JP2009252896A - Curable resin composition for printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for the printed wiring board capable of forming a curing film that sufficiently meets performance required as a permanent mask resist, and keeping a sufficiently high filtering speed even if filter paper with small pores is used. <P>SOLUTION: The curable resin composition for a printed wiring board comprises a curable resin (A), barium sulfate fine particles (B) whose surfaces are coated with aluminum compounds and organic silicon compounds, and a curing agent (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable resin composition for printed wiring boards, and more particularly, to a curable resin composition for printed wiring boards used as a permanent mask resist in a field requiring a highly thinned wiring pattern such as a solder resist for semiconductor packages. Related to things.

  In the printed wiring board field, conventionally, a permanent mask resist is formed on a printed wiring board. The permanent mask resist has a role of preventing solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in a joining process such as soldering when the mounting component is joined to the printed wiring board. Further, the permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used.

Conventionally, a permanent mask resist in the production of a printed wiring board is produced by a method such as screen printing of a thermosetting or ultraviolet curable resin composition (curable resin composition for printed wiring board).
For example, in a flexible wiring board using mounting methods such as FC, TAB, and COF, a thermosetting resin paste is screen printed except for a rigid wiring board, an IC chip, an electronic component, or an LCD panel and a connection wiring pattern portion, A permanent mask resist is formed by thermosetting (see, for example, Patent Document 1).
Further, in the case of a semiconductor package substrate such as a mother board, BGA (ball grid array), or CSP (chip size package) mounted on a personal computer, it is necessary to remove the permanent mask resist at that portion in order to join the mounting parts. Such a photosensitive resist that can be easily removed is used as a permanent mask resist (see, for example, Patent Document 2).
JP 2003-198105 A Japanese Patent Laid-Open No. 11-240930

  By the way, in recent years, with the high integration of electronic devices, the pitch of wiring patterns in printed wiring boards has been reduced.

  On the other hand, from the viewpoint of printability or surface hardness, inorganic fine particles or the like are generally added to the curable resin composition for a printed wiring board. However, in a wiring pattern with a narrow pitch, the inorganic fine particles are between the wiring patterns. When the width is larger than the width or when foreign matter or the like is mixed, the insulation reliability may be impaired.

  In order to solve such a problem, before producing a permanent mask resist, it is common to filter large-sized inorganic fine particles or foreign matters existing in the curable resin composition for printed wiring boards with a filter paper. is there. However, when a conventional curable resin composition for printed wiring boards is filtered using a filter paper having a small pore diameter in order to adapt to a wiring pattern with a narrow pitch, there is a problem that the filtration speed is remarkably reduced. .

  Accordingly, the present invention provides a printed wiring board that can maintain a sufficiently high filtration rate even when filter paper having a small pore diameter is used, and can produce a cured film that sufficiently satisfies the performance required as a permanent mask resist. An object of the present invention is to provide a curable resin composition.

  The present invention provides a curable resin composition for a printed wiring board comprising a curable resin (A), barium sulfate fine particles (B) surface-coated with an aluminum compound and an organosilicon compound, and a curing agent (C). provide.

  According to such a curable resin composition, a cured film that can maintain a sufficiently high filtration rate even when a filter paper having a small pore diameter is used, and sufficiently satisfies the performance required as a permanent mask resist. Can be produced.

The reason why such an effect is obtained by the curable resin composition of the present invention is not necessarily clear, but the present inventors consider as follows.
That is, in the conventional curable resin composition for printed wiring boards, the inorganic fine particles in the composition agglomerate, and the produced agglomerates clog the pores of the filter paper. To find out. On the other hand, the present inventors consider that the above-described effects can be obtained because the curable resin composition of the present invention can sufficiently suppress such aggregation.

  The curable resin (A) is preferably an acid-modified vinyl group-containing epoxy resin from the viewpoint that alkali development is possible and that the resolution and adhesion are excellent. Furthermore, the acid-modified vinyl group-containing epoxy resin includes a novolac type epoxy resin represented by the following general formula (I), a bisphenol cage type epoxy resin or a bisphenol F type epoxy resin represented by the following general formula (II), and the following general formula: A resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of salicylaldehyde type epoxy resins represented by (III) with a vinyl group-containing monocarboxylic acid (b), or this It is more preferable that it is resin obtained by making a polybasic acid anhydride (c) react with resin.

［式中、Ｘは水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）であり、Ｒは水素原子又はメチル基であり、ｎは１以上の整数である。］

[Wherein, X is a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or a methyl group, and n is 1 or more. Is an integer. ]

  It is preferable that the curable resin composition for printed wiring boards of the present invention further includes a compound (D) having at least one ethylenically unsaturated group in the molecule.

