is more preferably a compound represented by general formula (I-3).

In general formula (I-3), R ²³ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, and a naphthyl group. R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a benzofuranyl group, and a benzothienyl group.

Ar represents a single bond or a C1-C10 alkylene, vinylidene, phenylene, biphenylene, pyridylene, naphthylene, anthracene, thienylene , Furylene (furylene), 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl.

n is an integer from 0 to 1.

The alkyl group represented by R ²³ is preferably an alkyl group having 1 to 17 carbon atoms.

The alkoxy group represented by R ²³ is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R ²³ may have a substituent, and examples of the substituent group include alkyl groups (preferably carbon numbers 1 to 17), alkoxy groups (preferably carbon numbers 1 to 8), An amine group, an alkylamine group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamine group (preferably an alkyl group having 1 to 8 carbon atoms), etc.

The naphthyl group represented by R ²³ may have a substituent, and examples of the substituent group include the same substituents as the above-mentioned substituents that the phenyl group represented by R ²³ may have.

The alkyl group represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 17 carbon atoms.

The alkoxy group represented by R ²¹ and R ²² is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R ²¹ and R ²² may have a substituent, and examples of the substituent group include an alkyl group (preferably carbon number 1 to 17) and an alkoxy group (preferably carbon number 1 to 8), an amine group, an alkylamine group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamine group (preferably an alkyl group having 1 to 8 carbon atoms), etc.

The naphthyl group represented by R ²¹ and R ²² may have a substituent, and the substituent group may be the same as the above-mentioned substituents that the phenyl group represented by R ²¹ and R ²² may have.

Furthermore, in general formula (I-3), it is preferred that R ²¹ and R ²³ are each independently methyl or ethyl, R ²² is methyl or phenyl, Ar is a single bond or phenylene, naphthyl Or thienylene, n is 0.

As the compound represented by the general formula (I-3), the following compound No. 1 is more preferable.

In the case of using such an oxime ester-based photopolymerization initiator, in order to improve the sensitivity to exposure, it is preferably included in the general formula (II) The α-aminoacetophenone-based photopolymerization initiator and the like in the structural part shown are used together.

Examples of the α-aminoacetophenone-based photopolymerization initiator system including the structural part represented by general formula (II) include: 2-methyl-1-[4-(methylthio)phenyl]-2 -Morpholine acetone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-(dimethylamino)-2- [(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-heptanone, N,N-dimethylaminoacetophenone, etc.

Examples of the acylphosphine oxide-based photopolymerization initiator system including the structural part represented by the general formula (III) include: 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentyl Phosphine oxide, etc.

Examples of the titanocene-based photopolymerization initiator system represented by the general formula (IV) include: bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro -3-(1H-pyrrol-1-yl)-phenyl) titanium.

The blending amount of the (B) photopolymerization initiator relative to (A) 100 parts by mass of the carboxyl group-containing resin is preferably 0.01 to 100 parts by mass, and more preferably 0.5 to 80 parts by mass. When the blending amount of (B) photopolymerization initiator is 0.01 parts by mass or more relative to (A) 100 parts by mass of the carboxyl group-containing resin, the photocurability on copper becomes good, the coating film is not easily peeled off, and the The properties of the coating film such as chemical properties become good. On the other hand, when the blending amount of the photopolymerization initiator (B) is 100 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin, the light absorption of the (B) photopolymerization initiator becomes good , Deep hardening improved.

[(C) Thinner]

As the diluent (C), at least one of an organic solvent and a photopolymerizable monomer can be used.

As the organic solvent used as the diluent (C), for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydroxy groups such as toluene, xylene and tetramethyl benzene; Methylcellulose, butylcellulose, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether , Tripropylene glycol monomethyl ether and other alcohol ethers; ethyl acetate, butyl acetate, butyl lactate, celozul acetate, butyl celozul acetate, carbitol acetate, butyl Carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane, decane, etc.; petroleum ether, stone Petroleum solvents such as naphtha and solvent naphtha. These organic solvents can be used alone or in combination of two or more.

The purpose of using the organic solvent is to dissolve and dilute the aforementioned (A) carboxyl group-containing resin, thereby applying it in a liquid state, followed by temporary drying, thereby forming a film, and allowing contact exposure. The amount of organic solvent used is not limited to a specific ratio, and can be appropriately set according to the coating method selected.

