WO2011148620A1 - シート状樹脂組成物、該シート状樹脂組成物を用いた回路部品、電子部品の封止方法、接続方法、および固定方法、ならびに複合シート、該複合シートを用いた電子部品、および電子機器、複合シートの製造方法 - Google Patents
シート状樹脂組成物、該シート状樹脂組成物を用いた回路部品、電子部品の封止方法、接続方法、および固定方法、ならびに複合シート、該複合シートを用いた電子部品、および電子機器、複合シートの製造方法 Download PDFInfo
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- WO2011148620A1 WO2011148620A1 PCT/JP2011/002891 JP2011002891W WO2011148620A1 WO 2011148620 A1 WO2011148620 A1 WO 2011148620A1 JP 2011002891 W JP2011002891 W JP 2011002891W WO 2011148620 A1 WO2011148620 A1 WO 2011148620A1
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- RLPUGSHDOKGQIT-UHFFFAOYSA-N C=C(C1)C2=CC2CC1(N)O Chemical compound C=C(C1)C2=CC2CC1(N)O RLPUGSHDOKGQIT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a sheet-shaped resin composition, a circuit component using the sheet-shaped resin composition, an electronic component sealing method, a connection method, and a fixing method, a composite sheet, an electronic component using the composite sheet, and
- the present invention relates to a method for manufacturing electronic devices and composite sheets.
- an adhesive sheet used in the field of electronic components one made of a thermosetting resin composition such as an epoxy resin composition is known (for example, see Patent Document 1).
- the conventional adhesive sheet is not excellent in handling property and strength, and the embedding property of the adhesive sheet in the adhesive region is not excellent. Further, when processing an electronic component to which a conventional adhesive sheet is bonded, the adhesive sheet may be peeled off, and an adhesive sheet having a high adhesive force is required.
- a prepreg composed of a fiber base material and a thermosetting resin composition, for example, a glass epoxy prepreg is also used (for example, see Patent Document 2).
- a prepreg has relatively good handling properties and strength, it is not excellent in embedding property in the adhesive region, and the usable electronic parts are limited.
- the manufacture of a prepreg generally requires a dedicated large-sized coating machine, and further requires an organic solvent or the like.
- the thin plate-like resin sheet is adhered to the semiconductor and the substrate surface by providing viscosity and adhesive force, and the softened thin plate-like resin sheet is cured after the heat treatment to seal the semiconductor.
- a method is disclosed (see Patent Documents 3 to 5).
- Patent Documents 3 to 5 are techniques for sealing an electronic element using a sheet-like sealing resin, but it is described that it is preferable to use an epoxy resin as a thermosetting resin for a sealing material.
- an epoxy resin as a thermosetting resin for a sealing material.
- the cured product of the sealing resin is likely to be warped or twisted.
- the melt viscosity of the sealing resin is high, voids due to poor filling of the resin in the electronic element details are caused. The possibility of occurrence is high.
- JP 2002-60720 A Japanese Patent Laid-Open No. 2-102281 JP 2003-249510 A JP-A-10-125825 JP 2003-249510 A
- the present invention can be manufactured without the need for a large coating equipment like a conventional adhesive sheet, and can be manufactured without using an organic solvent, and there is little warping or twisting of the cured product, and sealing of circuit components. It aims at providing the sheet-like resin composition which can perform etc. easily.
- Another object of the present invention is to provide a circuit component using the sheet-shaped resin composition.
- an object of the present invention is to provide a sealing method, a connection method, and a fixing method for an electronic component using the sheet-shaped resin composition.
- Another object of the present invention is to provide a composite sheet using the sheet-shaped resin composition, an electronic component using the composite sheet, an electronic device, and a method for producing the composite sheet.
- the sheet-shaped resin composition of the present invention contains (A) a liquid bisphenol-type epoxy resin, (B) a solid polyfunctional epoxy resin having a softening point of 70 ° C. or less, and (C) a curing agent for epoxy resin as essential components.
- the circuit component of the present invention is characterized by being sealed or adhered with the sheet-shaped resin composition of the present invention.
- the electronic component sealing method of the present invention is a method for sealing an electronic component in which an electronic component mounted on a substrate is covered with the sheet-shaped resin composition of the present invention and is heat-cured, and the sheet-shaped resin composition The electronic component is covered with an object, and the periphery of the contact portion between the electronic component and the substrate is sealed to form a gap between the electronic component and the substrate.
- the electronic component connecting method includes a substrate having a first electrode for connection and an electronic component having a second electrode for connection via the first electrode and the second electrode.
- An electrical connection method comprising the step of electrically connecting the electronic component to the substrate using the sheet-shaped resin composition of the present invention.
- the electronic component fixing method of the present invention is a method of fixing an electronic component to a substrate or a casing, and is in contact with the substrate or the casing and the electronic component, and is a sheet-shaped resin composition of the present invention. And the substrate or the housing and the electronic component are fixed with the sheet-shaped resin composition.
- the composite sheet of the present invention has a resin layer having the sheet-shaped resin composition of the present invention and a fiber base layer having a fiber base material formed in close contact with at least one main surface of the resin layer.
- the electronic component of the present invention includes an electronic component element body and the composite sheet of the present invention that is disposed on at least a part of the surface of the electronic component element body and insulates the surface.
- the electronic device of the present invention includes an electronic component and the composite sheet of the present invention that seals the electronic component.
- the method for producing a composite sheet of the present invention comprises a step of kneading the components of the thermosetting resin composition at a temperature of 50 to 110 ° C. to obtain a kneaded product, and supplying the kneaded product to one side of a fiber substrate. Or after supplying the kneaded material between a pair of fiber base materials, pressing the kneaded material and the fiber base material to form a composite sheet integrally to obtain a composite sheet. And
- Sectional drawing which shows schematic structure of 1st Embodiment of a composite sheet.
- Sectional drawing which shows schematic structure of 2nd Embodiment of a composite sheet.
- Sectional drawing which shows schematic structure of the conventional prepreg.
- the cross-sectional schematic diagram which shows an example which showed the state which sealed the gap periphery formed between the board
- Process drawing for demonstrating the connection method of an electronic component Process drawing for demonstrating the connection method of an electronic component.
- Process drawing for demonstrating the connection method of an electronic component Process drawing for demonstrating the connection method of an electronic component.
- Process drawing for demonstrating the connection method of an electronic component Process drawing for demonstrating the connection method of an electronic component.
- the front view for demonstrating 2nd Embodiment of the fixing method of an electronic component The side view for demonstrating 2nd Embodiment of the fixing method of an electronic component.
- the sheet-shaped resin composition of the present invention contains (A) a liquid bisphenol-type epoxy resin, (B) a solid polyfunctional epoxy resin having a softening point of 70 ° C. or less, and (C) a curing agent for epoxy resin as essential components.
- the sheet-like resin composition of the present invention preferably contains (D) an inorganic filler in an amount of 10 to 80% by mass based on the total amount of the composition, and (E) preferably contains a flame retardant.
- a liquid bisphenol type epoxy resin is used as the component (A).
- the liquid bisphenol-type epoxy resin is not particularly limited as long as it is a liquid bisphenol-type compound having two or more epoxy groups in one molecule.
- bisphenol A type and bisphenol F type are preferable.
- liquid bisphenol A type epoxy resin is preferably used. Specific examples thereof include “R140P” (epoxy equivalent 188) manufactured by Mitsui Chemicals, “DER383” manufactured by Dow Chemical, and Japan Epoxy Resin. “Epicoat # 807” (epoxy equivalent 170) or the like is used.
- These liquid bisphenol type epoxy resins may be used alone or in combination of two or more.
- the liquid bisphenol type epoxy resin refers to a bisphenol type epoxy resin that exhibits a liquid state at 25 ° C.
- a solid polyfunctional epoxy resin having a softening point of 70 ° C. or lower is used as the component (B).
