JP2019045567A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

To provide a curable resin composition that can easily form a cured product pattern having an opening while using an inorganic filler with an average particle size of 300 nm or less, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and a printed wiring board having the cured product.SOLUTION: The curable resin composition contains (A) a photocurable component, (B) a photopolymerization initiator, (C) an inorganic filler with an average particle size of 1-300 nm and (D) an ultraviolet absorber.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a curable resin composition, a dry film, a cured product and a printed wiring board.

  For example, in the production of a printed wiring board, a curable resin composition is generally employed to form a permanent film such as a solder resist, and as such a curable resin composition, a dry film type composition or a liquid composition Have been developed (for example, Patent Document 1).

  2. Description of the Related Art In recent years, with the rapid progress of semiconductor components, electronic devices tend to be reduced in size, size, size, performance and multifunctionality. Following this tendency, miniaturization, thinning and increasing the number of pins of semiconductor packages have been put to practical use. Specifically, BGA (ball grid array), CSP (chip scale package), etc. are substituted for IC packages called QFP (quad flat pack package), SOP (small outline package), etc. An IC package called is used. Further, in recent years, FC-BGA (Flip Chip Ball Grid Array) has also been put to practical use as an IC package with higher density.

JP-A-61-243869 (claims)

  A further reduction in film thickness is required for permanent coatings such as solder resists formed on printed wiring boards (also referred to as package substrates) used for the above IC packages. However, when the film thickness is reduced, for example, there is a problem that the storage elastic modulus is relatively low and the strength of the cured film such as the breaking strength becomes insufficient. For such problems, it is conceivable to increase the blending ratio of the inorganic filler. However, in the case of a curable resin composition using an inorganic filler having an average particle size of 300 nm or less as the inorganic filler, the influence of halation at the time of exposure is large, the opening shape is unstable, or the small diameter opening property is insufficient. In some cases, it was difficult to form the opening. Then, in order to easily form the opening, it is conceivable to change the blending amount and type of the photopolymerization initiator, but it was still difficult to form the opening only by these changes and adjustments. .

  Therefore, an object of the present invention is to use a curable resin composition capable of easily forming a cured product pattern having an opening while using an inorganic filler having an average particle diameter of 300 nm or less, and the curable resin composition An object of the present invention is to provide a dry film having the obtained resin layer, a cured product of the curable resin composition or the resin layer of the dry film, and a printed wiring board having the cured product.

  As a result of intensive investigations by the present inventors, it was found that the ultraviolet ray absorption was performed on a curable resin composition containing (A) a photocurable component, (B) a photopolymerization initiator, and (C) an inorganic filler having an average particle diameter of 1 to 300 nm. It has been found that the problem can be solved by blending the agent, and the present invention has been completed.

  That is, the curable resin composition of the present invention comprises (A) a photocurable component, (B) a photopolymerization initiator, (C) an inorganic filler having an average particle size of 1 to 300 nm, and (D) an ultraviolet absorber. It is characterized by containing.

  It is preferable that the curable resin composition of this invention contains carbon black as said (D) ultraviolet absorber.

  It is preferable that the curable resin composition of this invention contains the said (D) ultraviolet absorber 0.01-10 mass% of the gross mass of solid content of the said curable resin composition.

  The curable resin composition of the present invention further comprises (C1) an inorganic filler having an average particle size of more than 300 nm, and the (C) inorganic filler having an average particle size of 1 to 300 nm and the (C1) average particle size It is preferable to contain 45 mass% or more of the total mass of solid content of the said curable resin composition by the total compounding quantity of the inorganic filler over 300 nm.

  The dry film of the present invention is characterized by having a resin layer obtained from the curable resin composition.

  The cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

  The printed wiring board of the present invention is characterized by having the cured product.

  According to the present invention, a curable resin composition capable of easily forming a cured product pattern having an opening while using an inorganic filler having an average particle diameter of 300 nm or less, obtained from the curable resin composition It is possible to provide a dry film having a resin layer, a cured product of the curable resin composition or the resin layer of the dry film, and a printed wiring board having the cured product.

It is a schematic diagram at the time of irradiating an ultraviolet-ray to the curable resin composition which does not contain an ultraviolet absorber using an inorganic filler whose average particle diameter is 300 nm or less. It is a schematic diagram at the time of irradiating an ultraviolet-ray to the curable resin composition of this invention which uses the inorganic filler whose average particle diameter is 300 nm or less, and contains an ultraviolet absorber. It is the microscope picture which expanded the opening part of the hardened | cured material of Example 1 1000 times. It is the microscope picture which expanded the opening part of the hardened | cured material of the comparative example 1 1000 times.

  The curable resin composition of the present invention comprises (A) a photocurable component, (B) a photopolymerization initiator, (C) an inorganic filler having an average particle diameter of 1 to 300 nm, and (D) a UV absorber. It is.

