JP5586729B2 - Photosensitive resin composition, cured product thereof, and printed wiring board having solder resist layer made of the cured product - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition excellent in coloring power and resolution, which can provide a solder resist layer having excellent concealability such as poor appearance of a circuit and high resolution.

  Alkali-developable photosensitive compositions are used in large quantities as solder resists for printed wiring boards. The solder resist is intended to protect the circuit of the printed circuit board, and the coloring power is an important characteristic that greatly influences the appearance of the printed wiring board and the concealability of the circuit.

  That is, when the coloring power of the solder resist is insufficient, the stain and discoloration of the copper circuit formed on the printed wiring board are conspicuous, and the yield rate of the printed wiring board is significantly reduced. More recently, the mounting process, which is a subsequent process of the printed wiring board, has been automated, and parts are attached by a machine. However, there is a problem that the solder resist and the copper circuit cannot be recognized well during image recognition. This phenomenon is also a problem in the case of AOI (Automatic Optical Inspection) which is the final inspection of the printed wiring board.

  Solder resists currently available on the market depend on the film thickness and copper pretreatment of the base material, but when expressed in the CIE L * a * b * display system, the L * value is 40 to 60 in green, and the a * value is − 10 to -28, b * value is 6 to 18, blue is L * value 40 to 60, a * value is -10 to -28, b * value is -6 to -18, especially green and blue A L * value of 40 to 50 is preferable from the viewpoint of AOI, and this level of coloring power is necessary.

  On the other hand, as photosensitivity characteristics of a photo solder resist, generally, a resist having a resolution of about 30 μm to 50 μm with a film thickness of about 20 μm is commercially available. However, recently, these solder resists have a problem that fine lines cannot be formed because the depth of curing is not sufficient for a printed circuit board having a high circuit thickness. Generally, since the solder resist is applied to a circuit-formed substrate, the resist thickness depends on the circuit thickness. For example, when the circuit thickness is 35 μm, the solder resist thickness is about 30 to 35 μm between circuits even when applied to 20 μm on the circuit, and 60 to 70 μm when the circuit thickness is 70 μm. Here, even if a substrate having a circuit thickness of 35 μm can form a resist line having a thickness of 50 μm, a substrate having a circuit thickness of 70 μm cannot form an image having a thickness of 100 μm.

In recent years, circuit boards used for components operating at high voltages have become increasingly thicker and denser, and a high-resolution solder resist that can be applied to the substrate is required.
By the way, phthalocyanine-based green and blue and auxiliary yellow colorants are generally used for solder resists, but since these colorants all have a large absorption in the ultraviolet region, the blending amount thereof If there is a large amount, good resolution will not be obtained due to the influence on the transmittance of ultraviolet rays. Therefore, it has been difficult to provide a photosensitive resin composition capable of forming a solder resist layer that simultaneously satisfies good concealability and high resolution.

JP 2000-7974 (Claims)

  An object of the present invention is to provide a photosensitive resin composition capable of forming a solder resist layer having high coloring power and excellent concealability and having a resolution with a high aspect ratio.

As a result of diligent research, the present inventors have found that the above-mentioned problem of resolution in conventional solder resists has been solved according to a photosensitive resin composition using at least a perylene-based colorant as a colorant. The inventors have found that it has coloring power and have completed the present invention.
That is, the present invention is a photosensitive resin composition comprising (A-1) a perylene colorant and (B) a carboxylic acid-containing resin.
In the photosensitive resin composition of the present invention, in one embodiment, the perylene colorant (A-1) contains at least a dye.

Moreover, the photosensitive resin composition of this invention WHEREIN: In one aspect | mode, a perylene type colorant (A-1) contains a pigment at least.
Moreover, the photosensitive resin composition of this invention is green or orange in one aspect | mode.
Moreover, the photosensitive resin composition of this invention can contain a phthalocyanine colorant (A-2) and / or another colorant in addition to a perylene colorant (A-1) in one aspect | mode.
Moreover, the photosensitive resin composition of this invention is an alkali developable photo solder resist in one aspect | mode.
Moreover, this invention is a dry film obtained by apply | coating and drying the said photosensitive resin composition on a carrier film in another aspect.

