TW200918585A - Inorganic filler and organic filler-containing curable resin composition, resist film coated printed wiring board, and method for producing the same - Google Patents

Abstract

A curable resin composition comprises: (I) 100 parts by weight of a curable resin; (II) 10 to 1200 parts by weight of an inorganic filler; and (III) 1 to 100 parts by weight of an organic filler having an elastic modulus of 1 to 2000 (MPa) and an average particle diameter of 0.01 to 10 μ m, wherein a content weight ratio of the components (II) and (III) is 1 to 41.

Description

200918585 VI. Description of the invention: [Mao:: the technical field of the genus] The circuit board η is about a kind of hardening resin composition, which can be used as a printed printing line, and is a white printed circuit board and used for mounting heat-generating components. The resist film ink used for the printing of the film is similar to that of the film; L no technology] Property knowers) Each of the hardening resins of the inorganic fillers is composed of a coloring agent (known in the heart of the oxidizing industry), which contains a printed circuit from the light _ for the anti-monetary filler to enhance ( Patent Document D ^ replaces the reflectivity of the white laminate in the visible short-wavelength region, Ρ has a thermosetting resin lacquer that contains high thermal conductivity to the like) as a heat-injective inorganic filler, which is used for 热= #High-density packaged components (such as power-electrical crystals), the cover insulating layer of the metal substrate is applied with high heat radiation (Patent 2). In any of the above cases, the inorganic When the filler is mixed with a large amount of the hard & composition, the resulting hard-dip rupture resistance is unfortunately insufficient. Therefore, for the functional money filling (four), the filling amount is from: "limit" and cannot be applied to the cured film. Sufficiently large functional properties (light reflectivity and heat radiation or the like). Document 1] 专利 专利 专利 专利 专利 脱 2 ] 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 320584 200918585 [Invention [Problem to be Solved by the Invention] An object of the present invention is to provide a curable resin composition which can impart greater functional properties to a cured film. In particular, it is an object of the present invention to provide a hardenability. a resin composition suitable for use as a resist ink for a white printed wiring board or the like for applying a resist film having excellent light reflectivity, crack resistance and yellowing resistance or the like. Alternatively, the present invention Another object is to provide a curable resin composition suitable for use as a resistive ink for a printed wiring board or the like to which a heat-generating component is mounted for application of excellent heat radiation, crack resistance and fading resistance. The resist film of the sex or the like. [Means for Solving the Problem] The inventors of the present invention conducted earnest research in order to achieve the above objects, and as a result, the inventors of the present invention completed the following invention. That is, the first aspect of the present invention. Provided is a curable resin composition comprising: (I) 100 parts by weight of a curable resin; (II) 10 to 1 part by weight of an inorganic filler; and (III) 1 100 parts by weight of an organic filler having an elastic modulus of from 1 to 2000 (MPa) and an average particle diameter of from 0.01 to 10 μm (/z HI), wherein the component (II) is (ΙΠ) The second aspect of the invention provides the curable resin composition according to the first aspect of the invention, wherein the component (II) is a white pigment and/or has a thickness of from 1.0 to 500 (W/ The material of the thermal conductivity of m · K) 4 320584 200918585 The third aspect of the invention provides the curable resin composition according to the fourth aspect of the invention, wherein the component (ιπ) contains rubber particles. According to a fourth aspect of the present invention, there is provided a method according to any one of the first to third aspects of the present invention, wherein the (four) chemical resin composition is a (Α) light-reversible resin composition containing the following resin ( Bu, (1-2) and components ((1) to (VI); (8) thermosetting resin composition containing the following resin U-2) and components (1)), (ΠΙ) and (8); or (6) photocurable resin composition And containing the following resins (Η) and components (9) to (V); (1-1) photocurable resin; (1-2) thermosetting Alicyclic; (II) an inorganic filler; (III) an organic filler; (IV) a photoreactive monomer; < ν) light hardener; and (VI) heat curing agent. According to a fifth aspect of the present invention, in the hard resin composition of the fourth aspect, the resin (1-1) is an acid group-containing acrylic resin obtained by using a fluorene-type unsaturated body = a fat-containing substance, the reaction product having a conversion in a molecular material; and / = !=(d) or an oxetane- and a compound as: an alicyclic-containing epoxy group and/or a lipid-containing acid group obtained by early polymerization The MW h of the A-inhibited A is said to have no (four) ring. The reaction product of the sigma, which is provided in the sixth aspect of the invention of < 320584 5 200918585 纟, a method for producing a printed wiring board coated with a resist film, wherein the resist film is from the invention according to the invention The curable resin composition of any one of the fifth aspect is formed. , the seventh party (four) provides a printed circuit board coated with a resist film manufactured by the method of the sixth aspect of the invention. The invention of the present invention can provide a curable resin composition which can be provided even when a prosthetic filler is mixed with a large amount of a curable resin composition, thereby contributing to a large amount of a mixture of functional inorganic fillers. A hardened film which is excellent in breaking and cracking resistance' thereby exerting greater functionality on the cured film [Embodiment] Λ Read the present invention will be described in detail with reference to the preferred embodiment. The composition of the curable resin according to the present invention The substance contains (1) fat. Examples of the component (I) include (M)#Bu^±tree", 匕栝ϋD first-setting resin. Regarding the resin (H), the g is in the molecule and has at least two a photocurable (particularly, ultraviolet curable) prepolymer of a olefinic type and a bond (particularly (polymer or polymer). Alternatively, it is preferred that the resin (1_1) has a value of 000 (special) The acid value of the average molecular weight of (4)(10)(6) and 3 Κ0Η/g (mgKOH/g)) or less (particularly, 3〇 to 16〇 (best, 40 to 130)). In hours, the imaging performance may be bipedal. Phase, ground, when the acid value is too large, the properties of the resist film ( Chemical resistance, adhesion to substrates, electrical insulation and hardness, or the like may deteriorate. Specific examples of the soil, such resins (H) include: (6): ;) obtained by polymerization using a dilute type as a basic monomer An acid group-containing acrylic acid and a ruthenium-containing epoxy group and/or an oxetanyl group are not combined with each other. 320584 6 200918585 Reaction product. 〆Acid-based acrylic resin as a raw material for preparing compound α-ii) It is obtained by polymerizing an ethylenically unsaturated acid as a basic monomer, and specific examples thereof include a homopolymer of an ethylenically unsaturated acid and a copolymer of an ethylenically unsaturated acid and "another monomer. At least one of these types can be used. Specific examples of the ethylenically unsaturated acid include (meth)acrylic acid, (mercapto)acrylic acid 2-carboxyethyl acrylate, (mercapto)acrylic acid 2-carboxy propyl vinegar, maleic anhydride, fumaric acid, croton Acid, cinnamic acid, monodecyl fumarate, anti-butanyl-ethyl ester, monopropyl fumarate, monomethyl succinate, monoethyl maleate, Monopropyl maleate, and sorbic acid. At least one of these types can be used. Specific examples of the "other monomer" mentioned above include (meth)propionic acid C1 to C8 alkyl ester [methyl (meth) acrylate and ethyl (meth) acrylate or the like], (曱2-hydroxyalkyl acrylate [2-methyl ketone (meth) acrylate, (meth) propyl phthalate 2 - ethyl acetoacetate and (meth) acrylate 2-hydroxy propyl vinegar or similar ], ethylene glycol monomethyl acetoacetate, ethylene glycol-methyl ether methacrylate, ethylene glycol monoethyl acrylate, ethylene glycol monoethyl methacrylate, glycerin Acrylic vinegar, glycerin methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tetramethylammonium methacrylate, tetrahydrofuran methyl methacrylate Amide acrylate, amide methacrylate, acrylonitrile, methacrylonitrile, acrylonitrile, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate Ester, butyl methacrylate, isobutyl acrylate, isobutyl acrylate, propylene 320584 7 200918585 enoic acid 2- Ethylhexyl ester, 2-ethylhexyl methacrylate, methyl acrylate, phenyl methacrylate, carbitol acrylate, carbitol carbitol (carbit〇1) Methacrylate), tetrahydrofuranyl methacrylate modified by ^_caprolactone, tetrahydrofuran methyl methacrylate denatured by ε-caprolactone, diethylene glycol ethoxylate, isodecyl acrylate, methacrylic acid Isodecyl ester, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl sulfonium decyl acrylate, stearyl acrylate and Stearyl acrylate or the like; a vinyl aromatic compound [eg, styrene, mercaptostyrene, vinyl toluene, p-chlorostyrene or the like]; an unsaturated guanamine compound [eg, (methyl) ) acrylamide, diacetone acrylamide, hydrazine-hydroxydecyl acrylamide, and hydrazine-butoxy methacrylamide or the like]; multiolefin compounds [eg, butadiene, isoprene, and Chloroprene or the like]; and others [ For example, (fluorenyl) acrylonitrile, methyl isoprenyl ketone, vinyl acetate, vinyl ether monomer (VeoVa monomer) (manufactured by Shell Chemical), ethyl propionate, and triterpene Vinyl acetate.] At least one of them may be used. Examples of the alicyclic epoxy group-containing and/or oxetane-based unsaturated compound as another preparation material of the compound (I-1 - i) are included in a compound containing a radical polymerizable unsaturated group and an alicyclic epoxy group and/or an oxetanyl group in the molecule. The alicyclic group-containing epoxy group and/or the oxetan group are not less than Examples of the compound and the compound include those shown by the following formula. [Formula 1] 320584 8 200918585 R1

