JP5771988B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition useful for producing a component-embedded substrate, an adhesive film having an adhesive layer using the thermosetting resin composition, and a method for producing a component-embedded substrate using the adhesive film. About.

  A printed wiring board is required to have a high density by being light and thin. Even in the component-embedded substrate, a component to be embedded becomes small, and high positional accuracy is required when embedding. Further, since it is necessary to reduce the size of the entire board, a material having high insulation is required between the embedded component and the circuit around the component.

  As a method for manufacturing a component-embedded substrate, a method is disclosed in which a component is temporarily fixed with a sheet agent and a sheet agent with an adhesive, and after the component is sealed with a resin, the sheet is removed (Patent Document 1). The specific composition is not disclosed. Moreover, since it is necessary to remove an adhesive after components sealing, the number of processes increases.

  Also disclosed is a method (Patent Document 2) in which a component is temporarily fixed to an electronic component mounting surface of a core substrate with an adhesive and the component is sealed with a resin. As the adhesive material, it is desirable to use a material that is electrically insulative and becomes vaporized or gas when high heat is applied. Specific examples of polymers to be used include acrylic resin, polyester resin, and maleation. It is said that oil resin, polybutene resin, epoxy resin, etc. can be used alone or as a mixture of any combination. In addition, in order to impart tackiness to these polymer resins, it is said that rosin-based, terpene-based and petroleum resin-based tackifying resins can be added as necessary. However, the specific composition of the adhesive material is not disclosed.

  Further, a method (Patent Document 3) is disclosed in which a component is temporarily fixed on an insulating substrate provided not only on a bonding portion of an electronic component but also on an entire surface, and the component is sealed with resin. Examples of the adhesive layer include epoxy resin-based, polyurethane-based, reactive acrylic-based, ultraviolet curable, and silicone-based materials. Examples include epoxy resin-based and silicone-based materials such as phenol resins, organic acid anhydrides, amines, and cured materials. It is disclosed that a curing agent such as an accelerator is used in combination. And the method of making it harden | cure by the heating at a curing temperature or irradiation of an ultraviolet-ray for fixing components is disclosed. However, the specific composition of the adhesive layer is not disclosed. Further, when an electronic component is fixed by thermosetting the adhesive layer, there is a problem that the fixing position accuracy of the component decreases due to melting of the adhesive layer. Further, curing with ultraviolet rays has a problem that the process becomes complicated.

JP 2002-204045 A JP 2004-296562 A JP 2007-42829 A

  The problem of the present invention is that the electronic component is fixed to the adhesive layer by the adhesiveness (tackiness) of the adhesive layer, and when the adhesive layer is thermally cured, the component-embedded substrate with high component fixing position accuracy and insulation reliability It is providing the thermosetting resin composition which can manufacture.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the present invention by using a specific thermosetting resin composition containing a liquid epoxy resin, a phenolic curing agent, an inorganic filler, and an acrylic resin. Was completed.

That is, the present invention includes the following contents.
[1] A thermosetting resin composition used for fixing components and forming an insulating layer on a component-embedded substrate, wherein the epoxy resin is liquid at 25 ° C. when the nonvolatile content of the thermosetting resin composition is 100% by weight. 25 to 40% by weight, acrylic resin 0.1 to 5% by weight, phenolic curing agent 5 to 30% by weight and inorganic filler 20 to 70% by weight.
[2] The thermosetting resin composition according to the above [1], wherein the acrylic resin is an acrylic ester copolymer.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the acrylic resin is an acrylic ester copolymer containing methyl acrylate, butyl acrylate, and acrylonitrile.
[4] The thermosetting resin composition according to the above [1] to [3], wherein the acrylic resin contains one or more groups selected from an epoxy group, a hydroxyl group, and a carboxyl group.
[5]
The thermosetting resin composition according to the above [1] to [4], wherein the acrylic resin contains a hydroxyl group and a carboxyl group.
[6] An adhesive film for fixing a component-embedded substrate and forming an insulating layer, having an adhesive layer formed of the thermosetting resin composition according to the above [1] to [5] on a support.
[7] The adhesive film according to [6], wherein the adhesive layer has a thickness of 5 to 100 μm. [8] The adhesive film according to [6] or [7], wherein the support is a plastic film.
[9] The adhesive film according to any one of [6] to [8], wherein a surface of the support on the adhesive layer side is subjected to a release treatment.
[10] A component-embedded substrate including a step of fixing an electronic component on the adhesive layer of the adhesive film according to any one of [1] to [9] and a step of thermally curing the adhesive layer to form an insulating layer Manufacturing method.

  According to the present invention, by using a specific thermosetting resin composition containing a liquid epoxy resin, a phenolic curing agent, an inorganic filler, and an acrylic resin, the electronic component can be controlled by the adhesiveness (tackiness) of the adhesive layer. When the adhesive layer is fixed to the adhesive layer and the adhesive layer is thermally cured, it is possible to provide a thermosetting resin composition capable of producing a component-embedded substrate having high component fixing position accuracy and insulation reliability.