- the solid polyfunctional epoxy resin having a softening point of 70 ° C. or lower include a mixture of a biphenyl skeleton-containing aralkyl epoxy resin represented by the following formula (1).
- m represents an integer of 1 to 4.
- n an integer of 1 to 10.
- the softening point of these solid polyfunctional epoxy resins is a value measured by the following method. ⁇ Measurement of softening point> Based on JISK2207, a sample is filled in a specified ring, supported horizontally in a water bath or a glycerin bath, a specified sphere is placed in the center of the sample, and the bath temperature is increased at a rate of 5 ° C. per minute. It is the temperature read when the encased sample contacts the bottom plate of the platform.
- NC3000 softening point 57 ° C.
- NC3000H softening point 70 ° C.
- the mass ratio (A) / (B) is required to be in the range of 10/90 to 30/70. If the liquid epoxy resin is less than the above range or the softening point of the solid epoxy resin exceeds 70 ° C., the sheet is unfavorably cracked or chipped. Moreover, when there are more liquid epoxy resins than the said range, or the softening point of a solid epoxy resin is too low, it will become difficult to form a sheet
- an epoxy resin curing agent is used as the component (C).
- the epoxy resin curing agent is not particularly limited, and can be arbitrarily selected from those conventionally used as a curing agent for epoxy resins.
- amine-based, phenol-based, and acid anhydrides can be used. Examples include physical systems.
- Preferable examples of the amine curing agent include dicyandiamide, aromatic diamines such as m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and m-xylylenediamine.
- Preferred examples of the system curing agent include phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins, and triazine-modified phenol novolak resins.
- the acid anhydride curing agent include alicyclic acid anhydrides such as methylhexahydrophthalic anhydride, aromatic acid anhydrides such as phthalic anhydride, and aliphatic dibasic acid anhydrides (PAPA). Examples thereof include halogen acid anhydrides such as aliphatic acid anhydrides and chlorendic acid anhydrides.
- One of these curing agents may be used alone, or two or more thereof may be used in combination.
- the amount of the epoxy resin curing agent used is usually 0.5 to 1.5 equivalents in terms of the equivalent ratio of the components (A) and (B) to the epoxy resin from the viewpoint of balance between curability and cured resin physical properties.
- the ratio is selected within a range of preferably about 0.7 to 1.3 equivalent ratio.
- a curing accelerator for epoxy resin in the sheet-like resin composition of the present invention, can be contained as necessary within the range where the effects of the present invention are not impaired.
- a hardening accelerator for epoxy resins From the things conventionally used as a hardening accelerator of an epoxy resin, arbitrary things can be selected suitably and can be used.
- urea aromatic dimethylurea, aliphatic dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), 3- (3-chloro-4-methylphenyl) -1,1 -Ureas such as dimethylurea, 2,4-bis (3,3-dimethylureido) toluene, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethylimidazole Imidazole compounds such as 2-isopropylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4,6-tris (dimethylaminomethylphenol, boron trifluoride amine complex, triphenylphosphine, etc.) Even if these hardening accelerators are used individually by 1 type, they can carry out.
- DCMU 3- (3,4-dichlorophenyl)
- the epoxy resin curing accelerator may be used in combination from the viewpoints of the balance between curing acceleration and physical properties of the cured resin, and the like. It is usually selected in the range of about 0.1 to 10 parts by weight, preferably 0.4 to 5 parts by weight with respect to 100 parts by weight of the resin.
- an inorganic filler in the sheet-shaped resin composition of this invention, can be contained as (D) component.
- the inorganic filler is not particularly limited.
- Commonly used materials such as metal hydrates such as magnesium oxide; titanium oxide; carbon black can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the mass average particle diameter of the inorganic filler is preferably in the range of 4 to 30 ⁇ m from the viewpoint of workability during production and filling efficiency.
- the mass average particle diameter is a value measured by a laser diffraction scattering method (for example, manufactured by Shimadzu Corporation, apparatus name: SALD-3100).
- the inorganic filler spherical silica is preferable, for example, “FB-959 (mass average particle diameter: 25 ⁇ m)” manufactured by Denki Kagaku Kogyo Co., Ltd. is suitable.
- the content of the inorganic filler is preferably 10 to 80% by mass based on the total amount of the resin composition.
- the content is preferably 50 to 80% by mass.
- the fiber base material is not provided, it is effective that the cured product is warped or twisted when the electronic component is sealed using the sheet-shaped resin composition by setting the content to 50% by mass or more. Can be suppressed.
- a coupling agent in the sheet-shaped resin composition of this invention, can be contained as needed from a viewpoint of a filling property.
- the coupling agent include silane-based, titanate-based, and aluminum-based, among which silane-based coupling agents are preferable.
- silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - (2-aminoethylaminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxy.
- An aminosilane compound such as aminoethyl) - ⁇ -aminopropyltriethoxysilane is preferably used, and the content of the silane coupling agent is about 0.03 to 5.0% by mass based on the total amount of the resin composition, preferably 0.1 to 2.5% by mass.
- a flame retardant as the component (E).
- a phosphorus compound for example, a phosphorus compound, a metal hydrate, etc. can be used.
- phosphorus compounds include (a) phosphazene compounds, (b) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, derivatives thereof, (c) phosphate ester compounds, (d) Examples include phosphoric ester amides.
- phosphazene compound of the above (a) a phosphazene compound which is substantially free of halogen and has a melting point of 80 ° C. or higher from the viewpoint of heat resistance, moisture resistance, flame retardancy, chemical resistance and the like.
- a phosphazene compound which is substantially free of halogen and has a melting point of 80 ° C. or higher from the viewpoint of heat resistance, moisture resistance, flame retardancy, chemical resistance and the like.
- Specific examples include cyclophosphazene oligomers represented by the following general formula (3).
- R 1 and R 2 each independently represents a hydrogen atom or an organic group containing no halogen, and k represents an integer of 3 to 10.
- examples of the organic group containing no halogen among R 1 and R 2 include an alkoxyl group having 1 to 10 carbon atoms, a phenoxy group, an amino group, and an allyl group. Examples of such phosphazene compounds include “SPB-100” manufactured by Otsuka Chemical Co., Ltd.
- Examples of the derivative include (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide represented by the formula (5).
- the compound represented by the above formula (4) is “SANKO-HCA” (trade name, manufactured by Sanko Co., Ltd.), and the compound represented by the above formula (5) is “SANKO HCA-HQ”. "[Product name, manufactured by Sanko Co., Ltd.]. Further, as a derivative, SANKO M-Acid-AH (trade name, manufactured by Sanko Co., Ltd.) is commercially available.
- Examples of the phosphoric acid ester compound of (c) above include esters using trivalent phosphates such as triphenyl phosphate and cresyl diphenyl phosphate, or polyhydric phenols such as resorcin, and monohydric phenols such as phenol and cresol. And a reactive phosphate ester “RDP” [trade name, manufactured by Ajinomoto Fine-Techno Co., Ltd.] in which at least one hydroxyl group of the polyhydric phenol is left as a reactive free radical.
- the condensed phosphate ester “PX-200” [manufactured by Daihachi Chemical Industry Co., Ltd., trade name] obtained by esterifying a free hydroxyl group in a phosphate ester, and the like.
- the phosphoric acid ester amide of (d) includes a bonding mode of phosphoric acid ester and phosphoric acid amide, and Japanese Patent Application Laid-Open Nos. 2001-139823, 2000-154277, and 10-175985.
- the phosphoric ester amides described in JP-A-8-59888 and JP-A-63-235363 can be used.
- Preferred phosphoric ester amides include condensed phosphoric ester amides.
- Examples of such phosphoric ester amides include N- (diaryloxyphosphinyl) -substituted alkylene amines, bis to tetrakis [(diaryloxyphosphinyl) amino] -substituted aromatic compounds, N- (cyclic alkyls).