I H2c «= c — COO r2^_ r3 In the formula, R1 represents hydrogen or CH3 (which may have a substituent). In the formula, R2 represents a divalent hydrocarbon group which may have a substituent. Specific examples of only 2 include the following groups: methylene, ethyl, propyl, tetralin, ethylethyl, pentamethylene, hexamethylene, polymethylene, phenyl Cyclohexyl, and benzodimethyl. In the formula, η represents 1 or 1. In the formula, the R group has an epoxide group which can form a condensed ring and/or a valence group of an oxacyclobutane group. Specific examples of r3 include a glycidyl group, an oxetanyl group, and the formulae shown below. [Formula 2]

Specific examples of the unsaturated compound containing an alicyclic epoxy group and/or an oxetane group include (meth)acrylic acid epoxypropyl group; (meth)acrylic acid C^ to C6 alkyl-2, 3_epoxypropyl ester [(meth)acrylic acid 2_methyl u-milyl propyl ester, (mercapto)acrylic acid 2_ethyl 2,3_epoxypropyl vinegar or class ^ a compound having an alicyclic epoxy group [(meth)acrylic acid 3'4 decyloxycyclohexylmethyl ester, (meth)acrylic acid & epoxycyclohexylethyl^ (methyl) 3, 4-epoxycyclohexylbutyl propyl acrylate is owed to 3' 4 epoxycyclohexyl decyl amide or the like]; and at least one of them can be used as shown in the following formula. 320584 9 200918585 [Formula 3] ch3