On the other hand, representative examples of the photopolymerizable monomer that can be used as the (C) diluent include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate , N-vinylpyrrolidone, acrylomorpholine, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth Group) acrylate, polyethylene glycol di(meth)acrylate, N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N,N-di Methylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, Melamine (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , Tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylic acid Ester, glycerol diglycidyl ether di(meth)acrylate, glycerin triglycidyl ether tri(meth)acrylate, isobranched (meth)acrylate, cyclopentadiene Mono- or di-(meth)acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ginsyl-hydroxyethyl isocyanurate, etc. (Meth)acrylic esters or polyhydric (meth)acrylates of ethylene oxide or propylene oxide adducts of these polyols; mono-, polyacrylic acid and hydroxyalkyl (meth)acrylate Two-, three- or more than three polyesters, etc. These photopolymerizable single systems can be used alone or in combination.

The purpose of using the above-mentioned photopolymerizable monomer is to dilute the (A) carboxyl group-containing resin so as to be in a state where it is easy to apply and to impart photopolymerizability.

When a photopolymerizable monomer is used as the diluent (C), the blending amount of the photopolymerizable monomer is preferably in the range of 5 to 40 parts by mass per 100 parts by mass of the total amount of the (A) carboxyl group-containing resin. Among the photopolymerizable monomers When the blending amount is 5 parts by mass or more, the effect of imparting photocurability is better. On the other hand, in the case of 40 parts by mass or less, the dryness of the touch of the coating film becomes good.

[(D) 1 multifunctional epoxy compound with at least 2 epoxy groups in the molecule]

(D) A polyfunctional epoxy compound having at least two epoxy groups in one molecule not only imparts heat resistance to the composition, but also improves adhesion to the base layer.

Examples of polyfunctional epoxy compounds having at least two epoxy groups in molecule (D) include, for example, Epikote 828, Epikote 834, Epikote 1001, Epikote 1004, EPICLON 840, and EPICLON manufactured by Mitsubishi Chemical Corporation. 850, EPICLON 1050, EPICLON 2055, EPO TOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Toto Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical, Sumitomo Chemical Bisphenol A of SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all trade names) manufactured by Industrial Corporation Type epoxy resin; Epikote YL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPO TOHTO YDB-400, YDB-500 manufactured by Toto Chemical Co., Ltd., DER542 manufactured by Dow Chemical Corporation, Sumitomo Chemical Industry Corporation Made of SUMI-EPOXY ESB-400, ESB-700, Asahi Kasei Brominated epoxy resins such as AER711, AER714, etc. (all trade names) manufactured by the industrial company; Epikote 152, Epikote 154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Corporation, and EPICLON manufactured by DIC Corporation N-730, EPICLON N-770, EPICLON N-865, EPO TOHTO YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S made by Toto Chemical Co., Ltd. , RE-306, SUMI-EPOXY ESCN-195X, ESCN-220 made by Sumitomo Chemical Industry Co., Ltd., AEROC-235, ECN-299 made by Asahi Kasei Industry Co., Ltd. (all are trade names) novolac epoxy resins; Bisphenol F-type epoxy resins such as EPICLON 830 manufactured by DIC Corporation, Epikote 807 manufactured by Mitsubishi Chemical Corporation, EPO TOHTO YDF-170, YDF-175, YDF-2004 manufactured by Toto Chemical Co., Ltd. (all are trade names); Hydrogenated bisphenol A type epoxy resins such as EPO TOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Chemical Industry Co., Ltd.; Epikote 604 manufactured by Mitsubishi Chemical Corporation, EPO TOHTO YH-434 manufactured by Toto Chemical Industry Co., Ltd. , SUMI-EPOXY ELM-120 manufactured by Sumitomo Chemical Industry Co., Ltd. (all are trade names) glycidylamine epoxy resin; hydantoin epoxy resin; CELLOXIDE 2021 manufactured by Daicel Chemical Industry Co., Ltd. (all are Alicyclic epoxy resin; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502 manufactured by Dow Chemical Corporation (all are trade names), trihydroxyphenylmethane epoxy resin Resin; bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or mixtures of these; EBPS manufactured by Nippon Kayaku -200, Bisphenol S type epoxy resins such as EPX-30 manufactured by ADEKA Corporation and EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac epoxy resins manufactured by Mitsubishi Chemical Corporation such as Epikote 157S (trade name) ; Epoxyte YL-931 manufactured by Mitsubishi Chemical Corporation (all are trade names) tetraphenol ethane type epoxy resin; Nissan Chemical Industry Corporation manufactured TEPIC etc. (all trade names) heterocyclic epoxy resins; Diglycidyl phthalate resins such as BLEMMER DGT manufactured by Nippon Oil Corporation; tetraglycidyl xylenol ethane resins manufactured by Toto Chemical Co., Ltd. such as ZX-1063; ESN- manufactured by Nippon Steel Chemical Co., Ltd. 190, ESN-360, naphthalene-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by DIC; HP-7200, HP-7200H manufactured by DIC, etc. have dicyclopentadiene skeleton Epoxy resin; glycidyl methacrylate copolymer epoxy resin of CP-50S, CP-50M, etc. manufactured by NOF Corporation; furthermore, the copolymerization of cyclohexyl maleimide and glycidyl methacrylate Polymerized epoxy resin; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-450 manufactured by Toto Chemical Co., Ltd.) Etc.), but not limited to this. These epoxy resins can be used alone or in combination of two or more. Among these, novolac-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins, or mixtures thereof are particularly preferred.