- Rangeoxyphosphinyl substituted alkyleneamines bis to tetrakis [(cyclic alkylenedioxyphosphinyl) amino] substituted aromatic compounds, N- (cyclic arylenedioxyphosphinyl) substituted alkyleneamines, bis to Tetrakis [(cyclic arylenedioxyphosphinyl) amino] -substituted aromatic compounds, 3,9-bis (N-substituted amino) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5 ] ] -Undecane-3,9-dioxides and the like.
- Phosphoric ester amide is available under the trade name “Phosphate ester amide flame retardant SP series (eg, SP-601, SP-670, SP-703, SP-720, etc.)” (manufactured by Shikoku Kasei Kogyo Co., Ltd.) it can.
- aluminum hydroxide or magnesium hydroxide is used, and as the aluminum hydroxide compound, for example, “H42M” manufactured by Showa Denko KK is preferably used.
- the flame retardant may be used alone or in combination of two or more.
- the content is preferably 5 to 50% by mass, more preferably based on the total amount of the resin composition from the viewpoint of the balance between flame retardancy and other physical properties, although it depends on the type of flame retardant. It is 10 to 40% by mass, more preferably 10 to 35% by mass.
- Stress reducing agents such as thermoplastic resins such as styrene copolymers; n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl ether, dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol Viscosity-reducing diluents such as: nonionic surfactants, fluorosurfactants, wetting improvers such as silicone oil, antifoaming agents, and the like can be appropriately contained.
- the resin composition thus obtained is cooled and then pressed with a molding machine under conditions of a temperature of about 50 to 100 ° C. and a pressure of 0.5 to 1.5 MPa to obtain the sheet-shaped resin composition of the present invention. Make it.
- the thickness of the sheet-shaped resin composition is usually about 0.1 to 2.0 mm, preferably 0.1 to 1.0 mm, depending on the application.
- Such a sheet-shaped resin composition has good handleability and moldability, and has little warpage and twist of the cured product.
- an electronic component can be easily sealed by laminating on an electronic element and heating, so that the sealing process is simplified and the manufacturing is easily performed. Can do.
- it can seal without obstructing the function of the electronic element which has an electronic function part, without requiring large equipment, manufacturing cost can be reduced.
- the sheet-like resin composition of the present invention can be formed into a composite sheet by providing a fiber substrate on at least one main surface thereof.
- FIG. 1 is a cross-sectional view showing a schematic configuration of the first embodiment of the composite sheet
- FIG. 2 is a cross-sectional view showing a schematic configuration of the second embodiment of the composite sheet
- FIG. 3 is sectional drawing which shows schematic structure of the conventional prepreg.
- the composite sheet 1 includes a fiber base layer 3 having a fiber base on one or both main surfaces of a resin layer 2 having a sheet-like resin composition. Are closely formed.
- the release film 4 which consists of a polyethylene terephthalate etc. is provided in both the main surfaces of the composite sheet 1, for example. The release film 4 is peeled off at the time of use, and the composite sheet 1 is used by being bonded to an electronic component element body or the like in order to manufacture an electronic component in the state shown in FIG. 1B or 2B, for example. .
- the fiber base layer 3 is formed in close contact with at least one main surface of the resin layer 2. According to such a composite sheet 1, since the fiber base material layer 3 is formed on the main surface, it is excellent in handling properties and strength, and without requiring a large facility for the fiber base material, Moreover, it can manufacture without passing through a complicated process. Moreover, when it adheres to an electronic component element
- FIG. 3 is a cross-sectional view showing a conventional prepreg 50.
- the conventional prepreg 50 has a fiber base material 51, and the fiber base material 51 is impregnated with a thermosetting resin composition 52.
- the conventional prepreg 50 requires a large facility such as an impregnation tank in order to impregnate the fiber base material 51 with the thermosetting resin composition 52, and also requires an organic solvent and the like.
- the fiber base material layer 3 is adhered to the main surface of the resin layer 2 so that the fiber base material is attached to the surface of the sheet-shaped resin composition as described later.
- It can be manufactured by supplying and pressing, or by supplying and pressing a melt composed of a constituent material of the sheet-like resin composition on the surface of the fiber base material, and requires a large-scale equipment having a fiber base material It can manufacture without passing through a complicated process.
- the ratio of the resin component in the composite sheet 1 is preferably 65 to 93% by volume.
- the adhesive force of the composite sheet 1 can be sufficient, and the resin bleeding from the composite sheet 1 and the warp at the time of curing of the composite sheet 1 can be suppressed. Peelability and crack resistance can also be improved.
- the resin content is less than 65% by volume, the resin content is small, so that the embeddability of the composite sheet 1 in an adhesive region where sealing or insulation is performed, for example, a recess between electrodes, is insufficient. There is a risk that peeling or cracking at the time of cutting, particularly during cutting, cannot be sufficiently suppressed.
- the proportion of the resin component exceeds 93% by volume, the amount of resin adhering to the surface of the fiber base material is large, and the outflow of the resin is increased, so that there is a greater amount of bleeding outside the adhesion region, and the composite sheet 1 Cracks are likely to occur.
- the ratio of the resin component means a ratio of the volume of the resin composition in the entire composite sheet 1.
- a resin composition means the resin composition which is a structural component of a sheet-like resin composition.
- the ratio [volume%] of the resin can be obtained from the following formula.
- Resin content [volume%] ⁇ (Thickness of composite sheet [ ⁇ m] ⁇ Mass of fiber substrate [g / m 2 ] / Specific gravity of fiber [g / cm 3 ]) / Composite sheet thickness [ ⁇ m] ⁇ ⁇ 100
- the composite sheet 1 has one glass cloth as a fiber substrate, the thickness of the composite sheet 1 is 160 [ ⁇ m], the mass of the glass cloth is 48 [g / m 2 ], and the specific gravity of the glass Is 2.54 [g / cm 3 ], it is determined as follows.
- the thickness of the resin layer 2 is preferably 30 to 500 ⁇ m. When the thickness is less than 30 ⁇ m, for example, the handling property of the sheet-like resin composition used for forming the resin layer 2 alone is not excellent. Further, when an electronic component is manufactured by adhering the composite sheet 1 to an electronic component element body, the composite sheet 1 may be peeled from the electronic component when the electronic component is processed, particularly at the time of cutting. On the other hand, when the thickness exceeds 500 ⁇ m, cracks are likely to occur in the resin layer 2 and it is difficult to reduce the thickness of the electronic component.
- the thickness of the fiber base layer 3 is preferably 30 to 180 ⁇ m. When the thickness is less than 30 ⁇ m, the handleability of a single fiber substrate used for forming the fiber substrate layer 3 is not excellent. On the other hand, when it exceeds 180 ⁇ m, it is difficult to impregnate the entire fiber base material with resin.
- the thickness of the composite sheet 1 can be appropriately selected depending on the thickness of the resin layer 2 and the fiber base layer 3 and the use of the composite sheet 1, but is preferably 100 to 500 ⁇ m.
- the plasticity of the resin composition constituting the resin layer 2 at normal temperature (25 ° C.) is preferably 60 to 90.
- the plasticity is less than 60, the flow-out of the resin composition cannot be suppressed, the bleeding to the outside of the adhesion area increases, leading to poor appearance and contamination around the adhesion area.
- the plasticity exceeds 90, voids in the adhesion region increase, which may cause poor adhesion or poor filling.
- the plasticity in this specification is measured by a parallel plate plasticity meter based on a method based on JIS K6249.
- the fiber base layer 3 is formed in close contact with at least one main surface of the resin layer 2.
- the fiber base material constituting the fiber base layer 3 is preferably impregnated with a resin composition that is a constituent of the sheet-like resin composition constituting the resin layer 2 in at least a part of the voids, and in particular.
- the entire void is preferably impregnated with the thermosetting resin composition constituting the resin layer 2. That is, the fiber base material constituting the fiber base layer 3 is preferably arranged so as to be embedded in the surface portion of the resin layer 2.