t 化 / (4) Η) can be obtained, for example, by the acid group-containing acrylic resin and the (4) and compound containing a lipid & epoxy group and / or oxetan group at about 2 ◦ It is prepared by reacting under the reaction conditions of about 1 to 5 hours. In the compound (ι-1-i), the number of the unsaturated groups per 1000 average molecular weight is preferably from 至·2 to 4.0 (particularly, 〇. 7 to 3.5). When the number of unsaturated groups is too small, the hardenability of the film may be insufficient to exhibit a poor (four) property to the material to be coated and a poor water or coffee. Conversely, when the number of t-rich t groups is too large, the addition of an acid group-containing acrylic resin to an unsaturated compound containing a sulfhydryl group and an oxetan group containing a ruthenium group The unsaturated compound containing an alicyclic epoxy group and/or an oxetane group may be thickened and gelled. Alternatively, the compound preferably has an average molecular weight of from 1 Torr to 1 Torr (particularly, from 3,000 to 70,000). When the molecular weight of the compound (b) is too small, the film may have poor water resistance. Conversely, when the babies are too large, compounds with high viscosity (di- 丨-丨) are not convenient to handle. Furthermore, the film may have deteriorated film thickness properties and have poor adhesion properties to the water resistant material to be coated. Further, the compound [I-1 - i) preferably has an acid value of 3 Torr or less. When the acid value is too large, the financial property has poor water resistance. The compound (I_1~i) is preferably obtained by partially reacting a copolymer of (mercapto)acrylic acid and 10 320584 200918585 alkyl (meth)acrylate with a glycidyl (meth)acrylate. Other examples of the s resin (1-1) include: an alicyclic group-containing epoxy group obtained by polymerizing an unsaturated compound containing an alicyclic epoxy group and/or an oxetanyl group as a basic monomer; / or oxetane resin, the reaction product with an acid group-containing unsaturated compound. The alicyclic epoxy group-containing and/or oxetane group-containing resin as a raw material for the preparation of the compound (I-1-ii) is via an alicyclic group-containing epoxy group and/or oxygen which will serve as a basic monomer. A heterocyclic butane-based unsaturated compound is obtained by polymerization. Specific examples thereof include a homopolymer of an unsaturated compound containing an alicyclic epoxy group and/or an oxocyclic group, and an unsaturated compound containing an alicyclic epoxy group and/or an oxetanyl group. Copolymer with "other-monomer" #. At least one of these types can be used. Examples of the unsaturated compound 4 containing an alicyclic epoxy group and/or an oxocyclohexane and the above 3-monomeric monomer include those exemplified in the description of the compound (I-1-i). Further examples of the acid group-containing unsaturation of the raw material include a compound having an unsaturated group and an acid group in the molecule. Specific examples of the acid group-containing compound and the compound include (meth) = 夂, (^ base) 2-carboxyethyl acrylate, (meth)acrylic acid 2 - propyl propyl vinegar and maleic anhydride. At least one type can be used. The fennel (1 1 u) can be For example, the alicyclic epoxy group-containing resin is reacted with the acid group-containing non-fresh compound under the conditions of ',, coffee, and about (1) hours. 320584 11 200918585 . In Il-ii), the number of the unsaturated groups per 1000 is preferably from 0.2 to 4.0 (particularly, from 0.7 to 3.5), and the average molecular weight thereof is preferably 1,000. To 100000 (particularly, 3000 to 70,000). Other examples of the resin (1-1) include (I-1-iii), which has a The epoxy group of the less than two epoxy group-containing polyfunctional epoxy compound is esterified with the carboxyl group of the unsaturated monocarboxylic acid, and further, the resulting radical is reacted with a saturated or unsaturated polybasic acid anhydride. Specific examples of the above polyfunctional epoxy compound include a novolac type epoxy resin (for example, by reacting with a phenol resin and epichlorohydrin and/or methyl epichlorohydrin via a phenol (such as phenol) , cresol and alkylphenol) and formaldehyde are reacted under an acid catalyst. At least one of them may be used. Preferred are an anthracene phenolic epoxy resin and a phenolic novolac epoxy resin. Examples of the saturated monobasic acid include those exemplified as the ethylenically unsaturated acid in the compound (I -1 - i). The unsaturated monobasic acid is preferably (fluorenyl) acrylic acid. It is fully esterified or partially self-contained. It is preferably fully esterified. Examples of the above polybasic acid anhydride include dibasic acid anhydride such as maleic acid, succinic anhydride, itaconic acid anhydride, 酉太Anhydride, tetrahydro S too anhydride, hexahydro i-anhydride, and methylhexahydrogen 1 major anhydride; and aromatic polyfunctional carboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride, and diphenyl ketone tetradecanoic acid The anhydride may be used. At least one of the types may be used. Preferred is tetrahydrophthalic anhydride and hexamethylene s-acid anhydride. 12 320584 200918585. For the reaction with the above polybasic acid anhydride, preferably 0.15 for each hydroxyl group produced. Molar (mol) or more polybasic acid anhydride. Another example of the resin (1-1) includes (I-1-iv) via alkyl (meth) acrylate / (fluorenyl) acrylate The reaction of the glycidyl ester copolymer with (meth)acrylic acid and further reacting the copolymer with a saturated or unsaturated polybasic acid anhydride. Examples of the (mercapto)alkyl acrylate include those exemplified as "another monomer" in the description of the compound (丨 - 丨 - i). In the preparation of the above copolymer, the mixing ratio of the alkyl (meth) acrylate to the (meth) propionate propyl acrylate is preferably 4 〇 : 6 〇 to 2 〇 mol ratio. The above copolymer preferably has an average molecular weight of from 5,000 to 70,000 (particularly, from 10,000 to 50,000). Examples of the above polybasic acid anhydrides include those exemplified in the description of the compound. The compound (I-oxime-iv) can be produced in the same manner as the compound (n-iii). Other examples of the resin (1-1) include (1-1 -v) which is via a hydroxyalkyl (meth) acrylate, an alkyl (meth) acrylate, and a nonyl propyl (meth) acrylate. The copolymer is reacted with (meth)acrylic acid and the copolymer is further reacted with a saturated or unsaturated polybasic acid anhydride. In the hydroxyalkyl (meth) acrylate, the hydroxyalkyl group is preferably a C1 to C6 aliphatic hydrocarbon group having a primary hydroxyl group. Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl acrylate and methacrylic acid 2 hydroxy 320584 13 200918585 • ethyl vinegar. At least one of these types can be used. Examples of the (meth)-propyl acetoate ester include those exemplified as "another monomer" in the description of the compound. In the preparation of the above-mentioned co-support, the mixing ratio of the (mercapto)acrylic acid via the base alkyl ester, the alkyl (meth) acrylate and the (meth) acrylic acid propylene vinegar is preferably from 10 to 50:10 to 70:20 to 60 (specially, 15 to 30:3 to 5:30 to 50) Moerby. The above copolymer preferably has an average molecular weight of 10,000 to 7 Å (particularly, 2 Å to 60,000). Examples of the above polyphthalic anhydride include those exemplified in the description of the compound. The compound (M-v) can be produced in the same manner as the compound (I-1-iii). Other examples of the resin (1-1) include (M_vi) by using a polyfunctional epoxy compound having at least two epoxy groups in the molecule, an unsaturated monobasic group, and at least two mercapto groups in the molecule. The reaction product of another reactive group compound (hereinafter also referred to as a hydroxyl group/reactive group-containing compound) is reacted with a saturated or unsaturated polybasic acid anhydride. Examples of the above-mentioned s-energy epoxy compound include those exemplified in the description of the compound. Examples of the above unsaturated monocarboxylic acid include those exemplified as the cation-type unsaturated acid in the compound (I-1-i). In the above-mentioned permeating group/reactive group-containing compound, the reactive group is a group reactive with an epoxy group and is a group having a different group. A specific example thereof is a package comprising a polyhydroxyl-containing monocarboxylic acid such as dimethylolpropionic acid. It may contain at least one of the types. In the preparation of the above reaction product, a photoreactive monomer which will be described later may be added as a component (IV) as an additive. 5至特别的约约9. 9 (1) (Specially, about 〇. 9). The polyfunctional epoxy compound, the unsaturated monocarboxylic acid, and the hydroxyl group-reactive group-containing compound is preferably about 0.8 to 1.3. To a total of 1. 1) the molar amount of the unsaturated monocarboxylic acid and the hydrazine-containing/reactive group-containing compound of the molar react with each other with respect to 1 equivalent of the epoxy group of the polyfunctional < epoxy compound. Further, the amount of the compound having a starting group/reactive group is preferably from 〇· to 〇·5 with respect to the total oxime of the 1 molar unsaturated monocarboxylic acid and the hydroxyl group-reactive group-containing compound. , about 0. 1 to 〇 · 3) Moer. In the preparation of the above reaction product, the reaction temperature may be from 60 to 150 depending on the reaction conditions thereof. The reaction time can be from 5 to 60 hours. Examples of the above polybasic acid anhydrides include those exemplified in the description of the compound (I-1_丨丨丨). The reaction of the above oxime anhydride with the reaction product is preferably carried out by reacting a polybasic acid anhydride of 〇1 to 9 with respect to the hydroxyl group of each equivalent of the reaction product prepared above at 60 to 15 (TC reaction 1 to Other examples of the resin (1-1) include: (M-Vii) a polycarboxylic acid resin containing an unsaturated group, and specific examples thereof include the use of an unsaturated polybasic acid anhydride (maleic anhydride or the like). And a copolymer of a vinyl group-containing aromatic hydrocarbon (styrene or the like) and a hydroxyalkyl (meth)acrylate. The above-mentioned (hydroxy) hydroxyalkyl ester is exemplified in the compound 320584 15 Other examples of the resin (Μ) include a polycarboxylic acid urethane resin containing an unsaturated group, and specific examples thereof include the use of the above (I-1). a reaction product obtained by reacting a reaction product, a saturated or unsaturated polybasic acid anhydride described in -V1) with a monobasic isocyanate containing an unsaturated group. Examples of the above polybasic acid anhydride include those exemplified in the description of the compound. one of Specific examples of the isocyanate include via methacrylic acid isocyanate, methacryloxyethyl isocyanate or organic diisocyanate (toluene diisocyanate, dinonyl diisocyanate, isophorone diisocyanate, hexamethylene a base diisocyanate or the like) with a (meth) acrylate [(hydroxy) hydroxyethyl acrylate and a hydroxypropyl (meth) acrylate or the like having a hydroxyl group in the molecule at an approximate molar ratio The reaction product obtained by the reaction or the like. First, the reaction product and the polybasic acid anhydride in the above (Ι-I-Vi) are reacted in the same manner as in the above (Il-vi) to prepare a compound (I 1 vi ii). Then, the unsaturation-containing monoisocyanate is reacted at a ratio of 5 equivalents per hydrazine equivalent of the hydroxyl group in the thus obtained resin at 60 to 100 DC for 5 to 15 hours to prepare a compound (H-viii). Other examples of the resin (1-1) include: di-ix) an unsaturated fatty acid partial adduct of an epoxy resin. Examples of such a compound (I-1-ix) include an unsaturated fatty acid partial addition product of an epoxy resin in a photo-thermosetting resin composition as described in Japanese Patent Laid-Open Publication No. 2003-105061. (Better, there will be no more than 320584 16 200918585 and the addition of fatty acids to the four (four) materials of Wei Shu 2 to the lion, especially 40 to 60% of the income). Weiji...the number of compounds (1-1 -ix) Further, examples of the (meth)acrylic acid addition product include a platy type epoxy resin and 20,80% of the phenolphthalein type epoxy resin: 40 of a cresol novolac type epoxy resin. 4% to 6〇% acrylic acid adduct of 60% acrylic 雔辂Α phenyl hydrazine type oxy-type resin: _ methacrylic acid adduct of bis-oxo-bar wax; 7 finely deleted epoxy resin 2〇 to m methyl propyl baking acid addition, and secret (4) _ epoxy resin ship m crotonic acid addition. Related resin (1-1), preferably compound (I-w), (H-(9), and (I-1-v) 〇代地' related resin (H), from the viewpoint of yellowing resistance, it is preferred that the molecular material has an aromatic ring. - The system is not used by As a raw material, for example, in the preparation of raw materials, when using a square & as a raw material for preparation, the surface fat (any process of the process), for example, in the beginning, middle or In the final step, the aromatic ring is appropriately hydrogenated to obtain a resin (1-1). Other examples of the 77 (I) include (丨-2) thermosetting resin. The related resin (1-2) 'from thermosetting properties and a cured film From the viewpoint of the nature and the like, light weight = an epoxy compound having at least two epoxy groups in the molecule. Alternatively, the average molecular weight thereof is preferably 3G glare Q (manufacturer, 35Q to 〇〇). Specific examples of the resin (1-2) such as η I ^ include a double-part s type epoxy resin, a hydrogen oxy-resin, a bisphenol-type epoxy resin, a biphenyl type epoxy resin, and tetradecyloxypropyltoluene formazan. Ethylene resin, (hydrogenated) bisphenol A type epoxy tree 320584 17 200918585 . Grease, bisphenol F type epoxy resin, oxygen resin, phenolic type bismuth bisphenol, % oxygen resin, phenolic novolac type cyclic amine Base epoxy resin, rubber, grease, clamp type ring gas resin, containing _ type epoxy resin, _ modified F% _ lipid, dicyclopentane Benzene can be used. It can be used at least in the form of a surface treatment and/or with: (long: burning = coupling agent or the like). Surface machine fill = wettability, dispersibility and surface gloss or the like. Examples of the improvement of the non-forming/knife (II) include the average particle diameter of the colorant, particularly the white pigment, preferably, for example, 0.01 to 2 0 (Specially, the white::::) micron. When the average particle diameter of the white pigment is 1 and the concealing property may deteriorate and the average particle diameter of the reflective 2 film is too large, the white pigment of the coated field is reduced. The physical property of the film. , , , ::: may increase the salt and alkali, examples include oxidation, oxidation, hydrogenation, sulfuric acid, zinc sulfide and oxidation. You can use 1 type. From the viewpoint of coloring strength and non-toxicity, preferred = strong due to oxidation or the like and having a reduced heat-resistant weathering surface treatment in the absence of surface treatment. Other examples in which the above-mentioned inorganic metal oxide is used to apply the component (9) to the titanium oxide include a thermally conductive material. The thermally conductive material 320584 18 200918585 preferably has a thermal conductivity of 1·〇 or greater (coefficient. When the thermal conductivity is over: :1; 0 to 5°_/m.K). Alternatively, the heat-light f+ material which may be made of g. preferably has a particle or powder form. The ten-average diameter is, for example, 0. 丨 until the average particle diameter is too small, and the fluidity can be 〇.5 to 5) microns. When the level is flat, a. is reduced and the high packing ratio is difficult to achieve. And the reduction of the second: = large 'surface unevenness may increase due to soil' specific examples of materials including Oxides such as oxidation! Lu (矾/二2; nitrides such as nitrogen brain, nitrided nitride::: such as carbonized carbide; metals such as copper, silver, and flux; and diamonds; At least one of them may be used. Specific examples of the component (1) other than the above include talc; barium sulfate, <<Taiwan' Shishi stone, such as oxidized stone powder, fine powder oxidized stone Xi, amorphous (four) stone, molten stone stone and crystal stone stone; from clay, acid-stained town, titanic acid i: carbon knocking calcium, calcium citrate, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate: Zinc hydroxide, mica, mica powder, bauxite, wrong soil, wrong stone, 'lumite talc, spinel, Fuminghong a powder made of sulphate and oxidized or similar, or a bead obtained by making them spherical; hollow beads coated by them; and glass fibers or the like. At least one type may be used. When it is desired to apply high light reflectivity to the cured film, the white pigment is preferably contained in the form of a component (Π). When the curable resin composition is particularly a resist ink for a white printed wiring board The content of the white pigment is from 5 to 80 (particularly, 19 320584 200918585 l〇 to 70)% by weight relative to the entire curable resin composition. Its *shi® helmet, sa Z$ can have a film of 40 μm The thickness of the cured film has a first error reflectance increased to _ or higher. Deuterated application of 11 ^ ^ ^ to the cured film. The fat composition preferably contains the thermally conductive material; =:: = tree resin The composition is particularly for the wearer's ink, which is used for the "hard" of the knife field, and the printed circuit board of the cow is preferably in the form of 5 to 8 = of the entire curable resin composition. Yu Xinshi, Am, (specially '10 to 70% by weight). =: The thermal conductivity of the resulting cured film can be increased to ι. Or, alternatively, when a high light reflectance is applied to the cured film at the same time, the curable resin composition preferably contains both the white pigment and the 'material as the component (1)). The white pigment and the thermally conductive material preferably have a content of (iv) from 10 to 70% by weight based on the entire hardenability (IV) composition. Particularly, the curable resin composition according to the present invention contains (III) an organic filler. The crack resistance of the cured film can be enhanced by the addition of the component (ΠΙ). These components (III) have an elastic modulus of 1 to 2 GGG [preferably, 丨 to (more than 100)] (MPa) and an average particle diameter of _ to 1 () (preferably, ^ '. When the modulus of elasticity is too small, the heat resistance of the flux deteriorates the physical properties. Conversely, when the modulus of elasticity is too large, the effect of the fracture resistance can be reduced. When the average particle size is too small, there is a component I ( The dispersibility of I) is reduced. Conversely, when the average particle is large, it tends to reduce the crack resistance, electrical insulation and solder heat resistance of the cured film. In the present invention, the organic filler and the inorganic filler are individually Average: 320584 20 200918585 HORIBA, Ltd. The diameter of the HORIBA, Ltd. is measured using a laser scattering particle size analyzer (product of La~91q). Examples of such components (Π) include rubber particles ± 丨卞. From the point of view of the rupture resistance of the cured film, the heat resistance of the solder, and the electrical insulating property, the rubber particles, the body examples include the diarrhea homopolymer ( In particular, linaloic rubber) particles and acrylic polymers (special , Wine / g of particles, especially by 'their core-shell particles are particularly preferred from the viewpoint of enhancing the adhesive strength and low stress effects seem, preferably those having a similar