It is a conceptual diagram of the evaluation method in a component fixability evaluation test. It is a conceptual diagram of the evaluation method in a component position shift evaluation test.

[Epoxy resin in liquid form at 25 ° C]
In the present invention, the “epoxy resin that is liquid at 25 ° C.” mainly improves the heat resistance and insulation of the cured product and contributes to the tackiness of the thermosetting resin composition. Specific examples of epoxy resins that are liquid at 25 ° C. include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac phenol type epoxy resins, naphthalene type epoxy resins, tertiary butyl catechol type epoxy resins, and butadiene structures. There are epoxy resins, aliphatic glycidyl ethers, glycidyl ethers of alcohols, and halides and hydrogenated products of these epoxy resins. These can be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, aliphatic glycidyl ether, and epoxy resin having a butadiene structure are preferable from the viewpoint of heat resistance and insulation reliability. Specific examples of such epoxy resins include liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), liquid bisphenol F type epoxy resin (“Epicoat 807” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene. Type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by Dainippon Ink & Chemicals, Inc.), aliphatic glycidyl ether (“ZX-1658” manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure ( Daicel Chemical Industries, Ltd. "PB-3600") etc. are mentioned. Two or more “epoxy resins that are liquid at 25 ° C.” may be used in combination.

  When the nonvolatile component of the thermosetting resin composition is 100% by weight, the upper limit of the content of the epoxy resin that is liquid at 25 ° C. prevents the adhesive force from increasing and the peelability of the cover film from deteriorating, Further, from the viewpoint of preventing the positional deviation of the components from being easily generated during film curing, 40% by weight is preferable, and 35% by weight is more preferable. On the other hand, when the nonvolatile component of the thermosetting resin composition is 100% by weight, the lower limit of the content of the epoxy resin that is liquid at 25 ° C. is from the viewpoint of preventing the component from becoming difficult to be fixed to the adhesive film. 25% by weight is preferable, and 30% by weight is more preferable.

[acrylic resin]
In the present invention, the “acrylic resin” mainly contributes to the tackiness of the thermosetting resin composition. Examples of the acrylic resin include polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyacrylic acid ester copolymer, polymethacrylic acid ester copolymer, and the like. The acrylic resin is particularly preferably an acrylic ester copolymer having excellent adhesiveness, and more preferably an acrylic acid methyl ester copolymer and an acrylic acid ethyl ester copolymer. Examples of the copolymer compound include methyl acrylate, butyl acrylate, vinyl acetate, acrylonitrile, acrylamide, and the like, and methyl acrylate, butyl acrylate, and acrylonitrile are particularly preferable. The acrylic acid methyl ester copolymer or acrylic acid ethyl ester copolymer preferably further contains one or more groups selected from an epoxy group, a hydroxy group, and a carboxyl group, and in particular, a hydroxyl group and / or a carboxyl group. It is preferable to contain a group. These can be used alone or in combination of two or more.

  When the non-volatile component of the thermosetting resin composition is 100% by weight, the upper limit of the acrylic resin content is to prevent the adhesive force from increasing, the peelability of the cover film from being poor, and inferior handling properties. Therefore, 5% by weight is preferable, and 3% by weight is more preferable. On the other hand, when the non-volatile component of the thermosetting resin composition is 100% by weight, the lower limit value of the acrylic resin content is 0. 0 from the viewpoint of preventing difficulty in fixing components due to a decrease in adhesiveness. 1 weight% is preferable and 0.5 weight% is more preferable.

The upper limit of the weight average molecular weight of the acrylic resin is 1, from the viewpoint of preventing the solubility in the solvent and the epoxy resin from being lowered and making it difficult to create a uniform thermosetting resin composition. 200,000 is preferable, and 900,000 is more preferable. On the other hand, the lower limit value of the weight average molecular weight of the acrylic resin is preferably 400,000 and more preferably 500,000 from the viewpoint of preventing the adhesiveness of the composition from being lowered and fixing components. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Specifically, commercially available acrylic resins include ARONTAC S-1511L, S-1511X, S-1515, S-1517 (manufactured by Toagosei Co., Ltd.) Toacron AR-601, AR-602, AR- 603 (manufactured by Toupe Co., Ltd.) Nipol AR-31, AR-51, AR-54 (manufactured by Nippon Zeon Co., Ltd.), Noxtite PA-301, PA-501, PA-502 (NOK Corporation) Manufactured), Teisan Resin WS-022, WS-023, SG-51, SG-70L, SG-80 (manufactured by Nagase ChemteX Corp.), KH-LT, KH-CT (Hitachi Chemical Industry Co., Ltd.) Manufactured). Two or more “acrylic resins” may be used in combination.

