WO2010116757A1

WO2010116757A1 - Solder resist composition, dry film using same, and printed wiring board

Info

Publication number: WO2010116757A1
Application number: PCT/JP2010/002599
Authority: WO
Inventors: 中条貴幸; 岡本大地; 伊藤信人; 有馬聖夫
Original assignee: 太陽インキ製造株式会社
Priority date: 2009-04-10
Filing date: 2010-04-09
Publication date: 2010-10-14
Also published as: JP2010249886A; JP5107960B2; TW201042381A; TWI480686B

Abstract

Disclosed is a solder resist composition which has achieved excellent developability and through hole developability, while maintaining solder heat resistance, electroless gold plating resistance and electrical characteristics which are equivalent to or higher than those of conventional solder resists. Also disclosed are a dry film or cured product of the solder resist composition, and a printed wiring board having a cured coating film of the solder resist composition. One embodiment of the solder resist composition contains a photosensitive resin that contains a structure represented by general formula (I) and has at least one ethylenically unsaturated group in each molecule, a photopolymerization initiator, and a carboxyl group-containing resin. Another embodiment of the solder resist composition contains a carboxyl group-containing photosensitive resin that contains a structure represented by general formula (I) and has at least one ethylenically unsaturated group in each molecule, and a photopolymerization initiator. Preferably, the solder resist composition additionally contains a thermosetting component. (In the formula, n represents an integer of 1-99.)

Description

Solder resist composition, dry film and printed wiring board using the same

The present invention relates to a solder resist composition that can form a cured film such as a solder resist that is excellent in developability and through-hole developability, and that is excellent in solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. The present invention also relates to a dry film and a cured product using such a solder resist composition, and a printed wiring board having a cured film formed using them.

The solder resist is intended to protect the circuit of the printed circuit board and is formed on the surface layer of the circuit board. In general, the substrate on which the circuit is formed has not only a circuit on the surface layer but also numerous holes called through holes. In the production of printed wiring boards, photo solder resist is generally employed, and dry film type photo solder resist and liquid photo solder resist are being developed. Among these, in consideration of environmental problems, an alkali development type photocurable thermosetting resin composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed in the past. (See Patent Documents 1 to 3, etc.).

Conventionally, when a solder resist is applied or laminated to a circuit board with through holes, the solder resist in the through holes flows into the through holes and is harder to develop than other places, making it difficult to remove the resist. was there. On the other hand, the development time is extended or the cone shape of the spray is devised and removed, but the increase in the development time not only lowers the productivity but also forms the necessary fine line pattern of the resist. However, there is a problem that an excessive developer attack is caused, an undercut is generated in a necessary fine shape, and it cannot be finally formed. Further, in recent years, the printed wiring board has been increased in density, multilayered, and through-holes have been reduced in size due to the reduction in the thickness of electronic components, and the above problems have become serious.

JP 61-243869 (Claims) JP-A-11-288091 (Claims) JP-A-5-32746 (Claims)

The present invention has been made in view of the problems of the prior art as described above, and its main purpose was to have solder heat resistance, electroless gold plating resistance, and electrical characteristics equivalent to or higher than those of conventional solder resists. An object of the present invention is to provide a solder resist composition having excellent developability and through-hole developability.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a solder resist composition, and a cured film such as a solder resist by the dry film and the cured product. An object of the present invention is to provide a printed wiring board formed.

In order to achieve the above object, according to the present invention, a photosensitive resin having a structure represented by the following general formula (I) and having at least one ethylenically unsaturated group in the molecule, a photopolymerization initiator, And a solder resist composition comprising a carboxyl group-containing resin.

(In the formula, n represents an integer of 1 to 99.)

In a preferred embodiment, the photosensitive resin comprises at least a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group after reacting lactic acid or a lactic acid oligomer with a compound having a plurality of cyclic ether groups in one molecule. It is the photosensitive resin obtained by making the compound which has these react.

According to another aspect of the present invention, a carboxyl group-containing photosensitive resin having a structure represented by the general formula (I) and having at least one ethylenically unsaturated group in the molecule, and a photopolymerization initiator are provided. A solder resist composition is provided.

In a preferred embodiment, the carboxyl group-containing photosensitive resin comprises at least a functional group capable of reacting with a hydroxyl group and an ethylenic group after reacting lactic acid or a lactic acid oligomer with a compound having a plurality of cyclic ether groups in one molecule. It is a carboxyl group-containing resin obtained by reacting a compound having an unsaturated group and further reacting with a polybasic acid anhydride.

In any of the above embodiments, the lactic acid or lactic acid oligomer is preferably fermented lactic acid derived from a natural product or an oligomer thereof.
In a more preferred embodiment, the solder resist composition of the present invention further contains a thermosetting component, and preferably further contains a colorant.

In addition, according to the present invention, the solder resist composition can be obtained by applying and drying the solder resist composition on a film, or by photocuring or further thermally curing the solder resist composition or the dry film. A cured product is also provided.
Furthermore, according to this invention, the printed wiring board which has the cured film formed with the said soldering resist composition or the said dry film is also provided.

The solder resist composition of the present invention includes a photosensitive resin having a structure represented by the general formula (I) and having at least one ethylenically unsaturated group in the molecule, a photopolymerization initiator, and a carboxyl group-containing resin. Or a carboxyl group-containing photosensitive resin having a structure represented by the general formula (I) and having at least one ethylenically unsaturated group in the molecule, and a photopolymerization initiator. It is a feature. That is, the photosensitive resin and the carboxyl group-containing photosensitive resin both contain the structure represented by the general formula (I) derived from lactic acid, and use lactic acid as one of the starting materials. Solder resist that has excellent developability and through-hole developability while maintaining solder heat resistance, electroless gold plating resistance, and electrical characteristics equivalent to or better than that of conventional solder resists. A composition can be provided. Furthermore, since the solder resist composition of the present invention contains at least one of a carboxyl group-containing photosensitive resin and a carboxyl group-containing resin, development with an alkaline aqueous solution becomes possible.

