WO2011033739A1 - Composition de résine thermodurcissable - Google Patents

Composition de résine thermodurcissable Download PDF

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Publication number
WO2011033739A1
WO2011033739A1 PCT/JP2010/005492 JP2010005492W WO2011033739A1 WO 2011033739 A1 WO2011033739 A1 WO 2011033739A1 JP 2010005492 W JP2010005492 W JP 2010005492W WO 2011033739 A1 WO2011033739 A1 WO 2011033739A1
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Prior art keywords
talc
manufactured
thermosetting resin
resin composition
silica
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PCT/JP2010/005492
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English (en)
Japanese (ja)
Inventor
小川　勇太
晋一朗 福田
邑田　勝人
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太陽ホールディングス株式会社
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Priority to CN201080039365.5A priority Critical patent/CN102482501B/zh
Priority to KR1020127005605A priority patent/KR101380103B1/ko
Publication of WO2011033739A1 publication Critical patent/WO2011033739A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • the present invention relates to a thermosetting resin composition and a dry film.
  • thermosetting resin used for the insulating layer of the circuit board is set to the linear expansion coefficient (17 ppm / ° C. based on the copper foil) of other materials used for the circuit board.
  • linear expansion coefficient it is required to reduce the linear expansion coefficient in a wide temperature range from the glass transition temperature to room temperature by expanding the use of the semiconductor package substrate and improving the performance.
  • a cured product of a conventional thermosetting resin has a high linear expansion coefficient of about 45 to 65 ppm / ° C. in a region close to the glass transition temperature, and tends to increase the linear expansion coefficient.
  • the semi-additive method has become the mainstream for circuit formation, and the formation of conductor layers by plating has become essential, improving the adhesion strength of conductor plating layers. Is required.
  • the insulating layer of the circuit board is required to have mechanical strength (elongation) in order to alleviate problems caused by the difference in expansion that occurs.
  • the dry film used to form the insulating layer of the circuit board prevents damage caused by various mechanical and thermal shocks to the semiconductor package substrate during manufacturing. desired.
  • Patent Document 1 discloses a technique for reducing the linear expansion coefficient without using a large amount of an inorganic filler by using a layered silicate compound having an exchangeable metal cation between crystals.
  • this method has a problem that the elongation rate is lowered and the adhesion strength of the conductor plating layer is greatly reduced.
  • Patent Document 2 discloses a technique of reducing the linear expansion coefficient by filling a thermosetting resin composition with spherical silica. However, since this method contains a large amount of spherical silica, the dry film-like composition before curing becomes brittle and there is a risk that handling properties may be reduced.
  • the present invention can improve the handleability and adhesion (laminate) of the dry film, and can reduce the linear expansion coefficient of a cured product (insulating layer) produced using this dry film. It aims at providing the thermosetting resin composition which was excellent also in adhesiveness and conductor plating adhesiveness (conductor plating peel strength).
  • the inventors of the present invention include a layered silicate compound having an exchangeable metal cation between crystals in a thermosetting resin composition according to Patent Document 1.
  • the effect of reducing the coefficient of linear expansion compared to silica is large, but the mechanical strength (elongation rate) of the coating film and the adhesion strength of the conductor plating layer are not improved, but talc is used for the layered silicate compound.
  • talc is used for the layered silicate compound.
  • thermosetting resin composition with spherical silica according to Patent Document 2
  • the dry film-like composition before curing becomes brittle and the handling property is lowered, while the use of silica and talc is found to improve the handling property, and the present invention has been completed.
  • thermosetting resin composition comprising a thermosetting resin, a phenolic curing agent, amorphous silica and talc.
  • the thermosetting resin composition according to (1) wherein the total amount of the amorphous silica and talc is 35 to 70% by mass in the nonvolatile content of the composition.
  • (6) The dry film as described in (5), wherein the linear expansion coefficient of the cured product at a curing temperature of 25 to 150 ° C. is 17 to 30 ppm / ° C.
  • thermosetting resin composition of the present invention by using amorphous silica and talc in combination with the thermosetting resin, it is possible to improve dry film handling and adhesion (laminate), The linear expansion coefficient of the cured product (insulating layer) of the thermosetting resin composition can be reduced, and the elongation rate, adhesion, and conductor plating adhesion (conductor plating peel strength) can be excellent.
  • the resin composition of the present invention contains a thermosetting resin, a phenol-based curing agent, amorphous silica, and talc.