[Phenolic curing agent]
In the present invention, the “phenolic curing agent” mainly functions as an epoxy resin curing agent. The phenolic curing agent is not particularly limited as long as it has a phenolic hydroxyl group and functions as a curing agent for an epoxy resin. Generally, a phenol compound having two or more phenolic hydroxyl groups in the molecule is used, and specific examples include phenol novolak resins and cresol novolak resins. Examples of commercially available phenolic curing agents include MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180. SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Toto Kasei Co., Ltd.), TD2090, TD2093, KA1160, KA1163, LA7052, LA7054, LA3018, LA1356 (manufactured by Dainippon Ink and Chemicals, Inc.) It is done. Two or more “phenolic curing agents” may be used in combination.

When the non-volatile component of the thermosetting resin composition is 100% by weight, the upper limit of the content of the phenol-based curing agent is to prevent a decrease in adhesive force and the curing agent component is excessive, such as heat resistance and insulation. From the viewpoint of preventing the deterioration of characteristics important as an insulating material, it is preferably 30% by weight, more preferably 25% by weight, still more preferably 20% by weight, and particularly preferably 15% by weight. On the other hand, when the non-volatile component of the thermosetting resin composition is 100% by weight, the lower limit of the content of the phenolic curing agent is that the curing agent component becomes too small and the curing of the resin becomes very slow, and the heat resistance From the viewpoint of preventing the deterioration of characteristics important as insulating materials such as insulating properties, 5% by weight is preferable, and 10% by weight is more preferable.

[Inorganic filler]
In the present invention, the “inorganic filler” is mainly used for the purpose of reducing the thermal expansion coefficient of the insulating layer to be formed. Specific examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Examples include barium oxide, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, among these, amorphous silica, fused silica, crystalline silica, synthetic silica, etc. The silica is particularly preferred. The silica is preferably spherical. These can be used alone or in combination of two or more.

The upper limit of the average particle size of the inorganic filler is preferably 3 μm or less, and more preferably 1.5 μm or less, from the viewpoint of insulation reliability. On the other hand, the lower limit value of the average particle size of the inorganic filler is 0.05 μm from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing when the thermosetting resin composition is a resin varnish. The above is preferable. The maximum particle size of the inorganic filler is preferably 5 μm or less from the viewpoint of insulation.

  The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

  When the non-volatile component of the thermosetting resin composition is 100% by weight, the upper limit of the content of the inorganic filler prevents the fluidity of the adhesive film from decreasing and makes it difficult to laminate with a vacuum laminator or the like. From the viewpoint of preventing the flexibility of the cured adhesive film from being greatly impaired and causing deterioration of the original cured product properties, 70% by weight is preferable, and 60% by weight is more preferable. On the other hand, when the non-volatile component of the thermosetting resin composition is 100% by weight, the lower limit of the content of the inorganic filler is that the fluidity of the resin varnish becomes too high, the handling property is deteriorated, and the film formation is reduced. From the viewpoint of preventing difficulty, 30% by weight is preferable, and 20% by weight is more preferable.

The inorganic filler is preferably surface-treated with a surface treatment agent such as an epoxy silane coupling agent, an aminosilane coupling agent, or a titanate coupling agent in order to improve moisture resistance. These may be used alone or in combination of two or more.

[Epoxy resin solid at 25 ° C]
The thermosetting resin composition of the present invention may be blended with a solid epoxy resin at 25 ° C. for the purpose of improving the Tg of the cured product accompanying the improvement in the crosslink density of the cured resin and the breaking strength. . Examples of the epoxy resin solid at 25 ° C. include a tetrafunctional naphthalene type epoxy resin, a bifunctional dicyclopentadiene type epoxy resin, and a trisphenol epoxy resin. Examples of commercially available products include EXA4700, EXA7200, Nippon Kayaku Co., Ltd. EPPN-502H manufactured by Dainippon Ink & Chemicals, Inc. Two or more “epoxy resins that are solid at 25 ° C.” may be used in combination. The content when blending a solid epoxy resin at 25 ° C. is preferably 30% by weight or less, preferably 20% by weight or less when the nonvolatile component of the thermosetting resin composition is 100% by weight. is there. If the content is too large, the adhesive film becomes brittle at room temperature, and handling properties deteriorate.

[Thermoplastic resin]
In the thermosetting resin composition of the present invention, a thermoplastic resin can be blended for the purpose of imparting appropriate flexibility to the cured thermosetting resin composition. Examples of such thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, and the like. Two or more “thermoplastic resins” may be used in combination. It is preferable to mix | blend the content of the thermoplastic resin in a thermosetting resin composition in the ratio of 0.5 to 60 weight%, and it is more preferable to mix | blend in the ratio of 3 to 50 weight%.

