TWI818912B - Curable resin compositions, dry films, cured products and printed wiring boards - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition that can easily form a cured material pattern having openings even if an inorganic filler with an average particle diameter of 300 nm or less is used, and a dry resin composition having a resin layer obtained from the composition. A film, a cured product of the resin layer of the composition or dry film, and a printed wiring board having the cured product. The solution is to contain (A) a photocurable component, (B) a photopolymerization initiator, (C) an inorganic filler with an average particle diameter of 1 to 300 nm, and (D) an ultraviolet absorber.

Description

Curable resin compositions, dry films, cured products and printed wiring boards

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

For example, in the manufacture of printed wiring boards, curable resin compositions are generally used to form permanent films such as solder resists. As such curable resin compositions, dry film-type compositions or liquid compositions have been developed. thing (for example, Patent Document 1).

In recent years, due to the rapid advancement of semiconductor components, electronic devices tend to become lighter, thinner, smaller, more powerful, and more multi-functional. Following this trend, semiconductor packages are becoming more compact, thinner, and have more pins. Specifically, IC packages called BGA (ball grid array), CSP (wafer scale package), etc. are used to replace IC packages called QFP (quad flat package), SOP (small outline package), etc. In addition, in recent years, FC-BGA (Flip Chip Ball Grid Array) has also been put into practical use as a higher density IC package. [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Laid-Open No. Sho 61-243869 (Patent Application Scope)

[Problem to be solved by the invention]

Permanent films such as solder resists formed on printed wiring boards (also called package substrates) used in IC packages as described above are required to be thinner. However, when thinned, there are problems such as low storage modulus and insufficient strength of the cured film such as burst strength. For such problems, it may be considered to increase the blending ratio of inorganic fillers. However, in a curable resin composition using an inorganic filler with an average particle diameter of 300 nm or less as the inorganic filler, the effect of halation during exposure is large, the opening shape is unstable, or the small diameter opening is insufficient. It is difficult to form an opening. Therefore, in order to easily form the opening, it is possible to consider changing the blending amount or type of the photopolymerization initiator. However, it is still difficult to form the opening only with such changes and adjustments.

Therefore, an object of the present invention is to provide a curable resin composition that can easily form a cured product pattern having openings even if an inorganic filler with an average particle diameter of 300 nm or less is used, and has the properties obtained from the curable resin composition. A dry film of the 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. [Means used to solve problems]

As a result of diligent research, the inventors found that a curable resin composition containing (A) a photocurable component, (B) a photopolymerization initiator, and (C) an inorganic filler with an average particle diameter of 1 to 300 nm is used. By blending an ultraviolet absorber into the material, the aforementioned problems can be solved, and the present invention is completed.

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

The curable resin composition of the present invention preferably contains carbon black as the aforementioned (D) ultraviolet absorber.

The curable resin composition of the present invention preferably contains the aforementioned (D) ultraviolet absorber in an amount of 0.01 to 10% by mass based on the total solid mass of the curable resin composition.

The curable resin composition of the present invention preferably further contains (C1) an inorganic filler with an average particle diameter exceeding 300 nm, and the aforementioned (C) inorganic filler with an average particle diameter of 1 to 300 nm and the aforementioned (C1) average particle diameter. The total blending amount of inorganic fillers exceeding 300 nm contains 45% by mass or more of the total solid mass of the curable resin composition.

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

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

The printed wiring board of the present invention is characterized by having the above-mentioned hardened material. [Effects of the invention]

According to the present invention, it is possible to provide a curable resin composition that can easily form a cured material pattern having openings even if an inorganic filler with an average particle diameter of 300 nm or less is used, and a resin obtained from the curable resin composition. The dry film of the layer, the curable resin composition or the cured product of the resin layer of the dry film, and the printed wiring board having the cured product.

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

In a curable resin composition using an inorganic filler with an average particle diameter of 300 nm or less, during exposure, the ultraviolet rays irradiated to the exposed part are reflected by the inorganic filler and have a great influence on the halo that causes hardening of the unexposed part. The opening shape is unstable, or the small-diameter opening has insufficient opening properties, making it difficult to form an opening. Figure 1 shows a schematic diagram when an inorganic filler with an average particle diameter of 300 nm or less is used and a curable resin composition containing no ultraviolet absorber is irradiated with ultraviolet rays. In Figure 1, (A) shows during exposure and (B) shows after exposure. As shown in Figure 1, during exposure (A), ultraviolet ray 4 does not directly irradiate the unexposed portion of the curable resin composition 2 covered by the mask 3, but the ultraviolet ray 4 is exposed through the inorganic filler 5 in the exposed portion. Scattering for hardening.

On the other hand, in the curable resin composition of the present invention that uses an inorganic filler with an average particle diameter of 300 nm or less and also adds an ultraviolet absorber, even if the ultraviolet rays irradiated on the exposed part during exposure are reflected by the inorganic filler, the ultraviolet rays are absorbed. The agent will also be absorbed, thus inhibiting the hardening of unexposed areas. Therefore, the influence of halation during exposure can be reduced, and a pattern of the cured film having openings can be easily formed. FIG. 2 shows a schematic diagram when an inorganic filler with an average particle diameter of 300 nm or less is used and the curable resin composition of the present invention containing an ultraviolet absorber is irradiated with ultraviolet rays. In the schematic diagram of FIG. 2 , similarly to FIG. 1 , (A) indicates during exposure and (B) indicates after exposure. As shown in FIG. 2 , in the curable resin composition 2 of the present invention, during (A) exposure, the ultraviolet ray 4 reflected by the inorganic filler 5 in the exposed part is absorbed by the ultraviolet absorber 6 and is therefore covered by the mask 3 The unexposed portion of the curable resin composition 2 is less susceptible to the influence of scattering of the ultraviolet ray 4 and the opening can be easily formed.