The photosensitive resin not containing a carboxyl group and the carboxyl group-containing photosensitive resin used in the solder resist composition of the present invention are mainly composed of a resin having an unsaturated double bond via the lactic acid skeleton represented by the general formula (I). Since it is introduced at a site away from the chain, it exhibits excellent photoreactivity, and by introducing a lactic acid skeleton, hydrophilicity is improved and a cured product having adhesion and flexibility can be obtained. . In addition, depending on the molecular design, the lactic acid content can be greatly increased, and an environment-friendly photocurable resin can be obtained. Furthermore, heat resistance can be imparted by selectively reacting a compound having a plurality of cyclic ether groups in one molecule capable of reacting with lactic acid. At this time, an epoxy resin can be easily used as a material capable of selectively reacting with lactic acid and imparting heat resistance.
Hereinafter, each constituent component of the solder resist composition of the present invention will be described in more detail.

First, the photosensitive resin containing no carboxyl group used in the present invention has a structure represented by the general formula (I) and has at least one ethylenically unsaturated group in the molecule. It can be easily obtained by reacting a compound having a plurality of cyclic ether groups in the molecule with lactic acid or a lactic acid oligomer and a compound having at least a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. Examples of the compound having at least a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group include an isocyanate compound containing one or more unsaturated groups in one molecule, an unsaturated group-containing monobasic acid or a monobasic acid. An anhydride or the like can be preferably used, but is not limited thereto.

Representative examples of the photosensitive resin used in the present invention include those shown in the following (1) and (2), but are not limited thereto.
(1) Lactic acid or a lactic acid oligomer is reacted with a compound having a plurality of cyclic ether groups in one molecule to synthesize a compound having a plurality of hydroxyl groups in one molecule. A photosensitive resin obtained by reacting an isocyanate compound containing one or more unsaturated groups in one molecule with the obtained compound.
(2) A photosensitive resin obtained by reacting lactic acid or a lactic acid oligomer with an unsaturated group-containing monobasic acid or monobasic acid anhydride with a compound having a plurality of cyclic ether groups in one molecule.

The photosensitive resin (1) has a very high photoreactivity and can increase the sensitivity of the solder resist. Further, although details are not completely clear, it has been clarified that alkali developability is improved when added to conventional general-purpose carboxyl group-containing resins. This is considered to be because the hydrophilicity is significantly increased by adding a photosensitive resin having a lactic acid skeleton structure represented by the general formula (I) to the carboxyl group-containing resin. On the other hand, the influence on the various properties of the solder resist, which is a concern due to the increased hydrophilicity, was obtained in comparison with the properties of the solder resist using the general-purpose carboxyl group-containing resin.

Also, as a result of comparing the developability of the photosensitive resin (2) above with the general-purpose carboxyl group-containing resin, it was confirmed that the developability was improved. In addition, the solder resist properties were also comparable to those of the solder resist using the general-purpose carboxyl group-containing resin.

The reaction when preparing the photosensitive resins of (1) and (2) is carried out by converting a compound having a plurality of cyclic ether groups in one molecule into lactic acid or a lactic acid oligomer and one or more unsaturated groups in one molecule. A method of simultaneously reacting an isocyanate compound containing an unsaturated group or an unsaturated group-containing monobasic acid or monobasic acid anhydride, or first reacting lactic acid or a lactic acid oligomer, and then containing one or more unsaturated groups in one molecule Any method of reacting an isocyanate compound or an unsaturated group-containing monobasic acid or monobasic acid anhydride can be employed. Such a reaction is usually carried out at about 50 to 150 ° C. in the presence or absence of an organic solvent as described later in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine is added as a catalyst as necessary. May be.

Moreover, the ratio of each component in the reaction (feeding ratio of raw materials) is such that the carboxyl group of the lactic acid or lactic acid oligomer is 1. with respect to 1 equivalent of the cyclic ether group of the compound having a plurality of cyclic ether groups in one molecule. The total of the hydroxyl groups generated by the reaction of the cyclic ether group of the compound having a plurality of cyclic ether groups in one molecule and the carboxyl group of lactic acid or lactic acid oligomer and the remaining hydroxyl group of lactic acid or lactic acid oligomer Is a functional group (isocyanate group or acid group) capable of reacting with an isocyanate compound containing one or more unsaturated groups in one molecule or a hydroxyl group of an unsaturated group-containing monobasic acid or monobasic acid anhydride. Is preferably in a ratio of 0.3 to 1.0 equivalent. Since the cyclic ether group remains at a ratio of less than 1.0 equivalent to 1 equivalent of the cyclic ether group of the compound in which the carboxyl group of lactic acid or lactic acid oligomer has a plurality of cyclic ether groups in one molecule, a side reaction is caused later. There is a risk of inviting. On the other hand, even if it is used in a large amount exceeding 1.0 equivalent, only 1 equivalent reacts theoretically, so that these compounds remain unreacted and become a factor of reducing the physical properties of the cured product. Therefore, it is not preferable.

Specific examples of the photosensitive resin used in the present invention are shown by structural formulas below.
First, a polyfunctional cresol-novolak type epoxy resin is used as a compound having a plurality of cyclic ether groups in one molecule, and lactic acid in lactic acid or a lactic acid oligomer contains one or more unsaturated groups in one molecule. When acryloyloxyethoxyethyl isocyanate is used as the compound, it is considered that a photosensitive resin represented by the following formula is obtained.

