TWI581060B - A photosensitive resin composition and a cured product thereof, and a hardened product thereof, a printed circuit board having a solder resist layer - Google Patents

Description

Printed circuit substrate having a solder resist layer formed of a photosensitive resin composition, a cured product thereof, and a cured product thereof

The present invention relates to a colored photosensitive resin composition. More specifically, the present invention provides a photosensitive resin composition having excellent coloring power and resolution, which has excellent releasability to mask a poor appearance of a circuit and the like, and has a high-resistance solder resist layer.

The alkali-developable photosensitive composition is used in a large amount as a solder resist for a printed wiring board. The solder resist is an object having a circuit for protecting a printed substrate, etc., but its coloring power is an important characteristic that greatly affects the appearance of the printed wiring board or the concealability of the circuit.

That is, when the coloring power of the solder resist is insufficient, the copper circuit formed on the printed wiring board is contaminated, or the yield of the printed wiring board is remarkably lowered due to extremely remarkable discoloration. In addition, the mounting steps of the process after the recent printing of the wiring board have been automated, and the components are mounted by the machine, so that it is difficult to identify the solder resist and the copper circuit when the image is recognized. This phenomenon also causes the same problem at the time of the final inspection of the AOI (Automatic Optical Inspection) of the printed wiring board. question.

Currently, the commercially available solder resists vary depending on the film thickness or the pretreatment of the copper of the substrate, but when expressed by the CIE L*a*b* display, the green L* value is 40 to 60. a* value is -10 to -28, b* value is 6 to 18, blue L* value is 40 to 60, a* value is -10 to -28, b* value is -6 to -18, special When the L* value of green and blue is 40 to 50 at the same time, it is preferable from the viewpoint of AOI, and it is generally necessary to have the coloring power of this degree.

Further, in general, a photosensitive resist having a film thickness of about 20 μm and having a resolution of about 30 μm to 50 μm is commercially available. However, recently, these solder resists have not been able to achieve a sufficient hardening depth for a printed substrate having a high circuit thickness, so there is still a problem that a minute line cannot be formed. In general, since the solder resist is applied to a substrate on which a circuit is formed, the thickness of the resist has a correspondence with the thickness of the circuit. For example, when the thickness of the circuit is 35 μm, when the thickness of the solder resist is applied to the circuit by 20 μm, it can be formed between the circuits by about 30 to 35 μm, and when the thickness of the circuit is 70 μm, it is about 60 to 70 μm. Among them, even if a 50 μm resist line can be formed on a substrate having a circuit thickness of 35 μm, there is still a problem that an image of 100 μm cannot be formed on a substrate having a circuit thickness of 70 μm.

Recently, a wiring board for a member driven by a high voltage has an increasing thickness and a high density, and a solder resist which is suitable for high resolution of the substrate is required.

However, the anti-solder resist is generally a green coloring agent using phthalocyanine green and blue as an auxiliary color, but either of these coloring agents is used in purple. Since the outer region has a large absorption, when the amount is too large, the ultraviolet ray permeability is affected and good resolution cannot be obtained. Therefore, there is still practical difficulty in providing a photosensitive resin composition which can form a solder resist layer which satisfies both good concealability and high resolution.

[Patent Document 1] JP-A-2000-7974, the scope of application of the patent

The present invention has an object of providing a photosensitive resin composition capable of forming a solder resist layer having a high coloring power and excellent concealability and having a high aspect ratio.

As a result of intensive research, the present inventors have found that when the coloring agent is at least a photosensitive resin composition obtained by using an anthraquinone coloring agent, the above problems relating to analyzability in the conventional solder resist can be solved, and sufficient coloring can be obtained. The effect of force, thus completing the present invention.

That is, the present invention relates to a photosensitive resin composition characterized by containing (A-1) an anthraquinone-based coloring agent and (B) a carboxylic acid-containing resin.

One embodiment of the photosensitive resin composition of the present invention is a dye containing at least an anthraquinone coloring agent (A-1).

Further, in one embodiment of the photosensitive resin composition of the present invention, the pigment containing at least the anthraquinone coloring agent (A-1) is contained.

Further, in one embodiment of the photosensitive resin composition of the present invention, the color tone is green or orange.

Further, in one embodiment of the photosensitive resin composition of the present invention, the phthalocyanine-based coloring agent (A-2) is contained in addition to the lanthanoid coloring agent (A-1). / or other coloring agent.

Further, one embodiment of the photosensitive resin composition of the present invention is an alkali developable photoresist.

Further, in the present invention, in another embodiment, the photosensitive resin composition is applied onto a supported film and dried to obtain a dry film.

Further, in the present invention, the other embodiment is a cured product obtained by curing the photosensitive resin composition or the dry film on a substrate on which a circuit is formed.

Further, in the present invention, another embodiment is a printed circuit board having a solder resist layer obtained from the cured material on a substrate on which a circuit is formed.

The photosensitive resin composition having a high coloring power and excellent resolvability of the present invention can provide a solder resist layer which is required for a printed wiring board which is high in thickness and high in density. Highly analytical and excellent concealed solder resist layer.