Each component of the curable resin composition of the present invention is described below. In addition, in this specification, (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and other similar expressions are also the same.

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

(A) The photocurable component is a compound having an ethylenically unsaturated group, and examples thereof include polymers, oligomers, monomers, etc., or mixtures thereof. By containing (A) a photocurable component, the curable resin composition can be hardened by exposure, and the strength of the cured film can be improved. (A) The photocurable component can be used individually or in combination of 2 or more types. As the compound having an ethylenically unsaturated group, commonly known photopolymerizable oligomers of photocurable monomers, photopolymerizable vinyl monomers, 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 phenol novolac epoxy (meth)acrylate, cresol novolak epoxy (meth)acrylate, and bisphenol type epoxy (meth)acrylate. Epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, etc. Polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc.

Photopolymerizable vinyl monomers include commonly used ones, such as styrene derivatives such as styrene, chlorostyrene, α-methylstyrene, vinyl acetate, vinyl butyrate, or vinyl benzoate. Vinyl esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isopentyl ether, vinyl-n- Vinyl ethers such as octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, etc.; acrylamide, methacrylamide, N -Hydroxymethacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide (Meth)acrylamides such as amines; allyl compounds such as triallyl isocyanate, diallyl phthalate, diallyl isophthalate, etc.; (methyl) 2-ethylhexyl acrylate, lauryl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, isocamphenyl (meth)acrylate, phenyl (meth)acrylate, phenoxy (meth)acrylate Esters of (meth)acrylic acid such as ethyl ester; hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc. ; Methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate and other alkoxyalkyl glycol mono(meth)acrylates; Ethylene glycol di(meth)acrylate, Butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylic acid Alkene polyol poly(meth)acrylate such as ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; diethylene glycol di(meth)acrylate, triethylene glycol Polyoxyalkylene glycol poly(meth)acrylic acid such as di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. Esters; poly(meth)acrylates such as hydroxytrimethylacetate neopentyl glycol ester di(meth)acrylate; ginseng [(meth)acryloyloxyethyl]isocyanurate Isocyanurate-type poly(meth)acrylates, etc.

(A) The photocurable component can be used individually or in combination of 2 or more types. (A) The blending ratio of the photocurable component is, for example, 0.1 to 55 mass %, preferably 0.2 to 50 mass %, in the solid content other than the solvent of the entire composition.

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

(B) Photopolymerization initiator includes, for example, bis-(2,6-dichlorobenzyl)phenylphosphine oxide and bis-(2,6-dichlorobenzyl)-2,5-dimethyl Phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthylphosphine Oxide, bis-(2,6-dimethoxybenzyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentanyl Phosphine oxide, bis-(2,6-dimethoxybenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzyl) -Bisylphosphine oxides such as phenylphosphine oxide; 2,6-dimethoxybenzyldiphenylphosphine oxide, 2,6-dichlorobenzyldiphenylphosphine oxide, Methyl 2,4,6-trimethylbenzylphenylphosphonate, 2-methylbenzyldiphenylphosphine oxide, isopropyl trimethylacetylphenylphosphonate, 2,4 , 6-Trimethylbenzyldiphenylphosphine oxide (Omnirad TPO manufactured by IGM) and other monobenzoylphosphine oxides; 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxy Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propane) Hydroxyacetophenones such as (benzyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin , benzoethylene glycol, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc. Inos; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michelone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4 , 4'-bisdiethylamine benzophenone and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Base-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2- [(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, etc. Ketones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone Thioxanthones such as anthraquinone, 2,4-diisopropylthioxanthone, etc.; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone , anthraquinones such as 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone, etc.; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzoic acid Benzoic acid esters such as ethyl-4-dimethylamine ester, 2-(dimethylamino)ethyl benzoate, p-dimethylbenzoic acid ethyl ester, etc.; 1,2-octanedione, 1-[4-(Phenylthio)-,2-(O-benzyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carb Oxime esters such as azole-3-yl]-,1-(O-acetyl oxime); bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro -3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl) Titanocenes such as base) phenyl] titanium; phenyl disulfide 2-nitrofluoride, butyoin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram di thioether etc. (B) The photopolymerization initiator can be used individually by 1 type, or in combination of 2 or more types. Among them, monocarboxylic acid phosphine oxides and oxime esters (hereinafter also referred to as monocarboxylic acid phosphine oxide photopolymerization initiators and oxime ester photopolymerization initiators respectively) are preferred, and 2 is more preferred. 4,6-Trimethylbenzyldiphenylphosphine oxide, ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]- ,1-(O-acetyl oxime).

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

[(C) Inorganic filler with an average particle diameter of 1 to 300 nm] The curable resin composition of the present invention contains (C) an inorganic filler with an average particle diameter of 1 to 300 nm as an essential component, but it is preferably combined. Use this inorganic filler and (C1) an inorganic filler with an average particle diameter exceeding 300 nm. Furthermore, from the viewpoint of improving strength, storage stability, and reducing the coefficient of linear expansion (CTE), it is preferable that the total mass of the (C) inorganic filler and (C) exceed 45% by mass of the total mass of the solid content of the composition. C1) Inorganic filler. This ratio is more effective when it is 60 mass % or more, 70 mass % or more, 80 mass % or more, and it is particularly effective when it is 83 mass % or more. Similarly, in order to improve the strength of the hardened material such as storage modulus, it is preferable to contain (C) an inorganic filler with an average particle diameter of 1 to 300 nm in an amount of 5% by mass or more of the total mass of the solid content of the composition, 10% by mass. It is more effective when it is more than 15% by mass, and it is particularly effective when it is more than 15% by mass. Here, in this specification, the average particle diameter of (C) inorganic filler and (C1) inorganic filler is not only the particle diameter of primary particles, but also includes the particle diameter of secondary particles (aggregates). Diameter (D50), which is the value of D50 measured by laser diffraction method. The measuring device of the laser diffraction method can be exemplified by Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. In addition, the maximum particle diameter (D100) and the particle diameter (D10) can also be measured similarly with the above-mentioned apparatus.