The core portion of the rubber polymer is a core-shell type rubber particle having a shell portion made of a glass polymer having a glass transition temperature (Tg) higher than that of the rubber polymer. More preferably, from the viewpoint of further enhancing the compatibility and dispersibility with the resin (particularly, epoxy resin) composition, the polymer portion forming the shell portion contains functional groups such as a carboxyl group, a hydroxyl group and an epoxy group. base). Other examples of the component (I11) include resin particles made of crosslinked polymethyl methacrylate. and crosslinked polybutyl methacrylate or the like. The crosslinked polymethyl methacrylate is obtained by subjecting methyl methacrylate monomer to emulsion polymerization and suspension polymerization, for example, in the presence of a crosslinkable monomer as needed. This crosslinking does not cause a rapid elastic modulus change exhibited in the thermoplastic, and causes high heat and enhanced thermal properties. A filler other than the components (II) and (ΠΙ) may be further added to the curable resin composition according to the present invention, for example, an antifoaming agent, a releasing agent, a finishing agent, a flame retardant, a viscosity modifier, and an increase. Plasticizers, antimicrobials, antifungals, leveling agents, stabilizers, couplers and antioxidants or the like. Further, 21 320584 200918585 thinner may be added to the curable resin composition according to the present invention. Other examples of dilution include organic solvents. Examples of the organic solvent include ketones such as mercaptoethyl and cyclohexanone; aromatic hydrocarbons such as toluene, -bifluorene and tetradecylbenzene, glycol ethers such as cellosolve, Methyl acesulfame, butyl acesulfame, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl Ether, and triethylene glycol monoethyl ether; acetates such as ethyl acetate, acetoacetate, cyproterone acetate, butyl cyproterone acetate, carbitol acetate, butyl carbitol Acetate, propylene glycol monomethyl ether '' acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; and petroleum Solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain and solvent petroleum brain. At least one of these types can be used. A thiol derivative may be further added to the curable resin composition according to the present invention. By adding a thiol derivative, the hardening reaction can be promoted and the adhesion property of the coating film can also be improved. Further, the thiol derivative has a function of reducing (the modulus of elasticity of the low-hardening film, and therefore, is an effective auxiliary material to promote the fracture resistance of the cured film. Examples of such thiol derivatives include three-menu Methyl propyl tris-(3-hydrothiopropionate), pentaerythritol tetra-(3-murine il-propionic acid g), mono-pentaerythritol hexa-(3-azinothiopropionic acid) And tris-[C3-hydrothiopropylpropoxy)-ethyl]iso-cyanate. At least one of them can be used. A low elastic curable resin can be further added to the curable resin composition according to the present invention. The Tg of the hardened resin can be lowered by adding a low elastic curable resin, and as a result, the crack resistance of the cured film can be further obtained 22 320584 200918585 (the elastic modulus of the special H curable resin is preferably, for example, 1 to 2000 (Mj) 4i_) (MPa). Examples include polymers partially containing functional groups such as acid groups and pure groups of the county, and the specific package is added to the acrylic system by ^ = energy group. The unsaturated resin-containing monomer of the copolymer is obtained as a resin, an anthrone resin, and a rubber resin such as butadiene. The olefin is used in the hardening tree according to the present invention (4) for the weight (4) component (1), the component („) The amount is two to 40 parts by weight, and the amount of the component ΙΠ component (ΙΠ) relative to (10) parts by weight is from 1 to 100 (contact, 5 to 80) parts by weight. Ip (II) When the amount is too small, it may not be possible to apply a sufficiently large thickness to the hardened film:: properties (light reflectivity and heat radiation or the like). Conversely, when the amount is over 牯, the fluidity may be poor to cause coating properties and insulating properties. Deterioration. If the amount of ingredient (III) is too small, it may not be able to apply enough to the hard Conversely, when the amount of the component (ΠΙ) is too large, the fluidity may be poor to deteriorate the coating property. Alternatively, the content ratio of the component (II) to the (III) is [that is, The component (Π)/component (丨丨丨) is 丨 to “(preferred, 5 to 25). When the weight ratio is too low, sufficient functional properties (light reflectivity) may not be applied to the cured film. And heat radiation or the like. Conversely, when the content by weight ratio is too high, it may not be possible to apply sufficiently large crack resistance to the cured film. Examples of the curable resin composition according to the present invention include light to thermosetting resin a composition [i.e., a resin composition capable of causing at least two-stage hardening of light (particularly, ultraviolet light) hardening and thermosetting]. Such light-thermosetting resins 320584 23 200918585 Examples of the composition include (A) resin (Μ) And (1-2), component (II) and (ΙΠ) 'component (10), photoreactive monomer, (7) light hardener, and (^) heat hardener. Examples of component (IV) include reactive diluent Specific examples include acrylic acid 2-reduction B, C 2—Linyi g|, N_vinyl t ketone, propylene “Merlin, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol propylene Dilute ester, N, [dimethyl methacrylate m methacrylamide, N, N dimethylaminopropyl propyl amine, dimethylaminoethyl acrylate, acrylonitrile. Propyl vinegar, melamine acrylate, diethylene glycol bis-acrylic acid vinegar, tri-ethylene glycol di-acrylate, propylene glycol di-acrylate, di-propylene glycol di-acrylate, di-propylene glycol di-acrylate, Polypropylene glycol di-acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl methyl acrylate, cyclohexyl acrylate, glycerol di-epoxypropyl ether di-acrylate, triglyceride Ethyl ether tri-acrylate, isodecyl acrylate, cyclopentadiene mono- or di-acrylate, hexanol, dimethicone, pentaerythritol, di-tris-propyl mercapto, di-pentaerythritol, Polyhydric alcohols such as tris-hydroxyethyl isomeric cyanurate or polyacrylates of oxidized acetamidine or propylene oxide adducts, respectively Yue acrylate above-mentioned acrylates, and a polybasic acid -, _ two, three - or three or more membered evening polyesters; and (meth) acrylic group via ester burning. At least one of these types can be used. Specific examples of the component (V) include acetophenones such as ethyl benzene, g, 2 - dimethoxy-2-phenyl acetophenone, 2, 2-diethoxy-2-phenyl acetophenone , p-Dimethylaminopropenylbenzene, 1-hydroxycyclohexyl phenyl ketone, 2 曱 一 24 24 320 320584 200918585 (methylthio). phenyl]-2-morphin-4-yl-endo Amino-1-(4-morpholin-4-ylphenyl)-butanone, 2-benzoinyl-2-diethylbenzene; diphenyl ketones, such as diphenyl _ and N, N-dimethylamino bis-dimethylaminodiphenyl ketone, 4, 4,-bis, methyl diphenyl fluorene, 4, 4,- ketone (Michler, s ketone) and 4-^ ^ ^Aminodiphenyl ketone, rice / i. sulphuric acid vinegar; benzoin ethers, such as benzophenone j 4 'methyl diphenyl ya shout, benzoin ethyl ether, benzoin bismuth benzoin, benzoin thiol酉similar, such as acetophenone dimethyl (10) and iso-isobutyl bond; , _ (thioxanthones), such as n-s- syl- fluorenyl ketone; ° plug?, Tian Gan ^ _ ton _ (thi〇xanth 〇ne), 2, 4-indanyl xanthone, 2, 4-diethylindole 4s, n.. 丞 鸣 and 2, 4-diisopropyl thiophene, anthraquinones ) , 哗^ .. Please be like 2-mercaptopurine, 2-ethylperoxide peroxides, such as peroxide and cumene peroxide; sulfur compounds such as 2, 4, 5-triaryl "Dimerization, riboflavin tetra-butyric acid _, 2-hydrogenthio benzoate, 2-hydrosulfanyl benzoate 2 氲 thiobenzobenzene 11 sypene oxidized double (2, 4, 6-trimercaptobenzoic acid)phenylphosphine, and tris-propylpropane propane tris(3-hydrothiopropionate), wherein at least one type of two component (V) can be used in combination with at least one photosensitizer For use, the photosensitizer is such as a tertiary amine such as N,N-dimethylaminoethyl benzoate, N,N-methylaminoisoamyl benzoate, 4-diguanamine benzoic acid pentane Ester, triethylamine and triethanolamine. Examples of the component (VI) include imidazole derivatives such as saponin, 2-methyl sulphate, 2-ethylimidazole, 2-ethyl-4-mercaptoimidazole, 2 _Phenyl taste. Sit, = phenyl-4, 5-di-hydroxymethylimidazole, 4-phenylimidazole, 丨-cyanoethyl_2- 320584 25 200918585 Phenyl taste. Sit and 1-(2 -Cyanoethyl)-2-ethyl~4_methyl miso; guanamines, such as guanamine Ethylamine and benzoguanamine; amine compounds such as dicyandiamide, benzoguanidine diamine, 4_(diguanylamino)_N,N-dimethylbenzamide, 4_decyloxy-N 'N-dimercaptomethylamine, 4_mercapto_N,N_-mercaptobenzylamine and melamine; and tris-methylmethylpropane tris(3-hydrothiopropionate). At least one of these types can be used. In the mixed composition of the resin composition (A) according to the present invention, the amount of each component is preferably the following with respect to 100 parts by weight of the resin ((2) and the amount of (1_2) = amount: component (1)) The quantity is for the special person, earning a round) The amount of the ingredient (III) is G1〇〇 (special amount, the amount is special, 5 times weight: = content is heavy = 2 to 20) weight (four) Compare it to 1 to 30 (particularly, 5 to 25). ^ Other materials of the sclerosing auditory composition according to the present invention include tamping