  It is preferable that the curable resin composition for printed wiring boards of this invention further contains a photoinitiator (E).

  The curable resin composition for a printed wiring board of the present invention preferably further contains an elastomer (F). Furthermore, the elastomer (F) is at least one elastomer selected from the group consisting of a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. Is more preferable.

The present invention further provides a curable resin composition for printed wiring boards, which gives a cured film having an elastic modulus of 1 to 100 MPa in dynamic viscoelasticity measurement in a temperature range of 200 to 220 ° C.
Here, the “cured film” refers to, for example, a curable resin composition for a printed wiring board applied to a printed wiring board so that the dry film thickness is 30 μm, and then the solvent is dried, and the UV exposure apparatus uses a 600 mJ / exposed with an energy of cm ^2, after 60 seconds development in 1% aqueous solution of sodium carbonate, was further exposed at an energy of 1 J / cm ² with an ultraviolet exposure device, a cured film formed by drying for 1 hour at 0.99 ° C. Show.
The dynamic viscoelasticity measurement of the cured film thus obtained is performed, for example, with the cured film having a length of 22.5 × width 3.0 × thickness 0.06 mm and a solid analyzer RSA II (manufactured by Rheometrics). Used, vibration frequency 1 Hz (6.28 rad / sec), measurement temperature 40 to 250 ° C. (temperature increase 5 ° C./min), strain 0.15%, mode is static force tracking dynamic force, initial static force 15 0.0 g.

  According to the present invention, a printed wiring that can maintain a sufficiently high filtration rate even when a filter paper having a small pore diameter is used and that can produce a cured film that sufficiently satisfies the performance required as a permanent mask resist. A curable resin composition for a plate can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

  The present invention relates to a curable resin (A), barium sulfate fine particles (B) surface-coated with an aluminum compound and an organosilicon compound (hereinafter simply referred to as “barium sulfate fine particles (B)”), and a curing agent (C And a curable resin composition for printed wiring boards (hereinafter simply referred to as “curable resin composition”). Hereinafter, each component will be described in detail.

<Curable resin (A)>
Examples of the curable resin (A) include an acid-modified vinyl group-containing epoxy resin, an epoxy resin having a butadiene structure or a silicon structure, a phenol resin, an acrylic resin, a thermosetting polyurethane, a photocurable polyurethane, a polybutadiene, and a water-added polybutadiene. Polyester, polycarbonate, polyether, polysulfone, polytetrafluororesin, polysilicone, melamine resin, polyamide, polyamideimide, polyimide and the like can be used. These can be used alone or in combination of two or more. Among these curable resins, an acid-modified vinyl group-containing epoxy resin is preferable because alkali development is possible and the resolution and adhesion are excellent.

  As the acid-modified vinyl group-containing epoxy resin, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid can be used. In particular, a novolak type epoxy resin represented by the following general formula (I), II) at least one epoxy resin (a) selected from the group consisting of a bisphenol Α type epoxy resin or a bisphenol F type epoxy resin represented by formula (II) and a salicylaldehyde type epoxy resin represented by the following general formula (III): It is preferable to use a resin (A ′) obtained by reacting a vinyl group-containing monocarboxylic acid (b).

［式中、Ｘは水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）であり、Ｒは水素原子又はメチル基であり、ｎは１以上の整数であり、好ましくは２〜１００の整数である。］

[Wherein, X is a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or a methyl group, and n is 1 or more. An integer of 2-100, preferably an integer of 2-100. ]

  The resin (A ′) is presumed to have a hydroxyl group formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b).

  As the novolac type epoxy resin represented by the general formula (I), there are a phenol novolac type epoxy resin and a cresol novolac type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol novolak resin, a cresol novolak resin and epichlorohydrin by a known method.

であるビスフェノールΑ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂は、例えば、下記一般式（ＩＶ）で示されるビスフェノールΑ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂の水酸基とエピクロルヒドリンを反応させることにより得ることができる。
水酸基とエピクロルヒドリンとの反応を促進するためには、反応温度５０〜１２０℃でアルカリ金属水酸化物存在下、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の極性有機溶剤中で反応を行うのが好ましい。反応温度が５０℃未満では反応が遅くなり、反応温度が１２０℃では副反応が多く生じる傾向にある。 Moreover, it is shown by general formula (II) and X is a glycidyl group:

The bisphenol-Α type epoxy resin and bisphenol F-type epoxy resin can be obtained, for example, by reacting the hydroxyl groups of bisphenolΑ-type epoxy resin and bisphenol F-type epoxy resin represented by the following general formula (IV) with epichlorohydrin. .
In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. When the reaction temperature is less than 50 ° C., the reaction is slow, and when the reaction temperature is 120 ° C., many side reactions tend to occur.

