KR20140050550A - Curable resin composition, curable resin composition for forming solder resist, cured film, and printed circuit board - Google Patents

Abstract

The present invention provides: a curable resin composition with excellent hiding power and high reflexibility, capable of obtaining a coated film where the decrease of reflexibility due to thermal history is controlled; a curable resin composition specifically for forming a solder resist; a cured film obtained from the composition; and a printed circuit board. The curable resin composition of the present invention contains an organic binder and titanium oxide, and additionally contains a blue inorganic coloring agent. [Reference numerals] (AA) Example 3 Reflectance graph; (BB) Reflectance(%); (CC) Wavelength; (DD) Example 3 Initial stage; (EE) Example 3 After heating

Description

Curable resin composition, curable resin composition for soldering resist formation, cured coating film and printed wiring board {CURABLE RESIN COMPOSITION, CURABLE RESIN COMPOSITION FOR FORMING SOLDER RESIST, CURED FILM, AND PRINTED CIRCUIT BOARD}

The present invention relates to a curable resin composition suitable as an insulating layer of a printed wiring board on which light emitting elements such as LEDs are mounted, in particular a curable resin composition for forming a solder resist, a cured coating film obtained from the composition, and a printed wiring board having the cured coating film. .

BACKGROUND ART In recent years, printed wiring boards are increasingly being used by being directly mounted on light emitting diodes (LEDs) emitting low power, such as backlights of liquid crystal displays such as portable terminals, personal computers, televisions, and light sources of lighting equipment.

In the solder resist film (insulation film) coat | covered and formed as a protective film on a printed wiring board, in addition to the characteristics, such as solvent resistance, hardness, solder heat resistance, and electrical insulation normally required for a solder resist film, it is also required to utilize LED light emission effectively. Therefore, a white insulating film excellent in reflectance of light is often formed. That is, in the use used by directly mounting the backlight of the above-mentioned liquid crystal display, the light source of a lighting fixture, etc., in order to form an insulating film, generally white insulating curable resin composition is used. And in order to color in white like this, titanium oxide is normally used as a coloring agent.

As such a white insulating curable resin composition, for example, Patent Literature 1 discloses a soldering resist composition in which colored pigments such as carbon black are mixed with white pigments such as titanium oxide so that the pattern of the conductor circuit can be concealed even if the solder resist film is thinned. Proposed. Moreover, in patent document 2, in order to acquire the outstanding storage stability, the white curable resin composition for printed wiring boards which mix | blends phthalocyanine and contains titanium oxide in high content is proposed.

However, even when the coloring pigment proposed in Patent Literature 1 is blended, the solder resist film discolors to yellowish brown due to the heat history when the solder resist composition is applied to the printed wiring board and cured, whereby the hiding power of the conductor circuit pattern is lowered. have.

In addition, in the white curable resin composition containing the phthalocyanine of patent document 2, although phthalocyanine is mix | blended in the point which is a pigment | dye with low discolorability by heat history, the solder resist film becomes yellowish brown by yellowing of the resin component by heat history. There is a case where the color is discolored and the hiding power for the conductor circuit pattern is lowered.

In order to solve the said problem, patent document 3 uses titanium oxide as a white curable resin composition from which the soldering resist film which was excellent in hiding power and suppressed discoloration by heat history is obtained, without damaging various characteristics, such as reflectance, resolution, and dimensional accuracy. As a coloring agent, what used the threne blue colorant is proposed.

Japanese Patent Publication No. 2005-311233 Japanese Patent Publication No. 2009-238771 Japanese Patent Publication No. 2012-150461

However, even when using the trench type blue coloring agent of patent document 3, it cannot be said that it is enough in the fall of the reflectance by reflectance and a thermal history.

This invention provides the curable resin composition which has the outstanding hiding power and high reflectance, and the fall of the reflectance by heat history was suppressed, especially the curable resin composition for soldering resist formation, the cured coating film obtained from this composition, and a printed wiring board. The purpose.

MEANS TO SOLVE THE PROBLEM The present inventors earned an excellent concealing power and high reflectance (especially the reflectance of the light of wavelength 680nm) as a soldering resist containing titanium oxide, and earnestly examined in order to obtain the resist by which the fall of the reflectance by the thermal history was suppressed and discoloration was suppressed. come. And by using a blue inorganic coloring agent as follows, it discovered that the remarkable improvement of a reflectance and the suppression of the fall by a heat history are obtained, and it reached this invention. In addition, it was found that the hiding power was excellent even when inorganic coloring agents other than blue were used.

The present invention is a curable resin composition comprising an organic binder and titanium oxide, the curable resin composition further comprising a blue inorganic colorant.

The preferable aspect of curable resin composition of this invention is listed below.

(1) An organic binder contains a reactive diluent and further contains a photopolymerizable initiator.

(2) A blue inorganic colorant is a pigment containing a silicate. Excellent hiding power and high reflectance are obtained.

(3) A blue inorganic colorant is a pigment containing sodium aluminum silicate. Even a small amount, excellent hiding power and high reflectance are obtained.

(4) A blue inorganic coloring agent is contained in 0.001-10 mass parts with respect to 100 mass parts of titanium oxides. 0.01-5 mass parts, especially 0.1-5 mass parts are preferable.

(5) It further contains a thermosetting component (especially an epoxy compound). As a result, excellent durability is obtained.

(6) It further contains antioxidant. This further suppresses a decrease in reflectance.

(7) It further contains another coloring agent.

Moreover, this invention also exists in curable resin composition characterized by further including an inorganic coloring agent as curable resin composition containing carboxyl group-containing resin, a photoinitiator, and titanium oxide. The above-mentioned preferable aspect (1)-(7) can also be applied to this curable resin composition. In particular, it is preferable to include another coloring agent.

This invention is also in curable resin composition for soldering resist formation containing the said curable resin composition.

The preferable aspect of the curable resin composition of the said invention can be applied to the curable resin composition for soldering resist formation of the said invention.

Moreover, this invention is also a cured coating film formed from the said curable resin composition, and also exists in the cured coating film characterized by the reflectance with respect to the light of wavelength 680nm 70% or more in the coating film surface when the film thickness is 20 micrometers.

The preferable aspect of the said cured coating film is listed below.

(1) The reflectance with respect to the light of the wavelength of 450-740 nm is 70% or more in the coating film surface when a film thickness is 20 micrometers.

(2) Based on the specification of IPC / JETEC J-STD-020, a heating temperature is set to 260 degreeC, and the reflectance with respect to the light of the wavelength of 680 nm of the coating film surface after performing 5 times of reflow is 70% or more. 5 times of reflow means the operation which returns to normal temperature 5 times through 10 second passes to an infrared furnace of 260 degreeC.