By containing two types of (C) inorganic filler and (C1) inorganic filler with different average particle diameters, and filling the gaps between the (C1) inorganic filler with the (C) inorganic filler, it is possible to obtain the remaining It is a curable resin composition that has fewer gaps and a small resin content, that is, a high mass ratio of filler to the total mass. In the same product of normal commercial products, the particle diameter originally varies by 2 to 3 times. At this ratio, fine particles cannot effectively enter the gap, so (C) inorganic filler and (C1) inorganic filler The average particle diameter of the agent preferably has a difference of more than 5 times. The larger the average particle diameter ratio between the (C) inorganic filler and the (C1) inorganic filler, the better. The average particle diameter of the (C1) inorganic filler is more preferably 8 times or more, and more preferably 10 times or more the average particle diameter of the (C) inorganic filler.

(C1) The average particle diameter of the inorganic filler is preferably 5 μm or less. (C1) The average particle diameter of the inorganic filler varies depending on the use of the curable resin composition. For example, in the use of forming a cured film on an IC package substrate, it is preferably 5 μm or less, and in a printed wiring board for motherboards, it is preferably 5 μm or less. In the use of forming a cured film, the thickness is preferably 30 μm or less, and in the use of molding (sealing), the thickness is preferably 40 μm or less. Furthermore, the particle diameter (D10) of the (C1) inorganic filler is preferably at least 5 times the average particle diameter (D50) of the (C) inorganic filler. If this ratio is 5 times or more, the filling efficiency of the gaps between the (C) inorganic filler and the (C1) inorganic filler will be improved, and the balance between the strength of the cured product and the lamination property of the dry film will be excellent.

The blending ratio of the two inorganic fillers (C) and (C1), in terms of volume ratio, is preferably (C): (C1)=5:5~1:9, more preferably 4:6~2:8 . If it is within the aforementioned range, it is possible to achieve a better balance between the strength of the cured product and the lamination properties of the dry film.

The materials of (C) inorganic filler and (C1) inorganic filler are not particularly limited. Examples include silica, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, and carbonic acid. Calcium, aluminum oxide, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc. Among them, silicon dioxide is particularly preferred because it inhibits the curing shrinkage of the cured material of the curable resin composition, resulting in lower CTE, and improves storage modulus, adhesion, hardness and other characteristics. Examples of silica include fused silica, spherical silica, amorphous silica, crystalline silica, and the like.

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

The surface treatment method of (C) inorganic filler and (C1) inorganic filler is not particularly limited, as long as a well-known and customary method is used, preferably a surface treatment agent with a curing reactive group, such as a curing reaction group. The base is used as an organic coupling agent to treat the surface of inorganic fillers.

As the coupling agent, silane-based, titanate-based, aluminate-based, zircoaluminate-based coupling agents can be used. Among them, silane coupling agents are particularly preferred. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-epoxypropyl Oxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. can be used alone or in combination. These silane coupling agents are preferably immobilized on the surface of the inorganic filler through adsorption or reaction in advance. Here, the processing amount of the coupling agent is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the inorganic filler. In addition, in the present invention, the coupling agent used for 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, styrene, methacryl, and acryl. Among them, at least one of a vinyl group and a (meth)acrylyl group is particularly preferred.

Thermosetting reactive groups include hydroxyl group, carboxyl group, isocyanate group, amine group, imine group, epoxy group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, and ethoxy group Methyl, ethoxyethyl, oxazolinyl, etc. Among them, at least one of an amine group and an epoxy group is particularly preferred.

Furthermore, 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 a surface-treated state, or may be blended individually. The surface of the inorganic filler and the surface treatment agent are not treated, and the inorganic filler is surface-treated in the composition, but it is preferably blended with an inorganic filler that has been surface-treated in advance. By blending inorganic fillers that have been surface-treated in advance, it is possible to prevent the decrease in crack resistance caused by the surface treatment agent that may remain during individual blending and has not been consumed in the surface treatment. When performing surface treatment in advance, it is preferable to mix a preliminary dispersion in which the inorganic filler is pre-dispersed in a solvent or a curable component. More preferably, the surface-treated inorganic filler is pre-dispersed in a solvent, and the preparatory dispersion is It is blended into the composition, or the surface-untreated inorganic filler is fully surface-treated before being dispersed in a solvent, and then the preliminary dispersion is blended into the composition. (C) Inorganic filler and (C1) inorganic filler can be blended with component (A) in powder or solid state according to the usage mode of the curable resin composition of the present invention, or can be dispersed in solvent or After the agent is mixed to form a slurry, it is blended with component (A) and the like.

[(D) Ultraviolet absorber] As mentioned above, from the viewpoint of improving the strength or storage modulus and reducing the coefficient of linear expansion (CTE), it is preferable to contain 45 mass % or more of the total mass of the solid content of the composition. The content of the (C) inorganic filler and (C1) inorganic filler is particularly preferably 83% by mass or more. However, when the blending ratio is increased, the formation of the opening becomes more difficult. However, by containing (D) ultraviolet absorber as an essential component in the curable resin composition of the present invention, even when the blending ratio of (C) inorganic filler and (C1) inorganic filler is high, it can be easily An opening is formed. Any ultraviolet absorber (D) of the present invention can be used as long as it absorbs light with a wavelength of 300 nm to 450 nm.

(D) Ultraviolet absorbers include inorganic ultraviolet absorbers such as carbon black and black titanium oxide (also called titanium black), or organic ultraviolet absorbers. Among them, carbon black is particularly the best from the viewpoint of the resolution of the hardened material.