［式中、Ｒは水素原子又はメチル基であり、ｎは１以上の整数である。］

[Wherein, R is a hydrogen atom or a methyl group, and n is an integer of 1 or more. ]

  Examples of the salicylaldehyde type epoxy resin represented by the general formula (III) include FΑE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) and the like.

Examples of the vinyl group-containing monocarboxylic acid (b) include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α- Acrylic acid derivatives such as cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides The half-ester compound which is a reaction product of is mentioned.
The half ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids (b) can be used singly or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl acrylate, hydroxyethyl Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tris Methacrylate, dipentaerythritol pentaacrylate, Data dipentaerythritol methacrylate, glycidyl acrylate, glycidyl methacrylate and the like.

  As a dibasic acid anhydride used for the synthesis | combination of the said half ester compound, what contains a saturated group and what contains an unsaturated group can be used. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Examples include acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

  In the reaction of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b), the vinyl group-containing monocarboxylic acid (b) is 0.6 to 1 with respect to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to make it react by the ratio used as 1.05 equivalent, and it is more preferable to make it react by the ratio used as 0.8-1.0 equivalent.

  The epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be reacted by dissolving in an organic solvent. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Furthermore, it is preferable to use a catalyst to promote the reaction. As the catalyst, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like can be used. The amount of the catalyst used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight as a total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).

  Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like, and the amount used thereof is a total of 100 parts by weight of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by weight. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  If necessary, vinyl group-containing monocarboxylic acid (b) and phenolic compounds such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. The polybasic acid anhydride can be used in combination.

  As the acid-modified vinyl group-containing epoxy resin, it is also preferable to use a resin (A ″) obtained by reacting the above-mentioned resin (A ′) with a polybasic acid anhydride (c).

  In the resin (A ″), the hydroxyl group in the resin (A ′) (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified. It is presumed that

  As the polybasic acid anhydride (c), one containing a saturated group or one containing an unsaturated group can be used. Specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be mentioned.

In the reaction of the resin (A ′) and the polybasic acid anhydride (c), the polybasic acid anhydride (c) is 0.1 to 1.0 equivalent per 1 equivalent of the hydroxyl group in the resin (A ′). By reacting, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.
The acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the curable resin composition in a dilute alkali solution is lowered, and when it exceeds 150 mgKOH / g, the electric properties of the cured film tend to be lowered. The reaction temperature between the resin (A ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

If necessary, as the epoxy resin (a), for example, a hydrogenated bisphenol-type epoxy resin can be partially used together. Further, as the acid-modified vinyl group-containing epoxy resin, a styrene-maleic acid resin such as a hydroxyethyl acrylate modified product of a styrene-maleic anhydride copolymer or a hydroxyethyl acrylate modified product of a styrene-maleic anhydride copolymer is used. It can also be used together.
The content of the curable resin (A) is preferably 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, and particularly preferably 15 to 40 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. Part. When the content of the curable resin (A) is within the above range, a coating film excellent in heat resistance, electrical properties, and chemical resistance can be obtained.

<Barium sulfate fine particles (B)>
The barium sulfate fine particles (B) are effective in HAST property (insulating property), crack resistance (heat shock resistance), high resolution, and can improve the aggregation preventing effect.

  As barium sulfate microparticles | fine-particles (B), what is commercially available as NanoFine BFN40DC (made by Nippon Solvay Co., Ltd.) can be used, for example.

  The aluminum compound that covers the surface of the barium sulfate fine particles (B) is preferably alumina.

  The content of the barium sulfate fine particles (B) is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. The amount is particularly preferably 25 parts by weight. When the content of the barium sulfate fine particles (B) is less than 1 part by weight or more than 50 parts by weight, the insulating properties, thermal shock resistance, and high resolution tend to be insufficient.

  When the surface coating amount by the aluminum compound in the barium sulfate fine particles (B) is small, the aggregation preventing effect is insufficient, and when it is too large, problems such as gelation of the curable resin (A) tend to occur due to catalytic action. .