  • thermosetting resin is not particularly limited as long as it is capable of curing reaction with the thermosetting resin itself and the thermosetting resin and its curing agent by heating.
  • a compound having at least two or more epoxy groups in the molecule is more preferable.
  • bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, phenol aralkyl type epoxy resin, naphthalene type epoxy resin, and heterocyclic ring Containing epoxy resin By hydrogenating all or part of the aromatics in these skeletons, it is possible to use those having improved transparency and reduced viscosity.
  • An episulfide resin in which the oxygen atom of the epoxy group is replaced with a sulfur atom can also be used.
  • thermosetting resin it is preferable to use a bisphenol S type epoxy resin or an epoxy resin having a naphthalene skeleton, from the viewpoint of reducing the linear expansion coefficient.
  • one type of thermosetting resin may be used, or two or more types of thermosetting resins may be used.
  • Examples of commercially available polyfunctional epoxy compounds include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, and Epicron 2055 manufactured by DIC Corporation, and Epototo YD-011 manufactured by Nippon Steel Chemical Co., Ltd. Epototo YD-013, Epototo YD-127, Epototo YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R.
  • Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epotot YDB-400, Epototo YDB-500 manufactured by Nippon Steel Chemical Co., Ltd., Dow D. made by Chemical Co. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumiepoxy ESB-400, Sumiepoxy ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. R.
  • ECN-235, A.I. E. R. Novolak type epoxy resins such as ECN-299 (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical, Epototo YDF-170, Epototo YDF-175, Epototo YDF-, manufactured by Nippon Steel Chemical Co., Ltd. 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); Epototo ST-2004, Epototo ST-2007, Epototo ST-3000 manufactured by Nippon Steel Chemical Co., Ltd.
  • glycidylamine type Poxy resin Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Japan; Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide CY-175, Araldide CY-179 manufactured by Ciba Japan All are trade names) cycloaliphatic epoxy resins; YL-933 manufactured by Mitsubishi Chemical Corporation, T.W. manufactured by Dow Chemical Co., Ltd. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YL-6121, YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.
  • Tetraphenylol ethane type epoxy resin Araldide PT810 made by Ciba Japan, Japan Heterocyclic epoxy resins such as TEPIC made by Kagaku Kogyo Co., Ltd. (both trade names); diglycidyl phthalate resins such as Bremer DGT made by NOF Corporation; ZX-1063 made by Nippon Steel Chemical Co., Ltd. Tetraglycidylxylenoylethane resin such as ESN-175, ESN-355, ESN-375 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, HP-5000, EXA-4700, EXA-4710 manufactured by DIC , EXA-7311, EXA-9900, etc.
  • epoxy resins can be used alone or in combination of two or more.
  • episulfide resin etc. which substituted the oxygen atom of the epoxy group of the said epoxy resin by the sulfur atom, etc. can be used.
  • the curing agent for the thermosetting resin used in the thermosetting resin composition of the present invention is a phenolic curing agent.
  • a phenolic curing agent containing a phenolic hydroxyl group as an epoxy resin curing agent, the linear expansion coefficient is reduced, and handling properties and laminating properties are excellent.
  • phenolic curing agents examples include phenol, o-cresol, p-cresol, bisphenol A, bisphenol F, bisphenol S, bisphenol, and naphthalenediol.
  • phenol novolak resins, o-cresol novolak resins, m-cresol novolak resins, and naphthalene skeleton-containing phenol resins, which are polycondensates of these phenols and aldehydes may be mentioned.
  • the triazine ring containing novolak resin which is a polycondensate of these phenols, aldehydes, and the compound which has a triazine ring is mentioned.
  • a phenolic curing agent having a softening point temperature of 120 ° C. or higher is preferably used.
  • the ring and ball method is generally used for the softening point temperature measurement. When it has the said value, reduction of the linear expansion coefficient in a wide temperature range can be aimed at by raising the glass transition temperature of hardened
  • phenolic curing agents examples include cresol-type novolac resins such as GPX-41 (trade name) manufactured by Gifu Seratec, and trisphenol methane types such as MEH-7500H (trade name) manufactured by Meiwa Kasei. Examples thereof include phenol resins and biphenyl aralkyl type phenol resins such as MEH-7851-4H manufactured by Meiwa Kasei Co., Ltd.