With respect to 100 parts by mass of (A) carboxyl group-containing resin, (D) the blending amount of a multifunctional epoxy compound having at least 2 epoxy groups in 1 molecule is preferably set to 0.6 to 2.8 equivalents in terms of epoxy equivalent, It is more preferably in the range of 0.8 to 2.5 equivalents. By combining at least 2 epoxy groups in (D)1 molecule The blending amount of the functional epoxy compound is set in the above range, and the composition can be given good heat resistance.

[(E) Black colorant]

(E) The black colorant may be an organic colorant or an inorganic colorant. For example, carbon black pigments such as CIPigment black 6, 7, 9, 18, etc., graphite pigments such as CIPigment black 8, 10, etc., iron oxide series such as CIPigment black 11, 12, 27, Pigment Brown 35, etc. Pigments; for example, KN-370 iron oxide manufactured by Toda Industries, 13M-T titanium black manufactured by Mitsubishi Materials, anthraquinone pigments such as CIPigment black 20, CIPigment black 13, 25, 29, etc. Cobalt oxide pigments, copper oxide pigments such as CIPigment black 15, 28, manganese pigments such as Cigigment black 14, 26, antimony oxide pigments such as CIPigment black 23, CIPigment black 30 Nickel oxide pigments such as CIPigment black 31, 32, perylene pigments of Lumogen Black FK4280 manufactured by BASF Japan, aniline pigments of Pigment Black 1, molybdenum sulfide or bismuth sulfide can also be exemplified as suitable pigments. Particularly preferred are carbon black and perylene pigments. In the case of carbon black-based and perylene-based pigments, the absolute value of ab value is closer to 0, so it is preferable to be blackened. These coloring agents can be used alone or in appropriate combination.

From the viewpoint of resolution, the blending amount of (E) the black colorant is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 1 part by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin. In the case of 0.01 parts by mass or more In addition, it is easy to blacken. When it is 5 parts by mass or less, the light transmittance is not likely to deteriorate.

[(F) Colorants other than black]

The curable composition of the present invention contains (F) a coloring agent other than black. As the coloring agent to be used, conventionally known coloring agents such as red, blue, green, yellow, and white can be used, and any one of pigments, dyes, and pigments can also be used. As a specific example, a number marked with a color index (C.I.; issued by The Society of Dyers and Colourists) can be cited as follows. However, from the standpoint of reducing the environmental load and the impact on the human body, it is preferable not to contain halogen.

(Red colorant)

As the red colorant system, there are monoazo system, disazo system, azo lake system (azolake) system, benzimidazolone system, perylene system, diketopyrrolopyrrole system, condensed azo system, anthraquinone system , Quinacridone, etc., specifically, those marked with a color index number as described below.

Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269; diazo system: Pigment Red 37,38,41; Monoazo lake system: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2 ,53:1,53:2,57:1,58:4,63:1, 63:2,64:1,68; benzimidazolone system: Pigment Red 171,175,176,185,208; perylene system: Solvent Red 135,179, Pigment Red 123,149,166,178,179,190,194,224; diketopyrrolopyrrole system: Pigment Red 254,255,264,270,272; condensed azo system: P 144,166,214,220,221,242; anthraquinone series: Pigment Red 168,177,216, Solvent Red 149,150,52,207; quinacridone series: Pigment Red 122,202,206,207,209

The blending amount of the red colorant is preferably 0 to 1 part by mass, more preferably 0.1 to 1 part by mass, and even more preferably 0.1 to 0.8 part by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin. When it is 1 part by mass or less, the light transmittance is not likely to deteriorate. Moreover, when it is 0.1 mass parts or more, it becomes easy to blacken.

(Blue colorant)

As the blue colorant system, there are phthalocyanine-based, anthraquinone-based, dioxazine-based, cobalt-based, etc. The pigment system is classified as Pigment, and the dye-based compound is Solvent, etc. Examples include those marked with color index numbers as follows. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Pigment system: Pigment Blue 15,15:1,15:2,15:3,15:4,15:6,16,60; dye system: Solvent Blue 35,45,63,67,68,70,83, 87,94,97,104,122,136

The blending amount of the blue colorant is preferably 0.1 to 2.5 parts by mass, and more preferably 0.2 to 1.5 parts by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin.

When it is 0.1 parts by mass or more, blackening is easy. When it is 2.5 parts by mass or less, the light transmittance is not likely to deteriorate.