Examples of organic ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamic acid ester derivatives, and anthranilic acid Ester derivatives, dibenzylmethane derivatives, etc. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2'-dihydroxy -4-Methoxybenzophenone and 2,4-dihydroxybenzophenone, etc. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-t-butylphenyl salicylate, and 2,4-di-t-butylphenyl salicylate. -3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, etc. Specific examples of benzotriazole derivatives include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methylbenzene) base) benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' ,5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy -3',5'-di-t-pentylphenyl)benzotriazole, etc. Specific examples of triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

The ultraviolet absorber may also 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 Co., Ltd., trade name), etc.

The above-mentioned organic ultraviolet absorber is preferably used in combination with carbon black. By combining it with carbon black, the resolution becomes more stable.

(D) Ultraviolet absorbers may be used alone or in combination of two or more types. (D) The ultraviolet absorber is effective in a small amount, and preferably contains 0.01 to 10% by mass of the total solid content of the composition. From the perspective of deep hardening properties that affect the resolution of the hardened product, it is more suitable Preferably, it is 0.02~7% by mass. When carbon black is contained as (D) the ultraviolet absorber, from the viewpoint of the resolution of the cured product, it is preferably contained in a range of 0.01 to 1% by mass of the total solid content of the composition, and more preferably contains the solid content of the composition. 0.02~0.5% by mass of the total mass of the composition, preferably 0.05~0.30% by mass of the total mass of the solid content of the composition.

((E) Thermosetting component) The curable resin composition of the present invention more preferably contains (E) a thermosetting component. Furthermore, the curable resin composition of the present invention more preferably contains an alkali-soluble resin as the thermosetting component (E) and a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule. By containing (E) a thermosetting component, the strength of the cured film can be improved. (E) A thermosetting component can be used individually or in combination of 2 or more types. (E) Any known thermosetting component can be used. For example, melamine resin, benzoguanamine resin, melamine derivatives, benzoguanamine derivatives, and other amine-based resins; isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, epoxy compounds, and oxetane compounds can be used. Alkane compounds, episulfide resins, bismaleimide, carbodiimide resins, alkali-soluble resins, etc. are known thermosetting components. Particularly preferred are compounds and alkali-soluble resins having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in the molecule.

The above-mentioned 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, there can be mentioned a compound having a plurality of cyclic (thio)ether groups in the molecule. Compounds with an epoxy group are also known as multifunctional epoxy compounds, compounds with multiple oxetane groups in the molecule are also known as multifunctional oxetane compounds, and compounds with multiple thioether groups in the molecule are also known as Episulfide resin, etc.

Polyfunctional epoxy compounds include 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 Epoxy resin; bisphenol novolak type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; epoxypropylamine type epoxy resin; hydantoin type epoxy resin; alicyclic type Epoxy resin; trihydroxyphenylmethane type epoxy resin; dixylenol type or diphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolak type epoxy resin; Tetraphenol ethane type epoxy resin; Heterocyclic epoxy resin; Diepoxypropyl phthalate resin; Tetraepoxypropylxylenyl ethane resin; Naphthyl-containing epoxy resin; Epoxy resin with dicyclopentadiene skeleton; epoxy resin copolymerized with glycidyl methacrylate; epoxy resin copolymerized with cyclohexylmaleimide and glycidyl methacrylate; epoxy group Modified polybutadiene rubber derivatives; CTBN modified epoxy resin, etc., but are not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Among these, novolak type epoxy resin, bisphenol type epoxy resin, dixylenol type epoxy resin, bisphenol type epoxy resin, bisphenol novolak type epoxy resin, naphthalene type epoxy resin are particularly preferred. Resins or mixtures thereof are preferred.

Polyfunctional oxetane compounds include, for example, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetane) Butylmethoxy)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-oxaacrylate cyclobutyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or Polyfunctional oxetane such as these oligomers or copolymers, in addition to oxetanol and novolak resin, poly(p-hydroxystyrene), Cardo-type bisphenols, and calixarenes etherates of resins such as calixresorcin aromatics, or sesquisiloxanes and other resins with hydroxyl groups. Other examples include copolymers of unsaturated monomers having an oxetane ring and (meth)acrylic acid alkyl esters.

Compounds with multiple cyclic thioether groups in the molecule include bisphenol A type episulfide resin, etc. In addition, an episulfide resin in which the oxygen atoms of the epoxy groups of the novolak-type epoxy resin are replaced with sulfur atoms using the same synthesis method can also be used.

Amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, hydroxymethylbenzoguanamine compounds, hydroxymethylacetylene urea compounds, and hydroxymethylurea compounds.

As the isocyanate compound, a polyisocyanate compound may be blended. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m -Aromatic polyisocyanates such as xylylene diisocyanate and 2,4-toluene isocyanate dimer; tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate Aliphatic polyisocyanates such as isocyanate, 4,4-methylene bis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and additions of the isocyanate compounds listed previously Composite, biuret and isocyanurate bodies, etc.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound that can react with the isocyanate blocking agent include the above-mentioned polyisocyanate compounds. Examples of isocyanate blocking agents include phenol-based blocking agents; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; thiol-based blocking agents; and acids. Amide-based capping agents; amide-imine-based capping agents; amine-based capping agents; imidazole-based capping agents; imine-based capping agents, etc.

Moreover, as (E) thermosetting component, it is preferable to contain the alkali-soluble resin which has an alkali-soluble group. Examples of the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, resins containing carboxyl groups, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. Among them, the alkali-soluble resin is particularly preferable if it is a carboxyl group-containing resin or a phenol resin because the adhesiveness with the substrate is improved. In particular, since it has excellent developability, the alkali-soluble resin is more preferably a resin containing a carboxyl group. The carboxyl group-containing resin is preferably a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, but it may also be a carboxyl group-containing resin that does not have an ethylenically unsaturated group. When the alkali-soluble resin has an ethylenically unsaturated group, it also functions as (A) the photocurable component. Furthermore, when the curable resin composition of the present invention contains an alkali-soluble resin, it can be used not only for alkali development but also for applications without alkali development.

