JP2014098139A - Curable resin composition, curable resin composition for forming solder resist, cured coating film, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of giving a coating film that has excellent concealing power and a high reflectance and suppresses reduction in the reflectance by a thermal history, and in particular, a curable resin composition for forming a solder resist, and a cured coating film and a printed wiring board obtained from the composition.SOLUTION: The curable resin composition comprises an organic binder and titanium oxide and further contains a blue inorganic colorant.

Description

  The present invention is a curable resin composition suitable as an insulating layer of a printed wiring board on which a light emitting element such as an LED is mounted, particularly a curable resin composition for forming a solder resist, and a cured coating film obtained from the composition, In addition, the present invention relates to a printed wiring board having this cured coating film.

  In recent years, printed wiring boards have been increasingly used for light-emitting diodes (LEDs) that emit light with low power, such as backlights for liquid crystal displays in portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures. ing.

  In the solder resist film (insulating film) that is formed on the printed wiring board as a protective film, in addition to the characteristics usually required for the solder resist film, such as solvent resistance, hardness, solder heat resistance, and electrical insulation, the light emission of the LED It is also required to effectively use. Therefore, in many cases, a white insulating film having excellent light reflectance is formed. That is, in an application that is directly mounted on a backlight of a liquid crystal display or a light source of a lighting fixture, a white insulating curable resin composition is generally used to form an insulating film. . And in order to color in this way, the titanium oxide is normally used as a coloring agent.

  As such a white insulating curable resin composition, for example, in Patent Document 1, a white pigment such as titanium oxide or the like such as carbon black is used so as to conceal the pattern of the conductor circuit even if the solder resist film is thinned. A solder resist composition containing a color pigment has been proposed. Patent Document 2 proposes a white curable resin composition for printed wiring boards, which contains phthalocyanine and contains titanium oxide at a high content in order to obtain excellent storage stability.

  However, even when the color pigment proposed in Patent Document 1 is blended, the solder resist film turns yellowish brown due to the heat history when the solder resist composition is applied to the printed wiring board and cured, and the conductor The concealing power for the circuit pattern may be reduced.

  Further, in the white curable resin composition containing phthalocyanine of Patent Document 2, phthalocyanine is blended because it is a pigment having low discoloration due to heat history, but the solder resist film is formed by yellowing of the resin component due to heat history. The color may turn yellowish brown, and the hiding power for the conductor circuit pattern may decrease.

  In order to solve the above disadvantages, Patent Document 3 discloses a white-cured solder resist film that is excellent in hiding power and suppresses discoloration due to thermal history without impairing various properties such as reflectance, resolution, and dimensional accuracy. As a conductive resin composition, a titanium oxide colorant using a selenium blue colorant has been proposed.

JP-A-2005-311233 JP2009-238771 JP2012-150461

  However, even when the selenium blue colorant disclosed in Patent Document 3 is used, it cannot be said that the reflectance and the reflectance are lowered due to thermal history.

  The present invention relates to a curable resin composition, in particular, a curable resin composition for forming a solder resist, which has an excellent hiding power and a high reflectance, and a cured coating film in which a decrease in reflectance due to thermal history is suppressed is obtained. An object of the present invention is to provide a cured coating film and a printed wiring board obtained from the composition.

  The present inventors are a solder resist containing titanium oxide, which has excellent hiding power and high reflectance (especially, reflectance of light having a wavelength of 680 nm), and has a decrease in reflectance and discoloration due to thermal history. In order to obtain resists that are suppressed, intensive studies have been made. The inventors have found that by using a blue inorganic colorant as described below, it is possible to obtain a significant improvement in reflectance and suppression of a decrease due to thermal history, and the present invention has been achieved. Further, it has been found that even when an inorganic colorant other than blue is used, the hiding power is excellent.

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

    Preferred embodiments of the curable resin composition of the present invention are listed below.

(1) It contains a reactive diluent as an organic binder, and further contains a photopolymerizable initiator.
(2) The blue inorganic colorant is a pigment containing silicate. Excellent hiding power and high reflectivity can be obtained.
(3) The blue inorganic colorant is a pigment containing sodium aluminum silicate. Even with a small amount, excellent hiding power and high reflectance can be obtained.
(4) A blue inorganic colorant is contained at 0.001 to 10 parts by mass with respect to 100 parts by mass of titanium oxide. 0.01 to 5 parts by mass, particularly 0.1 to 5 parts by mass is preferable.
(5) Furthermore, a thermosetting component (especially epoxy compound) is included. Thereby, excellent durability is obtained.
(6) Further, an antioxidant is included. Thereby, the fall of a reflectance is suppressed more.
(7) Further, another colorant is included.