  • the blending amount is preferably 3: 1 to 0.75: 1 in terms of the number of moles of epoxy groups and the number of moles of phenolic hydroxyl groups. If the compounding ratio is out of the range of 3: 1 to 0.75: 1, there is a concern that the laminating property is lowered and the insulation reliability is lowered. More preferably, it is 2.5: 1 to 1: 1, and still more preferably 2.3: 1 to 1.1: 1.
  • thermosetting resin composition of the present invention can contain a curing agent for other thermosetting resins as required, together with a phenolic curing agent.
  • the thermosetting resin curing agent is not particularly limited, and examples thereof include amines, acid anhydrides, carboxyl group-containing compounds, and hydroxyl group-containing compounds.
  • thermosetting resin composition of this invention can contain a hardening accelerator as needed.
  • a curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Examples thereof include amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide, and phosphorus compounds such as triphenylpho
  • Examples of commercially available curing accelerators include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T manufactured by San Apro, Inc. (All are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. It is not particularly limited to these, and any thermosetting resin or any one that promotes the reaction between the thermosetting resin and its curing agent may be used alone or in admixture of two or more. Absent.
  • Amorphous silica used in the thermosetting resin composition of the present invention is amorphous silicon dioxide and can be identified by an X-ray diffractometer.
  • the amorphous silica used in the thermosetting resin composition of the present invention is fine particles having an average particle size of about 0.1 to 10 ⁇ m.
  • the amorphous silica is not particularly limited, and examples thereof include spherical silica, spherical porous silica, plate-like silica, layered silica, mesoporous silica, and hollow silica.
  • spherical silica is preferably used because it has good dispersibility in the resin and imparts toughness of the resin. In the present invention, those having a sphericity of 0.8 or more are defined as spherical silica.
  • the method for producing the amorphous silica particles is not particularly limited, and methods known to those skilled in the art can be applied.
  • it can be manufactured by burning silicon powder by a VMC (Vap-erized Metal Combustion) method.
  • VMC Vehicle-erized Metal Combustion
  • a chemical flame is formed by a burner in an oxygen-containing atmosphere, and an amount of metal dust that forms part of the target oxide particles is formed in the chemical flame so that a dust cloud is formed.
  • deflagration is caused to obtain oxide particles.
  • amorphous silicas can be used alone or in combination of two or more. Note that crystalline silica is not desirable because of the concern about the influence of the human body.
  • Talc used in the thermosetting resin composition of the present invention refers to fine particles obtained by pulverizing talc and means hydrous magnesium silicate (chemical formula: 3MgO.4SiO 2 .H 2 O).
  • Talc is a kind of layered silicate, and since it does not contain exchangeable metal ions between crystals, it is characterized by being chemically stable.
  • the talc is not particularly limited, but is preferably pulverized and classified so that the average particle size is 2 ⁇ m or less, more preferably, the maximum particle size is controlled to 10 ⁇ m or less.
  • the non-crystalline silica and talc can be improved in dispersibility to components in the thermosetting resin composition by performing a surface treatment.
  • Silane compounds, titanate compounds, and the like are known as compounds used for the surface treatment, and the surface treatment may be performed in advance before blending, or may be added when the composition is blended.
  • the amorphous silica and talc are preferably blended so that the total amount (total mass) of the amorphous silica and talc is 35 to 70% by mass in the nonvolatile component of the thermosetting resin composition.
  • the total amount is less than 35% by mass, the effect of reducing the linear expansion coefficient of the cured product (insulating layer) of the thermosetting resin composition is poor.
  • it exceeds 70 mass% the elongation rate of the hardened
  • the non-crystalline silica and talc preferably have a talc mass of 5 to 90% by mass with respect to the total amount (total mass) of non-crystalline silica and talc.
  • the blending ratio is less than 5% by mass, the effect of improving the handleability of the dry film is poor, and when it exceeds 90% by mass, the effect of reducing the linear expansion coefficient of the cured product (insulating layer) is saturated while the elongation of the cured product is increased. The detrimental effect of the reduction increases, and the balance between the two characteristics deteriorates.
  • a more preferable blending ratio is 10 to 70% by mass, and further preferably 15 to 60% by mass.
  • thermosetting resin composition of the present invention includes, for example, the above-described thermosetting resin as necessary.
  • a resin that can be polymerized with a phenolic curing agent may be contained.