Moreover, the preferable aspect of the curable resin composition of the said invention can be applied to the cured coating film of the said invention.

Moreover, this invention also exists in the printed wiring board which has the said cured coating film.

The preferable aspect of the curable resin composition of the said invention can be applied to the printed wiring board of the said invention.

Curable resin composition of this invention adds blue inorganic pigment other than titanium oxide as a coloring agent to curable resin composition containing an organic binder. And the cured coating film obtained from this composition has the outstanding hiding power and high reflectance, and also the fall of the reflectance by heat history is suppressed. Therefore, the curable resin composition of this invention is useful for formation of a white cured coating film, for example, a soldering resist, and of course also useful for the printed wiring board using this. Moreover, curable resin composition of this invention is useful also in formation of colored cured coating film other than white.

1 is a graph showing reflectance at a wavelength of 360 to 740 nm of the coating film obtained in Example 3. FIG.
It is a graph which shows the reflectance in wavelength 360-740nm of the coating film obtained by the comparative example 2.

Curable resin composition of this invention has an organic binder and titanium oxide as a basic structural component. And a blue inorganic coloring agent is further included so that the coating film which has the outstanding hiding power and the high reflectance (especially the reflectance of the light of wavelength of 680 nm) and suppressed the fall of the reflectance by heat history can be obtained.

Titanium Oxide:

Although titanium oxide used as a white coloring agent in this invention may be rutile type titanium oxide or anatase type titanium oxide, it is preferable to use rutile titanium. Anatase-type titanium oxide, which is the same titanium oxide, has a higher whiteness than rutile-type titanium oxide and is often used as a white colorant. Since anatase-type titanium oxide has a photocatalytic activity, the resin in the insulating resin composition is particularly affected by light irradiated from the LED. May cause discoloration. On the other hand, the rutile type titanium oxide is slightly inferior to the anatase type, but has little optical activity. Therefore, deterioration (yellowing) of the resin due to light due to the light activity of titanium oxide is remarkably suppressed. It is also stable against heat. For this reason, when used as a white coloring agent in the insulating layer of the printed wiring board in which LED was mounted, high reflectance can be maintained over a long term. Also, titanium oxide is generally an titanium dioxide represented by TiO _2, is represented by TiO _X, and may be less than x is 2, 1.5 or higher.

As rutile type titanium oxide, a well-known thing can be used. There are two types of rutile titanium oxide production methods, a sulfuric acid method and a chlorine method, and in the present invention, those produced by either production method can be preferably used. Here, the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves it in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a precipitate of hydroxide, which is calcined at high temperature to take out rutile titanium oxide. Say the manufacturing method. On the other hand, the chlorine method refers to a production method using synthetic rutile or natural rutile as a raw material, reacting this with chlorine gas and carbon at a high temperature of about 1000 ° C. to synthesize titanium tetrachloride, and oxidizing this to extract rutile titanium oxide. Among them, the rutile type titanium oxide produced by the chlorine method is particularly effective in suppressing the deterioration (yellowing) of the resin due to heat, and is preferably used in the present invention.

Commercially available rutile type titanium oxide is, for example, Taipei R-820, Taipei R-830, Taipei R-930, Taipei R-550, Taipei R-630, Taipei R-680, Taipei R -670, Taipei R-680, Taipei R-670, Taipei R-780, Taipei R-850, Taipei CR-50, Taipei CR-57, Taipei CR-80, Taipei CR-90 , Taipei CR-93, Taipei CR-95, Taipei CR-97, Taipei CR-60, Taipei CR-63, Taipei CR-67, Taipei CR-58, Taipei CR-85, Taipei UT771 (above, Ishihara Sangyo Co., Ltd. product); Tie Pure R-100, Tie Pure R-101, Tie Pure R-102, Tie Pure R-103, Tie Pure R-104, Tie Pure R-105, Tie Pure R-108, Tie Pure R-900, Tie Pure R-902, Tai Pure R-960, Tai Pure R-706, Tai Pure R-931 (above, manufactured by DuPont); R-25, R-21, R-32, R-7E, R-5N, R-61N, R-62N, R-42, R-45M, R-44, R-49S, GTR-100, GTR- 300, D-918, TCR-29, TCR-52, FTR-700 (above Sakai Chemical Co., Ltd. make), etc. can be used.

Taipei CR-50, Taipei CR-57, Taipei CR-80, Taipei CR-90, Taipei CR-93, Taipei CR-95, Taipei CR-97, Taipei CR-60, Taipei CR-63, Taipei CR-67, Taipei CR-58, Taipei CR-85, Taipei UT771 (manufactured by Ishihara Sangyo Co., Ltd.); Tie Pure R-100, Tie Pure R-101, Tie Pure R-102, Tie Pure R-103, Tie Pure R-104, Tie Pure R-105, Tie Pure R-108, Tie Pure R-900, Tie Pure It is preferable to use R-902, Typure R-960, Typure R-706, and Typure R-931 (manufactured by DuPont).

In addition, a well-known thing can be used as anatase type titanium oxide. Commercially available anatase-type titanium oxides include titanium a-110, titanium a TCA-123E, titanium a-190, titanium a-197, titanium a-1, titanium a-1 (produced by Sakai Chemical Co., Ltd.); TA-100, TA-200, TA-300, TA-400, TA-500, TP-2 (manufactured by Fuji Titan Kogyo Co., Ltd.); Titanic JA-1, titanic JA-3, titanic JA-4, titanic JA-5, titanic JA-C (manufactured by Teika Co., Ltd.); KA-10, KA-15, KA-20, KA-30 (manufactured by Titan Kogyo Co., Ltd.); Taipei A-100, Taipei A-220, Taipei W-10 (manufactured by Ishihara Sangyo Co., Ltd.) and the like can be used.

The blending ratio of titanium oxide is preferably 20 to 600 parts by mass, and more preferably 20 to 400 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin when the organic binder is a carboxyl group-containing resin. When the blending ratio exceeds 600 parts by mass, the dispersibility of titanium oxide deteriorates, resulting in poor dispersion, which is not preferable. On the other hand, if it is less than 20 mass parts, since concealing power becomes low and it becomes difficult to obtain the insulating film of high reflectance, it is unpreferable. In addition, the compounding ratio of titanium oxide may be 20 to 80% of the whole composition.