  Examples of commercially available phenoxy resins include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YL6954, and YL6974 manufactured by Japan Epoxy Resin Co., Ltd.

  As the polyvinyl acetal resin, a polyvinyl butyral resin is preferable. Examples of commercially available polyvinyl acetal resin include, for example, Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd. S REC BH series, BX series, KS series, BL series, BM series, etc. are mentioned.

  As a commercial item of polyimide, for example, polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. may be mentioned. Also, linear polyimides (described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and polysiloxane skeleton-containing polyimides (JP-A-2002). Modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386.

  Examples of commercially available polyamideimides include polyamideimides “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Further, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned.

  Examples of commercially available products of polyethersulfone include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Examples of commercially available products of polysulfone include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.

[Curing accelerator]
In addition to the curing agent, the thermosetting resin composition of the present invention may further contain a curing accelerator for the purpose of shortening the curing time. Examples of the curing accelerator include imidazole compounds and organic phosphine compounds, and specific examples include 2-methylimidazole and triphenylphosphine. These may be used alone or in combination of two or more. When using a hardening accelerator, it is preferable to use a hardening accelerator in 0.1-3.0 mass% with respect to an epoxy resin.

[Additive]
The thermosetting resin composition of the present invention can further contain other components as necessary. Other components include, for example, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides; organic fillings such as silicone powder, nylon powder, and fluorine powder Agents: Thickeners such as Orben and Benton; Silicone-based, fluorine-based and other polymer antifoaming agents or leveling agents; Adhesion imparting agents such as imidazole-based, thiazole-based, triazole-based, and silane-based coupling agents; phthalocyanines -Coloring agents such as blue, phthalocyanine green, iodin green, disazo yellow, carbon black and the like. These may be used alone or in combination of two or more.

[Organic solvent]
Examples of the organic solvent for preparing the varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolve, and butyl. Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.

[Adhesive film]
The adhesive film of the present invention is composed of a support layer and an adhesive layer having tackiness formed on the support layer by a thermosetting resin composition. The adhesive layer may be formed on both sides of the support layer.

  A plastic film is preferably used as the support layer. In addition to the plastic film, release paper, copper foil, metal foil such as aluminum foil, and the like can also be used as the support layer. Examples of the plastic film include polyethylene terephthalate (hereinafter may be abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, and polyimide. Can be mentioned. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and an inexpensive polyethylene terephthalate film is particularly preferable. In the case of using a plastic film in the support, in particular, in order to make it peelable from the cured product layer of the thermosetting resin composition, the formation surface of the thermosetting resin composition layer is subjected to a release treatment. It is preferred to use a support having a mold layer. The metal foil can be removed with an etching solution, but when the thermosetting resin composition is thermoset using the plastic film as a support, it is difficult to peel the plastic film from the cured product without a release layer. Become. The release agent used for the release treatment is not particularly limited as long as the cured product can be removed from the support, and examples thereof include silicone release agents and alkyd resin release agents. A commercially available plastic film with a release layer may be used, and a preferable one is, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, Lintec Corporation. Examples include SK-1, AL-5, and AL-7. Further, the plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. Moreover, when using copper foil as a support body, you may utilize this copper foil as a conductor layer, without peeling. Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is used preferably.

  The thickness of the adhesive layer of the thermosetting resin composition is preferably 1 to 200 μm. In order to obtain an insulating resin sheet suitable for thinning, the range of 5 to 100 μm is more preferable, and the range of 5 to 40 μm is still more preferable. A range of ˜30 μm is particularly preferred. If the thickness of the adhesive layer is too thin, the insulation between the external terminals of the electronic component and the circuit tends to be insufficient, and the manufacturing tends to be difficult. On the other hand, if the thickness of the adhesive layer is too thick, it is difficult to reduce the thickness of the multilayer printed wiring board.

  The adhesive film of the present invention is prepared by first dissolving a thermosetting resin composition in an organic solvent to form a resin varnish, and then applying this onto a support layer and drying the solvent by hot air spraying or the like. It can be formed with a predetermined thickness.

  The protective film for the adhesive layer can prevent dust from adhering to the surface of the adhesive layer and scratches, and is effective for improving the reliability of a printed wiring board manufactured using such an insulating resin sheet. Here, examples of the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, polyimide, release paper, and aluminum foil. The protective film may be subjected to a release treatment such as a mud treatment, a corona treatment, or a silicone release film layer. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

[Manufacturing method of component embedded substrate]
The method for producing a component-embedded substrate using the adhesive film of the present invention includes at least (A) a step of fixing an electronic component on the adhesive layer of the adhesive film, and (B) thermosetting the adhesive layer to form an insulating layer. Process. The adhesive film of the present invention is characterized by having an adhesive force capable of firmly fixing components.