  In the case of a curable resin composition using an inorganic filler having an average particle size of 300 nm or less, during exposure, the effect of halation is that the ultraviolet light irradiated to the exposed area is reflected by the inorganic filler to promote curing of the unexposed area. The opening shape is unstable or the small diameter opening property is insufficient, making it difficult to form the opening. The schematic diagram at the time of irradiating an ultraviolet-ray to the curable resin composition which does not contain an ultraviolet absorber using the inorganic filler whose average particle diameter is 300 nm or less is shown in FIG. In FIG. 1, (A) shows during exposure and (B) shows after exposure. As shown in FIG. 1, during the exposure (A), the non-exposed area of the curable resin composition 2 coated with the mask 3 is not directly irradiated with the ultraviolet light 4, but the inorganic matter of the exposed area By the scattering of the ultraviolet light 4 by the filler 5, the curing proceeds.

  On the other hand, even in the case where an inorganic filler having an average particle size of 300 nm or less is used, in the curable resin composition of the present invention to which an ultraviolet absorber is additionally added, the ultraviolet rays irradiated to the exposed portion at the time of exposure are inorganic. Even if it is reflected by the filler, the ultraviolet absorber absorbs it, so curing of the unexposed area can be suppressed. For this reason, the influence of halation at the time of exposure can be reduced, and a pattern of a cured film having an opening can be easily formed. The schematic diagram at the time of irradiating an ultraviolet-ray to the curable resin composition of this invention which uses the inorganic filler of 300 nm or less in average particle diameter and contains an ultraviolet absorber in FIG. 2 is shown. Also in the schematic view of FIG. 2, as in FIG. 1, (A) shows during exposure and (B) shows after exposure. As shown in FIG. 2, in the curable resin composition 2 of the present invention, since the ultraviolet light 4 reflected by the inorganic filler 5 in the exposed area is absorbed by the ultraviolet light absorber 6 during (A) exposure, The unexposed area of the resulting curable resin composition 2 is less susceptible to the scattering of the ultraviolet light 4 and the opening can be easily formed.

  Below, each component of the curable resin composition of this invention is demonstrated. In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

[(A) photocurable component]
The photocurable component (A) contains a photocurable reactive group, but may contain both a photocurable reactive group and a thermosetting reactive group. That is, the (A) photocurable component may be a light and thermosetting component which contributes to both the photocuring reaction and the thermosetting reaction.

The photocurable component (A) is a compound having an ethylenically unsaturated group, includes a polymer, an oligomer, a monomer, and the like, and may be a mixture thereof. By containing a photocurable component (A), the curable resin composition can be cured by exposure and the strength of the cured film can be improved. The photocurable component (A) can be used singly or in combination of two or more.
As a compound which has an ethylenically unsaturated group, the photopolymerizable oligomer which is a well-known and usual photocurable monomer, a photopolymerizable vinyl monomer, etc. can be used.

  Examples of the photopolymerizable oligomer include unsaturated polyester oligomers, (meth) acrylate oligomers and the like. Examples of (meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylates, cresol novolac epoxy (meth) acrylates and bisphenol-type epoxy (meth) acrylates, urethane (meth) acrylates, epoxy urethanes (meth) 2.) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene modified (meth) acrylate and the like.

  As the photopolymerizable vinyl monomer, known and commonly used ones, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide (Meth) acrylamides such as luamide and N-butoxymethyl acrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; Alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Alkylenepolyol poly (meth) acrylates such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxy Polyoxyalkylene glycols such as methylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ) Acrylates; Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; and isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate Be

  The photocurable component (A) can be used singly or in combination of two or more. The blending ratio of the photocurable component (A) is, for example, 0.1 to 55% by mass, and preferably 0.2 to 50% by mass, in the solid content excluding the solvent of the entire composition.

[(B) Photopolymerization initiator]
The curable resin composition of the present invention contains (B) a photopolymerization initiator as an essential component. As the photopolymerization initiator (B), any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.

  (B) As the photopolymerization initiator, for example, bis- (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis- (2,6-dimethoxy benzoyl) phenyl phosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis- (2,4 , 6-Trimethylbenzoyl) -phenylphosphine And other bisacyl phosphine oxides; 2,6-dimethoxybenzoyl diphenyl phosphine oxide, 2,6-dichlorobenzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl phenyl phosphine methyl ester, 2-methyl Monoacyl phosphine oxides such as benzoyl diphenyl phosphine oxide, pivaloyl phenyl phosphine isopropyl ester, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide (Omnirad TPO manufactured by IGM); 1-hydroxy-cyclohexyl phenyl ketone , 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (4 Hydroxyacetophenones such as -hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl Benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methyl benzophenone, Michler's ketone, methyl benzophenone, 4,4'- Benzophenones such as dichlorobenzophenone and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, Acetophenones such as N, N-dimethylamino acetophenone; thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-diisopropyl thioxanthone, etc. Thioxanthones; Anthraquinones such as traraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone, etc. Acetophenone dimethyl ketal, benzyl dimethyl ketal etc. Ketals; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethylbenzoic acid ethyl ester and the like; 1,2-octanedione, 1- [4- (phenylthio)- , 2- (O-Benzoyloxime)], Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), etc. Esters; ((5-2,4-Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2 , 6-Difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium etc. titanocenes such as phenyldisulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, Tetramethylthiuram disulfide and the like can be mentioned. As the photopolymerization initiator (B), one type may be used alone, or two or more types may be used in combination. Among them, monoacyl phosphine oxides and oxime esters (hereinafter, also referred to as monoacyl phosphine oxide type photopolymerization initiator and oxime ester type photopolymerization initiator, respectively) are preferable, and 2,4,6-trimethyl benzoyl diphenyl phosphine The oxide, ethanone and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) are more preferable.