(Yellow colorant)

Examples of the yellow colorant system include monoazo system, disazo system, condensed azo system, benzimidazolone system, isoindolinone system, and anthraquinone system. Specifically, the following coloring agents can be mentioned.

Monoazo system: Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100,101,104,105,111,116,167,168,169,182,183; disazo system: Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198; condensed azo system: Pigment Yellow 93,94,95,128,155,166,180; benzimidazolone system: Pigment Yellow 120,151,154,156,175,181: isoindolinone system: Pigment Yellow 109,110,139,179, 185; Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24,108,193,147,199,202; the blending amount of the yellow colorant is preferably 0.1 to 1.5 parts by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin. When it is 0.1 parts by mass or more, blackening is easy. When it is 1.5 parts by mass or less, the light transmittance is not likely to deteriorate. Furthermore, the blending amount of the yellow colorant and the total blending amount of the red colorant is preferably 0.1 to 2.5 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. When it is 0.1 parts by mass or more, blackening is easy. When it is 2.5 parts by mass or less, the light transmittance is not likely to deteriorate.

(Green colorant)

As the green colorant system, there are a phthalocyanine system and an anthraquinone system. Specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used. The blending amount of the green colorant is preferably 0.2 to 2.0 parts by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin. When it is 0.2 parts by mass or more, blackening is easy. When it is 2.0 parts by mass or less, the light transmittance is not likely to deteriorate.

(Purple colorant)

Specific examples of the purple colorant include Pigment Violet 19, 29, 32, 36, 38, 42; Solvent Violet 13, 36 and the like.

The blending amount of the purple colorant is preferably 0.1 to 2.5 parts by mass, and more preferably 0.2 to 2.5 parts by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin.

When it is 0.1 parts by mass or more, blackening is easy. When it is 2.5 parts by mass or less, the light transmittance is not likely to deteriorate.

(Orange colorant)

Specific examples of orange colorants include Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71 , 73 etc.

The blending amount of the orange colorant is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.8 part by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin. When it is 0.05 mass parts or more, it becomes easy to blacken. When it is 1 part by mass or less, the light transmittance is not likely to deteriorate.

(Brown colorant)

Specific examples of the brown colorant include Pigment brown 23 and 25.

(White colorant)

Examples of the white colorant include zinc oxide shown in Pigment white 4, titanium oxide shown in Pigment white 6, and zinc sulfide shown in Pigment white 7. From the viewpoint of coloring power and non-toxicity, titanium oxide is particularly used Preferably, for example: TR-made by Fuji Titanium Industrial Corporation 600, TR-700, TR-750, TR-840, manufactured by Ishihara Industries R-550, R-580, R-630, R-820, CR-50, CR-60, CR-90, manufactured by Titan Industries KR-270, KR-310, KR-380 and other rutile titanium oxides, manufactured by Fuji Titanium Industries Corporation TA-100, TA-200, TA-300, TA-500, manufactured by Ishihara Industries Corporation A100, A220, Titan Industries The anatase titanium oxide produced by the company, such as KA-15, KA-20, KA-35, KA-90, etc. A small amount of white colorant may be added in a small amount, for example, to 0.1 to 3% by mass in the curable composition of the present invention, and an effect of improving blackness can be expected.

(F) Two or more coloring agents other than black can be combined. It is preferably 0.35 to 9.5 parts by mass relative to (A) 100 parts by mass of the carboxyl group-containing resin and (F) the blending amount of the coloring agent other than black. When it is 0.35 parts by mass or more, blackening is easy. When it is 9.5 parts by mass or less, the light transmittance is not easily deteriorated.

(Thermosetting catalyst)

It is preferable that the curable composition of the present invention further contain a thermosetting catalyst. Examples of the thermosetting catalyst system include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives such as ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4-( (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine Amine compounds such as amine compounds, adipic acid dihydrazide, sebacic acid dihydrazide, etc.; phosphorus such as triphenylphosphine Compounds etc. Examples of the commercially available products include: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U manufactured by SAN-APRO. -CAT3503N, U-CAT3502T (both are trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both are bicyclic amidine compounds and their salts), etc. Furthermore, it is not limited to these, as long as it is a thermosetting catalyst of epoxy resin or oxetane compound, or can promote the reaction of epoxy group and/or oxetane group and carboxyl group, These systems can be used alone or in combination of two or more. In addition, melamine diamine, ethylene melamine diamine, benzo melamine diamine, melamine, 2,4-diamino-6-methacryl oxyethyl-S-tri Azine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adducts, 2,4-diamino-6-methacryloyloxyethyl-S-triazine. S-triazine derivatives such as isocyanuric acid adducts are preferably used in combination with compounds that also function as tackifiers and thermosetting catalysts.