- the fiber substrate may be a woven fabric or a non-woven fabric, and can be any fiber substrate. Moreover, it does not specifically limit about the constituent material, It can be set as glass fiber, aromatic polyamide fiber, a cellulose fiber, a polyester fiber, etc., These can be used individually or in mixture of 2 or more types.
- the glass substrate is preferably glass cloth or glass paper, and glass cloth is particularly preferable.
- the type of glass cloth is not particularly limited, but plain woven E glass cloth defined in IPC-EG-140 is preferable, and 30-180 ⁇ m such as 1078 type, 1080 type, 1037 type, 1084 type, 2110 type, 7628 type. Thickness is particularly preferred.
- the composite sheet 1 includes, for example, a step of kneading the components of the sheet-shaped resin composition at a temperature of 50 to 110 ° C. to obtain a kneaded product, supplying the kneaded product to one side of a fiber base material, or After supplying between a pair of fiber base materials, it can manufacture through the process of shape
- the composite sheet 1 in which the fiber base layer 3 is formed in close contact with the main surface of the resin layer 2 can be easily manufactured.
- the composite sheet 1 which has the release film 4 can be manufactured by supplying the release film 4 to these one side or both sides with a kneaded material and a fiber base material.
- the supply form of the kneaded product is not particularly limited, and can be a lump, sheet, or melt.
- the kneaded product and the fiber base material may be molded by a batch method, or continuously by using a hot press or a pressure roll.
- the composite sheet 1 is manufactured by supplying the kneaded material to one side of a fiber base material, or supplying the kneaded material between a pair of fiber base materials and then passing them between a pair of pressure rolls.
- a method in which the sheet is integrally formed is preferable.
- the pair of pressure rolls is preferably capable of adjusting the gap size, for example, a diameter of 20 to 60 mm and a gap size of about 5 to 500 ⁇ m are preferable.
- FIG. 4 is a schematic configuration diagram showing a first embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1.
- the manufacturing apparatus 10 includes, for example, a supply device 11 that supplies the resin composition 5 that becomes the resin layer 2 in a molten form from a lump, and a base that supplies the fiber base 6 while the fiber base 6 is wound.
- the material roll 12, the release film 4 is wound and a pair of release film rolls 13 for supplying the release film 4, and the pair of guide rolls for guiding the fiber substrate 6 and the release film 4. 14.
- a pair of pressure rolls 15 for pressing the fiber base 6 and the release film 4 are included.
- the supply device 11, the base material roll 12, and the release film roll 13 are arranged corresponding to the laminated structure of the composite sheet 1.
- the fiber base 6 and the one release film 4 are wound around a part of the outer periphery of one guide roll 14 (the right guide roll 14) of the pair of guide rolls 14.
- the other release film 4 is disposed around a part of the outer periphery of the other guide roll 14.
- a pair of release films 4 is continuously supplied from a pair of release film rolls 13 between a pair of guide rolls 14, and a substrate roll 12 is provided therebetween.
- the fiber base 6 is continuously supplied from Further, between the fiber base 6 and the one release film 4, the resin composition 5 that has been melted from a lump is supplied from the supply device 11. Further, these supplies are passed between a pair of pressure rolls 15.
- the fiber base material 6 was embed
- the composite sheet 1 can be manufactured. In particular, it is possible to adjust the gap size of the pair of pressure rolls 15, and by passing the constituent material of the composite sheet 1 through these gaps, the degree of embedding of the fiber base material 6 in the resin composition 5 or The degree of impregnation of the resin composition 5 into the fiber base 6 can be adjusted, and the overall thickness of the composite sheet 1 can also be adjusted.
- FIG. 5 is a schematic configuration diagram showing a second embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1.
- a base material roll 12 is further added to the manufacturing apparatus 10 shown in FIG. 4, and a pair of base material rolls 12 is provided.
- the pair of base material rolls 12 are arranged so that the respective fiber base materials 6 are wound around a part of the outer periphery of the pair of guide rolls 14.
- a pair of release films 4 is continuously supplied from a pair of release film rolls 13 between a pair of guide rolls 14, and a pair of base materials is interposed therebetween.
- a pair of fiber base materials 6 are continuously supplied from the roll 12 for use.
- FIG. 6 is a schematic configuration diagram showing a third embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1.
- the manufacturing apparatus 10 has the same basic configuration as the manufacturing apparatus 10 shown in FIG. 4, but instead of the supply apparatus 11, a single sheet-shaped resin composition 7 is wound and the sheet-shaped resin composition 7 is wound. The point which has the roll 16 for sheets which supplies is different.
- the composite sheet 1 may be manufactured by supplying the sheet-shaped resin composition 7 directly.
- FIG. 7 is a schematic configuration diagram showing a fourth embodiment showing a manufacturing apparatus and a manufacturing method of the composite sheet 1.
- a base material roll 12 is further added to the manufacturing apparatus 10 shown in FIG. 6, and a pair of base material rolls 12 is provided.
- the composite sheet 1 which has a pair of fiber base material 6 in both the main surfaces of the resin layer 2 can be manufactured.
- the composite sheet 1 is formed by laminating the constituent materials in a predetermined order, and using a molding machine at about 50 to 100 ° C. It may be produced by pressing under conditions of temperature and pressure of 0.5 to 1.5 MPa.
- the sheet-shaped resin composition 7 and the composite sheet 1 of the present invention will be specifically described.
- the sheet-shaped resin composition 7 will be described as an example, but the composite sheet 1 can be applied by the same method.
- a circuit board on which electronic components such as a semiconductor, a chip resistor, a diode, and a capacitor are mounted is covered with the sheet-like resin composition 7 of the present invention and thermally cured, so that the surface is easily sealed and covered. It can be.
- sealing and coating operations can be performed as follows.
- the sheet is heated to a temperature of about 80 to 200 ° C., preferably 100 to 150 ° C.
- the fluidized resin composition 7 is fluidized so that there are no unfilled parts around the electronic component
- the fluidized resin is further heated at a temperature of 100 to 180 ° C. for about 0.5 to 2 hours.
- the circuit component of the present invention can be obtained by a simple operation of curing. In the circuit component obtained in this way, the cured product is less likely to warp or twist, and the occurrence of unfilled portions around the electronic component is also less.
- Sealing of an electronic component having a hollow portion such as a SAW device can be performed simply and with a high yield by the sheet-shaped resin composition 7 of the present invention.
- an electronic component mounted on a substrate is coated with a sheet-shaped resin composition 7 and heated to a temperature of about 80 to 150 ° C., preferably 100 to 150 ° C., to flow the sheet-shaped resin composition 7
- the sheet-like resin composition 7 that has been fluidized by heating for about 0.5 to 2 hours at a temperature of about 100 to 180 ° C. is cured to be formed between the electronic component and the substrate.
- the periphery of the gap can be sealed or filled.
- FIGS. 8 (a) to 8 (e) An example of the schematic cross-sectional view is shown in FIGS. 8 (a) to 8 (e).
- 7 is a sheet-shaped resin composition
- 31 and 32 are electronic components (31 is a chip-type device, 32 is a bump, for example)
- 33 is a substrate.
- sealing means a state in which a gap formed between an electronic component and a substrate is maintained as shown in FIGS. 8A, 8C, or 8D
- filling FIG. A state in which the resin composition is filled in the same gap as in (b) and (e) and the gap is eliminated.
- the gap formed between the electronic component and the substrate can be filled by adjusting the heating temperature or the like, or the gap is formed between the electronic component and the substrate.
- sealing can be performed in a state where the electronic function unit does not contact the resin composition or the substrate.
- sensor elements such as piezoelectric elements, such as a crystal oscillator, a circuit element which forms a high frequency circuit, a light receiving element, etc. are mentioned, for example.
- a substrate 41 having a land portion 42 as a first electrode is prepared.
- the substrate 41 can be composed of, for example, a glass substrate, a ceramic substrate, a resin substrate (BT, PET, etc.), a glass epoxy substrate (FR-4, FR-5), a metal plate whose surface is coated with a metal oxide, or the like. .