  The elemental composition of aluminum on the surface of the barium sulfate fine particles (B) is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, and 1.5 to 3.5 atomic%. Particularly preferred. The elemental composition of silicon on the surface of the barium sulfate fine particles (B) is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, and 1.5 to 3.5 atomic%. It is particularly preferred. Furthermore, the elemental composition of carbon on the surface of the barium sulfate fine particles (B) is preferably 10 to 30 atomic%, more preferably 15 to 25 atomic%, and particularly preferably 18 to 23 atomic%. These elemental compositions can be measured using XPS.

The curable resin composition of the present invention may contain inorganic fine particles other than the barium sulfate fine particles (B). Examples of inorganic fine particles other than the barium sulfate fine particles (B) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), Silicon nitride (Si ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate, aluminum oxide, aluminum hydroxide, magnesium hydroxide, lead titanate (PbO · TiO ₂ ), Lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO · Al ₂ O ₃ ), mullite (3Al ₂ O ₃ · 2SiO ₂ ), Cody Eraito _{(2MgO · 2Al 2 O 3 /} 5SiO 2), talc (3MgO · 4SiO ₂ · H O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO ₃ ), Calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), hydrotalcite, organic bentonite, mica, calcined kaolin, carbon (C), etc. From the viewpoint of improving heat resistance, it is preferable to use silica. These inorganic fine particles can be used singly or in combination of two or more.
The content of the inorganic fine particles other than the barium sulfate fine particles (B) is preferably 1 to 50 parts by weight, and 5 to 30 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. More preferably, it is particularly preferably 10 to 20 parts by weight.

  The barium sulfate fine particles (B) and other inorganic fine particles used in the curable resin composition of the present invention preferably have a maximum particle size of 0.1 to 20 μm, more preferably 0.1 to 10 μm, It is particularly preferably 0.1 to 5 μm, and most preferably 0.1 to 1 μm. When the maximum particle diameter exceeds 20 μm, the insulation reliability tends to be impaired.

<Curing agent (C)>
As the curing agent (C), a compound that itself cures with heat, ultraviolet rays, or the like, or a compound that cures with an acid-modified vinyl group-containing epoxy resin (curable resin (A)), a carboxyl group, a hydroxyl group and heat, ultraviolet rays, or the like Is preferred. By using a hardening | curing agent (C), the heat resistance of the cured film formed from a curable resin composition, adhesiveness, chemical-resistance, etc. can be improved.

  Examples of the curing agent (C) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, block type isocyanates; bisphenol Α type epoxy resins, bisphenol F type epoxide resins, hydrogenated bisphenol Α type epoxies. Epoxy compounds such as resins, brominated bisphenol cage epoxy resins, novolac epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, heterocyclic epoxy resins such as triglycidyl isocyanurate, and bixylenol epoxy resins; Examples include melamine compounds such as aminotriazine, hexamethoxymelamine, and hexabutoxylated melamine; and urea compounds such as dimethylolurea.

  From the viewpoint of further improving the heat resistance of the cured film, it is preferable to include an epoxy compound, an epoxy resin, and a block type isocyanate, and it is more preferable to use an epoxy compound and / or an epoxy resin and a block type isocyanate in combination.

  As the block type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Polyisocyanate compounds, and adducts, burettes and isocyanurates of these.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  A hardening | curing agent (C) is used individually by 1 type or in combination of 2 or more types. The content of the curing agent (C) is preferably 2 to 50 parts by weight, more preferably 5 to 40 parts by weight, and particularly preferably 10 to 30 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. It is. If it is less than 2 parts by weight, the heat resistance of the formed cured film tends to be low, and if it exceeds 50 parts by weight, the developability tends to decrease.

  To the curable resin composition of the present invention, an epoxy resin curing agent is added as a curing agent (C) for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the cured film to be formed. You can also.

  Specific examples of such an epoxy resin curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5. Imidazole derivatives such as hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazide These organic acid salts and / or epoxy adducts: amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S- Thoria Triazine derivatives such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris ( Tertiary amines such as dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; tributylphosphine, triphenylphosphine, tris-2-cyanoethyl Organic phosphines such as phosphine; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosnium chloride; Quaternary ammonium salts such as rutrimethylammonium chloride and phenyltributylammonium chloride; polybasic acid anhydrides as described above; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexa A fluorophosphate etc. are mentioned. These epoxy resin curing agents are used singly or in combination of two or more.

  The content of the epoxy resin curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition.

  The curable resin composition of the present invention may further contain a compound (D) having at least one ethylenically unsaturated group in the molecule, a photopolymerization initiator (E), and / or an elastomer (F). . Hereinafter, each component will be described.