  Specifically, (A) a step of fixing an electronic component or an electronic component and a circuit board on the adhesive layer of the adhesive film, (B) a step of thermosetting the adhesive layer to form an insulating layer, (C) sealing The component-embedded substrate is manufactured through a process of sealing the electronic component or the electronic component and the circuit board with a stopping resin composition, an adhesive film, or a prepreg.

  First, (A) in the step of fixing the electronic component or the electronic component and the circuit board on the adhesive layer of the adhesive film, the electronic component and, if necessary, the circuit board are fixed at a predetermined position on the adhesive layer surface having adhesiveness. Is done. The upper limit of the fixing temperature is preferably 70 ° C., more preferably 60 ° C., still more preferably 55 ° C., still more preferably 50 ° C., even more preferably 45 ° C., and 40 ° C. from the viewpoint of efficient work. Is particularly preferred. On the other hand, the lower limit of the temperature at the time of fixing is preferably −20 ° C., more preferably −10 ° C., further preferably −5 ° C., still more preferably 0 ° C., and 5 ° C. from the viewpoint of not reducing the adhesiveness. Particularly preferred is 10 ° C.

Next, (B) the electronic component and the circuit board are more firmly fixed on the insulating layer to be formed by the step of thermosetting the adhesive layer to form the insulating layer. The thermosetting is preferably performed at a curing temperature of 140 to 200 ° C, more preferably 150 to 180 ° C. The curing time is preferably 15 minutes to 2 hours, and more preferably 30 to 90 minutes.

Thereafter, (C) the electronic component or the electronic component and the circuit board are sealed with a sealing resin composition, an adhesive film, or a prepreg. For sealing, a method known to those skilled in the art can be employed. For example, a method of laminating an adhesive film having a thermosetting resin composition layer formed on a support with a laminator such as a vacuum laminator and thermosetting, a method of laminating a prepreg with a laminating press and thermosetting, etc.

  By using the adhesive film of the present invention, it is preferable to use a belt conveyor that can be accompanied by vibrations in the steps (A), (B), and (C). Further, by using the adhesive film of the present invention, the adhesive layer can be used as it is as a thermosetting layer. Further, by using the adhesive film of the present invention, it is possible to seal the electronic component with high positional accuracy. In addition, since the number of processes is reduced, it is possible to manufacture a component-embedded substrate at a lower cost.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, these do not restrict | limit this invention in any meaning. In the following description, “parts” means “parts by weight”.

Example 1
20 parts by weight of bisphenol type epoxy resin (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165), 8 parts by weight of epoxidized polybutadiene (“PB3600M” manufactured by Daicel Chemical Industries, Ltd., MEK solution having a nonvolatile content of 80% by weight) , 14 parts by weight of a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.), a novolac type phenol resin (“LA7054” manufactured by Dainippon Ink Co., Ltd.), a hydroxyl group equivalent of about 125, and a nonvolatile content of 60% by weight 25 parts by weight of methyl ethyl ketone (hereinafter abbreviated as MEK), 40 parts by weight of spherical silica ("SO-C4" manufactured by Admatechs), 6 parts of flame retardant filler ("HCA-HQ" manufactured by Sanko Co., Ltd.) Parts, 3 parts by weight of an organic filler (“AC3816N” manufactured by Ganz Kasei Co., Ltd.), butyral resin (“BL- manufactured by Sekisui Chemical Co., Ltd.) 10 parts by weight of toluene and methanol diluted to 1: 1 with a non-volatile content of 15%), and an acrylic ester copolymer resin (manufactured by Nagase ChemteX Corp. as “SG” -70L ", 0.85 parts by weight of a 1: 3% by weight MEK and toluene mixed solution of 12.5% by weight), 5 parts by weight of petroleum naphtha (" Ipsol 150 "manufactured by Pure Chemical Co., Ltd.), and Mixed with 21 parts by weight of MEK and uniformly dispersed with a high-speed rotary mixer, 25% by weight of a liquid epoxy resin in a thermosetting resin composition varnish (resin composition (non-volatile content), 14.2% by weight of a phenolic curing agent, Acrylic resin (0.10% by weight) was prepared. Next, the resin composition varnish was dried on a release-treated polyethylene terephthalate film (thickness 38 μm) (AL-5, manufactured by Lintec Corporation) (hereinafter abbreviated as 38 μm release PET). The composition layer (adhesive layer) was uniformly coated with a bar coater so that the thickness was 40 μm, and dried at 65 to 120 ° C. (average 100 ° C.) for 10 minutes (residual solvent amount in the resin composition layer: about 1% by weight). A polyethylene terephthalate film (thickness: 25 μm) (AL-5 manufactured by Lintec Co., Ltd.) (hereinafter abbreviated as 25 μm release PET) is bonded to the surface of the resin composition layer after drying. An adhesive film having a three-layer structure was prepared.