  • Such a polymerizable resin is not particularly limited. For example, cyanate ester resin, phenoxy resin, benzoxazine resin, modified polyphenylene ether resin, thermosetting modified amide imide resin, epoxidized polybutadiene rubber, rubber modified An epoxy resin etc. are mentioned. These polymerizable resins can be blended alone or in combination of two or more.
  • thermosetting resin composition of the present invention may contain an organic solvent for the purpose of adjusting viscosity and imparting coating properties.
  • organic solvent include ketones such as methyl ethyl ketone, cyclohexanone, acetone and methyl isobutyl ketone, acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate, and aromatics such as petroleum naphtha. Examples thereof include hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These organic solvents may be used alone or in combination of two or more.
  • thermosetting resin composition of the present invention if necessary, an antifoaming agent and / or a leveling agent such as silicone, fluorine and polymer, silane coupling agent such as imidazole, thiazole and triazole
  • an antifoaming agent and / or a leveling agent such as silicone, fluorine and polymer, silane coupling agent such as imidazole, thiazole and triazole
  • flame retardants such as phosphorus flame retardants and antimony flame retardants, antioxidants and rust inhibitors can be blended.
  • thermosetting resin composition of the present invention can form an insulating layer in the production of a multilayer substrate, and can be used industrially as a dry film such as flatness and film thickness uniformity.
  • the dry film of the present invention can be produced by a known method as follows. That is, a thermosetting resin composition varnish containing an organic solvent is applied to a support film as a support using a film coater, a film applicator, a bar coater, a die coater, etc., and is temporarily dried or temporarily cured. To form a dry film. And it is set as a 3 layer structure by laminating
  • the support film or protective film examples include films made of polyester such as polyethylene, polypropylene, and polyethylene terephthalate.
  • the support film and the protective film may be subjected to an embossing treatment, a corona treatment, a release agent treatment or the like so that they can be selectively peeled off when used.
  • the thickness of the dry film of the present invention is not particularly limited, but is preferably 5 to 150 ⁇ m. If it is thinner than 5 ⁇ m, the flatness after lamination becomes poor, and if it is thicker than 150 ⁇ m, the drying property of the varnish coated on the support film is lowered, and the productivity of the dry film is lowered. More preferably, it is 10 to 100 ⁇ m, and particularly preferably 15 to 75 ⁇ m.
  • the cured product of this dry film has a linear expansion coefficient between 25 and 150 ° C. of about 0.5 to 2 times (8 to 40 ppm / ° C.), particularly 17 to 30 ppm / ° C. It is preferable that it is ° C. If the linear expansion coefficient exceeds 30ppm / ° C, the semiconductor package substrate may be warped or broken due to cracks due to the stress caused by the difference in expansion due to temperature changes between different materials due to thermal history in the mounting process and reliability test. Is likely to occur.
  • a dry film is laminated on the wiring substrate that becomes the core substrate.
  • a base material used for a wiring board Generally a glass epoxy board
  • the insulating film can be formed on the wiring board by peeling the support film and thermosetting.
  • the thermosetting conditions can be selected according to the type of resin component, etc., but are generally set in the range of 140 to 200 ° C. for 15 to 180 minutes, preferably 160 to 190 ° C. for 30 to 120 minutes.
  • a via hole or a through hole is formed by drilling the insulating layer in order to obtain electrical connection with the core substrate.
  • the drilling step can be generally performed by a known method such as a drill, a carbon dioxide laser, or a UV-YAG laser.
  • a conductor layer is formed by plating.
  • wet plating is performed, and first, the surface of the hardened insulating layer is roughened.
  • a sodium hydroxide aqueous solution of permanganate is preferably used.
  • a conductor layer is formed by electroless copper plating through electroless copper plating.
  • the semi-additive method of removing a resist after patterning with a resist previously and performing electroless plating is used.
  • ⁇ Example 1> As a multifunctional epoxy resin, 60 parts of bisphenol S type epoxy resin (DIC Corporation, EXA-1517, epoxy equivalent of about 237), as liquid epoxy, mixed epoxy resin of bisphenol A type epoxy resin and bisphenol F type epoxy resin (Shinichi) Using 40 parts of Sakai Chemical Co., Ltd., ZX-1059, epoxy equivalent of about 165), 13 parts of cresol novolac resin (Gifu Seratsuk, GPX-41, hydroxyl equivalent of about 120) as phenolic curing agent (phenol novolac resin ( 12 parts of Meiwa Kasei Co., Ltd., HF-1M, hydroxyl equivalent of about 106, softening point temperature 86 ° C., 144 parts of amorphous silica (manufactured by Admatechs, SO-E2), talc (manufactured by Nippon Talc, SG -2000) 26 parts, 1-benzyl-2-phenylimidazole as curing accelerator (
  • thermosetting resin composition varnish (total amount of silica and talc in the nonvolatile component, about 58%, amount of talc in the total amount of silica and talc, about 15%).
