KR101701100B1 - Curable resin composition, dry film, cured article, and printed wiring board - Google Patents

Abstract

The present invention provides a curable resin composition, a dry film, a cured product, and a printed wiring board having high reflectivity as well as properties such as composition stability such as storage stability and solder resist such as solder heat resistance.
(A) a curable resin, (B) a white colorant, and (C) a photo-excitable inorganic filler subjected to a surface treatment. 10 g of the curable resin composition before curing was placed in 50 g of acetone to take out a primary insoluble component. Thereafter, the extracted primary insoluble component was put into 50 g of chloroform to take out a secondary insoluble component. Then, The insoluble component is put into 10 g of pure water and stirred at 30 캜 for 1 week to obtain a liquid having a pH of 6 to 12.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board,

The present invention relates to a curable resin composition (hereinafter, simply referred to as a "composition"), a dry film, a cured product and a printed wiring board, and more particularly to a curable resin composition, a dry film, .

Generally, a printed wiring board is formed by removing an unnecessary portion of a copper foil bonded to a laminate by etching to form a circuit wiring, and the electronic component is disposed at a predetermined place by solder. In such a printed wiring board, as a protective film for preventing the attachment of solder to a necessary portion and for preventing the conductor of the circuit from being exposed and corroded by oxidation or moisture, A solder resist is formed. Since the solder resist also functions as a permanent protective film for the circuit board, the solder resist is required to have various performances such as alkali developability and solder heat resistance. In addition, the dried coating film of the solder resist composition for forming the solder resist is also required to have touch-free dryness (no tackiness). In addition, as a premise having the aforementioned various performances, the storage stability of the composition becomes important.

In addition, in the case of a white solder resist, it is also important to have a high reflectance in addition to the required characteristics as a solder resist. As a technique for increasing the reflectance of a white solder resist, for example, Patent Document 1 discloses a white photo-curable and thermosetting solder resist composition containing a carboxyl group-containing resin having no aromatic ring and a rutile-type titanium oxide.

On the other hand, as another method for improving the reflectance, it is known that when a plurality of white resin composition layers are provided, the reflectance is improved by interface reflection. For example, Patent Document 2 discloses a solder resist layer comprising a layer made of a white alkali-developable photosensitive resin composition and a layer made of a white thermosetting resin composition superimposed on the layer.

According to the technique disclosed in Patent Document 1, a high reflectance is obtained, but from the viewpoint of energy saving, it is desired to further improve the reflectance. In addition, in the technique disclosed in Patent Document 2, in order to laminate the white resin composition layers into a plurality of layers, it is necessary to coat the white resin composition layer over the formed white resin composition layer, and the manufacturing process is very troublesome There was a difficulty.

Japanese Patent Application Laid-Open No. 2007-322546 Japanese Patent Application Laid-Open No. 2011-49476

It is an object of the present invention to provide a curable resin composition, a dry film, a cured product and a printed wiring board which have high reflectance as well as characteristics such as composition stability such as storage stability and solder resist such as solder heat resistance.

As a result of intensive studies, the inventors of the present invention have found that the use of a photo-excitable inorganic filler subjected to a surface treatment together with a white colorant such as titanium oxide in a curable resin composition results in a high reflectance of the cured coating film. As a result of further study by the present inventors, the inventors of the present invention found that it is possible to achieve a high reflectance in the entire wavelength range by adjusting the pH of the curable resin composition to a predetermined range in addition to the use of a white colorant and a photoexcitation inorganic filler in combination Thus, the present invention has been completed.

That is, the curable resin composition of the present invention is a curable resin composition containing (A) a curable resin, (B) a white colorant, and (C) a photo-

10 g of the curable resin composition before curing was placed in 50 g of acetone to take out the primary insoluble component. The extracted primary insoluble component was then added to 50 g of chloroform to take out the secondary insoluble component. Characterized in that the pH of the obtained liquid is 6 to 12 by adding the secondary insoluble component into 10 g of pure water and stirring at 30 캜 for 1 week.

The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention on a film.

The cured product of the present invention is obtained by curing the above-mentioned curable resin composition of the present invention or a dry film having a resin layer obtained by applying and drying the curable resin composition of the present invention.

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

According to the present invention, it becomes possible to realize a curable resin composition, a dry film, a cured product, and a printed wiring board, both having high reflectance as well as characteristics such as composition stability such as storage stability and solder resist such as solder heat resistance.

Fig. 1 is a graph showing the relationship between the wavelength and reflectance of each composition of Examples 3 and 9 and Comparative Example 4. Fig.

Hereinafter, embodiments of the present invention will be described in detail.

The curable resin composition of the present invention contains a curable resin (A), a white colorant (B), and a photo-excitable inorganic filler (C) subjected to surface treatment, and has a pH value measured under a predetermined condition 6 to 12 points. This makes it possible to provide a curable resin composition having high reflectance as well as properties such as composition stability such as storage stability and solder resist properties such as solder heat resistance.

