TWI476521B - A photohardenable resin composition and a hardened pattern, and a printed circuit board - Google Patents

Description

Photocurable resin composition and cured pattern, and printed circuit board

The present invention relates to an alkaline development type photocurable resin composition which is excellent in sensitivity to an active energy ray and which is useful as a solder resist (Solder Resist).

Recently, as a means of exposure for solder resists for printed circuit boards, laser scanning exposure has become popular from the viewpoint of excellent positional matching accuracy. The laser exposure is to form an image while scanning the solder resist on the circuit board formed by the mask without using a mask. However, in the past, the solder resist has a proper exposure amount of 200 mJ/cm ² or more, so it is necessary to expose the exposure. The disadvantage of very long time is that the high sensitivity height of the solder resist corresponding to the laser exposure is required.

In view of the above, a photosensitive composition capable of exhibiting a high photopolymerization ability has been proposed (for example, refer to Patent Document 1 and Patent Document 2). However, among the photosensitive compositions proposed so far, there is indeed a person who can exhibit a high photopolymerization ability, but when the laser is directly exposed, the sensitivity is not satisfactory, and the photosensitive composition is required. Among the characteristics other than sensitivity, it is also unsatisfactory. Specifically, the composition disclosed in Patent Document 1 is a compound having a cyclic ether group and an ethylenically unsaturated group in one molecule formed by forming a photosensitive resin containing a carboxyl group, and only the epoxy propyl group is mentioned. Although the methacrylate is not only insufficient in sensitivity, but when the amount of addition is too large, the developability tends to be deteriorated. On the other hand, in the case of the acrylate, when the caprolactone-denatured acrylate which elongates the molecule after the chain reaction of ε-caprolactone is used, the sensitivity is improved, but the dryness of the touch is extremely poor. The soldering heat resistance is also insufficient.

Further, the alkaline development type photo solder resist has problems from the viewpoint of durability. In other words, the alkaline development type photo solder resist has poor chemical resistance, water resistance, heat resistance, and the like as compared with the conventional thermosetting type and solvent development type. This is because the alkaline development type photo solder resist can perform alkaline development, so that a hydrophilic base is used as a main component. Therefore, the chemical liquid, water, water vapor, and the like are easily impregnated, so that the chemical resistance is lowered or the adhesion between the photoresist film and copper is lowered. As a result, the alkali resistance as a chemical resistance is weak, and in particular, in a semiconductor package such as BGA or CSP, it is particularly necessary for the PCT resistance (pressure cooker testability) of the heat and humidity resistance, but it is impossible under such severe conditions. The degree of maintenance for hours to tens of hours is the status quo. Further, in the PCBT test in which a voltage state was applied under PCT conditions, it was confirmed that defects occurred due to migration in almost a few hours.

[Patent Document 1] JP-A-2007-41502 (Patent Application)

[Patent Document 2] Japanese Patent Publication No. 2007-3590 (Application No.)

The present invention has been developed in view of the above problems, and has high sensitivity to the active energy ray, and is excellent in exposure hardenability by direct drawing, and has been improved as developability, dryness, and solder heat resistance. An alkaline development type photocurable resin composition which is used as a solder resist which is excellent in electroless gold plating property, alkali resistance, PCT, and PCBT resistance is a problem.

In order to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a photosensitive resin containing a carboxylic acid and a photocurable resin composition obtained by combining other components.

That is, the first aspect of the present invention contains (A-1) a carboxylic acid-containing photosensitive resin having a structure represented by the general formula (I), (B) a photopolymerization initiator, and (C) 1 molecule. A compound containing two or more ethylenically unsaturated groups is a photocurable resin composition characterized by alkaline development.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue.

Wherein (A-1) a carboxylic acid-containing photosensitive resin is reacted with (b) an unsaturated monocarboxylic acid in (a) a compound having two or more cyclic ether groups in one molecule; The resin obtained by (d) a polybasic acid anhydride is further reacted with a compound containing a cyclic ether group and an ethylenically unsaturated group in (e) one molecule.

Further, the compound containing a cyclic ether group and an ethylenically unsaturated group in (e) one molecule is 4-hydroxybutyl acrylate glycidyl ether.

In a second aspect of the present invention, (A-2) a carboxylic acid-containing photosensitive resin containing (A) a structure represented by the general formula (II) and a structure represented by the general formula (III), and (B) photopolymerization The starting agent and the compound containing two or more ethylenically unsaturated groups in one molecule of (C) are photocurable resin compositions which are characterized by alkaline development.

In the general formulae (II) and (III), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ⁷ represents An acid anhydride residue, n represents 0 or 1.

(A-2) The carboxylic acid-containing photosensitive resin is a compound in which (a) contains two or more cyclic ether groups in one molecule, and (b) an unsaturated monocarboxylic acid. And (c) reacting the unsaturated monocarboxylic anhydride to obtain a resin obtained by reacting (d) a polybasic acid anhydride, and reacting with a compound having a cyclic ether group and an ethylenically unsaturated group in (e) molecule; .

Further, the compound containing a cyclic ether group and an ethylenically unsaturated group in (e) one molecule is 4-hydroxybutyl acrylate glycidyl ether or glycidyl methacrylate.

Further, in the first and second aspects of the resin composition of the present invention, (B) the photopolymerization initiator is selected from the group consisting of an oxime ester photopolymerization initiator containing a structure represented by the general formula (III) (B- 1) An aminoacetophenone photopolymerization initiator (B-2) containing a structure represented by the general formula (IV), and a mercaptophosphine oxide photopolymerization system containing a structure represented by the general formula (V) One or a mixture of two or more of the starting agents (B-3):

In the general formulae (IV) to (VI), R ⁸ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear chain having a carbon number of 1 to 20, and a branch. a cyclic or cyclic alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl group having 2 to 20 carbon atoms Mercapto or benzhydryl (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), R ⁹ represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and carbon a linear, branched or cyclic alkyl group of 1 to 20 (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), and has a carbon number of 5 to 8 An alkyl group, an alkylene group having 2 to 20 carbon atoms or a benzhydryl group (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ¹⁰ and R ¹¹ each independently represent a straight carbon number of 1 to 12 a chain, branched or cyclic alkyl or arylalkyl group, each of R ¹² and R ¹³ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ¹² after binding and R ¹³ may form a cyclic alkyl ether group, R ¹⁴ and R ¹⁵ each independently represent a carbon number of 1 to 10 linear, branched a cyclic alkyl group, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may be substituted by a halogen atom, an alkyl group, or an alkoxy group), or an RC(=O)- group (wherein R is a carbon number) 1 to 20 hydrocarbon groups). However, the case where both of R ¹⁴ and R ¹⁵ are RC(=O)- groups is removed.

Further, the resin composition of the present invention further contains (D) a thermosetting component in the first and second aspects.

Further, in the first and second aspects, the resin composition of the present invention further contains (E) a colorant as a solder resist.

Another aspect of the present invention is a photocurable dry film obtained by applying the photocurable resin composition of the present invention to a carrier film and drying the film.

Further, another aspect of the present invention is a cured product pattern formed by using a resin layer formed of the photocurable resin composition, and a pattern of a cured product formed by irradiation with an active energy ray is formed in the pattern. Among them, the pattern irradiated by the active energy ray is formed by directly depicting the resultant using an active energy ray having a wavelength of 350 nm to 410 nm.

Further, another aspect of the present invention is a printed circuit board having the above-described cured pattern on a copper layer.

The best form of implementing the invention

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

In the first embodiment, the carboxylic acid-containing photosensitive resin (A-1) contained in the photocurable resin composition of the present invention contains a structure represented by the general formula (I) and contains a carboxylic acid in the molecule.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue.

The carboxylic acid-containing photosensitive resin (A-1) of the present invention is, for example, a carboxylic acid obtained by reacting a hydroxyl group-containing resin with a polybasic acid anhydride to form a carboxylic acid-containing photosensitive resin (A') as a half ester. One of the fractions is obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated group in the (e) molecule.