  • PET film polyethylene terephthalate film having a thickness of 38 ⁇ m using a bar coater, dried at 80 ° C. for 15 minutes, and dried for testing.
  • a film was prepared. The coating conditions of the bar coater were set so that the thickness of the thermosetting resin composition layer after drying was 25 ⁇ m.
  • Example 2 In the same manner as in Example 1, except for changing to 119 parts of amorphous silica (manufactured by Admatechs, SO-E2) and 51 parts of talc (manufactured by Nippon Talc, SG-2000), A dry film was obtained in which the total amount of talc was about 58% and the amount of talc in the total amount of silica and talc was about 30%.
  • amorphous silica manufactured by Admatechs, SO-E2
  • talc manufactured by Nippon Talc, SG-2000
  • Example 3 In the same manner as in Example 1 except for changing to 68 parts of amorphous silica (manufactured by Admatechs, SO-E2) and 102 parts of talc (manufactured by Nippon Talc, SG-2000), A dry film having a total talc amount of about 58% and a talc amount in the total amount of silica and talc of about 60% was obtained.
  • a polyfunctional epoxy resin 60 parts of a bisphenol S type epoxy resin (DIC, EXA-1517, epoxy equivalent of about 237) and as a liquid epoxy, a p-aminophenol type epoxy resin (Sumitomo Chemical Co., ELM-100, epoxy) The equivalent of about 106) is 40 parts, and the phenolic curing agent is cresol novolac resin (Gifu Seratsuk, GPX-41, hydroxyl equivalent: about 120), phenol novolac resin (Maywa Kasei, HF-1M, hydroxyl group) 15 parts by weight of about 106 equivalent, softening point temperature 86 ° C, 158 parts of amorphous silica (manufactured by Admatex, SO-E2), 31 parts of talc (manufactured by Nippon Talc, SG-2000), as a curing accelerator 0.5 part of 1-benzyl-2-phenylimidazole (manufactured by Shikoku Kas
  • a varnish was prepared (total amount of silica and talc in nonvolatile components, about 56%, amount of talc in total amount of silica and talc, about 17%).
  • the obtained varnish was uniformly applied onto a PET film having a thickness of 38 ⁇ m using a bar coater, and dried at 80 ° C. for 15 minutes to prepare a dry film for testing.
  • the coating conditions of the bar coater were set so that the thickness of the thermosetting resin composition layer after drying was 25 ⁇ m.
  • Example 5 It was changed to 158 parts of amorphous silica (manufactured by Admatechs, SO-E2) and 34 parts of talc (manufactured by Nippon Talc, SG-2000), and phenoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., FX293AM40, High heat-resistant grade, nonvolatile component 40%) Except for blending 11%, the total amount of silica and talc in the nonvolatile component is about 58%, and the amount of talc in the total amount of silica and talc is about An 18% dry film was obtained.
  • amorphous silica manufactured by Admatechs, SO-E2
  • talc manufactured by Nippon Talc, SG-2000
  • phenoxy resin manufactured by Nippon Steel Chemical Co., Ltd., FX293AM40, High heat-resistant grade, nonvolatile component 40%
  • a polyfunctional epoxy resin 80 parts of a naphthalene type epoxy resin (manufactured by DIC, HP-4032, epoxy equivalent of about 140), as a liquid epoxy, a mixed epoxy resin of bisphenol A type epoxy resin and bisphenol F type epoxy resin (Nippon Steel) 20 parts of Chemical Co., Ltd., ZX-1059, epoxy equivalent of about 165), 20 parts of cresol novolac resin (Gift Seratku, GPX-41, hydroxyl equivalent of about 120), phenol novolac resin (Maywa) 18 parts by Kasei Co., Ltd., HF-1M, hydroxyl equivalent of about 106, softening point temperature of 86 ° C., 150 parts of amorphous silica (manufactured by Admatechs, SO-E2), talc (manufactured by Nippon Talc, SG- 2000) 50 parts, 1-benzyl-2-phenylimidazole (Shikoku Chemicals) as
  • the obtained varnish was uniformly coated on a PET film having a thickness of 38 ⁇ m using a bar coder, and dried at 80 ° C. for 15 minutes to prepare a test dry film.
