CN102725323A - Sheet-like resin composition, circuit component using the sheet-like resin composition, method for sealing electronic component, method for connecting electronic component, method for affixing electronic component, composite sheet, electronic component - Google Patents
Sheet-like resin composition, circuit component using the sheet-like resin composition, method for sealing electronic component, method for connecting electronic component, method for affixing electronic component, composite sheet, electronic component Download PDFInfo
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- CN102725323A CN102725323A CN201180007104XA CN201180007104A CN102725323A CN 102725323 A CN102725323 A CN 102725323A CN 201180007104X A CN201180007104X A CN 201180007104XA CN 201180007104 A CN201180007104 A CN 201180007104A CN 102725323 A CN102725323 A CN 102725323A
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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
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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
- C08G59/4007—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
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Abstract
Disclosed is a sheet-like resin composition which contains, as essential ingredients, (A) a liquid bisphenol type epoxy resin, (B) a solid polyfunctional epoxy resin having a softening point of 70 DEG C or less and (C) a curing agent for epoxy resins. The sheet-like resin composition is characterized in that the (A)/(B) mass ratio is from 10/90 to 30/70.
Description
Technical field
The present invention relates to the flaky resin compsn, use the method for manufacture of sealing method, method of attachment and fixing means and the composite sheet of circuit elements device, the electronic devices and components of this flaky resin compsn, the electronic devices and components that use this composite sheet, electronics, composite sheet.
Background technology
In the past, as the adhesive sheet that uses in the electronic devices and components field, the known adhesive sheet that constitutes by compositions of thermosetting resin such as composition epoxy resins (for example with reference to patent documentation 1).But the operability of existing adhesive sheet and intensity are not good, and this adhesive sheet is not good to the landfill property of bonding region yet.In addition, the electronic devices and components that are bonded with existing adhesive sheet are added man-hour, this adhesive sheet is peeled off sometimes, requires to develop the high adhesive sheet of bonding force.
In addition,, also use the prepreg that constitutes by fiber base material and compositions of thermosetting resin, for example glass epoxide prepreg (for example with reference to patent documentation 2) as adhesive sheet.The operability and the strength ratio of prepreg are better, but not good to the landfill property of bonding region, spendable electronic devices and components are also limited.In addition, the manufacturing of prepreg generally needs special-purpose large-scale coating machine, also needs organic solvent etc.
Disclosed following method: cover with thermosetting resin, better be the lamellar resin sheet that epoxy resin constitutes as sealing material; Make its covering be installed in the semi-conductive whole surface on the real estate; Heating then; Make this lamellar resin sheet softening and make it have viscosity and bounding force, make this lamellar resin sheet and above-mentioned semi-conductor and aforesaid substrate face bonding by this, it is carried out heat treated after; The lamellar resin sheet of above-mentioned remollescent is solidified, by this with above-mentioned encapsulating semiconductor (with reference to patent documentation 3～5).
The technology of patent documentation 3～5 records is the technology of coming seal electronic element with flaky sealing resin; Though put down in writing the thermosetting resin of preferred use epoxy resin, had no record for other used in the kind of epoxy resin, sealing material blending composition as sealing material.This technology exists the cured article of sealing resin to be easy to generate the problem of warpage or distortion, when the melt viscosity of sealing resin is high, owing to resin is high to the bad possibility that causes producing space etc. of the filling of the thin portion of electronic component.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid is opened the 2002-60720 communique
Patent documentation 2: japanese patent laid-open 2-102281 communique
Patent documentation 3: Japanese Patent Laid is opened the 2003-249510 communique
Patent documentation 4: japanese patent laid-open 10-125825 communique
Patent documentation 5: Japanese Patent Laid is opened the 2003-249510 communique
Summary of the invention
The object of the present invention is to provide a kind of flaky resin compsn; This flaky resin compsn need not the such large-scale coating apparatus of existing adhesive sheet and can make; And with an organic solvent can not make; And the warpage of cured article or distortion are few, can carry out the sealing of circuit elements device etc. simply.The object of the invention also is to provide a kind of circuit elements device that uses this flaky resin compsn.The present invention also aims to provide a kind of sealing method, method of attachment and fixing means that uses the electronic devices and components of this flaky resin compsn.The object of the invention also is to provide a kind of method of manufacture of using the composite sheet of this flaky resin compsn, the electronic devices and components that use this composite sheet, electronics and this composite sheet.