Specific examples of the carboxyl group-containing resin include the compounds listed below (both oligomers and polymers are acceptable).

(1) By copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resin containing carboxyl groups obtained.

(2) By using diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and dimethylol propionic acid, dimethylol butyric acid, etc. containing carboxyl groups Diol compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and have phenolic properties Carboxyl group-containing urethane resin obtained by addition polymerization of diol compounds such as hydroxyl and alcoholic hydroxyl compounds.

(3) By using diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., with polycarbonate polyols, polyether polyols, and polyester polyols Amine obtained by addition polymerization of diol compounds such as alcohols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, etc. A urethane resin containing terminal carboxyl groups is formed by reacting the terminal end of the urethane ester resin with an acid anhydride.

(4) By using diisocyanate, it can be combined with bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and dixylenol-type epoxy resin. , (meth)acrylate or partial acid anhydride modified products of bifunctional epoxy resins such as biphenolic epoxy resins, carboxyl group-containing diol compounds and carboxyl group-containing amines obtained by addition polymerization of diol compounds. methyl formate resin.

(5) In the synthesis of the resin in the above (2) or (4), add a compound having one hydroxyl group and one or more (meth)acrylyl groups in the molecule such as hydroxyalkyl (meth)acrylate, Carboxyl group-containing urethane resin obtained by terminal (meth)acrylation.

(6) In the synthesis of the resin in the above (2) or (4), add an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, etc. in the molecule to have 1 isocyanate group and 1 or more ( Meth)acryl compound is a carboxyl-containing urethane resin obtained by terminal (meth)acrylation.

(7) React (meth)acrylic acid with a multifunctional epoxy resin, and add 2 of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl group present in the side chain A resin containing carboxyl groups obtained from acid anhydrides.

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

(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 generated primary hydroxyl group.

(10) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is then reacted with a monocarboxylic acid containing an unsaturated group. The reaction product is reacted with polybasic acid anhydride to obtain a carboxyl-containing resin.

(11) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propyl carbonate is reacted with a monocarboxylic acid containing an unsaturated group. , the obtained reaction product is reacted with polybasic acid anhydride to obtain a carboxyl-containing resin.

(12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenylethyl alcohol and a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid are mixed into one molecule. For the reaction of an epoxy compound having a plurality of epoxy groups, for the alcoholic hydroxyl group of the reaction product obtained, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexane A resin containing carboxyl groups obtained by reacting polybasic acid anhydrides such as acid anhydrides.

(13) To the resin containing carboxyl groups described in the above (1) to (12), further add glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. to the molecule having A carboxyl-containing resin composed of a compound of one epoxy group and one or more (meth)acrylyl groups.

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

Examples of compounds having a phenolic hydroxyl group include compounds having a biphenyl skeleton, a phenyl skeleton, or both skeletons thereof, and phenol, o-cresol, p-cresol, m-cresol, and 2,3-xylenol can be used. , 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, Phenol resins with various skeletons synthesized from hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, gallic acid, phloroglucinol, etc.

Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolac resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, and terpene-modified phenol. Resins, polyvinyl phenols, bisphenol F, bisphenol S type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensates of dihydroxynaphthalene and aldehydes, etc. Phenolic resin.

Examples of commercially available phenolic resins include HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Besmol CZ-256-A (manufactured by DIC Corporation), Shonol BRG- 555. Shonol BRG-556 (manufactured by Showa Denko Co., Ltd.), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), polyvinyl phenol CST70, CST90, S-1P, and S-2P (manufactured by Maruzen Oil Co., Ltd.).

The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. (A) When the acid value of the alkali-soluble resin is 20 mgKOH/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, the dissolution of the exposed part caused by the developer can be suppressed, and therefore the line can be suppressed from becoming thinner than necessary, or the exposed part and the unexposed part being displayed indiscriminately depending on the situation. The image liquid dissolves and peels off, and the resist pattern is drawn well.

The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 50,000, and further preferably in the range of 1,500 to 30,000. When the weight average molecular weight is 1,500 or more, the non-stick properties are good, and the moisture resistance of the coating film after exposure is good, which can suppress the reduction of the film during development and the reduction of resolution. On the other hand, when the weight average molecular weight is 50,000 or less, the developability is good and the storage stability is also excellent.

The alkali-soluble resin can be used alone or in combination of two or more types. The blending ratio of the alkali-soluble resin in the solid content other than the solvent of the entire composition is, for example, 0 to 55 mass %, preferably 3 to 50 mass %.

(E) A thermosetting component can be used individually or in combination of 2 or more types. (E) The blending ratio of the thermosetting component in the solid content other than the solvent of the entire composition is, for example, 0 to 55 mass %, preferably 1 to 50 mass %.

(Thermosetting Catalyst) When the curable resin composition of the present invention contains (E) a thermosetting component, it is preferable to also contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl -Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(di Amine compounds such as methylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. , hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazine, etc.; phosphorus compounds such as triphenylphosphine, etc. Furthermore, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used. ,4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine･isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as acryloyloxyethyl-S-triazine and isocyanuric acid adducts are preferably used together. These compounds also function as adhesion-imparting agents. with heat hardening catalyst.

Thermosetting catalysts can be used alone or in combination of two or more. The blending ratio of the thermosetting catalyst is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the thermosetting component (E).