Specifically, in the present invention, 10 g of the curable resin composition before curing is placed in 50 g of acetone to take out the first insoluble component, and then the first insoluble component is put into 50 g of chloroform to take out the second insoluble component, Further, it is necessary that the pH of the obtained liquid is 6 to 12 by adding the extracted second insoluble component into 10 g of pure water and stirring at 30 캜 for one week. By setting the pH value to 6 or more and 12 or less, a high reflectance can be obtained over the entire wavelength range in the resulting cured coating film. The pH value is suitably 6 to 9.

Next, each component of the curable resin composition of the present invention will be described. Further, in the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) Curable resin]

The curable resin composition of the present invention contains (A) a curable resin. The curable resin (A) used in the present invention may be a thermosetting resin (A-1) or a photo-curable resin (A-2), or a mixture thereof.

((A-1) thermosetting resin)

(A-1) The thermosetting resin may be a resin that is cured by heating to exhibit electrical insulation, and examples thereof include an epoxy compound, an oxetane compound, a melamine resin, and a silicone resin. Particularly, in the present invention, an epoxy compound and an oxetane compound can be suitably used, and these may be used in combination.

As the epoxy compound, a known compound having at least one epoxy group can be used, and among them, a compound having two or more epoxy groups is preferable. Examples thereof include monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether and glycidyl (meth) acrylate, bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, Cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl Ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl And tris (2-hydroxyethyl) isocyanurate. These compounds may be used alone or in combination of two or more. These may be used singly or in combination of two or more in accordance with the required characteristics.

Next, the oxetane compound will be described. (I)

Specific examples of the oxetane compound containing an oxetane ring represented by the formula ( ¹ ) in which R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms include 3-ethyl-3-hydroxymethyloxetane (OXT-101), 3-ethyl-3- (phenoxymethyl) oxetane (trade name OXT-211, (OXT-212 manufactured by Toagosei Co., Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene OXT-121), and bis (3-ethyl-3-oxetanylmethyl) ether (trade name OXT-221, manufactured by Doa Kosei KK). Further, an oxetane compound of phenol novolac type and the like are also exemplified. These oxetane compounds may be used in combination with the epoxy compound, or may be used alone.

((A-2) photocurable resin)

The photo-curable resin (A-2) may be a resin that is cured by irradiation with active energy rays to exhibit electrical insulation, and in the present invention, a compound having at least one ethylenic unsaturated bond in the molecule is preferably used Is used.

As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer and a photopolymerizable vinyl monomer for publicly known generations are used. Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. (Meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate and bisphenol epoxy Acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and polybutadiene modified (meth) acrylate.

Examples of the photopolymerizable vinyl monomers include known ones such as styrene derivatives such as styrene, chlorostyrene and? -Methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; N-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-butoxymethylacrylamide Meth) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; (Meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri , Alkylpolyol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) Meth) 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. These may be used singly or in combination of two or more kinds in accordance with required characteristics.

When the composition of the present invention is an alkali developing photosensitive resin composition, it is preferable to use a carboxyl group-containing resin as the curing resin (A). The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenic unsaturated group, and may or may not have an aromatic ring.

Specific examples of the carboxyl group-containing resin that can be used in the composition of the present invention include the following compounds (which may be oligomers or polymers) listed below.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene. When the carboxyl group-containing resin has an aromatic ring, at least one of the unsaturated carboxylic acid and the unsaturated group-containing compound may have an aromatic ring.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols, polyether Containing carboxyl groups in a diol compound such as polyol, polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, phenolic hydroxyl group and alcoholic hydroxyl group. Urethane resin. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate, the carboxyl group-containing dialcohol compound and the diol compound may have an aromatic ring.

(3) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- , A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the terminal of a urethane resin by a heavy-chain reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group . When the carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate compound, the diol compound and the acid anhydride may have an aromatic ring.

(4) a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a beacilene type epoxy resin and a biphenol type epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of the diisocyanate, the (meth) acrylate of the bifunctional epoxy resin or the partial acid anhydride modification thereof, the carboxyl group-containing dialcohol compound and the diol compound has an aromatic ring .

(5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) (Meth) acrylated carboxyl group-containing urethane resin. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule may have an aromatic ring.

(6) In the synthesis of the resin of the above (2) or (4), it is preferable to use a mixture of isophorone diisocyanate and pentaerythritol triacrylate, such as equimolar reactants, having one isocyanate group and at least one (meth) acryloyl group in the molecule (Meth) acrylate obtained by adding a compound to a carboxyl group-containing urethane resin. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and at least one (meth) acryloyl group in the molecule may have an aromatic ring.

(7) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to a hydroxyl group present in the side chain. When the photosensitive carboxyl-containing resin has an aromatic ring, at least one of the polyfunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.

