JP2003177528A - Photosensitive resin composition and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for use as a solder resist, which is free from anti-tackiness and excellent in heat resistance, flexibility and adhesiveness without other film properties being sacrificed, and can be designed so as to obtain properties in conformity with the end use thereof, and to provide a printed wiring board using the composition. <P>SOLUTION: In the photosensitive resin composition comprising (A) an active energy ray-curable resin having at least two ethylenically unsaturated linkages per molecule, (B) a photopolymerization initiator, (C) a diluent and (D) a thermosetting compound; wherein the (A) comprises a resin which is obtained by a process wherein an epoxy compound is successively reacted with an unsaturated monocarboxylic acid and with a polybasic acid to form a compound, which is then allowed to react with an epoxy resin to obtain the resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of forming an image by exposure to ultraviolet rays and development with a dilute aqueous alkaline solution, has excellent tackiness (dryness to the touch), and is flexible, adhesive, heat resistant and the like. The present invention relates to a photosensitive resin composition which is excellent in film performance and can maintain other coating film performance at a good level, and is suitable as, for example, a solder resist for printed wiring boards, and a printed wiring board using the same.

[0002]

2. Description of the Related Art A printed wiring board is used to mount a conductor circuit pattern on a board by soldering electronic parts to the soldering land of the pattern. The removed circuit portion is covered with a solder resist film as a permanent protective film.
This prevents the solder from adhering to unnecessary parts when soldering electronic components to the printed wiring board, and also prevents the circuit conductor from being directly exposed to air and corroded by oxidation or humidity. . Conventionally, the solder resist film has been mainly formed by pattern-forming the solution composition on a substrate by a screen printing method, drying by removing a solvent, and then curing by ultraviolet rays or heat.

However, recently, as the wiring density of a printed wiring board is required to be improved (densified), a solder resist composition (also referred to as a solder resist ink composition) is also required to have high resolution and high accuracy, and it is required for consumer use. A liquid photo solder resist method (photo-developing method), which is excellent in positional accuracy and coverage of conductor edges, has been proposed from screen printing methods regardless of whether the substrate is an industrial substrate or an industrial substrate. For example, in JP-A-50-144431 and JP-A-51-40451,
A solder resist composition comprising a bisphenol type epoxy acrylate, a sensitizer, an epoxy compound, an epoxy curing agent, etc. is disclosed. These solder resist compositions, a liquid composition which is a photosensitive resin composition is applied over the entire surface of a printed wiring board, after volatilizing the solvent, exposed to remove the unexposed portion using an organic solvent, It is to develop. However, the removal (development) of the unexposed portion with this organic solvent uses a large amount of the organic solvent, so that not only is there a risk of environmental pollution, fire, etc., but there is also the problem of environmental pollution, especially given to the human body. The current situation is that we are struggling to take measures against this, as the impact has recently been greatly highlighted.

In order to solve these problems, an alkali developing type photo solder resist composition which can be developed with a dilute aqueous alkali solution has been proposed. For example, JP-A-56-4
No. 0329 and JP-A-57-45785 disclose a material having a reaction product obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride as a base polymer. . In addition, Japanese Patent Publication 1-5439
No. 0, gazette, an active energy ray curable resin obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, and a photopolymerization initiator A photocurable liquid resist ink composition developable with a dilute alkaline aqueous solution containing is disclosed.

These liquid solder resist compositions are
By introducing a carboxyl group into epoxy acrylate, photosensitivity and developability in a dilute alkaline aqueous solution are imparted. The composition is further exposed to light and developed to obtain a desired composition. After forming the resist pattern, in general, for thermosetting, an epoxy compound is generally contained as a thermosetting component, and the carboxyl group of the side chain introduced into the above epoxy acrylate is reacted with the epoxy group. It is heat-cured to form a resist film having excellent adhesion, hardness, heat resistance, and electrical insulation. In this case, a curing agent for epoxy resin is generally used together with the epoxy resin.

[0006]

However, a solder resist composition containing a resin obtained by adding an unsaturated monocarboxylic acid to a novolac type epoxy resin and further adding a polybasic acid is For example, (meth) acrylic acid is used as the unsaturated monocarboxylic acid, and unsaturated dibasic acid such as maleic acid is used as the polybasic acid, but there is room for improvement in tackiness. Not only that, even if you try to design the coating such as heat resistance and gold plating resistance so that the flexibility and adhesion of the coating film will be significantly superior according to the purpose of use, it will bond to the novolac type epoxy resin. These reactants are chain compounds in which each monomolecular compound is bound, the range of each monomolecular compound is limited, and the skeleton itself to be incorporated is relatively simple. Since a and selection range is small Jo bond,
There is a problem that it is difficult to design the chain compound bound to the novolac type epoxy resin only by changing it within the limited range.

The first object of the present invention is to form an image by exposure to ultraviolet rays and development with a dilute aqueous alkali solution, which is excellent in tackiness (dryness to the touch), and has flexibility, adhesion, heat resistance and the like. It is an object of the present invention to provide a photosensitive resin composition which is excellent in coating film performance and can give a coating film pattern capable of maintaining other coating film performance well. A second object of the present invention is to improve the tackiness and heat resistance remarkably, and to remarkably improve the flexibility and the adhesion, for example, to improve the characteristics depending on the purpose of use so that gold plating can be performed well. It is to provide a photosensitive resin composition which can be easily designed. A third object of the present invention is to provide a printed wiring board before or after mounting an electronic component having a cured film of a solder resist film of a photosensitive resin composition that achieves the above object.