The present invention also provides:
A curable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and titanium oxide,
Furthermore, it exists also in the curable resin composition characterized by including an inorganic coloring agent. The aforementioned preferred embodiments (1) to (7) can also be applied to this curable resin composition. In particular, it is preferable to include another colorant.

  The present invention also resides in a curable resin composition for forming a solder resist comprising the curable resin composition.

  The preferred embodiment of the curable resin composition of the present invention can be applied to the curable resin composition for forming a solder resist of the present invention.

  Furthermore, the present invention is a cured coating film formed from the above-mentioned curable resin composition, and the reflectance with respect to light having a wavelength of 680 nm is 70% or more on the coating film surface when the film thickness is 20 μm. There is also a characteristic cured coating.

  Preferred embodiments of the cured coating film are listed below.

(1) On the coating film surface when the film thickness is 20 μm, the reflectance with respect to light having a wavelength of 450 to 740 nm is 70% or more.
(2) In accordance with the standard of IPC / JETEC J-STD-020, the heating temperature is set to 260 ° C., and after 5 reflows, the reflectance of the coating film surface with respect to light having a wavelength of 680 nm is 70%. That's it. Reflow 5 times means that the operation of passing through an infrared furnace at 260 ° C. for 10 seconds and returning to room temperature was repeated 5 times.

  Moreover, the suitable aspect of the said curable resin composition of this invention is applicable to the cured coating film of the said this invention.

  Furthermore, this invention exists also in the printed wiring board characterized by having the said cured coating film.

  The preferred embodiment of the curable resin composition of the present invention can be applied to the printed wiring board of the present invention.

  The curable resin composition of the present invention is obtained by adding a blue inorganic pigment to a curable resin composition containing an organic binder in addition to titanium oxide as a colorant. And the cured coating film obtained from this composition has the outstanding concealment power and high reflectance, and the fall of the reflectance by a heat history is also suppressed. Therefore, the curable resin composition of the present invention is useful for forming a white cured coating film, for example, a solder resist, and is naturally useful for a printed wiring board using the same. Furthermore, the curable resin composition of the present invention is also useful for forming colored cured coatings other than white.

FIG. 1 is a graph showing the reflectance at a wavelength of 360 to 740 nm of the coating film obtained in Example 3. FIG. 2 is a graph showing the reflectance at a wavelength of 360 to 740 nm of the coating film obtained in Comparative Example 2.

  The curable resin composition of the present invention has an organic binder and titanium oxide as basic components. In order to obtain a coating film having excellent hiding power and high reflectance (especially, reflectance of light having a wavelength of 680 nm) and suppressing reduction in reflectance due to thermal history, a blue inorganic colorant is further obtained. Is included.

Titanium oxide:
In the present invention, the titanium oxide used as the white colorant may be rutile titanium oxide or anatase titanium oxide, but rutile titanium is preferably used. Anatase-type titanium oxide, which is the same titanium oxide, has higher whiteness than rutile-type titanium oxide and is often used as a white colorant. However, since anatase-type titanium oxide has photocatalytic activity, it is particularly useful from LED. The irradiated light may cause discoloration of the resin in the insulating resin composition. In contrast, rutile-type titanium oxide is slightly inferior in whiteness to anatase-type, but has almost no photoactivity. Therefore, resin degradation (yellowing) due to light due to photoactivity of titanium oxide occurs. Remarkably suppressed and stable against heat. For this reason, when used as a white colorant in the insulating layer of the printed wiring board on which the LED is mounted, a high reflectance can be maintained for a long period of time. The titanium oxide is generally titanium dioxide represented by TiO _2, but may be represented by TiO _x , and x may be less than 2 or 1.5 or more.

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

  Examples of commercially available rutile-type titanium oxides include, for example, Typek R-820, Typek R-830, Typek R-930, Typek R-550, Typek R-630, Typek R-680, Typek R-670, and Typek R. -680, Type R-670, Type R-780, Type R-850, Type CR-50, Type CR-57, Type CR-80, Type CR-90, Type CR-93, Type CR-95, Type CR -97, Type CR-60, Type CR-63, Type CR-67, Type CR-58, Type CR-85, Type UT771 (manufactured by Ishihara Sangyo Co., Ltd.); Type Pure R-100, Type Pure R-101 Tai Pure R-10 Taipure R-103, Taipure R-104, Taipure R-105, Taipure R-108, Taipure R-900, Taipure R-902, Taipure R-960, Taipure R-706, Taipure R-931 (above, 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 (manufactured by Sakai Chemical Industry Co., Ltd.) and the like can be used.