  • the coating conditions of the bar coder were set so that the thickness of the thermosetting resin composition layer after drying was 25 ⁇ m.
  • Example 7 In the same manner as in Example 6 except that 225 parts of amorphous silica (manufactured by Admatechs, SO-E2) and 75 parts of talc (manufactured by Nippon Talc, SG-2000) were used, A dry film was obtained in which the total amount of talc was about 68% and the amount of talc in the total amount of silica and talc was 25%.
  • amorphous silica manufactured by Admatechs, SO-E2
  • talc manufactured by Nippon Talc, SG-2000
  • ⁇ Comparative Example 1> The total amount of silica and talc in the non-volatile component was about 58%, except that the talc that is the layered silicate in Example 1 was not blended and the mass of the talc was replaced with amorphous silica. A dry film having a talc amount of 0% in the total amount of talc was obtained.
  • Table 1 shows the components constituting the thermosetting resin compositions of the above Examples and Comparative Examples and their blending amounts.
  • Elongation at break mechanical strength: The dry films obtained in Examples and Comparative Examples were laminated on the glossy surface of copper foil with a vacuum laminator (CVP-300, manufactured by Nichigo Morton), and then the PET film was peeled off and cured at 180 ° C. for 60 minutes to be cured. I got a thing. Copper foil is removed from the cured product, a test piece having a width of about 5 mm and a length of about 80 mm is cut, and the elongation at break is measured using a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100N). did. The measurement conditions were a sample width of about 10 mm, a fulcrum distance of about 40 mm, a pulling speed of 1.0 mm / min, and the elongation rate until breakage was the elongation at breakage point.
  • CVP-300 vacuum laminator
  • Laminating properties The dry films obtained in Examples and Comparative Examples were subjected to surface treatment (MEC, CZ-8101, etching amount: about 1.0 ⁇ m) on a copper-clad laminate (vacuum laminator (Nichigo Morton, CVP-)). 300), the PET film was peeled off and cured at 180 ° C. for 60 minutes to prepare an evaluation substrate.
  • Lamination conditions were a temperature of 100 ° C., a lamination pressure of 0.5 MPa, a vacuum time of 20 seconds, a step down of 1 second, and a pressurization time of 19 seconds, and the state of the cured product after curing was visually evaluated.
  • ⁇ No problem in adhesion
  • ⁇ Partially lifted or peeled cured product
  • Conductor plating peel strength The dry films obtained in Examples and Comparative Examples were subjected to surface treatment (MEC, CZ-8101, etching amount: about 1.0 ⁇ m) on a copper-clad laminate (vacuum laminator (Nichigo Morton, CVP-)). 300), the PET film was peeled off and cured at 180 ° C. for 60 minutes to prepare an evaluation substrate.
  • surface treatment MEC, CZ-8101, etching amount: about 1.0 ⁇ m
  • a copper-clad laminate vacuum laminator (Nichigo Morton, CVP-)
  • the evaluation substrate is immersed in a swelling solution (Atotech Japan Co., Ltd., a mixture of Swelling Dip Securigant P and an aqueous sodium hydroxide solution (400 g / L)) at 80 ° C. for 10 minutes, and then a roughening solution (Atotech Japan Co., Ltd.).
  • a swelling solution Atotech Japan Co., Ltd., a mixture of Swelling Dip Securigant P and an aqueous sodium hydroxide solution (400 g / L)
  • a roughening solution Atotech Japan Co., Ltd.
  • Manufactured by Concentrate Compact CP and sodium hydroxide aqueous solution (400 g / L) at 80 ° C. for 20 minutes, and finally reduced solution (Atotech Japan Co., Ltd., Reduction Solution Securigant P500 and sulfuric acid mixture) was immersed in the solution at 50 ° C. for 5 minutes, and roughened.
  • the obtained conductor plating layer is cut with a depth of about 10 mm ⁇ about 80 mm to reach the dry film layer, peeled off a little to secure a grip margin, and then gripped with a gripping jig.