The carboxylic acid-containing photosensitive resin (A') which is half-esterified with an acid anhydride may, for example, be a compound containing two or more cyclic ether groups in one molecule of (a), and (b) an unsaturated monocarboxylic acid. After the reaction of the acid, the resin obtained by reacting the (d) polybasic acid anhydride is preferred, and specific examples thereof include the following resins.

(1) A carboxylic acid-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound (a) with an unsaturated monocarboxylic acid (b) and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d) ,

(2) A polyfunctional epoxy compound (a), an unsaturated monocarboxylic acid (b), at least one alcoholic hydroxyl group in one molecule, and one other than an alcoholic hydroxyl group which reacts with an epoxy group a reaction product of a reactive group compound, a carboxylic acid-containing photosensitive resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride (d),

(3) A polyfunctional oxetane compound (a) having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid (b), and the resulting denatured oxetane resin is obtained. a carboxylic acid-containing photosensitive resin obtained by reacting a first-order hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d), but is not limited thereto, and other examples include a hydroxyl group-containing polyol derivative or the like. A resin containing a hydroxyl group and a carboxyl group which is reacted with a saturated or unsaturated polybasic acid anhydride. Among them, the above (1), (2), and (3) have an unsaturated double bond, and therefore it is preferable from the viewpoint of photosensitivity.

In the second embodiment, the carboxylic acid-containing photosensitive resin (A-2) contained in the photocurable resin composition of the present invention contains a structure represented by the general formula (II) and a general formula (III). Structure, and the molecule contains a carboxylic acid.

In the general formulae (II) and (III), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, R ⁷ Represents an anhydride residue and n represents 0 or 1.

The carboxylic acid-containing photosensitive resin (A-2) of the present invention can be obtained according to the following procedure (1) or (2), but is not limited thereto.

which is,

(1) When a compound (a) having two or more cyclic ether groups in one molecule is simultaneously reacted with an unsaturated monocarboxylic acid (b) and an unsaturated monocarboxylic anhydride (c), the above cyclic ether is used. The first-stage and second-order hydroxyl groups formed by the reaction are reacted with a polybasic acid anhydride (d), and a compound (e) having a cyclic ether group and an ethylenically unsaturated group in one molecule is reacted.

(2) When a compound (a) containing two or more cyclic ether groups in one molecule is reacted with an unsaturated monocarboxylic acid (b), the reaction formed by the reaction of the cyclic ether group is 1 The first and second hydroxyl groups are simultaneously reacted with the unsaturated monocarboxylic anhydride (c) and the polybasic acid anhydride (d), and the resulting unsaturated monocarboxylic acid is removed by reduced pressure, and then one molecule contains a cyclic ether. The group is obtained by reacting a compound (e) having an ethylenically unsaturated group.

2 molecules used in the synthesis of the carboxylic acid-containing photosensitive resins (A-1) and (A-2) (sometimes collectively referred to as "carboxylic acid-containing photosensitive resin (A)") Examples of the compound (a) having a cyclic ether group or more include various known epoxy resins, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin. Resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol epoxy resin, bisxylenol epoxy resin, phenolic epoxy resin for phenol paint, cresol paint A phenolic epoxy resin, a phenolic epoxy resin for brominated phenol paint, a phenolic epoxy resin such as a phenolic epoxy resin for bisphenol A; a diepoxypropyl terephthalate, six Diepoxypropyl phthalate, dimer acid propylene oxide Epoxypropyl ester compound; triepoxypropyl trimeric isocyanate, N, N, N', N'-tetraepoxypropyl m-xylene diamine, N, N, N', N'-tetracyclic Ethoxypropyl bisaminomethylcyclohexane, N,N-diepoxypropyl aniline and other epoxy propylamine compounds; epoxy propyl (meth) acrylate, copolymerization with other polymerizable monomers Further, examples of the resin include an oxetane resin, a copolymerized resin containing an oxetane-based (meth) acrylate and a polymerizable monomer thereof. Among them, a phenolic epoxy resin for phenol paint and a phenolic epoxy resin for cresol paint are preferred because they can improve a cured film having excellent heat resistance under high sensitivity. Further, the phenolic epoxy resin for cresol paint having a softening point of 60 ° C or higher is also excellent in finger-drying property, and therefore is preferable.

These polyfunctional epoxy compounds can be used individually or in combination of 2 or more types.

Further, in the present specification, the term "(meth)acrylate" means acrylate, methacrylate, and the generic term of these mixtures, and has the same meaning for other similar expressions.

Examples of the unsaturated monocarboxylic acid (b) used for the synthesis of the carboxylic acid-containing photosensitive resin (A) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, and β-benzene. Ethylene acrylate, β-oxo-methacrylic acid, etc. can be used individually or in combination of 2 or more types.

The unsaturated monocarboxylic anhydride (c) used for the synthesis of the carboxylic acid-containing photosensitive resin (A-2) is exemplified by acrylic acid anhydride and methacrylic anhydride, and these may be used alone or in combination of two or more. These unsaturated monocarboxylic anhydrides (c) are necessary for the formation of the structure represented by the general formula (I) contained in the carboxylic acid-containing photosensitive resin (A) of the present invention. The effect is that the concentration of the photosensitive group can be increased, so that the sensitivity is effectively improved, and the development property can be improved without explaining it in detail. It is presumed that the concentration of the hydroxyl group present in the resin is lowered to increase the hydrophobicity, and the affinity with other components having no carboxyl group is increased, and the emulsification effect is further improved. Further, in the alkali resistance of one of the objects of the present invention, the effect of reducing the hydroxyl group and the increase in the crosslinking density are better than when the photosensitive resin containing a carboxylic acid is used in the past. Other reduction effects as hydroxyl groups are also effective for pressure cooker (PCT) resistance and PCBT resistance added to the voltage in the pressure cooker.

Examples of the polybasic acid anhydride (d) used for the synthesis of the carboxylic acid-containing photosensitive resin (A) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic acid. An acid anhydride, methyl hexahydrophthalic anhydride, itaconic anhydride, methyl endomethyl acid tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride may be used alone or in combination of two or more.

The compound (e) containing a cyclic ether group and an ethylenically unsaturated group in one molecule of the synthesis of the carboxylic acid-containing photosensitive resin (A) is exemplified by 2-hydroxyethyl (meth) acrylate. Epoxypropyl ether, 2-hydroxypropyl (meth) acrylate epoxy propyl ether, 3-hydroxypropyl (meth) acrylate epoxy propyl ether, 2-hydroxybutyl (meth) acrylate Ester epoxypropyl ether, 4-hydroxybutyl (meth) acrylate epoxy propyl ether, 2-hydroxypentyl (meth) acrylate epoxy propyl ether, 6-hydroxyhexyl (meth) acrylate Ester epoxypropyl ether, hydroxycyclohexyl (meth) acrylate glycidyl ether, epoxy propyl (meth) acrylate, and the like. Among them, 4-hydroxybutyl acrylate glycidyl ether in a carboxylic acid-containing photosensitive resin (A-1), 4-hydroxybutyl group in a carboxylic acid-containing photosensitive resin (A-2) Acrylate epoxypropyl ether and epoxy propyl methacrylate are preferred because of their moderate productivity and photocurability.

The addition amount of the compound (e) having a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably from 5% equivalent to 40% by weight, more preferably from 10% by weight to 30%, based on the acid anhydride residue. equivalent. When the amount of addition is 5% equivalent or more, the maximum development image may become shorter or the dryness of the touch may be changed when the sensitivity is increased or the resistance of the electroless gold plating is improved. Poor, not good.

It is necessary to form the structure represented by the general formula (I) and the general formula (III) by the denaturation of the compound (e).