In addition, a polyfunctional cresol-novolak type epoxy resin is used as a compound having a plurality of cyclic ether groups in one molecule, and as lactic acid or unsaturated group-containing monobasic acid or monobasic acid anhydride of lactic acid or lactic acid oligomer ( When using (meth) acrylic acid, it is thought that the photosensitive resin as shown to a following formula is obtained.

Further, a polyfunctional cresol-novolak type epoxy resin is used as a compound having a plurality of cyclic ether groups in one molecule, lactic acid as a lactic acid or lactic acid oligomer, and anhydrous (meta) as an unsaturated group-containing monobasic acid or monobasic acid anhydride. ) When acrylic acid is used, a photosensitive resin as shown in the following formula is considered to be obtained.

The total number of repeating units a to c, the total number of d and e, and the total number of f to i shown in the respective structural formulas are the same as those of the compound having a plurality of cyclic ether groups in one molecule used. Lactic acid or a lactic acid oligomer for a compound having a plurality of cyclic ether groups in one molecule but not more than the number of cyclic ether groups and an isocyanate compound or unsaturated group containing one or more unsaturated groups in one molecule It can adjust arbitrarily according to the reaction ratio of a basic acid or a monobasic acid anhydride.

Next, the carboxyl group-containing resin used in the present invention has a structure represented by the general formula (I) and has at least one ethylenically unsaturated group in the molecule. It can be easily obtained by reacting a resin with a polybasic acid anhydride. By introducing a carboxyl group by further reacting the hydroxyl group of the photosensitive resin with a polybasic acid anhydride, it can be made soluble in an alkaline aqueous solution. In this reaction, the polybasic acid anhydride is generally used in an amount of 0.1 to 1.0 mol with respect to 1 mol of the hydroxyl group of the photosensitive resin, preferably the acid of the carboxyl group-containing photosensitive resin to be formed. The added amount is such that the value is about 20 to 150 mgKOH / g, more preferably 20 to 100 mgKOH / g.

The addition reaction of polybasic acid anhydride to the photocurable resin is carried out in the presence or absence of an organic solvent as described below, and the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. The reaction is usually performed at about 50 to 150 ° C. If necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, naphthenic acid, laurin Metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium such as acid, stearic acid, oleic acid, and octoenoic acid may be added as a catalyst. These catalysts can be used alone or in admixture of two or more.

Representative examples of the carboxyl group-containing photosensitive resin of the present invention include those shown in the following (3) and (4), but are not limited thereto.
(3) Lactic acid or a lactic acid oligomer is reacted with a compound having a plurality of cyclic ether groups in one molecule to synthesize a hydroxyl group-containing compound. A carboxyl group-containing photosensitive resin obtained by reacting the obtained compound with an isocyanate compound containing one or more unsaturated groups in one molecule and then reacting with a polybasic acid anhydride.
(4) After reacting lactic acid or a lactic acid oligomer with an unsaturated group-containing monobasic acid or monobasic acid anhydride with a compound having a plurality of cyclic ether groups in one molecule, further reacting with a polybasic acid anhydride Carboxyl group-containing photosensitive resin obtained by making it.

As a feature of the carboxyl group-containing photosensitive resin (3) above, it has been clarified that the developability is remarkably excellent as compared with general-purpose carboxyl group-containing resins. This is considered to be because the hydrophilicity is significantly increased by introducing the lactic acid skeleton unit of the general formula (I) into the carboxyl group-containing resin unit. On the other hand, the influence on the various properties of the solder resist, which is a concern due to the increased hydrophilicity, was obtained in comparison with the properties of the solder resist using the general-purpose carboxyl group-containing resin.

Further, as a result of comparing the developability with the general-purpose carboxyl group-containing resin, it was confirmed that the developability of the carboxyl group-containing photosensitive resin (4) was improved. In addition, the solder resist properties were also comparable to those of the solder resist using the general-purpose carboxyl group-containing resin.

Furthermore, a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule may be reacted with the carboxyl group-containing photosensitive resin of (3) and (4) above. The addition amount of the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule is desirably 5 to 40% equivalent to the acid anhydride residue of the carboxyl group-containing photosensitive resin, and more preferably. Is 10-30% equivalent. When the added amount is less than 5% equivalent, there is no effect in improving the solder resist characteristics. On the other hand, when the added amount exceeds 40% equivalent, the maximum development life is shortened and the dryness to touch is deteriorated.

Specific examples of the carboxyl group-containing photosensitive resin used in the present invention are shown by structural formulas below.
First, a polyfunctional cresol-novolak type epoxy resin is used as a component, lactic acid of lactic acid or a lactic acid oligomer, and acryloyloxyethoxyethyl isocyanate is used as an isocyanate compound containing one or more unsaturated groups in one molecule. When tetrahydrophthalic anhydride is used as the basic acid anhydride, it is considered that a carboxyl group-containing photosensitive resin as shown in the following formula can be obtained.

Also, using polyfunctional cresol-novolak type epoxy resin, lactic acid among lactic acid or lactic acid oligomer, (meth) acrylic acid as unsaturated group-containing monobasic acid or monobasic acid anhydride, tetrahydro anhydride as polybasic acid anhydride When phthalic acid is used, it is considered that a carboxyl group-containing photosensitive resin as shown in the following formula is obtained.