Cl4 ^ is a knife (Π), (ΠΙ), and (¥1). The composition of the fat composition (8) is divided into two components: (1) two == ° ° parts by weight of the tree (four): the amount of (III) is 丨 'other '40 to 100 〇) parts by weight; The amount is 0.5 to _part =: to 8° by weight; and the contents of the components (5) and (III) are 60 parts by weight. Alternatively, the component (II) is further reduced by 1 to 1 (particularly, 5 to 25). Further, the curable resin composition according to the present invention is surrounded by light 320584 26 200918585, a solid tree residue. The light Chenshu toucher includes (6) a resin (1-1) and components (11) to (V). The resin composition (6) may further comprise the component (VI). In the mixed composition of the tree composition (6) according to the present invention, the amount of each component is preferably the amount of the resin (H) relative to the basis of HK) by weight: in the case of 7 knives (1), it is difficult to 12 (10) (Special, cents pay) parts by weight; ingredients (jll) are 1 to _ special, 5 to 8 ()) parts by weight; ingredients are 1 to 50 (particularly, 5 to 4 inches) Parts by weight; and the amount of the component (7) is from 40 to 4,000 parts by weight, from 3 to 30 parts by weight. Alternatively, the content of the component (π) to (1(1) is preferably from 1 to 30 (particularly, from 5 to 25). The resin composition (A) according to the present invention may be, for example, first light-emitting (wavelength) .300 to 450 nm (nm), exposure: 2 () () JL1 remuneration / cm / cm (cm / cm2)) primary hardening, and then secondary hardening by heating (from 100 to 17 (TC The resin composition (8) according to the present invention can be subjected to C hardening (for example, from 100 to 170 for 20 to 120 minutes) by heating, for example, the resin composition (6) according to the present invention can be, for example, via, for example, , hardened by light (wavelength .300 to 450 nm, exposure: 2 〇〇 to 1 〇〇〇 millijoules per square centimeter (mj/cm 2 )). The heat is mentioned by the use of at least Two types of hardeners each having different reaction initiation conditions (wavelength and temperature or the like) are carried out in multiple stages. For example, the heat curing can be performed in primary hardening (from 1 to 12 Torr. (3 for 1 to 60 minutes) ) and secondary hardening (in 130 to 17 (TC for 20 to 120 minutes) in two stages. 27 320584 2009185 The curable resin composition according to the present invention can also be applied to any of the resist film forming methods of the printed wiring board. In particular, the use of a smooth printed wiring board as a printed wiring board can enhance the coating of the circuit and The reliability and the shielding property (copper circuit shielding property) can be effectively further improved. [Examples] <Preparation of Photocurable Resin> Preparation Example 1 was equipped with a scrambler, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas. Into a separable flask of the introduction tube, 250 parts by weight of dipropylene glycol monomethyl ether and 10 parts by weight of tert-butyl peroxy-2-ethylhexanoate were charged, and they were heated to 95 °C. Then, a mixture of 170 parts by weight of mercaptoacrylic acid, 130 parts by weight of decyl decyl acrylate, 250 parts by weight of dipropylene glycol monodecyl ether and 10 parts by weight of azobis(decyl valeronitrile) was subjected to 4 hours. During the dropwise addition -' was added to the bottle. Further, they were aged for 5 hours to obtain a methacrylic acid-methacrylic acid methacrylate copolymer solution having a carboxyl group. Then, in the resin solution, 7% was passed. Oxygen-93% nitrogen While mixing the gas, 200 parts by weight of (3,4-epoxycyclohexyl)decyl methacrylate, 2 parts by weight of triphenylphosphine, and 1 part by weight of hydroquinone-mercaptoether are added, and l 〇〇 ° C for their addition reaction for 19 hours to obtain a polybasic acid buffer solution containing an unsaturated group. When measuring the physical properties of the resin of the multi-acid acid resin containing the base and the base, the solid content thereof It is 51%, its acid value is 105 mg KOH/g; the double bond equivalent is 490 g/mole; and its weight average molecular weight Mw (based on polystyrene) is 13,000. 28 320584 200918585 . Preparation 2 In the detachable bottle with reflux condenser, thermometer and glass tube for nitrogen replacement, 140 parts by weight of methacrylic acid methacrylate and 6 〇 replacement parts of thiol propylene Acidic, 200 parts by weight of carbitol 月 酉曰 · · · 重 重 重 月 月 月 和 和 和 和 和 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 They were heated in a nitrogen stream, and 50% was obtained by polymerizing for 5 hours, and the material/liquid mixture was added to the above 5 % copolymer solution, and hydrazine was added in an amount of 0.5 parts by weight. And propylene, and 0.4 parts by weight of dimethylbenzylamine, and their addition reaction at 100 C for 24 hours. Then, 9 parts by weight of tetrahydro-glycolic acid and 158 parts by weight of carbitol acetate vinegar were added thereto, and reacted at 100 C for 3 hours to obtain an unsaturated group-containing polycarboxylic acid resin solution having 5 (solid content of U, double bond equivalent of 35 g/mole; acid value of w mg leg/g and weight average molecular weight of 26 coffee (based on polystyrene). - Preparation Example 3 for assembly In a four-necked flask with a stirrer and a reflux condenser, the weight of the A-type transitional epoxy tree wins 68q, (4) coffee (10) (four)