Blue inorganic colorant:

Although the blue inorganic coloring agent (generally a blue inorganic pigment) of this invention is added in order to improve the hiding power of titanium oxide as a white coloring agent, the fall of the reflectance by addition of the said coloring agent is also fully suppressed. In particular, since the composition of this invention contains a blue inorganic coloring agent, the reflectance with respect to the light of the wavelength of 680 nm of the coating film surface obtained from a composition shows the value with very high. The light having a wavelength of 680 nm is almost orange light, and it has been found by the present inventors that when the reflectance of the light is high, the reflectance of full visible light tends to be improved. Generally, when the blue colorant is used, the reflectance of the light of 680 nm wavelength tends to fall, but it turned out that the reflectance of the light of 680 nm wavelength hardly falls by using a blue inorganic colorant. Therefore, the reflectance of the light of 680 nm wavelength of the cured coating film (film thickness of 20 micrometers) formed from the curable resin composition of this invention is generally 70% or more, 75% or more is preferable, and 80% is especially preferable.

It is preferable that the reflectance with respect to the light in the full-wavelength area | region of 450-740 nm also is 70% or more in the coating film surface when a film thickness is 20 micrometers.

Moreover, it also turned out that this cured coating film shows high reflectance even after long-term heating (heat history). For example, in accordance with the standard of IPC / JETEC J-STD-020, the heating temperature is set to 260 ° C., and the reflectance of light with a wavelength of 680 nm on the surface of the coating film after performing five reflows is generally 60% or more, 65% or more is preferred, especially 70%.

The blue inorganic colorant of the present invention is an inorganic colorant that exhibits blue color, and is an inorganic colorant (generally inorganic pigment) which exhibits maximum (maximum) absorption in the wavelength range of 410 to 470 nm in the wavelength range of visible light (380 to 750 nm).

Examples of blue inorganic pigments include ultramarine blue (Color Index Generic Name): Pigment Blue 29), French Ultramarine, Lapis Lazuli, Azlite, Prussian Blue (Prussian Blue; Color Index Name: Pigment) Blue 27); Blue composite oxide pigments such as aluminum-cobalt oxide, aluminum-zinc-cobalt oxide, silicon-cobalt oxide and silicon-zinc-cobalt oxide; Smalto (color index name: pigment blue 32), cobalt blue (aluminum cobalt (color index name: pigment blue 28)), tartaric acid cobalt (color index name: pigment blue 35), cobalt chrome blue (color index name : Pigment Blue 36), cobalt-aluminum-silicon oxide, cobalt zinc silicate (color index name: Pigment Blue 74), cobalt-zinc-silicon oxide (composition: spinel of CoO, Al ₂ O ₃ , SiO ₂ ), etc. And cobalt pigments.

Moreover, the pigment containing silicate, such as particle | grains which coat | covered titanium oxide on natural mica, can also be used. Natural mica is generally IM _2-3 □ _1-0 T ₄ O ₁₀ A ₂ (I is K, Na, Ca, if desired Ba, Rb, Cs, NH ₄ , M is Al, Mg, Fe , and Li, Ti, and according to the desired Mn, Cr, Zn, V, □ is the public and, T is Si, Al, Fe ^{3 +,} and according to the desired Be, B and, a is OH, F, desired And Cl, O, S).

Ultramarine blue (color index name: Pigment Blue 29) and the particle | grains which coated titanium oxide on natural mica are preferable, and ultramarine blue (color index name: Pigment Blue 29) is especially preferable. As a result, excellent hiding power and high reflectance are obtained. Ultramarine blue is usually a complex of sodium silicate containing sulfur (Na _8-10 Al ₆ Si ₆ O ₂₄ S _2-4 ). As a result, excellent hiding power and high reflectance can be obtained even in a small amount.

The average particle diameter of the blue inorganic colorant is generally preferably 0.01 to 10 µm and 0.05 to 5 µm, particularly preferably 0.05 to 3 µm. Here, an average particle diameter means an average primary particle diameter. Average particle diameter (D50) can be measured by a laser diffraction / scattering method.

It is preferable to contain a blue inorganic coloring agent in 0.001-10 mass parts with respect to 100 mass parts of titanium oxides. 0.01-5 mass parts is more preferable, 0.1-5 mass parts is especially preferable. When the compounding ratio is less than 0.001 parts by mass, since concealability is lowered, it is not preferable. On the other hand, when it exceeds 10 mass parts, since initial stage reflectance falls, it is unpreferable.

As the inorganic colorant other than blue, conventionally known colorants such as red, green, yellow, white, black, purple, orange and brown can be used. For example, metal oxide type, titanium black, etc. are mentioned.

Examples of the organic binder include carboxyl group-containing resins, reactive diluents as monomers, thermosetting components, and thermoplastic components.

Carboxyl group-containing resin

Although it does not specifically limit as carboxyl group-containing resin, Resin containing arbitrary carboxyl groups can be used, Especially carboxyl group-containing resin which does not have an aromatic ring is preferable. This resin which has a carboxyl group can use both photosensitive carboxyl group-containing resin which has one or more photosensitive unsaturated double bonds, and carboxyl group-containing resin which does not have photosensitive unsaturated double bond, and is not limited to a specific thing. In particular, what does not have an aromatic ring (which may be an oligomer or a polymer) can be used suitably among resin enumerated below. Moreover, you may use what used the epoxy resin as a starting material, the phenol resin as the starting material, etc. as carboxyl group-containing resin which has an aromatic ring.

(1) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate-based polyols and polyethers Carboxyl group-containing by polyaddition reaction of diol compounds, such as a compound polyol, a polyester type polyol, a polyolefin type polyol, an acryl type polyol, a bisphenol A alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group and an alcoholic hydroxyl group. Urethane resin.

(2) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol Terminal carboxyl group-containing urethane resin which makes acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as a compound which has a bisphenol-A alkylene oxide adduct diol, a phenolic hydroxyl group, and an alcoholic hydroxyl group. .

(3) bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified substance, the carboxyl group-containing dialcohol compound, and a diol compound.

(4) In the synthesis | combination of resin of said (1) or (3), the compound which has one hydroxyl group and one or more (meth) acryloyl groups in molecule | numerators, such as hydroxyalkyl (meth) acrylate, is added, Terminal (meth) acrylated carboxyl group-containing urethane resin.

(5) One isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin of the above-mentioned (1) or (3). The carboxyl group-containing urethane resin which added the compound which has, and was terminal (meth) acrylated.