[0008]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that novolak type epoxy resins are not compatible with a predetermined unsaturated polybasic acid, for example, an epoxy compound having a ring structure. A photosensitive resin composition containing a resin obtained by sequentially reacting a saturated monocarboxylic acid and an unsaturated polybasic acid together with other normally used components has a coating film with good tackiness (not sticky) and a cured film thereof. Is flexible, has good adhesion to printed circuit boards, and has good heat resistance.
Moreover, the inventors have found that by selecting the type of the epoxy compound, the tackiness and heat resistance of these performances, and the flexibility and the adhesion to the substrate can be significantly improved, and the present invention has been completed. . That is, the present invention is (1)
A photosensitive resin composition containing (A) an active energy ray-curable resin having an ethylenically unsaturated bond, (B) a photopolymerization initiator, (C) a reactive diluent and (D) a thermosetting compound, The (A) active energy ray-curable resin having an ethylenically unsaturated bond causes an epoxy compound to react with a radically polymerizable unsaturated monocarboxylic acid, and the generated hydroxyl group is saturated or unsaturated polybasic acid or saturated or Photosensitive resin containing epoxy compound-modified unsaturated polybasic acid-modified epoxy resin obtained by reacting epoxy resin-modified unsaturated polybasic acid obtained by reacting unsaturated polybasic acid anhydride A composition is provided. The present invention also provides (2) the photosensitive resin composition according to (1) above, wherein (A) the active energy ray-curable resin having an ethylenically unsaturated bond has an acid value of 40 to 160 mgKOH / g. ), The epoxy compound-modified unsaturated polybasic acid is an epoxy compound selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin, and unsaturated monocarboxylic acid Is a compound obtained by reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride, which is reacted with the epoxy compound-modified unsaturated polybasic acid. The epoxy resin to be made is novolac type epoxy resin, triglycidyl isocyanurate, bisphenol type epoxy resin, The photosensitive resin composition according to (1) or (2) above, which is at least one epoxy resin selected from the group consisting of a phenyl type epoxy resin and a glycidyl amine type epoxy resin, (4), an epoxy compound-modified unsaturated poly At least two epoxy compounds whose basic acid is selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin are reacted with unsaturated monocarboxylic acid, and the generated hydroxyl group The photosensitive resin composition according to the above (1) or (2), which is a compound obtained by reacting a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride with
(5) In the above (1) to (4), the photopolymerization initiator (B) is used in a proportion of 0.2 to 30 g relative to 100 g of the active energy ray-curable resin (A) having an ethylenically unsaturated bond. Any of the photosensitive resin compositions, (6), (A)
2 to 40 g of the reactive diluent (C) is added to 100 g of the active energy ray-curable resin having an ethylenically unsaturated bond.
The photosensitive resin composition according to any one of the above (1) to (5), which is used in the ratio of (7), (D), an epoxy compound as a thermosetting compound, alone or together with other thermosetting compounds, The ratio used alone or in combination is (A)
The photosensitive resin composition according to any one of (1) to (6), which is in a ratio of 5 to 100 g with respect to 100 g of an active energy ray-curable resin having an ethylenically unsaturated bond,
(8) A printed wiring board before or after mounting an electronic component coated with a solder resist film having a cured film of the photosensitive resin composition according to any one of (1) to (7) above. is there.

In the present invention, "(A) active energy ray-curable resin having at least two ethylenically unsaturated bonds in one molecule" means "an epoxy compound is reacted with an unsaturated monocarboxylic acid, Epoxy obtained by reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride (hereinafter sometimes referred to as a saturated or unsaturated polybasic acid or its anhydride) "Epoxy-based compound-modified unsaturated polybasic acid-modified novolac-type epoxy resin obtained by reacting a system-based compound-modified unsaturated polybasic acid with a novolac-type epoxy resin" is preferable, but a resin containing the resin as a main component may also be used. An epoxy compound-modified compound obtained in the same manner except that another epoxy resin is used instead of the above novolac type epoxy resin. It can also be used in combination sum polybasic acid-modified epoxy resin. A polyfunctional epoxy compound is used as the epoxy compound. As the polyfunctional epoxy compound, a compound having a ring structure is preferable,
For example, a compound having an aromatic ring typified by a benzene ring or an isocyanuric acid ring in the polymer skeleton may be used. Epoxy equivalent of epoxy compound is 90
Is preferably from the viewpoint of improving the photosensitivity of the epoxy compound-modified unsaturated polybasic acid-modified novolac type epoxy resin finally obtained, and its molecular weight is from 200 to 1,000.
Is preferable in that it is easy to control the reaction when synthesizing the resin. Specifically, one selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin, more preferably at least two types, that is, one type, preferably two types, Three or four types of epoxy compounds may be mentioned. The at least two epoxy compounds are reacted with a radically polymerizable unsaturated monocarboxylic acid, and the generated hydroxyl group is reacted with a saturated or unsaturated polybasic acid or an anhydride thereof to modify the above epoxy compound-modified unsaturated compound. It is preferred to obtain polybasic acids. When a mixture of two or more kinds of epoxy compounds is used, the less radically polymerizable unsaturated monocarboxylic acid is less than 1 mol per mol of the epoxy group, the less the amount of the epoxy compound. Other molecules for a hydroxyl group generated by the addition of a radical-polymerizable unsaturated monocarboxylic acid to one molecule, or for a carboxyl group generated by the reaction of a saturated or unsaturated polybasic acid or its anhydride to be reacted later The epoxy compound can be easily added, and this is the same for the compound bonded in this way. Therefore, the epoxy compound used by mixing is likely to be a resin in which a plurality of molecules are bonded to each other.
On the contrary, when the amount of the radical-polymerizable unsaturated monocarboxylic acid is more than 1 mol, the mixture of various epoxy compounds and the radical-polymerizable unsaturated monocarboxylic acid used in mixture is more likely to be a mixture. The epoxy compound-modified unsaturated polybasic acid is at least two kinds selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin, that is, two kinds and three kinds thereof. Or 4
Obtained by reacting each epoxy compound of the epoxy compounds with an unsaturated monocarboxylic acid, and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride. It may be a mixture of the respective compounds.

Examples of the triglycidyl isocyanurate include TEPIC-G (epoxy equivalent 105, manufactured by Nissan Chemical Co., Ltd.). As the bisphenol type epoxy resin, Epicoat 8 is used as the bisphenol A type.
28 (epoxy equivalent 190, liquid at normal temperature, manufactured by Yuka Shell Co., Ltd.), Epicoat 1001 (epoxy equivalent 460, manufactured by Yuka Shell Co., Ltd.) and the like. As the above-mentioned biphenyl type epoxy resin, YX-4000 (2,6-xylenol dimer glycidyl ether, epoxy equivalent 18
8, glass transition temperature 105 to 110 ° C., made by Yuka Shell Co., Ltd., YL-6121 (epoxy equivalent 172, glass transition temperature 111 ° C., made by Yuka Shell Co., Ltd.) and the like.

When each of the above-mentioned epoxy compounds is reacted with a radically polymerizable unsaturated monocarboxylic acid, the epoxy group is cleaved by the reaction between the epoxy group and the carboxyl group to form a hydroxyl group and an ester bond. The saturated monocarboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like, but at least one of acrylic acid and methacrylic acid (hereinafter sometimes referred to as (meth) acrylic acid). .)
Is preferred, and acrylic acid is particularly preferred. There is no particular limitation on the reaction method of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid, and for example, the reaction can be performed by heating the epoxy resin and acrylic acid in a suitable diluent. Examples of the diluent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. , Petroleum ether,
Petroleum solvents such as petroleum naphtha, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, ethyl acetate, butyl acetate,
Cellosolve acetate, butyl cellosolve acetate,
Examples thereof include acetic acid esters such as carbitol acetate and butyl carbitol acetate. Examples of the catalyst include amines such as triethylamine and tributylamine, phosphorus compounds such as triphenylphosphine and triphenylphosphate, and the like.