Hereinafter, the present invention will be described in detail.

In the photosensitive resin composition of the present invention, the coloring agent is characterized in that the (A-1) anthraquinone-based coloring agent is used as the first component, and in one embodiment, the coloring matter obtained from the phthalocyanine-based coloring agent may be used. A green or orange photosensitive resin composition is present. Thus, the coloring agent of the present invention will first be described.

(A-1) lanthanide colorant

The photosensitive resin composition containing the lanthanide coloring agent (A-1) of the present invention The material can be imparted with high resolution to the conventional coloring photoresist, particularly the solder resist for printed wiring boards. The reason for this is that the conventionally used coloring agents are phthalocyanine-based pigments such as phthalocyanine green and phthalocyanine blue, and those obtained from ruthenium and Isoindoline-based yellow pigments. That is, the phthalocyanine system has a large absorption between 300 nm and 400 nm, and the yellow pigment has a large absorption in a long wavelength region (380 nm to 450 nm) having a relatively high permeability, so that the light generated by the light source cannot be sufficiently obtained. The bottom of the resist will cause a reduction in the depth of hardening.

Further, when the lanthanoid coloring agent is compared with the above coloring agent, it has less absorption in the ultraviolet ray region and has sufficient coloring power, and thus has high resolving power, so that a resist material such as a solder resist can be provided. A photosensitive resin composition which is required for heat resistance and electrical insulation.

In the present invention, a conventionally known substance may be used as the coloring agent, and any one of a pigment, a dye, and a coloring agent may be used, or two or more types may be used in combination. In the present invention, the term "pigment" refers to a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), and the dye is a compound classified as Solvent et al. (Solvent et al.), or Lumogen. (registered trademark) and other substances.

Among the lanthanide coloring agents, those indicated as green, yellow, orange, red, purple, ochre, etc., are marked with a color index (C.I.; The Society of Dyers and Colourists, Inc.) numbered as shown below.

- Green: Solvent Green 5

- Orange: Solvent Orange 55

- red: Solvent Red 135, 179; Pigment Red 123, 149, 166, 178, 179, 190, 194, 224;

- Purple: Pigment Violet 29

- Twilight: Pigment Black 31, 32

It is also possible to use an anthraquinone-based coloring agent other than the above, for example, Lumogen (registered trademark) F Yellow 083, Lumogen F Orange 240, Lumogen F Red305, Lumogen of BASF Corporation, which is known to have a color indexing number. F Green 850, etc., which has the same absorption in the ultraviolet region as the other lanthanide compounds and has high coloring power, can also be used in combination.

In the case of considering the coloring property and the ultraviolet ray absorption amount, the addition ratio of the oxime coloring agent is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0, based on 100 parts by mass of the carboxylic acid-containing resin described later. Parts by mass.

Among them, preferred as the lanthanoid coloring agent are Solvent Green 5, Solvent Orange 55, Solvent Red 135, Solvent Red 179, Lumogen (registered trademark), and the like, and particularly preferred is Solvent Green 5. The pigment is preferably Pigment Black31.

In the range which does not inhibit the object of the present invention, other coloring agents (any one of a pigment, a dye, and a coloring matter) other than the lanthanide may be contained in a desired amount, and the coloring agents are exemplified below. Among them, a mixture of a phthalocyanine coloring agent (A-2) and an anthraquinone coloring agent (A-1) is preferred.

(1) Blue colorant

The blue coloring agent is, for example, a phthalocyanine-based or an anthraquinone-based coloring agent, and a pigment is classified into a pigment (Pigment), and specifically, for example, a color index (CI; The Society of Dyers) And Colourists issued a number of compounds, etc.

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.

Dye systems can be used, for example

Solvent Blue 35, Solvent Blue 45, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. A phthalocyanine coloring agent substituted with or without a metal may be used in addition to the above.

(2) Green colorant

The green coloring agent has the same phthalocyanine system or lanthanide system. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 20, Solvent Green 28, or the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine-based coloring agent can also be used.

(3) yellow colorant

The yellow coloring agent has an anthraquinone, an isoindolinone type, a condensed azo type, a benzimidazolone type, a monoazo type, a bisazo type, etc., and a specific example is as follows. content.

(蒽醌系)

Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202;

(isoguanolinone)

Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;

(condensed azo)

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;

(benzimidazolone)

Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;

(monoazo)

Pigment Yellow1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183;

(double azo)

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

(4) Red colorant

The red coloring agent is, for example, a monoazo type, a bisazo type, a monoazo lake type, a benzimidazolone type, a diketopyrrolopyrrole type, a condensed azo type, an anthraquinone type, a quinophthalone type, etc. Specifically, for example, the contents exemplified below.

(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;

(double azo)

Pigment Red 37,38,41;

(single azo lake system)

Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1, 58:4, 63:1, 63:2, 64:1, 68;

(benzimidazolone)

Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;

(diketopyrrolopyrrole)

Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;

(condensed azo)

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;

(蒽醌系)

Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;

(quinacridone)

Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

For the purpose of adjusting other color tones, a coloring agent such as purple, orange, brown, or enamel may be added.

