JP5291893B2 - Photocurable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a colored photocurable resin composition containing no halogen-containing phthalocyanine green. More specifically, the present invention relates to a colored photocurable resin composition that does not contain a halogen-containing phthalocyanine green and that can provide a solder resist layer that has excellent concealment of appearance defects caused by discoloration due to oxidation of a copper circuit.

  In general, a solder resist is applied in a state where a copper circuit is formed on a glass epoxy substrate of a printed wiring board, and an image is formed by exposure, and development and thermal curing are performed to form a film. Since the copper circuit is formed on the base material, the resist coating surface is thicker than the copper circuit. When a solder resist is applied or laminated thereon, the base material is thick, the copper circuit is thin, and the edge portion of the copper circuit is further thinned. Usually, the solder resist is formed to protect the copper circuit. Its role is to hide the heat and moisture of the copper circuit, electrical discoloration, scratches and dirt on the copper circuit, and the like. However, in the situation where the thickness of the solder resist is different as described above, it is difficult to cover the copper circuit in appearance. On the other hand, a colorant is usually added to the resist ink, and increasing the concentration makes it difficult to see the appearance defect.

  In recent solder resists, from the viewpoint of reducing environmental burden, solder resists using phthalocyanine blue and yellow colorants that do not have halogen atoms are widely used instead of chlorinated phthalocyanine green, which is a conventional green colorant ( For example, see Patent Document 1). In addition, phthalocyanine blue is used as a solder resist as it is in blue to insist that it is clearly halogen-free from the appearance. However, the blue solder resist ink and the green solder resist ink with the blue colorant and the yellow colorant are less concealed than the green color with phthalocyanine green, and the function as a colorant that makes it difficult to see the appearance defects is sufficient. It has been found that there are cases where this is not possible, as explained below.

  That is, the current solder resist is image-cured by photocuring and finally subjected to heat curing treatment. The temperature at this time is appropriate at 150 ° C. for about 30 to 60 minutes, but in reality the temperature and time are not constant and differ slightly depending on the substrate manufacturer. In particular, when the temperature is high and the processing time is long, the substrate using blue which has poor concealability has a problem that the resist cannot conceal the discoloration due to oxidation of the copper circuit and the appearance of the substrate deteriorates. This problem can also occur in the green solder resist ink using the halogen-free blue colorant and the yellow colorant as described above, and it has been confirmed by the present inventors that the concealability is weaker than that of phthalocyanine green. . Further, when marking ink is applied on the substrate, since the marking is further printed and thermally cured after the solder resist is cured, the discoloration of the copper circuit is accelerated, and the appearance problem becomes more serious. Furthermore, pressure and heat may be applied in order to correct the warpage of the substrate that occurs when the solder resist is thermally cured, and similarly, discoloration of the circuit is regarded as a problem.

  The most unfavorable phenomenon of discoloration of these copper circuits is a state where only the edge of the circuit (where the resist is thin) is discolored even on the same copper circuit. In this case, the substrate is inferior due to inconsistency with inspection data during inspection or mounting of the substrate. On the other hand, discoloration is recognized, but such a problem does not occur when the copper circuit can be recognized as another part uniformly.

These problems have been reported before, but become particularly noticeable when a colorant such as phthalocyanine blue having no halogen atom is used instead of phthalocyanine green (to make the colorant halogen-free). .
Japanese Patent Laid-Open No. 2000-7974 (Claims, Prior Art)

  Then, an object of this invention is to provide the colored photocurable resin composition which can form the soldering resist layer excellent in the concealment property of the appearance defect resulting from the discoloration by oxidation of a copper circuit.

  As a result of intensive studies, the present inventors have found that, according to a colored photocurable resin composition using at least a red colorant as a colorant, the concealability of a conventional solder resist using a halogen-free colorant is improved. The above problems have been solved, and it has been found that the halogen content in the solder resist layer can be reduced without degrading the concealability by using a halogen-free red colorant, and the present invention has been completed.

  That is, the present invention contains (A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, (C) a compound having two or more ethylenically unsaturated groups in the molecule, and (D) a red colorant. It is a photocurable resin composition that can be developed with a diluted alkaline solution.

  In one embodiment, the photocurable resin composition of the present invention may contain (E1) a blue colorant (for example, phthalocyanine blue) and / or (E2) a yellow colorant in addition to the red colorant (D). Its color may be blue, green, purple or orange.

  Moreover, the photocurable resin composition of this invention is a red colorant in which the red colorant (D) does not contain a halogen and an azo group in one aspect | mode.