(8) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, with (meth) acrylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group. When the photosensitive carboxyl-containing resin has an aromatic ring, at least one of the bifunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting hydroxyl group of the first kind. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride may have an aromatic ring.

(10) A process for producing a polyoxyalkylene polyoxyalkylene polyol, which comprises reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

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

(12) A process for producing an epoxy compound having a plurality of epoxy groups in a molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a compound having an unsaturated (meth) Containing carboxylic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and adipic acid to the alcoholic hydroxyl group of the reaction product obtained by reacting a carboxylic acid group-containing monocarboxylic acid Containing photosensitive resin. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the epoxy compound, the compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, the unsaturated group-containing monocarboxylic acid and the polybasic acid anhydride, You can have a ring.

(13) The resin composition according to any one of the above items (1) to (12), further comprising one or more epoxy groups in the molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) (Meth) acryloyl group is added to the photosensitive resin composition. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one epoxy group and at least one (meth) acryloyl group in the molecule may have an aromatic ring.

Since the carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution becomes possible.

Among them, it is preferable to use a carboxyl group-containing resin derived from styrene or a styrene derivative because a composition having excellent solder heat resistance can be obtained.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mg KOH / g, and more preferably in the range of 40 to 180 mg KOH / g. If it is in the range of 20 to 200 mgKOH / g, the adhesion of the coating film is obtained, the alkali development is facilitated, the dissolution of the exposed portion by the developer is suppressed, the line is not thinned more than necessary, .

The weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. When the content is within this range, the tack free performance is good, the wettability of the film after exposure is good, and the film is hardly reduced at the time of development. When the weight average molecular weight is in the above range, the resolution is improved, the developing property is good, and the storage stability is improved. More preferably, it is from 5,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography.

When an epoxy resin and a carboxyl group-containing resin are used in combination as the curable resin (A), the equivalent of the epoxy group contained in the epoxy resin is preferably 2.0 or less, more preferably 2.0 or less, per 1 equivalent of the carboxyl group contained in the carboxyl- Is not more than 1.5, and even more preferably not more than 1.0. This is because, if an epoxy group is contained, it tends to be discolored.

[(B) White colorant]

Examples of the white colorant (B) include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, zinc white, zinc sulphate and lead thiophthalate. From the viewpoint of the effect of suppressing discoloration due to heat, Is preferably used. (B) a white colorant, the composition of the present invention can be made white, and a high reflectance can be obtained.

The titanium oxide may be titanium oxide having any one of the rutile type, the anatase type and the rhamstellite type, and one type may be used alone, or two or more types may be used in combination. The person of seudel light type titanium oxide, indigo seudel light type Li _{0. 5} TiO ₂ by chemical oxidation.

Use of the rutile titanium oxide in the above is preferable because heat resistance can be further improved, discoloration due to light irradiation is hardly caused, and quality can not be lowered even in a severe use environment. In particular, by using rutile type titanium oxide surface-treated with aluminum oxide such as alumina, the heat resistance can be further improved. (B) When titanium oxide is used as the white colorant, the content of the rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is suitably not less than 10% by mass, more preferably not less than 30% by mass, The upper limit is 100 mass% or less, that is, the whole amount of titanium oxide may be rutile-type titanium oxide surface-treated with the aluminum oxide. As the rutile titanium oxide surface-treated with the aluminum oxide, for example, CR-58 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile type titanium oxide titanium oxide, R-630 manufactured by Tosoh Corporation, . It is also preferable to use rutile-type titanium oxide surface-treated with silicon oxide, and in this case, heat resistance can be further improved. Further, it is also preferable to use rutile-type titanium oxide surface-treated with both aluminum oxide and silicon oxide, and for example, CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile type chlorinated titanium oxide.

In addition, since the anatase type titanium oxide has lower hardness than that of the rutile type, when the anatase type titanium oxide is used, the formability of the composition becomes better.

The blending amount of the (B) white colorant is preferably in the range of 5 to 80 mass%, more preferably in the range of 10 (mass%) to 10 To 70% by mass.

[(C) photo-excitable inorganic filler]

The (C) surface-treated, photo-excited inorganic filler used in the present invention refers to a surface treatment of a photoexcited inorganic filler with an inorganic component or an acidic liquid. In the present invention, as described above, in the curable resin composition, a photoexposure inorganic filler (C) surface-treated with (B) a white colorant is used, and further, It is possible to realize a high reflectance in the cured coating film. The use of a product which has been subjected to a surface treatment as a photo-excipient inorganic filler means that the product is insolubilized or poorly soluble on the surface of the photo-excitable inorganic filler by the surface treatment to drastically improve the water- This is because the effect of maintaining high reflectance over a long period of time can be obtained even under the condition that water exists.

Examples of the photo-excitable inorganic filler include strontium aluminate and zinc sulfide. In particular, strontium aluminate can be suitably used. These photoexposure inorganic fillers may be used alone or in admixture of two or more. Examples of inorganic components used in the surface treatment include silica (glass), alumina, zirconia, and the like. As a method of surface treatment using an inorganic component, a known method can be used, and it is not particularly limited.