  (B) A photoinitiator can be used individually by 1 type or in combination of 2 or more types. The blending ratio of the (B) photopolymerization initiator is, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the (A) photocurable component.

[(C) Inorganic filler having an average particle size of 1 to 300 nm]
The curable resin composition of the present invention contains (C) an inorganic filler having an average particle size of 1 to 300 nm as an essential component, and this inorganic filler and (C1) an inorganic filler having an average particle size exceeding 300 nm It is preferable to use in combination. Furthermore, containing 45% by mass or more of the total mass of the solid content of the composition (C) inorganic filler and (C1) inorganic filler in total enhances strength and storage stability, and linear expansion coefficient (CTE) It is preferable from the viewpoint of lowering it. This ratio is more effective when it is 60 mass% or more, 70 mass% or more, 80 mass% or more, and particularly effective when it is 83 mass% or more. Similarly, the inorganic filler (C) having an average particle size of 1 to 300 nm contains 5% by mass or more of the total mass of the solid content of the composition in order to improve the strength of the cured product such as storage elastic modulus. Is more effective when it is 10% by mass or more, and particularly effective when it is 15% by mass or more.
Here, in the present specification, the average particle size of the (C) inorganic filler and (C1) inorganic filler is not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates). (D50), which is a value of D50 measured by a laser diffraction method. As a measuring apparatus by a laser diffraction method, Microtrac MT3300EXII made by Nikkiso Co., Ltd. is mentioned. The maximum particle size (D100) and the particle size (D10) can be measured similarly by the above-described apparatus.

  By containing two types of (C) inorganic fillers and (C1) inorganic fillers having different average particle sizes, and filling the (C) inorganic fillers with the (C) inorganic filler, the remaining clearance can be reduced It is possible to obtain a curable resin composition having a low resin content, that is, a high proportion of the mass of the filler in the total mass. Even within the same product as a normal commercial product, the particle diameter originally has a variation of 2 to 3 times, but at that ratio, fine particles do not effectively enter the gaps, so (C) inorganic filler, (C1 The average particle diameter of the inorganic filler preferably has a difference of 5 times or more. The larger the average particle diameter ratio of the (C) inorganic filler and the (C1) inorganic filler, the better. The average particle size of the (C1) inorganic filler is more preferably 8 times or more, and still more preferably 10 times or more the average particle size of the (C) inorganic filler.

  The average particle size of the (C1) inorganic filler is preferably 5 μm or less. The average particle diameter of the (C1) inorganic filler varies depending on the application of the curable resin composition, and is preferably 5 μm or less in applications where a cured film is formed on an IC package substrate, for example. It is preferable that it is 30 micrometers or less in the use which forms, and it is preferable that it is 40 micrometers or less in a mold (sealing) application. Furthermore, it is preferable that the particle diameter (D10) of the (C1) inorganic filler is 5 times or more of the average particle diameter (D50) of the (C) inorganic filler. The filling efficiency of (C) inorganic filler to the crevice of (C1) inorganic filler as this ratio is five or more improves, and it excels in the balance of the intensity of hardened material, and the lamination nature of a dry film.

  The compounding ratio of the (C) and (C1) inorganic fillers is preferably (C) :( C1) = 5: 5 to 1: 9 by volume ratio, and is 4: 6 to 2: 8. More preferable. Within the above range, the strength of the cured product and the laminating property of the dry film can be further enhanced.

  The materials of (C) the inorganic filler and (C1) the inorganic filler are not particularly limited. For example, silica, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, titanium oxide, Aluminum hydroxide, silicon nitride, aluminum nitride and the like can be mentioned. Among them, silica is preferable, and the curing shrinkage of the cured product of the curable resin composition is suppressed, the CTE becomes lower, and the properties such as the storage elastic modulus, the adhesion, and the hardness are improved. As silica, fused silica, spherical silica, amorphous silica, crystalline silica and the like can be mentioned.

  The presence or absence of the surface treatment of the (C) inorganic filler and the (C1) inorganic filler is not particularly limited. However, as described above, since the curable resin composition of the present invention has a low resin content, it is preferable that the (C) inorganic filler and the (C1) inorganic filler be surface-treated to enhance the dispersibility. . Cohesion can also be prevented by using a filler that has been surface-treated.

  The surface treatment method of (C) inorganic filler and (C1) inorganic filler is not particularly limited, and a known and commonly used method may be used, but a surface treatment agent having a curable reactive group, for example, a curable reactive group is an organic group It is preferable to treat the surface of the inorganic filler with a coupling agent or the like.

  As a coupling agent, coupling agents such as silane type, titanate type, aluminate type and zircoaluminate type can be used. Among them, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy Examples include cyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like, and these can be used alone or in combination. It is preferable that these silane coupling agents are previously immobilized on the surface of the inorganic filler by adsorption or reaction. Here, it is preferable that the processing amount of the coupling agent with respect to 100 mass parts of inorganic fillers is 0.5-10 mass parts. In the present invention, the coupling agent applied to the inorganic filler is not included in the compound having an ethylenically unsaturated group.

  Examples of the photocurable reactive group include ethylenically unsaturated groups such as vinyl group, styryl group, methacryl group and acryl group. Among them, at least one of vinyl group and (meth) acrylic group is preferable.