(6) a carboxyl group-containing resin obtained by copolymerization of a compound having an unsaturated carboxylic acid and an unsaturated double bond,

(7) Photosensitive carboxyl group-containing resin obtained by reaction of the compound which has an oxirane ring and ethylenically unsaturated group in 1 molecule to carboxyl group-containing (meth) acrylic-type copolymer resin,

(8) An unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule, and a saturated or unsaturated polybasic acid anhydride is produced in the secondary hydroxyl group. Photosensitive carboxyl group-containing resin obtained by making it react,

(9) A photosensitive hydroxyl group and a carboxyl group-containing resin obtained by making a hydroxyl-containing polymer react with saturated or unsaturated polybasic acid anhydride, and then reacting the produced | generated carboxylic acid with the compound which has one epoxy group and an unsaturated double bond in 1 molecule, respectively.

(10) Photosensitive carboxyl group-containing resin obtained by making a polyfunctional epoxy compound react with unsaturated monocarboxylic acid, and making polybasic acid anhydride react with one part or all part of the secondary hydroxyl group produced by this reaction.

(11) A polybasic acid anhydride is reacted with a polyfunctional epoxy compound, a compound having one reactor other than a hydroxyl group reacting with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid. Carboxyl group containing photosensitive resin obtained by making it react.

(12) A carboxyl group-containing photosensitive resin obtained by making an unsaturated group containing monocarboxylic acid react with the reaction product of resin which has phenolic hydroxyl group, alkylene oxide, or cyclic carbonate, and making polybasic acid anhydride react with the obtained reaction product.

(13) A polyfunctional anhydride of a polybasic anhydride with respect to an alcoholic hydroxyl group of the reaction product obtained by reacting a polyfunctional epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group-containing monocarboxylic acid. Carboxyl group containing photosensitive resin obtained by making anhydride group react.

Among these, the air which has a carboxyl group obtained by reaction of (a) carboxyl group-containing (meth) acrylic copolymer resin which is photosensitive carboxyl group-containing resin of said (7), and (b) compound which has an oxirane ring and ethylenically unsaturated group in 1 molecule. Total resin is preferred.

The carboxyl group-containing (meth) acrylic copolymer resin of (a) is obtained by copolymerizing (meth) acrylic acid ester with a compound having one unsaturated group and at least one carboxyl group in one molecule. Examples of the (meth) acrylic esters constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone- (Meth) acrylates such as methoxyethyleneglycol (meth) acrylate, ethoxyethyleneglycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxyethyl (Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like Agent) and the like acrylates. These may be used independently, or may mix and use 2 or more types. In addition, in this specification, a (meth) acrylate is a term which generically refers to an acrylate and a methacrylate, and it is the same also about another similar display.

Moreover, as a compound which has one unsaturated group and at least 1 carboxyl group in 1 molecule, the modified unsaturated monocarboxylic acid chain-stretched between acrylic acid, methacrylic acid, an unsaturated group, and a carboxylic acid, for example, (beta) -carboxyethyl (meth ) Acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having ester bond by lactone modification, modified unsaturated monocarboxylic acid having ether bond, and further The thing containing two or more carboxyl groups, such as maleic acid, in a molecule | numerator is mentioned. These may be used independently, or may mix and use 2 or more types.

(b) As a compound which has an oxirane ring and an ethylenically unsaturated group in 1 molecule, what is necessary is just a compound which has an ethylenically unsaturated group and an oxirane ring in 1 molecule, For example, glycidyl (meth) acrylate and (alpha) -methyl glycidyl (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3, 4-epoxycyclohexylmethylamino acrylate etc. are mentioned. Especially, 3, 4- epoxycyclohexyl methyl (meth) acrylate is preferable. The compound which has an oxirane ring and ethylenically unsaturated group in these (b) 1 molecule may be used independently, or may mix and use 2 or more types.

The acid value of the carboxyl group-containing resin (A) is preferably in the range of 50 to 200 mg KOH / g. If the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion in the weak alkaline aqueous solution. When it exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured film. The mass average molecular weight of the carboxyl group-containing resin (A) is preferably in the range of 5,000 to 100,000. If the weight average molecular weight is less than 5,000, the tendency of dry-to-dry tendency is remarkably lowered. In addition, when the mass average molecular weight exceeds 100,000, it is not preferable because it causes a problem that developability and storage stability are significantly deteriorated.

Photopolymerization initiator

As a photoinitiator, well-known and common radical photoinitiators, such as an alkyl phenone type, a thioxanthone type, a benzoin ether type, a benzyl ketal type, an acyl phosphine oxide type, an oxime ether type, an oxime ester type, a titanocene type, are mentioned, An oxime ester photoinitiator containing the structural moiety represented by the following general formula (I), The alpha-aminoacetophenone type photoinitiator containing the structural moiety represented by the following general formula (II), and a structure represented by the following general formula (III) It is preferable to contain 1 type (s) or 2 or more types chosen from the group which consists of the acyl phosphine oxide type photoinitiator containing a part, and the titanocene type photoinitiator represented by following General formula (IV).

In the formula, R ¹ may be substituted with a hydrogen atom, a phenyl group (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 (may be substituted with one or more hydroxyl groups, and alkyl May have one or more oxygen atoms in the middle of the chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (alkyl group having 1 to 6 carbon atoms or a phenyl group) May be substituted). R ² may be substituted with a phenyl group (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 (may be substituted with one or more hydroxyl groups, and one in the middle of the alkyl chain) Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) Indicates. R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl alkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ⁵ , R ⁶ may be bonded to form a cyclic alkyl ether group. R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, or 1 to 20 carbon atoms. A carbonyl group (except the case where both R <^5> and R <^6> is a carbonyl group of 1-20 carbon atoms) is shown. R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group or a heterocyclic ring-containing halogenated aryl group.

Examples of the oxime ester photopolymerization initiator including the structural moiety represented by the general formula (I) include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), a compound represented by the following formula (I-1), 2- (acetyl Oxyiminomethyl) thioxanthene-9-one, and the compound represented by the following general formula (I-2), etc. are mentioned.

In formula (I-2), R ¹¹ is synonymous with R ¹ in the formula (I), and R ¹² and R ¹⁴ are each independently synonymous with R ² in the formula (I). R ¹³ 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, and a carbon atom having 2 to 12 carbon atoms. 12 alkoxycarbonyl groups (when the number of carbon atoms in the alkyl group constituting the alkoxyl group is 2 or more, the alkyl group may be substituted with one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain) or a phenoxycarboxyl group Indicates.

Among these, the compound represented by the said general formula (I-1), 2- (acetyloxyiminomethyl) thioxanthene-9-one, and the compound represented by general formula (I-2) are especially preferable. As a commercial item of the said compound, CGI-325, Irgacure OXE01, Irgacure OXE02 by BASF Japan company is mentioned.