Flaky resin compsn of the present invention is that to comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature be that solid-state polyfunctional epoxy resin and (C) hardener for epoxy resin below 70 ℃ is as the flaky resin compsn of essential composition; It is characterized in that the mass ratio of said (A)/(B) is 10/90～30/70.
Circuit elements device of the present invention is characterised in that, with flaky resin compsn sealing of the present invention or bonding forming.
The sealing method of electronic devices and components of the present invention is to cover the sealing method that is installed in the electronic devices and components that are heating and curing behind the electronic devices and components on the substrate with flaky resin compsn of the present invention; It is characterized in that; Cover said electronic devices and components with said flaky resin compsn; Airtight around the contact part with said electronic devices and components and said substrate, between said electronic devices and components and said substrate, form the gap.
The method of attachment of electronic devices and components of the present invention is methods that substrate with first electrode that connects usefulness and the electronic devices and components with second electrode that is connected usefulness are connected with said second electrode electricity via said first electrode; It is characterized in that, comprise the operation that said electronic devices and components is electrically connected with said substrate with flaky resin compsn of the present invention.
The fixing means of electronic devices and components of the present invention is the methods that electronic devices and components are fixed in substrate or framework; It is characterized in that; Flaky resin compsn of the present invention is arranged such that said substrate or said framework contact with said electronic devices and components, said substrate or said framework and said electronic devices and components is fixed with said flaky resin compsn.
Composite sheet of the present invention is characterised in that, comprises resin layer and fiber base material layer, and said resin layer has flaky resin compsn of the present invention, the driving fit of said fiber base material layer be formed at said resin layer at least one side interarea and have fiber base material.
Electronic devices and components of the present invention are characterised in that, comprise electronic devices and components main body and composite sheet of the present invention, and said composite sheet is configured on the surface of at least a portion of said electronic devices and components main body and with said surface insulation.Electronics of the present invention is characterised in that, comprises the composite sheet of the present invention of electronic devices and components and the said electronic devices and components of sealing.
The method of manufacture of composite sheet of the present invention is characterised in that, comprising: the constituent of compositions of thermosetting resin is mixing under 50～110 ℃ temperature, obtain the operation of mixing thing; With said mixing thing be conducted to fiber base material one side or be conducted to said mixing thing between a pair of fiber base material after, through pushing said mixing thing and said fiber base material it is configured as sheet integratedly, obtain the operation of composite sheet.
The simple declaration of accompanying drawing
Fig. 1 is the sectional view of brief configuration of first embodiment of expression composite sheet.
Fig. 2 is the sectional view of brief configuration of second embodiment of expression composite sheet.
Fig. 3 is the sectional view of the brief configuration of the existing prepreg of expression.
Fig. 4 is the explanatory view of first embodiment of the method for manufacture of explanation composite sheet.
Fig. 5 is the explanatory view of second embodiment of the method for manufacture of explanation composite sheet.
Fig. 6 is the explanatory view of the 3rd embodiment of the method for manufacture of explanation composite sheet.
Fig. 7 is the explanatory view of the 4th embodiment of the method for manufacture of explanation composite sheet.
Fig. 8 is a schematic sectional view, is depicted as around the formed gap between the electronic devices and components of expression with substrate and installation an example of the state behind the airtight or filling gap with sealing material.
Fig. 9 is the process chart that is used to explain the method for attachment of electronic devices and components.
Figure 10 is the process chart that is used to explain the method for attachment of electronic devices and components.
Figure 11 is the process chart that is used to explain the method for attachment of electronic devices and components.
Figure 12 is the process chart that is used to explain the method for attachment of electronic devices and components.
Figure 13 is the process chart that is used to explain the method for attachment of electronic devices and components.
Figure 14 is the front view of first embodiment that is used to explain the fixing means of electronic devices and components.
Figure 15 is the side-view of first embodiment that is used to explain the fixing means of electronic devices and components.
Figure 16 is the front view of first embodiment that is used to explain the fixing means of electronic devices and components.
Figure 17 is the front view of second embodiment that is used to explain the fixing means of electronic devices and components.