<Compound (D) having at least one ethylenically unsaturated group in the molecule>
The compound (D) having at least one ethylenically unsaturated group in the molecule is preferably a compound having a molecular weight of 1000 or less, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates, mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc. (Meth) acrylamides, aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, Polyhydric alcohols such as pentaerythritol and tris-hydroxyethyl isocyanurate, or polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, etc. (Meth) acrylates of phenolic ethylene oxide or propylene oxide adducts, glycidyl ether (meth) acrylates such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate Acrylamide, acrylonitrile, diacetone acrylamide, styrene, vinyltoluene and the like. These compounds (D) having at least one ethylenically unsaturated group in the molecule are used singly or in combination of two or more.

  The content of the compound (D) having at least one ethylenically unsaturated group in the molecule is preferably 5 to 50 parts by weight, more preferably 8 to 100 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. 40 parts by weight, particularly preferably 10 to 30 parts by weight. If it is less than 5 parts by weight, the photosensitivity tends to be low and the exposed part tends to elute during development, and if it exceeds 50 parts by weight, the heat resistance tends to decrease.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is suitably used when the curable resin composition is a photocurable resin composition.

  Examples of the photopolymerization initiator (E) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, Acetophenones such as 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, N, N-dimethylaminoacetophenone; 2 -Anthraquinones such as methyl anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; 2,4-dimethylthioxanthone Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4, Benzophenones such as 4′-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide: 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. These photoinitiators (E) can be used individually by 1 type or in combination of 2 or more types.

  Furthermore, photopolymerization initiation aids such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. The agents can be used alone or in combination of two or more.

  The content of the photopolymerization initiator (E) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, particularly preferably 2 to 100 parts by weight of the solid content of the curable resin composition. ~ 5 parts by weight. If it is less than 0.5 part by weight, the exposed part tends to elute during development, and if it exceeds 20 part by weight, the heat resistance tends to decrease.

<Elastomer (F)>
The elastomer (F) can be suitably used when the curable resin composition of the present invention is used for a semiconductor package substrate. By adding the elastomer (F) to the curable resin composition of the present invention, an acid-modified vinyl group-containing epoxy resin (curable resin (A)) is caused by a crosslinking reaction (curing reaction) caused by ultraviolet rays or heat. Is cured and shrunk, strain (internal stress) is applied to the inside of the resin, and the problem that flexibility and adhesiveness are reduced can be solved.

  Thereby, in the dynamic viscoelasticity measurement in the temperature range of 200 to 220 ° C. which is the temperature at the time of reflow, the elastic modulus of the cured film can be reduced to 1 to 100 MPa, and the shear adhesiveness with the sealing material is improved. Can do. If the elastic modulus is less than 1 MPa, the mechanical strength decreases, and if it exceeds 100 MPa, the shear adhesive strength decreases. Such characteristics are particularly useful when used for a semiconductor package substrate.

  Examples of the elastomer (F) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers (F) are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

  Examples of the styrenic elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer. In addition to styrene, which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used. More specifically, Tufprene, Solprene T, Asaprene T, Tuftec (manufactured by Asahi Kasei Kogyo Co., Ltd.), Elastomer Α R (manufactured by Aron Kasei), Kraton G, Super Reflex (manufactured by Shell Japan), JSR TR, TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Nippon Zeon), TPE-SB series (Sumitomo Chemical Industries, Ltd.) ), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, Kuraray Co., Ltd.), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industry) Can do.

  The olefin-based elastomer is a copolymer of an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as isoprene, α-olefin copolymers, and carboxy-modified NBR obtained by copolymerizing butadiene-acrylonitrile copolymers with methacrylic acid. More specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. Is mentioned. More specifically, Miralastoma (Mitsui Petrochemical), EXＥCT (Exxon Chemical), ENGΑGE (Dow Chemical), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (Nippon Synthetic Rubber Co., Ltd.), butadiene -Acrylonitrile copolymer "NBR series" (manufactured by Nippon Synthetic Rubber Co., Ltd.), or both end carboxyl group-modified butadiene-acrylonitrile copolymer "XER series" (manufactured by Nippon Synthetic Rubber Co., Ltd.), polybutadiene partially Epoxylated polybudadiene “BF-1000” (manufactured by Nippon Soda Co., Ltd.) or the like can be used.

Urethane elastomers are composed of structural units of a hard segment composed of low-molecular glycol and diisocyanate and a soft segment composed of a high-molecular (long-chain) diol and diisocyanate.
As the low-molecular glycol, for example, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number average molecular weight of the short chain diol is preferably 48 to 500.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6 -Hexylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
Specific examples of the urethane-based elastomer include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink), sylactolan E790, and the like.