- a conductive paste 43 is applied on the land portion 42 of the substrate 41.
- a resin containing a resin as a base resin and added with conductive particles can be used.
- the sheet-like resin composition 7 is disposed in the land portion 42 and the conductive paste 43 non-formation region in the substrate 41.
- an electronic component 44 is prepared.
- An electrode pad 45 as a second electrode is formed on the lower surface of the electronic component 44.
- Metal electrode bumps 46 are formed on the electrode pads 45 by electrolytic plating via a barrier metal film such as Cr—Cu or Ti—Pd.
- the metal electrode bump 46 can be made of, for example, Au, Ag, or Cu.
- a solder material can be supplied and reflowed to form a solder bump.
- the conductive paste 43 is provided on the land portion 42 of the substrate 41, but may be provided on the metal electrode bump 46.
- the electronic component 44 is placed on the substrate 41 so that the positions of the metal electrode bumps 46 of the electronic component 44 and the conductive paste 43 of the substrate 41 coincide with each other, and the pressure of 80 to 150 is applied under a pressure of 0 to 0.1 Pa. Heat to a temperature of about °C. Then, after the conductive paste 43 and the sheet-shaped resin composition 7 are melted simultaneously, the conductive paste 43 and the sheet-shaped resin composition 7 are collectively cured by cooling. As a result, as shown in FIG. 13, the substrate 41 and the electronic component 44 are electrically connected by the electrical connection body 47 that is a cured product such as the conductive paste 43, and the sheet-shaped resin composition 7. It is mechanically connected by the cured product 8.
- the conductive paste 43 and the sheet-shaped resin composition 7 are melted and cured all at once, and the substrate 41 and the electronic component 44 are electrically and mechanically connected. In addition, it is sufficient to carry out a one-step heating process. In addition, since the conductive paste 43 and the sheet-shaped resin composition 7 are fluidized simultaneously by the heat treatment described above, the pressure applied to the electronic component 44 can be 0.1 Pa at the maximum. Therefore, even when the electronic component 44 is fragile, the electronic component 44 is not destroyed.
- FIGS. 14 to 16 are process diagrams for explaining a method of connecting a vibration motor as an electronic component to a substrate in the present embodiment.
- 14 and 16 are front views for explaining a connection method of the vibration motor
- FIG. 15 is a side view regarding the connection method of the vibration motor shown in FIG.
- a substrate or casing 51 and a vibration motor 52 are prepared.
- the substrate or casing 51 is made of, for example, a glass epoxy plate or a metal plate with a metal oxide coated on the surface.
- the vibration motor 52 has, for example, a motor body 520 and an eccentric weight 522.
- the motor body 520 is covered with the sheet-shaped resin composition 7 cut to a predetermined length, and the end of the sheet-shaped resin composition 7 contacts the substrate or the casing 51. Fixed.
- the contact fixing of the sheet-shaped resin composition 7 to the substrate or the housing 51 can be performed via a predetermined adhesive, or the sheet-shaped resin composition 7 is partially melted and fixed. You can also.
- the sheet-shaped resin composition 7 by heating the sheet-shaped resin composition 7, the sheet-shaped resin composition 7 is softened and a part of the substrate or the casing 51 and a part of the motor main body 520. Softened and melted in a state of straddling, a contact portion between a part of the substrate or the casing 51 and the motor main body 520 spreads along each surface, and is cured in this state to become a cured product 8 as shown in the figure,
- the vibration generator 50 can be manufactured. Therefore, the substrate or casing 51 and the vibration motor 52 can be firmly bonded and fixed.
- 17 to 19 are process diagrams for explaining another connection method of the vibration motor in the present embodiment.
- 17 and 19 are front views for explaining a connection method of the vibration motor
- FIG. 18 is a side view of the connection method of the vibration motor shown in FIG.
- the sheet-shaped resin composition 7 is laminated on the substrate or the casing 51, and the vibration motor 52 is disposed on the sheet-shaped resin composition 7.
- the vibration motor 52 is embedded in the sheet-shaped resin composition 7 partially melted by its own weight at the time of melting before curing.
- the periphery of the vibration motor 52 rises and the periphery of the vibration motor 52 is held on a wide surface. Thereafter, the sheet-shaped resin composition 7 is bonded and fixed by a cured product 8.
- the substrate or casing 51 and the motor main body 520 that is, the vibration motor 52 are arranged so as to be in contact with the sheet-shaped resin composition 7 disposed therebetween, respectively, and the sheet-shaped resin composition
- the object 7 is heat-cured and fixed to constitute the vibration generator 10.
- the sheet-shaped resin composition 7 is thinner than an elastic body such as rubber, and in the present embodiment, the sheet-shaped resin composition 7 is heat-cured, so that a part of the vibration motor 52 is melted. It is embedded in the resin composition 7.
- the vibration motor can be fixed to the substrate or the housing easily and inexpensively.
- the sheet-shaped resin composition 7 of the present invention is used for manufacturing an electronic component by adhering to the surface of the electronic component element body and insulating the surface. Moreover, the sheet-like resin composition 7 of this invention is used for manufacture of an electronic device by covering an electronic component and sealing this electronic component, for example.
- an electronic component For example, a semiconductor element, a resistor, a diode, a capacitor
- the electronic component include a hollow device such as a surface acoustic wave device (SAW device), a crystal device, a high-frequency device, and an acceleration sensor.
- FIG. 20 shows an example of an electronic component element body used for manufacturing an electronic component.
- the electronic component element 61 includes, for example, an element body 62 and two external connection electrodes 63 provided separately on the surface of the element body 62.
- the distance between the electrodes of the two external connection electrodes 63 is 2.0 mm, and the electrode height is 0.3 mm.
- the sheet-like resin composition 7 is used, for example, for insulation between the two external connection electrodes 63.
- the insulation by the sheet-like resin composition 7 can be performed as follows, for example.
- the sheet-shaped resin composition 7 is placed between the two external connection electrodes 63. Thereafter, the sheet-shaped resin composition 7 is fluidized by heating to a temperature of about 80 to 200 ° C., preferably 100 to 150 ° C. Further, the fluidized sheet-shaped resin composition 7 is cured by heating at a temperature of 100 to 180 ° C. for about 0.5 to 2 hours. By doing so, as shown in FIGS. 21 and 22, the electronic component 64 can be obtained by appropriately covering and insulating between the external connection electrodes 63 with the sheet-like resin composition 7 (cured product). . At this time, by using the composite sheet 1 instead of the sheet-like resin composition 7, it becomes easy to obtain a flat surface as shown in FIG.
- ⁇ Sheet-shaped resin composition> (1) Gel time Based on the test tube method of JISC2105, the time until a sheet-like resin composition became a gel was measured in an oil bath at 100 ° C. (2) Sheet characteristics Evaluation was made according to the following criteria. ⁇ : Flexible at room temperature, no cracks or chips are generated, and it is not liquid. (Triangle
- Warpage A sheet-shaped composition (30 mm ⁇ 20 mm) is placed on a FR-4 substrate (45 mm ⁇ 30 mm) having a thickness of 0.3 mm, cured at 100 ° C. for 2 hours, and the height of the four corners of the cured substrate is set. The average value was measured and used as an index of warpage.
- Examples 1 to 9 and Comparative Examples 1 to 3 Each raw material having the composition shown in Table 1 was charged into a kneader and stirred and mixed at 70 ° C. for 1 hour to prepare each resin composition. Next, each resin composition was cooled to 30 ° C., and then press molded with a molding machine under the conditions of 70 ° C. and 1.0 MPa to form a sheet having a thickness of 0.5 mm, and each sheet-shaped resin composition was produced.
- Liquid epoxy resin (1) R140P: bisphenol A type epoxy resin manufactured by Mitsui Chemicals (number average molecular weight: 380, epoxy equivalent: 190) (2) DER383J: bisphenol A type epoxy resin manufactured by Dow Chemical Co. (epoxy equivalent: 190) (3) Epicoat # 807: Bisphenol F type epoxy resin manufactured by Japan Epoxy Resin Co. (epoxy equivalent: 160 to 175) 2.