(Organic solvent) The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when coating a substrate or a carrier film. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellulose, methylcellulose, butylcellulose, and carbitol. Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether Glycol ethers such as base ethers; ethyl acetate, butyl acetate, butyl lactate, cellulose acetate, butyl cellulose acetate, carbitol acetate, butyl carbitol ethyl Acid esters, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane, decane, etc.; petroleum ether, naphtha, solvents Known and commonly used organic solvents such as petroleum solvents such as naphtha are used. These organic solvents can be used individually or in combination of 2 or more types.

(Other optional components) In the curable resin composition of the present invention, a photoinitiating additive, a cyanate ester compound, an elastomer, a mercapto compound, a thermosetting catalyst, and a urethane catalyst can be further blended as needed. Media, thixotropic agent, adhesion accelerator, block copolymer, chain transfer agent, polymerization inhibitor, copper damage inhibitor, antioxidant, anti-rust agent, micronized silica, organic bentonite, montmorillonite, etc. Tackifiers, defoaming agents and/or leveling agents of polysilicone, fluorine, polymer, etc., silane coupling agents of imidazole, thiazole, triazole, etc., hypophosphite, phosphate ester derivatives , phosphorus compounds and other phosphorus compounds, flame retardants, colorants, etc. components. Those known in the field of electronic materials can be used.

The curable resin composition of the present invention can be used as a dry film or in liquid form. When used as a liquid, it may be 1 liquid or 2 or more liquids.

The curable resin composition of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board as a solder resist, a cover lay, an interlayer insulating layer, etc., and is particularly useful for forming a solder resist. In addition, the curable resin composition of the present invention can be used as a thin film to form a cured product with excellent coating film strength. Therefore, it can also be suitably used in printed wiring boards that require thinning, such as IC packaging substrates (printed for IC packaging). The formation of pattern layer in wiring board). Furthermore, from the viewpoint of having a high elastic modulus and low CTE, the cured product obtained from the curable resin composition of the present invention can be suitably used for patterns in IC package substrates that have a thin total thickness and insufficient rigidity. The formation of layers.

The curable resin composition of the present invention may be in the form of a dry film including a carrier film (support) and a resin layer composed of the above-mentioned curable resin composition formed on the carrier film. During dry film formation, the curable resin composition of the present invention can be diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, using a notch wheel coater, a blade coater, a die lip coater, or a rod coater. , extrusion coater, reverse roller coater, transfer roller coater, gravure coater, spray coater, etc., the carrier film is coated with a uniform thickness, usually dried at a temperature of 50~130℃ for 1~30 minutes to obtain the film. The coating film thickness is not particularly limited. Generally speaking, the film thickness after drying is appropriately selected within the range of 1 to 150 μm, preferably 10 to 60 μm.

The carrier film can be a plastic film, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like. film. The thickness of the carrier film is not particularly limited, and is generally appropriately selected within the range of 10 to 150 μm.

After the resin layer of the curable resin composition of the present invention is formed on the carrier film, a peelable cover film is preferably further laminated on the surface of the resin layer for the purpose of preventing dust, etc. from adhering to the surface of the resin layer. Peelable cover films can be used, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., as long as the bonding force between the resin layer and the cover film is stronger than the resin layer and the carrier film when the cover film is peeled off. The one with smaller connecting force will suffice.

Furthermore, in the present invention, the curable resin composition of the present invention may be coated on the above-mentioned cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, in the present invention, both a carrier film and a cover film can be used as a film coated with the curable resin composition of the present invention when producing a dry film.

The printed wiring board of the present invention has a cured product obtained from a resin layer of the curable resin composition or dry film of the present invention. The manufacturing method of the printed wiring board of the present invention, for example, uses the above-mentioned organic solvent, adjusts the curable resin composition of the present invention to a viscosity suitable for the coating method, and uses the dip coating method, the flow coating method, the roller coating method, and the curable resin composition of the present invention. After coating on the substrate by coating method, rod coater method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried at a temperature of 60~100°C. (temporarily dried) to form a non-sticky resin layer. In the case of a dry film, after the resin layer is bonded to the base material using a laminating machine or the like so that the resin layer is in contact with the base material, the carrier film is peeled off to form a resin layer on the base material.

Examples of the above-mentioned base material include a printed wiring board or a flexible printed wiring board with a circuit formed in advance using copper or the like. Examples of the base material include those using paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, Copper-clad laminates for high-frequency circuits such as glass cloth/nonwoven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyphenylene ether, polyphenylene ether/cyanate ester, etc. The materials are copper-clad laminates of all grades (FR-4, etc.); others include metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, Ceramic substrates, wafer boards, etc.

The volatilization drying after coating the curable resin composition of the present invention can be carried out using a hot air circulation drying oven, IR oven, heating plate, convection oven, etc. (Using a heat source equipped with a steam-based air heating method, the dryer It is carried out by the method of counter-current contact with the hot air inside and the method of blowing the support from the nozzle).

After forming a resin layer on the substrate, a photomask with a specific pattern is formed, selectively exposed with active energy rays, and the unexposed portion is developed with a dilute alkali aqueous solution (such as 0.3~3 mass% sodium carbonate aqueous solution). Form a pattern of hardened matter. Further, by irradiating the hardened material with active energy rays and then heating and hardening (for example, 100~220°C), or by heating and hardening and then irradiating active energy rays, or only by heating and hardening for final trimming and hardening (formal hardening), close contact is formed. A cured film with excellent properties such as toughness and hardness.

The exposure machine used for the above-mentioned active energy ray irradiation only needs to be equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and can irradiate ultraviolet rays in the range of 350~450nm. It can also be directly used. Drawing device (such as a laser direct imaging device that directly draws an image with a laser using CAD data from a computer). The light source or laser light source of the direct drawing machine can be in the range of the maximum wavelength of 350~450nm. Although the exposure amount used to form an image varies depending on the film thickness, etc., it can generally be in the range of 10~1000mJ/ ^cm2 , preferably 20~800mJ/ ^cm2 .