In another aspect, the present invention is a cured product obtained by curing the photosensitive resin composition or the dry film on a circuit-formed substrate.
Moreover, this invention is a printed wiring board which has the soldering resist layer which consists of the said hardened | cured material on the board | substrate with which the circuit was formed in another aspect.

  With the photosensitive resin composition of the present invention having high coloring power and excellent resolution, it has high resolution and excellent demand as a solder resist layer for printed wiring boards, which are increasing in circuit thickness and density. It has become possible to provide a solder resist layer that simultaneously satisfies the concealability.

The figure which shows the Munsell hue ring. The schematic diagram which shows the cross-sectional shape of the pattern which consists of a cured coating film of the photosensitive resin composition.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention is characterized by containing (A-1) a perylene-based colorant as a colorant. In one embodiment, the photosensitive resin composition may further contain a phthalocyanine-based colorant. Is a photosensitive resin composition capable of exhibiting a green or orange color. First, the colorant of the present invention will be described.

(A-1) Perylene-based colorant The photosensitive resin composition containing the perylene-based colorant (A-1) of the present invention relates to a solder resist for a printed wiring board, in particular with respect to an originally colored photoresist. Gives high resolution. The reason is that conventionally used colorants use phthalocyanine pigments such as phthalocyanine green and phthalocyanine blue, and anthraquinone and isoindoline yellow pigments. In other words, the phthalocyanine system has a large absorption from 300 nm to 400 nm, and the yellow pigment system has a large absorption in the long wavelength region (380 nm to 450 nm) having a relatively high transmittance, so that the light from the light source can be sufficiently delivered to the bottom of the resist. However, the curing depth is reduced.

  On the other hand, perylene-based colorants have less absorption in the ultraviolet region and sufficient coloring power than the above colorants, resulting in high resolution and heat resistance and electrical insulation required for resist materials such as solder resists. A photosensitive resin composition having both properties can be provided.

  In the present invention, a conventionally known colorant can be used as the colorant, and any of a pigment, a dye, and a pigment may be used, and two or more kinds may be mixed and used. In the present invention, the pigment means a compound classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists), and the dye is in Solvent et al. Refers to classified compounds, Lumogen (R), etc.

  Perylene-based colorants include green, yellow, orange, red, purple, black, and other colors that have the following color index numbers (CI; issued by The Society of Dyers and Colourists). Can be mentioned.

-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
-Black: Pigment Black 31, 32
Perylene colorants other than those described above can also be used. For example, Lumogen (registered trademark) F Yellow 083, Lumogen F Orange 240 from BASF, which is known as a light-collecting fluorescent dye, although there is no color index number, Lumogen F Red305, Lumogen F Green850, and the like can be used because they have little absorption in the ultraviolet region and high coloring power like other perylene compounds.

The blending ratio of the perylene-based colorant is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the (B) carboxylic acid-containing resin to be described later in consideration of colorability and ultraviolet absorption. Preferably it is 0.05-3.0 mass parts.
Here, dye systems such as Solvent Green 5, Solvent Orange 55, Solvent Red 135, Solvent Red 179, and Lumogen (registered trademark) are preferable as the perylene-based colorant, and Solvent Green 5 is particularly preferable. In the pigment system, Pigment Black 31 is preferable.

  As long as the object of the present invention is not hindered, other colorants other than the perylene type (which may be any of pigments, dyes, and dyes) may optionally be included, and these colorants are exemplified below. Of these, mixing of the phthalocyanine colorant (A-2) and the perylene colorant (A-1) is preferable.

(1) Blue colorant Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds classified as pigments. Specifically, the following color index (CI; The Society of Dyers) and Colourists, Inc.).

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, and Pigment Blue 60.

As a dye system,
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. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine colorants can also be used.

(2) Green colorants Green colorants are similarly phthalocyanine and anthraquinone. Specifically, use Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 20, Solvent Green 28, etc. Can do. In addition to the above, metal-substituted or unsubstituted phthalocyanine colorants can also be used.