  Moreover, the photocurable resin composition of this invention contains the (F) thermosetting component further in one aspect | mode.

  Moreover, the photocurable resin composition of this invention is apply | coated and used on copper in one aspect | mode.

  Moreover, this invention is a photocurable dry film obtained by apply | coating the said photocurable resin composition to a carrier film, and drying in another aspect.

  Moreover, this invention is a blue, green, purple, or orange hardened | cured material of the said photocurable resin composition in another aspect.

  Moreover, this invention is the blue, green, purple, or orange hardened | cured material of the said dry film in another aspect.

  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 copper circuit was formed in another aspect.

  According to the present invention, it is possible to provide a colored solder resist layer of blue, green, purple or orange that is excellent in concealing discoloration due to oxidation of a copper circuit. In particular, it is effective as a blue solder resist ink that replaces a general-purpose blue solder resist ink that has a problem of concealment. In addition, the solder resist layer obtained by the present invention has a very low halogen content, and the amount of halogen gas generated during coating combustion is significantly reduced.

Hereinafter, the present invention will be described in detail.
As described above, the photocurable resin composition of the present invention is characterized in that at least (D) a red colorant is used as a colorant instead of the conventional halogen-containing phthalocyanine green, and in one aspect, the red colorant In addition to (D), it is a photocurable resin composition that contains (E1) a blue colorant and / or (E2) a yellow colorant and can exhibit a blue, green, purple, or orange color.

  First, the colorant of the present invention will be described. 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. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

  Examples of the red colorant (D) include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, and the like. And the color index (CI; issued by The Society of Dyers and Colorists) such as

-Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269;
-Disazo: Pigment Red 37, 38, 41;
Monoazo 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;
-Benzimidazolone series: Pigment Red 171, 175, 176, 185, 208;
-Perylene series: Solvent Red 135, 179; Pigment Red 123, 149, 166, 178, 179, 190, 194, 224;
-Diketopyrrolopyrrole system: Pigment Red 254, 255, 264, 270, 272;
-Condensed azo: Pigment Red 220, 144, 166, 214, 220, 221, 242;
-Anthraquinone series: Pigment Red 168; 177, 216; Solvent Red 149, 150, 52, 207;
-Quinacridone series: Pigment Red 122, 202, 206, 207, 209.
Although not particularly limited, a red colorant containing no azo group is preferably used from the viewpoint of safety and harmlessness.

  As the blue colorant (E1), there are phthalocyanine and anthraquinone, and pigments are compounds classified as Pigments, specifically, those having the following color index numbers. Can be mentioned.

-Pigment type: Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60;
-Dye system: Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70.
In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

  The yellow colorant (E2) includes monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like, and specifically, the following color index numbers are assigned. Can be mentioned.

-Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202;
-Isoindolinone series: Pigment Yellow 110, 109, 139, 179, 185;
-Condensed azo: Pigment Yellow 93, 94, 95, 128, 155, 166, 180;
-Benzimidazolone series: Pigment Yellow 120, 151, 154, 156, 175, 181;
-Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183;
-Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
Although not particularly limited, a yellow colorant containing no azo group is preferably used from the viewpoint of safety and harmlessness.

  In the present invention, the mixing ratio of the red colorant and the blue colorant and / or the yellow colorant is the color tone desired by the solder resist layer made of the resulting photocurable resin composition and its cured film, specifically, , Blue, green, purple, or orange.

  In the present invention, the blue, green, purple and orange colors exhibited by the photocurable resin composition and the cured film of the present invention are blue, green, purple and orange when observed with the naked eye by a viewer. It has a color tone that can be recognized. Specifically, when the appearance color tone of the photocurable resin composition and its cured film was measured and displayed by the method prescribed in JISZ8721, the Munsell Hue Ring (New Color Table Series 2 supervised by the Japan Color Research Institute) On the 10,000-cell system issued by Nippon Color Research Co., Ltd. (see Fig. 1), 5BG to less than 3P (blue), 9Y to less than 5BG (green), 3P to less than 7RP (purple), 9R to less than 7YR (orange) ), And preferably has a saturation of 1 or more and less than 16, lightness of 1 or more and less than 9, more preferably a saturation of 2 or more and less than 15, and a lightness of 2 or more and less than 9. .

  The specific blending ratio is not unclear because it is affected by the type of colorant used and the type of other additives, but usually, the red colorant (D): blue colorant (by weight ratio) E1): Yellow colorant (E2) = 1: 0 to 50: 0 to 50. Moreover, in order to perform sufficient coloring, it is 0.05-3.0 mass% of the whole composition amount as a total amount of a red colorant (D), a blue colorant (E1), and a yellow colorant (E2). It is preferable to mix | blend in a ratio.