Furthermore, using polyfunctional cresol-novolak type epoxy resin, lactic acid among lactic acid or lactic acid oligomer, methacrylic anhydride as unsaturated group-containing monobasic acid or monobasic acid anhydride, tetrahydrophthalic anhydride as polybasic acid anhydride When is used, it is considered that a carboxyl group-containing photosensitive resin as shown in the following formula is obtained.

Note that the total number of j to l, the total number of m and o, and the total number of p to s shown in each structural formula are less than or equal to the number of cyclic ether groups used. -Components for novolak type epoxy resin, lactic acid or lactic acid oligomer, isocyanate compound containing one or more unsaturated groups in one molecule, or unsaturated group-containing monobasic acid or monobasic acid anhydride, polybasic acid anhydride It can be arbitrarily adjusted according to the reaction ratio.

The acid value of the carboxyl group-containing photosensitive resin is preferably in the range of 20 to 150 mgKOH / g, more preferably in the range of 20 to 100 mgKOH / g. If the acid value of the carboxyl group-containing photosensitive resin is less than 20 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 150 mgKOH / g, dissolution of the exposed area by the developer proceeds, so the line may be thinner than necessary. In some cases, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to form a normal resist pattern. In particular, when the acid value of the carboxyl group-containing photosensitive resin of the present invention is 60 to 120 mg KOH / g, a faster development speed can be obtained than a general-purpose carboxyl group-containing photosensitive resin having the same acid value, and the through hole developability is improved. To be advantageous. In addition, when the acid value of the carboxyl group-containing photosensitive resin is 20 to 60 mg KOH / g, it is difficult to develop with a general-purpose photosensitive carboxyl group-containing resin having the same acid value, and the shape of the exposed portion is not clean, Although an undeveloped residue tends to remain in the film part, in the case of the carboxyl group-containing photosensitive resin of the present invention, a result exceeding the expectation that development can be performed without any problem can be obtained.

The representative examples (1) to (4) of the photosensitive resin not containing a carboxyl group and the carboxyl group-containing photosensitive resin have excellent characteristics, respectively. In view of this balance, the carboxyl group-containing photosensitive resin (3) is particularly preferred.
In the case of the photosensitive resins (1) and (2) above, other general-purpose carboxyl group-containing resins are added to impart alkali developability, but the carboxyl groups of (3) and (4) above. A contained photosensitive resin may be added as a carboxyl group-containing resin.

Examples of the compound having a plurality of cyclic ether groups in one molecule used for the synthesis of the photosensitive resin not containing the carboxyl group and the carboxyl group-containing photosensitive resin include various known and conventional epoxy resins such as bisphenol A type epoxy resins, Bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin , Glycidyl ether compounds such as brominated phenol novolac epoxy resin and bisphenol A novolac epoxy resin; terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Glycidyl ester compounds such as diglycidyl ester, dimer acid; triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidyl metaxylenediamine, N, N, N ′, N′-tetraglycidyl bisaminomethylcyclohexane A glycidylamine compound such as N, N-diglycidylaniline can be used. Among these, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are preferable because they can provide a cured coating film having high sensitivity and excellent heat resistance. Furthermore, a cresol novolac type epoxy resin having a softening point of 60 ° C. or higher is more preferable because it is excellent in dryness to touch. These polyfunctional epoxy compounds can be used alone or in combination of two or more.

The lactic acid or lactic acid oligomer used for the synthesis of the photosensitive resin not containing a carboxyl group and the carboxyl group-containing photosensitive resin may be any of D-form, L-form or DL-form, and naturally-occurring lactic acid derivatives. As a commercially available product, Musashino Lactic Acid (registered trademark) F manufactured by Musashino Chemical Laboratory can be used. Moreover, you may use the lactic acid oligomer which carries out dehydration condensation between molecules and has a moderate repeating structure.

As an isocyanate compound containing one or more unsaturated groups in one molecule used for the synthesis of the photosensitive resin not containing the carboxyl group and the carboxyl group-containing photosensitive resin, one isocyanate group in one molecule and There is no particular limitation as long as it is an isocyanate compound having one or more ethylenically unsaturated groups. Specific examples include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, and modified products thereof. Commercially available products include “Karenz MOI” (methacryloyloxyethyl isocyanate), “Karenz AOI” (acryloyloxyethoxyethyl isocyanate), “Karenz MOI-EG” (methacryloyloxyethoxyethyl isocyanate), “Karenz MOI BM” (Karenz MOI isocyanate block), “Karenz MOI-BP” (Karenz MOI isocyanate block), and “Karenz BEI” (1,1-bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa Denko KK ing. These trade names are registered trademarks. Furthermore, a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, etc. Can be used. These compounds can be used alone or in combination of two or more.

Examples of the unsaturated group-containing monobasic acid or monobasic acid anhydride used in the synthesis of the photosensitive resin containing no carboxyl group and the carboxyl group-containing photosensitive resin include acrylic acid, methacrylic acid, acrylic acid anhydride, and methacrylic acid. An anhydride etc. are mentioned, These can be used individually or in combination of 2 or more types.

Polybasic acid anhydrides used for the synthesis of the carboxyl group-containing photosensitive resin include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3, 6 -Cycloaliphatic dibasic anhydrides such as endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl anhydride Aliphatic or aromatic dibasic acid anhydrides such as succinic acid, phthalic anhydride, trimellitic anhydride, or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclo Pentane tetracarbo Acid dianhydride, pyromellitic acid anhydride, an aliphatic or aromatic tetracarboxylic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride and the like, can be used one or two or more of these.

Examples of the compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, and 3-hydroxypropyl (meth) acrylate. Glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether or glycidyl (meta ) Epoxy group-containing ethylenically unsaturated monomers such as acrylates can be mentioned, and these can be used alone or in combination of two or more. Among such epoxy-containing ethylenically unsaturated monomers in one molecule, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl methacrylate are particularly preferred. It is preferable because it has moderate productivity and photocurability.