Examples of the polyester elastomer include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with a methyl group, an ethyl group, a phenyl group, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used individually by 1 type or in combination of 2 or more types.
Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And a dihydric phenol represented by the following general formula (V).

［但し、ＹはＣ１〜Ｃ１０のアルキレン基、Ｃ４〜Ｃ８のシクロアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ_２−からなる群から選択され、又は直接ベンゼン環同士が結合しており、Ｒ^１及びＲ^２はハロゲン又はＣ１〜Ｃ１２のアルキル基であり、ｌ、ｍは０〜４の整数であり、ｐは０又は１である。］

[However, Y is selected from the group consisting of a C1-C10 alkylene group, a C4-C8 cycloalkylene group, —O—, —S—, —SO ₂ —, or benzene rings are directly bonded to each other; R ¹ and R ² are halogen or a C1 to C12 alkyl group, l and m are integers of 0 to 4, and p is 0 or 1. ]

  Specific examples of the dihydric phenol represented by the general formula (V) include bisphenol soot, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition, a multiblock copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used. There are various grades depending on the type, ratio, and molecular weight of the hard and soft segments. Specific examples include Hytrel (manufactured by DuPont-Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.

Polyamide elastomers are broadly classified into two types: polyether block amide type and polyether ester block amide type using polyamide for the hard segment and polyether or polyester for the soft segment.
As the polyamide, polyamide-6, 11, 12 or the like is used. As the polyether, polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used. Specifically, UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEB 、 X (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MS Japan), Nopamid ( Mitsubishi Chemical Co., Ltd.), Glais (Dainippon Ink Co., Ltd.), etc. can be used.

  The acrylic elastomer is mainly composed of acrylic acid ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used. Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. are used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized. Specifically, an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, or the like can be used.

  Silicone elastomers are mainly composed of organopolysiloxane, and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  In addition to the above-described elastomer, a rubber-modified epoxy resin can also be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the above bisphenol F type epoxy resin, bisphenol エ ポ キ シ type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, in terms of shear adhesion, both terminal carboxyl group-modified butadiene-acrylonitrile copolymers and Espel (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), which are polyester elastomers having hydroxyl groups, are used. preferable.

The content of the elastomer (F) is preferably 2 to 30 parts by weight, more preferably 4 to 20 parts by weight, and particularly preferably 5 to 15 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition. is there. If it is less than 2 parts by weight, the elastic modulus in the high temperature region of the cured film tends not to decrease, and if it exceeds 30 parts by weight, the unexposed part tends not to be eluted with the developer.
In order to further improve the flexibility of the cured film, a thermoplastic resin (G) can be added to the curable resin composition of the present invention.
Examples of the thermoplastic resin (G) include acrylic resins and urethane resins.
The content when the thermoplastic resin (G) is contained is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the solid content of the curable resin composition.

  The curable resin composition of the present invention includes, as necessary, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and hydroquinone. , Polymerization inhibitors such as methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol, thickeners such as benton and montmorillonite, silicone, fluorine and vinyl resin antifoaming agents, silane coupling agents, diluents, etc. Various conventional additives can be added. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorous compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can also be added.

  As the diluent, for example, an organic solvent can be used. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  A diluent is used individually by 1 type or in combination of 2 or more types.

  The diluent content can be appropriately adjusted from the viewpoint of applicability of the curable resin composition.

  The curable resin composition of the present invention can be obtained by uniformly kneading and mixing the above-described components with a roll mill, a bead mill or the like.

The curable resin composition of the present invention can be used, for example, to form an image and produce a cured film as follows.
That is, it is applied to a copper-clad laminate with a film thickness of 10 to 200 μm by a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method or the like, and the coating film is then applied at 60 to 110 ° C. After drying, the negative film is brought into direct contact (or non-contact through a transparent film) and irradiated with active light (eg, ultraviolet light), preferably 10 to 1,000 mJ / cm ² , and then unexposed. The portion is dissolved and removed (developed) with a dilute alkaline aqueous solution or an organic solvent. Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet exposure) and / or post-heating to obtain a cured film. The post-exposure is preferably, for example, 1 to 5 J / cm ² , and the post-heating is preferably 100 to 200 ° C. for 30 minutes to 12 hours.

  Moreover, the curable resin composition of the present invention can be laminated on a support to form a photosensitive element. The thickness of the layer made of the curable resin composition is preferably 10 to 100 μm. As the support, a film having a thickness of 5 to 100 μm such as polyethylene terephthalate is preferably used. The layer comprising the curable resin composition is preferably formed by applying and drying a solution of the curable resin composition on the support film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this. In addition, the numerical value in Tables 1-4 shows a compounding quantity (part by weight).