  In the present invention, in addition to the colorant, a colorant such as purple, orange, brown, black may be added for the purpose of adjusting the color tone. Specifically, Pigment Violet 19, 23, 29, 32, 36 , 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI 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 7 1, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25; C.I. Pigment Black 1, C.I. Pigment Black 7, and the like.

Next, (A) carboxylic acid-containing resin will be described.
As the carboxylic acid-containing resin (A) contained in the photocurable resin composition of the present invention, a known and commonly used resin compound containing a carboxylic acid in the molecule can be used. Furthermore, a carboxylic acid-containing photosensitive resin (A ′) having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance.
Specific examples include the resins listed below.

(1) a carboxylic acid-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond;
(2) Glycidyl (meth) acrylate or 3,4-epoxycyclohexyl is a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and one or more other compounds having an unsaturated double bond. Carboxylic acid-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant with a compound having an epoxy group and an unsaturated double bond, such as methyl (meth) acrylate, or (meth) acrylic acid chloride,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that A photosensitive carboxylic acid-containing copolymer resin obtained by reacting an unsaturated carboxylic acid such as (meth) acrylic acid with the coalescence, and reacting a polybasic acid anhydride with the generated secondary hydroxyl group,
(4) To a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than that, a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; A carboxylic acid-containing photosensitive resin obtained by reacting a compound having an unsaturated double bond,
(5) a carboxylic acid-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(6) After reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with an epoxy group and a compound having an unsaturated double bond in one molecule. Hydroxyl and carboxylic acid-containing photosensitive resin obtained by
(7) a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, at least one alcoholic hydroxyl group in one molecule, and a compound having one reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group A carboxylic acid-containing photosensitive resin obtained by reacting a reaction product with a saturated or unsaturated polybasic acid anhydride,
(8) Saturated or unsaturated polybasic with respect to the primary hydroxyl group in the modified oxetane resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule. A carboxylic acid-containing photosensitive resin obtained by reacting an acid anhydride, and (9) containing a carboxylic acid obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting with a polybasic acid anhydride Examples of the resin further include carboxylic acid-containing photosensitive resins obtained by reacting a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule, but are not limited thereto. Not.

  Among these examples, preferred are the carboxylic acid-containing resins (2), (5), and (7) above. Particularly, the carboxylic acid-containing photosensitive resin (9) is photocurable and cured. It is preferable from the viewpoint of coating film characteristics.

  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 (A) as described above has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.

  The acid value of the carboxylic acid-containing resin (A) is preferably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 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 (A) changes with resin frame | skeleton, what is generally 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 inferior. 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 (A) 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.

Next, (B) the photopolymerization initiator will be described.
Examples of the photopolymerization initiator (B) include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1 Acetophenones such as-(4-morpholinophenyl) -butanone-1, N, N-dimethylaminoacetophenone; benzophenone, methylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimene Benzophenones such as ruaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide; benzyl; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Benzoin ethers; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquino Anthraquinones such as 2-aminoanthraquinone and 2,3-diphenylanthraquinone; Organic peroxides such as benzoyl peroxide and cumene peroxide; 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2 Thiol compounds such as mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone, etc. Organic halogen compounds; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) and the like. These compounds can be used alone or in combination of two or more.

  Further, the photopolymerization initiator (B) includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. Secondary amines, titanocenes such as bis (η5-cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, 2- (acetyloxyiminomethyl) thio Xanthen-9-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) Photosensitizers such as oxime esters such as -9H-carbazol-3-yl]-, 1- (O-acetyloxime) It can be used in combination with one or two or more.

  A preferable combination of the photopolymerization initiator (B) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (for example, Irgacure 369 manufactured by Ciba Specialty Chemicals): Irgacure is a registered trademark) and bis (η5-cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (for example, manufactured by Ciba Specialty Chemicals) , Irgacure 784), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, Lucylin TPO manufactured by BASF) and 2- (acetyloxyiminomethyl) thioxanthen-9-one (for example, manufactured by Ciba Specialty Chemicals) CGI-325) or bis (2,4,6-trimethylbenzene) Benzoyl) - phenyl phosphine oxide (e.g., Ciba Specialty Chemicals Inc., a combination of Irgacure 819), and the like.