Specific examples are, for example, Pigment Violet 19, 23, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, and the like.

In the present invention, the addition ratio of the coloring agent may be added to the color tone required for the resistive resist layer formed by the obtained photosensitive resin composition or the cured film thereof, and specifically, it may be added to the green or orange color which can be exhibited. Full proportion.

In the present invention, the green and orange colors exhibited by the photosensitive resin composition or the cured film thereof mean that the color of the green and orange colors can be recognized by the observer when observed by the naked eye. Specifically, it is a Munsell color hue ring hue ring which is measured and displayed by the method specified in JIS Z8721 and shows the appearance color tone of the photosensitive resin composition and the cured film thereof. New basic color table series 2 Munsell system Japan Color Research Co., Ltd. issued; refer to Figure 1), 10Y to 10BG (green), 10R to 10YR (orange) hue range, more preferably chroma 2 or more , not up to 16, the brightness is 2 or more, less than 9, more preferably the chroma is 3 or more, less than 15, the brightness is 3 or more, less than 9 is less than the green, orange, etc. The color of the content.

The addition ratio of the quinone-based coloring agent (A-1) to other coloring agents is affected by the type of the coloring agent to be used or the type of other additives, and thus cannot be uniformly standardized, but can be appropriately set, for example, In comparison with the addition ratio of the phthalocyanine coloring agent (A-2), the oxime coloring agent (A-1): phthalocyanine coloring agent (A-2) = 1:0 to 1:20 in terms of mass ratio The ratio is added as well.

Next, each constituent component other than the coloring agent of the photosensitive resin composition of the present invention will be described in detail.

As the photosensitive resin composition of the present invention, a material as described below can be used.

(B) carboxylic acid-containing resin

In the composition of the present invention, when a purpose such as alkali developability is imparted, a carboxylic acid-containing resin (B) having a carboxyl group in a molecule can be used, and various conventionally known resin compounds can be used. In particular, the carboxylic acid-containing photosensitive resin (B') having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance. Further, the unsaturated double bond is preferably produced from acrylic acid or methacrylic acid or a derivative thereof.

Specific examples of the carboxylic acid-containing resin (B) are preferably the compounds listed below.

(1) A carboxylic acid-containing resin obtained by copolymerizing (meth)acrylic acid with an unsaturated group-containing material.

(2) combination of diisocyanate and dialohol containing carboxylic acid A carboxylic acid ester-containing urethane resin obtained by a polyaddition reaction of a compound and a diol compound.

(3) Photosensitive carboxylic acid-containing amine group obtained by polyaddition reaction of a diisocyanate with a bifunctional epoxy (meth) acrylate or a partial acid anhydride modified product thereof, a carboxylic acid-containing diol compound and a diol compound Formate resin.

(4) In the synthesis of the resin of the above (2) or (3), a terminal (meth)acrylated product obtained by adding one hydroxyl group to one or more compounds having a (meth)acryl group in the molecule A carboxylic acid urethane resin.

(5) In the synthesis of the resin of the above (2) or (3), a terminal (meth)acrylated product obtained by adding one isocyanate group to one or more compounds having a (meth)acryl group in the molecule A carboxylic acid-containing urethane resin.

(6) A photosensitive carboxylic acid-containing resin obtained by reacting a bifunctional and polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a diproton anhydride to a hydroxyl group present in a side chain.

(7) The polyfunctional epoxy resin obtained by epoxidation of the hydroxyl group of the bifunctional (solid) epoxy resin with epichlorohydrin is further reacted with (meth)acrylic acid, and the resulting hydroxyl group is further added to the diproton anhydride. Photosensitive carboxylic acid containing resin.

(8) A carboxylic acid-containing polyester resin obtained by reacting a bifunctional propylene oxide resin with a dicarboxylic acid to form a hydroxy group of a first-stage hydroxy group.

(9) The photosensitive resin-containing carboxy group obtained by further adding the above-mentioned resin to a compound having one epoxy group and one or more (meth)acrylic groups in one molecule Acid resin.

Further, in the present specification, the (meth) acrylate is an acryl, a methacrylate, and a collective term for these mixtures, and other similar expressions are also the same.

The carboxylic acid-containing resin (B) can be developed via a dilute aqueous alkali solution because the skeleton ‧ polymer has a plurality of free carboxyl groups in its side chain.

Further, the acid value of the carboxylic acid-containing resin (B) is preferably in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid value of the carboxylic acid-containing resin is less than 40 mgKOH/g, it is difficult to develop the alkali, and when it exceeds 200 mgKOH/g, since the developer promotes dissolution of the exposed portion, the line exceeding the necessity is narrowed. There is a possibility that the exposed portion and the unexposed portion cannot be distinguished and the developer is dissolved and peeled off at the same time, and the formation of a normal resist pattern cannot be formed, which is not preferable.