In the reaction of the above-mentioned epoxy compound and the radically polymerizable unsaturated monocarboxylic acid, a polyfunctional epoxy compound having two or more epoxy groups in one molecule is used as the epoxy compound, and at least two of them are used.
A radically polymerizable unsaturated monocarboxylic acid is reacted with each epoxy group. As a result, at least a dibasic epoxy compound-modified unsaturated polybasic acid can be obtained by reacting a saturated or unsaturated polybasic acid or an anhydride thereof described below. When the epoxy compound is bifunctional, one equivalent of the radically polymerizable unsaturated monocarboxylic acid is reacted with one equivalent of the epoxy group of the epoxy compound. When the epoxy compound is trifunctional or more, it is preferable to react 0.7 to 1.2 equivalents of the radical-polymerizable unsaturated monocarboxylic acid per 1 equivalent of the epoxy group contained in the epoxy compound, such as acrylic acid or methacrylic acid. When using at least one of the acids, more preferably 0.
Add 8 to 1.0 equivalent to react. If the amount of the radically polymerizable unsaturated monocarboxylic acid is less than 0.7 equivalent, gelation may occur during the synthetic reaction in the subsequent step, or the stability of the resin may be reduced. Further, when the radical-polymerizable unsaturated monocarboxylic acid is in excess, a large amount of unreacted carboxylic acid remains, which may deteriorate various properties (for example, water resistance) of the cured product. The reaction between the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is preferably carried out in a heated state, and the reaction temperature is preferably 80 to 140 ° C. If the reaction temperature exceeds 140 ° C, the radical-polymerizable unsaturated monocarboxylic acid is likely to undergo thermal polymerization and the synthesis may become difficult. If the reaction temperature is lower than 80 ° C, the reaction rate becomes slow, which is not preferable in actual production. There is. When using a plurality of types of the epoxy compound, or when using a single type of the epoxy compound,
When it is desired to bond individual molecules of each epoxy compound, it is preferable to react 0.4 to 0.9 mol of the radically polymerizable unsaturated monocarboxylic acid with 1 mol of the epoxy group. In the reaction of the epoxy compound and the radically polymerizable unsaturated monocarboxylic acid in the diluent, it is preferable that the blending amount of the diluent is 20 to 50% with respect to the total weight of the reaction system. The reaction product of the epoxy resin and the radical-polymerizable unsaturated monocarboxylic acid can be subjected to the next reaction with the polybasic acid as a solution of the diluent without isolation.

The unsaturated monocarboxylic acid-oxidized epoxy compound, which is a reaction product of the epoxy compound and the radically polymerizable unsaturated monocarboxylic acid, is reacted with a saturated or unsaturated polybasic acid or an anhydride thereof. To obtain an unsaturated polybasic acid modified with an epoxy compound. Such polybasic acids include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid,
3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid,
3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycol Examples thereof include acids, and examples of polybasic acid anhydrides include these anhydrides. These compounds may be used alone or in combination of two or more. The saturated or unsaturated polybasic acid or its anhydride reacts with the hydroxyl group formed by the reaction of the above-mentioned epoxy compound and the radical-polymerizable unsaturated monocarboxylic acid, and has a free carboxyl group. The amount of the saturated or unsaturated polybasic acid or the anhydride thereof to be reacted is such that the reaction product of the epoxy compound and the radical-polymerizable unsaturated monocarboxylic acid has two hydroxyl groups in one molecule. In this case, it is 1 mol per 1 mol of the hydroxyl group, but when the number of the hydroxyl groups is 3 or more in one molecule, it is preferable to adjust so that at least 2 of them react. Saturated or unsaturated polybasic acid or its anhydride is added to the above unsaturated monocarboxylic oxide epoxy compound, dehydration condensation reaction, water generated during the reaction is preferably taken out continuously from the reaction system, The reaction is preferably performed in a heated state, and the reaction temperature is preferably 70 to 130 ° C. If the reaction temperature exceeds 130 ° C, the ones bound to the epoxy resin or the radically polymerizable unsaturated groups of the unreacted monomer may easily undergo thermal polymerization, which may make the synthesis difficult. The speed becomes slow, which may be unfavorable in actual manufacturing.

In the present invention, the epoxy compound-modified unsaturated polybasic acid thus obtained is reacted with an epoxy resin. As the epoxy resin, a novolac type epoxy resin is preferable, and as this novolac type epoxy resin, Can be used as long as it is a bifunctional or higher-functional novolac type epoxy resin, and there is no limitation on the epoxy equivalent, but it is usually 1,000 or less, preferably 100 to 5
00 is used. For example, phenol novolac type epoxy resins such as bisphenol A type, bisphenol F type and bisphenol AD type, cresol novolac type epoxy resins such as о-cresol novolac type, bisphenol A novolac type epoxy resin, bisphenol modified novolac type epoxy resin, polyfunctional Examples thereof include modified novolac type epoxy resin. Further, those obtained by introducing a halogen atom such as Br or Cl into these resins can also be mentioned. These epoxy resins may be used alone or in combination of two or more.

In the present invention, the above epoxy compound-modified unsaturated polybasic acid and the above novolak type epoxy resin are reacted to obtain an epoxy compound-modified unsaturated polybasic acid modified novolak type epoxy resin. The epoxy compound-modified unsaturated polybasic acid is converted into a carboxyl group of 1. per equivalent of the epoxy group of the novolac type epoxy resin.
The reaction is preferably carried out in an amount of 1 to 4.0 equivalents, more preferably 1.6 to 3.0 equivalents. When the epoxy compound-modified unsaturated polybasic acid is less than 1.1 equivalents,
The stability of the obtained resin may decrease. Further, if the amount of the epoxy compound-modified unsaturated polybasic acid is excessive, a large amount of unreacted carboxylic acid remains, which may deteriorate various properties (for example, water resistance) of the cured product. The reaction between the novolac type epoxy resin and the epoxy compound-modified unsaturated polybasic acid is preferably carried out in a heated state, and the reaction temperature is preferably 80 to 140 ° C. If the reaction temperature is higher than 140 ° C, the epoxy compound-modified unsaturated polybasic acid is likely to undergo thermal polymerization, which may make the synthesis difficult. If the reaction temperature is lower than 80 ° C, the reaction rate becomes slow, which is not preferable in actual production. Sometimes. In the reaction of the above novolac type epoxy resin and the epoxy compound-modified unsaturated polybasic acid, it is preferable that the diluent content is 20 to 50% with respect to the total weight of the reaction system. The reaction product can be used as a solution in a diluent without isolation. The acid value of the epoxy compound-modified unsaturated polybasic acid-modified novolak type epoxy resin thus obtained is preferably 40 to 160 mgKOH / g. If the amount is less than this, the developability is likely to be deteriorated, and if the amount is more than this, the water resistance of the cured film of the photosensitive resin composition using this resin is likely to be deteriorated, thereby affecting its performance.