  Moreover, the suitable range of the usage-amount of the above photoinitiators (B) becomes like this. Preferably it is 1-30 mass parts with respect to 100 mass parts of carboxylic acid containing photosensitive resin (A), More preferably, it is 5-5. The ratio is 25 parts by mass. When the mixture ratio of a photoinitiator is less than the said range, the photocurability of the composition obtained will worsen. On the other hand, when the amount is larger than the above range, the properties of the resulting cured coating film are deteriorated, and the storage stability of the composition is deteriorated.

Next, (C) a compound having two or more ethylenically unsaturated groups in the molecule will be described.
The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and the carboxylic acid-containing resin (A ) Is insolubilized in an aqueous alkali solution or assists insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, 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-based resin can improve photocurability without deteriorating the dryness to touch, and the compound (C) having two or more ethylenically unsaturated groups in such a molecule. A compounding ratio is 5-100 mass parts with respect to 100 mass parts of said carboxylic acid containing resin (A), More preferably, it is a ratio of 1-70 mass parts. When the blending amount 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.

Next, (F) thermosetting component will be described.
A thermosetting component (F) can be added to the photocurable resin composition of the present invention in order to impart heat resistance. Particularly preferred is a thermosetting component (F) 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. Or a compound having two or more of two kinds of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (F-1), at least two oxetanyl in the molecule A compound having a group, that is, a polyfunctional oxetane compound (F-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (F-3), and the like.

  As the polyfunctional epoxy compound (F-1), for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050 manufactured by Dainippon Ink & Chemicals, 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.D. 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 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, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 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 EPOCOAT 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumitomo Chemical Industries 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 (F-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 compound (F-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending ratio of the thermosetting component (F) 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 carboxylic acid-containing resin (A). -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 (F) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electricity This is not preferable because the insulating 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 photocurable resin of the present invention, when the thermosetting component (F) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain (G) a thermosetting catalyst. Examples of such thermosetting catalyst (G) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 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. 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 mixing ratio of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, carboxylic acid-containing resin (A) or thermosetting component (F) having two or more cyclic (thio) ether groups in the molecule. 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 photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (F-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, Inc. XP 0516, XP 0525, XP 0314 (all are product grades) Name) can also be used. These may be used alone or in combination of two or more.

  The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A). Part. When the blending ratio of the filler exceeds 300 parts by mass, the viscosity of the photosensitive composition is increased, the printability is lowered, and the cured product becomes brittle.

  Furthermore, the photocurable resin composition of the present invention uses an organic solvent for the synthesis of the carboxylic acid-containing resin (A) and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. can do.

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photocurable resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite. Known and commonly used thickeners, silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, etc. The known and conventional additives such as can be blended.

  Next, the printed wiring board which has the dry resist obtained using the photocurable resin composition of this invention, hardened | cured material, and the soldering resist layer which consists of this hardened | cured material is demonstrated.

  The photocurable resin composition according to the present invention can be applied to a carrier film by conventional means and dried to obtain a photocurable dry film. The photocurable resin composition according to the present invention or this dry film becomes a cured product by being photocured on copper. Photocuring can be performed by an ultraviolet exposure apparatus, but curing is performed by a laser light source, particularly laser light having a wavelength of 350 to 410 nm. The printed wiring board according to the present invention is obtained by thermosetting after such photocuring.

  Specifically, a dry film, a cured product, and a printed wiring board are formed as follows. That is, the photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and is applied on the substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (eg, 0.3 The resist pattern is formed by development with a ~ 3% sodium carbonate aqueous solution). Furthermore, in the case of the composition containing the thermosetting component (F), for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxylic acid-containing resin (A) and the molecule A cured coating film that is excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics by reacting with a thermosetting component (F) having two or more cyclic (thio) ether groups. Can be formed.

  In addition, even when the thermosetting component (F) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Depending on the purpose and application, heat treatment (thermosetting) may be performed.

  High frequency circuit using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester, etc. Examples include materials such as copper clad laminates, and copper graded laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like.

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

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

The exposure equipment used for the active energy ray irradiation includes a laser direct lithography system (laser direct imaging system), an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, and a mercury short arc lamp. Or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

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

  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.

<Synthesis of carboxylic acid-containing resin>
The carboxylic acid-containing resin (A) 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 (A-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%.

<Examples 1-7 and Comparative Examples 1-2>
The varnish (A-1) obtained by the synthesis of the carboxylic acid-containing resin and the components shown in Table 1 were kneaded with a three-roll mill at the blending ratio shown in the same table to obtain a photocurable resin composition. .