This effect was confirmed to be a multiplication effect by high sensitivity, alkali resistance, PCT, and PCBT resistance which are improved by the crosslinking density. These effects are all obtained by a reaction of a glycidyl methacrylate or a glycidyl acrylate having a cyclic ether group and an ethylenically unsaturated group in one molecule, but when the same denatured resin is used, for example, When the addition amount (20% or more) of the epoxy methacrylate is increased, the developability is deteriorated, and when the amount of addition is decreased, the effect such as high sensitivity is weakened. However, when a compound having a cyclic ether group and an ethylenically unsaturated group in one molecule having a moderate aliphatic chain of the present invention is added, even if the amount of addition is increased, the image forming property is still good and the sensitivity is high or improved. PCT and PCBT resistant. On the other hand, when the component of R ² of the general formula (I) and the component of R ⁶ of the general formula (III) is a long-chain alkyl group having 7 or more carbon atoms, the dryness of the touch is deteriorated, or conversely, the developability is deteriorated. Not good.

Further, in the carboxylic acid-containing photosensitive resin (A-2) which is denatured by (c) and denatured by (e), a general formula for forming a structure by reaction with an unsaturated monocarboxylic anhydride (c) is used. The structures of (II) and (III) have sufficient developability even in a state where the amount of addition is 20% or more. Although this phenomenon is explained in detail, it is known that the hydroxyl group formed when the cyclic ether compound is reacted with an unsaturated monocarboxylic acid is consumed by an unsaturated monocarboxylic anhydride, and the hydrophilicity and hydrophobicity may be more clear, and emulsification may be obtained. effect.

The above-mentioned carboxylic acid-containing resin (A) has a plurality of free carboxyl groups in the side chain of the skeleton ‧ polymer, so that alkaline development can be performed.

Further, the acid value of the carboxylic acid-containing resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkaline development is difficult to carry out. On the other hand, when it exceeds 200 mgKOH/g, the exposure portion is dissolved by the developing solution, so that it is necessary to shorten the necessary process or the like. When it is necessary to perform the dissolution and peeling with the developing liquid under the unexposed exposure portion and the unexposed portion, it is difficult to draw the normal photoresist pattern, which is not preferable.

Further, the weight average molecular weight of the carboxylic acid-containing resin (A) varies depending on the resin skeleton, and is usually 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the tack free performance is deteriorated, or the moisture resistance of the coating film after exposure is deteriorated, the film is reduced at the time of development, and the resolution is remarkably deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated, and the storage stability may be deteriorated.

The blending ratio of the carboxylic acid-containing resin (A) is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total mass of the resin composition. When the amount is less than the above range, the film strength may be lowered. On the other hand, when it is more than the above range, the viscosity is improved, or the coatability and the like are lowered, which is not preferable.

In the present invention, in addition to the above-mentioned carboxylic acid-containing photosensitive resin (A), a conventionally known carboxylic acid resin may be further added, and a photosensitive carboxylic acid resin is particularly preferred.

Next, the photopolymerization initiator (B) will be described.

As the photopolymerization initiator (B), an oxime ester photopolymerization initiator (B-1) selected from the group consisting of the following general formula (IV) is used, and the following general formula (V) is contained. A-aminoacetophenone photopolymerization initiator (B-2) having a structure, and a mercaptophosphine oxide photopolymerization initiator containing a structure represented by the following general formula (VI) (B- 3) One type or two or more types of photopolymerization initiators are preferred.

In the general formulae (IV) to (VI), R ⁸ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a linear chain having 1 to 20 carbon atoms. a branched or cyclic alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number of 2 to 20 An alkanoyl group or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ⁹ represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), and has a carbon number of 5 to 8. a cycloalkyl group, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and each of R ¹⁰ and R ¹¹ independently represents a carbon number of 1 to 12; a chain, branched or cyclic alkyl or arylalkyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ¹² after binding and R ¹³ may form a cyclic alkyl ether group, R ¹⁴ and R ¹⁵ each independently represent a carbon number of 1 to 10 linear, branched a cyclic alkyl group, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may be substituted by a halogen atom, an alkyl group, or an alkoxy group), or an RC(=O)- group (wherein R is a carbon number) 1 to 20 hydrocarbon groups). However, the case where both of R ¹⁴ and R ¹⁵ are RC(=O)- groups is removed.

The oxime ester photopolymerization initiator (B-1) having the structure represented by the above general formula (IV) is preferably 2-(ethenyloxyimine A) represented by the following formula (VII). Base) thioxanthene-9-one:

The compound of the following general formula (VIII):

(wherein R ¹⁶ represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group or a benzamidine group; And an alkoxycarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl group; The chain may have one or more oxygen atoms in the middle, or a phenoxycarbonyl group, and R ¹⁷ and R ¹⁹ each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and carbon. a linear, branched or cyclic alkyl group of 1 to 20 (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), and a cycloalkane having 5 to 8 carbon atoms. a group having 2 to 20 carbon atoms or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ¹⁸ represents a hydrogen atom or a phenyl group (alkane having 1 to 6 carbon atoms) a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and may have one or more in the middle of the alkyl chain) Oxygen atom), cycloalkyl group having 5 to 8 carbon atoms, carbon number 2 to 20 Acyl or a benzoyl group (which may be a carbon atoms or a phenyl group substituted with an alkyl group having 1 to 6); and a compound of the following general formula (IX) shown in the:

(wherein R ²⁰ , R ²¹ and R ²⁶ each independently represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom. Or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, M represents O, S or NH, and m and n each independently represent an integer of 0 to 5).

Among them, 2-(ethylideneoxyiminemethyl)thioxanthene-9-one represented by the formula (VII) and a compound represented by the formula (VIII) are preferred. CGI-325, IRGACURE OXE01, IRGACURE OXE02, etc. by Ciba Specialty Chemicals Co., Ltd. are mentioned as a commercial item. These oxime ester-based photopolymerization initiators may be used singly or in combination of two or more.

The α-aminoacetophenone photopolymerization initiator containing the structure represented by the general formula (V) includes 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinoacetone-1, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)- 2-[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. As the commercial item, IRGACURE 907, IRGACURE 369, IRGACURE 379, etc. by Ciba Specialty Chemicals Co., Ltd. are mentioned.

Examples of the mercaptophosphine oxide-based photopolymerization initiator containing the structure represented by the general formula (VI) include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis (2). ,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide Things and so on. As a commercial item, LUCILINTPO by BASF Corporation, IRGACURE 819 by Ciba Specialty Chemicals, etc. are mentioned.

The blending ratio of the photopolymerization initiator (B) is preferably from 0.01 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). When the amount is less than 0.01 parts by mass, the photocurability on the copper may be insufficient, the coating film may be peeled off, or the coating properties such as chemical resistance may be lowered. On the other hand, when it exceeds 30 parts by mass, the light absorption of the photopolymerization initiator (B) on the surface of the solder resist coating film becomes intense, and the deep hardenability tends to be lowered, which is not preferable.

Further, in the case of the oxime ester-based photopolymerization initiator containing the structure represented by the above formula (IV), the amount thereof is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the carboxylic acid-containing resin (A). The mass fraction is more preferably 0.01 to 5 parts by mass.

In the composition of the present invention, a photopolymerization initiator other than the above compound, or a photopolymerization initiation aid and a sensitizer may be used, and examples thereof include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthone compound. A ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, and the like.

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

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

Specific examples of the anthrone compound include 2-methylindole, 2-ethylindole, 2-t-butylindole, and 1-chloroindole.

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

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

Specific examples of the benzophenone compound include benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, and 4-benzoic acid. Mercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound include a compound having an ethanolamine compound and a dialkylaminobenzene structure, and examples thereof include 4,4'-dimethylaminobenzophenone (Nisa, manufactured by Nippon Soda Co., Ltd.). Dialkylaminobenzophenone, 7-(diethylamino)-4-methyl, etc., such as MABP), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) -2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) and the like, a dialkylamino group-containing coumarin compound, 4-dimethyl group Ethyl benzoic acid ethyl ester (Kayako EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Biotech Co., Ltd.), 4-dimethylamino benzoic acid ( N-butoxy)ethyl (Quantacure BEA, manufactured by International Biotech Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (Kaija Kia DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethyl Amino benzoic acid 2-ethylhexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

The above is also preferably a thioxanthone compound and a tertiary amine compound. When the thioxanthone compound is contained, it is preferable from the deep hardening level, and also 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, A thioxanthone compound such as 2,4-diisopropylthioxanthone is preferred.