- YDCN704 Cresol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd. (epoxy equivalent: 210, softening point: 90 ° C.) 3.
- Curing agent (1) DICY: Dicyandiamide manufactured by Nippon Carbide Corporation (2)
- EH-4370S Modified aliphatic polyamine manufactured by ADEKA Corporation 4.
- Curing accelerator U-CAT3502T aromatic dimethylurea manufactured by Sun Apro Inorganic filler FB-959: spherical silica manufactured by Denki Kagaku Kogyo Co., Ltd. (mass average particle diameter: 25 ⁇ m) 6).
- the blending amount is put in an inorganic filler.
- each of the examples is basically good in terms of sheet characteristics, fluidity during melting, flame retardancy, and warpage.
- Comparative Example 1 (A) a liquid bisphenol-type epoxy resin is not used, or in Comparative Example 2 (A) a liquid bisphenol-type epoxy resin and (B) a soft solid having a softening point of 70 ° C. or less.
- the mass ratio (A) / (B) of the functional epoxy resin is out of the range of 10/90 to 30/70, the sheet characteristics are those with a softening point exceeding 70 ° C. as in Comparative Example 3 when melted. The liquidity of is poor.
- the sheet-like resin composition of the present invention can be produced without the need for a large coating facility as in the case of a conventional adhesive sheet, and can be produced without using an organic solvent, and there is little warping or twisting of the cured product. Circuit components can be easily sealed.
- Such a sheet-shaped resin composition can be used suitably for manufacture of a circuit component, sealing of an electronic component, connection, and fixation.
- the sheet-like resin composition of this invention can be used suitably for manufacture of an electronic component as a composite sheet.
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Abstract
Description
本発明のシート状樹脂組成物は、(A)液状ビスフェノール型エポキシ樹脂、(B)軟化点が70℃以下の固形状多官能エポキシ樹脂、および(C)エポキシ樹脂用硬化剤を必須成分として含むシート状樹脂組成物であって、上記(A)/(B)質量比が10/90~30/70であることを特徴とする。本発明のシート状樹脂組成物は、(D)無機フィラーを組成物全量の10~80質量%含有することが好ましく、また(E)難燃剤を含有することが好ましい。
本発明のシート状樹脂組成物においては、(A)成分として液状ビスフェノール型エポキシ樹脂が用いられる。この液状ビスフェノール型エポキシ樹脂としては、1分子中に2個以上のエポキシ基を有する液状のビスフェノール型化合物であればよく、特に制限はないが、例えばビスフェノールA型およびビスフェノールF型が好適である。このうち、液状ビスフェノールA型エポキシ樹脂が好ましく用いられ、その具体的例としては、三井化学社製の「R140P」(エポキシ当量188)、ダウケミカル社製の「DER383」、ジャパンエポキシレジン社製の「エピコート#807」(エポキシ当量170)等が使用される。これらの液状ビスフェノール型エポキシ樹脂は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。なお、本発明において、液状ビスフェノール型エポキシ樹脂とは、25℃において液状を呈するビスフェノール型エポキシ樹脂を指す。
本発明のシート状樹脂組成物においては、(B)成分として、軟化点が70℃以下の固形状多官能エポキシ樹脂が用いられる。この軟化点が70℃以下の固形状多官能エポキシ樹脂としては、例えば下記式(1)で表されるビフェニル骨格含有アラルキル型エポキシ樹脂の混合物が挙げられる。下記式(1)中、mは1~4の整数を示す。
<軟化点の測定>
JISK2207に基づいて、規定の環に試料を充填し、水浴またはグリセリン浴中で水平に支え、試料の中央に規定の球を置いて浴温を毎分5℃の速さで上昇させ、球を包み込んだ試料が環台の底板に接触した時に読み取った温度である。
本発明のシート状樹脂組成物においては、(C)成分としてエポキシ樹脂用硬化剤が用いられる。このエポキシ樹脂用硬化剤としては、特に制限はなく、従来エポキシ樹脂の硬化剤として使用されているものの中から任意のものを適宜選択して用いることができ、例えばアミン系、フェノール系、酸無水物系等が挙げられる。アミン系硬化剤としては、例えばジシアンジアミドや、m-フェニレンジアミン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルスルホン、m-キシリレンジアミン等の芳香族ジアミン等が好ましく挙げられ、フェノール系硬化剤としては、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールA型ノボラック樹脂、トリアジン変性フェノールノボラック樹脂等が好ましく挙げられる。また、酸無水物系硬化剤としては、例えばメチルヘキサヒドロ無水フタル酸等の脂環式酸無水物、無水フタル酸等の芳香族酸無水物、脂肪族二塩基酸無水物(PAPA)等の脂肪族酸無水物、クロレンド酸無水物等のハロゲン系酸無水物等が挙げられる。これらの硬化剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。このエポキシ樹脂用硬化剤の使用量は、硬化性および硬化樹脂物性のバランス等の点から、上記(A)および(B)成分のエポキシ樹脂に対する当量比で、通常0.5~1.5当量比程度、好ましくは0.7~1.3当量比の範囲で選定される。
本発明のシート状樹脂組成物においては、本発明の効果が損なわれない範囲で、必要に応じて、エポキシ樹脂用硬化促進剤を含有させることができる。このエポキシ樹脂用硬化促進剤としては、特に制限はなく、従来エポキシ樹脂の硬化促進剤として使用されているものの中から、任意のものを適宜選択して用いることができる。例えば、ウレアとして芳香族ジメチルウレア、脂肪族ジメチルウレア、3-(3,4-ジクロロフェニル)-1,1-ジメチルウレア(DCMU)、3-(3-クロロ-4-メチルフェニル)-1,1-ジメチルウレア、2,4-ビス(3,3-ジメチルウレイド)トルエン等のウレア類、2-エチル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、2-メチルイミダゾール、2-エチルイミダゾール、2-イソプロピルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール等のイミダゾール化合物、2,4,6-トリス(ジメチルアミノメチルフェノール、三フッ化ホウ素アミン錯体、トリフェニルホスフィン等を例示することができる。これらの硬化促進剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。このエポキシ樹脂用硬化促進剤の使用量は、硬化促進性および硬化樹脂物性のバランス等の点から、上記(A)、(B)成分のエポキシ樹脂100質量部に対し、通常0.1~10質量部程度、好ましくは0.4~5質量部の範囲で選定される。