Figure 18 is the side-view of second embodiment that is used to explain the fixing means of electronic devices and components.
Figure 19 is the front view of second embodiment that is used to explain the fixing means of electronic devices and components.
Figure 20 be the expression used composite sheet the electronic devices and components main body one the example sectional view.
Figure 21 be the expression used composite sheet electronic devices and components one the example sectional view.
Figure 22 is another routine sectional view that the electronic devices and components of composite sheet have been used in expression.
The mode that carries out an invention
At first, flaky resin compsn of the present invention is described.
[flaky resin compsn]
Flaky resin compsn of the present invention is that to comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature be that solid-state polyfunctional epoxy resin and (C) hardener for epoxy resin below 70 ℃ is as the flaky resin compsn of essential composition; It is characterized in that the mass ratio of said (A)/(B) is 10/90～30/70.Flaky resin compsn of the present invention better is (D) mineral filler that contains 10～80 quality % of total composition, and better is to contain (E) fire retardant.
[(A) composition]
In the flaky resin compsn of the present invention, use liquid bisphenol type epoxy resin as (A) composition.
As this liquid bisphenol type epoxy resin, get final product so long as have the bisphenol type compound of the liquid state of 2 above epoxy group(ing) in 1 molecule, there is not qualification especially, for example preferred bisphenol A-type and Bisphenol F type.Wherein, The preferred liquid bisphenol A type epoxy resin that uses; As its concrete example, can use " エ ピ コ ー ト #807 " (epoxy equivalent (weight) 170) etc. of " DER383 ", japan epoxy resin company (ジ ャ パ Application エ Port キ シ レ ジ Application society) system of " R140P " (epoxy equivalent (weight) 188), Dow Chemical (the ダ ウ ケ ミ カ Le society) system of Mitsui Chemicals company (Mitsui Chemicals society) system.These liquid bisphenol type epoxy resin can use a kind separately, also can make up use more than 2 kinds.Among the present invention, liquid bisphenol type epoxy resin is meant the bisphenol-type epoxy resin that is in a liquid state under 25 ℃.
[(B) composition]
In the flaky resin compsn of the present invention, using softening temperature as (B) composition is the solid-state polyfunctional epoxy resin below 70 ℃.As this softening temperature is the solid-state polyfunctional epoxy resin below 70 ℃, the for example mixture of the aralkyl-type epoxy resin that contains the bis-phenol skeleton of following formula (1) expression of can giving an example.In the following formula (1), m representes 1～4 integer.
[changing 1]
The mixture of the dicyclopentadiene-type epoxy resin of the following formula (2) of also can giving an example expression etc.In the following formula (2), n representes 1～10 integer.
[changing 2]
The softening temperature of these solid-state polyfunctional epoxy resins is the values that record through following method.
< mensuration of softening temperature >
According to JISK2207, in the ring of regulation, fill sample, horizontal support is in water-bath or glycerol bath; Place the ball of regulation in the central authorities of sample; Make and bathe the speed rising of temperature with 5 ℃ of PMs, when the sample that is wrapped in ball contacts with the base plate of ring platform, read temperature, this temperature is softening temperature.
As this softening temperature is the commercial goods of the solid-state polyfunctional epoxy resin below 70 ℃, preferably uses " NC3000 (57 ℃ of softening temperatures) ", " NC3000H (70 ℃ of the softening temperatures) " of Japanese chemical drug company (Japanese chemical drug society) system etc.
Among the present invention; Through and be the solid-state polyfunctional epoxy resin below 70 ℃ with (A) liquid bisphenol type epoxy resin with (B) softening temperature; That is, two kinds of epoxy resin that fusing point is different mix, the flaky resin compsn of the behavior that can obtain to demonstrate under the room temperature in the form of sheets, be in a liquid state under the high temperature.
Among the present invention, require the mass ratio of said (A)/(B) to be in 10/90～30/70 the scope.If liquid-state epoxy resin is less than the softening temperature of said scope or solid epoxy resin and is higher than 70 ℃, then sheet material cracks or fragment, and is undesirable.If liquid-state epoxy resin is low excessively more than the softening temperature of said scope or solid epoxy resin, then be difficult for forming sheet material.Consider that from above-mentioned angle mass ratio (A)/(B) better is 15/85～25/75 scope, the lower limit of the softening temperature of solid epoxy resin is generally about 40 ℃.