(3) Yellow colorant Examples of the yellow colorant include anthraquinone series, isoindolinone series, condensed azo series, benzimidazolone series, monoazo series, and disazo series. Specific examples include the following.

(Anthraquinone)
Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202;
(Isoindolinone series)
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;
(Benz imidazolone series)
Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;
(Monoazo)
PigmentYellow1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183;
(Disazo series)
PigmentYellow12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198.

(4) Red colorant Examples of red colorants include monoazo, disazo, monoazo lake, benzimidazolone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Things.

(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 series)
Pigment Red 37,38,41;
(Monoazo lake)
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;
(Benz imidazolone series)
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 and Pigment Red 242;
(Anthraquinone)
Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;
(Quinacridone series)
Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Other colorants such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.
Specifically, 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, etc. There is.

  In the present invention, the blending ratio of the colorant is set to a ratio sufficient for exhibiting a desired color tone, specifically, green or orange, of the obtained photosensitive resin composition or a solder resist layer made of the cured film thereof. There is a need.

  In the present invention, the green and orange colors exhibited by the photosensitive resin composition and its cured film refer to those having a color tone that is recognized as green and orange when observed with the naked eye by a viewer. . Specifically, when the appearance color tone of the photosensitive resin composition and its cured film was measured and displayed by the method specified in JISZ8721, the Munsell Color Ring (New Basic Color Table Series 2 supervised by the Japan Color Research Institute) System belongs to hue range from 10Y to 10BG (green), 10R to 10YR (orange), and preferably has a saturation of 2 or more and less than 16 Is more than 2 and less than 9, and more preferably exhibits a chromatic color of green or orange with a saturation of 3 or more and less than 15 and a lightness of 3 or more and less than 9.

  The blending ratio of the perylene-based colorant (A-1) and the other colorant is affected by the type of the colorant used and the type of other additives, and thus can be unconditionally set. The blending ratio with the phthalocyanine colorant (A-2) is a mass ratio, and the ratio of perylene colorant (A-1): phthalocyanine colorant (A-2) = 1: 0 to 1:20. It is preferable to mix.

Next, each component other than the colorant of the photosensitive resin composition of the present invention will be described in detail.
The following materials can be used for the photosensitive resin composition of the present invention.

(B) Carboxylic acid-containing resin In the composition of the present invention, a carboxylic acid-containing resin (B) having a carboxyl group in the molecule is used for the purpose of imparting alkali developability, and various conventionally known resin compounds can be used. . In particular, a carboxylic acid-containing photosensitive resin (B ′) having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.

As specific examples of the carboxylic acid-containing resin (B), the following compounds are preferable.
(1) A carboxylic acid-containing resin obtained by copolymerization of (meth) acrylic acid and an unsaturated group-containing material.
(2) A carboxylic acid-containing urethane resin by a polyaddition reaction of a diisocyanate, a carboxylic acid-containing dialcohol compound, and a diol compound.
(3) Photosensitive carboxylic acid-containing urethane resin by polyaddition reaction of diisocyanate and bifunctional epoxy (meth) acrylate or its partial acid anhydride modified product, carboxylic acid-containing dialcohol compound and diol compound.
(4) A terminal (meth) acrylated carboxylic acid-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule is added during the synthesis of the resin of (2) or (3). .
(5) A terminal (meth) acrylated carboxylic acid-containing urethane in which a compound having one isocyanate group and one or more (meth) acryl groups in the molecule is added during the synthesis of the resin of (2) or (3). 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 dibasic acid anhydride to a hydroxyl group present in the side chain.
(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Carboxylic acid-containing resin.
(8) A carboxylic acid-containing polyester resin obtained by reacting a difunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(9) A photosensitive carboxylic acid-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resin.
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.

Since the carboxylic acid-containing resin (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.
Moreover, the acid value of the said carboxylic acid containing resin (B) has the preferable range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxylic acid-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds, so that the line becomes thinner than necessary. Depending on the case, 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 draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxylic acid containing resin (B) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The blending ratio of such a carboxylic acid-containing resin (B) is preferably 20 to 60% by mass and more preferably 30 to 50% by mass in the entire 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 becomes high and the coating property and the like deteriorate, which is not preferable.
These carboxylic acid-containing resins can be used without being limited to the above, and can be used singly or in combination.