Chemicals, Inc., products, preparation J mouth mouth ¥乳当量=215). 196 parts of propylene glycol-methyl ether acetate vinegar was added thereto and dissolved under heating.着 、 、 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 At (10). c This was added to the mouth and 72 parts by weight (1 equivalent) of acrylic acid was gradually added dropwise thereto. Let them react about 32 small (iv) to obtain a reaction product having an acid value of U mg leg/g. This reaction product (light base: hydrazine equivalent) was cooled to hydrazine, 320584 29 200918585 and 76 parts by weight (0.5 equivalent) of tetrahydrophthalic anhydride was added thereto. Let them react for about 8 hours' and take it out after cooling. Thus, a carboxyl group-containing resin solution was obtained which had a solid acid value of 65% of a nonvolatile matter and 773⁄4 g of K〇jj/g. &lt;Preparation of Curable Resin Composition> Examples 1 to 11 and Comparative Examples 1 to 9 According to the wave composition shown in Tables 1 and 3, the mixed components were prepared by kneading the three-roll mill materials by themselves. Light--sex tree surplus (Examples 1 to 3, 5, 7 to 11 and Comparative Examples 1 to 9) 'Thermosetting resin composition (real

The elastic modulus of the organic filler showed that the sample was molded by molding at 150 to 2 GGC for 10 minutes using a vacuum press and measured using a tensile tester.

The average particle size of each of the organic fillers and inorganic fillers in Tables 1 and 3 is a laser-scattered particle size distribution analyzer (u_9iq, 臓ΐβΑ, which is used to determine the sample and dispersion of organic fillers or inorganic fillers. The medium «human sample tube, and dispersed in the ultrasonic bath for 10 minutes. Rand, tears and girls......... In the average particle size of the test machine filler, the use of organic double A liquid conversion epoxy resin and humectant (weight ratio: Π is. ML·

The average particle size. In the test filler, bisphenol 320584 30 200918585 The curable resin composition (Examples 1 to 5, 7 to 11 and Comparative Examples 1 to 9) was applied to the printed circuit via stencil printing (1 〇〇 mesh polyester). On the entire surface of the substrate (thickness: 1 mm (mm), copper circuit thickness: 6 μm, l/s = 10 0 μm/10 0 μm). These curable resin compositions were placed in a hot air circulation type drying oven, and preliminary dried (80 ° C, 20 minutes) to obtain a dried coating film (film thickness: 20 μm). Then, the above coating film was irradiated with an ultraviolet ray irradiation apparatus (ORC Manufacturing Ltd, model HMW-680C) at 500 mJ/cm 2 through a negative film for flux resist to perform primary photohardening. The film was developed in a 1 wt% sodium carbonate solution to form an exposure hardened (preliminary photohardening) resist film pattern on the substrate. Then, the substrate was initially thermally hardened (10 Torr, 30 minutes), and then completely cured (15 (TC '60 minutes). Thus 'made a printed wiring board coated with a solder resist film (Manufacturing Example 1 to 5, 7 to 11 and Comparative Examples 1 to 9). Production Example 6 A curable resin composition (Example 6) was applied to the same printed wiring as described above by stencil printing (丨2〇网网) On the entire surface of the substrate, the curable resin composition was preliminarily dried (8 (rc, 2 min) to obtain a dried film (film thickness: 2 μm). The dried coating film was completely hardened (15〇c ' Printed wiring board coated with a solder resist film (manufacturing example 6) for 60 minutes) (Evaluation test of curable resin composition) ^ Curable resin composition (Examples to 丨丨 and Comparative Example) 9) Various evaluations are performed by the following methods: Tables 2 and 4 show the results of the evaluations of the evaluations of 320584 200918585. (Contact Dryness) / Coating of the curable resin composition on the surface of the printed wiring substrate Then, the printed circuit substrate is placed in the heat In a gas-circulating drying oven, it was dried (80 ° C '20 minutes). Then, the surface on which the composition of the curable tree scorpion was coated was strongly pushed by a finger to detect adhesion and the coating was measured. State: 〇 (good): Adhesion and fingerprint retention were not observed at all. “△” (average): Adhesion on the surface and fingerprint retention were observed slightly. X (poor). Significantly observed adhesion on the surface and The fingerprint is left in. (developing property) The developing solution of the 1% by weight sodium carbonate solution is applied to the printing process of the above-mentioned printed circuit board process coated with the solder resist film under the spray pressure of 2. 〇xl 〇 5pa The mouth cloth was placed for 60 seconds, and the state in which the unexposed portion was removed was visually determined. "〇 (good): The ink was completely removed in the development to promote the image. X (poor): there was a presence in the image. Unexposed portion (Photosensitivity) A ST 21 stage exposure meter (manufactured by Stawerf Corporation) was attached to a dry coating film, and the film was irradiated with ultraviolet rays having an overall light of 5 μm/cm 2 and Exposure. Then, at 1% carbonic acid The film was developed in a solution at a spray pressure of 2·Οχι〇5pa for 6 seconds, and the order of the uncoated film was ensured. <Evaluation test of the solder resist film (hardened film)> 320584 200918585 1 Various evaluation tests of the solder resist films (Manufacturing Examples 1 to 11 and Manufacturing Comparative Examples 1 to 9) of the printed wiring board were carried out by the following methods. Tables 2 and 4 show the evaluation test results (pencil hardness) pencil The hardness was evaluated in accordance with JIS K5600. (Adhesive property) According to JIS K5600, a test piece having a width of 1 mm was grid-formed to produce 100 cells, and a peel test was performed using a Scotch tape. The peeling of the lattice was observed and the following evaluation criteria were used. “〇” (good): The cross-cut part is not peeled off. "△" (average): The cross-cut portion was slightly peeled off into the peeled Scotch tape. "X" (poor): 40% or more of the cross-cut portion is peeled off into the stripped Scotch tape. (Solvent resistance) The test piece was immersed in room temperature isopropanol for 30 minutes, and abnormality in appearance was observed. Then, a peel test was performed using Scotch tape (R). Use the following evaluation criteria. “〇” (good): The appearance of the film was not abnormal, and there was no swelling and no peeling. "X" (poor): Expansion and peeling of the film were observed. (Acid resistance) The test piece was immersed in a room temperature 10% aqueous hydrogen chloride solution for 30 minutes. The abnormality in appearance was observed and then, a peel test was performed using Scotch tape. 33 320584 200918585 , using the following evaluation criteria. “〇” (good): The appearance of the film was not abnormal, and there was no swelling and no peeling. "X" (poor): Expansion and peeling of the film were observed. (Solder Heat Resistance) A fluxing agent W-2704 (manufactured by MEC Co., Ltd.) for a flattener was coated on a test piece and immersed in a solder bath of 288 ° C for 1 second. Repeat the same procedure three times. The test piece was cooled to room temperature, and a peel test was performed using Scotch tape (R) to use the following evaluation criteria. (Good): The appearance of the coating film is not abnormal, and there is no swelling and μ peeling. For the method. (Poor): Expansion and peeling of the coating film were observed. On behalf of the ground, after the solder heat resistance test, according to the next 彳 $ rupture evaluation (good): no cracks were observed. (Average): A slight crack was observed. x (poor): There is a significant crack. Adhesive