The weight average molecular weight of the photosensitive resin and the carboxyl group-containing photosensitive resin varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 50,000, more preferably in the range of 5,000 to 200,000. It is. If the weight average molecular weight is less than 2,000, the tack-free performance (touch-drying property) of the coating film may be inferior, the moisture resistance of the coating film after exposure is poor, film loss occurs during development, and the resolution is low. It may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 50,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The double bond equivalent of the photosensitive resin and the carboxyl group-containing photosensitive resin is preferably 100 g / equivalent or more and 1000 g / equivalent or less. It is preferable that the double bond equivalent is 200 g / equivalent or more and 600 g / equivalent or less because the photocurability is improved. Moreover, from the point which makes flexibility more favorable, as for a double bond equivalent, 300 g / equivalent or more is more preferable, and 450 g / equivalent or more is further more preferable.

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

Furthermore, in addition to the above-described photosensitive resin not containing a carboxyl group and a carboxyl group-containing photosensitive resin, a known and commonly used carboxyl group-containing resin can be used in combination. For example, a carboxyl group-containing resin having poor developability and the above-mentioned photosensitive resin not containing a carboxyl group and a carboxyl group-containing photosensitive resin, in particular, the photosensitive resin or carboxyl group-containing photosensitive resin described in (1) to (4) above. By using together, it becomes possible to improve developability significantly, without deteriorating the various characteristics of a solder resist. In addition, when using only the photosensitive resin which does not contain a carboxyl group, in order to make the composition developable with an alkaline aqueous solution, it is necessary to use such a carboxyl group-containing resin together.

As specific examples of such a carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are preferable.
(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.
(5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
(6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.
(7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.
(8) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(9) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acrylic groups in one molecule to the resins (1) to (8).
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

These carboxyl group-containing resins can be used without being limited to those listed above, and can be used singly or in combination. Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
Moreover, the suitable range of the acid value and weight average molecular weight of the said carboxyl group containing resin is the same as the said carboxyl group containing photosensitive resin, and the reason is also the same. Further, the blending amount of such a carboxyl group-containing resin is 20 to 80% by mass, preferably as the total amount of the photosensitive resin not containing a carboxyl group and the carboxyl group-containing photosensitive resin in the entire composition. A range of 30 to 60% by mass is appropriate.

Examples of the photopolymerization initiator include an oxime ester photopolymerization initiator having a group represented by the following general formula (II), and an α-aminoacetophenone photopolymerization initiator having a group represented by the following general formula (III). It is preferable to use at least one photopolymerization initiator selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (IV).

In the formula, R ⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁵ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). It may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ¹⁰ and R ¹¹ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group Wherein one of R ¹⁰ and R ¹¹ may represent a R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V): The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

In the formula, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹³ and R ¹⁵ are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). Optionally substituted with 1 to 6 alkyl groups or phenyl groups).

In the formula, R ¹⁶ , R ¹⁷ and R ²² each independently represents an alkyl group having 1 to 12 carbon atoms,
R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
x and y each independently represents an integer of 0 to 5.

Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, and N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

Examples of the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. And oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

The amount of such photopolymerization initiator is such that the photosensitive resin does not contain a carboxyl group and / or 100 parts by mass of a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin (if two or more types are used, those The range of 0.01 to 30 parts by weight, preferably 0.5 to 15 parts by weight, is appropriate for the total amount). When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. . On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes violent and the deep-part curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (II), the blending amount thereof is a photosensitive resin not containing the carboxyl group and / or a carboxyl group-containing photosensitive resin or a carboxyl group. The amount is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the contained resin (the total amount when two or more types are used).

Other photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photocurable thermosetting resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketals. Examples thereof include compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenones such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Contained coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA, Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, International Bio-Synthetics), 4-dimethylaminobenzoic acid n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid (Van Dyk) Esol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
As a compounding quantity of such a thioxanthone compound, the photosensitive resin which does not contain the said carboxyl group, and / or 100 mass parts of carboxyl group-containing photosensitive resin or carboxyl group-containing resin (when using 2 or more types, those totals are included. The ratio is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to the amount). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, among which a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. A dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a color pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of such a tertiary amine compound is such that the photosensitive resin does not contain a carboxyl group and / or 100 parts by mass of a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin (if two or more types are used, The total amount is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such a photopolymerization initiator, photoinitiator auxiliary, and sensitizer is 100 parts by mass of the photosensitive resin not containing a carboxyl group and / or a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin (two types). When using the above, it is preferable that the total amount is 35 mass parts or less. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

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

Further, the polyfunctional mercaptan-based compound is not particularly limited. For example, fat such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc. Aromatic thiols such as aromatic thiols, xylylene dimercaptan, 4,4'-dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercapto acetate), polyethylene glycol bis (mercapto acetate), propylene glycol bis (Mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tet Poly (mercaptoacetate) polyhydric alcohols such as kiss (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohol such as erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, And poly (mercaptobutyrate) s such as 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate).

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

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

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

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

A thermosetting component can be added to the solder resist composition of the present invention to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. A curable resin can be used. Particularly preferred is a thermosetting compound having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter, abbreviated as “cyclic (thio) ether groups”) in the molecule.

Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule The compound which has this, ie, an episulfide resin etc. are mentioned.

