JP4663679B2 - Photocurable resin composition, dry film, cured product, and printed wiring board - Google Patents

Description

  The present invention relates to a photocurable resin composition that can be developed with a dilute alkaline solution, particularly a solder resist composition that is exposed to ultraviolet light or laser, a dry film thereof, a cured product, and a printed wiring board.

  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.

  This solder resist is applied in a state in which a copper circuit is formed on a glass epoxy substrate of a printed wiring board, and an image is formed by exposure, developed, and thermally cured 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.

  In the edge portion of the circuit where the copper circuit is likely to be thin, when the coloring power is insufficient, the copper is discolored in the heat history after the solder resist is formed, and only the thin portion appears discolored in appearance. Typical thermal history includes marking thermosetting, warping, preheating before mounting, mounting, and the like.

  For this reason, conventionally, the problem that only the edge portion of the copper circuit appears to be discolored has been solved by adding a colorant to the solder resist to increase the coloring power.

  However, when a large amount of colorant is added, there are the following problems during exposure. That is, the solder resist is generally colored green and blue, and a phthalocyanine compound having excellent heat resistance and chemical resistance is used as the colorant (see Patent Document 1). However, the phthalocyanine compound has a large absorption in the ultraviolet region and a large change in absorption from 350 nm to 400 nm. When this colorant is used, since the absorption is large in the ultraviolet region, the solder resist is disadvantageous for obtaining a curing depth. Also, commercially available ultraviolet exposure apparatuses have different ultraviolet wavelength distributions depending on the lamp. Therefore, when this colorant is used, since there are many changes in absorption in the ultraviolet region, it is difficult to develop a solder resist having the same resolution with different exposure apparatuses (lamps).

Recently, laser scanning exposure has become widespread from the viewpoint of excellent alignment accuracy in the exposure of solder resist. Laser exposure requires extremely high sensitivity, but at the same time, it is also required to obtain a resist profile with high resolution and good shape. In addition, unlike UV lamp exposure, laser exposure uses light of a single wavelength, so it is important how much resist absorption is relative to that wavelength. Light from the light source used is used as a photopolymerization initiator. Sensitivity is determined by effective absorption. However, the presence of a light absorber such as a colorant is not only disadvantageous for increasing the sensitivity, but also prevents light from being transmitted to the bottom and causes an undercut. Therefore, if a phthalocyanine compound having a large absorption in the ultraviolet region is added so as to obtain a coloring power sufficient to conceal the discoloration of the edge portion of the copper circuit, a desired curing depth cannot be obtained and undercut occurs. In order to prevent this, the amount of the photopolymerization initiator must be reduced, but if this is done, exposure cannot be performed with high sensitivity. Conversely, if the amount of the phthalocyanine compound is adjusted so that there is no undercut, and the concentration of the photopolymerization initiator is increased, sufficient sensitivity can be obtained, but the coloring power is insufficient and discoloration of the edge portion of the copper circuit. Can't hide.
JP 2000-7974, CLAIMS

  An object of the present invention is to provide a composition that is sufficiently colored while adjusting absorption in the ultraviolet region, has high sensitivity in ultraviolet rays and laser exposure, and has a good curing depth.

  Furthermore, even if a blue colorant or a green colorant is added to these compositions to change the resist to green or blue, it is sufficient to suppress appearance defects such as discoloration of the copper circuit with a smaller amount than before. An object of the present invention is to provide a composition having excellent coloring power, high sensitivity and good curing depth.

  In order to achieve this object, the present invention comprises the following arrangement.

(1) (A) a carboxylic acid-containing resin, (B1) a red colorant, (C) an oxime photopolymerization initiator, (D) a compound having two or more ethylenically unsaturated groups in the molecule,
The blending amount of the (B1) red colorant is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the (A) carboxylic acid-containing resin, and the (C) oxime-based photopolymerization initiator. The blending amount is 0.01 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxylic acid-containing resin, and (D) blending of a compound having two or more ethylenically unsaturated groups in the molecule. The amount is 5 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A) . The photocurable resin composition for a solder resist, which can be developed with a dilute alkali solution.

(2) One or two kinds selected from the group consisting of yellow colorant (B2) and blue colorant (B3) are contained, and the solder resist can be developed with the dilute alkali solution according to (1) Photocurable resin composition.