  As a thermosetting reaction group, a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group, etc. Can be mentioned. Among them, at least one of an amino group and an epoxy group is preferable.

The surface-treated inorganic filler of (C) inorganic filler and (C1) inorganic filler may be contained in the curable resin composition of the present invention in the surface-treated state, and the surface-untreated inorganic filler The filler and the surface treatment agent may be separately blended to surface-treat the inorganic filler in the composition, but it is preferable to blend an inorganic filler which has been surface-treated in advance. By blending an inorganic filler which has been surface-treated in advance, it is possible to prevent a decrease in crack resistance and the like due to the surface treatment agent which is not consumed in the surface treatment which may remain when it is separately blended. In the case of surface treatment in advance, it is preferable to blend a predispersion solution in which an inorganic filler is predispersed in a solvent or a curable component, and the surface treated inorganic filler is predispersed in a solvent and the predispersion solution is blended in the composition. Alternatively, it is more preferable to mix the predispersion solution into the composition after surface treatment is sufficiently carried out upon predispersing the surface-untreated inorganic filler in a solvent.
The (C) inorganic filler and (C1) inorganic filler may be blended with the component (A) or the like in the form of powder or solid depending on the use mode of the curable resin composition of the present invention, and mixed with a solvent or dispersant After making into a slurry, you may mix | blend with (A) component etc.

[(D) UV absorber]
As described above, from the viewpoint of increasing the strength and storage elastic modulus and lowering the linear expansion coefficient (CTE), the (C) inorganic filler and (C1) inorganic filler are 45% by mass or more of the total mass of the solid content of the composition It is preferable to contain, and it is preferable to contain especially 83 mass% or more, but when a compounding ratio is made high, formation of an opening becomes more difficult. However, in the curable resin composition of the present invention, the inclusion of the (D) ultraviolet absorber as an essential component facilitates the opening even when the compounding ratio of (C) inorganic filler and (C1) inorganic filler is high. Can be formed.
As the (D) ultraviolet absorber according to the present invention, any one can be used as long as it absorbs light with a wavelength of 300 nm to 450 nm.

  (D) As an ultraviolet absorber, inorganic type ultraviolet absorbers, such as carbon black and black titanium oxide (it is also called titanium black), an organic type ultraviolet absorber, etc. can be mentioned. Among these, carbon black is most preferable from the viewpoint of the resolution of the cured product.

  Examples of organic UV absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, and dibenzoylmethane derivatives. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone Can be mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-t And -butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and the like. Specific examples of benzotriazole derivatives include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 And 4-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of triazine derivatives include hydroxyphenyl triazine, bisethylhexyl oxyphenol methoxyphenyl triazine and the like.

  The UV absorber may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, BASF Japan Ltd. make, brand name) etc. are mentioned.

  The organic ultraviolet absorber is preferably used in combination with carbon black. The resolution is further stabilized by using it in combination with carbon black.

  As the ultraviolet absorber (D), one type may be used alone, or two or more types may be used in combination. (D) The ultraviolet absorber is effective in a small amount, and it is preferable to contain 0.01 to 10% by mass of the total mass of the solid content of the composition, and from the viewpoint of deep curing that affects the resolution of the cured product Therefore, 0.02 to 7% by mass is more preferable. When carbon black is contained as the (D) ultraviolet absorber, it is preferable to contain 0.01 to 1% by mass of the total mass of the solid content of the composition, from the viewpoint of resolution of the cured product. It is more preferable to contain 0.02-0.5 mass% of the total mass of solid content, and it is especially preferable to contain 0.05-0.30 mass% of the total mass of solid content of a composition.

((E) Thermosetting component)
The curable resin composition of the present invention more preferably contains (E) a thermosetting component. Further, the curable resin composition of the present invention more preferably contains, as the (E) thermosetting component, an alkali-soluble resin and a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule. (E) By containing a thermosetting component, the strength of the cured film can be improved. The thermosetting component (E) can be used singly or in combination of two or more.
As the thermosetting component (E), any known one can be used. For example, known resins such as melamine resins, benzoguanamine resins, amino derivatives such as melamine derivatives and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins, alkali soluble resins, etc. Of thermosetting components can be used. Particularly preferred are compounds having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) and alkali-soluble resins in the molecule.

  The compound having a plurality of cyclic (thio) ether groups in the molecule is preferably a compound having a plurality of 3, 4 or 5 membered cyclic (thio) ether groups in the molecule, for example, in the molecule Examples thereof include compounds having a plurality of epoxy groups, ie, polyfunctional epoxy compounds, compounds having a plurality of oxetanyl groups in the molecule, ie, polyfunctional oxetanes, and compounds having a plurality of thioether groups in the molecule, ie, episulfide resin.

  As polyfunctional epoxy compounds, epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolac type epoxy resin; biphenol novolac type epoxy resin; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof Bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylol ethane type epoxy resin; heterocyclic epoxy resin; diglycidyl Tetralate resin; tetraglycidyl xylenoyl ethane resin; epoxy resin containing naphthalene group; epoxy resin having dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; epoxy modified Examples include polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like, but are not limited thereto. These epoxy resins can be used singly or in combination of two or more. Among these, novolac epoxy resins, bisphenol epoxy resins, bixylenol epoxy resins, biphenol epoxy resins, biphenol novolac epoxy resins, naphthalene epoxy resins or mixtures thereof are preferable.