The acidic liquid may be at least one selected from the group consisting of nitric acid, hydrochloric acid, carbonic acid, sulfuric acid, sulfuric acid, silicic acid, boric acid, phosphoric acid, phosphorous acid, polyphosphoric acid, sodium phosphate monobasic, sodium hexametaphosphate, acetic acid, butyric acid, propionic acid, caprylic acid, But are not limited to, stearic acid, acrylic acid, methacrylic acid, oxalic acid, succinic acid, malic acid, tartaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, salicylic acid, benzoic acid, Among acid-generating compounds such as acids, taurine, ascorbic acid, silanolic acid, phosphonic acid, crotonic acid, maleic acid, lactic acid and the like acids and salts of these acids such as potassium salt, sodium salt, ammonium salt and acid anhydride Among them, it is preferable to use a phosphoric acid-based compound consisting of phosphoric acid and phosphoric acid such as phosphoric acid, phosphorous acid, polyphosphoric acid, and sodium phosphate, and sulfuric acid , A phosphate-based compound is particularly preferred. The inorganic component and the acidic liquid may be used alone or in combination of two or more.

Here, the surface treatment with an acidic liquid can be carried out under the condition of pH 3 or less by using the acidic liquid, for example, a method of immersing a photoexcited inorganic filler in an aqueous solution containing an acidic liquid, A method of spraying an aqueous solution onto a photoexciting inorganic filler, and a method of bringing an acidic liquid into contact with the surface of the photoexciting inorganic filler in a high-humidity atmosphere. Among these methods, a method of immersing a photoexcited inorganic filler in an aqueous solution containing an acidic liquid is preferable in that the reaction can be carried out simply and efficiently.

Concretely, water of about 1 to 1000 mass times, preferably about 2 to 100 mass times, more preferably about 3 to 10 mass times, of the photo-excitable inorganic filler is prepared, and the above acidic liquid Is dissolved to a concentration of about 0.01 to 30 mass%, preferably about 0.5 to 10 mass%. At this time, in order to adjust the solubility of the acidic liquid, a part of the water is replaced with a water-soluble organic solvent such as methanol, ethanol, acetone, dioxane, dimethylformamide (DMF) or dimethylsulfoxide It is also possible. The amount of the organic solvent to be used in this case is not particularly limited and may be a range that does not inhibit the reaction of the metal oxide of the photoexcited inorganic filler with the acidic liquid. In addition, a surfactant may be added to the aqueous solution in order to improve the dispersibility of the photo-excitable inorganic filler. The type and amount of the surfactant can be appropriately adjusted in accordance with the kind and amount of the photoexcitation-based inorganic filler to be used.

Next, a photoexposure inorganic filler is added to an aqueous solution containing an acidic liquid and uniformly dispersed by stirring to react the acidic liquid and the metal oxide of the photoexcited inorganic filler. The treatment temperature at this time is not particularly limited, but it is usually from 20 ° C or higher, preferably from 50 ° C to lower than the boiling point, and the treatment time is from 0.5 to 120 minutes, preferably from 10 to 60 It can be done in minutes.

After the surface treatment with the acidic liquid, an alkali treatment may be performed using at least one alkaline compound selected from an alkali or an alkali-generating compound. The alkali treatment is carried out at a pH of 4 to 9, preferably at a pH of 4 to 7. By performing the alkali treatment, the durability of the water-resistant property of the photo-excitable inorganic filler by the surface treatment using the acidic liquid is improved, and the water resistance is maintained even in long-term use at a high temperature. It is considered that this is because the reaction product formed on the surface of the photo-excitable inorganic filler is modified to be more rigid by the alkali treatment. As the alkali to be used for the alkali treatment, sodium hydroxide, lithium hydroxide, calcium hydroxide, potassium hydroxide, strontium hydroxide, ammonia and the like are used, but sodium hydroxide is preferably used. As the alkali generating compound, sodium secondary phosphate, sodium tertiary phosphate, sodium hexametaphosphate, sodium acetate, strontium oxide and the like are preferably used, but sodium tertiary phosphate is preferably used. Organic alkaline compounds such as monoethanolamine, triethanolamine, guanidine, stearylamine, and pyridine may also be used.

The means for alkali treatment is not particularly limited and can be carried out, for example, as follows. That is, after the treatment with the acidic liquid, the supernatant is removed, and an appropriate amount of water is newly added. Then, the pH can be adjusted to 4 to 9 by gradually adding the alkaline compound while stirring with a mixer or the like. The treatment temperature at this time is not particularly limited, but usually the liquid temperature is set at about 20 캜 or higher, preferably 50 캜 to lower than the boiling point. The treatment time is usually 0.5 to 120 minutes, preferably 10 to 60 minutes.