本発明のシート状樹脂組成物においては、(D)成分として無機フィラーを含有させることができる。この無機フィラーとしては特に制限はなく、例えばボールミル等で粉砕した溶融シリカ、火炎溶融することで得られる球状シリカ、ゾルゲル法等で製造される球状シリカ等のシリカ類;アルミナ;水酸化アルミニウムや水酸化マグネシウム等の金属水和物;酸化チタン;カーボンブラック等、通常用いられているものを使用することができる。これらは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。当該無機フィラーの質量平均粒子径は、製造時の作業性および充填効率の観点から、4~30μmの範囲にあることが好ましい。なお、この質量平均粒子径は、レーザ回折散乱方式(例えば、島津製作所製、装置名:SALD-3100)により測定された値である。
本発明のシート状樹脂組成物においては、充填性の観点から、必要に応じてカップリング剤を含有させることができる。カップリング剤としては、シラン系、チタネート系、アルミニウム系等が挙げられるが、これらの中でシラン系カップリング剤が好ましい。シラン系カップリング剤としては、特にγ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-(2-アミノエチルアミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリエトキシシラン、γ-アニリノプロピルトリメトキシシラン、γ-アニリノプロピルトリエトキシシラン、N-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリメトキシシランおよびN-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリエトキシシラン等のアミノシラン化合物が好ましく用いられる。当該シランカップリング剤の含有量は、樹脂組成物全量に基づき、0.03~5.0質量%程度、好ましくは0.1~2.5質量%である。
本発明のシート状樹脂組成物においては、(E)成分として難燃剤を用いることが好ましい。当該難燃剤としては特に制限はなく、例えばリン化合物や、金属水和物等を用いることができる。リン化合物としては、例えば(a)ホスファゼン化合物、(b)9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドや、その誘導体、(c)リン酸エステル化合物、(d)リン酸エステルアミド等がある。
本発明のシート状樹脂組成物においては、他の任意成分として、本発明の効果を阻害しない範囲で、シリコーンゴムやシリコーンゲル等の粉末、シリコーン変性エポキシ樹脂やフェノール樹脂、メタクリル酸メチル-ブタジエン-スチレン共重合体のような熱可塑性樹脂等の低応力化剤;n-ブチルグリシジルエーテル、フェニルグリシジルエーテル、スチレンオキサイド、t-ブチルフェニルグリシジルエーテル、ジシクロペンタジエンジエポキシド、フェノール、クレゾール、t-ブチルフェノール等の粘度降下用希釈剤;ノニオン系界面活性剤、フッ素系界面活性剤、シリコーンオイル等の濡れ向上剤や消泡剤等を適宜含有させることができる。
本発明のシート状樹脂組成物の調製方法に特に制限はないが、例えば下記のようにして調製することができる。まず、前述した(A)液状ビスフェノール型エポキシ樹脂、(B)軟化点が70℃以下の固形状多官能エポキシ樹脂、および(C)エポキシ樹脂用硬化剤、さらに必要に応じて用いられる各種任意成分を高速混合機等により、均一に混合したのち、ニーダー、二本ロール、連続混練装置等で十分混練する。混練温度としては50~110℃程度が好ましい。このようにして得られた樹脂組成物を冷却後、成形機にて50~100℃程度の温度、圧力0.5~1.5MPaの条件でプレスして、本発明のシート状樹脂組成物を作製する。シート状樹脂組成物の厚さは、用途にもよるが、通常0.1~2.0mm程度、好ましくは0.1~1.0mmである。
本発明のシート状樹脂組成物には、その少なくとも一方の主面に繊維基材を設けて複合シートとすることができる。
樹脂分の割合[体積%]
={(複合シートの厚さ[μm]-繊維基材の質量[g/m2]/繊維の比重[g/cm3])
/複合シートの厚さ[μm]}×100
例えば、複合シート1が繊維基材として1枚のガラスクロスを有するものであって、複合シート1の厚さが160[μm]、ガラスクロスの質量が48[g/m2]、ガラスの比重が2.54[g/cm3]の場合、以下のようにして求められる。
樹脂分の割合[体積%]
={(160[μm]-48[g/m2]/2.54[g/cm3])/160[μm]}×100
=88
複合シート1は、例えば、シート状樹脂組成物の構成成分を50~110℃の温度で混練して混練物を得る工程と、混練物を繊維基材の片面に供給し、または混練物を1対の繊維基材間に供給した後、混練物を繊維基材に押圧することによりシート状に一体に成形する工程と経て製造することができる。
半導体、チップ抵抗、ダイオード、コンデンサー等の電子部品の実装された回路基板は、本発明のシート状樹脂組成物7を被せて熱硬化させることにより、簡単に表面を封止および被覆して回路部品とすることができる。本発明のシート状樹脂組成物7による電子部品の封止、被覆方法は特に制限はなく、例えば下記のようにして封止、被覆作業を行うことができる。
SAWデバイスのような中空部分を有する電子部品の封止は、本発明のシート状樹脂組成物7により簡便かつ歩留まり良く行うことができる。まず、例えば、基板上に実装された電子部品をシート状樹脂組成物7で被覆し、80~150℃程度、好ましくは100~150℃の温度に加熱して、シート状樹脂組成物7を流動化させた後、さらに100~180℃程度の温度にて、0.5~2時間程度加熱して流動化したシート状樹脂組成物7を硬化させて電子部品と基板との間に形成された隙間周辺を密閉または隙間を充填することができる。
本発明のシート状樹脂組成物7を用いて電子部品と基板との電気的接続を簡易かつ歩留まり良く行うことができる。図9~13は、電子部品の接続方法を説明するための工程図である。
本発明のシート状樹脂組成物7を用いて小型電子機器等の電子部品を、固定治具無しで基板や筐体に簡易かつ歩留まり良く固定することができる。図14~16、および17~19で説明する。
本発明のシート状樹脂組成物7は、電子部品素体の表面に接着し、該表面を絶縁して電子部品の製造に用いられる。また、本発明のシート状樹脂組成物7は、例えば、電子部品に被せ、該電子部品を封止して電子機器の製造に用いられる。電子部品としては、特に制限されないが、例えば、半導体素子、抵抗器、ダイオード、コンデンサーが挙げられる。また、電子部品としては、弾性表面波装置(SAWデバイス)、水晶デバイス、高周波デバイス、加速度センサー等の中空デバイスが挙げられる。
(1)ゲルタイム
JISC2105の試験管法に準拠して、100℃のオイルバス中でシート状樹脂組成物がゲルになるまでの時間を測定した。
(2)シート特性
次の判定基準で評価した。
○:室温で柔軟であり、割れおよび欠けが発生せず、かつ液状でない。
△:室温で柔軟であり、液状ではないが、割れまたは欠けが発生。
×:シート化が不可能。
(3)溶融時の流動性
FR-4基板上に設置した2mm角のチップをシート状組成物で封止し、埋め込み性を目視にて確認した。硬化条件は100℃、2時間である。下記の判定基準で評価した。
○:良好。
×:部品周りに未充填箇所がある。
(4)溶融粘度
レオメーター(RhenemetricScientific社製)にて測定(100℃)した。
<硬化物>
(5)ガラス転移点
TMA/SS150(セイコーインスツルメンツ社製)において、室温→200℃(昇温スピード10℃/分)まで昇温して、ガラス転移点を測定した。
(6)難燃性
UL94に準拠して、試験片厚み1.6mmで難燃性を評価した。
(7)反り
厚さ0.3mmのFR-4基板(45mm×30mm)にシート状組成物(30mm×20mm)をのせ、100℃で2時間硬化させ、硬化後の基板の四隅の高さを測り、その平均値を反りの指標とした。
第1表に示す配合組成の各原料をニーダーに仕込み、70℃で1時間撹拌混合して、各樹脂組成物を調製した。次いで、各樹脂組成物それぞれを30℃に冷却後、成形機により、70℃、1.0MPaの条件でプレス成形して厚さ0.5mmのシートとし、各シート状樹脂組成物を作製した。
1.液状エポキシ樹脂
(1)R140P:三井化学社製のビスフェノールA型エポキシ樹脂(数平均分子量:380、エポキシ当量:190)
(2)DER383J:ダウケミカル社製のビスフェノールA型エポキシ樹脂(エポキシ当量:190)
(3)エピコート#807:ジャパンエポキシレジン社製のビスフェノールF型エポキシ樹脂(エポキシ当量:160~175)
2.固形状エポキシ樹脂
(1)NC3000:日本化薬社製のビフェニル骨格含有多官能型エポキシ樹脂(エポキシ当量:285、軟化点:57℃)
(2)NC3000H:日本化薬社製のビフェニル骨格型エポキシ樹脂(エポキシ当量:290、軟化点:70℃)
(3)YDCN704:東都化成社製のクレゾールノボラック型エポキシ樹脂(エポキシ当量:210、軟化点:90℃)
3.硬化剤
(1)DICY:日本カーバイド社製のジシアンジアミド
(2)EH-4370S:ADEKA社製の変性脂肪族ポリアミン
4.硬化促進剤
U-CAT3502T:サンアプロ社製の芳香族ジメチルウレア
5.無機フィラー
FB-959:電気化学工業社製の球状シリカ(質量平均粒子径:25μm)
6.難燃剤
(1)SPB-100:大塚化学社製のホスファゼン化合物〔前記一般式(3)におけるR1およびR2がいずれもフェニル基、kが3以上〕