The above epoxy compound-modified unsaturated polybasic acid-modified novolac type epoxy resin can also be used as a photosensitive resin. However, one or more radically polymerizable unsaturated groups and an epoxy group are added to the carboxyl group of this resin. A radically polymerizable unsaturated group may be further introduced by reacting the glycidyl compound contained therein to further improve the photosensitivity. This photosensitive resin with improved photosensitivity has a photopolymerization reaction because the radically polymerizable unsaturated group is bonded to the side chain of the polymer skeleton of the precursor photosensitive resin by the reaction of the last glycidyl compound. It has high photosensitivity and can have excellent photosensitivity. Examples of the compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether and the like. In addition, you may have two or more glycidyl groups in 1 molecule. These compounds may be used alone or as a mixture. The glycidyl compound is added to a solution of the epoxy compound-modified unsaturated polybasic acid-modified novolak type epoxy resin and reacted, but usually 0.05 to 0.
The reaction is carried out at a ratio of 5 mol. The photosensitivity (sensitivity) of the photosensitive resin composition containing the obtained photosensitive resin and the thermal management width (the thermal allowable limit of the coating film curing degree that can be removed during development of the unexposed portion corresponding to drying of the coating film) In consideration of the electric characteristics such as the control range) and the electric insulation, it is preferably 0.
It is advantageous to react in a proportion of 1 to 0.5 mol. The reaction temperature is preferably 80 to 120 ° C. The photosensitive resin comprising the glycidyl compound-added epoxy compound-modified unsaturated polybasic acid-modified novolak type epoxy resin thus obtained preferably has an acid value of 45 to 250 mgKOH / g. The above was reacted with an epoxy compound-modified unsaturated polybasic acid was a novolac type epoxy resin, but instead of the novolac type epoxy resin, a novolac type epoxy resin, triglycidyl isocyanurate, a bisphenol type epoxy resin, It may be at least one kind of epoxy resin selected from the group consisting of a biphenyl type epoxy resin and a glycidyl amine type epoxy resin, that is, one or more kinds of epoxy resins, and the specific resins mentioned above may be used as each of these resins. It can be used according to the above novolac type epoxy resin.

In the present invention, in addition to the above-mentioned component (A), it is mixed with "(B) photopolymerization initiator" and "(C) diluent", and further with "(D) thermosetting compound". When used, it can be used as the photosensitive resin composition of the present invention, and can be suitably used, for example, as a solder resist composition for producing a printed wiring board. The "(B) photopolymerization initiator" is not particularly limited, and any conventionally known one can be used. Specifically, as typical ones, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-
1-one, 4- (2-hydroxyethoxy) phenyl-2-
(Hydroxy-2-propyl) ketone, benzophenone, p
-Phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chloro Examples thereof include thioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, and P-dimethylaminobenzoic acid ethyl ester. These can be used alone or in combination of two or more. The amount of the photopolymerization initiator used is usually 0.5 to 50 g per 100 g of the active energy ray-curable resin as the component (A). Below 0.5g,
The photocuring reaction of the active energy ray-curable resin of the component (A) becomes difficult to proceed, and if it exceeds 50 g, the effect is not improved for the amount added, rather it is economically disadvantageous and the curing The mechanical properties of the coating film may deteriorate. From the viewpoints of photocurability, economy, mechanical properties of the cured coating film, etc., the amount used is preferably 2.0 to 30 g.

The "(C) diluent" means at least one of a photopolymerizable monomer and an organic solvent. The photopolymerizable monomer is called a reactive diluent, which further enhances the photocuring of the photosensitive resin as the component (A),
It is preferably used for obtaining a coating film having acid resistance, heat resistance, alkali resistance and the like, and a compound having at least two double bonds in one molecule is preferably used. An organic solvent may be used to adjust the viscosity and the drying property of the photosensitive resin composition containing the photosensitive resin as the component (A), but if it is not necessary, it may not be used. When the photocurability of only the photosensitive resin as the component (A) is sufficient, the photopolymerizable monomer may not be used. Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate. , Neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphoric acid di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate Acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate,
Examples of reactive diluents include propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The above-mentioned difunctional to hexafunctional and other polyfunctional reactive diluents can be used either in a single product or in a mixed system of a plurality of products. The amount of the reactive diluent added is usually selected in the range of 2.0 to 40 g per 100 g of the active energy ray-curable resin as the component (A). The amount added is 2.0
If it is less than g, sufficient photo-curing cannot be obtained and sufficient properties such as acid resistance and heat resistance of the cured coating film cannot be obtained.
If the amount added exceeds 40 g, tack will be severe, and the artwork film will tend to adhere to the substrate during exposure, making it difficult to obtain the desired cured coating film. The amount of the reactive diluent added is preferably 4.0 to 20 g from the viewpoint of preventing the artwork film from adhering to the substrate, such as photocurability, acid resistance and heat resistance of the cured coating film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, cyclohexane and alicyclic carbon such as methylcyclohexane. Petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate. And acetic acid esters such as butyl carbitol acetate.