After the alkali treatment, the supernatant is removed, filtered, rinsed and sufficiently dried to obtain the desired photoexcited inorganic filler subjected to the surface treatment (C). The drying conditions at this time are not particularly limited, but they can be usually dried at a temperature of 20 ° C or more for 2 hours or more. The surface-treated photoexposure inorganic filler can be obtained in powder form by sieving, if necessary. The thus-obtained (C) surface-treated, photoexposure inorganic filler can maintain very good water resistance over a long period of time because it has a solubility of less than 1 g in 100 g of water at 40 캜 and also has heat resistance.

As the photo-excipient inorganic filler (C) subjected to the surface treatment, when the pH is measured by the same method as the above-mentioned curable resin composition, it is preferable that the pH value is 6 or more and 12 or less, desirable.

The amount of the photoexcitation inorganic filler (C) in the composition of the present invention is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more, based on 100 parts by mass of the curable resin (A) in terms of solid content. The upper limit is preferably 500 parts by mass or less, more preferably 300 parts by mass or less. By setting the blending amount of the (C) photo-excitatory inorganic filler to 0.1 parts by mass or more, a high reflectivity that is not available in the past can be achieved.

[(D) Photopolymerization initiator]

In the composition of the present invention, when (A-2) a photocurable resin is used, it is preferable to further add (D) a photopolymerization initiator. Generally, when a photopolymerization initiator is added, the photopolymerization initiator absorbs light, so that the reflectance may decrease. In the present invention, by blending the above-mentioned (B) white colorant and (C) Even if a photopolymerization initiator is added, the reflectance can be increased. As the photopolymerization initiator (D), any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator may be used.

(D) a photopolymerization initiator such as bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- , 4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, Monoacylphosphine oxides such as valylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO, manufactured by BASF Japan Co., Ltd.); 1-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 2-methyl-1-phenyl-propan-1-one, 2-hydroxy- Hydroxyacetophenones such as 1-one; Benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- Acetophenones such as (dimethylamino) -2 - [(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthones such as isopropylthioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; Ethane, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole Yl] -, 1- (O-acetyloxime); Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) Titanocenes such as bis [2,6-difluoro-3- (2- (1-phenyl-1-yl) ethyl) phenyl] titanium; Phenyl disulfide 2-nitrofluorene, butyloline, anisoo ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. All the above photopolymerization initiators may be used alone or in combination of two or more.

Above all, photopolymerization initiators of acylphosphine oxides such as bisacylphosphine oxides and monoacylphosphine oxides are preferable because they are less sticky and excellent in discoloration inhibiting effect. Among them, the use of bisacylphosphine oxides is preferable in that sensitivity and non-stickiness can be further improved.

The blending amount of the photopolymerization initiator (D) is 0.1 to 50 parts by mass relative to 100 parts by mass of the curable resin (A) in terms of solid content. By blending the photopolymerization initiator (D) in this range, the photocurability on copper becomes satisfactory, the curability of the coating becomes good, the coating film properties such as chemical resistance are improved, and the deep curing property is also improved. More preferably, it is 1 to 40 parts by mass with respect to 100 parts by mass of the curable resin (A).

[(E-1) Curing Agent and (E-2) Curing Catalyst]

In the composition of the present invention, when a thermosetting resin (A-1) is used, the (E-1) curing agent and / or the (E-2) curing catalyst may be further added.

Examples of the curing agent (E-1) include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, isocyanate compounds, and polymeric compound compounds. Among them, polyfunctional phenol compounds and polycarboxylic acids and acid anhydrides thereof are preferably used in terms of workability and insulating properties.

The polyfunctional phenol compound may be a compound having two or more phenolic hydroxyl groups in one molecule, and may be a known one. Specific examples thereof include phenol novolac resins, cresol novolac resins, bisphenol A, allyl bisphenol A, bisphenol F, novolak resins of bisphenol A, vinylphenol copolymer resins, and the like, and have a high reactivity and an effect of improving heat resistance , Phenol novolak resin is particularly preferable. Such a polyfunctional phenol compound is additionally reacted with an epoxy compound and / or an oxetane compound in the presence of a suitable curing catalyst.

Examples of the polycarboxylic acid and its acid anhydride include compounds having two or more carboxyl groups in one molecule and their acid anhydrides, and examples thereof include copolymers of (meth) acrylic acid, copolymers of maleic anhydride, condensates of dibasic acids . Examples of commercially available products include John Krill (product group name) manufactured by BASF Corporation, SMA resin (product group name) manufactured by Satomasa, and polyazelaic anhydride made by Shin-Nippon Rika Co.,

The compounding ratio of these (E-1) curing agents is usually sufficient in the quantitative ratio and is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass, per 100 parts by mass of the thermosetting resin (A-1) to be.