Alternatively, the evaluation method is performed after the solder heat resistance test. According to JIS K5600, a test piece having a width of 1 mm was used as a grid of j 100 and a peel test was performed using a Scotch tape. Observe the dice and k out using the following evaluation criteria. Thai] away from 〇" (good): the cross-cut portion is not peeled off. c〇tch △" (average): The cross-cut portion is slightly peeled off to the tough open $34 32〇584 200918585 tape. "X,' (poor): 40% or more of the cross-cut portion is peeled off to the peeling

Inside the Scotch tape. (Zhongjin resistance) The test substrate was immersed in an acidic degreasing solution (Nihon MacDiarmid Co., Ltd., manufactured by Nihon MacDiarmid Co., Ltd.) in an acid degreasing solution (Nihon MacDiarmid Co., Ltd.) for 3 minutes, and then washed with water. Next, the test substrate was immersed in a room temperature of 14.4% by weight aqueous ammonium persulfate solution for 3 minutes, and washed with water. Further, the test substrate was immersed in a room temperature 10% by volume aqueous sulfuric acid solution for 1 minute, and washed with water. Next, the substrate was immersed in a 30 °C catalyst solution (10% by volume aqueous solution of metal plating activator 350 manufactured by Meltex Co., Ltd.) for 2 minutes, and washed with water. The substrate was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melplate Ni-865M, 20% by volume aqueous solution, pH 4. 6) at 85 ° C for 20 minutes to carry out nickel plating. The substrate was then immersed in a 1 vol% sulfuric acid aqueous solution at room temperature for 1 minute and washed with water. Then, the substrate was immersed in a gold plating solution at 95 ° C (manufactured by Meltex Co., Ltd., 15 volumes of UP and 3 vol% aqueous potassium cyanide solution, pH 6) for 10 minutes to carry out electroless gold plating, and washed with water. Immerse in 6 〇C water for 3 minutes, wash with water, and dry. The Sc〇tch tape was adhered to the ^electroless gold plating evaluation substrate and the tape was peeled off. Observe its condition. (Good): No abnormality. Average): A slight peeling was observed. X (poor): A large peel was observed. (HAST resistance) 320584 35 200918585 A test substrate is allowed to stand for 168 hours, and the applied voltage side β of dC 5V is applied between the comb electrodes of line/space=1 〇0 μm/1 〇〇 micro-seeking. A flux resist was applied to the 130 ° C and 85% unsaturated pressurized container. Observe the anomalous appearance of the sacrifice and measure the insulation resistance before and after the test. For the insulation resistance, "R8340A" (digits made by ADVANTEST from rsj resistance / minute ammeter) was used and a DC voltage of 10 V was applied for 1 minute in accordance with the insulation resistance test standard of JPCA-HDO1. The insulation resistance is then measured in the applied state. “〇” (good): The appearance of the film is not abnormal. * "△" (average): The electrode did not swell and did not peel off, but the electrode was observed to fade. X (poor): The film is swelled and/or peeled off. (Color difference change) Using a spectral colorimeter CM-2600d [manufactured by Konica Minolta Sensing Corporat on], the L*a*b* colorimetric measurement after hardening and three times of reflux 〇6{1〇¥) (spike temperature: 260) The color difference (ΔΕ%!) was measured by 1^8*1)* colorimetric measurement after ° (:, 5 seconds). (Spectral reflectance) The reflectances of 450, 550 and 600 nm were measured by a spectral colorimeter CM-2600d via a hardened L*a*b* colorimetric measurement. (Thermal Conductivity λ) The thermal diffusivity (〇:) was measured by the laser Frasch method according to the standard of JIS R1611, and the thermal conductivity was calculated from the specific heat (Cp) and the density (p). 36 320584 200918585 λ = a χ Cp χ p (heat shock resistance) Repeat the test at -40 ° C for 30 minutes and at 125 ° C for 30 minutes, and after 100 repetitions, observe the test piece with a microscope. . Use the evaluation criteria below. “〇” (good): No cracks were observed on the film. "△" (average): A slight crack was observed on the coating film. “χ ” (poor): Cracks were observed on the film. 37 320584 200918585 Table 1 f.

Mixed composition (parts by weight) Example 1 2 3 4 5 6 7 8 9 10 11 Photocurable resin Preparation Example 1 200 — — 200 — — 200 200 200 200 200 Preparation Example 2 One 200 Preparation Example 3 — — 154 — 200 — — — — — — Thermosetting resin bisphenol A epoxy resin 15 10 — — 10 80 15 15 15 15 15 3, 3', 5, 5'-tetradecylbiphenyl type epoxy resin 15 10 20 — 20 — 15 15 15 15 15 Phenol phenolic epoxy resin — 10 10 — — 20 — — — — — No filler titanium oxide (surface treated particles, average particle size: 0.3 μm) 500 — — 60 — — 1269.2 101.5 203.1 500 500 Alumina (average particle size: 3 μm, thermal conductivity: 30. 2 W/m · K) — 600 — — 500 600 — — — — — Barium sulfate (surface treated particles, average Particle size: 0.3 μm) 20 10 300 20 20 50 50.8 4.1 8.1 20 20 Acrylic rubber for organic filler (modulus of elasticity: 15 MPa, average particle diameter: 0.5 μm) 25 — — — — 105.6 2.6 105.6 — — Acrylic rubber (modulus of elasticity: 20 M Pa, average particle size: 0.1 μm) — 15 — — — 30 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Polybutyl methacrylate (elastic modulus: 400 MPa, average particle diameter: 5 μm) 20 Acrylic rubber (elastic modulus: 5 MPa, average particle diameter: 1.0 μm) 25 38 320584 200918585 f Organic filler (elastic modulus) : 1000 MPa, average particle diameter: 6.0 μm) 25 Acrylic rubber (elastic modulus: 0.5 MPa, average particle diameter: 1.0 μm) Organic filler (elastic modulus: 3000 MPa, average particle diameter: 8.0 μm) Cross-linked poly(decyl methacrylate) (elastic modulus: 2300 MPa, average particle size: 25 microns) Thinner Dipentaerythritol hexa-acrylate (DPHA) 20 20 — — 20 — 20 20 20 20 20 Di-trihydroxyl Acetylene-tetra-acrylic acid S 5 5 20 25 — — 5 5 5 5 5 carbitol acetate 30 30 20 10 20 10 80 20 30 40 40 hardener oxidation double (2, 4, 6 -tridecylbenzhydryl)phenylphosphine 12 12 — 4 — - 12 12 12 12 12 2-mercapto-H4-(methylthio)phenyl]-2-methylline-4_yl-propene Rl-ketone — 12 — 12 — — — — — — 2, 4~ Diethyl 0 ketolone 1 1 1 1 1 - 1 1 1 1 1 Trimethylolpropane tris(3-hydrothiopropionate ) — — — 2 — 1 — — — — — Melamine 2 2 2 2 2 - 2 2 2 2 2 Dicyanodiamine 1-0.1 — — 5 — — — — — 2-Phenyl-4, 5-dihydroxy Methylimidazole - - - - - 4 - - one - other polydimethyl oxime 1 1 1 1 1 1 1 1 1 1 1 39 320584 200918585 &gt; Table 2 Example 1 2 3 4 5 6 7 8 9 10 11 Dry-drying 〇〇〇〇〇 - 〇〇〇〇〇 Imaging 〇〇〇〇〇 - 〇〇〇〇〇 Photosensitivity 10 8 9 11 8 — 8 11 9 9 9 Manufacturing Example 1 2 3 4 5 6 7 8 9 10 11 Pencil hardness 8H 8H 8H 6H 8H 8H 8H 7H 6H 8H 8H Adhesive properties 〇〇〇〇Δ 〇Δ 〇〇〇〇Solvent resistance 〇〇〇〇〇〇〇〇〇〇Δ Acidic 〇〇〇 〇〇〇〇〇 〇〇〇surface state 〇〇〇〇△ 〇Δ 〇〇〇〇flux heat resistance peel test 〇〇〇〇〇〇〇Δ 〇〇〇detection crack resistance 〇〇〇〇Δ 〇Δ 〇〇〇〇 黏 adhesion property 〇〇〇〇Δ 〇Δ capsule gold plating resistance 〇〇〇〇〇〇〇〇〇〇〇 estimated appearance 〇〇〇〇〇〇〇〇〇〇〇 starting value 1.3 1.5 1.2 1.7 1, 1 1,7 L2 1.8 1.2 1.5 1.4 (χ1013Ω) After 168 hours (^103⁄4) 58.0 30.7 22.3 3.2 1.49 35.4 32 52 47.2 31.6 29 Thermal shock 〇〇〇〇Δ 〇〇〇〇〇〇 Color difference change (△E% b) 5 4.8 10 4.6 12 13 4.5 5.6 5.6 7.1 6.8 Spectral reflectance (%) 450 nm 85 2 71 91 80 82 86 86 550 nm 81 — 2 68 — — 88 77 80 82 83 600 nm 79 — 2 65 — — 85 73 77 79 79 Thermal conductivity (W/m · K) 0.5 1.2 0.5 0.5 1.0 2.0 — — — — — 40 320584 200918585