  • AGS-100N manufactured by Shimadzu Corporation
  • the conductor plating peel strength was measured. The measurement conditions were room temperature, the pulling speed was 50 mm / min, and the average load when peeling 35 mm was measured.
  • ⁇ Peel strength exceeding 4 N / cm
  • ⁇ Peel strength of 2 N / cm to 4 N / cm
  • Comparative Example 4 which does not contain talc and is replaced with amorphous silica has a high linear expansion coefficient.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention porte sur une composition de résine thermodurcissable dont le coefficient de dilation linéaire peut être réduit et les propriétés de manipulation peuvent être améliorées. La composition de résine thermodurcissable est caractérisée en ce qu'elle comprend une résine thermodurcissable, un agent durcisseur phénolique, une silice non cristalline et du talc.
PCT/JP2010/005492 2009-09-15 2010-09-07 Composition de résine thermodurcissable WO2011033739A1 (fr)

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JP2009-213626 2009-09-15

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JP5468954B2 (ja) * 2010-03-26 2014-04-09 パナソニック株式会社 液状エポキシ樹脂組成物と半導体装置
JP2013082873A (ja) * 2011-09-28 2013-05-09 Sekisui Chem Co Ltd Ｂステージフィルム及び多層基板
KR101942325B1 (ko) * 2012-02-10 2019-04-11 쓰리엠 이노베이티브 프로퍼티즈 컴파니 부식 방지 코팅
JP6742796B2 (ja) 2015-07-21 2020-08-19 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
JP6808985B2 (ja) * 2016-06-09 2021-01-06 住友ベークライト株式会社 樹脂膜、キャリア付樹脂膜、プリント配線基板および半導体装置
JP7085857B2 (ja) * 2017-03-01 2022-06-17 ナミックス株式会社 樹脂組成物、チップ抵抗器の保護膜、およびチップ抵抗器
JP2023082224A (ja) * 2020-04-14 2023-06-14 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、配線板及び電子部品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280427A (ja) * 1988-09-14 1990-03-20 Asahi Denka Kogyo Kk 硬化性エポキシ樹脂組成物
JP2001049220A (ja) * 1999-08-05 2001-02-20 Nippon Steel Chem Co Ltd フィルム状接着剤用組成物
WO2005056632A1 (fr) * 2003-12-08 2005-06-23 Sekisui Chemical Co., Ltd. Composition de resine thermodurcissable, feuille de resine et feuille de resine destinee a un substrat isole
WO2008087890A1 (fr) * 2007-01-15 2008-07-24 Taiyo Ink Mfg. Co., Ltd. Composition de résine thermodurcissable
WO2008126411A1 (fr) * 2007-04-10 2008-10-23 Sumitomo Bakelite Co., Ltd. Composition de résine époxy, pré-imprégné, laminé, planche de câblage imprimé multicouches, dispositif semi-conducteur, feuille de résine isolante et procédé de fabrication d'une planche de câblage imprimé multicouches

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2649841C (fr) * 2006-04-28 2013-11-26 Hitachi Chemical Co., Ltd. Composition de resine, preimpregne, stratifie et carte de cablage
JP5024205B2 (ja) * 2007-07-12 2012-09-12 三菱瓦斯化学株式会社 プリプレグ及び積層板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280427A (ja) * 1988-09-14 1990-03-20 Asahi Denka Kogyo Kk 硬化性エポキシ樹脂組成物
JP2001049220A (ja) * 1999-08-05 2001-02-20 Nippon Steel Chem Co Ltd フィルム状接着剤用組成物
WO2005056632A1 (fr) * 2003-12-08 2005-06-23 Sekisui Chemical Co., Ltd. Composition de resine thermodurcissable, feuille de resine et feuille de resine destinee a un substrat isole
WO2008087890A1 (fr) * 2007-01-15 2008-07-24 Taiyo Ink Mfg. Co., Ltd. Composition de résine thermodurcissable
WO2008126411A1 (fr) * 2007-04-10 2008-10-23 Sumitomo Bakelite Co., Ltd. Composition de résine époxy, pré-imprégné, laminé, planche de câblage imprimé multicouches, dispositif semi-conducteur, feuille de résine isolante et procédé de fabrication d'une planche de câblage imprimé multicouches

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JP5588646B2 (ja) 2014-09-10
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KR101380103B1 (ko) 2014-03-31
KR20120052380A (ko) 2012-05-23
CN102482501B (zh) 2015-08-05

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