(Example 2)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 21 parts by weight, and an acrylic ester copolymer resin (“SG-70L manufactured by Nagase ChemteX Corporation)” was used. ”12.5 wt% MEK and toluene 1.3: 1 mixed solution) was changed to 17.2 parts by weight (25.0 wt% liquid epoxy resin in the resin composition (nonvolatile content), The adhesive film was obtained by the same method as Example 1 except a phenol type hardening | curing agent 13.9 weight% and acrylic resin 2 weight%.

(Example 3)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 22 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Was changed to 13 parts by weight, and further an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 44.5 parts by weight (Example 1) except that the liquid epoxy resin in the resin composition (nonvolatile content) was 25.0% by weight, the phenolic curing agent was 13.5% by weight, and the acrylic resin was 5% by weight. By the same method, an adhesive film was obtained.

Example 4
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 26 parts by weight, and a naphthalene type tetrafunctional epoxy (manufactured by Dainippon Ink Co., Ltd. “HP-4700”). )) Was changed to 9 parts by weight (Example 1) except that the liquid epoxy resin in the resin composition (nonvolatile content was 30% by weight, the phenolic curing agent was 14.2% by weight, and the acrylic resin was 0.1% by weight). By the same method, an adhesive film was obtained.

(Example 5)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 26 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Is changed to 8 parts by weight, and further an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 17.3 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile content) was 30% by weight, the phenolic curing agent was 13.9% by weight, and the acrylic resin was 2% by weight). By the method, an adhesive film was obtained.

(Example 6)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 27 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Is changed to 7 parts by weight, and further an acrylic ester copolymer resin ("SG-70L" manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 44.5 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile content) was 30% by weight, the phenolic curing agent was 13.5% by weight, and the acrylic resin was 5% by weight). By the method, an adhesive film was obtained.

(Example 7)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), Spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) was changed to 37 parts by weight, and acrylic acid ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Co., Ltd.), nonvolatile content 12 0.5 wt% MEK and toluene 1.3: 1 mixed solution) was changed to 0.83 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin 39 in the resin composition (nonvolatile content)). An adhesive film was obtained in the same manner as in Example 1 except for 0.8 wt%, phenolic curing agent 14.5 wt%, and acrylic resin 0.1 wt%.

(Example 8)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), And spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) is changed to 35 parts by weight. Further, an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corp.), nonvolatile content 12.5 wt% of MEK and toluene 1.3: 1 mixed solution) was changed to 16.4 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin 39 in the resin composition (nonvolatile content)). An adhesive film was obtained in the same manner as in Example 1 except for .8 wt%, phenolic curing agent 14.6 wt%, and acrylic resin 1.99 wt%.

Example 9
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), And spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) is changed to 32 parts by weight. Further, an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corp.), nonvolatile content 12.5 wt% of MEK and toluene 1.3: 1 mixed solution) was changed to 41 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin in resin composition (non-volatile content) 40 weights) %, Phenolic curing agent 14.6% by weight, acrylic resin 4.99% by weight), an adhesive film was obtained in the same manner as in Example 1.

(Comparative Example 1)
0.43 parts by weight of the acrylic ester copolymer resin of Example 1 (“SG-70L” manufactured by Nagase ChemteX Corp., 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) In the same manner as in Example 1, except that the liquid epoxy resin in the resin composition (nonvolatile content) was 25 wt%, the phenolic curing agent was 14.2 wt%, and the acrylic resin was 0.05 wt%. A film was obtained.

(Comparative Example 2)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 22 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Was changed to 13 parts by weight, and further an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 53.9 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile content) was 25% by weight, the phenolic curing agent was 13.4% by weight, and the acrylic resin was 6% by weight). By the method, an adhesive film was obtained.

(Comparative Example 3)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 26 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Was changed to 9 parts by weight, and further an acrylic ester copolymer resin ("SG-70L" manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 0.43 parts by weight (Example 1) except that the liquid epoxy resin in the resin composition (nonvolatile content was 30% by weight, the phenolic curing agent was 14.2% by weight, the acrylic resin was 0.05% by weight). By the same method, an adhesive film was obtained.

(Comparative Example 4)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 28 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Is changed to 7 parts by weight, and further an acrylic ester copolymer resin ("SG-70L" manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 54 parts by weight (by the same method as in Example 1 except that liquid epoxy resin 30% by weight, phenolic curing agent 13.3% by weight, acrylic resin 6% by weight in the resin composition (nonvolatile content)). An adhesive film was obtained.

(Comparative Example 5)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), And spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) was changed to 37 parts by weight. Further, acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation), non-volatile content 12.5 wt% MEK and toluene 1.3: 1 mixed solution) was changed to 0.4 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin in resin composition (non-volatile content)) The adhesive film was obtained by the same method as Example 1 except 40 weight%, phenolic hardening | curing agent 14.6 weight%, and acrylic resin 0.05 weight%.