The (E-2) curing catalyst is a catalyst which, when a compound which can be a curing catalyst in the reaction of an epoxy compound and / or an oxetane compound with the curing agent (E-1) ≪ / RTI > Specific examples of the curing catalyst include a tertiary amine, a tertiary amine salt, a quaternary onium salt, a tertiary phosphine, a crown ether complex, and a phosphonium iodide. Of these, Or a combination of two or more.

Of these, imidazoles such as 2E4MZ, C11Z, C17Z and 2PZ, azine compounds of imidazoles such as 2MZ-A and 2E4MZ-A, imidazoles such as 2MZ-OK and 2PZ- (All trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomalonitrile and the derivatives thereof, and the like; imidazole hydroxymethyls such as 2PHZ and 2P4MHZ Amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane and organic acid dihydrazide, 1,8-diazabicyclo [ (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecene-7 (trade name DBU, (Trade name: ATU, manufactured by Ajinomoto Co., Ltd.) or triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyl And organic phosphine compounds such as diphenylphosphine.

The mixing ratio of these (E-2) curing catalysts is usually sufficient and is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermosetting resin (A-1) .

[(F) Antioxidant]

The composition of the present invention preferably further comprises (F) an antioxidant. (F) The effect of preventing oxidation deterioration of the curable resin or the like and preventing discoloration can be obtained by containing the antioxidant, and the effect of improving the heat resistance and improving the resolution (line width reproducibility) can be obtained . In other words, depending on the kind of the (B) white colorant, the light may be reflected and absorbed to deteriorate the resolution. (F) By containing the antioxidant, (B) So that resolution can be obtained.

(F) Examples of the antioxidant include a radical scavenger such as a radical scavenger for neutralizing a generated radical, and a peroxide decomposer for decomposing a generated peroxide into a harmless substance to prevent generation of new radicals. A combination of more than two species can be used.

Specific examples of the antioxidant (F) serving as a radical scavenger include hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6- T-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5- Phenol-based compounds such as di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as methaquinone and benzoquinone, And amine-based compounds such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and phenothiazine. As a commercially available product, for example, IRGANOX 1010 (manufactured by BASF Japan Co., Ltd.) may be used.

Examples of the antioxidant (F) which functions as a release of peroxide include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3 , 3'-thiodipropionate, and the like.

Above all, use of a phenol-based antioxidant is preferable in that the discoloration-inhibiting effect, heat resistance, and good resolution are further obtained.

When the antioxidant (F) is used, its amount is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.01 part by mass to 5 parts by mass with respect to 100 parts by mass of the curable resin (A). (F) If the amount of the antioxidant is 0.01 part by mass or more, the effect of the addition of the above-described antioxidant can be reliably obtained. On the other hand, when the amount is 10 parts by mass or less, It is possible to obtain good properties for touch-up drying and coating properties.

In addition, the antioxidant (F), especially the phenolic antioxidant, may exhibit additional effects when used in combination with the heat-resistant stabilizer, so that the resin composition of the present invention may also contain a heat-resistant stabilizer.

Examples of the heat-resistant stabilizer include phosphorus-based, hydroxylamine-based, and sulfur-based heat stabilizers. The heat stabilizer may be used alone or in combination of two or more.

When the heat stabilizer is used, its blending amount is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the (A) curable resin.

The composition of the present invention may contain a reactive diluting solvent. The reactive diluting solvent is used for improving the workability by adjusting the viscosity of the composition and for increasing the cross-linking density or improving the adhesiveness, etc., and a photo-curing monomer or the like can be used. As the photocurable monomer, the above-mentioned photopolymerizable vinyl monomers and the like can be used.

The blending ratio of the reactive diluting solvent is preferably 1 to 100 parts by mass, more preferably 1 to 70 parts by mass based on 100 parts by mass of the curable resin (A). By setting the mixing ratio within the above range, photocurability is improved, pattern formation is facilitated, and the strength of the cured film can be improved.

The composition of the present invention may contain an organic solvent for the purpose of preparation of the composition and viscosity adjustment when the composition is applied to a substrate or a carrier film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; And petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

In the composition of the present invention, other additives known in the field of electronic materials may be added. Examples of other additives include heat polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial and antifungal agents, antifoaming agents, leveling agents, fillers, thickeners, adhesion promoters, A colorant, a photoinitiator, a sensitizer, a curing accelerator, a release agent, a surface treatment agent, a dispersant, a dispersion aid, a surface modifier, a stabilizer, and a phosphor.

Next, the dry film of the present invention has a resin layer obtained by applying and drying the composition of the present invention on a carrier film. In forming the dry film, first, the composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity. Thereafter, a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Coater, spray coater or the like to coat the carrier film with a uniform thickness. Thereafter, the coated composition is dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film after the resin layer comprising the composition is formed on the carrier film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. The cover film may be smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

Further, in the present invention, the resin layer may be formed by applying the composition of the present invention on the cover film and drying, and a carrier film may be laminated on the surface of the resin layer. That is, as the film to which the composition of the present invention is applied when producing the dry film in the present invention, either a carrier film or a cover film may be used.