[(C) composition]
In the flaky resin compsn of the present invention, use hardener for epoxy resin as (C) composition.There is not special qualification as this hardener for epoxy resin, can be from use solidifying agent arbitrarily, can give an example for example amine, phenol, anhydrides etc. as suitably selecting the solidifying agent of curing agent for epoxy resin use in the past.As amine curing agent; But preference is for example like Dyhard RU 100, mphenylenediamine, 4; 4 '-diaminodiphenyl-methane, 4; Aromatic diamines such as 4 '-diaminodiphenylsulfone(DDS), m-xylene diamine etc., as the phenol solidifying agent, but preference is for example like lacquer resins, cresols lacquer resins, bisphenol A-type novolac resin, triazine modified linear phenol-aldehyde resin etc.As acid anhydride type curing agent, the for example halogen acid anhydrides such as aromatic anhydrides such as alicyclic acid anhydrides, Tetra hydro Phthalic anhydride, binary aliphatic acid anhydrides aliphatic anhydride such as (PAPA), hexachloroendomethylene-tetrahvdrophthalic anhydride such as methylhexahydrophthalic anhydride etc. of can giving an example.These solidifying agent can use a kind separately, also can make up use more than 2 kinds.Consider from solidified nature and cured resin physical properties balance equal angles; The consumption of this hardener for epoxy resin is in respect to as said (A) and (B) equivalence ratio of the epoxy resin of composition, is being generally about 0.5～1.5 equivalence ratio, is being preferably selected in the scope of 0.7～1.3 equivalence ratio.
[any composition: used for epoxy resin curing catalyst]
In the flaky resin compsn of the present invention, can in the scope that does not influence effect of the present invention, contain the used for epoxy resin curing catalyst as required.Do not have special qualification as this used for epoxy resin curing catalyst, can from the curing catalyst that in the past used as the curing catalyst of epoxy resin, suitably select to use curing catalyst arbitrarily.For example, can give an example as aromatic series dimethyl urea, aliphatics dimethyl urea, the 3-(3, the 4-dichlorophenyl)-1 of urea; 1-dimethyl urea (DCMU), 3-(3-chloro-4-aminomethyl phenyl)-1; 1-dimethyl urea, 2, ureas such as two (3, the 3-dimethyl-urea groups) toluene of 4-; Imidazolium compoundss such as 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; 2,4,6-three (dimethylamino methyl) phenol, boron trifluoride amine complex, triphenylphosphine etc.These curing catalysts can use a kind separately, also can make up use more than 2 kinds.Consider from solidifying promotion property and cured resin physical properties balance equal angles; The consumption of this used for epoxy resin curing catalyst is with respect to as said (A) and (B) epoxy resin 100 mass parts of composition, is being generally about 0.1～10 mass parts, is being preferably selected in the scope of 0.4～5 mass parts.
[(D) composition]
In the flaky resin compsn of the present invention, can contain mineral filler as (D) composition.Do not have special qualification as this mineral filler, the spherical silicon dioxide that for example can use fused silica through pulverizing such as ball mills, get through the flame fusion, spherical silicon dioxide of making through sol-gel method etc. etc. are silica-based; Aluminum oxide; Metal hydrate such as white lake and Marinco H; Titanium oxide; The mineral filler that carbon black etc. are commonly used.These mineral fillers can be used a kind separately, also can make up use more than 2 kinds.The operability during from manufacturing and the angle of charging efficiency consider that the mass median diameter of this mineral filler better is to be in the scope of 4～30 μ m.This mass median diameter is that (for example Shimadzu Seisakusho Ltd.'s system is installed name: the value that SALD-3100) records through the laser diffraction and scattering mode.