Further, the weight average molecular weight of the carboxylic acid-containing resin (B) varies depending on the resin skeleton, and is usually about 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the tackfree performance is deteriorated, so that the moisture resistance of the coating film after exposure is deteriorated, the film is reduced during development, and the resolution is largely deteriorated. Moreover, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is deteriorated.

The addition ratio of the carboxylic acid-containing resin (B) is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total composition. When it is less than the above range, it is not preferable because the film strength is lowered. Moreover, when it is more than the above range, since the viscosity is too high, the coating property may be lowered. Shape, but not good.

These carboxylic acid-containing resins are not limited to the above-mentioned uses, and they may be used alone or in combination of a plurality of them.

(C) Photopolymerization initiator

The photosensitive resin composition of the present invention is obtained by containing a photopolymerization initiator (C).

The photopolymerization initiator (C) is selected from the group consisting of an oxime ester photopolymerization initiator, an α-aminoethylbenzene photopolymerization initiator, and a mercaptophosphine oxide photopolymerization initiator. One or more kinds of photopolymerization initiators are preferred.

The oxime ester photopolymerization initiator is commercially available, for example, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by Ciba Specialty Chemicals Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., and the like. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.

α-Aminoethyl benzene-based photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl-2-di Methylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoethyl benzene, and the like. Commercially available products include IRGACURE 907, IRGACURE 369, IRGACURE 379, etc., manufactured by Ciba Specialty Chemicals.

Mercaptophosphine oxide photopolymerization initiator, for example, 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis(2,4,6-trimethylphenylhydrazine)-phenylphosphine oxide , bis(2,6-dimethoxybenzoquinone)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are, for example, RUSIRIN TPO (trade name) manufactured by BASF Corporation, IRGACURE 819 manufactured by Ciba Specialty Chemicals Co., Ltd., and the like.

The addition ratio of the photopolymerization initiator (C) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (B). When the amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated, which is not preferable. When the amount is more than 30 parts by mass, the surface of the anti-solder resist coating film of the photopolymerization initiator (C) has a strong light absorption, so that the deep hardenability tends to be lowered, which is not preferable.

In addition, in the case of the oxime ester-based photopolymerization initiator, the addition ratio is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (B). It is better.

Further, in the photosensitive resin composition of the present invention, a photopolymerization initiator other than the above compounds, or a photoinitiator auxiliary agent and a sensitizer, for example, a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantane can be used. A thioxanthone compound, a ketal compound, a benzophenone compound, a thioxanthone compound, a tertiary amine compound, and the like.

Specific examples of the benzoin compound are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Specific examples of the acetophenone compound, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenyl acetophenone, 1, 1-Dichloroethyl benzene benzene.

Specific examples of the hydrazine compound include, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, and 1-chlorohydrazine.

Specific examples of the thioxanthone compound, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthene ketone.

Specific examples of the ketal compound are, for example, acetophenone ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound, for example, benzophenone, 4-phenylindole diphenyl sulfide, 4-benzoquinone-4'-methyldiphenyl sulfide, 4-benzoquinone-4'- Ethyl diphenyl sulfide, 4-phenylhydrazine-4'-propyl diphenyl sulfide.

Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (NISOKIYUA MABP, manufactured by Nippon Soda Co., Ltd.) )), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminobenzophenone, 7-(diethylamino)-4 a 2-alkylamino group-containing oxalicin compound such as methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylloxacin), 4 -Ethyl dimethylamino benzoate (KAYAKIYU EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB, manufactured by International Microbiological Technology Co., Ltd.), 4-dimethylamino benzoic acid (n-butoxy)ethyl (Quantacure BEA, manufactured by International Microbiological Technology Co., Ltd.), p-dimethylamino benzoic acid isoamyl ethyl ester (KAYAKIYU DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino group 2-ethylhexyl benzoate (Esolol 507, manufactured by Van Dyk), 4,4'-diethylaminobiphenyl Ketone (EAB made by Baotu Valley Chemical Co., Ltd.).

Among the above, it is preferred to use a thioxanthone compound and a tertiary amine compound. When the thioxanthone compound is contained, it is preferable from the viewpoint of deep hardenability and the like, among which 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthene A thioxanthone compound such as a ketone or a 2,4-diisopropylthioxanthone is preferred.

The addition ratio of the thioxanthone compound is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less based on 100 parts by mass of the carboxylic acid-containing resin (B). When the addition ratio of the thioxanthone compound is too large, the thick film hardenability is lowered, which is also disadvantageous because it causes an increase in cost.

a tertiary amine compound, preferably a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound having a maximum absorption wavelength of 350 to 410 nm contains a dialkylamine group The oxalin compound is optimal. The dialkylaminobenzophenone compound, for example, 4,4'-diethylaminobenzophenone, is preferred because it is also less toxic. The herbicidal compound containing a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm has a color absorption of less color, and forms a photosensitive composition having colorless transparency, which is colored for use. In the case of the agent, the color of the body of the colorant can be reacted, and a colored solder resist film can be provided. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect with respect to laser light having a wavelength of 400 to 410 nm. .