  Among the above, manufactured by the chlorine method, the Taipei CR-50, the Taipei CR-57, the Taipei CR-80, the Taipei CR-90, the Taipei CR-93, the Taipei CR-95, the Taipei CR-97, the Taipei CR-60, Taipei CR-63, Taipei CR-67, Taipei CR-58, Taipei CR-85, Taipei UT771 (manufactured by Ishihara Sangyo Co., Ltd.); Taipei Pure R-100, Taiwan Pure R-101, Taiwan Pure R-102, Taiwan Pure R-103 Taipure R-104, Taipure R-105, Taipure R-108, Taipure R-900, Taipure R-902, Taipure R-960, Taipure R-706, Taipure R-931 (manufactured by DuPont Co., Ltd.) It is preferable.

  Moreover, as an anatase type titanium oxide, a well-known thing can be used. As commercially available anatase type titanium oxide, TITON A-110, TITON TCA-123E, TITON A-190, TITON A-197, TITON SA-1, TITON SA-1L (manufactured by Sakai Chemical Industry Co., Ltd.); TA-100, TA-200, TA-300, TA-400, TA-500, TP-2 (manufactured by Fuji Titanium Industry Co., Ltd.); TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA -5, TITANIX JA-C (manufactured by Teika Co., Ltd.); KA-10, KA-15, KA-20, KA-30 (manufactured by Titanium Industry Co., Ltd.); Type A-100, Type A-220, Type W-10 (Ishihara Sangyo Co., Ltd. product) etc. can be used.

  When the organic binder is a carboxyl group-containing resin, the compounding ratio of titanium oxide is preferably 20 to 600 parts by mass, more preferably 20 to 400 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending ratio exceeds 600 parts by mass, the dispersibility of titanium oxide is deteriorated, resulting in poor dispersion. On the other hand, if it is less than 20 parts by mass, the hiding power is reduced, and it is difficult to obtain an insulating film having a high reflectivity. Moreover, 20-80% of the whole composition may be sufficient as the compounding ratio of a titanium oxide.

Blue inorganic colorant:
The blue inorganic colorant of the present invention (generally a blue inorganic pigment) is added to improve the hiding power of titanium oxide as a white colorant, but the decrease in reflectance due to the addition of the colorant is also sufficiently suppressed. ing. In particular, when the composition of the present invention contains a blue inorganic colorant, the reflectance of the coating film surface obtained from the composition with respect to light having a wavelength of 680 nm exhibits a very high value. The light having a wavelength of 680 nm is substantially orange light, but it has been clarified by the present inventors that the reflectance of all visible rays tends to be improved when the reflectance of this light is high. In general, when a blue colorant is used, the reflectance of light having a wavelength of 680 nm tends to be reduced. However, it is found that the reflectance of light having a wavelength of 680 nm is hardly lowered by using a blue inorganic colorant. It was. Therefore, the reflectance of light having a wavelength of 680 nm of a cured coating film (film thickness 20 μm) formed from the curable resin composition of the present invention is generally 70% or more, preferably 75% or more, and particularly 80%. preferable.

  On the surface of the coating film when the film thickness is 20 μm, the reflectance for light in the entire wavelength region of 450 to 740 nm is also preferably 70% or more.

  Furthermore, it was also found that this cured coating film exhibits a high reflectance even after prolonged heating (thermal history). For example, in accordance with the standard of IPC / JETEC J-STD-020, the heating temperature is set to 260 ° C., and after 5 reflows, the reflectance to light having a wavelength of 680 nm on the coating surface is generally 60%. Or more, preferably 65% or more, particularly preferably 70%.

  The blue inorganic colorant of the present invention is an inorganic colorant exhibiting a blue color. Generally, in the wavelength range of visible light (380 to 750 nm), the inorganic colorant exhibits a maximum (maximum) absorption rate in the wavelength range of 410 to 470 nm. Agent (generally an inorganic pigment).

Examples of blue inorganic pigments include
Ultramarine Blue (Color Index Generic Name): Pigment Blue 29), French Ultramarine, Lapis Lazuli, Azurite, Prussian Blue (Prussia Blue; Color Index Name: Pigment Blue 27);
Blue complex 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 (cobalt aluminate (color index name: Pigment Blue 28)), cobalt stannate (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 formula: CoO / Al ₂ O ₃ / SiO ₂ spinel), etc. And cobalt pigments.

In addition, pigments containing silicate such as particles in which natural mica is coated with titanium oxide can also be used. Natural mica is generally IM _2-3 □ _1-0 T ₄ O ₁₀ A ₂ (I is K, Na, Ca, optionally Ba, Rb, Cs, NH ₄ , M is Al , Mg, Fe, Li, Ti, optionally Mn, Cr, Zn, V, □ are vacancies, T is Si, Al, Fe ³⁺ , optionally Be, B, A is OH, F and optionally Cl, O, S).