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

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

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

The compounding amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is 1 equivalent of the carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin (when two or more kinds are used). Is in the range of preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 2 equivalents with respect to the total amount thereof. When the compounding amount of thermosetting components having multiple cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in decreased heat resistance, alkali resistance, electrical insulation, etc. Therefore, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

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

The compounding amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, the above-mentioned carboxyl group-containing photosensitive resin or carboxyl group-containing resin or thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass (when two or more types are used, the total amount thereof).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The compounding amount of the urethanization catalyst is sufficient in the usual quantitative ratio, for example, the photosensitive resin not containing the carboxyl group and / or the carboxyl group-containing photosensitive resin or the carboxyl group-containing resin 100 parts by mass (two or more kinds). Is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to the total amount thereof.

Furthermore, a melamine derivative, a benzoguanamine derivative or the like can be added as a thermosetting component to the solder resist composition of the present invention. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (manufactured by Sanwa Chemical Co., Ltd.).
The said thermosetting component can be used individually or in combination of 2 or more types.

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

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

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

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: 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.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

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

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

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

The blending ratio of the colorant as described above is not particularly limited, but the photosensitive resin not containing the carboxyl group and / or the carboxyl group-containing photosensitive resin or the carboxyl group-containing resin 100 parts by mass (two or more are used). In some cases, the total amount is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass.

The solder resist composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, at least one selected from the group consisting of known and commonly used inorganic fillers and organic fillers can be used, but inorganic fillers, particularly barium sulfate, spherical silica and talc are preferably used. Furthermore, it is good also as a white resist by adding a titanium oxide as a white filler. Further, in order to further impart flame retardancy, metal oxide fine particles may be added, and specific examples include aluminum hydroxide, magnesium hydroxide, boehmite and the like. These fillers can be blended alone or in combination of two or more.

The amount of these fillers is based on 100 parts by weight of the photosensitive resin not containing a carboxyl group and / or a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin (the total amount when two or more types are used). The amount is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass. When the blending amount of the filler exceeds 300 parts by mass, the viscosity of the solder resist composition is increased, the printability is lowered, and the cured product becomes brittle, which is not preferable.

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

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

Furthermore, the photosensitive composition of the present invention is applied to a substrate or a carrier film for the synthesis of a photosensitive resin not containing a carboxyl group, a carboxyl group-containing photosensitive resin or a carboxyl group-containing resin, or preparation of a composition. In order to adjust the viscosity, an organic solvent can be used.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the solder resist composition of the present invention has a feature to prevent oxidation. , Radical scavengers that invalidate the generated radicals and / or antioxidants such as peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals can do.

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

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

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

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

In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the solder resist composition of the present invention has, in addition to the above-mentioned antioxidant, to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.

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

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

The solder resist composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thixotropic agents such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, silicone-based, fluorine-based, Known and commonly used additives such as a defoaming agent and / or a leveling agent such as a polymer, a silane coupling agent such as an imidazole, a thiazole, and a triazole, and a rust preventive can be blended.

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

The solder resist composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A tack-free coating film can be formed by coating by a method such as a coating method and volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and making it dry and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (eg, 0.3 A resist pattern is formed by development with a 3% sodium carbonate aqueous solution). Further, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group-containing photosensitive resin and / or the carboxyl group-containing resin has a plurality of cyclic ether groups and / or in the molecule. A thermosetting component having a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

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

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

After applying the photocurable resin composition of the present invention and evaporating and drying as follows, the resulting coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As an exposure apparatus used for the active energy ray irradiation, an ultraviolet exposure apparatus equipped with a high-pressure mercury lamp or a metal halide lamp or a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a CAD data from a computer) is used. Can do. The active energy ray may be any one of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gas laser, a solid state laser, and a semiconductor laser as long as light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 800 mJ / cm ² , preferably 10 to 500 mJ / cm ² , more preferably 10 to 300 mJ / cm ² .

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

The solder resist composition of the present invention is used in the form of a dry film having a solder resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance, in addition to a method of directly applying the solder resist composition to a substrate in liquid form. You can also The case where the solder resist composition of this invention is used as a dry film is shown below.

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

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying the solder resist composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater or the like, and then drying it.
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

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

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples do not limit the present invention, and all modifications may be made without departing from the spirit of the present invention. It is included in the technical scope of the present invention. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

Resin synthesis example 1
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after the inside of the system was replaced with an air atmosphere, 221 g of diethylene glycol monoethyl ether acetate, 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) 148 g (1.05) was obtained. The reaction mixture was reacted at 85 ° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution had disappeared. Furthermore, 122 g (0.8 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 90.4 mgKOH / g and a solid content of 64%. . The double bond equivalent of the solid content was 545, and the lactic acid content was 16%. This is designated as resin varnish A′-1.

Resin synthesis example 2
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after replacing the inside of the system with an air atmosphere, 199 g of diethylene glycol monoethyl ether acetate, acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) 148 g (1.05) was obtained. The reaction mixture was reacted at 85 ° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution had disappeared. Further, 83.6 g (0.55 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 69.9 mgKOH / g and a solid content of 64%. Obtained. The solid double bond equivalent was 507, and the lactic acid content was 17%. This is designated as resin varnish A′-2.

Resin synthesis example 3
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after the inside of the system was replaced with an air atmosphere, 237 g of diethylene glycol monoethyl ether acetate, 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) 148 g (1.05) was obtained. The reaction mixture was reacted at 85 ° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution had disappeared. Furthermore, 122 g (0.8 mol) of tetrahydrophthalic anhydride was charged and reacted at 110 ° C. for 3 hours. Further, 28.4 g (0.2 mol) of glycidyl methacrylate was added and reacted at 115 ° C. for 4 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 72.6 mgKOH / g and a solid content of 64%. . The solids double bond equivalent was 479 and the lactic acid content was 15%. This is designated as resin varnish A′-3.