  As a polyfunctional oxetane compound, for example, 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-methyl-3-oxetanylmethoxy) methyl] benzene Oxetane alcohol and novolac resin, in addition to multifunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and their oligomers or copolymers , 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.

  As a compound which has several cyclic thioether group in a molecule | numerator, bisphenol-A-type episulfide resin etc. are mentioned. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of novolak-type epoxy resin to the sulfur atom using the same synthetic method can also be used.

  Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds and methylolurea compounds.

  A polyisocyanate compound can be blended as an isocyanate compound. As polyisocyanate compounds, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolylene isocyanate dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the isocyanate compounds mentioned above Adducts, biuret body and isocyanurate products thereof.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate blocking agent, for example, a phenol based blocking agent; a lactam based blocking agent; an active methylene based blocking agent; an alcoholic based blocking agent; an oxime based blocking agent; a mercaptan based blocking agent; an acid amide based blocking agent; Amine based blocking agents; imidazole based blocking agents; imine based blocking agents and the like.

  Moreover, it is preferable to contain the alkali-soluble resin which has alkali-soluble group as (E) thermosetting component. Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Among them, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because the adhesion with the base is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because it is excellent in developability. The carboxyl group-containing resin is preferably a carboxyl group-containing photosensitive resin having an ethylenic unsaturated group, but may be a carboxyl group-containing resin not having an ethylenic unsaturated group. When the alkali-soluble resin has an ethylenically unsaturated group, it also functions as (A) a photocurable component. In addition, when the curable resin composition of this invention contains alkali-soluble resin, you may use not only the use which carries out alkali development but the use which does not carry out alkali development.

  Specific examples of the carboxyl group-containing resin include the compounds listed below (which may be either an oligomer or a polymer).

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylol propionic acid and dimethylol butanoic 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 type polyol, a polyolefin type polyol, an acrylic type polyol, a bisphenol A type alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and 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 the terminal of a urethane resin by the 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.

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

  (5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added Meta) Acrylated carboxyl group-containing urethane resin.

  (6) During synthesis of the resin of the above (2) or (4), an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, such as one isocyanate group and one or more (meth) acryloyl groups in the molecule The compound which it has is added and the terminal (meth) acrylated carboxyl group-containing urethane resin.

  (7) A carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to a hydroxyl group present in a side chain Containing resin.

  (8) A carboxyl group-containing resin obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the generated hydroxyl group .

  (9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (10) A reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a substance.

  (11) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, (meth) Reaction with unsaturated group-containing monocarboxylic acid such as acrylic acid and the like to the alcoholic hydroxyl group of the reaction product obtained, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydride A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.

  (13) In addition to the carboxyl group-containing resin described in the above (1) to (12) etc., one epoxy group and one or more epoxy groups per molecule such as glycidyl (meth) acrylate and .alpha.-methylglycidyl (meth) acrylate Meta) carboxyl group-containing resin formed by adding a compound having an acryloyl group.

  Among the above-mentioned carboxyl group-containing resins, carboxyl group-containing resins described in (1), (7), (8) and (10) to (13) are preferable.

  Examples of the compound having a phenolic hydroxyl group include compounds having a biphenyl skeleton or a phenylene skeleton or both of them, phenol, ortho cresol, para cresol, meta cresol, 2,3-xylenol, 2,4-xylenol, 2 5, 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. And phenolic resins having various skeletons synthesized by

  Moreover, as compounds having a phenolic hydroxyl group, for example, phenol novolac resin, alkylphenolvolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F Examples thereof include known and commonly used phenolic resins such as bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, and condensate of dihydroxynaphthalene and aldehyde.

  As a commercial item of a phenol resin, HF1H60 (made by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (made by Dainippon Printing Co., Ltd.), Ve-Sole CZ-256-A (made by DIC), a show Nord BRG-555, Shonol BRG-556 (made by Showa Denko), CGR-951 (made by Maruzen Petroleum Co., Ltd.), polyvinyl phenol CST 70, CST 90, S-1 P, S-2 P (made by Maruzen Petroleum) can be mentioned. .

  The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 mg KOH / g, and more preferably in the range of 40 to 150 mg KOH / g. (A) When the acid value of the alkali-soluble resin is 20 mg KOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, dissolution of the exposed area by the developer can be suppressed, and thus the line may be faded more than necessary or, depending on the case, dissolution peeling in the developer regardless of the exposed area and the unexposed area. It is possible to draw a resist pattern well by suppressing the deformation.

  Although the weight average molecular weight of alkali-soluble resin changes with resin frame | skeleton, the range of 1,500-50,000, and also 1,500-30,000 is preferable. When the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and a reduction in resolution can be suppressed. On the other hand, when the weight average molecular weight is 50,000 or less, developability is good and storage stability is also excellent.

  The alkali-soluble resin can be used singly or in combination of two or more. The blend ratio of the alkali-soluble resin is, for example, 0 to 55% by mass, and preferably 3 to 50% by mass, in the solid content excluding the solvent of the entire composition.