The above-mentioned developing method can be carried out by immersion method, shower method, spray method, brush method, etc. The developing liquid can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine Alkaline aqueous solutions of the same kind. The curable resin composition of the present invention is not only used for forming a pattern of a cured film using the above-mentioned developer, but can also be used for applications without pattern formation, such as molding applications (sealing applications). [Example]

Examples and comparative examples are described below to specifically illustrate the present invention, but the present invention is not limited to the following examples. Furthermore, the following "parts" and "%" are based on mass unless otherwise specified.

(Examples 1 to 6 and Comparative Example 1) (Synthesis of alkali-soluble resin) Novolak type cresol resin (trade name) was introduced into an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device. "Shonol CRG951" manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4) 119.4 parts, potassium hydroxide 1.19 parts and toluene 119.4 parts, while stirring, replace the system with nitrogen and heat to increase the temperature. Then, slowly drop 63.8 parts of propylene oxide, and react at 125~132°C, 0~4.8kg/ ^cm2 for 16 hours. After that, it was cooled to room temperature, 1.56 parts of 89% phosphoric acid was added and mixed to the reaction solution, and potassium hydroxide was neutralized to obtain a novolak type with a non-volatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9g/eq.) Cresol resin in propylene oxide reaction solution. For every 1 equivalent of phenolic hydroxyl groups, the average addition of propylene oxide is 1.08 moles. 293.0 parts of the obtained novolak type cresol resin propylene oxide reaction solution, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were introduced into a reaction chamber equipped with a mixer, a thermometer and an air blowing tube. In the container, air was blown into the mixture at a rate of 10 ml/min, and the mixture was reacted at 110° C. for 12 hours while stirring. The water generated by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water was distilled. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was substituted with 118.1 parts of diethylene glycol monoethyl ether acetate using an evaporator and distilled off to obtain a novolac-type acrylate resin solution. Next, 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown in at a speed of 10 ml/min while stirring. , while slowly adding 60.8 parts of tetrahydrophthalic anhydride, react at 95~101°C for 6 hours, and then take it out after cooling. In this way, a solution of a photosensitive carboxyl group-containing resin with a solid content of 65% and an acid value of the solid content of 87.7 mgKOH/g was obtained. Hereinafter, this carboxyl group-containing photosensitive resin will be referred to as (E) alkali-soluble resin of Synthesis Example 1.

(Preparation of (C1) Inorganic filler (silica)) 700g of spherical silica (Admafine SO-E2) manufactured by Admatechs and 300g of PMA (propylene glycol monomethyl ether acetate) as a solvent were placed into beads. The mill uses 0.5μm zirconia beads for dispersion processing. Repeat this three times, filter with a 3 μm filter, and prepare a silica slurry with an average particle diameter of 500 nm. In addition, 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)) Use silicon dioxide slurry (YA050C, PMA (propylene glycol monomethyl ether acetate) solvent) with vinyl and an average particle diameter of 50 nm from Admatechs. In addition, the (C) inorganic filler has a particle diameter D10 of 20 nm and a maximum particle diameter D100 of 0.2 μm.

((C1) Preparation of inorganic filler (alumina)) As an alumina slurry with an average particle diameter of 4 μm, spherical alumina (DAW-03) manufactured by Denki Chemical Co., Ltd. was used.

((C) Preparation of inorganic filler (alumina)) Denki Chemical Co., Ltd.'s spherical alumina (ASFP-20) was used as an alumina slurry with an average particle diameter of 300 nm.

Various ingredients shown in the following table are blended at the solid content ratios shown in the table, preliminarily mixed with a mixer, and then kneaded with a bead mill to prepare a curable resin composition. The obtained curable resin compositions were applied onto a 38 μm polyester film using an applicator, and dried at 80° C. for 20 minutes to prepare a dry film having a resin layer with a thickness of 20 μm.

(Resolution) Apply the curable resin composition to the entire surface of the copper foil, dry it at 80°C for 30 minutes, and use a direct imaging exposure device (light source) so that the exposure amount becomes 50 mJ/cm ² on the composition. (a high-pressure mercury lamp) for light irradiation and development with a 1wt% sodium carbonate aqueous solution at 30°C to form a pattern of the hardened object. After the pattern is formed, it is evaluated whether an opening diameter of 80 μm can be formed and whether the shape is good. ◎: An opening can be formed, and the wall surface of the opening has a straight shape. ○: An opening can be formed. ×: The opening cannot be formed.

(Storage Modulus) With the glossy side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) facing up, dry films of each of the examples and comparative examples produced above were dried using a vacuum laminating machine (CVP- 300: Nikko-Materials Co., Ltd.), with the resin layer in contact with the copper foil, laminated in the first chamber at 80°C with a vacuum pressure of 3hPa and a vacuum time of 30 seconds, then with a pressing pressure of 0.5MPa and a pressing time Press for 30 seconds and peel off the carrier film. After irradiating it with ultraviolet rays in a UV conveyor belt furnace at a cumulative exposure dose of 1000mJ/ ^cm2 , it was heated at 170°C for 60 minutes to harden it. Thereafter, the cured film was peeled off from the copper foil, and the sample was cut out into a measurement size (dimensions of 40 mm×10 mm×20 μm (length×width×thickness)). The sample was subjected to a tensile testing device AG-X (manufactured by Shimadzu Corporation), and the storage modulus at 25° C. was measured at a tensile speed of 1 mm/sec. ◎: The storage modulus at 25℃ is above 10GPa. ○: Storage modulus at 25°C is 8GPa or more. ×: The storage modulus at 25°C is less than 8GPa.