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

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

  The blue inorganic colorant is preferably contained at 0.001 to 10 parts by mass with respect to 100 parts by mass of titanium oxide. 0.01-5 mass parts is more preferable, and 0.1-5 mass parts is especially preferable. When the blending ratio is less than 0.001 part by mass, the concealability is lowered, which is not preferable. On the other hand, if it exceeds 10 parts by mass, the initial reflectance is inferior, which is not preferable.

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

  Examples of the organic binder include a carboxyl group-containing resin, a reactive diluent as a monomer, a thermosetting component, and a thermoplastic component.

Carboxyl group-containing resin The carboxyl group-containing resin is not particularly limited, and a resin containing any carboxyl group can be used, but a carboxyl group-containing resin having no aromatic ring is particularly preferable. The resin having a carboxyl group includes a photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds, and a carboxyl group-containing resin having no photosensitive unsaturated double bond. Any of them can be used and is not limited to a specific one. In particular, among the resins listed below, those having no aromatic ring (any of oligomers or polymers) can be preferably used. In addition, as a carboxyl group-containing resin having an aromatic ring, a resin using an epoxy resin as a starting material or a resin using a phenol resin as a starting material may be used.

  (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, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (2) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate and bifunctional epoxy resin such as 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, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin described in (1) or (3) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing urethane resin.

  (5) During the synthesis of the resin described in (1) or (3) above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

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

  (7) a photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule;

  (8) An unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond. A photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride,

(9) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with a compound having one epoxy group and an unsaturated double bond in each molecule. A photosensitive hydroxyl group- and carboxyl group-containing resin.

  (10) A photosensitive carboxyl group obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a polybasic acid anhydride with some or all of the secondary hydroxyl groups produced by this reaction. Containing resin.

  (11) A polyfunctional epoxy compound is reacted with a compound having one reactive group other than a hydroxyl group that reacts with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

  (12) Obtained by reacting a reaction product of a resin having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride. Carboxyl group-containing photosensitive resin.

  (13) A 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. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride group of a polybasic acid anhydride with an alcoholic hydroxyl group.

  Among these, (a) the carboxyl group-containing (meth) acrylic copolymer resin (b), which is the photosensitive carboxyl group-containing resin of (7), and (b) an oxirane ring and an ethylenically unsaturated group in one molecule. A copolymer resin having a carboxyl group obtained by a reaction with a compound having an aromatic group is preferred.

  The carboxyl group-containing (meth) acrylic copolymer resin (a) is obtained by copolymerizing a (meth) acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group in one molecule. Obtained. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Containing (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy Triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more. In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  In addition, examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid in which a chain is extended between the unsaturated group and the carboxylic acid. For example, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond due to lactone modification, etc., modified unsaturated having an ether bond Examples thereof include monocarboxylic acids, and those containing two or more carboxyl groups in the molecule, such as maleic acid. These may be used alone or in combination of two or more.

  (B) The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule. For example, glycidyl (meth) acrylate, α -Methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexyl Examples include methylamino acrylate. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.

  It is desirable that the carboxyl group-containing resin (A) has an acid value in the range of 50 to 200 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion with a weak alkaline aqueous solution. When it exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured coating. Moreover, it is preferable that the mass mean molecular weight of carboxyl group-containing resin (A) exists in the range of 5,000-100,000. If the mass average molecular weight is less than 5,000, the dryness to touch tends to be extremely poor. On the other hand, if the mass average molecular weight exceeds 100,000, it is not preferable because developability and storage stability are remarkably deteriorated.

Photopolymerization initiator As the photopolymerization initiator, known radical photopolymerization initiators such as alkylphenone, thioxanthone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, oxime ester, and titanocene are used. An oxime ester photopolymerization initiator containing a structural part represented by the following general formula (I), an α-aminoacetophenone light containing a structural part represented by the following general formula (II) Selected from the group consisting of a polymerization initiator, an acylphosphine oxide photopolymerization initiator containing a structural moiety represented by the following general formula (III), and a titanocene photopolymerization initiator represented by the following general formula (IV). It is preferable to contain 1 type (s) or 2 or more types.

In the formula, R ¹ 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 (one May be substituted with the above 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, or 2 to 20 carbon atoms. An alkanoyl group or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group). R ² represents 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 (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 ( And may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or alkyl having 1 to 6 carbon atoms. Represents a group, or R ⁵ and R ⁶ may combine 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, an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, or the number of carbon atoms 1 to 20 carbonyl groups (except when both R ⁵ and R ⁶ are carbonyl groups having 1 to 20 carbon atoms). R ⁹ and R ¹⁰ each independently represents a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.

  As the oxime ester photopolymerization initiator containing the structural portion represented by the general formula (I), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), a compound represented by the following formula (I-1), 2 Examples include-(acetyloxyiminomethyl) thioxanthen-9-one and compounds represented by the following general formula (I-2).