The blending ratio of the thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). When the compounding ratio of the thioxanthone compound is too large, the thick film hardenability is lowered, which is associated with an increase in the cost of the product, which is not preferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure, preferably a dialkylaminobenzophenone compound, and a dialkylamine-containing couma bean having a maximum absorption wavelength of 350 to 410 nm The compound is particularly good. As the dialkylamino benzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. The dicoumarin-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength of an ultraviolet region, so that the coloration is less, and a colorless transparent photosensitive composition can be provided, and a coloring pigment is used, and the reaction is carried out. A colored solder resist film of the color of the coloring pigment itself. Particularly, it is preferred that 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect to laser light having a wavelength of 400 to 410 nm.

The blending ratio of the carboxylic acid-containing photosensitive resin (A) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). When the compounding ratio of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. When the amount is more than 20 parts by mass, the light absorption on the surface of the dry solder resist film by the tertiary amine compound is intense, and the deep hardenability tends to be lowered.

These photopolymerization initiators, photopolymerization start aids, and sensitizers can be used singly or as a mixture of two or more types.

The total amount of the photopolymerization initiator (B), the photopolymerization initiation aid, and the sensitizer is in the range of 35 parts by mass or less based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). good. When it exceeds 35 mass parts, the deep hardenability by these light absorption tends to fall.

Next, a description will be given of a compound (C) having two or more ethylenically unsaturated groups in the molecule.

The compound (C) having two or more ethylenically unsaturated groups in the molecule of the photocurable resin composition of the present invention is photocured by irradiation with an active energy ray to contain the aforementioned ethylenically unsaturated group. The photosensitive resin (A) of a carboxylic acid is insoluble in an alkaline aqueous solution, or it is insoluble. Examples of such a compound include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and ginseng; a polyhydric alcohol such as a hydroxyethyl tripolyisocyanate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and these phenols Polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts; glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether And a polyvalent acrylate such as a glycidyl ether such as triepoxypropyl tripolyisocyanate; and melamine acrylate; and/or each methacrylate corresponding to the above acrylate.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a phenolic epoxy resin for cresol paint, or a hydroxy acrylic acid such as pentaerythritol triacrylate further having a hydroxyl group of the epoxy acrylate resin may be used. An epoxy urethane acrylate compound in which an ester is reacted with a semi-urethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can not only improve the dryness of the touch but also improve the photocurability.

The compounding ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is preferably from 1 to 100 parts by mass, more preferably from 100 to 100 parts by mass, per 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). The ratio of 5 to 70 parts by mass. When the blending ratio is less than 1 part by mass, the photocurability is lowered, and the pattern formation of the alkaline development after the active energy ray irradiation is difficult to proceed. On the other hand, when it exceeds 100 parts by mass, the solubility in an aqueous alkaline solution is lowered, and the coating film tends to be weak, which is not preferable.

Next, the thermosetting component (D) will be described.

In the photocurable resin composition of the present invention, a thermosetting component (D) may be added to impart heat resistance. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in the molecule.

Examples of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule include a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a ring. Examples of the compound having one or two types of the thioether group include a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1) having at least two molecules in the molecule. The above oxetanyl compound, that is, a polyfunctional oxetane compound (D-2) or a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (D-3) Wait.

Examples of the polyfunctional epoxy compound (D-1) include Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, and Edolon 2055 manufactured by Dainippon Ink and Chemicals. Epotohto YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by The Dow Chemical Co., Ltd., Araldite 6071, Araldite 6084, Araldite GY250, Araldite GY260 from Ciba Specialty Chemicals Shumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, Inc., AER330, AER331, AER661, AER664, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. (all are trade names) Bisphenol A type epoxy resin; Epikote YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by Dainippon Ink and Chemicals Co., Ltd., Epotohto YDB-400 manufactured by Tosho Kasei Co., Ltd., YDB-500, DER542 manufactured by The Dow Chemical Co., Ltd. , Araldite 8011 manufactured by Ciba Specialty Chemicals, Shumi-epoxy ESB-400 manufactured by Sumitomo Chemical Industries, ESB-700, Asahi Kasei Brominated epoxy resin of AER711, AER714, etc. (both trade names) manufactured by Industrial Co., Ltd.; Epikote 152, Epikote 154, manufactured by Nippon Epoxy Co., Ltd., DEN431, DEN438, manufactured by The Dow Chemical Co., Ltd., Dainippon Ink Chemistry Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by Industrial Co., Ltd., Epotohto YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., Araldite ECN1235 manufactured by Ciba Specialty Chemicals Co., Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN manufactured by Nippon Kayaku Co., Ltd. -201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Shumi-epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, Ltd., AERECN-235, ECN-299, manufactured by Asahi Kasei Kogyo Co., Ltd. A phenolic epoxy resin for paints (both trade names); Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epikote 807 manufactured by Japan Epoxy Resin Co., Ltd., Epotohto YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd. , bisphenol F type epoxy resin of Araldite XPY306 (all trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.; Epotohto ST-2004, ST-2007, ST-3000 manufactured by Dongdu Chemical Co., Ltd. Product name), such as hydrogenated bisphenol A type epoxy resin; Epikote 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotohto YH-434 manufactured by Tohto Kasei Co., Ltd., Araldite MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Shumi-Epoxy ELM manufactured by Sumitomo Chemical Industries, Ltd. Epoxypropylamine type epoxy resin such as 120 (all trade name); hydantoin type epoxy resin such as Araldite CY-350 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.; CELLOXIDE 2021 manufactured by Daicel Chemical Industry Co., Ltd., Ciba Specialty Chemicals Company's alicyclic epoxy resin such as AralditeCY175, CY179, etc. (all are trade names); YL-933 made by Japan Epoxy Co., Ltd., TEN, EPPN-501, EPPN-502, etc. by The Dow Chemical Co., Ltd. A trishydroxyphenylmethane type epoxy resin of the trade name); a bisphenol type or a bisphenol type ring such as YL-6056, YX-4000, and YL-6121 (all trade names) manufactured by Nippon Epoxy Co., Ltd. Oxygen resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., and bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Japan E made by epoxy resin company A phenolic epoxy resin for bisphenol A paint such as pikote 157S (trade name); a tetraphenol ethane epoxy resin such as Epikote YL-931 manufactured by Nippon Epoxy Co., Ltd., Araldite 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (all trade names) Resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names), heterocyclic epoxy resin, and bismuth propyl phthalate such as BLEMMER DGT manufactured by Nippon Oil & Fats Co., Ltd. Resin; tetradecyl propyl xylene decyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA- manufactured by Dainippon Ink Chemical Industry Co., Ltd. 4750, EXA-4700 and other naphthalene groups contain epoxy resin; Epoxy resin with dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink Chemical Industry Co., Ltd.; CP-50S and CP- manufactured by Nippon Oil Co., Ltd. 50M and other epoxy propyl methacrylate copolymerized epoxy resin; and copolymerized epoxy resin of cyclohexyl maleic anhydride and propylene methacrylate; epoxidized polybutadiene Rubber derivatives (eg PB-360 by Daicel Chemical Industry) 0, etc., CTBN-modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.) and the like are not limited thereto. These epoxy resins may be used singly or in combination of two or more. Among them, phenolic epoxy resin, heterocyclic epoxy resin, bisphenol A epoxy resin or a mixture thereof is particularly preferred.

The polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3). -oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl) 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methyl Acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or these oligomers or Examples of the polyfunctional oxetane such as a copolymer include oxetane, phenol resin for lacquer, poly(p-hydroxystyrene), cardo type bisphenol, and calixarene. An etherified product of a resin having a hydroxyl group such as resorcinol calixarene or sesquioxanes. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the episulfide compound (D-3) include bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide resin or the like in which the oxygen atom of the epoxy group of the phenolic epoxy resin is replaced by a sulfur atom can be used by the same synthesis method.

The compounding ratio of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably 0.6 to 1 equivalent of the carboxyl group of the carboxylic acid-containing photosensitive resin (A). 2.5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the compounding ratio of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film, and heat resistance and alkali resistance are obtained at this time. Electrical insulation, etc. will decline. On the other hand, when it exceeds 2.5 equivalents, the low molecular weight cyclic (thio)ether gene remains in the dried coating film, and the strength of the coating film or the like is lowered, which is not preferable.

When the thermosetting component (D) is used as the photocurable resin composition of the present invention, it is preferred to use a thermosetting catalyst in combination. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1- Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-di An amine compound such as methylbenzylamine, a bisamine compound such as diammonium adipate or diammonium azelate; a phosphorus compound such as triphenylphosphine, or the like, and, as a person to be trafficked, for example, four countries can be formed. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Industrial Co., Ltd., U-CAT3503N and U-CAT3502T (all are dimethylamine blocks) manufactured by SAN-APRO Co., Ltd. The trade name of the isocyanate compound), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic hydrazine compounds and salts thereof). However, unless otherwise specified, only the thermosetting catalyst of the epoxy resin or the oxetane compound or the reaction of the epoxy group and/or the oxetanyl group with the carboxyl group may be promoted, and may be used alone or in combination. Use after the above. Further, guanamine, methyl decylamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene-2 can be used. 4-Diamino-S-triazine, 2-ethylene-4,6-diamino-S-triazine ‧ trimeric isocyanate adduct, 2,4-diamino-6-methyl propylene An S-triazine derivative such as a mercaptooxyethyl-S-triazine/trimeric isocyanate adduct, preferably a compound having a function as an adhesion imparting agent and the above-mentioned thermosetting catalyst Use.

The blending ratio of the thermosetting catalyst is sufficient, and is preferably 0.1 to 20 parts by mass, for example, 100 parts by mass of the carboxylic acid-containing photosensitive resin (A) or the thermosetting component (D). More preferably, it is 0.5 to 15.0 parts by mass.

Next, the coloring agent (E) used in the photocurable resin composition of the present invention will be described.

A coloring agent can be added to the photocurable resin composition of the present invention. As the coloring agent, a conventionally known coloring agent such as red, blue, green, yellow or black, a pigment, a dye, or a dye may be used. However, it is preferable to use a halogen-free and azo-containing compound from the viewpoint of environmental load reduction and influence on the human body.

Blue colorant:

The blue coloring agent may be a phthalocyanine-based or an anthraquinone-based pigment, and the pigment is classified into a pigment (Pigment), and specific examples thereof include the following color index (CI; The Society of Dyers and Colourists) number: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 and more. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

Green colorant:

As the green coloring agent, a phthalocyanine system or a guanidine system is similarly used, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, or the like can be used. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

Yellow colorant:

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

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

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

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

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

Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

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

Red colorant:

Examples of the red coloring agent include monoazo type, diazo type, azo precipitating color, benzimidazolone type, perylene type, dioxopyrrolopyrrole type, condensed azo type, lanthanide type, and quinine. Specific examples of the acridone or the like include the following.

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.

Bismuth: Pigment Red 37, 38, 41.

Single azo precipitation system: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53: 2. 57:1, 58:4, 63:1, 63:2, 64:1, 68.

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

Perylene: 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.

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

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

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

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

Other coloring agents such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.

Specific examples include 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 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 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 7, and the like.

The specific blending ratio of the colorant is affected by the type of the coloring agent to be used or other additives, and therefore it is not possible to describe the quality of the carboxylic acid-containing photosensitive resin (A) 100 of the photosensitive resin composition of the present invention. In terms of parts, it is preferred to add 0 parts by mass to 5 parts by mass. More preferably, when it is used in an amount of from 0.05 part by mass to 3 parts by mass, the particularly preferred colorant is blue and green in the form of phthalocyanine, lanthanide, yellow in the lanthanide, red in the dioxopyrrolopyrrole, ruthenium. And has no halogen atoms. Further, the pigments are blue and green. From the viewpoint of heat resistance, the blue, green, and red colorants of the dye system are preferably from the viewpoint of sensitivity and resolution.

Since the photocurable resin composition of the present invention can improve the physical strength and the like of the coating film, a filler can be added as necessary. As such a filler, a conventionally known inorganic or organic filler can be used, and in particular, barium sulfate, spherical cerium oxide, and talc are preferably used. And a compound having one or more ethylenically unsaturated groups or NANOCRYL (trade name) XP 0396, XP 0596, XP manufactured by Hanse-Chemie Co., Ltd. in which the above-mentioned polyfunctional epoxy resin (D-1) is dispersed. 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all products grade name), or NANOPOX (trade name) XP 0516, XP 0525, XP 0314 manufactured by Hanse-Chemie Co., Ltd. (all are Product grade name) and so on. These can be used individually or in combination of 2 or more types.

The blending ratio of the filler is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). When the compounding ratio of the filler exceeds 300 parts by mass, the viscosity of the photosensitive composition becomes high, so that the printability is lowered, or the cured product is weak, which is not preferable.

Further, the photocurable resin composition of the present invention may be prepared by synthesizing or synthesizing the carboxylic acid-containing photosensitive resin (A) or applying viscosity to a substrate or a carrier film. Solvent.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 2-methoxyethanol, methyl 2-methoxyethanol, and butyl group; a glycol ether such as 2-methoxyethanol, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether or triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol, ethylene glycol, propylene glycol, etc. Alcohols; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent oil. The organic solvent may be used singly or as a mixture of two or more.

In the photocurable resin composition of the present invention, a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol or thiodiphenylamine may be added as necessary. , known as tackifiers such as fine powdered cerium oxide, organic bentonite, and microcrystalline kaolinite, antifoaming agents such as polyfluorene, fluorine, and polymer, and/or coating agents, imidazole, thiazole, A well-known conventional additive such as a triazole-based decane coupling agent, an oxidation inhibitor, and an anti-caries agent.

The photocurable resin composition of the present invention is adjusted, for example, to the viscosity of the coating method by the organic solvent, and is applied to the substrate by an impregnation coating method, a flow coating method, a roll coating method, or a bar coating method. After coating by a method, a curtain printing method, a curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 60 to 100 ° C to form a non-sticky (tack) Free) on the film. Alternatively, the composition of the present invention is applied onto a carrier film, dried to form a dry film, and after being wound up, it is applied to a substrate to form a resin insulating layer.

The coating film obtained as described above or the resin layer on the carrier film (also referred to as "resin layer" at the same time as the "coating film") is exposed by irradiation with an active energy ray to expose the exposed portion (by the active energy ray) Part of the illumination) hardens.

Specifically, by contact (or non-contact method), by forming a pattern of the mask, exposure by selective active energy lines, or direct exposure of the active energy line using a laser direct exposure machine, etc. The unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% aqueous soda carbonate solution) to form a photoresist pattern. Further, for example, after heating and heat-hardening at a temperature of about 140 to 180 ° C, the carboxyl group of the carboxylic acid-containing resin (A) and the molecule have two or more cyclic ether groups and/or cyclic sulfur. The thermosetting component of the ether group is reacted, and can be formed into a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.

Examples of the substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, and fluorine/polyethylene. ‧PPO ‧Cyanate esters, etc., copper-plated laminates of all grades (FR-4, etc.) made of copper-clad laminates for high-frequency circuits, other polyimide films, PET films, glass substrates, and ceramic substrates , wafer board, etc.