(Comparative Example 6)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), Spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) is changed to 30 parts by weight, and acrylic acid ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corp.), nonvolatile content 12.5 wt% MEK and toluene 1.3: 1 mixed solution) was changed to 49.2 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin in resin composition (nonvolatile content)) The adhesive film was obtained by the same method as Example 1 except 40 weight%, the phenol type hardening | curing agent 14.6 weight%, and acrylic resin 6 weight%.

(Comparative Example 7)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 16 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ) Was changed to 19 parts by weight, and further an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation, a 1.3: 1 mixed solution of MEK and toluene having a nonvolatile content of 12.5% by weight) Was changed to 17.2 parts by weight (the liquid epoxy resin in the resin composition (nonvolatile content) was 20% by weight, the phenolic curing agent was 13.9% by weight, and the acrylic resin was 2% by weight). By the method, an adhesive film was obtained.

(Comparative Example 8)
The bisphenol type epoxy resin of Example 1 (“ZX1059” manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 165) was changed to 35 parts by weight, and a naphthalene type tetrafunctional epoxy (“HP-4700” manufactured by Dainippon Ink Co., Ltd.). ), And the spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) is changed to 23 parts by weight. Further, an acrylic ester copolymer resin (“SG-70L” manufactured by Nagase ChemteX Corporation), nonvolatile content 12.5 wt% MEK and toluene 1.3: 1 mixed solution) was changed to 14.5 parts by weight, and MEK was changed to 5 parts by weight (liquid epoxy resin in resin composition (non-volatile content)) The adhesive film was obtained by the same method as Example 1 except 45 weight%, the phenol type hardening | curing agent 16.6 weight%, and acrylic resin 2 weight%.

Using the adhesive films of Examples and Comparative Examples, Tg (glass transition temperature) measurement, insulation resistance value measurement, tack force measurement, 25 μm release PET (cover film) peelability evaluation, component fixability evaluation, The maximum component position deviation was measured.

<Tg (glass transition temperature) measurement>
The 25 μm release PET was peeled off from the adhesive films prepared in Examples and Comparative Examples, and a 200 mm × 200 mm polyimide film (Ube Industries (Ube Industries, Ltd., manufactured by Nichigo Morton Co., Ltd., “Morton-724”) was peeled off. Co., Ltd., “UPILEX50S”). Vacuum suction was performed for 30 seconds, and thereafter, pressure-resistant rubber was used under the condition of pressing at a pressure of 1 kg / cm ² for 30 seconds. The 38 μm release PET of the sample prepared above was peeled off, placed in a batch oven, and heated at 180 ° C. for 90 minutes to cure the resin composition layer (adhesive layer). The Tg of the cured product was measured with a thermal analyzer (“DMS6100” manufactured by Seiko Instruments Inc.).

<Measurement of insulation resistance value>
The 25 μm release PET of the adhesive film prepared in Examples and Comparative Examples was peeled off, and a TAB tape (L / S = 15 μm / 15 μm) with a batch type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., “Morton-724”) Laminated to Mitsui Kinzoku Co., Ltd., “AJ-C0002-30 / 40”). Lamination was performed under the conditions of vacuum suction for 30 seconds and then pressing with pressure-resistant rubber at a pressure of 1 kg / cm ² for 30 seconds. The 38 μm release PET of the sample prepared above was peeled off, and heated in a batch oven at 180 ° C. for 90 minutes to cure the resin composition layer (adhesive layer). The resistance value of the cured sample was measured and used as the initial resistance value. Subsequently, the sample was left in a HAST tester (“ETAC PM422” manufactured by Enomoto Kasei Co., Ltd.) at 130 ° C. and 85 wt% Rh for 100 hours, and then the resistance value (HAST resistance value) was measured.

<Measurement of tack force>
The 25 μm release PET of the adhesive films prepared in Examples and Comparative Examples was peeled off and attached to a jig dedicated to the apparatus, and the tack force on the resin composition layer (adhesive layer) side was measured. The apparatus uses a probe tack tester (TE6002 manufactured by Tester Sangyo Co., Ltd.), a φ5.05 mm stainless probe, and presses the probe against the adhesive layer surface of the adhesive film at 25 ° C., a load of 1 kgf / cm ² , and a contact speed of 5 mm / min. Hold for 10 seconds. Thereafter, peeling was performed at a peeling speed of 1 mm / min, and the load at that time was measured. This measurement was performed five times, and the average value of the three measured values excluding the maximum value and the minimum value was taken as the tack force. 0.25 N or less was determined as ND within the measurement error.