The composition of the present invention may be coated on a substrate by a suitable coating method such as dip coating, flow coating, roll coating, bar coating, screen printing, Curtain coating method and the like, and then the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 占 폚 to form a non-sticky resin layer. In the case of a dry film obtained by applying the above composition onto a carrier film or a cover film and drying the film, the composition layer of the present invention is brought into contact with the base material by means of a laminator or the like, Whereby a resin layer can be formed.

As the base material, there may be used a resin such as a paper phenol, a paper epoxy, a glass cloth epoxy, a glass polyimide, a glass cloth / nonwoven epoxy, a glass cloth / paper epoxy, a synthetic fiber epoxy, · Copper-clad laminate for high-frequency circuit using polyethylene · polyphenylene ether, polyphenylene oxide · cyanate, etc. It is possible to use copper clad laminate of all grades (FR-4 etc.), other metal substrate, polyimide film , A PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

The volatile drying performed after application of the composition of the present invention can be carried out by a hot air circulation type drying furnace, a hot plate, a convection oven or the like (a hot air circulation type drying furnace equipped with a heat source of air heating by steam, And a method of spraying onto the support from a nozzle).

The composition of the present invention forms a cured film (cured product) excellent in various properties such as heat resistance, chemical resistance, moisture absorption, adhesion, electrical properties, etc. by heating at a temperature of, for example, about 100 to 180 ° C .

Further, by applying the composition of the present invention and subjecting the obtained resin layer after volatilization and drying of the solvent to exposure (light irradiation), the exposed portion (light irradiated portion) is cured. Concretely, the photoresist is selectively exposed to an active energy beam through a photomask having a pattern formed thereon by a contact or noncontact method, or directly pattern-exposed by a laser direct exposure machine to form an unexposed portion in a dilute alkali aqueous solution , 0.3 to 3 mass% aqueous sodium carbonate solution) to form a resist pattern.

The exposure apparatus used for the active energy ray irradiation may be a device which mounts a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. and irradiates ultraviolet rays in the range of 350 to 450 nm, Devices (e.g., laser direct imaging devices that draw images directly with a laser by CAD data from a computer) can also be used. As the lamp light source or the laser light source of the direct shot, the maximum wavelength may be in the range of 350 to 410 nm. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally within the range of 20 to 800 mJ / cm 2, preferably 20 to 600 mJ / cm 2.

Examples of the developing method include dipping, showering, spraying, brushing and the like. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

The composition of the present invention is suitably used for forming a cured film on a printed wiring board, more suitably used for forming a permanent film, and more preferably used for forming a solder resist or a coverlay. The curable resin composition of the present invention can also be used for forming a solder dam. Further, by making the composition of the present invention white, the light emitted from a light emitting diode (LED) or an electroluminescence (EL) used as a light source thereof in a backlight of a liquid crystal display of a lighting apparatus, a portable terminal, a personal computer, To reflectors that reflect light.

Example

Hereinafter, the present invention will be described in more detail with reference to examples.

(Synthesis Example of Varnish A (Curable Resin)) [

42 parts by mass of methacrylic acid, 43 parts by mass of methyl methacrylate, 35 parts by mass of styrene, 35 parts by mass of benzyl acrylate, and 100 parts by mass of carbitol acetate 100 were added to a four-necked flask equipped with a reflux condenser, a thermometer, , 0.5 part by mass of lauryl mercaptan and 4 parts by mass of azobisisobutyronitrile were added and the mixture was heated at 75 DEG C for 5 hours under a nitrogen stream to proceed the polymerization reaction to obtain a copolymer solution (solid content concentration: 50% by mass) . To this, 0.05 parts by mass of hydroquinone, 23 parts by mass of glycidyl methacrylate and 2.0 parts by mass of dimethylbenzylamine were added and an addition reaction was carried out at 80 DEG C for 24 hours. Then, 35 parts by mass of carbitol acetate was added, To obtain a copolymer resin solution (varnish A).

The thus obtained varnish A had a solid content concentration of 65% by mass and an acid value of solid content of 70 mgKOH / g.

Each component was compounded according to the formulation shown in the following table, premixed in a stirrer, dispersed with a three-roll mill and kneaded to prepare a composition. The amounts in the tables represent parts by mass. The compositions of each of the obtained examples and comparative examples were evaluated as follows. The results are shown together in the following table.

(1) pH

10 g of each composition before curing was placed in 50 g of acetone to take out the primary insoluble component. Thereafter, the primary insoluble component was put into 50 g of chloroform. Thereafter, the secondary insoluble component was taken out, A second insoluble component was added to 10 g of pure water and stirred at 30 캜 for one week to obtain a liquid. The pH of the obtained liquid was measured.