As this mineral filler better is spherical silicon dioxide, for example preferred Denki Kagaku Kogyo kabushiki system " FB-959 (mass median diameter: 25 μ m) " etc.The content of this mineral filler better is to be 10～80 quality % with respect to the resin combination total amount.Here, do not process following composite sheet, promptly be not provided with under the situation of fiber base material on the flaky resin compsn, be preferably 50～80 quality %.Be not provided with under the situation of fiber base material, reach more than the 50 quality %, when coming sealed electronic element, can suppress cured article effectively and produce warpage or distortion with the flaky resin compsn through making content.In addition, reach below the 80 quality %, can suppress effectively that the flaky resin compsn cracks or the flowability when fragment, fusion descends, produce phenomenons such as not filling the position around the components and parts through making content.On the other hand, process under the situation of composite sheet,, then can suppress the warpage of cured article etc. if content reaches more than the 10 quality %.In addition, process under the situation of composite sheet, reach below the 50 quality % through making content, the flowability in the time of can improving fusion suppresses not fill the generation at position, and is therefore preferred.Use under the situation of metal hydrate as mineral filler, also play the effect of fire retardant.
[any composition: coupling agent]
In the flaky resin compsn of the present invention, consider, can contain coupling agent as required from the angle of fillibility.As coupling agent, the silicane of can giving an example, titanate ester, aluminium class etc., wherein preferred silane class coupling agent.As silane coupling agent, especially preferably use gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane and N-β-(N-vinyl benzyl amino-ethyl)-amino silane compounds such as γ-An Jibingjisanyiyangjiguiwan.The content of this silane coupling agent is about 0.03～5.0 quality % with respect to the resin combination total amount, is preferably 0.1～2.5 quality %.
[(E) composition]
In the flaky resin compsn of the present invention, better be to use fire retardant as (E) composition.Do not have special qualification as this fire retardant, for example can use phosphorus compound, metal hydrate etc.As phosphorus compound, (a) phosphazene compound, (b) 9 are for example arranged, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound and verivate thereof, (c) phosphate compound, (d) phosphoric ester amides etc.
As said (a) phosphazene compound, be not halogen-containing in fact compound, consider that from thermotolerance, wet fastness, flame retardancy, chemical-resistant equal angles preferably using fusing point is the phosphazene compound more than 80 ℃.As a specific example, can the give an example ring phosphonitrile oligopolymer of formula (3) expression.
[changing 3]
In the said general formula (3), R
1And R
2Represent Wasserstoffatoms or not halogen-containing organic group respectively independently, k representes 3～10 integer.In the said general formula (3), as R
1And R
2In not halogen-containing organic group, the alkoxyl group of the carbon number 1～10 for example of can giving an example, phenoxy, amino, allyl group etc.As such phosphazene compound, the chemistry of the "-f " flag Da of Da mound chemical company mound for example society can give an example) " SPB-100 " of system etc.
Said (b) 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound has the structure of formula (4) expression.
[changing 4]
In addition, as its verivate, (2, the 5-the dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound of for example formula (5) expression etc. of can giving an example.
[changing 5]
The compound of following formula (4) expression can be used as " SANKO-HCA " [Sanko Co., Ltd.'s system, trade(brand)name] and obtains, and the compound of following formula (5) expression can be used as " SANKO HCA-HQ " [Sanko Co., Ltd.'s system, trade(brand)name] and obtains.As verivate, also have " SANKO M-Acid-AH " ［ Sanko Co., Ltd.'s system, trade(brand)name ］ on market, to sell.
As said (c) phosphate compound, the for example add-on type SULPHOSUCCINIC ACID ESTER such as triphenylphosphate, tricresyl phosphate biphenyl ester of can giving an example; Use polyphenol such as Resorcinol and monohydric phenols such as phenol, cresols to carry out response type SULPHOSUCCINIC ACID ESTER " RDP " [the meticulous scientific & technical corporation of aginomoto (monosodium glutamate Off ア イ Application テ Network ノ society) makes, trade(brand)name] that at least one hydroxyl in esterification and this polyphenol left behind as reactive free group etc.; And the condensed type SULPHOSUCCINIC ACID ESTER " PX-200 " that formed by esterification of the free hydroxyl group in the response type SULPHOSUCCINIC ACID ESTER [big eight chemical industrial companies (big eight chemical industry societies) system, trade(brand)name] etc.