As the volatilization drying to be carried out after applying the photocurable resin composition of the present invention, a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, or the like can be used (using a heat source having a method of heating by air of steam) The hot air in the dryer is subjected to a flow contact method and a method in which the nozzle is blown toward the support.

As the exposure machine used for the active energy ray irradiation, an ultraviolet ray irradiation device and a direct drawing device (a direct image device for drawing an image by direct activation of active energy rays from CAD data of a computer) can be used. As the active energy ray, only laser light having a maximum wavelength of 350 to 410 nm or a light source that emits light by discharge of mercury vapor, for example, a short arc lamp or a (ultra) high pressure mercury lamp, may be used, and the type of laser may be used. It is either a gas laser or a solid laser. Further, the amount of exposure varies depending on the film thickness or the like, but is generally 5 to 200 mJ/cm ² , preferably 5 to 100 mJ/cm ² , and more preferably 5 to 50 mJ/cm ² . As the direct drawing device, for example, a laser manufactured by Hitachi via mechnics, manufactured by Fujifilm Co., Ltd., manufactured by Dainippon Screen, or ORC, can be used to vibrate or lend laser light having a maximum wavelength of 350 to 410 nm. A light source that emits light by discharge of mercury vapor can be used, for example, only as a device using a short arc lamp or an (ultra) high pressure mercury lamp.

As the developing method, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, and citric acid can be used as the developing solution by an impregnation method, a shower method, a spray method, a combing method, or the like. An alkaline aqueous solution such as sodium, ammonia or amine.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

<Synthesis of a carboxylic acid-containing photosensitive resin> Resin Synthesis Example 1

Synthesis example of carboxylic acid-containing photosensitive resin (varnish (A-1-1)) having a structure of 4-hydroxybutyl acrylate glycidyl ether

In a 2 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 197 g of diethylene glycol monoethyl ether acetate was charged with a phenolic epoxy resin for o-cresol paint "EPICLON N- 695" 214 g (having a number of epoxy groups (total number of aromatic rings): 1.0 mol), 72 g of acrylic acid (1.0 mol), and 0.29 g of hydroquinone were stirred at 100 ° C to obtain a homogeneous solution. Next, 0.86 g of triphenylphosphine was charged, and after heating at 110 ° C for 2 hours, 0.23 g of triphenylphosphine was further added thereto, and the mixture was heated to 120 ° C and then reacted for 12 hours. The obtained reaction liquid was charged with 197 g of sorbes 150 and 144 g (0.95 mol) of tetrahydrophthalic anhydride, and the reaction was carried out at 110 ° C for 4 hours. 40.05 g (0.2 mol) of 4-hydroxybutyl acrylate epoxypropyl ether and 45.9 g of propylene glycol methyl ether acetate were added to the obtained reaction liquid, and the mixture was stirred and heated to 110 ° C, and kept at 110 ° C to continue. 6 hours reaction. After cooling the reaction product to room temperature, a viscosity-adjusting solution was obtained. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 52% by mass and a solid content acid value of 90 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing photosensitive resin is referred to as varnish (A-1-1).

Resin Synthesis Example 2

In a 3 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 215 g of carbitol acetate, phenolic epoxy resin "N-680" 428 g of cresol paint, acrylic acid 72 g, 154 parts by mass of methacrylic anhydride and 0.58 g of hydroquinone were heated to 100 ° C with stirring to obtain a homogeneous solution. Next, 1.72 g of triphenylphosphine was charged, and after heating at 110 ° C for 2 hours, 0.46 g of triphenylphosphine was further added, and the mixture was heated to 120 ° C, and further reacted for 12 hours. To the obtained reaction liquid, 215 g of sorbes 150 and 152 g of tetrahydrophthalic anhydride were charged, and the reaction was carried out at 110 ° C for 4 hours. Further, 28.4 g of glycidyl methacrylate was added to the obtained reaction solution, and the mixture was stirred and heated to 110 ° C, and the reaction was continued at 110 ° C for 6 hours. After cooling the reaction product to room temperature, a viscosity-adjusting solution was obtained. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 54 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing photosensitive resin is referred to as varnish (A-2-1).

Resin Synthesis Example 3

In a 3 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 233 g of carbitol acetate and 428 g of a phenolic epoxy resin "N-680" for cresol paint were placed. 115 g of acrylic acid, 61.6 parts by mass of methacrylic anhydride and 0.58 g of hydroquinone were heated to 100 ° C with stirring to obtain a homogeneous solution. Next, 1.72 g of triphenylphosphine was charged, and after heating to 110 ° C for 2 hours, 0.46 g of triphenylphosphine was further added, and the mixture was heated to 120 ° C and then reacted for 12 hours. To the obtained reaction liquid, 233 g of sorbes 150 and 243 g of tetrahydrophthalic anhydride were placed, and the reaction was carried out at 110 ° C for 4 hours. Further, 56.8 g of glycidyl methacrylate was added to the obtained reaction solution, and the mixture was further stirred and heated to 110 ° C, and the reaction was continued at 110 ° C for 6 hours. After cooling the reaction product to room temperature, a viscosity-adjusting solution was obtained. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 74 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing photosensitive resin is referred to as varnish (A-2-2).

Resin Synthesis Example 4

In a 3 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 238 g of carbitol acetate and 428 g of a phenolic epoxy resin "N-680" for cresol paint were placed. 115 g of acrylic acid, 61.6 parts by mass of methacrylic acid, and 0.58 g of hydroquinone were heated and stirred at 100 ° C to be uniformly dissolved. Next, 1.72 g of triphenylphosphine was charged, and the mixture was heated to 110 ° C, and after reacting for 2 hours, 0.46 g of triphenylphosphine was further added thereto, and the mixture was heated to 120 ° C and then reacted for 12 hours. To the obtained reaction liquid, 238 g of sorbes 150 and 243 g of tetrahydrophthalic anhydride were placed, and the reaction was carried out at 110 ° C for 4 hours. Further, 80 g of 4-hydroxybutyl acrylate epoxypropyl ether was added to the obtained reaction solution, and the mixture was further stirred and heated to 110 ° C, and the reaction was continued at 110 ° C for 6 hours. After cooling the reaction product to room temperature, a viscosity-adjusting solution was obtained. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 73 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing resin is referred to as varnish (A-2-3).

Comparative Synthesis Example 1 (varnish (R-1))

700g of diethylene glycol monoethyl ether acetate was charged with phenolic epoxy resin for o-cresol paint [made by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average The functional group number 7.6] 1070 g (the number of epoxy groups (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were heated to 100 ° C with stirring to obtain a homogeneous solution. Next, 4.3 g of triphenylphosphine was charged, and after heating to 110 ° C, the reaction was carried out for 2 hours, and then 1.6 g of triphenylphosphine was added thereto, and the mixture was heated to 120 ° C for further 12 hours. 562 g of aromatic hydrocarbon (sorbeso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were placed in the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was placed in the obtained reaction mixture, and the mixture was reacted at 115 ° C for 4 hours to obtain a resin solution having a solid content of 87 mg KOH/g and a solid content of 65%. This was used as a varnish (R-1).

Comparative Synthesis Example 2 (varnish (R-2))

685 g of diethylene glycol monoethyl ether acetate was charged with phenolic epoxy resin for o-cresol paint [made by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average The functional group number 7.6] 1070 g (the number of epoxy groups (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were heated to 100 ° C with stirring to obtain a homogeneous solution. Next, 4.3 g of triphenylphosphine was charged, and after heating to 110 ° C for 2 hours, 1.6 g of triphenylphosphine was further added thereto, and the mixture was heated to 120 ° C and then reacted for 12 hours. 530 g of aromatic hydrocarbon (sorbeso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were placed in the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours. Further, 71.0 g (0.5 mol) of glycidyl methacrylate was added to the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours to obtain a resin solution having a solid content of 103 mg KOH/g and a solid content of 65%. This was used as a varnish (R-2).