As an alpha-aminoacetophenone type photoinitiator containing the structural part represented by the said General formula (II), 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propane, 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, etc. are mentioned. Commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.

As an acyl phosphine oxide type photoinitiator containing the structural part represented by the said General formula (III), 2,4,6- trimethyl benzoyl diphenyl phosphine oxide and bis (2,4, 6- trimethyl benzoyl)-phenyl phosphine jade Seed, bis (2, 6- dimethoxy benzoyl) -2, 4, 4- trimethyl- pentyl phosphine oxide, etc. are mentioned. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure 819 by BASF Japan Corporation, etc. are mentioned.

As the metallocene titanocene photoinitiator of the formula (IV) bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro -3- (1H- pyrrol-1- (I) -phenyl) titanium is mentioned. As a commercial item, Irgacure 784 by BASF JAPAN company, etc. are mentioned.

When the organic binder is carboxyl group-containing resin, the compounding ratio of such a photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, Preferably it is the ratio of 0.5-15 mass parts. If the compounding ratio of a photoinitiator is less than 0.01 mass part with respect to 100 mass parts of said carboxyl group-containing resins, photocurability on copper will run short, and a coating film will peel or coating film properties, such as chemical resistance, are unpreferable. On the other hand, when the compounding ratio of a photoinitiator is more than 30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, since deep part sclerosis | hardenability falls by the light absorption of a photoinitiator, it is not preferable.

Moreover, in the case of the oxime ester type photoinitiator represented by said Formula (I-1), the compounding ratio becomes like this. Preferably it is 0.01-20 mass parts, More preferably, 0.01-5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. Ratio. When using such an oxime ester photoinitiator, since it may react with a copper atom at the interface with copper foil, and the function as a photoinitiator may be inactivated, it is preferable to use together with the said alpha-aminoacetophenone type photoinitiator etc. . In addition, the compounding ratio of a photoinitiator may be 0.01-30% of the whole composition.

Reactive diluent

As a reactive diluent, the compound which has functional groups, such as ethylenically unsaturated group, a hydroxyl group, a carboxyl group, and an amino group, is generally used in a molecule | numerator. In particular, it is preferable to use the compound which has an ethylenically unsaturated group in a molecule | numerator. The compound having an ethylenically unsaturated group in the molecule can be photocured by irradiation with an active energy ray to render the photosensitive resin composition of the present invention insoluble in an aqueous alkali solution or to insolubilize it. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acryl The rate can be used, Specifically, Hydroxyalkyl acrylates, such as 2-hydroxymethylacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Amino alkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates such as water; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; Not limited to the above, acrylates and melamine acrylates in which polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols are directly acrylated or urethane acrylated through diisocyanates And at least any one of each of the methacrylates corresponding to the acrylate.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone di in the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxyurethane acrylate compounds etc. which reacted the half urethane compound of diisocyanate, such as isocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compound which has an ethylenically unsaturated group in said molecule may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable in view of photoreactivity and resolution, and when the compound having two ethylenically unsaturated groups in one molecule is used, the coefficient of thermal expansion of the cured product is lowered. It is preferable at the point that generation | occurrence | production of peeling at the time of PCT is reduced.

As for the compounding quantity of the compound which has an ethylenically unsaturated group in such a molecule | numerator, 2-50 mass% of the whole composition is preferable. When the compounding quantity is less than 2 mass%, photocurability falls and pattern formation becomes difficult by alkali image development after active energy ray irradiation. On the other hand, when it is more than 50 mass%, the solubility with respect to a dilute alkali aqueous solution falls and a coating film will fall. More preferably, it is 3-40 mass%.

(Organic solvent)

An organic solvent can be used for viscosity adjustment for apply | coating to a base material and a carrier film.

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; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents may be used individually by 1 type, and 2 or more types may be used as a mixture.

Thermosetting components (also called thermosetting components)

Curable resin composition of this invention contains a thermosetting component. It can be expected that the heat resistance is improved by adding the thermosetting component. The thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives and benzoguanamine derivatives, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and epi Known thermosetting resins, such as sulfide resin, bismaleimide, and carbodiimide resin, can be used. Particularly preferred is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter, omitted from cyclic (thio) ether groups) in the molecule.

The thermosetting component which has a some cyclic (thio) ether group in the said molecule | numerator is a compound which has any one or two types of groups of a 3, 4 or 5 membered cyclic (thio) ether group in a molecule | numerator, for example, multiple in a molecule | numerator The compound which has an epoxy group, ie, a polyfunctional epoxy compound, the compound which has a some oxetanyl group in a molecule | numerator, ie, the polyfunctional oxetane compound, the compound which has a some thioether group in a molecule | numerator, ie, episulfide resin, etc. are mentioned. .

Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as adecaizer O-130P, adecaizer O-180A, adecaser D-32 and adecaser D-55; JER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., Epiclone 840, Epiclone 850, Epiclone 1050, Epiclone 2055, Doto Epoto YD-011, YD-013, YD-127, YD-128, DER manufactured by Kasei Co., Ltd. 317, D.E.R. 331, D.E.R. 661, D.E.R. 664, Sumitomogagaku Kogyo Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A.E.R. 330, A.E.R. 331, A.E.R. 661, A.E.R. 664 (all trade names), bisphenol A type epoxy resin; YDC-1312, hydroquinone type epoxy resin, YSLV-80XY bisphenol type epoxy resin, and YSLV-120TE thioether type epoxy resin (all manufactured by Totogsei Co., Ltd.); JERYL903 manufactured by Mitsubishi Chemical Co., Ltd., Epiclone 152, Epiclone 165, manufactured by DIC Corporation, Efototo YDB-400, YDB-500, manufactured by Totogsei Co., Ltd., manufactured by Dow Chemical Co., Ltd. DER 542, Sumitomogagaku Kogyo Co., Ltd. Sumiepoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd. A.E.R. 711, A.E.R. Brominated epoxy resins, such as 714 (all are brand names); JER152, jER154 by Mitsubishi Chemical Co., Ltd., D.E.N. by Dow Chemical Co., Ltd. 431, D.E.N. 438, Epiclone N-730, Epiclone N-770, Epiclone N-865, Doto Co., Ltd. Etoto YDCN-701, YDCN-704, Nippon Kayaku Co., Ltd. ) EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomogagaku Kogyo Co., Ltd. Novolak-type epoxy resins, such as AERECN-235 and ECN-299 (all are brand names); Biphenol novolak-type epoxy resins, such as Nippon Kayaku Co., Ltd. product NC-3000 and NC-3100; Bisphenol F-type epoxy resins of Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, and YDF-2004 manufactured by Totogsei Co., Ltd .; Hydrogenated bisphenol A type epoxy resins such as Etoto ST-2004, ST-2007, ST-3000 (trade name) manufactured by Totosei Co., Ltd .; Glycidylamine types such as jER604 by Mitsubishi Chemical Co., Ltd., Efototo YH-434 by Totogase Co., Ltd., Sumiepoxy ELM-120 by Sumitomo Chemical Co., Ltd. (all brand name) Epoxy resins; Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celoxide 2021 and CY179 manufactured by Daicel Chemical Industries, Ltd. (both trade names); Trihydroxyphenylmethane type epoxy resins, such as Mitsubishi Chemical Co., Ltd. make YL-933, Dow Chemical Co., Ltd. T.E.N., EPPN-501, EPPN-502 (all are brand names); Bixylenol type or biphenol type epoxy resins, such as Mitsubishi Chemical Co., Ltd. make, YL-6056, YX-4000, and YL-6121 (all are brand names); Bisphenol S-type epoxy resins, such as Nippon Kayaku Co., Ltd. product EBPS-200, Adeka company EPX-30, and DIC company EXA-1514 (brand name); Bisphenol A novolak-type epoxy resins, such as Mitsubishi Chemical Co., Ltd. jER157S (brand name); Tetraphenylolethane type epoxy resins, such as Mitsubishi Chemical Co., Ltd. product jERYL-931 (all are brand names); Heterocyclic epoxy resins such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); Diglycidyl phthalate resins such as Nippon Yushi Corporation Brenma DGT; Tetraglycidyl xylenoylethane resins such as Toto Kasei Co., Ltd. ZX-1063; Naphthalene group-containing epoxy resins such as Shinnitetsu Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer type epoxy resins such as Nippon Yushi Corporation CP-50S and CP-50M; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Totogsei Co., Ltd.) Although these etc. are mentioned, It is not limited to these. These epoxy resins may be used alone or in combination of two or more. Especially among these, a novolak-type epoxy resin, a bixylenol-type epoxy resin, a biphenol-type epoxy resin, a biphenol novolak-type epoxy resin, a naphthalene-type epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) Methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate In addition to polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), caldo-type bisphenols, calix arenes, calyx resorcinrenes, or Ether ether with resin which has hydroxyl groups, such as a silsesquioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has a some cyclic thioether group in a molecule | numerator, Mitsubishi Chemical Co., Ltd. bisphenol-A episulfide resin YL7000 etc. are mentioned, for example. An episulfide resin in which an oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using a similar synthesis method.

As for the compounding quantity of the thermosetting component which has a some cyclic (thio) ether group in such a molecule, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl group of the said carboxyl group-containing resin, or 1 equivalent of phenol group of a phenol resin. When the blending amount is less than 0.6, a carboxyl group remains in the solder resist, and heat resistance, alkali resistance, electrical insulation and the like are lowered. On the other hand, when it exceeds 2.5 equivalents, the strength and the like of the coating film deteriorate because a low molecular weight cyclic (thio) ether group remains in the dried coating film. More preferably, it is 0.8-2.0 equivalent.

Moreover, as for the compounding quantity of the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator, 0.1-50 mass% of the whole composition is preferable. When the compounding amount is less than 0.1% by mass, sufficient toughness of the coating film is not obtained. On the other hand, when it exceeds 50 mass%, storage stability falls. More preferably, it is 1-30 mass%.

Moreover, as another thermosetting component, amino resins, such as a melamine derivative and a benzoguanamine derivative, are mentioned. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycol uril compounds, and methylol urea compounds. In addition, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound are each methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. It is obtained by converting a methylol group into an alkoxy methyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. In particular, melamine derivatives having a formalin concentration of 0.2% or less, which is good for the human body or the environment, are preferable.

As these commercial items, for example, Cymel 300, East 301, East 303, East 370, East 325, East 327, East 701, East 266, East 267, East 238, East 1141, East 272, East 202, East 1156, Copper 1158, Copper 1123, Copper 1170, Copper 1174, Copper UFR65, Copper 300 (all manufactured by Mitsui Cyanamid, Inc.), Nickal Rock Mx-750, Copper Mx-032, Copper Mx-270, Copper Mx-280, Copper Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (all are manufactured by Sanwa Chemical Co., Ltd.), etc. are mentioned. These thermosetting components may be used alone or in combination of two or more.

The compound which has several isocyanate group or blocked isocyanate group can be added to curable resin composition used by this invention in 1 molecule. Examples of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule thereof include a polyisocyanate compound and a block isocyanate compound. A blocked isocyanate group is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When the isocyanate group is heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group. By adding the said polyisocyanate compound or a block isocyanate compound, hardenability and toughness of the hardened | cured material obtained are improved.

As such a polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.

As a specific example of aromatic polyisocyanate, for example, 4,4'- diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5- diisocyanate, o-xylene diisocyanate , m-xylene diisocyanate, 2, 4-tolylene dimer, and the like.

Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Moreover, the adduct body, the biuret body, the isocyanurate body, etc. of the isocyanate compound mentioned above are mentioned.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. As an isocyanate compound which can react with a blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example.

As an isocyanate blocking agent, For example, phenol type blocking agents, such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -flareolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime block agents, such as formaldehyde doxime, acetaldehyde, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

A block isocyanate compound may be commercially available, for example, the grade BL-3175, BL-4165, BL-1100, BL-1265, the discount module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Disdis Mortum 2170, dismotum 2265 (all manufactured by Sumitomo Biureur Urethane Co., Ltd.), coronate 2512, coronate 2513, coronate 2520 (all Nippon Polyurethane High School Co., Ltd.), B-830, B-815, B-846, B- 870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.), etc. are mentioned. In addition, the schedule BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. The compound which has several isocyanate group or blocked isocyanate group in such one molecule can be used individually by 1 type or in combination of 2 or more types.

As for the compounding quantity of the compound which has some isocyanate group or blocked isocyanate group in 1 molecule, 0.1-50 mass% of the whole composition is preferable. When the compounding amount is less than 0.1% by mass, sufficient toughness of the coating film is not obtained. On the other hand, when it exceeds 50 mass%, storage stability falls. More preferably, it is 1-30 mass%.

Examples of the phenol resins include phenol novolak resins, alkyl phenol novolak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins, polyvinylphenols, and phenol / naphthol. Conventionally well-known things, such as resin, the (alpha)-naphthol frame | skeleton containing phenol resin, and triazine containing cresol novolak resin, are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Hereinafter, arbitrary components will be described.

Antioxidant, silicone resin, etc. are mentioned as an arbitrary component.