The blending amount of the thermosetting catalyst is sufficient at a ratio generally used, for example, with respect to (A) a carboxyl group-containing resin, or (D) a multifunctional epoxy compound 100 having at least 2 epoxy groups in 1 molecule The part by mass is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15.0 parts by mass.

(filler)

Furthermore, in the curable composition of the present invention, for the purpose of improving the characteristics of the adhesiveness, mechanical strength, linear expansion coefficient, etc. of the cured product, Further blended with inorganic fillers or organic fillers. As such a filler, for example, barium sulfate, barium titanate, silica powder, fine powdered silica, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica Commonly used fillers such as powder.

(Any other ingredients)

The hardenable composition of the present invention can be further blended with hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, gallnut, phenothiazine, etc. as needed. At least any one of well-known and commonly used thickeners, silicone-based, fluorine-based, polymer-based defoamers and leveling agents such as polymerization inhibitors, fine powdered silica, organic bentonite, montmorillonite, etc. , Imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, photopolymerization sensitizers, light stabilizers, dispersants, hardening accelerators, flame retardants, flame retardant additives, (D) multifunctional Well-known and commonly used additives such as thermosetting components other than epoxy compounds.

The curable composition of the present invention is preferably black. In addition, it is preferable that the L* value of the cured product obtained by a colorimeter serving as a reference for displaying blackness is 35 or less in the SCI method. From the viewpoint of blackness, it is preferable that the a* value is -1.0 to 2.0 and the b* value is -3.0 to 1.1. More preferably, the a* value is -0.5~0.5, and the b* value is -2.0~0.5.

Furthermore, from the viewpoint of blackness, the curable composition of the present invention preferably contains a purple colorant as a coloring agent other than (F) black. In particular, the curable composition of the present invention preferably contains 0.05 to 1.0 mass of black colorant relative to 100 mass parts of (A) carboxyl group-containing resin. Parts, and 0.2 to 2.0 parts by mass of purple colorant. The curable composition containing a purple coloring agent as a coloring agent other than (F) black has an a* value of 0.07 to 1.55 and a b* value of -1.0 to 1.1.

The curable composition of the present invention is suitable for the formation of a hardened film such as a solder resist or an interlayer insulating layer of a printed wiring board or a flexible printed wiring board, especially for printed wiring boards with high density and high fineness Medium, suitable for the formation of resist patterns with high density and high blackness. The curable composition of the present invention can also be used for printing inks, inkjet inks, photomask production materials, printing proofing production materials, etching resists, solder resists, partition walls of plasma display panels (PDP), Production of mask patterns for dielectric patterns, electrode (conductor circuit) patterns, wiring patterns for electronic parts, conductive pastes, conductive films, black matrix, etc.

The curable composition of the present invention can be prepared as a dry film coated and dried on a carrier film (support). When the film is dried, the curable composition of the present invention can be adjusted to an appropriate viscosity by dilution with the above-mentioned organic solvent, and a point coater, blade coater, lip coater, stick type Coater (rod coater), squeeze coater (squeeze coater), reverse coater, transfer roll coater, gravure coater, sprayer are equal to the carrier film coated to a uniform thickness, usually 50 to 130 Drying is carried out at a temperature of ℃ for 1 to 30 minutes to form a dry coating film. Although the coating film thickness is not particularly limited, in general, the film thickness after drying is appropriately selected within the range of 0.1 to 100 μm, preferably 0.5 to 50 μm.

As the carrier film, a plastic film can be used, preferably Plastic films such as polyester films such as polyethylene terephthalate, polyimide films, polyimide films, polypropylene films, polystyrene films, etc. are used. Although the thickness of the carrier film is not particularly limited, in general, it is appropriately selected within the range of 0.1 to 150 μm.

In this case, it is preferable that after the coating film is formed on the carrier film, a peelable coating film is further laminated on the surface of the coating film to prevent dust and the like from adhering to the surface of the coating film. As the peelable coating system, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the coating film is peeled off, the adhesion force between the coating film and the coating film is better than that of the coating film The adhesive force with the carrier film is smaller.

In addition, after adjusting the curable composition of the present invention to a viscosity suitable for a coating method using the above-mentioned organic solvent, by dip coating method, shower coating method, roll coating method, bar coating method, screen printing method , Curtain coating method, die coating method, etc. are applied on the substrate, and the organic solvent contained in the composition is volatilized and dried (pre-hardened) at a temperature of about 50-90°C, thereby forming a non-sticky drying Coated film. In addition, in the case of applying and drying the curable composition of the present invention on a carrier film as a film and winding it as a dry film, the lamination machine or the like is used to bring the coating film of the composition into contact with the substrate After being attached to the substrate, the carrier film is peeled off, whereby a coating layer can be formed on the substrate.