In formula (I-2), R ¹¹ has the same meaning as R ¹ in general formula (I), and R ¹² and R ¹⁴ have the same meaning as R ² in general 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, or 2 to 2 carbon atoms. 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 phenoxycarboxylic group.

  Among these, the compound represented by the above formula (I-1), 2- (acetyloxyiminomethyl) thioxanthen-9-one, and the compound represented by the general formula (I-2) are particularly preferable. Examples of commercially available compounds include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by BASF Japan.

  Examples of the α-aminoacetophenone photopolymerization initiator containing the structural portion 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 BASF Japan.

  Examples of the acylphosphine oxide photopolymerization initiator containing the structural portion represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenyl. Examples thereof include phosphine oxide 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 BASF Japan.

Examples of the titanocene photopolymerization initiator represented by the general formula (IV) include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole). Mention may be made of -1-yl) -phenyl) titanium. Examples of commercially available products include Irgacure 784 manufactured by BASF Japan.

  When the organic binder is a carboxyl group-containing resin, the mixing ratio of such a photopolymerization initiator 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 carboxyl group-containing resin. The ratio of parts. When the blending ratio of the photopolymerization initiator is less than 0.01 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, the photocurability on copper is insufficient, the coating film peels off, and the chemical resistance Since the coating film properties such as the above are deteriorated, it is not preferable. On the other hand, when the blending ratio of the photopolymerization initiator exceeds 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin, the deep part curability is lowered due to light absorption of the photopolymerization initiator, which is not preferable.

  In the case of the oxime ester photopolymerization initiator represented by the formula (I-1), the blending ratio is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferably, it is the ratio of 0.01-5 mass parts. When such an oxime ester photopolymerization initiator is used, it reacts with copper atoms at the interface with the copper foil, and the function as the photopolymerization initiator may be deactivated. It is preferable to use it together with a polymerization initiator or the like. The blending ratio of the photopolymerization initiator may be 0.01 to 30% of the whole composition.

Reactive diluent As the reactive diluent, a compound having a functional group such as an ethylenically unsaturated group, a hydroxyl group, a carboxyl group or an amino group in the molecule is generally used. In particular, it is preferable to use a compound having an ethylenically unsaturated group in the molecule. A compound having an ethylenically unsaturated group in the molecule can be photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the photosensitive resin composition of the present invention in an alkaline aqueous solution. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate can be used, Specifically, hydroxyalkyl acrylates such as 2-hydroxymethyl acrylate, 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-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; N, N-di Aminoalkyl acrylates such as tilaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethyloxides Polyvalent acrylates such as adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylates, bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trig Polyglycerides of glycidyl ether such as ricidyl isocyanurate; not limited to the above, but polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol are directly acrylated or urethane acrylated via diisocyanate Examples include acrylates, melamine acrylate, and at least one of each methacrylate corresponding to the acrylate.

  Furthermore, 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 resin can improve photocurability without deteriorating the touch drying property.

  A compound having an ethylenically unsaturated group in the molecule as described above may be used alone or in combination of two or more. In particular, a compound having 4 to 6 ethylenically unsaturated groups in one molecule is preferable from the viewpoint of photoreactivity and resolution, and a compound having two ethylenically unsaturated groups in one molecule is used. And the linear thermal expansion coefficient of hardened | cured material falls and it is preferable from generation | occurrence | production of peeling at the time of PCT being reduced.

  As for the compounding quantity of the compound which has an ethylenically unsaturated group in the above molecules, 2-50 mass% of the whole composition is preferable. When the blending amount is less than 2% by mass, the photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays. On the other hand, when it exceeds 50 mass%, the solubility with respect to dilute alkali aqueous solution falls, and a coating film becomes weak. More preferably, it is 3 to 40% by mass.

(Organic solvent)
The organic solvent can be used for viscosity adjustment for application to a substrate or 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; 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 an organic solvent may be used individually by 1 type, and may be used 2 or more types as a mixture.

Thermosetting component (also called thermosetting component)
The curable resin composition of the present invention contains a thermosetting component. It can be expected that heat resistance is improved by adding a thermosetting component. Examples of thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, bis Known thermosetting resins such as maleimide and carbodiimide resins 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 abbreviated as cyclic (thio) ether groups) in the molecule.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having any one of the three, four or five-membered cyclic (thio) ether groups in the molecule or a plurality of two types of groups. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, That is, an episulfide resin etc. can be mentioned.

  Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as Adeka Sizer O-130P, Adeka Sizer O-180A, Adeka Sizer D-32, and Adeka Sizer D-55 manufactured by ADEKA; jER828 and jER834 manufactured by Mitsubishi Chemical Corporation. , JER1001, jER1004, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epoto YD-011, YD-013, YD manufactured by Tohto Kasei Co., Ltd. -127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. 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); YDC-1312, hydroquinone type epoxy resin, YSLV-80XY bisphenol type epoxy resin, YSLV-120TE thioether type epoxy resin (all manufactured by Toto Kasei Co., Ltd.); JERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Co., Ltd., A.C. manufactured by Asahi Kasei Kogyo Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC Corporation, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd. , EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); biphenol novolac type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd .; Epicron 830 manufactured by DIC Corporation JER807 manufactured by Mitsubishi Chemical Co., Ltd. Etototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd .; Epototo ST-2004 manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as ST-3000 (trade name); jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumi-epoxy manufactured by Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as ELM-120 (all trade names); Hydantoin type epoxy resin; Iseru Chemical Industrial Co., Ltd. Celloxide 2021, cycloaliphatic epoxy resin CY179 like (all trade names); Mitsubishi Chemical Co., Ltd. YL-933, Dow Chemical Co. of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) such as trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc. Bixylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC, etc .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; Nissan Chemical Industries Heterocyclic epoxy resin such as TEPIC manufactured by Co., Ltd. (all trade names); manufactured by NOF Corporation Diglycidyl phthalate resin such as Renmer DGT; Tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Toto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP manufactured by DIC Corporation Naphthalene group-containing epoxy resins such as -4032, EXA-4750, and EXA-4700; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; CP-50S and CP manufactured by Nippon Oil & Fats Co., Ltd. -50M glycidyl methacrylate copolymer epoxy resin; further copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy Resin (for example, Toto Kasei Ltd.) of YR-102, YR-450, etc.) and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, bixylenol-type epoxy resins, biphenol-type epoxy resins, biphenol novolac-type epoxy resins, naphthalene-type epoxy resins or mixtures thereof are particularly preferable.

  Examples of the polyfunctional oxetane compound 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-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo-type bis Phenol ethers, calixarenes, calix resorcin arenes or etherified products such as the 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 having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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 amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is 0.6 to 1 equivalent of the carboxyl group of the carboxyl group-containing resin or 1 equivalent of the phenol group of the phenol resin. 2.5 equivalents are preferred. 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 the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, thereby reducing the strength of the coating film. More preferably, it is 0.8-2.0 equivalent.

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

  Furthermore, other thermosetting components include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM (all manufactured by Sanwa Chemical Co., Ltd.). Such thermosetting components can be used alone or in combination of two or more.

  A compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the curable resin composition used in the present invention. Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds. The blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces. By adding the polyisocyanate compound or the blocked isocyanate compound, the curability and the toughness of the resulting cured product are improved.

As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Examples thereof include m-xylylene diisocyanate and 2,4-tolylene dimer.

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

  Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds can be used.

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

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; 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, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, milk Alcohol-based blocking agents such as methyl and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine Etc.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry 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.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used alone or in combination of two or more.

  The compounding amount of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 0.1 to 50% by mass of the whole composition. When the blending amount is less than 0.1% by mass, sufficient coating film toughness cannot be obtained. On the other hand, when it exceeds 50 mass%, storage stability falls. More preferably, it is 1-30 mass%.

  Examples of phenol resins include phenol novolac resins, alkylphenol volac resins, bisphenol A novolac resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, cresol / naphthol resins, polyvinylphenols, phenol / naphthol resins, Conventionally known materials such as an α-naphthol skeleton-containing phenol resin and a triazine-containing cresol novolac resin can be used. These can be used alone or in combination of two or more.

  Hereinafter, arbitrary components will be described.

Examples of optional components include antioxidants and silicone resins.
It is preferable to add an antioxidant to the photocurable resin composition in order to prevent oxidation. In many polymer materials, once oxidation begins, oxidative degradation occurs one after another in a chain, leading to functional degradation of the polymer material. Antioxidants such as peroxide decomposers that break down oxides into harmless substances and prevent the generation of new radicals are effective.

  Examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2- Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-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) -s-triazine -Phenols such as 2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4 Piperidyl) - sebacate, and amine compounds such as phenothiazine and the like.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (all manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 292 Name).

  Examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipropio Examples thereof include sulfur compounds such as nates.

  The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (Asahi Denka Co., trade name), Mark AO-412S (Adeka Argus Chemical Co., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name). These antioxidants can be used alone or in combination of two or more.

  If necessary, the curable resin composition of the present invention may be a known conventional polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, or the like, or a known conventional polymerization inhibitor such as finely divided silica, organic bentonite, or montmorillonite. Thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, silica, barium sulfate, calcium carbonate, etc. Known and commonly used additives such as a filler can be blended, and a colorant can be blended within a range that does not impair the white color of the curable resin composition of the present invention.

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

[Dry film]
The dry film of the present invention has a curable resin layer formed by applying and then drying the curable resin composition of the present invention. The dry film of the present invention is used by laminating a curable resin layer so as to be in contact with a substrate.