(C) Photopolymerization initiator The photosensitive resin composition of the present invention may contain a photopolymerization initiator (C).
The photopolymerization initiator (C) is at least one photopolymerization selected from the group consisting of oxime ester photopolymerization initiators, α-aminoacetophenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators. It is preferred to use an initiator.
Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, Inc., and N-1919 manufactured by ADEKA. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  Examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethyl Examples include aminoacetophenone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  The blending ratio of such a photopolymerization initiator (C) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (B). Range. If it 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 (C) becomes violent, and the deep curability tends to decrease, which is not preferable.

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

  Furthermore, in the photosensitive resin composition of the present invention, photopolymerization initiators other than the above-mentioned compounds, photoinitiator assistants, and sensitizers can be used. For example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthones Examples thereof include compounds, ketal 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 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 benzophenone 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) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -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-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

  Of the above, thioxanthone compounds and tertiary amine compounds are preferred. The inclusion of a thioxanthone compound is preferable from the viewpoint of deep curable properties, and among these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferable.

  The mixing ratio of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxylic acid-containing resin (B). If the mixing ratio 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, and among them, 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. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is less colored because the maximum absorption wavelength is in the ultraviolet region, and uses a colorant 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.

  As a compounding ratio of such a tertiary amine compound, the proportion of 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the carboxylic acid-containing resin (B). It is. When the mixing ratio of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried 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.

(D) Compound having two or more ethylenically unsaturated groups in the molecule The photosensitive resin composition of the present invention may contain a 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 photocured by irradiation with active energy rays to insolubilize or help insolubilize the carboxylic acid-containing resin (B) in an alkaline aqueous solution. Is. 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 alcohols or polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglyceride Jill 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, or 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.

  The compounding ratio of the compound (D) having two or more ethylenically unsaturated groups in the molecule is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the (B) carboxylic acid-containing resin. Preferably, it is the ratio of 1-70 mass parts. When the blending ratio is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

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

  The thermosetting component (F) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Alternatively, a compound having two or more of two kinds of groups is preferable. For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), at least two oxetanyl in the molecule A compound having a group, that is, a polyfunctional oxetane compound (E-2), a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (E-3), and the like.

  As the polyfunctional epoxy compound (E-1), for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, manufactured by Dainippon Ink & Chemicals, Inc. Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. 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); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Industries Sumi-epoxy ESCN-195X, ESCN- 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all are trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Tohto Kasei Hydrogenated bisphenol A type epoxy resin, such as Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd. Epoxy ELM-120 etc. All are trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Chemicals Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by 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. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin; Epicoat YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Name) Tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both are trade names); Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene groups such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Methacrylate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. 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 (E-2) 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- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) 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 Scan phenols, 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 episulfide compound (E-3) include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. 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 blending ratio of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 relative to 1 equivalent of the carboxyl group of the (B) carboxylic acid-containing resin. -2.5 equivalent, More preferably, it exists in the range used as 0.8-2.0 equivalent. When the blending ratio of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalents, carboxyl groups remain in the solder resist film, heat resistance, alkali resistance, This is not preferable because the electrical insulation property is lowered. 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.

  In the photosensitive resin composition of this invention, when using the thermosetting component (E) which has a 2 or more cyclic | annular (thio) ether group in the said molecule | numerator, it is preferable to contain the (F) thermosetting catalyst. . Examples of such thermosetting catalyst (F) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2. -Imidazole derivatives such as phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy- Amine compounds such as N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and the like are also commercially available. As a thing For example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (both dimethylamine block isocyanates manufactured by San Apro) Compound trade names), 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. Also, 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 and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The proportion of these thermosetting catalysts (F) is sufficient in the usual quantitative ratio. For example, (B) a thermosetting component having two or more cyclic (thio) ether groups in the carboxylic acid-containing resin or molecule. (E) Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.