These coating films can be cured by light, for example, by irradiation with active energy rays, or thermally cured by heating to a temperature of 100 to 250°C to obtain a cured product.

Examples of the above-mentioned substrate system include a printed circuit in which a circuit is formed in advance In addition to brush wiring boards or flexible printed wiring boards, paper phenol, epoxy paper, epoxy glass cloth, polyimide glass, epoxy glass cloth/nonwoven fabric, epoxy All grades (FR-, such as glass cloth/paper, epoxy synthetic fiber, fluorine/polyethylene/polyphenylene oxide, polyphenylene oxide/cyanate, etc. for high-frequency circuit copper-clad laminates, etc.) 4) Copper-clad laminates, other polyimide films, PET films, glass substrates, ceramic substrates, wafer boards, etc.

After applying the curable composition of the present invention, the volatile drying system can use a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, etc., and a heat source equipped with an air heating method by steam can be used. The method of countercurrent contact of hot air in the dryer and the method of blowing on the support from the nozzle.

The exposure machine used as the active energy ray irradiation may be a device that is equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halogen lamp, a mercury short-arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Furthermore, direct exposure A drawing device (for example, a laser direct imaging device that draws an image by irradiating direct active energy rays with CAD data from a computer). As the light source of the direct-scanner, it is only necessary to use light having a maximum wavelength in the range of 350 to 410 nm. The amount of exposure used for image formation varies depending on the film thickness and the like, but generally it can be set to 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

In addition, as the developing method, it can be performed by dipping method, shower method, spray method, brush method, etc., and as the developing liquid system, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicon Sodium, ammonia, Alkaline aqueous solutions such as amines.

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are quality standards unless otherwise specified.

[Synthesis of Carboxyl Resin A-1]

600g of diethylene glycol monoethyl ether acetate was filled with o-cresol novolac type epoxy resin [made by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95°C, epoxy equivalent 214 , The average number of functional groups 7.6] 1070g (epoxypropyl number (total number of aromatic rings): 5.0 moles), acrylic acid 360g (5.0 moles), and hydroquinone 1.5g, heated and stirred to 100 ℃, uniformly dissolved.

Next, 4.3 g of triphenylphosphine was charged, and the reaction was heated to 110°C for 2 hours, and then the temperature was raised to 120°C, and the reaction was further carried out for 12 hours. To the obtained reaction liquid, 415 g of aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mole) of tetrahydrophthalic anhydride were charged, and the reaction was carried out at 110° C. for 4 hours, followed by cooling to obtain photosensitive Carboxyl-containing resin solution (solid content acid value 89mgKOH/g, solid content 65%). Let this be the resin solution A-1.

[Synthesis of Carboxyl Resin A-2]

With a thermometer, nitrogen introduction device and alkylene oxide introduction device The autoclave equipped with a stirring device was filled with novolac-type cresol resin (manufactured by Showa Denko Corporation, trade name "Shonol CRG 951", OH equivalent: 119.4), 119.4g, potassium hydroxide 1.19g, and toluene 119.4g. The system was replaced with nitrogen while stirring, and the temperature was increased by heating.

Next, 63.8 g of propylene oxide was slowly dropped, and the reaction was carried out at 125 to 132° C. and at 0 to 4.8 kg/cm ² for 16 hours. After that, it was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to this reaction solution to neutralize potassium hydroxide to obtain a novolak-type cresol resin with 62.1% of nonvolatile components and a hydroxyl value of 182.2 g/eq. The reaction solution of propylene oxide. The phenolic hydroxyl group added 1.08 moles of alkylene oxide per 1 equivalent.

The obtained novolac-type cresol resin alkylene oxide reaction solution 293.0g, acrylic acid 43.2g, methanesulfonic acid 11.53g, methylhydroquinone 0.18g and toluene 252.9g were charged with a stirrer, thermometer and air Into the reactor blown into the tube, air was blown at a rate of 10 ml/min, and the reaction was carried out at 110° C. for 12 hours while stirring. The water produced by the reaction was distilled as an azeotropic mixture with toluene, and 12.6 g of water was distilled off.

Then, it was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of 15% sodium hydroxide aqueous solution, followed by water washing. Thereafter, toluene was distilled off while being substituted with 118.1 g of diethylene glycol monoethyl ether acetate in 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 in at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrophthalic anhydride was slowly added, and the reaction was carried out at 95 to 101° C. for 6 hours to obtain a photosensitive carboxyl group-containing resin solution (solid content acid value 88 mgKOH/g, solid content 71%). Let this be the resin solution A-2.

[Preparation of carboxyl group-containing resin A-3]

CYCLOMER ACA Z320 (solid component acid value 135 gKOH/g, solid component 39%) manufactured by Daicel Corporation was used. Let this be the resin solution A-3.