(Coefficient of Linear Expansion (CTE)) With the shiny side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) facing upward, the dry films of the above-produced Examples and Comparative Examples were used in the same manner as above. The vacuum laminating machine laminates the resin layer in contact with the copper foil, thereby forming a resin layer on the copper foil and peeling off the carrier film. After irradiating it with ultraviolet rays in a UV conveyor belt furnace at a cumulative exposure dose of 1000mJ/ ^cm2 , it was heated at 170°C for 60 minutes to harden it. Thereafter, the cured film was peeled off from the copper foil, and the sample was cut out to a measurement size (dimensions of 5 mm×50 mm×20 μm (length×width×thickness)) and used as TMA6100 manufactured by Seiko Instruments. For TMA measurement, the test load is 5g, the sample is heated from room temperature at a heating rate of 10°C/min, and measured twice continuously. The intersection point of two different tangent lines in the second linear expansion coefficient is the glass transition temperature (Tg), and the evaluation is performed in terms of the linear expansion coefficient (CTE (α1)) in the region below Tg. The judgment criteria are as follows. ◎: CTE below Tg temperature is 10ppm or less. ○: CTE below Tg temperature is 20 ppm or less. ×: CTE below Tg temperature exceeds 20 ppm.

*1: Laromer LR8863 manufactured by BASF (photocurable component) *2: Omnirad TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) manufactured by IGM (photopolymerization initiator) *3: The above-prepared (C1) inorganic filler, silicon dioxide *4: The above-prepared (C) inorganic filler, silicon dioxide *5: The above-mentioned (C1) inorganic filler, alumina *6: The above-mentioned ( C) Inorganic filler, alumina *7: MA-100 (UV absorber) manufactured by Mitsubishi Chemical Corporation *8: 13M-C (UV absorber) manufactured by Mitsubishi Materials Corporation *9: TINUVIN460 (UV absorber) manufactured by BASF Corporation *10: EPICLON N-730A manufactured by DIC Corporation (thermosetting component) *11: Alkali-soluble resin (solid content 65 mass %) of Synthesis Example 1 (thermosetting component)

As shown in the above table, it consists of (A) photocurable component, (B) photopolymerization initiator, (C) inorganic filler with an average particle diameter of 1 to 300 nm, and carbon black or black titanium oxide, etc. (D) The cured product obtained from the dry film of Examples 1 to 6 of the ultraviolet absorber has a high storage modulus, a low coefficient of linear expansion (CTE), and high resolution, so that the opening can be easily formed. On the other hand, in Comparative Example 1 which does not contain the ultraviolet absorber (D), the resolution of the cured product was poor and it was difficult to form the opening. FIG. 3 is a microscopic photograph showing the opening of the hardened material of Example 1 enlarged 1000 times, and FIG. 4 is a microscopic photograph showing the opening of the hardened material of Comparative Example 1 magnified 1000 times. In Example 1, the opening wall surface can be opened in a straight shape, whereas in Comparative Example 1, the opening wall surface cannot be opened.

In addition, from Examples 1 to 6, it can be seen that the best ultraviolet absorber (D) is carbon black, and a small amount is effective. Especially when it contains 0.02 to 0.5 mass% of the total solid mass of the composition, it can be easily The opening is formed and the resolution is excellent.

Furthermore, from Examples 1 and 5, it can be seen that as (C) the inorganic filler with an average particle diameter of 1 to 300 nm, and (C1) the inorganic filler with an average particle diameter exceeding 1 to 300 nm, the storage modulus, line From the viewpoint of coefficient of expansion (CTE), silica is preferred.

1‧‧‧Cure material 2‧‧‧Cure resin composition 3‧‧‧Mask 4‧‧‧Ultraviolet light 5‧‧‧Inorganic filler 6‧‧‧Ultraviolet absorber

[Fig. 1] A schematic diagram when an inorganic filler with an average particle diameter of 300 nm or less is used and a curable resin composition containing no ultraviolet absorber is irradiated with ultraviolet rays. [Fig. 2] A schematic diagram illustrating the use of an inorganic filler with an average particle diameter of 300 nm or less and irradiation of ultraviolet rays to the curable resin composition of the present invention containing an ultraviolet absorber. [Figure 3] A microscopic photograph of the opening of the hardened product of Example 1 magnified 1000 times. [Figure 4] A microscopic photograph of the opening of the hardened product of Comparative Example 1 magnified 1000 times.

1‧‧‧hardened material

2‧‧‧Cure resin composition

3‧‧‧Mask

4‧‧‧UV

5‧‧‧Inorganic filler

6‧‧‧UV absorber

Claims (6)

A curable resin composition characterized by containing (A) a photocurable component, (B) a photopolymerization initiator, (C) an inorganic filler with an average particle diameter of 1 to 300 nm, (C1) an average particle diameter exceeding The total blending amount of the inorganic filler with an average particle size of 300nm and (D) the ultraviolet absorber, the aforementioned (C) inorganic filler with an average particle diameter of 1 to 300nm, and the aforementioned (C1) inorganic filler with an average particle diameter exceeding 300nm is A material containing more than 45% by mass of the total solid content of the curable resin composition, the aforementioned (C) inorganic filler with an average particle diameter of 1 to 300 nm, and the aforementioned (C1) inorganic filler with an average particle diameter exceeding 300 nm, All are silica and/or alumina. The curable resin composition according to claim 1, which contains carbon black as the ultraviolet absorber (D). The curable resin composition according to claim 1 or 2, which contains 0.01 to 10 mass % of the aforementioned (D) ultraviolet absorber based on the total solid mass of the curable resin composition. A dry film characterized by having any one of claims 1 to 3 The resin layer obtained from the curable resin composition. A cured product characterized by being obtained by curing the resin layer of the curable resin composition according to any one of claims 1 to 3 or the dry film according to claim 4. A printed wiring board characterized by having the hardened material according to claim 5.