The addition ratio of the third-grade amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (B). The addition rate of the tertiary amine compound is less than 0.1 mass. In the case of a portion, there is a tendency that a sufficient sensitizing effect is not obtained. When the amount is more than 20 parts by mass, a strong light absorption is formed on the surface of the dry solder resist coating film due to the tertiary amine compound, and the deep hardenability tends to be lowered.

These photopolymerization initiators, photoinitiator adjuvants, and sensitizers may be used singly or in combination of two or more types.

(D) a compound having two or more ethylenically unsaturated groups in the molecule

The photosensitive resin composition of the present invention is obtained by containing the compound (D) having two or more ethylenically unsaturated groups in the molecule.

The compound (D) having two or more ethylenically unsaturated groups in the molecule is photohardened by irradiation with an active energy ray to help the formation of the carboxylic acid-containing resin (B) insolubilize or insolubilize the aqueous alkali solution. Compound. Such compounds, such as diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; hexane diol, trimethylolpropane, pentaerythritol, dipentaerythritol, three a polyhydric alcohol such as a hydroxyethyl tripolyisocyanate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and the like Polyol acrylates such as phenolic ethylene oxide adducts or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, three a polyvalent acrylate such as glycidyl ether such as glycidyl tripolyisocyanate; and melamine acrylate; and/or each methacrylate corresponding to the above acrylate.

In addition, a polyfunctional epoxy such as a cresol novolak type epoxy resin a resin, an epoxy acrylate resin obtained by reacting with acrylic acid, or a hydroxyl group of the epoxy acrylate resin, a hydroxy acrylate such as pentaerythritol triacrylate or a diisocyanate such as isophorone diisocyanate. The epoxy urethane acrylate compound obtained by reacting a carbamide compound or the like. These epoxy acrylate-based resins can improve photocurability without causing a decrease in finger-drying property.

The addition ratio of the compound (D) having two or more ethylenically unsaturated groups in the above-mentioned molecules is preferably from 5 to 100 parts by mass, more preferably from 100 to 100 parts by mass, based on 100 parts by mass of the above-mentioned (B) carboxylic acid-containing resin. The ratio of 1 to 70 parts by mass. When the addition ratio is less than 5 parts by mass, the photocurability is lowered, and the alkali development after irradiation with the active energy ray is not easy to form a pattern, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered, and the coating film is brittle, which is also undesirable.

(E) thermosetting ingredients

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

The thermosetting component (F) having two or more cyclic (thio)ether groups in the molecule, a cyclic ether group having a ring of 3, 4 or 5 members in the molecule, or a cyclic thioether group One or a compound having two or more kinds of two types of groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1) having at least 2 in the molecule More than one propylene oxide-based compound, that is, a polyfunctional propylene oxide compound (E-2), a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (E) -3) Wait.

The above-mentioned polyfunctional epoxy compound (E-1), for example, Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 manufactured by Dainippon Ink and Chemicals Co., Ltd., manufactured by Toho Chemical Co., Ltd. EpotootoYD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664, made by Dow Chemical Company, Araldite 6071, Araldite6084, AralditeGY250, AralditeGY260, Sumitomo Chemical Industry Co., Ltd. - Epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. by Asahi Kasei Industrial Co., Ltd. (all are trade names) Bisphenol A type epoxy resin; Epikote YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon 165, Epotooto YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Ltd. Araldite 8011 manufactured by Ciba Specialty Chemical Company, Smith-Epoxy ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd., ESB-700, AER711 manufactured by Asahi Kasei Industrial Co., Ltd. Brominated epoxy resin such as AER714 (both trade names); Epikote 152, Epikote 154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., and Epiclon N-730 manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epiclon N-770, Epiclon N-865, Dongdu Huacheng The company's Epotooto YDCN-701, YDCN-704, Ciba Specialty Chemicals' Araldite ECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307, Nippon Chemical Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, ST-Epoxy ESCN-195X manufactured by Sumitomo Chemical Industries Co., Ltd., ESCN-220, AERECN-235, ECN-299 manufactured by Asahi Kasei Kogyo Co., Ltd. (all are trade names), novolak-type epoxy resin Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epikote 807 manufactured by Japan Epoxy Resin Co., Ltd., Epotooto YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldite XPY306 manufactured by Ciba Specialty Chemicals Co., Ltd. Product name) bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin such as Epotooto ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; Epikote 604 manufactured by Japan Epoxy Resin Co., Ltd. EpotootoYH-434 manufactured by Dongdu Chemical Co., Ltd., AralditeMY720 manufactured by Ciba Specialty Chemicals Co., Ltd., and Schmidt Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all are trade names) Ciba ‧ special Hydantoin type epoxy resin such as Araldite CY-350 (trade name) manufactured by Chemical Co., Ltd.; Cerokisaito 2021 manufactured by DAICEL Chemical Industry Co., Ltd., Araldite CY175, CY179 manufactured by Ciba Specialty Chemicals Co., Ltd., etc. Aliphatic epoxy resin of the product name; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Co., Ltd. Epoxy resin; YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Nippon Epoxy Co., Ltd. Bixylenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink Chemical Industry Co., Ltd. Bisphenol S type epoxy resin such as (product name); bisphenol A novolac type epoxy resin such as Epikote 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; Epikote YL-931, steam manufactured by Japan Epoxy Resin Co., Ltd. Argentite 163, which is manufactured by Baxter Chemical Co., Ltd. (all of which are trade names), tetraphenolate type epoxy resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names) Heterocyclic epoxy resin; diglycidyl benzoate resin such as Blemmer DGT manufactured by Nippon Oil Co., Ltd.; tetraglycidyl xylene oxirane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; Nippon Steel Chemical Co., Ltd. Ethylene-based epoxy resin such as ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd.; HP-7200, HP-made by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin having a dicyclopentadiene skeleton such as 7200H; a glycidyl methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc. manufactured by the company of the company of the present invention; in addition, a copolymerized epoxy resin such as cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, YR-102, YR-450 manufactured by Tosho Kasei Co., Ltd.), etc. Not limited to this content. These epoxy resins may be used alone or in combination of two or more. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