Resin synthesis example 4
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after replacing the inside of the system with an air atmosphere, 181 g of diethylene glycol monoethyl ether acetate, 148 g (1.05) of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) was obtained. The reaction mixture was reacted at 85 ° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution had disappeared. Further, 51.7 g (0.34 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 49.0 mgKOH / g and a solid content of 64%. Obtained. The double bond equivalent of the solid content was 477, and the lactic acid content was 18%. This is designated as resin varnish A′-4.

Resin synthesis example 5
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after replacing the inside of the system with an air atmosphere, 169 g of diethylene glycol monoethyl ether acetate, 148 g (1.05) of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) was obtained. The reaction mixture was reacted at 85 ° C. for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution had disappeared. Further, 30.4 g (0.20 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 3 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 28.6 mgKOH / g and a solid content of 64%. Obtained. The solid double bond equivalent was 457, and the lactic acid content was 19%. This is designated as resin varnish A′-5.

Intermediate synthesis example 1
A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 1000 g of 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) (10 moles as lactic acid), and nitrogen was blown into the flask. While raising the temperature to 120 ° C., the reaction was carried out for 11 hours while removing the contained water and the desorbed water due to intermolecular dehydration esterification of lactic acid as needed to obtain a resin solution having an acid value of 207 mgKOH / g. This is designated as lactic acid oligomer intermediate X-1.

Resin synthesis example 6
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 147 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), lactic acid oligomer intermediate (X-1) 216 g (0.8 mol), acrylic acid 14.4 g (0.2 mol), di-t-butylhydroxytoluene 2.21 g and hydroquinone 0. 22 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.68 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. in an air atmosphere, and the reaction was performed for 8 hours. Subsequently, 281 g of diethylene glycol monoethyl ether acetate and 106 g (0.75 mol) of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) were charged into the resulting reaction solution at 3 ° C. for 3 hours. A time reaction was performed, and it was confirmed by an infrared spectrophotometer that the peak (2270 cm ⁻¹ ) of the isocyanate group in the solution disappeared. Further, 152 g (1.0 mol) of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 4 hours to obtain a carboxyl group-containing photosensitive resin solution having a solid content acid value of 89.3 mgKOH / g and a solid content of 62%. . The double bond equivalent of the solid content was 736, and the lactic acid content was 31%. This is designated as resin varnish A′-6.

Resin synthesis example 7
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 111 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), DL-lactic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 90%) 50.0 g (0.5 mol as lactic acid), methacrylic anhydride (manufactured by Degussa Japan, molecular weight 154) 77.0 g (0.5 mol), 1.67 g of di-t-butylhydroxytoluene and 0.17 g of hydroquinone were charged and heated to 100 ° C. to uniformly dissolve. Next, 1.27 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. in an air atmosphere, and the reaction was performed for 10 hours while removing the contained water from the system as needed. Subsequently, 88.2 g (0.58 mol) of tetrahydrophthalic anhydride and 126 g of diethylene glycol monoethyl ether acetate were charged into the obtained reaction solution, and the reaction was performed at 110 ° C. for 6 hours. The solid content acid value was 101 mgKOH / g, A carboxyl group-containing photosensitive resin solution having a solid content of 64% was obtained. The double bond equivalent of the solid content was 421, and the lactic acid content was 11%. This is designated as resin varnish A′-7.

Resin synthesis example 8
In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and cresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-680, softening point 82 ° C., epoxy equivalent 211) 211 g (1.0 mol), 90% lactic acid (manufactured by Musashino Chemical Laboratory, Musashino lactic acid 90F, purity 90%) 100 g (1.0 mol as lactic acid), 1.51 g of di-t-butylhydroxytoluene and hydroquinone 0.15 g was charged and heated to 100 ° C. to dissolve uniformly. Next, 1.14 g of triphenylphosphine was charged, the temperature was raised to 110 ° C. while blowing nitrogen, and the reaction was carried out for 10 hours while removing the contained water from the system as needed. Subsequently, after the inside of the system was replaced with an air atmosphere, 152 g of diethylene glycol monoethyl ether acetate, 148 g (1.05) of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI, molecular weight 141) was obtained. Mol) was prepared and reacted at 85 ° C. for 3 hours. The infrared spectrophotometer confirmed that the peak of the isocyanate group (2270 cm ⁻¹ ) in the solution disappeared, and the solid content acid value 12.7 mgKOH / g, A photosensitive resin solution having a solid content of 64% was obtained. The double bond equivalent of the solid content was 429, and the lactic acid content was 20%. This is called resin varnish A-1.

Resin varnish C-1:
A carboxyl group-containing cresol novolac epoxy acrylate (UNIDIC R-2000, solid content acid value 84.3 mgKOH / g, solid content 64%, solid content double bond equivalent 367) manufactured by DIC Corporation was used.

Resin varnish C-2:
A carboxyl group-containing modified cresol novolac epoxy acrylate (DICLITE UE-9210, solid content acid value 82.9 mgKOH / g, solid content 62%, solid content double bond equivalent 361) manufactured by DIC Corporation was used.

Examples 1 to 14 and Comparative Examples 1 and 2
Using the resin varnish prepared in the above resin synthesis example, the various components shown in Table 1 are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and soldered. A photosensitive resin composition for resist was prepared. It was 15 micrometers or less when the dispersion degree of the photosensitive resin composition obtained here was evaluated by the particle size measurement by the grindometer by Eriksen.