(3) The oxime photopolymerization initiator (C) is an oxime ester photopolymerization initiator represented by the following general formula (I), and further an α-amino represented by the following general formula (II): The solder according to (1) or (2), comprising one or two of an acetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator represented by the following general formula (III): Photo-curable resin composition for resist.

(In the formula, R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Which may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl A group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). It may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) And may be substituted with an alkyl group or a phenyl group. )

(Wherein R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded. )

(Wherein R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, an alkoxy group, a halogen atom, an alkyl group, or Represents an aryl group substituted with an alkoxy group, wherein one of R ⁷ and R ⁸ represents an R—C (═O) — group (where R represents a hydrocarbon group having 1 to 20 carbon atoms); May be good.))
(4) The oxime ester photopolymerization initiator (C) represented by the general formula (I) is an oxime ester photopolymerization initiator represented by the following formula (IV) (3) The photocurable resin composition for solder resists described in 1.

(5) The oxime ester photopolymerization initiator (C) represented by the general formula (I) is an oxime ester photopolymerization initiator represented by the following general formula (V) (3) ) A photocurable resin composition for solder resists.

(In the formula, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms. To 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain) Or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups may be substituted))
(6) The photocurable resin composition for a solder resist according to any one of (1) to ( 5 ), further comprising (E) a thermosetting component.

(7) The photocurable resin composition for solder resists according to any one of (2) to (6) , wherein the composition has a color tone selected from the group of blue, green, orange, and purple .

(8) A photocurable dry film obtained by applying and drying the photocurable resin composition for a solder resist according to any one of (1) to ( 7 ) on a carrier film.

(9) A cured product obtained by photocuring the photocurable resin composition for a solder resist according to any one of (1) to ( 7 ) or the dry film according to claim 8 on copper.

(10) A cured product obtained by photocuring the photocurable resin composition for a solder resist according to any one of (1) to ( 7 ) or the dry film according to ( 8 ).

(11) A printed wiring obtained by photocuring the photocurable resin composition for a solder resist according to any one of (1) to ( 7 ) or the dry film according to ( 8 ), followed by thermosetting. Board.

(Definition of composition and solder resist color)
The color of the composition and solder resist is distinguished by the symbol shown in the hue ring and Munsell hue ring in accordance with JISZ8721 (supervised by the Japan Color Research Institute, New Basic Color Table Series 2 published by Munsell System, Nippon Color Research Co., Ltd.). (See Munsell hue circle Figure 1).

Red Range from 7RP to less than 9R Orange Range from 9R to less than 7YR Yellow Range from 7YR to less than 9Y Green Range from 9Y to less than 5BG Blue Range from 5BG to less than 3P Purple Range from 3P to less than 7RP.

  Further, the lightness and saturation differ depending on the ground (glass epoxy base material or copper circuit, or surface-treated copper circuit), but the saturation is 1 or more and less than 16, and the lightness is 1 or more and less than 9, more preferably saturation. It is preferably 2 or more and less than 15 and lightness is 2 or more and less than 9 (lightness and saturation are based on JISZ8102 JISZ8721).

  Furthermore, it is preferable that the suitable measurement conditions are on a copper circuit with a solder resist thickness of 20 to 30 μm.

  In the present invention, the printed wiring board refers to a board in which a conductor pattern is formed on the surface of an electrically insulating board using a printing technique such as a screen printing method or a photo-etching method. And a flexible wiring board.

  In the present invention, the composition is sufficiently colored while adjusting the absorption in the ultraviolet region by using a red or yellow colorant and an oxime photopolymerization initiator, and has a high sensitivity and a good curing depth in ultraviolet and laser exposure. Offer things. Furthermore, even if a blue colorant or a green colorant is added to these compositions to change the resist to green or blue, it is sufficient to suppress appearance defects such as discoloration of the copper circuit with a smaller amount than before. Therefore, it is possible to provide a composition having a high coloring power, a high sensitivity and a good curing depth.

  Hereinafter, each component of the photocurable resin composition of the present invention will be described in detail.

(A) Carboxylic acid-containing resin 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 properties.

  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.

  Moreover, the acid value of the said carboxylic acid containing resin (A) is the 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 (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 compounding quantity of such carboxylic acid containing resin (A) is 20-60 mass% in all the compositions, Preferably it is 30-50 mass%. 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 or the coating property and the like are lowered, which is not preferable.