<Evaluation of 25 μm release PET (cover film) peelability>
The adhesive films produced in the examples and comparative examples were cut into about 10 cm square, and the 38 μm release PET side was fixed to a fixed stage (a stage on which the sheet can be fixed by decompression). Next, at room temperature (25 ° C.), only the 25 μm release PET at one corner of the four corners was picked by hand and pulled up about 5 cm vertically at an angle of 90 ° to the adhesive film. The case where it peeled between 25 micrometer mold release PET and an adhesive layer is (circle), it peeled between an adhesive layer and 38 micrometer mold release PET, or the case where an adhesive film did not peel between layers but peeled from the fixed stage was set as x.

<Evaluation of component fixability>
25 μm release PET was peeled off from the adhesive films prepared in Examples and Comparative Examples, and laminated on one side of a 26 mm × 76 mm slide glass by a batch type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., “Morton-724”). . Lamination was performed under the conditions of vacuum suction at room temperature (25 ° C.) for 30 seconds and then pressing with a pressure resistant rubber at a pressure of 1 kg / cm ² for 30 seconds.

The 38 μm release PET of the sample prepared above was peeled off, and three 1608 chip capacitors were placed on the adhesive film with tweezers. Next, vacuum suction is performed for 30 seconds with a batch type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., “Morton-724”), and then 1 kg / cm for 30 seconds at room temperature (25 ° C.) using a pressure-resistant rubber. ^The capacitor was fixed on the adhesive film under the condition of pressing at a pressure of ² .

  The capacitor fixed on the adhesive film was peeled in the vertical direction with tweezers, and the trace of the capacitor left on the surface of the adhesive layer was observed. As shown in FIG. 1, if there was a trace on the surface of the adhesive layer in accordance with the shape of the capacitor, the symbol “◯” was given.

<Measurement of maximum component displacement>
A slide glass in which the component was fixed by the same method as the evaluation of the component fixing property was prepared, and the amount of misalignment immediately after the capacitor was fixed and after curing was measured in the manner shown in FIG.

Measurement of the position of the parts after fixing the parts is performed by determining the origins A and B as shown in FIG. 2 with a length measuring machine (trade name, MF-UD2017B, manufactured by Mitutoyo Corporation). The distance (W, X, Y, Z) was measured from the (corner).

The sample was cured by placing the sample in a batch oven so that the resin was vertical and heating at 180 ° C. for 30 minutes to cure the resin composition layer (adhesive layer).

The positions of the parts after curing were measured by measuring the distances (W ′, X ′, Y ′, Z ′) from the origins A and B determined before curing and the corners (four corners) of the parts after curing. (| W'-W |, | X'-X |, | Y'-Y |, | Z'-Z |) are component displacement amounts, and the maximum of these four numerical values is the maximum component displacement amount. did. Those in which the part was peeled off from the adhesive layer during curing were determined as ND.

  From Table 1, it can be seen that the adhesive films of the examples have good component fixing properties, a small maximum component positional deviation amount, and good peelability of the cover film (25 μm release PET). On the other hand, when the tack force is low, the adhesive film of the comparative example is inferior in component fixing property, so the maximum component position shift is large, and when the tack force is too strong, the peelability of the cover film (25 μm release PET) is lowered Yes.

Claims (11)

A thermosetting resin composition used for fixing components and forming an insulating layer on a component-embedded substrate, wherein when the nonvolatile content of the thermosetting resin composition is 100% by weight, a liquid epoxy resin at 25 ° C. is 25 to 25%. 40% by weight, 0.1 to 5% by weight of an acrylic resin containing one or more groups selected from an epoxy group, a hydroxyl group, and a carboxyl group, 5 to 30% by weight of a phenolic curing agent, and 20 of an inorganic filler Thermosetting resin composition containing -70% by weight. The thermosetting resin composition of claim 1 Symbol placement acrylic resin is an acrylic acid ester copolymer. The thermosetting resin composition according to claim 1 or 2, wherein the acrylic resin is an acrylic acid ester copolymer containing methyl acrylate, butyl acrylate, and acrylonitrile. The thermosetting resin composition according to any one of claims 1 to 3 , wherein the acrylic resin has a weight average molecular weight of 400,000 to 1,200,000. The thermosetting resin composition according to any one of claims 1 to 4 , wherein the acrylic resin contains a hydroxyl group and a carboxyl group. The adhesive film used for component fixation and insulation layer formation of a component built-in board which has an adhesive layer formed with the thermosetting resin composition of any one of Claims 1-5 on a support body. The adhesive film according to claim 6, wherein the adhesive layer has a thickness of 5 to 100 μm. The adhesive film according to claim 6 or 7 , wherein the support is a plastic film. The adhesive film according to any one of claims 6 to 8 , wherein a surface of the support on the adhesive layer side is subjected to a release treatment. A method for manufacturing a component-embedded substrate, comprising: a step of fixing an electronic component on the adhesive layer of the adhesive film according to any one of claims 6 to 9 ; and a step of thermally curing the adhesive layer to form an insulating layer. Component-embedded board obtained by using the adhesive film according to any one of claims 6-9.

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