The above-mentioned "(D) thermosetting compound" is a photosensitive resin composition of the present invention, which can improve the performance of the coating film after post-curing after the coating film is exposed and developed. Epoxy compounds and other thermosetting compounds may be mentioned, but it is preferable to include at least an epoxy compound in the photosensitive resin composition, and four kinds of compounds listed as the above epoxy compounds as the epoxy compound, that is, Triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin can be mentioned. In addition to them, as aliphatic epoxy resin,
Araldite CY-179 (manufactured by Ciba) and the like,
Examples of the dicyclopentadiene type epoxy resin include an epoxy resin based on a modified polyhydric phenol resin obtained by polyaddition reaction of dicyclopentadiene and phenol in the presence of a Lewis acid catalyst, and a xylene type epoxy resin. As EXA-4580L (manufactured by Dainippon Ink and Chemicals Incorporated), as naphthalene type epoxy resin,
Examples thereof include a tetrafunctional naphthalene skeleton type epoxy resin, and examples thereof include compounds obtained by the method described in JP-A-4-217675 or a method analogous thereto. The above dicyclopentadiene type epoxy resin and naphthalene type epoxy resin can be made into a cured product having a small water absorption. Other than epoxy compounds,
Examples of oxetane compounds include TDO and XDO (manufactured by Ube Industries, Ltd.), diallyl phthalate compounds, bismaleimide compounds and the like.

The above-mentioned "(D) thermosetting compound" is usually added in a proportion of 5 to 150 g with respect to 100 g of the active energy ray-curable resin as the component (A). If the added amount is less than 5 g, it tends to be difficult to obtain sufficient adhesion, heat resistance and gold plating resistance as a solder resist coating film after post-curing according to the present invention, and if it exceeds 150 g, the coating film before post-curing is likely to occur. Developability and pot life stability are likely to decrease. From these things, the addition amount of this epoxy thermosetting compound is preferably 50 to 1
It is 00 g. The above-mentioned epoxy thermosetting compound, in combination with dicyandiamide as a reaction accelerator, at least one organic acid salt of dicyandiamide and its derivatives, melamine compounds, imidazole compounds, known epoxy curing accelerators such as phenol compounds, Post curing of the coating can also be facilitated. The photosensitive resin composition of the present invention containing an organic acid salt of dicyandiamide or a derivative thereof in an appropriate amount as a latent thermosetting agent has a long pot life and storage stability even when using dicyandiamide or an N-substituted dicyandiamide. In addition to having excellent properties, the coating film can have a wide heat management range. The amount of the reaction accelerator used is selected in the range of 0.1 to 10 g per 100 g of the component (A). The heat resistance, moisture resistance, electric insulation, chemical resistance, acid resistance, solvent resistance, adhesion, flexibility, and hardness of the resist film obtained by using the above thermosetting compound or a combination of this with a reaction accelerator It is possible to improve various properties such as, and is useful as a solder resist for a printed wiring board.

In addition to the above-mentioned components, the photosensitive resin composition of the present invention may optionally contain various additives, for example, fillers composed of inorganic pigments such as silica, alumina, talc, calcium carbonate and barium sulfate. A known coloring pigment such as a phthalocyanine-based organic pigment such as phthalocyanine green or phthalocyanine blue or an azo-based organic pigment or an inorganic pigment such as titanium dioxide, a paint additive such as a defoaming agent or a leveling agent may be contained.

The photosensitive resin composition of the present invention obtained as described above is applied in a desired thickness to a printed wiring board having a circuit pattern formed by etching a copper foil of a copper clad laminate, for example. At a temperature of 60 to 80 ° C
After heating for about 60 minutes to volatilize the solvent, a negative film with a translucent pattern except for the soldering lands of the above circuit pattern is brought into close contact with this, and ultraviolet rays are radiated from above to this soldering land. The coating film is developed by removing the non-exposed area corresponding to the above with a dilute aqueous alkaline solution. The dilute alkali aqueous solution used at this time is generally a 0.5 to 5 mass% sodium carbonate aqueous solution, but other alkalis can also be used. Then 140
The desired solder resist film can be formed by post-curing for 10 to 60 minutes with a hot air circulation type dryer at ˜160 ° C. In this way, a printed wiring board coated with a solder resist film is obtained, and electronic components are connected, fixed and mounted by soldering by a jet soldering method or a reflow soldering method. A circuit unit is formed. In the present invention, the subject includes both a printed wiring board coated with a solder resist film before mounting the electronic component and a printed wiring board mounted with the electronic component on the printed wiring board.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION With reference to each component and its component ratio used in Examples described later, similar compounds selected from the above-mentioned compounds of each component and the above-mentioned preferable range of each component ratio will be described below. The invention of the general concept including the embodiments can be constructed.

[0025]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Resin Production Example 1 (Photosensitive resin as the component (A),
Hereinafter, the same as in Resin Production Example 8) 315 g of triglycidyl isocyanurate (manufactured by Nissan Kagaku Co., Ltd., TEPIC-G, epoxy equivalent 105) and 216 g of acrylic acid were dissolved in 630 g of carbitol acetate, and reacted under reflux to obtain an epoxy acrylate. Got Next, 460 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the mixture was reacted under reflux until the acid value of the reaction product solution reached 103 mgKOH / g. Phenol novolac resin (Shell, Epicoat 152, epoxy equivalent 180) 18 was added to the obtained reaction product.
0 g was added, and the acid value of the reaction product solution was 62 mg KO.
The reaction was carried out under reflux until H / g. The photosensitive resin solution thus obtained contains 65% of solid resin component.
The acid value of the resin component was 96 mgKOH / g.

Resin Production Example 2 In 540 g of carbitol acetate, 380 g of bisphenol type epoxy resin (Epicote 828, epoxy equivalent 190, manufactured by Shell Co.) and 144 g of acrylic acid were dissolved and reacted under reflux to obtain an epoxy acrylate. .
Next, 300 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the reaction product solution was reacted under reflux until the acid value reached 82 mgKOH / g. 180 g of phenol novolac resin (Epicote 152, epoxy equivalent 180, manufactured by Shell Co.) in the obtained reaction product.
Acid value of the reaction product solution is 37 mgKOH
The reaction was carried out under reflux until it reached / g. The photosensitive resin solution thus obtained had a resin component of solid content of 65%, and an acid value of the resin component of 56 mgKOH / g.

Resin Production Example 3 530 g of carbitol acetate was added to a biphenyl type epoxy resin (YX4000, manufactured by Shell Co., epoxy equivalent 1).
80) 360 g and acrylic acid 144 g were dissolved and reacted under reflux to obtain epoxy acrylate. Then
To this epoxy acrylate was added 300 g of hexahydrophthalic anhydride, and the acid value of the reaction product solution was 84 mg.
The reaction was carried out under reflux until KOH / g. To the obtained reaction product, 180 g of phenol novolac resin (Epicote 152, epoxy equivalent 180, manufactured by Shell Co.) was added, and the reaction product solution was reacted under reflux until the acid value became 37 mgKOH / g. In the photosensitive resin solution thus obtained, the resin component of the solid content was 65%, and the acid value of the resin component was 57 mgKOH / g.