The above polyfunctional propylene oxide compound (E-2), for example, bis[(3-methyl-3-epoxypropane methoxy)methyl]ether, bis[(3-ethyl-3-epoxypropane A) Oxy)methyl]ether, 1,4-bis[(3-methyl-3-epoxypropanemethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-epoxy) Propane methoxy)methyl]benzene, (3-methyl-3-epoxypropane) methacrylate, (3-ethyl-3-epoxypropane) methacrylate, (3-methyl- 3-propylene oxide) methyl methacrylate, (3-ethyl-3-epoxypropane) methyl methacrylate or polyfunctional propylene oxides such as these oligomers or copolymers, such as epoxy An etherified product of a resin having a hydroxyl group such as propanol, a novolak resin, a poly(p-hydroxystyrene), a caged bisphenol, a calixarene, a cup-resorcinol aromatic hydrocarbon, or a sesquioxane. Other examples include, for example, a copolymer of an unsaturated monomer having a propylene oxide ring and an alkyl (meth)acrylate.

The epoxy sulfur compound (E-3) is, for example, a bisphenol A type epoxy resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the like. Further, an epoxy epoxide or the like obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

In the above molecule, the addition ratio of the thermosetting component (E) having two or more cyclic (thio)ether groups is preferably from 0.6 to 2.5 based on 1 equivalent of the carboxyl group of the (B) carboxylic acid-containing resin. The equivalent weight is more preferably in the range of 0.8 to 2.0 equivalents. When the addition ratio of the thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film, and heat resistance and alkali resistance are caused. , electrical insulation, etc. are reduced, but not good. Moreover, when it exceeds 2.5 equivalents, the ring of low molecular weight The (thio)ether group will remain on the dried coating film, which may cause a decrease in the strength of the coating film or the like, which is not preferable.

In the photosensitive resin composition of the present invention, a thermosetting component (E) having two or more cyclic (thio)ether groups in the above molecule is used, and it is preferred to contain (F) a thermosetting catalyst. The thermosetting catalyst (F), for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine , 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethyl An amine compound such as a benzylamine, a hydrazine compound such as diammonium adipate or a bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like, or a commercially available product such as a product manufactured by Shikoku Chemicals Co., Ltd. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (any of which is a trade name of an imidazole compound), U-CAT3503N, U-CAT3502T manufactured by SAN-APRO Co., Ltd. (either of them is dimethylamine) The trade name of the blocked isocyanate compound), DBU, DBN, U-CATSA102, and U-CAT5002 (either of which is a bicyclic hydrazine compound and a salt thereof).

In particular, it is not limited to this range, as long as it can promote a thermosetting catalyst of an epoxy resin or a propylene oxide compound, or a reactor of an epoxy group and/or an oxypropylene group and a carboxyl group, These may be used alone or in combination of two or more. Further, hydrazine, methyl decylamine, benzopyrene, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4-di can be used. Amino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ three An S-triazine derivative such as a polyisocyanate adduct or a 2,4-diamino-6-methylpropenyloxyethyl-S-triazine/trimeric isocyanate addition product, preferably It is used in combination with the aforementioned thermosetting catalyst in order to use it as a functional compound of an adhesion enhancer.

The addition ratio of the thermosetting catalyst (F) may be a ratio of a normal amount, for example, to (B) a carboxylic acid-containing resin or a thermosetting hardening having two or more cyclic (thio)ether groups in a molecule. The component (E) is 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

In order to improve the physical strength of the coating film, the photosensitive resin composition of the present invention may be added with a filler in accordance with the necessity thereof. As the filler, a conventionally known inorganic or organic filler can be used, and in particular, barium sulfate, spherical cerium oxide and talc are preferably used. Further, a metal hydroxide such as titanium oxide or a metal oxide or aluminum hydroxide can be used as a filler for the extender pigment. The addition ratio of the filler is preferably 75 mass% or less, more preferably 0.1 to 60 mass%, based on the total amount of the composition. When the addition ratio of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, coating and formability are lowered, and the cured product is embrittled, which is not preferable.