Comparative Synthesis Example 3 (varnish (R-3))

Introduced a phenolic epoxy resin for cresol paint (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92) in a 2 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube. °C, epoxy equivalent 220) 660g, carbitol acetate 421.3g, and solvent oil 180.6g, heated at 90 ° C, stirred, dissolved. Next, after cooling to 60 ° C, 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added, and the reaction was carried out at 100 ° C for 12 hours to obtain a reaction product having an acid value of 0.2 mgKOH/g. Here, 241.7 g of tetrahydrophthalic anhydride was charged and heated to 90 ° C for 6 hours. Thereby, a solution of a carboxylic acid-containing resin (A) having an acid value of 50 mgKOH/g, a double bond equivalent (g mass per 1 mole of resin of the unsaturated group), and a weight average molecular weight of 7,000 was obtained. Hereinafter, the solution of the carboxylic acid-containing resin is referred to as varnish (R-3).

Comparative Synthesis Example 4 (varnish (R-4))

2 liters of separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 94 parts by mass of carbitol acetate, and a phenolic epoxy resin for cresol paint (Daily Ink Chemical Industry) (Stock), N-680, epoxy equivalent = 214 g / equivalent) 214 parts by mass, heated to 90 ° C with stirring and dissolved. 0.05 parts by mass of hydroquinone and 1.0 part by mass of triphenylphosphine were added to the resin solution. The mixture was heated to 85 to 95 ° C, and 72 parts by mass of acrylic acid was gradually added dropwise thereto, and the reaction was carried out for 24 hours to obtain a reaction product having an acid value of 0.2 mgKOH/g. Here, 76 g of tetrahydrophthalic anhydride was charged, and the mixture was heated to 85 ° C to carry out a reaction for 8 hours. To the solution, ipusol #150 94g manufactured by Idemitsu Petrochemical Co., Ltd. was added and stirred well. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 73 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing photosensitive resin is referred to as varnish (R-4).

Comparative Synthesis Example 5 (varnish (R-5))

In a 2 liter separation flask equipped with a stirrer, a thermometer, a circulation cooling tube, a titration funnel, and a nitrogen introduction tube, 225 g of diethylene glycol monoethyl ether acetate was charged with a phenolic epoxy resin for o-cresol paint [Great Japan Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6] 428 g, 144 g of acrylic acid, and hydroquinone 0.6 g, heated to 100 ° C with stirring to obtain a homogeneous solution . Next, 1.72 g of triphenylphosphine was charged, and after heating to 110 ° C for 2 hours, 0.64 g of triphenylphosphine was further added thereto, and the mixture was heated to 120 ° C and then reacted for 12 hours. 225 g of aromatic hydrocarbon (sorbeso 150) and 243 g of tetrahydrophthalic anhydride were placed in the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours. Further, 56.8 g of a glycidyl methacrylate was charged into the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours. Thus, a solution of a carboxylic acid-containing resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 77 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing resin is referred to as varnish (R-5).

Comparative Synthesis Example 6 (varnish (R-6))

In a 3 liter separation flask equipped with a stirrer, a thermometer, a reflux cooling tube, a titration funnel, and a nitrogen introduction tube, 215 g of carbitol acetate and 428 g of a phenolic epoxy resin "N-680" for cresol paint were placed. 72 g of acrylic acid, 154 g of methacrylic anhydride, and 0.58 g of hydroquinone were heated to 100 ° C with stirring to obtain a homogeneous solution. Next, 1.72 g of triphenylphosphine was charged, and the mixture was heated to 110 ° C, and after reacting for 2 hours, 0.46 g of triphenylphosphine was further added thereto, and the mixture was heated to 120 ° C and then reacted for 12 hours. To the obtained reaction liquid, 215 g of sorbes 150 and 152 g of tetrahydrophthalic anhydride were placed, and the reaction was carried out at 110 ° C for 4 hours, followed by cooling to obtain a viscous liquid. Thus, a solution of a carboxylic acid-containing photosensitive resin (A) having a nonvolatile content of 66% by mass and a solid content acid value of 70 mgKOH/g was obtained. Hereinafter, the solution of the carboxylic acid-containing photosensitive resin is referred to as varnish (R-6).

<Example 1>

The various components shown in Table 1 were added to each ratio (parts by mass) in the resin solution of the above-mentioned synthesis example, and the mixture was preliminarily mixed by a stirrer, and then kneaded by three grinders to prepare a photocurable resin composition. The degree of dispersion of the obtained photocurable resin composition was measured by a particle size analyzer manufactured by Erichsen Co., Ltd., and it was 15 μm or less after evaluation.

Performance evaluation <Optimum exposure amount>

Each of the prepared photocurable resin compositions was polished on a 35 μm copper circuit pattern substrate, washed with a buffer roller (BUFF Roller), washed with water, dried, and then subjected to curtain printing. The coating was dried under a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, a direct drawing device for semiconductor lasers with a maximum wavelength of 355 nm (Paragon 8000 manufactured by Orbotech Co., Ltd.) and a direct drawing exposure machine for carrying high-pressure mercury lamps (ultra-high pressure mercury lamps equipped with direct exposure machine Marcusx manufactured by Nippon Curtain Co., Ltd.) or high An exposure apparatus for holding a mercury lamp (a mercury short-arc lamp equipped with an exposure machine manufactured by ORC) was exposed to a step tablet (Kodak No. 2) for 60 seconds (30 ° C, 0.2 MPa, 1 mass% sodium carbonate aqueous solution) When the pattern of the step tablet remaining in the time is 7 segments, it is the optimum exposure amount.

<Maximum development screen>

Each of the photocurable resin compositions described above was entirely coated by curtain printing on a copper foil substrate having a pattern, and dried at 80 °C. The substrate was taken out every 10 minutes between 20 minutes and 80 minutes after the start of drying and cooled at room temperature. On the substrate, 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, and the maximum allowable drying time of the residual residue was taken as the maximum development screen.

<finger dryness>

Each of the above-mentioned photocurable resin compositions was applied by curtain printing on a copper foil substrate having a pattern, dried at 80 ° C for 20 minutes, and cooled to room temperature. On the substrate, a negative film made of PET was pressed under a reduced pressure condition for one minute by ORC Co., Ltd. (HMW 680-GW20), and thereafter, a state in which the film was peeled off when the negative film was peeled off was evaluated.

○: The film was peeled off without resistance.

△: Although the film was peeled off, there was a slight trace on the film.

×: When the film was peeled off, it was resistant, and there was a clear trace on the film.

Characteristic test: (Production of coating film evaluation substrate)

Each of the photocurable resin compositions described above was applied to a copper foil substrate having a pattern formed by curtain printing, dried at 80 ° C for 20 minutes, and cooled to room temperature. A direct drawing device for holding a semiconductor laser having a maximum wavelength of 355 nm on the substrate, and exposing the solder resist pattern to an optimum exposure amount, and applying a spray pressure of 2 kg/cm ² to a 1% Na ₂ CO ₃ aqueous solution at 30 ° C A 60-second imaging was performed to obtain a photoresist pattern. The substrate was subjected to ultraviolet irradiation under the conditions of an accumulated exposure amount of 1000 mJ/cm ² in a UV belt conveyor, and then heated at 150 ° C for 60 minutes to be hardened. The following characteristics were evaluated for the obtained printed substrate (evaluation substrate).

<hue>

The color of the cured product after heat curing of each of the photocurable resin compositions was visually judged.

<Soft solder heat resistance>

The evaluation substrate coated with the rosin-based co-solvent was preliminarily impregnated into a soldering groove set at 260 ° C to dilute the alcohol-based cleaning solvent, and the expansion and flaking of the photoresist layer were visually evaluated. The judgment criteria are as follows.

○: No peeling was observed even if the immersion was repeated three or more times for 10 seconds.