(B) Colorant As the colorant, a conventionally known colorant can be used, and any of a pigment, a dye, and a pigment may be used. Specifically, the following can be used.

(B1) Red colorant Examples of red colorants include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Include the following colorants.

(Monoazo)
PigmentRed 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)
PigmentRed 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)
Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208
(Perylene)
Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224
(Diketopyrrolopyrrole)
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
Among these red colorants, absorption is particularly small in the ultraviolet region. In addition, a material having a small change in absorption from 350 to 400 nm is preferable. Furthermore, colorants other than azo compounds and non-halogen compounds are preferred from the viewpoint of environmental pollution.

  Suitable red colorants include Pigment Red 177, Pigment Red 264, and the like.

  The amount of the red colorant is 0.01 to 5.0 parts by mass, preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A) in consideration of colorability and ultraviolet absorption. 3.0 parts by mass.

(B2) Yellow colorant Examples of the yellow colorant include monoazo series, disazo series, condensed azo series, benzimidazolone series, isoindolinone series, anthraquinone series, and the like. Specific examples include the following colorants.

(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)
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)
PigmentYellow12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198
Among these yellow colorants, absorption is particularly small in the ultraviolet region. In addition, a material having a small change in absorption from 350 to 400 nm is preferable. Furthermore, colorants other than azo compounds and non-halogen compounds are preferred from the viewpoint of environmental pollution.

Suitable yellow colorants include Solvent Yellow 163, Pigment Yellow 24,
Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202, Pigment Yellow 110, Pigment Yellow 109,
Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185, Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156,
Pigment Yellow 175, Pigment Yellow 181, etc. are mentioned.

  The blending amount of the yellow colorant is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A) in consideration of colorability and ultraviolet absorption. Part.

(B3) Blue colorant The blue colorant is blended to make the color tone of the composition green, blue or orange.

  Blue colorants to be blended include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and (Issued by Colorists)).

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

  Among these blue colorants, absorption is particularly small in the ultraviolet region. In addition, a material having a small change in absorption from 350 to 400 nm is preferable.

Suitable blue colorants include Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6,
Pigment Blue 16, Pigment Blue 60, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 136 67, Solvent Blue 70 and so on.

  The amount of the blue colorant is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin in consideration of colorability and ultraviolet absorption. .

  The compounding amount of the blue colorant of the blue colorant mixed with the red colorant and the yellow colorant is carboxylic acid-containing resin (A) in consideration of colorability and ultraviolet absorption amount in order to make the hue green or blue. The total amount of the colorant is 0.5 to 5 parts by mass, preferably 0.5 to 4 parts by mass with respect to 100 parts by mass.

(Other colorants)
In the present invention, for the purpose of making the color tone of the composition green, blue or orange, a colorant having a color tone other than the above, such as green, purple, orange, brown or black, can be added within a range not impairing the purpose of the present invention. .

Green colorants include phthalocyanine series and anthraquinone series.
Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28
Etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Other colorants other than green include 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 71, CI Pigment Orange 73
CI pigment brown 23, CI pigment brown 25; CI pigment black 1, CI pigment black 7, and the like.

(C) Oxime-based photopolymerization initiator In the present invention, any oxime-based photopolymerization initiator can be used.
An oxime ester photopolymerization initiator having a group represented by the general formula (I) is preferable. Further, from the group consisting of an α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (II) and an acylphosphine oxide photopolymerization initiator having a group represented by the general formula (III). It is preferable to use one or more selected photopolymerization initiators. By using a photopolymerization initiator having a group represented by the general formula (II) or the general formula (III), there is an effect of expanding the photosensitive region with respect to a long wavelength light source.

  Examples of the oxime ester photopolymerization initiator having a group represented by the above general formula (I) include the above formula (IV) 2- (acetyloxyiminomethyl) thioxanthen-9-one and the above general formula (V). The compound which has group represented by these is more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

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

  Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  The blending amount of such a photopolymerization initiator (C) is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A). You can choose. 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 having a group represented by the general formula (I), the blending amount is preferably 0.01 with respect to 100 parts by mass of the carboxylic acid-containing resin (A). It is desirable to select from a range of ˜20 parts by mass, more preferably 0.01 to 5 parts by mass.