Resin Production Example 4 In 760 g of carbitol acetate, 480 g of a glycidylamine type epoxy resin (YH-434, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 120) and 288 g of acrylic acid were dissolved and reacted under reflux to react with epoxy acrylate. Got
Next, 460 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the reaction product solution was reacted under reflux until the acid value became 85 mgKOH / g. 180 g of phenol novolac resin (Epicote 152, epoxy equivalent 180, manufactured by Shell Co.) in the obtained reaction product.
Acid value of the reaction product solution is 52 mgKOH /
The reaction was carried out under reflux until g. In the photosensitive resin solution thus obtained, the resin component of the solid content was 65%, and the acid value of the resin component was 80 mgKOH / g.

Production Example 5 of resin: To 675 g of carbitol acetate, 210 g of triglycidyl isocyanurate (manufactured by Nissan Kagaku, TEPIC-G, epoxy equivalent 105), bisphenol epoxy resin (manufactured by Shell, Epicoat 828, epoxy equivalent 1)
90) 190 g and acrylic acid 216 g were dissolved and reacted under reflux to obtain an epoxy acrylate. Then
Hexahydrophthalic anhydride (460 g) was added to this epoxy acrylate, and the acid value of the reaction product solution was 96 mg.
The reaction was carried out under reflux until KOH / g. To the obtained reaction product, 180 g of phenol novolac resin (Shell, Epicoat 152, epoxy equivalent 180) was added, and the reaction product solution was reacted under reflux until the acid value became 58 mgKOH / g. In the photosensitive resin solution thus obtained, the resin component of the solid content was 65%, and the acid value of the resin component was 89 mgKOH / g.

Resin Production Example 6 315 g of triglycidyl isocyanurate (manufactured by Nissan Kagaku Co., TEPIC-G, epoxy equivalent 105) and 216 g of acrylic acid were dissolved in 785 g of carbitol acetate and reacted under reflux to react with epoxy acrylate. Obtained. Next, 462 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the reaction product solution was reacted under reflux until the acid value reached 95 mgKOH / g. To the obtained reaction product, 460 g of bisphenol A type epoxy resin (Shell Chemical Co., Epicoat 1001, epoxy equivalent 460) was added, and the reaction product solution was reacted under reflux until the acid value became 50 mgKOH / g. The photosensitive resin solution thus obtained had a resin content of 65% in solid content and an acid value of 77 mgKO in the resin content.
It was H / g.

Resin Production Example 7 To 785 g of carbitol acetate, 210 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC-G, epoxy equivalent 105), bisphenol A type epoxy resin (Shell Chemical Co., Epicoat 828, epoxy equivalent). 190) 190 g and acrylic acid 216 g were dissolved and reacted under reflux to obtain an epoxy acrylate.
Next, 462 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the mixture was reacted under reflux until the acid value of the reaction product solution reached 88 mgKOH / g. Bisphenol A type epoxy resin (manufactured by Shell Chemical Co., Epicoat 1001, epoxy equivalent 46
0) 460 g was added, and the acid value of the reaction product solution was 47.
The reaction was carried out under reflux until the mgKOH / g was reached. The photosensitive resin solution thus obtained has a resin component of solid content of 65%, and an acid value of the resin component of 73 mgKOH /
It was g.

Production Example 8 of Resin: To 822 g of carbitol acetate, 210 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC-G, epoxy equivalent 105), biphenyl type epoxy resin (manufactured by Shell Chemical Co., YX-4000, epoxy equivalent). 18
0) 180 g and acrylic acid 216 g were dissolved and reacted under reflux to obtain an epoxy acrylate. Next, hexahydrophthalic anhydride 4 was added to the epoxy acrylate.
62 g was added, and the acid value of the reaction product solution was 89 mgK.
The reaction was carried out under reflux until OH / g. A bisphenol A type epoxy resin (Shell Chemical Co., Epicoat 1001, epoxy equivalent 460) 460 was added to the obtained reaction product.
g, and the acid value of the reaction product solution is 47 mgKOH
The reaction was carried out under reflux until it reached / g. The photosensitive resin solution thus obtained had a resin component of solid content of 65%, and an acid value of the resin component of 73 mgKOH / g.

Resin Production Example 9 (for Comparative Example) 315 g of triglycidyl isocyanurate (manufactured by Nissan Kagaku, TEPIC-G, epoxy equivalent 105) and 216 g of acrylic acid were dissolved in 510 g of carbitol acetate and reacted under reflux. To obtain an epoxy acrylate. Next, 416 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the mixture was reacted under reflux until the acid value of the reaction product solution reached 103 mgKOH / g. The photosensitive resin solution thus obtained had a resin component of solid content of 65% and an acid value of 160%.
It was mgKOH / g.

Resin Production Example 10 (for Comparative Example) In 354 g of carbitol acetate, 360 g of phenol novolac resin (Epicote 152, epoxy equivalent 180, manufactured by Shell Co.) and 144 g of acrylic acid were dissolved,
The reaction was carried out under reflux to obtain an epoxy acrylate. Next, 154 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the acid value of the reaction product solution was 55.
The reaction was carried out under reflux until the mgKOH / g was reached. The photosensitive resin solution thus obtained has a resin component of solid content of 65% and an acid value of the resin component of 85 mgKOH /
It was g.

Production Example 11 of Resin (for Comparative Example) 354 g of carbitol acetate and bisphenol A
920 g of a type epoxy resin (manufactured by Shell Co., Epicoat 1001, epoxy equivalent 460) and 144 g of acrylic acid were dissolved and reacted under reflux to obtain an epoxy acrylate. Next, 308 g of hexahydrophthalic anhydride was added to this epoxy acrylate, and the reaction product solution was reacted under reflux until the acid value became 53 mgKOH / g. The photosensitive resin solution thus obtained has a solid resin component of 65% and an acid value of 82 m.
It was gKOH / g.

Example 1 100 g of the photosensitive resin solution ((A) photosensitive resin) obtained in Production Example 1 of resin, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 1-propan-1-one ((B) photopolymerization initiator) 8 g, trimethylolpropane triacrylate ((C) reactive diluent) 8
g, triglycidyl tris (2-hydroxyethyl) isocyanurate ((D) thermosetting compound) 8 g, phthalocyanine green 0.5 g and talc 8 g are added and mixed and dispersed with a three-roll to prepare a photosensitive resin composition. A solution was prepared. About this photosensitive resin composition, sensitivity, heat management width, tackiness, hardness, solder heat resistance, acid resistance, adhesion,
Table 1 shows the results of examining the solvent resistance, gold plating resistance, and electrical characteristics (insulation resistance value, discoloration) by the test methods described below.