(2)H42M:昭和電工社製の水酸化アルミニウム(粒子径:1.5μm)
Claims (18)
- (A)液状ビスフェノール型エポキシ樹脂、(B)軟化点が70℃以下の固形状多官能エポキシ樹脂、および(C)エポキシ樹脂用硬化剤を必須成分として含むシート状樹脂組成物であって、
前記(A)/(B)質量比が10/90~30/70であることを特徴とするシート状樹脂組成物。 - さらに、(D)質量平均粒子径4~30μmの球状シリカを組成物全量に対し10~80質量%含むことを特徴とする請求項1記載のシート状樹脂組成物。
- さらに、(E)難燃剤としてホスファゼン化合物を含むことを特徴とする請求項1記載のシート状樹脂組成物。
- 請求項1記載のシート状樹脂組成物によって封止または接着されてなることを特徴とする回路部品。
- 基板上に実装された電子部品を請求項1記載のシート状樹脂組成物によって被覆し、加熱硬化する電子部品の封止方法であって、
前記シート状樹脂組成物によって前記電子部品を被覆し、前記電子部品と前記基板との接触部周辺を密閉して前記電子部品と前記基板との間に隙間を形成させることを特徴とする電子部品の封止方法。 - 80~150℃下で、前記シート状樹脂組成物を流動化させた後、さらに100~180℃下にて、0.5~2時間加熱して流動化した前記シート状樹脂組成物を硬化させることを特徴とする請求項6記載の電子部品の封止方法。
- 接続用の第1の電極を有する基板と、接続用の第2の電極を有する電子部品とを、前記第1の電極および前記第2の電極を介して電気的に接続する方法であって、
請求項1記載のシート状樹脂組成物を用いて前記電子部品を前記基板に電気的に接続する工程を備えることを特徴とする電子部品の接続方法。 - 前記基板の前記第1の電極上に導電性ペーストを配置する工程と、
前記基板の前記第1の電極の非形成領域に前記シート状樹脂組成物を配置する工程と、
前記電子部品を、前記第2の電極と前記基板の前記第1の電極とが接触するようにして前記基板上に搭載し、前記導電ペーストおよび前記シート状樹脂組成物を同時に加熱硬化させて、前記電子部品を前記基板に電気的に接続する工程と、
を備えることを特徴とする請求項8記載の電子部品の接続方法。 - 基板または筐体に電子部品を固定する方法であって、
前記基板または前記筐体と前記電子部品とに接触するようにして請求項1記載のシート状樹脂組成物を配置し、前記基板または前記筐体と前記電子部品とを前記シート状樹脂組成物で固定することを特徴とする電子部品の固定方法。 - 前記シート状樹脂組成物で前記電子部品上を覆い、加熱軟化または加熱溶融により硬化させて、前記基板または前記筐体と前記電子部品とを接着固定することを特徴とする請求項10記載の電子部品の固定方法。
- 前記シート状樹脂組成物を前記基板または前記筐体の電子部品搭載面に載置し、前記シート状樹脂組成物上に前記電子部品を搭載した後、前記シート状樹脂組成物を加熱軟化または加熱溶融により加熱硬化させて、前記基板または前記筐体と前記電子部品とを接着固定することを特徴とする請求項10記載の電子部品の固定方法。
- 請求項1記載のシート状樹脂組成物を有する樹脂層と、
前記樹脂層の少なくとも一方の主面に密着形成された繊維基材を有する繊維基材層と
を有することを特徴とする複合シート。 - 前記複合シートにおける樹脂分の割合は65~93体積%であることを特徴とする請求項13記載の複合シート。
- 前記繊維基材は、無機繊維基材および有機繊維基材から選ばれる少なくとも1種であることを特徴とする請求項13記載の複合シート。
- 電子部品素体と、
前記電子部品素体の少なくとも一部の表面上に配置され、前記表面を絶縁する請求項13記載の複合シートと
を有することを特徴とする電子部品。 - 電子部品と、
前記電子部品を封止する請求項13記載の複合シートと
を有することを特徴とする電子機器。 - 請求項1記載のシート状樹脂組成物の構成成分を50~110℃の温度で混練して混練物を得る工程と、
前記混練物を繊維基材の片面に供給し、または前記混練物を1対の繊維基材間に供給した後、前記混練物を前記繊維基材に押圧することによりシート状に一体に成形して複合シートを得る工程と
を有することを特徴とする複合シートの製造方法。
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JP2005226004A (ja) * | 2004-02-13 | 2005-08-25 | Nippon Steel Chem Co Ltd | エポキシ樹脂の製造方法、エポキシ樹脂組成物及び硬化物 |
JP2006124434A (ja) * | 2004-10-26 | 2006-05-18 | Matsushita Electric Works Ltd | エポキシ樹脂無機複合シート及び成形品 |
JP2006332150A (ja) * | 2005-05-24 | 2006-12-07 | Sumitomo Bakelite Co Ltd | カバーレイフィルム用樹脂組成物、カバーレイフィルムおよびそれを用いたフレキシブルプリント回路板 |
JP2007238769A (ja) * | 2006-03-08 | 2007-09-20 | Sumitomo Bakelite Co Ltd | 樹脂組成物、樹脂フィルム、カバーレイフィルムおよびフレキシブルプリント回路板 |
WO2008020594A1 (fr) * | 2006-08-17 | 2008-02-21 | Nipponkayaku Kabushikikaisha | Résine époxy liquide modifiée, composition de résine époxy contenant celle-ci et produit cuit dérivé |
WO2010061980A1 (ja) * | 2008-11-28 | 2010-06-03 | 味の素株式会社 | 樹脂組成物 |
-
2011
- 2011-05-24 WO PCT/JP2011/002891 patent/WO2011148620A1/ja active Application Filing
- 2011-05-24 CN CN201180007104.XA patent/CN102725323B/zh not_active Expired - Fee Related
- 2011-05-24 KR KR1020127017351A patent/KR20130079311A/ko not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2005105159A (ja) * | 2003-09-30 | 2005-04-21 | Sumitomo Bakelite Co Ltd | 樹脂組成物、カバーレイおよびフレキシブルプリント配線板 |
JP2005226004A (ja) * | 2004-02-13 | 2005-08-25 | Nippon Steel Chem Co Ltd | エポキシ樹脂の製造方法、エポキシ樹脂組成物及び硬化物 |
JP2006124434A (ja) * | 2004-10-26 | 2006-05-18 | Matsushita Electric Works Ltd | エポキシ樹脂無機複合シート及び成形品 |
JP2006332150A (ja) * | 2005-05-24 | 2006-12-07 | Sumitomo Bakelite Co Ltd | カバーレイフィルム用樹脂組成物、カバーレイフィルムおよびそれを用いたフレキシブルプリント回路板 |
JP2007238769A (ja) * | 2006-03-08 | 2007-09-20 | Sumitomo Bakelite Co Ltd | 樹脂組成物、樹脂フィルム、カバーレイフィルムおよびフレキシブルプリント回路板 |
WO2008020594A1 (fr) * | 2006-08-17 | 2008-02-21 | Nipponkayaku Kabushikikaisha | Résine époxy liquide modifiée, composition de résine époxy contenant celle-ci et produit cuit dérivé |
WO2010061980A1 (ja) * | 2008-11-28 | 2010-06-03 | 味の素株式会社 | 樹脂組成物 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021124735A1 (ja) * | 2019-12-17 | 2021-06-24 | 日東電工株式会社 | 磁性シートの製造方法 |
JP7493933B2 (ja) | 2019-12-17 | 2024-06-03 | 日東電工株式会社 | 磁性シートの製造方法 |
Also Published As
Publication number | Publication date |
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CN102725323A (zh) | 2012-10-10 |
KR20130079311A (ko) | 2013-07-10 |
CN102725323B (zh) | 2015-08-19 |
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