  The thermosetting component (E) can be used singly or in combination of two or more. The compounding ratio of the thermosetting component (E) is, for example, 0 to 55% by mass, and preferably 1 to 50% by mass, in the solid content excluding the solvent of the entire composition.

(Thermal curing catalyst)
When the curable resin composition of the present invention contains (E) a thermosetting component, it is preferable to contain a thermosetting catalyst in combination. Examples of the heat curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Examples thereof include amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine and the like. Moreover, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino It is also possible to use S-triazine derivatives such as -S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc., preferably as these adhesion promoters The compound which also functions is used together with the thermosetting catalyst.

  A thermosetting catalyst can be used individually by 1 type or in combination of 2 or more types. It is preferable that the compounding ratio of a thermosetting catalyst is 0.1-20 mass parts with respect to 100 mass parts of (E) thermosetting components.

(Organic solvent)
The curable resin composition of the present invention can contain an organic solvent for the purpose of preparation of the composition, viscosity adjustment when applied to a substrate or a carrier film, and the like. Organic solvents include 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 ether Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used singly or in combination of two or more.

(Other optional ingredients)
In the curable resin composition of the present invention, if necessary, a photopolymerization assistant, a cyanate compound, an elastomer, a mercapto compound, a thermosetting catalyst, a urethane forming catalyst, a thixo agent, an adhesion accelerator, a block copolymer Chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as finely divided silica, organic bentonite and montmorillonite, and defoamers such as silicones, fluorines, and polymers And / or components such as flame retardants such as leveling agents, silane coupling agents such as imidazoles, thiazoles, and triazoles, phosphinates, phosphoric acid ester derivatives, phosphorus compounds such as phosphazen compounds, coloring agents, etc. . As these, those known in the field of electronic materials can be used.

  The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

  The curable resin composition of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a coverlay, an interlayer insulating layer and the like, and is particularly useful for forming a solder resist. In addition, since the curable resin composition of the present invention can form a cured product excellent in coating film strength even with a thin film, a printed wiring board requiring thin film formation, for example, an IC package substrate (a printed wiring board used for an IC package) It can use suitably also for formation of the pattern layer in these. Furthermore, the cured product obtained from the curable resin composition of the present invention should be suitably used for forming a pattern layer in an IC package substrate having a small total thickness and insufficient rigidity even in the point of high modulus and low CTE. It can be said that

  The curable resin composition of the present invention can also be in the form of a dry film provided with a carrier film (support) and a resin layer composed of the above curable resin composition formed on the carrier film. In dry film formation, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater The coating can be applied to a uniform thickness on a carrier film by a gravure coater, a spray coater or the like, and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to obtain a film. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 1-150 micrometers by film thickness after drying, Preferably it selects suitably in 10-60 micrometers.

  As the carrier film, a plastic film is used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyamide imide film, a polypropylene film, a polystyrene film or the like is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in 10-150 micrometers.

  After forming the resin layer of the curable resin composition of the present invention on a carrier film, a cover film which can be peeled off is further formed on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to laminate. As a peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when peeling the cover film, the adhesive force between the resin layer and the carrier film Also, the adhesion between the resin layer and the cover film may be smaller.

  In the present invention, the curable resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface of the resin layer. That is, as a film which apply | coats the curable resin composition of this invention, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film.

  The printed wiring board of the present invention has a cured product obtained from the resin layer of the curable resin composition or dry film of the present invention. As a method for producing a printed wiring board of the present invention, for example, a dip coating method is performed on a substrate by adjusting the curable resin composition of the present invention to a viscosity suitable for a coating method using the above-mentioned organic solvent, After applying by a method such as flow coating method, roll coating method, bar coater method, screen printing method or curtain coating method, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C. Form a tack-free resin layer. In the case of a dry film, the resin layer is attached to the substrate by a laminator or the like such that the resin layer is in contact with the substrate, and then the carrier film is peeled off to form the resin layer on the substrate.

  Examples of the substrate include printed wiring boards and flexible printed wiring boards on which a circuit is previously formed of copper etc., paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy Using materials such as synthetic fiber epoxy, fluorocarbon resin · polyethylene · polyphenylene ether, copper-clad laminates for high frequency circuits using polyphenylene oxide · cyanate, etc. Copper-clad laminates of all grades (FR-4 etc.) Other examples include metal plates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like.

  The volatilization drying performed after applying the curable resin composition of the present invention is carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. It can be carried out by using a method of making a hot current in countercurrent contact and a method of spraying a support from a nozzle).

  After forming a resin layer on a substrate, it is selectively exposed to active energy rays through a photomask having a predetermined pattern formed thereon, and the unexposed area is a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution) It develops by this and forms the pattern of hardened | cured material. Further, the cured product is irradiated with active energy rays and then heat cured (for example, 100 to 220 ° C.), or heat cured after irradiation with active energy rays, or final finish cured (main cure) only by heat curing. It forms a cured film excellent in various properties such as hardness and hardness.

As an exposure unit used for the above-mentioned active energy ray irradiation, a high pressure mercury lamp lamp, an ultra high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp etc. may be mounted, and any apparatus which irradiates ultraviolet rays in the range of 350 to 450 nm may be used. Furthermore, a direct drawing device (for example, a laser direct imaging device which draws an image directly by a laser by CAD data from a computer) can also be used. As a lamp light source or laser light source of a direct writing machine, the maximum wavelength may be in the range of 350 to 450 nm. Exposure for image formation may vary depending thickness, etc., generally 10~1000mJ / cm ^2, preferably be in the range of 20~800mJ / cm ^2.