Remarks:
* 1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Japan)
* 2: 2,4-Diethylthioxanthone (KAYACURE DETX-S: Nippon Kayaku Co., Ltd.)
* 3: 2- (acetyloxyiminomethyl) thioxanthen-9-one * 4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- ( 0-acetyloxime) (Irgacure OXE 02: manufactured by Ciba Japan)
* 5: Dipentaerythritol pentaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.)
* 6: Modified novolac epoxy resin (EPICLON N-865: manufactured by DIC Corporation)
* 7: Tris (2,3-epoxypropyl) isocyanurate (TEPIC-HP: manufactured by Nissan Chemical Industries)
* 8: C.I. I. Pigment Blue 15: 3
* 9: C.I. I. Pigment Yellow 147
* 10: Barium sulfate B30, manufactured by Sakai Chemical Co., Ltd. * 11: Diethylene glycol monoethyl ether acetate * 12: Aromatic organic solvent (Ipsol 150, manufactured by Idemitsu Kosan Co., Ltd.)

Performance evaluation:
<Optimum exposure amount>
The photocurable thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was buffed, washed with water, dried, and heated at 80 ° C. It was dried for 60 minutes in a circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp and a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, and development (30 ° C., 0.2 MPa, 1 wt. % Sodium carbonate aqueous solution) was carried out in 60 seconds, and the optimum exposure dose was when the remaining step tablet pattern was 7 steps.

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

<Developability of through hole>
A 1.0 mmt copper-clad laminate was drilled with a 200 μm drill, and through-hole plating was performed by a conventional method to prepare a substrate on which 400 through-holes having a measured value of approximately 150 μm were formed. The substrate was filled with the photocurable thermosetting resin composition by printing the photocurable thermosetting resin compositions of the Examples and Comparative Examples twice on the substrate by screen printing, and filling the hole with 80 ° C. It dried for 30 minutes with the hot-air circulation type drying furnace, and cooled to room temperature. Thereafter, development was carried out for 120 seconds under the condition of a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa, and evaluation was performed according to the following criteria.
◎: 100% through hole can be developed by developing once or twice ○: 100% through hole can be developed by developing 3 to 5 times △: By developing 3 to 5 times 50-99% through hole development possible ×: Through hole development rate of 50% or less even after 5 developments

<Resolution and resolution when through-hole development is possible>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was coated with the photocurable thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. , And dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. As the exposure pattern, a negative film was used in which lines of 20/30/40/50/60/70/80/90/100 μm were drawn in the space portion. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and heat cured at 150 ° C. for 60 minutes to obtain a cured coating film. The minimum residual line of the obtained cured coating film was determined using an optical microscope adjusted to a magnification of 200, and this was defined as resolution.
Moreover, the same test as described above was performed for the photocurable thermosetting resin compositions of the respective examples and comparative examples at a time during which the through hole can be developed. The minimum remaining line of the obtained cured coating film was similarly determined using an optical microscope adjusted to a magnification of 200 times, and this was defined as the resolution when through-hole development was possible. In addition, if all the lines have been developed, they will be marked as-.

<Maximum development life>
The composition of each example and comparative example was applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C., taken out every 10 minutes from 20 to 80 minutes, and allowed to cool to room temperature. did. The substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

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

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.
○: No change is observed Δ: Only a slight change ×: The coating film swells or swells and falls off

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

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

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

<Electrical characteristics>
Using an IPC B-25 comb-type electrode B coupon instead of the copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No change at all △: Only a slight change ×: Migration has occurred

Examples 15 to 21 and Comparative Example 3
<Dry film evaluation>
The compositions of Examples 1 to 7 and Comparative Example 1 shown in Table 1 were diluted with methyl ethyl ketone, applied onto a PET film and dried at 80 ° C. for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. did. Further, a cover film was laminated thereon to produce a dry film, which were designated as Example 15-21 and Comparative Example 3, respectively. Thereafter, the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the coating film property evaluation of the examples. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then heat-cured with a hot air dryer at 150 ° C. for 60 minutes to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.

As is apparent from the results shown in Tables 2 and 3, the solder resist composition of the present invention has excellent developability and through-hole developability as compared with conventional solder resist compositions, and the conventional Compared with various characteristics of solder resists using general-purpose carboxyl group-containing resins, it is clear that they have equivalent characteristics, which is very useful.

Claims

A solder comprising a photosensitive resin having a structure represented by the following general formula (I) and having at least one ethylenically unsaturated group in the molecule, a photopolymerization initiator, and a carboxyl group-containing resin. Resist composition.

(In the formula, n represents an integer of 1 to 99.)
The photosensitive resin reacts a compound having a plurality of cyclic ether groups in one molecule with a compound having at least a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group after reacting lactic acid or a lactic acid oligomer. The solder resist composition according to claim 1, wherein the solder resist composition is a photosensitive resin obtained.
A solder resist composition comprising a carboxyl group-containing photosensitive resin having a structure represented by the following general formula (I) and having at least one ethylenically unsaturated group in the molecule, and a photopolymerization initiator: object.

(In the formula, n represents an integer of 1 to 99.)
The carboxyl group-containing photosensitive resin has at least a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group after reacting lactic acid or a lactic acid oligomer with a compound having a plurality of cyclic ether groups in one molecule. The solder resist composition according to claim 3, which is a carboxyl group-containing resin obtained by reacting a compound and further reacting with a polybasic acid anhydride.
A dry film obtained by applying and drying the solder resist composition according to any one of claims 1 to 4 on a film.
The hardened | cured material obtained by photocuring or further heat-curing the dry film obtained by apply | coating and drying this soldering resist composition on a film, or the soldering resist composition as described in any one of the said Claim 1 to 4 .
A printed wiring board having the cured product according to claim 6.