(Formulation Examples 1-10, Comparative Formulation Examples 1-10)
Formulations were blended according to the blending compositions shown in Tables 1 to 4 and kneaded with a three roll mill to prepare compositions of Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 10. In Formulation Examples 1 to 10, BFN40DC and ASA (trade name, manufactured by Nippon Solvay Co., Ltd.), which are barium sulfate fine particles surface-coated with an aluminum compound and an organosilicon compound, were used as the barium sulfate fine particles (B). . Further, in Comparative Formulation Examples 1 to 10, B-35 (manufactured by Sakai Chemical Industry Co., Ltd., trade name), which is a barium sulfate fine particle surface-coated with an alumina-silica compound, as a comparative barium sulfate fine particle (B ′). ), Sedimentary barium # 100 (trade name, manufactured by Sakai Chemical Industry Co., Ltd.), which is fine barium sulfate particles that are not surface-coated with an aluminum compound.

  For the barium sulfate fine particles used in Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 10, the primary particle size (maximum particle size) is measured using a scanning electron microscope (manufactured by Hitachi, Ltd., model number: S-4200). went. The measurement results are shown in Table 5.

  [Filterability]: Using a SUS sheet filter (φ293 mm, pore diameter 14 μm), filtration was performed at a filtration pressure of 0.2 MPa. The elapsed time and the weight of the filtered curable resin composition were measured, and the filtration rate until the filtration rate and the filtration rate became 1 kg / min or less was examined. Tables 6 and 7 show the evaluation results for Formulation Examples 1 to 5 and Comparative Formulation Examples 1 to 5. FIG. 1 shows the filtration results of Formulation Examples 1 and 2 and Comparative Formulation Examples 1 and 2. In addition, the tendency similar to the result shown to Tables 6-7 was obtained for the filterability of the compounding examples 6-10 and the comparative compounding examples 6-10.

(Examples 1-5, Comparative Examples 1-5)
[Preparation of test piece]
Compositions (1) and (2) were mixed in the combinations shown in Tables 8 and 9, and curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared. These curable resin compositions were applied to a copper substrate by a screen printing method so that the film thickness after drying was 20 μm, and then dried at 75 ° C. for 15 minutes with a hot air circulation dryer. Next, a negative mask having a predetermined pattern was brought into close contact with the coating film and exposed to 600 mJ / cm ² using an ultraviolet exposure device. Thereafter, spray development was performed with a 1% by weight aqueous sodium carbonate solution for 60 seconds at a pressure of 1.8 kgf / cm ² , and the unexposed area was dissolved and developed. Next, 1000 mJ / cm < ² > exposure was carried out using the ultraviolet exposure apparatus, and it heated at 150 degreeC for 1 hour, and produced the test piece.

  The following test was done about the curable resin composition or test piece obtained in Examples 1-5 and Comparative Examples 1-5. The results are shown in Tables 10 and 11.

[Photosensitivity]: The curable resin composition was applied to a copper substrate by a screen printing method so that the film thickness after drying was 20 μm, and then dried at 75 ° C. for 15 minutes with a hot air circulation dryer. Step tablet 21 steps (made by Stoffer) was adhered to the obtained coating film, irradiated with ultraviolet rays with an integrated exposure amount of 600 mJ / cm ² , developed with 1% by weight sodium carbonate aqueous solution or chlorocene for 60 seconds, and then not developed. The number of steps of the remaining coating film was confirmed.
○: 8 steps or more Δ: 5 to 7 steps ×: 4 steps or less

[Aperture Diameter]: The curable resin composition was applied to a copper substrate by a screen printing method so that the film thickness after drying was 20 μm, and then dried at 75 ° C. for 15 minutes with a hot air circulation dryer. The obtained coating film is irradiated with 600 mJ / cm ² of ultraviolet light directly or through a transparent film (non-contact) with a negative film dotted with φ80 μm and φ110 μm light non-transparent areas in a 1 × 1 cm square area Then, the coating film opening diameter was measured using a microscope (HIROX, model number: KH-3000) after image formation.
○: Opening diameter of 80% or more (64 μm or more for φ80 μm negative film, 88 μm or more for φ110 μm negative film).
X: Opening diameter of 80% or less (64 μm or more for φ80 μm negative film, 88 μm or more for φ110 μm negative film).