According to the blending shown in Table 1 below, each component was blended and stirred, and dispersed with a 3-roller to prepare each curable composition. In addition, the blending amount in Table 1 shows parts by mass.

Carboxyl group-containing resin solution A-1: Varnish A-1 (solid content: 65%, acid value: 89mgKOH/g)

Carboxyl group-containing resin solution A-2: Varnish A-2 (solid content: 71%, acid value: 88mgKOH/g)

Carboxyl group-containing resin solution A-3: Varnish A-3 (manufactured by Daicel Corporation) CYCLOMER (ACA) Z320 (solid content: 39%, acid value: 135mgKOH/g))

Photopolymerization initiator B-1: Irgacure 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one) manufactured by BASF Japan

Photopolymerization initiator B-2: Dimer oxime ester photopolymerization initiator having a carbazole structure (the above compound No. 1)

Photopolymerization initiator B-3: Oxime ester photopolymerization initiator

Thinner C-1: Dipropylene glycol monomethyl ether (DPM)

Thinner C-2: NK Ester A-9550 (multifunctional acrylate) manufactured by Shin Nakamura Chemical Company

Multifunctional epoxy compound D-1: N870-75EA (bisphenol A type epoxy resin) manufactured by DIC Corporation

Multifunctional epoxy compound D-2: TEPIC-HP

Black colorant E-1: CKT-7198 (carbon black) manufactured by Resino Color Company

Blue colorant F-1: ε-phthalocyanine blue

Red colorant F-2: PY8025

紫Violet B Purple colorant F-3: 2

Violet B

Yellow colorant F-4: CROMOPHTAL yellow AGR

Orange colorant F-5: Diketopyrrolopyrrole Orange TR

Hardening catalyst G-1: Melamine

Hardening catalyst G-2: Tricyandiamide

Additive H-1: KS-66 (silicone defoamer) manufactured by Shin-Etsu Silicone

Filler I-1: B-30 (barium sulfate) manufactured by Sakai Chemical Company

Filler I-2: SiO ₂

(assessment method)

<a* value and b* value>

The curable compositions of each example and each comparative example were applied to the washed copper flat-coated substrates by screen printing, and dried in a hot air circulation drying oven at 80°C for 10 minutes to form a dry coating. Then, the film was exposed at an exposure level with a sensitivity of 7 steps by an exposure machine equipped with a metal halide lamp manufactured by Oak Manufacturing Co., Ltd. Thereafter, development was carried out with a 1% by weight Na ₂ CO ₃ aqueous solution at a spray pressure of 0.1 MPa for 1 minute, and then, a hot-air circulation type drying furnace was used for thermal curing at 150° C. for 60 minutes to obtain a cured coating film. . For the obtained cured coating film, using a spectrophotometer (manufactured by Konica Minolta, CM-2600d), the value of the L*a*b* color system on the coating film was measured according to JIS Z 8729, and the brightness The L*a*b* value of the index is evaluated as an indicator of blackness. Both a*b* values indicate that the closer to 0, the better the blackness. The obtained results are shown in Table 2 below.

<absorbance>

In the measurement of absorbance, an ultraviolet-visible spectrophotometer (Ubest-V-570DS manufactured by Japan Spectroscopy Corporation) and an integrating sphere device (ISN-470 manufactured by Japan Spectroscopy Corporation) are used. After applying the hardenable composition of each of the foregoing examples and each comparative example to a glass plate using an applicator, it was dried using hot air circulation The furnace was dried at 80°C for 30 minutes to produce a dry coating film of the curable composition on the glass plate. Using an ultraviolet-visible spectrophotometer and an integrating sphere device, the absorbance reference line of 500 to 300 nm is measured on the same glass plate as the glass plate coated with the curable composition. The absorbance of the prepared glass plate with a dry coating film was measured, and the absorbance of the dry coating film was calculated from the reference line to obtain the absorbance at the wavelength of 355 nm of the target light. In order to prevent the deviation of the absorbance caused by the deviation of the coating film thickness, the coating thickness caused by the applicator is changed in four stages to perform this operation, and a graph of the coating thickness and the absorbance of 355nm is prepared and calculated from the approximate formula The absorbance of the dried coating film with a film thickness of 25 μm is taken as the respective absorbance. The obtained results are shown in Table 2 below.

<sensitivity>

The curable composition of each example and comparative example was applied to the washed copper flat-coated substrate by screen printing so as to become 10 μm after drying, and dried at 80° C. for 10 minutes in a hot air circulation drying furnace . Place a trapezoidal plate (41 steps) made by Stouffer on this coating film, and expose it with an exposure machine equipped with a metal halide lamp made by Oak Manufacturing Co., Ltd. at an exposure amount of 300mJ/cm ² , and investigate by 1wt% Na ₂ CO ₃ aqueous solution was developed at a spray pressure of 0.1 MPa for 1 minute and the number of remaining segments. The greater the number of remaining segments, the better the sensitivity and the better. The obtained results are shown in Table 2 below.