(2) Storage stability

Each composition was put in a plastic container of 30 g volume in an appropriate amount and stored at room temperature for 180 days, and the state of the composition after storage was visually evaluated. The criteria are as follows.

?: No gelation.

X: Gelled.

(3) Solder heat resistance

Each composition was applied to the entire surface of the FR-4 material by screen printing and cured for 30 minutes in a hot air circulation type drying furnace at 150 캜 to obtain a substrate. The obtained substrate was coated with a rosin-based flux, immersed in a solder bath set at 260 DEG C in advance, washed with denatured alcohol, and evaluated for expansion and exfoliation of the resist layer by visual observation. The criteria are as follows.

○: The peeling was not confirmed even if the immersion for 10 seconds was repeated three times or more.

X: The resist layer was expanded and peeled within 3 times of immersion for 10 seconds.

(4) Reflectance

Each composition was applied to the entire surface of the FR-4 material by screen printing and cured for 30 minutes in a hot air circulation type drying furnace at 150 캜 to obtain a substrate. The coating film surface of the obtained substrate was measured for the reflectance at a wavelength of 450 nm with respect to a spectroscopic colorimeter (CM-2600d, manufactured by Konica Minolta Sensing Co., Ltd.).

For each of the compositions of Examples 3 and 9 and Comparative Example 4, the reflectance in a wavelength range of 350 to 750 nm was measured in the same manner. The results are shown in the graph of Fig.

* 1-1) Varnish A

* 1-2) Varnish B (Lumiflon 200F, manufactured by Asahi Glass Co., Ltd.)

* 1-3) Varnish C (X-22-3701E, manufactured by Shinetsu Chemical Industry Co., Ltd.)

* 2-1) Titanium oxide (Taipei CR-58, manufactured by Ishihara Sangyo Co., Ltd.)

* 2-2) Titanium oxide (R-931, manufactured by DuPont)

* 2-3) Titanium oxide (TiONA 696, manufactured by CRISTAL)

* 3) Luminessus V1 (light-excited inorganic filler subjected to surface treatment), LUMINESUS

* 4) LUMINESUS V2 (light-excited inorganic filler with surface treatment), LUMINESUS

* 5) N luminous flux (G-300M) (a photo-excitatory inorganic filler without surface treatment), Nemoto Tokushu Chemical Co., Ltd.

* 6) MFTG (tripropylene glycol methyl ether), manufactured by Nippon Nyukazai Co., Ltd.

* 7) Melamine (curing catalyst), manufactured by Nissan Chemical Industries, Ltd.

8) Irganox 1010 (phenol type), BASF Japan Co., Ltd.

* 9) KS-66, manufactured by Shin-Etsu Silicone Co., Ltd.

* 10) Disperbyk-111, manufactured by Big Chem Japan Co., Ltd.

* 11) Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.

* 12) LMP-100, manufactured by Fuji Talc Co., Ltd.

* 13) TEPIC-HP, manufactured by Nissan Chemical Industries, Ltd.

* 14) TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.

As shown in the above table, in the composition of each Example containing a curable resin, a white colorant, and a photo-excited inorganic filler subjected to surface treatment and the pH value satisfying a predetermined range, It was confirmed that a high reflectance was obtained without deteriorating the characteristics of the solder resist such as solder resistance and solder heat resistance. From the comparison of reflectance data between Examples 3 and 9 and Comparative Example 4 shown in Fig. 1, it was found that the effect of improving the reflectivity was obtained for a wide wavelength range.

From the results of Examples 1 to 13, it was found that the reflectance was improved while maintaining solder heat resistance and storage stability in a composition containing a surface-treated photoexcitation inorganic filler having a pH of 6 to 12. On the other hand, from the results of Comparative Examples 1 to 3, it was found that the storage stability was deteriorated in the composition containing the photo-excitatory inorganic filler whose pH was outside the range of 6 to 12 and which was not surface-treated. From the results of Comparative Examples 4 and 5, it was also found that, even if the pH is 6 to 12, the reflectance is lowered unless a photo-excitable inorganic filler or a white coloring agent is added.

Claims (4)

A curable resin composition comprising (A) a curable resin, (B) rutile titanium oxide, and (C) strontium aluminate subjected to surface treatment,
10 g of the curable resin composition before curing was placed in 50 g of acetone to take out the primary insoluble component. The extracted primary insoluble component was then added to 50 g of chloroform to extract the secondary insoluble component. Wherein the pH of the liquid obtained by adding the second insoluble component into 10 g of pure water and stirring at 30 캜 for one week is 6 to 12. The curable resin composition for a printed wiring board according to claim 1, A dry film having a resin layer obtained by coating and drying the curable resin composition for a printed wiring board according to claim 1 on a film. A cured product obtained by curing a dry film having a resin layer obtained by applying and drying the curable resin composition for a printed wiring board according to claim 1 or the curable resin composition for a printed wiring board according to claim 1. A printed wiring board having the cured product according to claim 3.

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