It is preferable to add antioxidant to a photocurable resin composition in order to prevent oxidation. Most of the high molecular materials, once oxidized, sequentially deteriorate oxidatively, and cause deterioration of the function of the high molecular materials, and decompose radical supplements or peroxides that cause the generated radicals into harmless substances, Antioxidants such as peroxide decomposers that prevent new radicals from occurring are effective.

Antioxidants that act as radical supplements are, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 Methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl Phenolic compounds such as) -s-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, and bis (2,2,6,6-tetramethyl Amine compounds, such as 4-piperidyl)-sebacate and phenothiazine, etc. are mentioned.

A radical supplement may be commercially available, for example, adecastab AO-30, adecastab AO-330, adecastab AO-20, adecastab LA-77, adecastab LA-57, adecastab LA-67, adecastab LA-68, adecastab LA-87 (all manufactured by Asahi Denka Co., Ltd.), Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Tinubin 111FDL , Tinubin 123, tinubin 144, tinubin 152, tinubin 292, tinubin 5100 (all manufactured by BASF Japan Co., Ltd.), and the like.

As antioxidant which acts as a peroxide decomposer, phosphorus compounds, such as a triphenyl phosphite, pentaerythritol tetralauryl thio propionate, a dilauryl thiodipropionate, distearyl 3,3'- thiodi Sulfur type compounds, such as propionate, etc. are mentioned.

A peroxide decomposer may be commercially available, for example, Adecastab TPP (made by Asahi Denka Co., Ltd., brand name), mark AO-412S (made by Adeka Agusugagaku Co., Ltd. brand name), smiller TPS (Sumitomogaga Co., Ltd.) Co., Ltd. make, brand name) etc. are mentioned. These antioxidants can be used individually or in combination of 2 or more types.

Curable resin composition of this invention is well-known and commonly used, such as well-known conventional polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, montmorillonite, etc. Known conventional additives such as thickeners, antifoaming agents and / or leveling agents such as silicone, fluorine and polymers, silane coupling agents such as imidazoles, thiazoles and triazoles, and inorganic fillers such as silica, barium sulfate and calcium carbonate It can further mix | blend and can mix | blend a coloring agent in the range which does not impair the white of curable resin composition of this invention.

The thermosetting resin composition of this invention is adjusted to the viscosity suitable for a coating method with the said organic solvent, and is apply | coated on a base material by methods, such as a screen printing method. After application | coating, a cured coating film can be obtained by heating and thermosetting at the temperature of 140 degreeC-180 degreeC, for example. Or after application | coating, the cured coating film can be obtained by irradiating the accumulated light quantity of 5-5000mJ / cm <^2> with the measurement wavelength centering on 350 nm, for example with a metal halide lamp.

[Dry Film]

The dry film of this invention has curable resin layer formed by drying, after apply | coating curable resin composition of this invention. The dry film of the present invention is used by laminating the curable resin layer in contact with a substrate.

In the dry film of the present invention, the curable resin composition is uniformly applied to a carrier film by a suitable method such as a blade coater, a lip coater, a comma coater, a film coater, and dried to form the curable resin layer described above. It can manufacture by laminating | covering a cover film on it. The cover film and the carrier film may use the same film material or different films.

In the dry film of this invention, the film material of a carrier film and a cover film can use all the well-known things used for a dry film.

As a carrier film, thermoplastic films, such as polyester films, such as polyethylene terephthalate of 2-150 micrometers thickness, are used, for example.

Although a polyethylene film, a polypropylene film, etc. can be used as a cover film, what has a smaller adhesive force with a curable resin layer than a carrier film is good.

100 micrometers or less are preferable and, as for the film thickness of the curable resin layer on the carrier film of this invention, the range of 5-50 micrometers is more preferable.

[Printed circuit board]

The printed wiring board of the present invention has a resin insulating layer formed of a curable resin composition on a substrate. Here, a resin insulating layer means the said cured coating film. The printed wiring board of this invention can be manufactured by a well-known method. For example, after apply | coating curable resin composition of this invention to the patterned copper foil base material, a resin insulating layer is formed by carrying out pattern exposure at a predetermined exposure amount. By continuing to develop, the printed wiring board of this invention is obtained. In addition, after exposure, curing may be further promoted by irradiating or heating the resin insulating layer with ultraviolet rays. As the substrate, resin, ceramics, and metal can be used.

It is preferable to use the light whose maximum wavelength exists in the range of 350-410 nm for exposure. By setting the maximum wavelength in this range, radicals can be efficiently generated from the photopolymerization initiator. Moreover, although the exposure amount changes with film thickness etc., it can harden | cure with the accumulated light quantity of 5-5000mJ / cm <^2> generally.

As a developing solution, a dilute alkali aqueous solution (for example, 0.3-3 wt% sodium carbonate aqueous solution) can be used.

100 micrometers or less are preferable and, as for the total film thickness of the resin insulating layer in the printed wiring board of this invention, the range of 5-50 micrometers is more preferable.

[Example]

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, below, "part" and "%" are mass references | standards unless there is particular notice.

[Examples 1 to 18 and Comparative Examples 1 to 3]

(Manufacture of Curable Resin Composition)

It mix | blended in the ratio (mass part) shown to Tables 1 and 2 with the various components shown in following Table 1 and Table 2, pre-mixed with a stirrer, and kneaded with three roll mills to manufacture curable resin composition.

The detail of the used material of the said Table 1 is as follows.

Carboxyl group-containing resin

Cycloma P (ACA) Z-250 (product name): manufactured by Daicel Chemical Industries, Ltd.

R-2000 (Product Name): Manufactured by DIC Corporation.

Photopolymerization initiator

Irgacure 907 (product name): manufactured by BASF Japan.

Kayakure DETX-S (product name): manufactured by Nippon Kayaku Co., Ltd.

Tarocure 1173 (product name): manufactured by BASF Japan.

Reactive diluent

DPHA (Product Name): manufactured by Nippon Kayaku Co., Ltd.

DPM (product name): Dow Chemical Co., Ltd. make.

Thermosetting ingredients

JER828 (Product Name): manufactured by Mitsubishi Chemical Corporation.

ICTEP-S (product name): manufactured by Nissan Gakuku Kogyo Co., Ltd.

HF-1 (Product Name): manufactured by Meiwa Kasei Kogyo Co., Ltd.

Titanium oxide

Taipei CR-97 (product name): manufactured by Ishihara Sangyo Co., Ltd.

Inorganic Colorants (Blue Inorganic Pigments)

PB-80 (product name) (ultramarine blue (average particle diameter: 1 micrometer)): Dai-Ichi Chemical Co., Ltd. make.