△: When the immersion was repeated three times or more for 10 seconds, it was slightly peeled off.

X: When immersed for 10 seconds within 3 times, expansion and peeling of the photoresist layer were observed.

<electroless gold plating resistance>

Electroplating using an electroless nickel plating bath and an electroless gold plating bath of a commercial product under conditions of nickel 0.5 μm and gold 0.03 μm, and visually evaluating the presence or absence of peeling of the resist layer or the presence or absence of plating penetration. The peeling of the photoresist layer was evaluated by tape peeling. The judgment criteria are as follows.

○: Infiltration was slightly observed after plating, and there was no peeling after peeling off the tape.

△: Only the infiltration phenomenon was observed after plating, and peeling occurred after peeling off the tape.

×: Peeling after plating.

<Electrical Absolute>

Instead of the copper foil substrate, an evaluation electrode substrate was fabricated under the above conditions using a comb-type electrode Bcoupon of IPC B-25, and a bias voltage of DC 100 V was applied to the comb-shaped electrode, and a constant temperature and humidity chamber of 85 ° C and 85% RH was confirmed in 1,000. There is no migration after time. The judgment criteria are as follows.

○: No change at all

△: only slightly changed

×: Migration phenomenon

<Alkaline resistance>

The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution at room temperature for 30 minutes, and the film was infiltrated or eluted by visual observation, and peeling was confirmed by tape peeling.

○: No penetration or dissolution occurred, and no peeling was observed after peeling off the tape.

△: No infiltration or dissolution, but peeling was only slightly observed after peeling off the tape.

×: Peeling after infiltration or stripping.

<PCT tolerance>

The evaluation substrate was subjected to a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.), and subjected to treatment at 121 ° C, saturated, and 0.2 Mpa for 50 hours. The state of the coating film was visually confirmed, and the tape was peeled off. Confirm stripping. The judgment criteria are as follows.

○: No penetration or dissolution occurred, and no peeling was observed after peeling off the tape.

△: No infiltration or dissolution, and peeling was only slightly observed after peeling off the tape.

×: Peeling after infiltration or stripping.

<PCBT tolerance>

In place of the copper foil substrate, an evaluation substrate was produced under the above conditions using a comb electrode Bcoupon of IPC B-25, and a bias voltage of DC 30 V was applied to the comb electrode, and a PCT device (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.) was used. The treatment was carried out for 96 hours under the conditions of 121 ° C and a humidity of 97% to evaluate the presence or absence of discoloration and migration. The judgment criteria are as follows.

○*: No discoloration or migration occurred.

○: Only a slight discoloration or migration occurred.

△: Discoloration and migration occurred.

×: The color change is remarkable, and the migration from one electrode to the other electrode is performed.

The results are shown in Table 2.

<Example 2>

The composition examples 1 and 8 used in Example 1 were diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C for 30 minutes. Thereafter, the dry film was thermally laminated, and the obtained sample was subjected to the same evaluation, and the results are shown in Table 5.

<Dry film evaluation>

The composition examples 2 and 8 used in Example 1 were diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. . A dry film is obtained after the cover film is attached thereto. Thereafter, the cover film was peeled off, and the film was subjected to thermal lamination on the copper foil substrate on which the pattern was formed, and then exposed under the same conditions as those of the substrate evaluated for the coating film characteristics of Example 1. After the peeling exposure, the carrier film was heat-hardened by a hot air dryer at 150 ° C for 60 minutes to prepare a test substrate. For the test substrate having the obtained hardened film, an evaluation test of each characteristic was carried out in the above test method and evaluation method. The results are shown in Table 3.

As a result of the results shown in Tables 3 to 5 of Examples 1 and 2, the photocurable resin composition comprising the carboxylic acid-containing photosensitive resin (A) of the present invention is compared with the conventional resin. High sensitivity and development, dryness to touch, soft solder heat resistance, electroless gold plating resistance, alkali resistance, PCT resistance, and PCBT resistance are also excellent, and can be used as a photoresist ink. Further, the photocurable resin composition of the present invention is highly sensitive to monochromatic light or laser light such as i-line or h-line or to an ultraviolet light source such as a high-pressure mercury lamp.

Claims (12)

An alkali-developable photocurable resin composition comprising (A-2) a carboxylic acid-containing photosensitive resin containing a structure represented by the general formula (II) and a structure represented by the general formula (III), (B) a photopolymerization initiator, and (C) a compound containing two or more ethylenically unsaturated groups in one molecule, In the general formulae (II) and (III), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, R ⁷ represents an acid anhydride residue, and n represents 0 or 1. The photocurable resin composition capable of alkaline development according to the first aspect of the invention, wherein the (A-2) carboxylic acid-containing photosensitive resin contains two or more rings in (a) one molecule. The compound of the ether group is reacted with (b) an unsaturated monocarboxylic acid and (c) an unsaturated monocarboxylic acid anhydride, and then the (e) molecule is contained in the resin which reacts the (d) polybasic acid anhydride. A carboxylic acid-containing photosensitive resin obtained by reacting a cyclic ether group with a compound of an ethylenically unsaturated group. The photocurable resin composition capable of alkaline development according to the first aspect of the patent application, wherein the (e) molecule contains a cyclic ether group and an ethyl group is not The compound of the saturated group is 4-hydroxybutyl acrylate glycidyl ether. An alkali-developable photocurable resin composition according to claim 2, wherein the compound having a cyclic ether group and an ethylenically unsaturated group in the (e) molecule is 4-hydroxybutyl acrylate Epoxypropyl ether or glycidyl methacrylate. The photocurable resin composition capable of alkaline development according to the first aspect of the invention, wherein the (B) photopolymerization initiator is one or more selected from the group consisting of the following general formula (IV); The oxime ester photopolymerization initiator of the structure, the aminoacetophenone photopolymerization initiator containing the structure represented by the following general formula (V), and the oxime having the structure represented by the following general formula (VI) a mixture of phosphine oxide photopolymerization initiators, In the general formulae (IV) to (VI), R ⁸ represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a linear chain having 1 to 20 carbon atoms. a branched or cyclic alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl group having 2 to 20 carbon atoms. Mercapto or benzhydryl (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), R ⁹ represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and carbon a linear, branched or cyclic alkyl group of 1 to 20 (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), and a cycloalkane having 5 to 8 carbon atoms. a base having 2 to 20 carbon atoms or a benzhydryl group (substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R ¹⁰ and R ¹¹ each independently represent a linear chain having 1 to 12 carbon atoms. a branched or cyclic alkyl or arylalkyl group, each of R ¹² and R ¹³ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ¹² and R after binding ¹³ may form a cyclic alkyl ether group, R ¹⁴ and R ¹⁵ each independently represent a carbon number of 1 to 10 linear, branched or cyclic An alkyl group, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may be substituted by a halogen atom, an alkyl group, or an alkoxy group), or an RC(=O)- group (wherein R represents a carbon number of 1 to 20) Hydrocarbyl group, except that both of R ¹⁴ and R ¹⁵ are RC(=O)- groups. The photocurable resin composition which can be alkaline-developed as in the first aspect of the patent application, further comprising (D) a thermosetting component. The photocurable resin composition which can be alkaline-developed as in the first aspect of the patent application, which is a solder resist further containing (E) a colorant. A photocurable dry film obtained by coating and drying a photocurable resin composition of the first aspect of the patent application on a carrier film. A cured image pattern formed by using a resin layer formed from the photocurable resin composition of claim 1 of the patent application, characterized in that the pattern formation is performed by an active energy ray Subject to irradiation. A cured product pattern characterized in that the pattern formation by irradiation with an active energy ray according to claim 9 of the patent application is directly depicted using an active energy ray having a wavelength of 350 nm to 410 nm. A printed circuit board characterized by having a hardened pattern of the ninth aspect of the patent application on the copper layer. A printed circuit board characterized by having a hardened pattern of the tenth item of the patent application on the copper layer.