  About the photocurable resin composition of Examples 1-7 and Comparative Examples 1-2, performance and a characteristic were evaluated according to the following evaluation criteria. The results are shown in Table 2.

Performance evaluation:
<Optimal exposure / sensitivity>
The photocurable resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were coated on the entire surface by screen printing after washing a circuit pattern substrate having a copper thickness of 35 μm after buffing, washing with water, and drying, 80 ° C. For 60 minutes in a hot air circulating drying oven. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a metal halide lamp, and remains after being developed (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) in 60 seconds. When the pattern of the step tablet to be used is 7 steps, the optimum exposure amount was set.

<Resolution>
The screen printing method of the photocurable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2, after the circuit pattern substrate having a line / space of 300/300 and a copper thickness of 35 μm was polished with buffalo, washed with water and dried. And dried for 30 minutes in a hot air circulating drying oven at 80 ° C. After drying, exposure was performed using an exposure apparatus equipped with a metal halide lamp. As the exposure pattern, direct drawing data or a photomask for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, development was performed with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.

  It calculated | required using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times.

Characteristic test:
(Production of Evaluation Substrate) The compositions of Examples and 1-4 and Comparative Examples 1-2 were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and then released to room temperature. Cool down. This substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus equipped with a metal halide lamp, and developed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 2 kg / cm ^2. Got a pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Color of coating film>
About the solder resist of the said Example and comparative example, the color of hardened | cured material was judged visually.

<Copper circuit discoloration>
The evaluation substrate was further heated at 150 ° C. for 2 hours, and the degree of discoloration on the copper circuit was judged as follows.

○○: No discoloration.

○: Although the color is slightly discolored compared to the initial state, there is no difference between the thin and thick portions of the resist.

Δ: Discoloration is observed, but there is no difference between the thin and thick portions of the resist.

X: Discoloration is recognized in the thin part of the resist, and the difference from the thick part is remarkable.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.

○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.

(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.

X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After the presence / absence was evaluated, the resist was peeled off by tape peeling after being dipped in a solder bath for 10 seconds, washed and dried under the solder heat resistance test conditions. The judgment criteria are as follows.

○: No change is seen at all.

Δ: Slight penetration was observed after plating, and peeling after solder heat resistance was observed.

X: There is peeling after plating.

<Corrosion resistance>
Using an IPC B-25 comb-type electrode B coupon instead of a copper foil substrate, an evaluation board was prepared under the above conditions, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C., 85% R.D. H. The presence or absence of migration after 1,000 hours was confirmed in a constant temperature and humidity chamber. The judgment criteria are as follows.

○: No change is observed Δ: Slightly changed ×: Migration occurs <Acid resistance>
The evaluation substrate was immersed in a 10 vol% H2SO4 aqueous solution for 30 minutes at room temperature, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows.

○: No soaking, melting or peeling.

Δ: Slight penetration, dissolution or peeling is confirmed.

X: Significant infiltration, dissolution or peeling.

The figure which shows the Munsell hue ring.

Claims (11)

(A) a carboxylic acid-containing resin, (B) a photopolymerization initiator, (C) a compound having two or more ethylenically unsaturated groups in the molecule, and (D) a photocurable resin composition containing a red colorant A photocurable resin composition for a solder resist of a printed wiring board that can be developed with a dilute alkaline solution, which is used on a substrate on which a copper circuit is formed. However, it does not contain a black colorant.   Furthermore, (E1) The photocurable resin composition of Claim 1 containing a blue coloring agent.   The photocurable resin composition according to claim 2, wherein the blue colorant (E1) is phthalocyanine blue.   Furthermore, (E2) The photocurable resin composition of any one of the Claims 1 thru | or 3 containing a yellow coloring agent.   The photocurable resin composition according to any one of claims 1 to 4, wherein the color tone is blue, green, purple, or orange.   The photocurable resin composition according to any one of claims 1 to 5, wherein the red colorant (D) is a red colorant containing no halogen or azo group.   Furthermore, (F) The photocurable resin composition of any one of the Claims 1 thru | or 6 containing a thermosetting component.   The photocurable dry film obtained by apply | coating and drying the photocurable resin composition of any one of Claims 1 thru | or 7 on a carrier film.   A blue, green, purple or orange cured product of the photocurable resin composition according to any one of claims 1 to 7.   The blue, green, purple, or orange cured product of the dry film according to claim 8.   The printed wiring board which has the soldering resist layer which consists of a hardened | cured material of Claim 9 or 10 on the board | substrate with which the copper circuit was formed.

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