The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkaline solutions such as ammonia and amines can be used.
The curable resin composition of the present invention may be used not only for forming a pattern of a cured film with a developer as described above, but also for applications where a pattern is not formed, for example, mold application (sealing application).

  EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, “parts” and “%” are all based on mass unless otherwise noted.

(Examples 1 to 6 and Comparative Example 1)
(Synthesis of alkali soluble resin)
119.4 parts of a novolac cresol resin (trade name "Shonol CRG 951", manufactured by Showa Denko, OH equivalent: 119.4) in an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device. 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced, the system was replaced with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide was gradually added dropwise, and reacted at 125 to 132 ° C., 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution is cooled to room temperature, and 1.56 parts of 89% phosphoric acid is added to and mixed with this reaction solution to neutralize potassium hydroxide, and nonvolatile components 62.1%, hydroxyl value 182.2 mg KOH / g (307. The propylene oxide reaction solution of the novolak-type cresol resin which is 9 g / eq. Was obtained. This was an average of 1.08 moles of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of a propylene oxide reaction solution of the obtained novolak cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methyl hydroquinone and 252.9 parts of toluene, a stirrer, temperature It was introduced into a reactor equipped with a meter and an air blowing tube, air was blown in at a rate of 10 ml / min, and allowed to react at 110 ° C. for 12 hours while stirring. The water produced by the reaction was distilled off 12.6 parts of water as an azeotropic mixture with toluene. Thereafter, the reaction solution was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, while replacing the toluene with 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator, the solution was distilled off to obtain a novolac-type acrylate resin solution. Next, 332.5 parts of the obtained novolak-type acrylate resin solution and 1.22 parts of triphenylphosphine are introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and the air is supplied at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride were gradually added, reacted at 95 to 101 ° C. for 6 hours, and taken out after cooling. In this way, a solution of a photosensitive carboxyl group-containing resin having a solid content of 65% and an acid value of the solid content of 87.7 mg KOH / g was obtained. Hereinafter, this carboxyl group-containing photosensitive resin is referred to as (E) Alkali-soluble resin of Synthesis Example 1.

(Preparation of (C1) inorganic filler (silica))
Dispersion treatment was carried out using 700 g of spherical silica (Admafine SO-E2) manufactured by Admatech, 300 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 0.5 μm zirconia beads in a bead mill. This was repeated three times and filtered with a 3 μm filter to prepare a silica slurry having an average particle size of 500 nm. The (C1) inorganic filler 1 has a particle diameter D10 of 250 nm and a maximum particle diameter D100 of 3 μm.

((C) Preparation of inorganic filler (silica))
A silica slurry (YA050C, PMA (propylene glycol monomethyl ether acetate) solvent) having an average particle diameter of 50 nm having a vinyl group of Admatech was used. The (C) inorganic filler has a particle diameter D10 of 20 nm and a maximum particle diameter D100 of 0.2 μm.

(Preparation of (C1) Inorganic Filler (Alumina))
As alumina slurry having an average particle diameter of 4 μm, spherical alumina (DAW-03) manufactured by Electrochemical Corporation was used.

(Preparation of (C) inorganic filler (alumina))
Spherical alumina (ASFP-20) manufactured by Electrochemical Company was used as an alumina slurry having an average particle size of 300 nm.

  The various components shown in the following table were blended at a solid content ratio shown in the table, and after being premixed with a stirrer, they were kneaded with a bead mill to prepare a curable resin composition. The obtained curable resin composition was each coated on a 38 μm polyester film using an applicator, and dried at 80 ° C. for 20 minutes to produce a dry film having a resin layer with a thickness of 20 μm.

(Resolution)
The curable resin composition is coated on the entire surface of a copper foil, dried at 80 ° C. for 30 minutes, and lighted by a direct imaging exposure device (light source is a high pressure mercury lamp) so that one exposure amount is 50 mJ / cm ² on the composition. It was irradiated and developed with an aqueous solution of 1 wt% sodium carbonate at 30 ° C. to form a cured product pattern. After patterning, it was evaluated whether an opening diameter of 80 μm could be formed and the shape was good.
:: The opening can be formed, and the wall surface of the opening has a straight shape.
○: An opening can be formed.
X: The opening can not be formed.

(Storage elastic modulus)
With the shiny side (copper foil) of GTS-MP foil (Furukawa Circuit Foil Co., Ltd.) facing up, the dry films according to the examples and comparative examples prepared above are made to have the resin layer in contact with the copper foil After laminating using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.) in a first chamber at 80 ° C. under a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, a press pressure of 0.5 MPa and a press time of 30 seconds Pressing was performed under the conditions to peel off the carrier film. The film was irradiated with ultraviolet light at a cumulative exposure of 1000 mJ / cm ² in a UV conveyor furnace and then cured by heating at 170 ° C. for 60 minutes. Then, after peeling a cured film from copper foil, the sample was cut out to measurement size (size (length x width x thickness) of 40 mm x 10 mm x 20 micrometers). The sample was subjected to a tensile test apparatus AG-X (manufactured by Shimadzu Corporation), and the storage elastic modulus at 25 ° C. was measured at a tensile speed of 1 mm / sec.
◎: Storage modulus at 25 ° C. is 10 GPa or more.
○: Storage elastic modulus at 25 ° C. is 8 GPa or more.
X: Storage elastic modulus is less than 8 GPa at 25 ° C.