  In the dry film of the present invention, the curable resin composition is uniformly applied to the carrier film by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater, and dried to form the curable resin layer described above. Preferably, it can be produced by laminating a cover film thereon. The cover film and the carrier film may be the same film material or different films.

In the dry film of the present invention, as the film material for the carrier film and the cover film, any known materials used for the dry film can be used.
As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.

  As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesive force with the curable resin layer is smaller than that of the carrier film.

  The film thickness of the curable resin layer on the carrier film of the present invention is preferably 100 μm or less, and more preferably in the range of 5 to 50 μm.

[Printed wiring board]
The printed wiring board of the present invention has a resin insulating layer formed from a curable resin composition on a base material. Here, the resin insulating layer means the cured coating film. The printed wiring board of the present invention can be produced by a known method. For example, after applying the curable resin composition of the present invention to a patterned copper foil base material, the resin insulation layer is formed by pattern exposure with a predetermined exposure amount. Next, development is performed to obtain the printed wiring board of the present invention. In addition, hardening may be further accelerated | stimulated by irradiating a resin insulating layer with an ultraviolet-ray after an exposure, or heating. Examples of the substrate include resin, ceramics, and metal.

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

As a developing solution, dilute alkaline aqueous solution (for example, 0.3-3 wt% sodium carbonate aqueous solution)
Can be used.
The total film thickness of the resin insulating layer in the printed wiring board of the present invention is preferably 100 μm or less, and more preferably in the range of 5 to 50 μm.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

[Examples 1 to 18 and Comparative Examples 1 to 3]
(Preparation of curable resin composition)
Blended in the proportions (parts by mass) shown in Tables 1 and 2 together with various components shown in Tables 1 and 2 below, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a curable resin composition did.

Details of the materials used in Table 1 are as follows.
Carboxyl group-containing resin Cyclomer 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 Ltd.
KAYAKURE DETX-S (product name): manufactured by Nippon Kayaku Co., Ltd.
Darocur 1173 (product name): manufactured by BASF Japan.
Reactive diluent DPHA (product name): manufactured by Nippon Kayaku Co., Ltd.
DPM (product name): manufactured by Dow Chemical Co., Ltd.
Thermosetting component JER828 (product name): manufactured by Mitsubishi Chemical Corporation.
ICTEP-S (product name): manufactured by Nissan Chemical Industries, Ltd.
HF-1 (product name): manufactured by Meiwa Kasei Kogyo Co., Ltd.
Titanium oxide Type CR CR-97 (product name): manufactured by Ishihara Sangyo Co., Ltd.
Inorganic colorant (blue inorganic pigment)
PB-80 (product name) (Ultramarine Blue (average particle size: 1 μm)): manufactured by Daiichi Kasei Kogyo Co., Ltd.
Iriodin 221 rutile fine blue (product name): manufactured by Merck.
Cobalt Titanium Green: Pigment Green 50 Dainipponside Green # 9320 (green inorganic colorant) manufactured by Dainichi Seika.
Black iron oxide: Pigment Black 11 TAROX BL-100 (inorganic colorant) manufactured by Titanium Industry.
(Organic pigment)
Fast Gen Blue 5380 (product name): manufactured by DIC Corporation.
(G) Antioxidant IRGANOX 1010 (product name): manufactured by BASF.
(Additive)
Melamine (product name): manufactured by Nissan Chemical Industries, Ltd.
2PHZ-PW (product name): manufactured by Shikoku Kasei Kogyo Co., Ltd.
(Defoamer)
KS-66 (product name): manufactured by Shin-Etsu Chemical Co., Ltd.

(Physical properties of curable resin composition)
(Examples 1-14 and Comparative Examples 1-3)
The thermosetting resin compositions of Examples 1 to 14 and Comparative Examples 1 to 3 containing a blue inorganic pigment were printed on a FR-4 substrate on which a circuit was formed by screen printing so that the dry coating film was about 20 μm. Then, preliminary drying was performed at 80 ° C. for 30 minutes in a BOX furnace. After preliminary drying, the coating film was exposed to 700 mJ / cm ^{2 with} an exposure device (OMW HMW-680GW) and then developed with a 1% aqueous sodium carbonate solution at 30 ° C. After development, a substrate for characteristic test was prepared by post-curing at 150 ° C. for 60 minutes in a BOX furnace.

(Examples 15 and 16)
The thermosetting resin compositions of Examples 15 and 16 were printed on a circuit-formed FR-4 substrate by screen printing so that the dried coating film was about 20 μm, and post-cured at 150 ° C. for 60 minutes in a BOX furnace. Thus, a substrate for characteristic test was produced.