Iriodine 221 rutile pine blue (trade name): manufactured by Merck.

Cobalt Titanium Green: Pigment Green 50 Dainichi Sekaze Dipyroxide Green # 9320 (a green inorganic colorant).

Black iron oxide: Pigment Black 11 Titanium Co., Ltd. Tarox BL-100 (inorganic colorant).

(Organic pigment)

Firstgen Blue 5380 (product name): manufactured by DIC Corporation.

(G) antioxidant

Irganox 1010 (product name): manufactured by BASF Corporation.

(additive)

Melamine (product name): manufactured by Nissan Gakuku Kogyo Co., Ltd.

2PHZ-PW (Product Name): manufactured by Shikoku Chemical Co., Ltd.

(Defoamer)

KS-66 (product name): manufactured by Shin-Etsu Chemical Co., Ltd.

(Physical Properties of Curable Resin Composition)

(Examples 1 to 14 and Comparative Examples 1 to 3)

Each of the thermosetting resin compositions of Examples 1 to 14 and Comparative Examples 1 to 3 containing a blue inorganic pigment was printed on a FR-4 substrate having a circuit formed so as to have a dry coating of about 20 μm by screen printing, and then to 80 ° C. in a box furnace. Preliminary drying of 30 minutes was performed. After preliminary drying, 700mJ / cm <^2> exposure was performed with the exposure apparatus (HMW-680GW by Oak Corporation) on the coating film, and it developed by 30 degreeC and the 1% sodium carbonate aqueous solution. After the development, the substrate was cured for 60 minutes at 150 ° C. in a box furnace to prepare a substrate for characteristic tests.

(Examples 15 and 16)

The thermosetting resin compositions of Examples 15 and 16 were printed on a FR-4 substrate having a circuit formed so as to have a dry coating film of about 20 μm by screen printing, and then cured at 150 ° C. for 60 minutes in a box furnace to prepare a substrate for characteristic tests.

(Examples 17 and 18)

The curable resin compositions of Examples 17 and 18 were printed on a FR-4 substrate with circuit formation so that the dry coating film was about 20 μm, and 1000 mJ / cm ^{2 was} irradiated with a UV conveyor such as a high-pressure mercury lamp 80 W ³ to provide a substrate for characteristic testing. Produced.

evaluation

(1) hiding power for conductor patterns (circuits)

The hiding power of the cured coating film with respect to the conductor pattern which is copper foil with respect to the test board | substrate after post-curing (1 hour at 150 degreeC) was visually observed. Evaluation was made according to the following criteria.

(Double-circle): There is no difference in the color tone on a conductor pattern image and a base material.

○: slight yellowing at the edge of the conductor pattern.

(Triangle | delta): Slight yellowing on a conductor pattern.

X: Yellowing exists on a conductor pattern.

(2) Reflectance (%)

Initial stage: The reflectance in the wavelength of 360-740 nm was measured with the spectrophotometer (CM-2600d, the Konica Minolta Sensing Co., Ltd. product) on the coating film surface after the post-curing test substrate.

After heating: According to the standard of IPC / JETEC J-STD-020, heating temperature was set to 260 degreeC, and the coating film surface after performing 5 times of reflow spectrophotometer (CM-2600d, Konica Minolta Sensing Co., Ltd. product). The reflectance in the wavelength of 360-740 nm was measured. 5 times of reflow means the operation which returns to normal temperature 5 times through 10 second passes to an infrared furnace of 260 degreeC.

(3) Hue

It confirmed visually about the test board after post-cure.

The obtained results are shown in Table 1 and Table 2 above.

The reflectance of Examples 1-11, 15-18, and Comparative Examples 1-3 was shown with respect to wavelength 450nm and wavelength 680nm. The reflectance in the wavelength of 360-740 nm was shown only in Example 3 and the comparative example 2 in FIG. 1 and FIG.

As apparent from the above results, the coating film formed of the curable resin composition containing the blue inorganic colorant of the present invention exhibits excellent hiding power while maintaining high reflectance. Moreover, the reflectance after heating hardly falls. Moreover, also when it contains inorganic coloring agents other than blue, it is excellent in hiding property.

On the other hand, the coating film obtained from curable resin composition (Comparative example 1) which does not contain such a blue inorganic coloring agent is excellent in reflectance but inadequate hiding power. Moreover, although the coating film formed from the curable resin composition (comparative example 2) containing phthalocyanine blue (first gene blue 5380) as a blue coloring agent shows the outstanding hiding power, the reflectance is falling. Moreover, since the reflectance of 680 nm fell, the coating film of the comparative example 2 showed the yellowing tendency. Moreover, although the coating film formed from curable resin composition (comparative example 3) containing a trench type | system | group dye as a blue coloring agent shows the outstanding hiding power, the reflectance is falling. In addition, the coating film of Comparative Example 3 exhibits a yellowing tendency because the reflectance of 680 nm is reduced. In addition, the coating films of Comparative Examples 2 and 3 are remarkably lowered in reflectance after heating.

Claims (13)

A curable resin composition comprising an organic binder and titanium oxide, the curable resin composition further comprising a blue inorganic colorant. The curable resin composition according to claim 1, further comprising a reactive diluent as an organic binder and further comprising a photopolymerizable initiator. The curable resin composition according to claim 1 or 2, wherein the blue inorganic colorant is a pigment containing a silicate. The curable resin composition according to claim 1 or 2, wherein the blue inorganic colorant is a pigment containing sodium aluminum silicate. Curable resin composition of Claim 1 or 2 containing a blue inorganic coloring agent in 0.001-10 mass parts with respect to 100 mass parts of titanium oxides. A curable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, and titanium oxide, the curable resin composition further comprising an inorganic colorant. The curable resin composition of any one of Claims 1, 2, and 6 which further contains another coloring agent. The curable resin composition according to any one of claims 1, 2 and 6, further comprising a thermosetting component. The curable resin composition according to any one of claims 1, 2 and 6, further comprising an antioxidant. The curable resin composition according to any one of claims 1, 2 and 6, which is used for soldering resist formation. The cured coating film formed from the curable resin composition according to any one of claims 1, 2 and 6, wherein the reflectance of light having a wavelength of 680 nm is 70% or more on the surface of the coating film when the film thickness is 20 µm. The cured coating film characterized by the above-mentioned. The cured coating film of Claim 11 whose reflectance with respect to the light in the full-wavelength region of 450-740 nm is 70% or more in the coating film surface when a film thickness is 20 micrometers. It has a cured coating film of Claim 11, The printed wiring board characterized by the above-mentioned.

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