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

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate-based resin can improve photocurability without deteriorating the touch-drying property. The compound (D) having two or more ethylenically unsaturated groups in such a molecule. A compounding quantity 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.

  When using the said mixture, it represents with alpha-oxime ester photoinitiator which has group represented by general formula (I), and general formula (II) with respect to 100 mass parts of carboxylic acid containing resin (A). 1 or more types of photoinitiators selected from the group consisting of an aminoacetophenone photopolymerization initiator having a group represented by the following formula and an acylphosphine oxide photopolymerization initiator having a group represented by formula (III): To 15 parts by mass, preferably 3 to 10 parts by mass.

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

  The thermosetting component (E) 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 (E1), and at least two oxetanyl groups in the molecule. A compound having two or more thioether groups in the molecule, that is, an episulfide resin (E3).

  Examples of the polyfunctional epoxy compound (E1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epicron 2055 manufactured by Dainippon Ink & Chemicals, Inc. Etototo 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 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, 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 Co., Ltd. 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 (E2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [( 3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl- In addition to polyfunctional oxetanes such as 3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, and oxetane alcohol Novolac resin, poly (p-hydroxystyrene), cardo type vinyl 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 (E3) 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 amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2. with respect to 1 equivalent of the carboxyl group of the carboxylic acid-containing resin. It is in the range of 5 equivalents, more preferably 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in 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.

  When the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,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 isocyanate compounds) Product 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. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-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 blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio, for example, carboxylic acid-containing resin (A) or thermosetting component (E) 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.

Filler The photocurable composition of the present invention may 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, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having two or more ethylenically unsaturated groups in the molecule or the polyfunctional epoxy resin (E1). , XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) manufactured by Hanse-Chemie, XP 0516, XP 0525, XP 0314 (all products) Grade name) can also be used. These may be used alone or in combination of two or more.

  The blending amount 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 amount of the filler exceeds 300 parts by mass, the viscosity of the photocurable composition becomes high and the printability is lowered, or the cured product becomes brittle.

Organic Solvent Further, the photocurable resin composition of the present invention is an organic solvent for the synthesis of the carboxylic acid-containing resin (A) and for adjusting the composition, or for adjusting the viscosity for application to a substrate or carrier film. Can be used.

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

Other compounding components The photo-curable 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, phenothiazine, fine silica, and organic bentonite. , Known and commonly used thickeners such as montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, Known and commonly used additives such as rust preventives can be blended.

  In addition, the present invention includes other photopolymerization initiators typified by benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds, A sensitizer can be mix | blended in the range which does not interfere with the objective of this invention.

  The photocurable resin composition according to the present invention preferably has a color tone of green or blue. Such a color tone is suitably obtained by blending a single colorant or a mixture of a plurality of colorants.

Dry Film, Cured Product, Printed Wiring Board The photocurable resin composition according to the present invention thus obtained can be coated and dried on a carrier film by conventional means 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 (for example, 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 (E), 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 The thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups reacted with each other, and was excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. A cured coating film can be formed.

  In addition, even when the thermosetting component (E) 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.

Resin synthesis example 1
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy Equivalent 220) 660 g, carbitol acetate 421.3 g, and solvent naphtha 180.6 g were introduced, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 60 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g. Got. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for 6 hours. As a result, a solution of a carboxylic acid-containing resin (A) having an acid value of 50 mgKOH / g, a double bond equivalent (g weight of resin per mole of unsaturated groups) of 400, and a weight average molecular weight of 7,000 was obtained. Hereinafter, this carboxylic acid-containing resin solution is referred to as A-1 varnish.

Formulation Examples and Examples Various components shown in Comparative Examples are blended in proportions (parts by mass) of the formulation examples, premixed with a stirrer, kneaded with a three-roll mill, and a photosensitive resin composition for solder resist is obtained. Prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.

  In addition, all the numerical values regarding the composition in a table | surface show a mass part. Comparative Example 1 in Tables 1 and 2 is an example in which an oxime photopolymerization initiator is blended, but a red colorant or a yellow colorant is not blended. In Comparative Example 2, a red colorant or a yellow colorant is blended. In this example, no oxime-based photopolymerization initiator is added. Comparative Example 1 in Tables 3 and 4 is an example in which an oxime photopolymerization initiator is blended but no red colorant or yellow colorant is blended, and Comparative Example 2 is a red colorant or an oxime photopolymerization initiator. This is an example in which a yellow colorant is not blended.