3 Table I Mixed composition (parts by weight) Comparative Example 3 5 Photosetting resin Preparation Example 1 Preparation Example 2 Preparation Example 3 200 200 200 200 200 200 200 200 200 Thermosetting resin bisphenol A type epoxy resin 3, 3,, 5,5'-tetramethylbiphenyl type epoxy resin phenolic novolac type epoxy resin 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Inorganic filler titanium oxide (surface treated particles, Average particle size: 0.3 μm) Alumina (average particle diameter: 3 μm, thermal conductivity: 30.2 W/m * K) Barium sulfate (surface-treated particles, average particle diameter: 〇. 3 μm) Acrylic rubber (elasticity Modulus: 15 MPa, average particle diameter: 0.5 μm) Acrylic rubber (elastic modulus: 20 MPa, average particle diameter: 0.1 μm) Anthrone rubber (elastic modulus: 200 MPa, average particle diameter: ·1.0 μm) 500 200 1650.0 66,0 105.6 25.4 1.0 1269.2 50.8 114.: 500 500 50.8 2.0 145.: 105. 4.6 2.6 20 20 Organic filler cross-linked poly(butyl acrylate) (elastic modulus: 400 MPa, average particle size: 5 μm) Acrylic acid Rubber (elastic modulus: 5MPa, average particle size: 1 .0 micron) Organic filler (elastic modulus: 1000 MPa, average particle diameter: 6.0 μm) Acrylic rubber (elastic modulus: D. 5 MPa, average particle diameter: 1.0 μm) 25 Organic filler (modulus of elasticity: 3000 MPa) , average particle diameter: 8.0 μm) 25 cross-linked polymethyl methacrylate (elastic modulus: 2300 MPa, average particle diameter: 25 μm) 41 320584 20 200918585 Dilution #J dipentaerythritol hexa-acrylate (DPHA) — — 20 20 20 20 20 20 20 Di-trihydroxydecylpropane tetra-acrylate 25 25 5 5 5 5 5 5 5 carbitol acetate 20 20 80 10 100 30 20 40 40 Hardener oxidation double (2, 4, 6 -trimethylphenyl hydrazino)phenylphosphine 12 — 12 12 12 12 12 12 12 2~methyl-1-[4-(methylthio)phenyl]-2-morpholin-4-yl-propane -1- Ketone - 12 — — — — — — A 2, 4-diethyl thioxanthone 1 1 1 1 1 1 1 1 1 Trimethylolpropane tris(3-arylthiopropionate) — Melamine 2 2 2 2 2 2 2 2 2 dicyandiamide 0.5 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 1 1 1 1 1 1 42 320584 200918585 * Table 4 Comparative Example 1 2 3 4 5 6 7 8 9 Contact Dryness 〇〇〇〇〇〇〇 〇 〇 Imaging 〇〇〇〇〇〇〇〇〇 Photosensitivity 9 10 6 11 7 10 11 9 9 Manufacturing Comparative Example 1 2 3 4 5 6 7 8 9 Pencil hardness 8H 8H 8H 6H 7H 5H 7H 7H 8H Adhesive property XXX 〇〇〇〇〇△ Solvent resistance 〇〇〇〇〇〇〇〇X Acid resistance 〇〇〇〇〇〇〇〇〇 surface state 〇 XX 〇 X 〇〇 Δ Δ flux heat resistance stripping test 〇 XX Δ △ 〇〇 Δ Δ rupture resistance XXX Δ 〇〇 Δ 〇 X results of adhesion Properties XXX Δ 〇〇〇〇X Gold plating resistance Δ XX 〇Δ 〇〇〇Δ Evaluation appearance △ XX 〇Δ 〇〇Δ Δ Starting value (χ1013Ω) 1.1 1.1 1.3 1.7 1.6 1.4 1.6 1.3 1.7 168 hours later (χΙΟ 'Ώ) 1.00 1.50 9.4 43 11 32.5 35.4 24.2 A thermal shock resistance Δ XX Δ Δ 〇 Δ 〇 Δ chromatic aberration change (△E*ab) — — 4.6 5.8 5.3 5.9 5.1 7.5 7.4 Spectral reflectance (3⁄4) 450 nm 86 — 92 58 88 61 81 85 85 550 nm 82 — 90 55 85 58 79 82 83 600 nm 79 — 87 51 82 55 76 78 78 Thermal conductivity (W/m · K) 0.5 0.4 — — — — Items one (1) to (3) represent the following in Tables 1 and 3. (1) : Epoxy equivalent: 173 g / equivalent (g / eq) (2) : Epoxy equivalent: 188 g / equivalent (3): Epoxy equivalent: 178 g / equivalent as apparent from Tables 1 to 4 Alkali-developing flux according to the present invention 43 320584 200918585 Resist ink (using, for example, a ring grease) has excellent error-free soldering. Unsaturated polybasic (tetra) trees are similar, and Huai &amp; resistance, resistance (preventing peeling) And to prevent fading) or = two when the flux resist ink is placed in high temperature, the material can be highly L 4 j. Functional inorganic filling can achieve high reflectivity and high thermal conductivity. The m is a curable resin composition that can correspond to a high performance rate of an electronic device. The 4 inch other person's inventor has tested the ink to have a solder resisting resistance and a small color-blocking property of the resisting agent, and has enhanced long-term high temperature fading resistance and (10) spear reflectance. This ink is very useful as a white solder resist for LED substrates or the like. [Simple description of the diagram] •fe 〇 [Description of main component symbols] M»,

320584 44

Claims (1)

200918585 • VII. Patent application scope: 1. A curable resin composition comprising: (I) parts by weight of hardening resin; (Π) 10 to 1200 parts by weight of inorganic filler; and I (III) The organic filler has an elastic modulus of 1 to 2000 (MPa) and an average particle diameter of 〇·〇1 to J〇micron, wherein the weight ratio of the component (π) to (ΠΙ) is 丨 to 41 / 2. The curable resin composition according to claim 1, wherein the component (π) is a white pigment and/or a material having a thermal conductivity of h 0 to 5 〇〇 (w/m • illusion. 3 The hardenable resin composition of the first aspect of the invention, wherein the component (III) contains a rubber particle. The hardenable resin composition of the first aspect of the invention, wherein the curable resin composition It is (A) a photo-thermosetting resin composition containing the following resins (1-1), (1-2) and components (II) to (VI); (B) a thermosetting resin composition containing the following resins (1) -2) and component (II), (in) and (VI), or (c) photocurable resin composition 'which contains the following tree (I _ 1) and components (II) to (V); (1-1) photocurable resin; (Ϊ-2) thermosetting resin; (Π) inorganic filler; (III) organic filler; CIV) light Reactive monomer; (V) light hardener; and 45 320584 200918585 (νι) thermal hardener. 5. The curable resin composition of claim 4, wherein the resin (1-1) is an acid group-containing acrylic resin obtained by polymerizing an ethylenically unsaturated acid as a basic monomer, and a reaction product of an alicyclic epoxy group and/or an oxetanyl group-unsaturated compound which does not have an aromatic ring in the molecule; and/or is via an alicyclic group-containing epoxy group and/or a reaction product of an alicyclic epoxy group-containing epoxy group and/or an oxetanyl group-containing resin and an acid group-containing unsaturated compound obtained by polymerizing an unsaturated compound of an oxetane group as a basic monomer, the reaction The product does not have an aromatic ring in the molecule. A method of producing a printed wiring board coated with a resist film, wherein the resist film is formed from the curable resin composition according to any one of claims 1 to 5. 7. A printed wiring board coated with a resist film is manufactured by the method of the patent application No. -6. 46 320584 200918585 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: There is no chemical formula in this case. 320584