Examples 2 to 8 In Example 1, instead of the photosensitive resin solution obtained in Resin Production Example 1, the photosensitive resin solutions obtained in Resin Production Examples 2 to 8 were used. A photosensitive resin composition solution was prepared in the same manner except for the above, and the results of the same tests as in Example 1 are shown in Table 1.

Comparative Examples 1 to 3 In Example 1, instead of the photosensitive resin solution obtained in Resin Production Example 1, the photosensitive resin solutions obtained in Resin Production Examples 9 to 11 were used. A photosensitive resin composition solution was prepared in the same manner except for the above, and the results of the same tests as in Example 1 are shown in Table 1.

The test method is as follows. (1) A sensitivity 21-step step tablet was applied to a test plate by screen printing with each of the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 to a thickness of 35 μm (before drying). , Dry to make coated substrate, 200mJ / cm ²
Was exposed to ultraviolet light at a dose of 1%, a 1% aqueous sodium carbonate solution was used, and development was carried out for 60 seconds at a spray pressure of 0.2 MPa · s, and the maximum number of steps at which the coating film completely remained was evaluated. The larger the number of steps, the better the photosensitivity. (2) Heat management width A photosensitive resin composition of each of Examples 1 to 5 and Comparative Examples 1 and 2 having a thickness of 35 μm was applied to a substrate (copper-clad laminate) that had been surface-treated in advance by screen printing. Each coated substrate was prepared by applying (before drying) and preliminarily drying at 80 ° C. for 10 minutes at an interval of 10 minutes, and UV exposure was performed at a dose of 200 mJ / cm ² to obtain 1% sodium carbonate. Development was carried out for 60 seconds using an aqueous solution at a spray pressure of 0.2 MPa · s, and the longest predrying time described above that could completely remove the coating film was determined and evaluated. (3) Tackiness (dryness to the touch) A photosensitive resin composition of each of Examples 1 to 5 and Comparative Examples 1 and 2 described above is applied to a surface-treated substrate (copper-clad laminate) by a screen printing method. Is applied to a thickness of 35 μm (before drying) and dried at 80 ° C. for 20 minutes to prepare a coated substrate,
A negative film was brought into close contact with the surface of the coating film, and after exposure, the extent of adhesion of the coating film to the negative film was examined and evaluated as follows. ◎ No sticking or sticking marks at all ○ Sticking marks on the surface of the coating film △ Resistance when peeling off × Adhesion of the coating film on the negative film

(3) Coating film performance A substrate (copper-clad laminate) which has been surface-treated in advance is screen-printed with 35 μm of each of the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 described above. To a thickness (before drying) to prepare each coated substrate, and each coated substrate was dried at 80 ° C. for 20 minutes. A negative film was brought into close contact with this substrate, and after exposure, development processing was performed with a 1 mass% sodium carbonate aqueous solution to form a pattern. Next, this substrate was thermally cured at 150 ° C. for 60 minutes to prepare a test piece having a cured coating film, and the coating film performance was evaluated. (A) The pencil hardness cured coating film was measured according to JIS K-5400 6.14. (B) A test piece having a solder heat resistant cured coating film was dipped in a solder bath at 260 ° C. for 30 seconds in accordance with the test method of JIS C 6481,
A peeling test using a cellophane adhesive tape (cellophane is a trade name) was set as one cycle, and the coating film state after performing a total of 1 to 3 cycles was visually evaluated. ⊚: No change in coating film after 3 cycles ○: Slight change after 3 cycles Δ: Change after 2 cycles ×: Peeling after 1 cycle (c) Acid resistance After soaking the test piece with a cured coating film in a 10% by mass aqueous sulfuric acid solution at room temperature for 30 minutes, after washing with water, a peeling test with a cellophane adhesive tape was performed to observe the peeling and discoloration of the coating film and visually check the acid resistance. It was evaluated by. ⊚: No change observed ○: Slight change Δ: Significant change X: Swelled and peeled coating film

(D) A test piece having a solvent resistant cured coating film was dipped in methylene chloride at room temperature for 30 minutes, washed with water, and then subjected to a peeling test with a cellophane adhesive tape to observe peeling and discoloration of the coating film. The solvent resistance was visually evaluated. ⊚: No change observed ○: Slight change Δ: Remarkably changed ×: Swelled and peeled coating film (e) Gold cured anti-curing coating film After the gold plating on the test piece, a peeling test with a cellophane adhesive tape was performed to observe the peeling and discoloration of the cured coating film, and the gold plating property was visually evaluated as follows. ⊚: No change observed ○: Slight change Δ: Significant change X: Swelled and peeled coating film

(F) IPC SM-840B, B-25 on the cured coating film of the electrical property test piece.
Place a comb-shaped electrode B coupon, 60 ℃, 90% RH
A direct current voltage of 100 V was applied in a constant temperature and humidity chamber of (relative humidity), the insulation resistance value (Ω) after 500 hours was measured, and discoloration was observed, and the degree of discoloration was visually evaluated as follows. . ⊚: No change observed ○: Slight change Δ: Significant change X: Swelled and peeled coating film

[0043]

[Table 1]

From the results shown in Table 1, in the case of Comparative Example 1 using the resin corresponding to the component (A) obtained in the same manner as in Example 1 except that the novolac type epoxy resin was not used, thermal management was performed. The width, acid resistance and gold plating resistance are poor, and in Comparative Example 2 in which a resin obtained by reacting a novolac type epoxy resin with acrylic acid and then an unsaturated dibasic acid is used, the tackiness is poor. Example 1 using an epoxy compound-modified unsaturated polybasic acid-modified epoxy resin obtained by reacting an epoxy resin-modified unsaturated polybasic acid with an epoxy resin such as a novolac type epoxy resin
In addition to the insulation resistance being substantially the same, those of No. 8 have good performances, and among them, Example 1 using an epoxy resin having an isocyanuric acid skeleton as the epoxy compound of the epoxy compound-modified unsaturated polybasic acid Particularly, the tackiness and the heat resistance of the solder are excellent, and the one of Example 2 using the bisphenol type epoxy resin has good gold plating resistance, and the cured coating film is flexible. And the adhesiveness is remarkably excellent, and the one of Example 3 using the biphenyl type epoxy resin is remarkably excellent in that it is hardly discolored among the electric characteristics, and an example using the glycidyl amine type epoxy resin. No. 4 has excellent photosensitivity and heat resistance. Among them, the one of Example 5 in which the epoxy resin having an isocyanuric acid skeleton and the bisphenol type epoxy resin are used in combination can have the outstanding advantages of those of Examples 1 and 2 and can be said to be particularly excellent. The synergistic effect of both can be exhibited. The same applies to the combinations of the other Examples 1 to 5. As the epoxy compound of the epoxy compound-modified unsaturated polybasic acid, an epoxy resin having an isocyanuric acid skeleton is used alone or in combination with a bisphenol A type epoxy resin or a biphenyl type epoxy resin. Examples 6 to 8 in which a bisphenol A type epoxy resin was used as an epoxy resin to be reacted with a basic acid were excellent in all properties, and the insulation resistance was about the same level. It goes without saying that the resin obtained by reacting an unsaturated dibasic acid is used in Comparative Example 3 and is more remarkable than Comparative Examples 1 and 2 which are superior in many points. Excellent, Examples 1 to 5
Some properties are superior to those of