Formulation example A component A-1 varnish 154 parts (solid content 100 parts)
B component Aminoanthraquinone compound Attached table C component Photopolymerization initiator Attached table D component Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku) 20 parts E component Phenol novolac type epoxy resin (DEN-431 made by Dow Chemical) 15 parts Boxylenol type epoxy Resin (YX-4000 manufactured by Japan Epoxy Resin Co., Ltd.) 25 parts Other components Barium sulfate (barium sulfate B30 manufactured by Sakai Chemical Co., Ltd.) 100 parts Thermosetting catalyst Dicyandiamide 0.3 part Thermosetting catalyst Melamine 5 parts Pigment Attached Table Silicone antifoaming agent 3 parts DPM (dipropylene glycol monomethyl ether) 5 parts Tables 1 and 2 show examples and comparative examples of compositions in which (B) (C) and a colorant are added in addition to the above blending examples. The characteristic evaluation at this time evaluated the characteristic using the 355 nm laser exposure machine by the Orbotec company.

* 1: 2- (acetyloxyiminomethyl) thioxanthen-9-one * 2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyl oxime)
* 3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide * 4: Irg907 (manufactured by Ciba Specialty Chemicals)
In Tables 3 and 4, the characteristics were evaluated using ORC EXP-2960 equipped with a mercury short arc lamp in place of the 355 nm laser exposure machine manufactured by Orbotech used in Tables 1 and 2.

Performance evaluation:
<Optimal exposure / sensitivity>
The photocurable resin compositions of Examples and Comparative Examples were coated with a screen printing method on the entire surface after buffing a circuit pattern substrate having a copper thickness of 35 μm, buffed, dried, and dried at 80 ° C. with hot air circulation. Dry in oven for 60 minutes. After drying, the film is exposed through a step tablet (Kodak No. 2) using a direct writing device equipped with a semiconductor laser having a maximum wavelength of 355 nm or an exposure device equipped with a mercury short arc lamp, and developed (30 ° C., 0.2 MPa, The optimal exposure dose was when the pattern of the step tablet remaining when the 1 mass% aqueous sodium carbonate solution) was performed in 60 seconds was 7 steps.

<Resolution and line shape>
The photocurable resin compositions of Examples and Comparative Examples were applied to the circuit pattern substrate having a line / space of 300/300 and a copper thickness of 35 μm after polishing with buffalo, washed with water, dried, and screen-printed at 80 ° C. For 30 minutes in a hot air circulation drying oven. After drying, the film was exposed using a direct writing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm or an exposure apparatus equipped with a mercury short arc 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 photocurable 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 photocurable resin composition for soldering resists 200 times (resolution). Moreover, after cutting the center part of the line and performing mirror finish, the upper diameter, lower diameter, and film thickness of the minimum remaining line of the cured coating film were measured using an optical microscope adjusted to 1000 times. The shape at that time was evaluated from A to E as shown in the figure (line shape). 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.

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 Here, not only A evaluation but also C evaluation and D evaluation are levels that can be used as solder resists. On the other hand, those with B evaluation have insufficient surface curability and inferior appearance and electrical characteristics, and those with E evaluation have a level that the line and undercut portions are easily peeled off and cannot be used as a solder resist. .

Characteristic test:
Evaluation board | substrate preparation method: The composition of each said Example and a comparative example is apply | coated whole surface by screen printing on the copper foil board | substrate with which pattern formation was carried out, and it dried at 80 degreeC for 20 minutes, and stood to cool to room temperature. This substrate is exposed to a solder resist pattern with an optimum exposure amount using a direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm or an exposure device equipped with a mercury short arc lamp, and sprayed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. Development was performed for 60 seconds under a pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed wiring board (evaluation board) were evaluated as follows.

<Color of coating film>
The color of the hardened | cured material was judged visually by the soldering resist of the said Example and comparative example.

<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.

<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 <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.

<Acid resistance>
The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. Judgment criteria are as follows.

○: No soaking, melting or peeling.

Δ: Slight penetration, dissolution or peeling is confirmed.

X: Significant infiltration, dissolution or peeling.

<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.