(Examples 17 and 18)
The curable resin compositions of Examples 17 and 18 were printed on a FR-4 substrate on which a circuit was formed by screen printing so that the dry coating film was about 20 μm, and then 1000 mJ in a high-pressure mercury lamp 80 W 3 lamp UV conveyor furnace. / Cm ^{2 was} irradiated to produce a characteristic test substrate.

Evaluation (1) Concealing Power for Conductor Pattern (Circuit) With respect to the test substrate after post-cure (1 hour at 150 ° C.), the concealing power of the cured coating film on the conductor pattern, which is a copper foil, was visually observed. Evaluation was performed according to the following criteria.
(Double-circle): There is no difference in the color tone on a conductor pattern and a base material.
○: Slightly yellowed at the edge of the conductor pattern.
Δ: Some yellowing on the conductor pattern.
X: Yellowing occurred on the conductor pattern.

(2) Reflectance (%)
Initial: About the test substrate after the post-cure, the reflectance at a wavelength of 360 to 740 nm was measured on the coating film surface with a spectrocolorimeter (CM-2600d, manufactured by Konica Minolta Sensing Co., Ltd.).
After heating: In accordance with the standard of IPC / JETEC J-STD-020, the heating temperature was set at 260 ° C., and the surface of the coating film after the reflow was performed 5 times was measured with a spectrocolorimeter (CM-2600d, Konica Minolta). Sensing Co., Ltd.), the reflectance at a wavelength of 360 to 740 nm was measured. Reflow 5 times means that the operation of passing through an infrared furnace at 260 ° C. for 10 seconds and returning to room temperature was repeated 5 times.

(3) Color tone The test substrate after post-cure was confirmed visually.
The obtained results are shown in Tables 1 and 2 above.
The reflectances of Examples 1 to 11, 15 to 18 and Comparative Examples 1 to 3 are shown for a wavelength of 450 nm and a wavelength of 680 nm. The reflectances at wavelengths of 360 to 740 nm are shown in FIGS. 1 and 2 for Example 3 and Comparative Example 2 only.

  As is clear from the above results, the coating film formed from the curable resin composition containing the blue inorganic colorant of the present invention exhibits excellent hiding power while maintaining high reflectance. Furthermore, the reflectance after heating hardly decreases. Moreover, even when it contains inorganic colorants other than blue, it is excellent in concealment.

  On the other hand, although the coating film obtained with such a curable resin composition not containing a blue inorganic colorant (Comparative Example 1) has excellent reflectivity, it does not have sufficient hiding power. In addition, the coating film formed from the curable resin composition (Comparative Example 2) containing phthalocyanine blue (Fast Gen Blue 5380) as the blue colorant exhibits excellent hiding power, but the reflectance decreases. Yes. Moreover, since the reflectance of 680 nm is falling, the coating film of the comparative example 2 has shown the yellowing tendency. Furthermore, a coating film formed from a curable resin composition containing a selenium dye as a blue colorant (Comparative Example 3) also exhibits excellent hiding power, but has a reduced reflectance. In addition, the coating film of Comparative Example 3 shows a yellowing tendency because the reflectance at 680 nm is lowered. Moreover, the coating film of Comparative Examples 2 and 3 has a remarkable decrease in reflectance after heating.

Claims (13)

A curable resin composition comprising an organic binder and titanium oxide,
Furthermore, the curable resin composition characterized by including a blue inorganic coloring agent.   The curable resin composition of Claim 1 which contains a reactive diluent as an organic binder, and also contains a photopolymerization 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 any one of claims 1 to 3, wherein the blue inorganic colorant is a pigment containing sodium aluminum silicate.   The curable resin composition according to any one of claims 1 to 4, wherein the blue inorganic colorant is contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of titanium oxide. A curable resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and titanium oxide,
Furthermore, the curable resin composition characterized by including an inorganic coloring agent.   Furthermore, another coloring agent is included, The curable resin composition of any one of Claims 1-6 characterized by the above-mentioned.   Furthermore, a thermosetting component is included, The curable resin composition of any one of Claims 1-7 characterized by the above-mentioned.   Furthermore, antioxidant is included, The curable resin composition of any one of Claims 1-8 characterized by the above-mentioned.   It is an object for solder resist formation, The curable resin composition of any one of Claims 1-9 characterized by the above-mentioned.   It is the cured coating film formed from the curable resin composition of any one of Claims 1-10, Comprising: The reflectance with respect to the light of a wavelength of 680 nm is 70 on the coating-film surface when a film thickness is 20 micrometers. % Cured film characterized by being at least%.   The cured coating film according to claim 11, wherein the coating film surface with a film thickness of 20 μm has a reflectance of 70% or more for light in the entire wavelength region of 450 to 740 nm.   A printed wiring board comprising the cured coating film according to claim 11.

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