[Adhesion]: According to JIS K5400, 100 test pieces having a 1 mm size were prepared and subjected to a peel test using a cellophane tape. The state of peeling of the goblet was observed and evaluated according to the following criteria.
○: 90/100 or more, no peeling Δ: 50/100 or more to less than 90/100, no peeling ×: 0/100 to less than 50/100, no peeling

[Solvent resistance]: The test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

[Acid resistance]: The test piece was immersed in a 10% by weight hydrochloric acid aqueous solution at room temperature for 30 minutes, and after confirming that there was no abnormality in the appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

[Alkali resistance]: A test piece was immersed in a 5% by weight aqueous sodium hydroxide solution at room temperature for 30 minutes, and after confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape.
○: No abnormality in the appearance of the coating film and no peeling ×: No abnormality in the appearance of the coating film or peeling

[Solder heat resistance]: A rosin-based flux or a water-soluble flux was applied to the test piece and immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.
○: There is no abnormality (peeling, blistering) in the coating film appearance and there is no solder peeling ×: There is an abnormality (peeling, blistering) in the coating film appearance, or there is solder peeling

[Thermal shock resistance]: The test piece was subjected to thermal history with -55 ° C./30 minutes and 125 ° C./30 minutes as one cycle, and after 1,000 cycles, the test piece was visually observed and observed with a microscope.
○: No crack occurrence ×: Crack occurrence

[Insulating]: A curable resin composition was applied to an insulating evaluation substrate on which a comb wiring with a copper wiring interval of 10 μm was printed by a screen printing method so as to have a dry film thickness of 20 μm, and then at 75 ° C. after drying for 15 minutes, exposed with 600 mJ / cm ² using an ultra-high pressure mercury lamp, after 60 seconds developed by 1% sodium carbonate at 30 ° C., was exposed at 1000 mJ / cm ² using an ultra-high pressure mercury lamp, at 170 ° C. A heat treatment was performed for 1 hour to produce an insulating evaluation substrate. The obtained insulating evaluation substrate is subjected to a current of 20 V under the conditions of 130 ° C., 85% RH, and 2 atm. After 100 hours, the resistance value was measured with a tester (manufactured by ADVANTEST, model number: TR8601).
○: Resistance value of 1.0 × 10E + 9Ω or more ×: Resistance value of 1.0 × 10E + 9Ω or less

It is a figure which shows the filtration result of the mixing examples 1 and 2 and the comparative mixing examples 1 and 2. FIG.

Claims (9)

A curable resin (A);
Barium sulfate fine particles (B) surface-coated with an aluminum compound and an organosilicon compound;
A curable resin composition for printed wiring boards, comprising a curing agent (C).   The curable resin composition for printed wiring boards according to claim 1, wherein the curable resin (A) is an acid-modified vinyl group-containing epoxy resin.   The curable resin composition for printed wiring boards according to claim 1 or 2, further comprising a compound (D) having at least one ethylenically unsaturated group in the molecule.   The curable resin composition for printed wiring boards according to any one of claims 1 to 3, further comprising a photopolymerization initiator (E).   The curable resin composition for printed wiring boards according to any one of claims 1 to 4, further comprising an elastomer (F). The acid-modified vinyl group-containing epoxy resin is a novolac type epoxy resin represented by the following general formula (I), a bisphenol cage type epoxy resin or a bisphenol F type epoxy resin represented by the following general formula (II), and the following general formula ( The resin obtained by reacting at least one epoxy resin (a) selected from the group consisting of salicylaldehyde type epoxy resins represented by III) with a vinyl group-containing monocarboxylic acid (b), Item 3. A curable resin composition for printed wiring boards according to Item 2.

[Wherein, X is a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or a methyl group, and n is 1 or more. Is an integer. ] The acid-modified vinyl group-containing epoxy resin is a novolac type epoxy resin represented by the following general formula (I), a bisphenol cage type epoxy resin or a bisphenol F type epoxy resin represented by the following general formula (II), and the following general formula ( A polybasic acid anhydride is obtained by reacting the vinyl group-containing monocarboxylic acid (b) with at least one epoxy resin (a) selected from the group consisting of salicylaldehyde type epoxy resins represented by III) The curable resin composition for printed wiring boards according to claim 2, which is a resin obtained by reacting the product (c).

[Wherein, X is a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), R is a hydrogen atom or a methyl group, and n is 1 or more. Is an integer. ]   The elastomer (F) is at least one elastomer selected from the group consisting of a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. Item 6. A curable resin composition for printed wiring boards according to Item 5.   A curable resin composition for printed wiring boards, which gives a cured film having an elastic modulus of 1 to 100 MPa in dynamic viscoelasticity measurement in a temperature range of 200 to 220 ° C.

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