A: No discoloration

◯: Discolored slightly compared to the initial, but no difference between thin and thick resist portions Δ: Discoloration is observed, but there is no difference between thin and thick resist portions.

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

As is clear from the results shown in Tables 1 to 4, the Examples of the present invention are all excellent in terms of sensitivity, resolution, line shape, and copper circuit discoloration. On the other hand, none of the comparative examples in which the colorant according to the present invention was blended had excellent sensitivity, resolution, line shape, and copper circuit discoloration as in the examples of the present invention. .

  As an additional test, the compositions of Examples 9 to 15 were used instead of an exposure apparatus equipped with a high-pressure mercury lamp, using a direct drawing apparatus (Mercurex manufactured by Dainippon Screen Mfg. Co., Ltd.) equipped with an ultrahigh-pressure mercury lamp. An evaluation substrate was produced. As a result of evaluating the characteristics of the coating film, exactly the same results were obtained when using an exposure machine equipped with a mercury short arc lamp.

Explanatory drawing which shows the Munsell hue ring. In the schematic diagram of the cross-sectional shape of the resin composition obtained by exposure / development, A to E show different evaluation shapes.

Explanation of symbols

1a Design value of line width 1b Resin composition after exposure and development 1c Substrate

Claims (11)

(A) a carboxylic acid-containing resin, (B1) a red colorant, (C) an oxime photopolymerization initiator, (D) a compound having two or more ethylenically unsaturated groups in the molecule,
The blending amount of the (B1) red colorant is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the (A) carboxylic acid-containing resin, and the (C) oxime-based photopolymerization initiator. The blending amount is 0.01 to 30 parts by mass with respect to 100 parts by mass of the (A) carboxylic acid-containing resin, and (D) a compound having two or more ethylenically unsaturated groups in the molecule. The amount is 5 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxylic acid-containing resin . The photocurable resin composition for a solder resist, which can be developed with a dilute alkali solution. The photo-curing property for a solder resist which can be developed with a dilute alkali solution according to claim 1, characterized in that it contains one or two selected from the group of yellow colorant (B2) and blue colorant (B3). Resin composition. The oxime photopolymerization initiator (C) is an oxime ester photopolymerization initiator represented by the following general formula (I), and further an α-aminoacetophenone light represented by the following general formula (II): It contains 1 type or 2 types of a polymerization initiator and the acylphosphine oxide type photoinitiator represented by the following general formula (III), The photocurability for solder resists of Claim 1 or 2 characterized by the above-mentioned. Resin composition.

(In the formula, R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more). Which may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or benzoyl A group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). It may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) And may be substituted with an alkyl group or a phenyl group. )

(Wherein R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded. )

(Wherein R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, an alkoxy group, a halogen atom, an alkyl group, or Represents an aryl group substituted with an alkoxy group, wherein one of R ⁷ and R ⁸ represents an R—C (═O) — group (where R represents a hydrocarbon group having 1 to 20 carbon atoms); May be good.)) The oxime ester photopolymerization initiator (C) represented by the general formula (I) is an oxime ester photopolymerization initiator represented by the following formula (IV). Photocurable resin composition for solder resist.

The oxime ester photopolymerization initiator (C) represented by the general formula (I) is an oxime ester photopolymerization initiator represented by the following general formula (V). Photocurable resin composition for solder resist.

(In the formula, R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 carbon atoms. To 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms in the middle of the alkyl chain) Or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups may be substituted)) Furthermore, (E) thermosetting component is contained, The photocurable resin composition for soldering resists in any one of the Claims 1 thru | or 5 characterized by the above-mentioned. 7. The photocurable resin composition for a solder resist according to claim 2 , wherein the composition has a color tone selected from the group of blue, green, orange and purple. The photocurable dry film obtained by apply | coating and drying the photocurable resin composition for solder resists in any one of Claim 1 thru | or 7 to a carrier film. Hardened | cured material obtained by photocuring the photocurable resin composition for solder resists in any one of Claims 1 thru | or 7 , or the dry film of Claim 8 on copper. Hardened | cured material obtained by photocuring the photocurable resin composition for solder resists in any one of Claims 1 thru | or 7 , or the dry film of Claim 8 . The printed wiring board obtained by photocuring the photocurable resin composition for solder resists in any one of Claims 1 thru | or 7 , or the dry film of Claim 8 after thermosetting.

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