(Linear expansion coefficient (CTE))
With the shiny side (copper foil) of GTS-MP foil (Furukawa Circuit Foil Co., Ltd.) facing up, the dry films according to the examples and comparative examples prepared above are made to have the resin layer in contact with the copper foil By bonding using a vacuum laminator in the same manner as above, a resin layer was formed on the copper foil and the carrier film was peeled off. The film was irradiated with ultraviolet light at a cumulative exposure of 1000 mJ / cm ² in a UV conveyor furnace and then cured by heating at 170 ° C. for 60 minutes. Then, after peeling a cured film from copper foil, the sample was cut out to measurement size (size (length x width x thickness) of 5 mm x 50 mm x 20 micrometers), and it used for Seiko Instruments Inc. TMA6100. In the TMA measurement, the sample was heated twice from room temperature at a heating rate of 10 ° C./min with a test weight of 5 g and measured twice in succession. The intersection point of two tangents having different linear expansion coefficients at the second time was regarded as a glass transition temperature (Tg), and was evaluated as a linear expansion coefficient (CTE (α1)) in the region below Tg. The judgment criteria are as follows.
◎: CTE less than 10 ppm at Tg temperature or less.
○: CTE below 20 ppm is 20 ppm or less.
X: CTE more than 20 ppm below Tg temperature.

* 1: LAROMER LR8863 manufactured by BASF (photocurable component)
* 2: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM (photopolymerization initiator)
* 3: (C1) inorganic filler prepared above, silica * 4: (C) inorganic filler prepared above, silica * 5: above (C1) inorganic filler, alumina * 6: above (C) inorganic filler, alumina * 7: MA-100 (ultraviolet absorber) manufactured by Mitsubishi Chemical Corporation
* 8: Mitsubishi Materials 13M-C (UV absorber)
* 9: TINUVIN 460 (UV absorber) manufactured by BASF
* 10 Epiclon N-730A manufactured by DIC (thermosetting component)
* 11: Alkali-soluble resin of Synthesis Example 1 (solid content 65% by mass) (thermosetting component)

  As shown in the above table, (D) ultraviolet rays such as carbon black or black titanium oxide together with (A) photocurable component, (B) photopolymerization initiator, (C) inorganic filler having an average particle diameter of 1 to 300 nm The cured product obtained from the dry film of Examples 1 to 6 containing an absorbent has a high storage elastic modulus, a low coefficient of linear expansion (CTE), a high resolution, and easily forms an opening. The result is On the other hand, in Comparative Example 1 in which the ultraviolet absorber (D) was not contained, the resolution of the cured product was poor, and the formation of the opening became difficult. The microscope picture which expanded the opening part of the hardened | cured material of Example 1 in FIG. 3 by 1000 times is shown, and the microscope picture which expanded the opening part of the hardened | cured material of Comparative Example 1 by 1000 times in FIG. 4 is shown. In Example 1, although the opening wall surface was able to open by straight shape, in Comparative Example 1, it was not able to open.

  Further, from Examples 1 to 6, as the (D) UV absorber, carbon black is most preferable, and a small amount is effective, and in particular, 0.02 to 0.5% by mass of the total mass of the solid content of the composition Then, it can be understood that the opening can be easily formed and the resolution is excellent.

  Furthermore, from Examples 1 and 5, (C) an inorganic filler having an average particle diameter of 1 to 300 nm, and (C1) an inorganic filler having an average particle diameter exceeding 1 to 300 nm, storage elastic modulus, linear expansion coefficient ( It is understood that silica is preferable from the viewpoint of CTE).

1 Cured Material 2 Curable Resin Composition 3 Mask 4 UV Light 5 Inorganic Filler 6 UV Absorbent

Claims (7)

(A) photocurable component,
(B) Photopolymerization initiator,
A curable resin composition comprising (C) an inorganic filler having an average particle diameter of 1 to 300 nm, and (D) an ultraviolet absorber.   The curable resin composition according to claim 1, wherein the ultraviolet absorber (D) contains carbon black.   The curable resin composition according to claim 1, wherein the ultraviolet absorber (D) is contained in an amount of 0.01 to 10% by mass based on the total mass of the solid content of the curable resin composition.   Furthermore, the total blending amount of (C1) an inorganic filler having an average particle size exceeding 300 nm, and the inorganic filler having the above (C) average particle size of 1 to 300 nm and the inorganic filler having the above (C1) average particle size exceeding 300 nm The curable resin composition according to any one of claims 1 to 3, containing 45% by mass or more of the total mass of the solid content of the curable resin composition.   It has a resin layer obtained from the curable resin composition as described in any one of Claims 1-4, The dry film characterized by the above-mentioned.   A cured product obtained by curing the curable resin composition according to any one of claims 1 to 4 or the resin layer of a dry film according to claim 5. A printed wiring board comprising the cured product according to claim 6.