  The photosensitive resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, metal hydroxides such as titanium oxide, metal oxides, and aluminum hydroxide can be used as extender pigment fillers. The blending ratio of the filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the total amount of the composition. When the blending ratio of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, the coating and moldability are lowered, and the cured product becomes brittle, which is not preferable.

  Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the (B) carboxylic acid-containing resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. be able to.

  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 , Propylene glycol butyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, etc. Esters; ethanol, propanol, ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, and the like petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  If necessary, the photosensitive resin composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite and the like. Conventional thickeners, antifoaming agents and / or leveling agents such as silicones, fluorines and polymers, silane coupling agents such as imidazoles, thiazoles and triazoles, antioxidants, rust inhibitors, etc. Such known and commonly used additives can be blended.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “part” means “part by mass” unless otherwise specified.

[Example 1]
<Synthesis of carboxylic acid-containing resin>
The carboxylic acid-containing resin (B) of the present invention was prepared according to the following synthesis example.
Cresole novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., “Epiclon” (registered trademark) N-695, epoxy equivalent: 220) is placed in a four-necked flask equipped with a stirrer and a reflux condenser. Then, 214 parts of carbitol acetate was added and dissolved by heating.

Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction solution (referred to as varnish (B-1)) was taken out. The carboxylic acid-containing resin thus obtained had a solid acid value of 100 mgKOH / g and a nonvolatile content of 65%.

<Formulation example>
The following components were preliminarily mixed with a stirrer in the following blending amounts, and then kneaded with a three-roll mill to prepare each photosensitive resin composition for solder resist (Composition Examples 1 to 8). Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the Grindometer by Eriksen. Composition Examples 6 to 8 are examples in which no perylene colorant (A-1) according to the present invention is blended.

Component A Each colorant described in Table 1 Each part by mass described in Table 1 Component B varnish (B-1) 154 parts (solid content 100 parts)
Component C 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoamino
Propan-1-one 10 parts
2,4-Diethylthioxanthone 1 part D component Dipentaerythritol hexaacrylate
(DPHA / Nippon Kayaku) 20 parts E component Phenol novolac epoxy resin
(Den-431 manufactured by Dow Chemical Company) 15 parts
Bixylenol type epoxy resin
(YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) 25 parts F component Dicyandiamide 0.3 part Other components Barium sulfate (barium sulfate B30 manufactured by Sakai Chemical Co., Ltd.) 100 parts Silicone-based antifoaming agent 3 parts DPM (dipropylene glycol monomethyl ether) 5 parts.

Resist performance evaluation:
[Evaluation Board Fabrication Method]
The compositions of Examples 1 to 8 obtained as described above were applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. Using this exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp on this substrate, the solder resist pattern is exposed at an optimal exposure amount, and developed with a 1% Na 2 CO 3 aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was 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 of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Color tone / L * a * b * value>
According to the said evaluation board | substrate preparation method, the cured coating film of the photosensitive resin composition of Examples 1-8 was produced. The film thickness was prepared so that the film thickness after drying was 25 ± 2 μm. The obtained cured coating film was visually confirmed to determine the color tone, and the colors of Examples 2, 3, 4, 7, and 8 were measured using a spectrocolorimeter. CM-2600d manufactured by KONICA MINOLTA was used for the spectrocolorimeter, and CIE L * a * b * was used for the color system. The value measured in the SCI mode on the uniform coating film surface on the copper foil substrate was taken as the colorimetric value. The evaluation results are shown in Table 2.

  Further, for comparison, the color tone and L * a * b * value were similarly evaluated for various types of PSR-4000 manufactured by Taiyo Ink Manufacturing Co., Ltd., which are commercially available solder resists with good color tone. The results are shown in Table 3. It has been confirmed that none of the PSR-4000 uses a perylene colorant.

<Optimum exposure amount>
The copper-clad laminate is polished with buffalo, washed with water and dried. The photosensitive resin compositions of Examples 1 to 8 are applied by screen printing and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus through a photomask (manufactured by Eastman Kodak Company, Step Tablet No. 2). What was irradiated was used as a test piece, and after developing for 60 seconds with a developer (sodium carbonate aqueous solution) having a spray pressure of 2 kg / cm ² , the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of steps of the remaining coating film was 6 was determined as the appropriate exposure amount. The evaluation results are shown in Table 2.