In Comparative Examples 1 to 3, since the epoxy resin is reacted with acrylic acid and then hexahydrophthalic anhydride, these reactants have relatively low molecular weights in which the portion bonded to the epoxy resin does not have a ring structure. It is a chain. On the other hand, the epoxy compound-modified unsaturated polybasic acid-modified epoxy resin used in the examples has a ring structure in two stages in its skeleton (ring structure of epoxy resin reacted first and epoxy resin reacted last) In addition to having heat resistance and high molecular weight, the coating film of the solder resist composition using this is tacky (sticky)
It is considered that the cured coating film is improved, the solder heat resistance when the cured coating film contacts molten solder is also improved, and the flexibility and adhesion of the cured coating film are also improved. Even if the chain compound of the above-mentioned monomolecular compound (chain compound of acrylic acid and hexahydrophthalic anhydride) is bonded to the novolac type epoxy resin, if the bonded compound has a relatively low molecular weight, the solder resist composition Even if the cured film of the coating film is easily fragile and lacks in flexibility, not only does it become a tough film, but it also contributes to the improvement of the adhesion of the glass fiber reinforced epoxy resin to the substrate. Since there is no characteristic to obtain, it can be considered that the cured film is inferior to that of the example in terms of flexibility and adhesion to the substrate. In the above-mentioned invention, the “photosensitive resin composition” may be a “photosensitive resin composition for solder resist”, or may be a “printed wiring board coated with a solder resist film and a method for producing the same”, and The present invention may be limited to the above-mentioned numerical values and other limitations, and further to a limitation in which a plurality of these arbitrary numbers are combined.

[0046]

According to the present invention, an image can be formed by exposure to ultraviolet light and development with a dilute aqueous alkali solution, and it is excellent in tackiness (dryness to the touch), and has flexibility, adhesion and heat resistance. It is possible to give a pattern of a coating film that is excellent in film performance and can also maintain other coating film properties well, especially improving tackiness and heat resistance, and remarkably improving flexibility and adhesion. Thus, it is possible to provide a photosensitive resin composition which can be easily designed such that characteristics suitable for the purpose of use can be obtained so that, for example, gold plating can be improved satisfactorily. And
It is possible to provide a printed wiring board before or after mounting an electronic component having a cured film of a solder resist film of the photosensitive resin composition.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuyuki Hasegawa             16 Samuragahara 2 Ita, Iruma City, Saitama Prefecture             La Kaken Co., Ltd. F term (reference) 2H025 AA10 AA14 AB15 AC01 AD01                       BC14 BC42 BC74 BC81 BC85                       CA01 CA27 CC03 CC20 FA03                       FA17                 4J027 AE10 BA19 BA24 BA29                 4J036 AB17 AD07 AD08 AH01 AH04                       AH15 CA21 CA24 CD07 JA09                 5E314 AA25 AA27 AA32 BB11 BB12                       CC01 FF01 GG08 GG11 GG19

Claims (8)

[Claims] 1. An active energy ray-curable resin having (A) an ethylenically unsaturated bond, (B) a photopolymerization initiator,
In the photosensitive resin composition containing (C) a diluent and (D) a thermosetting compound, the (A) active energy ray-curable resin having an ethylenically unsaturated bond is radically polymerizable unsaturated to an epoxy compound. An epoxy compound-modified unsaturated polybasic acid obtained by reacting a monocarboxylic acid with the resulting hydroxyl group and reacting a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride with an epoxy resin A photosensitive resin composition containing an epoxy compound-modified unsaturated polybasic acid-modified epoxy resin obtained by the reaction. 2. The acid value of the active energy ray-curable resin (A) having an ethylenically unsaturated bond has an acid value of 40 to 160 mgK.
The photosensitive resin composition according to claim 1, which is OH / g. 3. The epoxy compound-modified unsaturated polybasic acid is one type of epoxy compound selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin, and unsaturated. A compound obtained by reacting a monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride, wherein the epoxy compound-modified unsaturated polybasic The epoxy resin to be reacted with an acid is at least one epoxy resin selected from the group consisting of novolac type epoxy resin, triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin. 2. The photosensitive resin composition according to 2. object. 4. An epoxy compound-modified unsaturated polybasic acid is incompatible with at least two epoxy compounds selected from the group consisting of triglycidyl isocyanurate, bisphenol type epoxy resin, biphenyl type epoxy resin and glycidyl amine type epoxy resin. The photosensitive compound according to claim 1 or 2, which is a compound obtained by reacting a saturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid or a saturated or unsaturated polybasic acid anhydride. Resin composition. 5. The photopolymerization initiator (B) is used in a proportion of 0.2 to 30 g per 100 g of the active energy ray-curable resin (A) having an ethylenically unsaturated bond. The photosensitive resin composition according to item 1. 6. The (C) diluent is at least one of a photopolymerizable monomer and an organic solvent, and the photopolymerizable monomer is added to (A) 100 g of an active energy ray-curable resin having an ethylenically unsaturated bond. And at least one of organic solvents
The photosensitive resin composition according to claim 1, wherein the seed is used in a proportion of 2 to 40 g. 7. (D) An epoxy compound is used alone or together with other thermosetting compounds as the thermosetting compound, and the ratio of the amount used alone or in combination is (A).
The photosensitive resin composition according to any one of claims 1 to 6, wherein the amount is 5 to 100 g relative to 100 g of the active energy ray-curable resin having an ethylenically unsaturated bond. 8. A printed wiring board before or after mounting an electronic component coated with a solder resist film having a cured film of the photosensitive resin composition according to any one of claims 1 to 7.