Further, in the photosensitive resin composition of the present invention, an organic solvent can be used for the purpose of synthesizing or preparing a composition of the above-mentioned (B) carboxylic acid-containing resin, or for adjusting the viscosity of the substrate or the supported film. .

These organic solvents are, for example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve and methylcellulose Agent, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethylene glycol ethers; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, methyl lactate Ethyl lactate, butyl lactate and other esters; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, Solvent petroleum brain, etc. Petroleum solvent, etc. These organic solvents may be used singly or in combination of two or more.

The photosensitive resin composition of the present invention may further contain hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, gallic phenol, phenothiphenyl, if necessary. A known conventionally used tackifier, fine powder of cerium oxide, organic bentonite, montmorillonite, or the like, a defoaming agent such as polyfluorene, a fluorine, or a polymer, and/or a leveling agent. A known and customary additive such as a decane coupling agent such as an imidazole system, a thiazole system or a triazole system, an antioxidant or a rust inhibitor.

[Fig. 1] A diagram showing a Munsell hue circle.

Fig. 2 is a cross-sectional view showing a pattern formed by a cured coating film of a photosensitive resin composition.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but The invention is not limited by the following examples. In addition, the "parts" referred to below are intended to mean "parts by mass" unless otherwise specified.

[Example 1] <Synthesis of carboxylic acid-containing resin>

The carboxylic acid-containing resin (B) of the present invention is produced according to the following synthesis examples.

220 parts of cresol novolac type epoxy resin ("Epiclon" (registered trademark) N-695, epoxy equivalent: 220) manufactured by Dainippon Ink and Chemicals Co., Ltd. was added to four ports with a blender and a reflux cooler. In the flask, 214 parts of carbitol acetate was added and dissolved by heating.

Next, 0.46 parts of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was gradually dropped, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 106 parts of tetrahydrobenzoic anhydride was added thereto, and the reaction was carried out for 8 hours. After cooling, the reaction solution (also referred to as wax (B-1)) was taken out. The carboxylic acid-containing resin obtained in the above manner had a solid content of an acid value of 100 mgKOH/g and a nonvolatile content of 65%.

<Additional example>

The following components were pre-mixed in a blender with the following addition amounts, and then kneaded by a three-roll mill mill to prepare photosensitive resin compositions for respective solder resists (composition examples 1 to 8). Among them, the dispersion degree of the obtained photosensitive resin composition was measured using a particle size tester (Grind) manufactured by Erichsen Co., Ltd. Meter) The particle size measurement was carried out and the evaluation result was carried out, and it was found to be 15 μm or less. In the composition examples 6 to 8, the lanthanide coloring agent (A-1) of the present invention was not added in any of the examples.

[Table 1]

Receptor performance evaluation: [Method of Making Evaluation Substrate]

The composition of Examples 1 to 8 obtained by the above method was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried at 80 ° C for 20 minutes, and allowed to cool to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus (manufactured by AOKO Co., Ltd.) provided with a metal halide lamp, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed. The development was carried out for 60 seconds under the conditions of a pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under the conditions of a total exposure amount of 1000 mJ/cm ² in a UV transfer furnace, and then heated and cured at 150 ° C for 60 minutes. The following characteristics were evaluated on the obtained printed substrate (evaluation substrate).

<hue ‧L*a*b* value>

According to the above-described method for producing a substrate, the cured coating film of the photosensitive resin compositions of Examples 1 to 8 was produced. The film thickness was prepared to have a thickness of 25 ± 2 μm after drying. The obtained hardened coating film was visually confirmed to distinguish the color tone, and in Examples 2, 3, 4, 7, and 8, the color measurement was performed using a spectrophotometer. The spectrophotometer was a CM-2600d manufactured by KONICA MINOLTA Co., Ltd., and the color was CIE L*a*b*. On the surface of the uniform coating film on the copper foil substrate, the value measured by the SCI mode was used as the color measurement value. The evaluation results are shown in Table 2.

Further, for comparison, the color tone and the L*a*b* value were evaluated in the same manner for various products of PSR-4000 manufactured by Sun Ink Manufacturing Co., Ltd., which is a commercially available product having a good color tone. The results are shown in Table 3. Further, it was confirmed that none of the PSR-4000 used an anthraquinone coloring agent.

<Optimum exposure>

The copper-clad laminate substrate was polished with a polishing drum, washed with water, and dried. The photosensitive resin compositions of Examples 1 to 8 were applied by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out by a high-pressure mercury lamp exposure apparatus by a light mask (manufactured by Kodak Eastman Co., Ltd., stepping platform No. 2). The substrate after the irradiation was used as a test pellet, and after developing for 20 seconds by spraying a developing solution (aqueous sodium carbonate solution) of 2 kg/cm ^{2 ,} the number of remaining coating films was visually determined. The exposure amount in which the number of segments of the remaining coating film is 6 is the optimum exposure amount. The evaluation results are shown in Table 2.