<Resolution / Line cross-sectional shape>
As a substrate, a copper-clad laminate having a copper thickness of 35 μm, 50 μm, and 70 μm, respectively, and a circuit pattern having a line / space of 300/300 formed thereon, pre-treated with buffalo polishing, washed with water, and dried Using. The photosensitive resin composition of Examples 1-8 was apply | coated by the screen-printing method on the said board | substrate with which the pre-processing was performed, and was dried for 30 minutes with an 80 degreeC hot-air circulation type drying furnace. After drying, exposure was performed using a high pressure mercury lamp exposure apparatus. As the exposure pattern, a pattern for drawing a 50/60/70/80/90/100 μm line in the space portion was used. The exposure amount was the exposure amount obtained by the optimum exposure amount evaluation. After exposure, development was performed with an aqueous sodium carbonate solution to form a pattern, and the width of the remaining minimum line was defined as resolution. Furthermore, after obtaining a cured coating film by thermosetting at 150 ° C. for 60 minutes, the cross section of the line portion of the designed value 100 μm of the cured coating film was observed.

  This cross-sectional shape was evaluated in five stages A to E as shown in the schematic diagram shown in FIG. The drawing shows a schematic diagram when the following phenomenon occurs. In particular, in the case of evaluation A, the deviation from the design value was within 5 μm for both the upper and lower parts of the line. The results are shown in Table 2. Here, the best evaluation is A, the worst evaluation is E, and the C evaluation is usable as a solder resist although there is room for improvement.

  Furthermore, for the purpose of comparison, cross-sectional evaluation with a circuit board having a thickness of 70 μm was similarly performed on various types of PSR-4000 manufactured by Taiyo Ink Manufacturing Co., Ltd., which are commercially available solder resists having good color tone. The results are shown in Table 3.

A evaluation: ideal state according to design width B evaluation: occurrence of biting of surface layer due to insufficient development resistance C evaluation: undercut state D evaluation: occurrence of line thickening due to halation etc. E evaluation: line thickening and undercut of surface layer Occurs

<Solder heat resistance>
According to the said evaluation board | substrate preparation method, the cured coating film of the photosensitive resin composition of Examples 1-8 was produced. The film thickness was prepared so that the film thickness after drying was 25 ± 2 μm. This was repeated three times for 10 seconds in a solder bath heated to 260 ° C., and peeling or discoloration of the coating film was visually confirmed. As a result, no peeling or discoloration was confirmed in any of the evaluation substrates prepared using Examples 1-8.

[Example 2]
The photosensitive resin compositions of Examples 2 and 7 were diluted with methyl ethyl ketone and coated on a carrier film. This was heat-dried to form a photosensitive resin composition layer having a thickness of 20 μm, and dried for 30 minutes with a hot air dryer at 80 ° C. Further, a cover film was bonded onto the obtained coating film to obtain a dry film. Thereafter, the cover film was peeled off, the obtained film was heat-laminated on the patterned copper foil substrate, and then exposed using an exposure apparatus (manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp. After the exposure, the carrier film was peeled off, and heat-cured for 60 minutes with a hot air dryer at 150 ° C. to prepare a test substrate. The test substrate having the obtained cured film was subjected to an evaluation test of each characteristic by the test method and the evaluation method in Example 1. The results were the same as Example 2 and Example 7 in Example 1.

Claims (5)

  A photosensitive resin composition comprising (A-1) a perylene-based colorant, (A-2) a phthalocyanine-based colorant, and (B) a carboxylic acid-containing resin, which is an alkali-developable photo solder resist. The photosensitive resin composition according to claim 1, wherein the color tone is green or orange. The dry film obtained by apply | coating the photosensitive resin composition of Claim 1 or 2 on a carrier film, and drying. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2 or the dry film according to claim 3 on a circuit-formed substrate. The printed wiring board which has the soldering resist layer which consists of hardened | cured material of Claim 4 on the board | substrate with which the circuit was formed.

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