<resolution>

The curable resin composition of each example and comparative example was applied to the copper flat-coated substrate by screen printing, and dried at 80° C. for 30 minutes. Exposure was performed using a negative film with L/S=50/500 at an optimal exposure amount, and a 1% Na ₂ CO ₃ aqueous solution at 30° C. was developed under a spray pressure of 2 kg/cm ² for 60 seconds to obtain a pattern. After development, the relief shape was observed with an optical microscope and evaluated as follows. The obtained results are shown in Table 2 below. The relief shapes of Example 2 and Comparative Example 2 are shown in Figs. 1 and 2 respectively.

◎: Any of the pattern distortion, over-width, and base erosion (the difference between the top and bottom dimensions) cannot be confirmed.

○: Any one of slight pattern distortion, excessive width, and undercut (the difference between the size of the top and the bottom) was confirmed.

×: Any one of obvious pattern distortion, excessive width, and undercut (the difference between the size of the top and the bottom) was confirmed.

<Gold plating resistance (adhesion)>

The curable composition of each example and comparative example was applied to the patterned copper foil substrate by screen printing in such a way that the dry film thickness was 20 μm, dried at 80° C. for 30 minutes, and allowed to cool To room temperature. On this substrate, an exposure device equipped with a high-pressure mercury lamp was used to expose the pattern at an optimal exposure amount, and then, a 30-degree 1wt% sodium carbonate aqueous solution was developed under a spray pressure of 0.2 MPa for 60 seconds. , And get the pattern. This substrate was post-cured at 150° C./60 minutes to obtain an evaluation substrate with a pattern of cured objects.

For the evaluation substrate, use a commercially available electroless nickel plating bath and electroless The gold plating bath is plated under the conditions of nickel 5 μm and gold 0.05 μm at 80 to 90°C. After the plating evaluation board was visually evaluated for the presence or absence of plating infiltration, the peeling of the resist layer was evaluated by tape peeling. The criteria for each judgment are as follows. The obtained results are shown in Table 2 below.

◎: No penetration was observed after plating, and there was no peeling after the tape was peeled off.

○: Only penetration was observed after plating, but there was no peeling after the tape was peeled off.

△: A little penetration was observed after plating, and a little peeling after the tape was peeled off.

×: Penetration was confirmed after plating, and peeling was also observed after the tape was peeled off.

It was confirmed that the curable composition of any example was excellent in resolution and blackness of the cured product. In contrast, the aforementioned absorbance is not satisfied The hardenable compositions of Comparative Examples 1 to 3 were confirmed to have poor resolution. In addition, Comparative Example 4, which does not satisfy the aforementioned absorbance, can be confirmed to have poor resolution when compared with Example 2 having a similar composition.

Claims (9)

A hardenable composition containing the following components: (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) diluent, (D) at least 2 epoxy in 1 molecule The multifunctional epoxy compound based on (E) black colorant, and (F) coloring agent other than black, characterized in that the coloring agent other than (F) black contains at least one of purple coloring agent and orange coloring agent, The film thickness of the dried coating film is 1.5 or less per wavelength of 365 nm at 25 μm, 1.0 or less at 385 nm, and 1.0 or less at 405 nm. A hardenable composition containing the following components: (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) diluent, (D) at least 2 epoxy in 1 molecule Based multifunctional epoxy compound, (E) black colorant, and (F) coloring agent other than black, characterized in that the aforementioned (B) photopolymerization initiator contains a dimerized oxime ester-based photopolymerization initiator The thickness of the dried coating film is 25 or less, the absorbance of wavelength 365nm is 1.5 or less, the absorbance of 385nm is 1.0 or less, and the absorbance of 405nm wavelength is 1.0 or less. The curable composition according to claim 1 or 2, wherein the coloring agent other than (F) black contains at least one of a red coloring agent, a blue coloring agent, and a yellow coloring agent. A dry film characterized by having a resin layer obtained by coating and drying the curable composition according to any one of claims 1 to 3 on a film. A hardened product characterized by hardening at least one of the curable composition according to any one of claims 1 to 3 and the resin layer of the dry film according to claim 4. A printed wiring board characterized by having a hardened product as in claim 5. A method for manufacturing a dry film, characterized by using the hardenable composition according to any one of claims 1 to 3. A method for manufacturing a hardened product, characterized by using the hardenable composition according to any one of claims 1 to 3. A method for manufacturing a printed wiring board, characterized by using at least any one of the curable composition according to any one of claims 1 to 3 and the dry film according to claim 4.

Images