<Resolve ‧ line section shape>

The substrate is formed on a substrate having a circuit pattern of 300/300 lines formed on a copper-clad laminate having copper thicknesses of 35 μm, 50 μm, and 70 μm, and is subjected to pre-treatment polishing drum polishing, washed with water, and dried. By. The photosensitive resin compositions of Examples 1 to 8 were applied by screen printing on the substrate subjected to the pretreatment, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out using a high pressure mercury lamp exposure apparatus. The exposure pattern is a pattern in which a line of 50/60/70/80/90/100 μm is drawn for use in the space portion. The amount of exposure is the amount of exposure that is evaluated using the optimum amount of exposure. After the exposure, development was carried out with an aqueous solution of sodium carbonate to form a pattern, and the width of the remaining minimum line was made analytical. Further, after hard curing at 150 ° C for 60 minutes to obtain a cured coating film, a cross section of a line portion having a design value of 100 μm of the cured coating film was observed.

This section is a pattern diagram as shown in Fig. 2, and will be evaluated as A~. E and other five stages. The figure shows a pattern diagram showing the following phenomenon. In particular, in the case of the A evaluation, the offset generated by the design value is within 5 μm of the upper and lower portions of the line. The results are shown in Table 2. Among them, the best evaluation is A, the worst evaluation is E, and C is evaluated as a space for improvement as a solder resist, but it is usable.

In addition, for the comparison, a variety of products of the PSR-4000 manufactured by Sun Ink Manufacturing Co., Ltd., which is a commercially available product, were subjected to cross-sectional evaluation of a 70 μm circuit thickness substrate. The results are shown in Table 3.

A evaluation: ideal state as shown by design width

B evaluation: surface layer erosion caused by insufficient developability

C evaluation: bottom cut state

D evaluation: the line is too expanded due to fading

E evaluation: the surface layer is too broad and the bottom cut state occurs.

[Table 2]

<Solder heat resistance>

The photosensitivity of the examples 1 to 8 were prepared according to the above-mentioned method for producing the substrate. A hardened coating film of a resin composition. The film thickness was produced so that the film thickness after drying was 25 ± 2 μm. This was immersed in a solder bath heated to 260 ° C for 10 seconds, and was repeated three times to visually confirm whether or not the coating film was peeled off or discolored. As a result, it was confirmed that the evaluation substrates produced in Examples 1 to 8 were not peeled or discolored in any of them.

[Example 2]

The photosensitive resin compositions of Examples 2 and 7 were diluted with methyl ethyl ketone and applied onto a supported film. This was heated and dried to form a photosensitive resin composition layer having a thickness of 20 μm, and dried by a hot air dryer at 80 ° C for 30 minutes. Subsequently, a cover film (CoverFilm) was attached to the obtained coating film to obtain a dry film. Subsequently, the cover film was peeled off, and the film obtained by thermal lamination of the patterned copper foil substrate was used, and secondly, exposure was performed using an exposure apparatus (manufactured by AOKO Co., Ltd.) provided with a metal halide lamp. After the exposure, the load film was peeled off and heat-hardened by a hot air dryer at 150 ° C for 60 minutes to prepare a test substrate. For the test substrate having the obtained cured film, the evaluation test of various characteristics was carried out in accordance with the test method and evaluation method of Example 1. As a result, in Example 1, Example 2 and Example 7 were the same.

Claims (7)

A photosensitive resin composition comprising (A-1) an anthraquinone coloring agent, (A-2) a phthalocyanine coloring agent, and (B) a carboxylic acid-containing resin, and a carboxylic acid containing the (B) 100 parts by mass of the resin, containing 0.05 to 3.0 parts by mass of the above (A-1) anthraquinone-based coloring agent, and the addition ratio of the (A-1) anthraquinone-based coloring agent to the (A-2) phthalocyanine-based coloring agent by mass ratio (A-1) anthraquinone coloring agent: (A-2) phthalocyanine coloring agent = 1:0.5 to 1:20, and is an alkali-developable photo-resistance resist. The photosensitive resin composition of claim 1, wherein the anthraquinone coloring agent (A-1) contains at least a dye. The photosensitive resin composition of claim 1, wherein the anthraquinone coloring agent (A-1) contains at least a pigment. The photosensitive resin composition of claim 1, wherein the anthraquinone coloring agent (A-1) contains at least a pigment and a dye. A dry film obtained by coating and drying a photosensitive resin composition according to any one of claims 1 to 4 on a supported film. A cured product obtained by applying a photosensitive resin composition according to any one of claims 1 to 4, or a dry film obtained by coating and drying the photosensitive resin composition on a supported film, It is obtained by hardening a substrate on which a circuit is formed. A printed circuit board having a solder resist layer composed of a cured material as claimed in claim 6 of the invention, on a substrate on which a circuit is formed.