As said (d) phosphoric ester amides; The coupling scheme that comprises SULPHOSUCCINIC ACID ESTER and phosphoramide can also use Japanese Patent Laid to open 2001-139823 communique, Japanese Patent Laid and open 2000-154277 communique, japanese patent laid-open 10-175985 communique, japanese patent laid-open 8-59888 communique, Japanese Patent Laid and open phosphoric ester amides of putting down in writing in the clear 63-235363 communique etc.As preferred phosphoric ester amides, the condensed phosphoric acid esters amides of can giving an example.As such phosphoric ester amides; Can give an example for example N-(two aryloxy phosphinyls) substituted alkylene amine, two～four [(two aryloxy phosphinyls) amino] substituted aromatic compound class, N-(cyclic alkylidene dioxy base phosphinyl) substituted alkylene amine, two～four [(cyclic alkylidene dioxy base phosphinyl) amino] substituted aromatic compound class, N-(ring-type arylidene dioxy base phosphinyl) substituted alkylene amine, two～four [(ring-type arylidene dioxy base phosphinyl) amino] substituted aromatic compound class, 3; Two (the N-substituted-aminos)-2 of 9-; 4,8,10-four oxa-s-3; 9-two phospha spiral shell [5.5]-undecanes-3,9-dioxide class etc.Phosphoric ester amides can be used as trade(brand)name " phosphoric ester amides based flame retardant SP series (for example SP-601, SP-670, SP-703, SP-720 etc.) " [Shikoku Chem's (four countries change into industry) system] and obtains.
On the other hand,, can use aluminium hydroxide, magnesium hydroxide as the kind of metal hydrate, as aluminum hydroxide compound, for example clear " H42M " that makes with electrician company (clear and electrician society) of preferred use.
Among the present invention, said fire retardant can use a kind separately, also can make up use more than 2 kinds.Its content depends on the kind of fire retardant, considers from the angle of flame retardancy and other physical properties balance, is preferably 5～50 quality % with respect to the resin combination total amount, better is 10～40 quality %, further better is 10～35 quality %.
[other any composition]
In the flaky resin compsn of the present invention; As other any composition, can in the scope that does not influence effect of the present invention, suitably contain the low-stress agent such as thermoplastic resin of powder, silicone modified epoxy and resol, MBSs and so on such as Zylox and silica gel; Viscosity reduction degree such as n-butyl glycidyl ether, phenyl glycidyl ether, Styrene oxide 98min., tert-butyl-phenyl glycidyl ether, Dicyclopentadiene (DCPD) epoxide, phenol, cresols, tert.-butyl phenol are used thinner; Wellability rising agents such as nonionic class tensio-active agent, fluorine class tensio-active agent, silicone oil and skimmer etc.
[method for making of flaky resin compsn]
Flaky resin preparation of compositions method of the present invention does not have special qualification, and preparation for example can be described below.At first; Is that solid-state polyfunctional epoxy resin, (C) hardener for epoxy resin below 70 ℃ and the various any composition that uses as required mix equably with high-speed mixer etc. with said (A) liquid bisphenol type epoxy resin, (B) softening temperature, uses kneader, twin-roll machine, continuous mixing device etc. fully mixing then.As melting temperature, be preferably about 50～110 ℃.After the resin combination cooling that obtains as stated, pressurize under the condition of the temperature about 50～100 ℃, pressure 0.5～1.5MPa with forming mill, process flaky resin compsn of the present invention.The thickness of flaky resin compsn depends on purposes, is generally about 0.1～2.0mm, is preferably 0.1～1.0mm.
Processing property, the plasticity of this flaky resin composition itself are good, and the warpage of cured article or distortion are few.By this flaky resin compsn, for example, can therefore can simplify sealing process easily with the electronic devices and components sealing through being layered in post-heating on the electronic component, make easily.In addition, need not main equipment can seal under the situation of the function that does not influence the electronic component with electric function portion, therefore can realize the reduction of manufacturing cost.
[composite sheet]
In the flaky resin compsn of the present invention, can on its at least one side's interarea, fiber base material be set and process composite sheet.
Fig. 1 is the sectional view of brief configuration of first embodiment of expression composite sheet, and Fig. 2 is the sectional view of brief configuration of second embodiment of expression composite sheet.Fig. 3 is the sectional view of the brief configuration of the existing prepreg of expression.
Fig. 3 is the sectional view of the existing prepreg 50 of expression.The structure of existing prepreg 50 is: have fiber base material 51, soaking in this fiber base material 51 has compositions of thermosetting resin 52.Existing prepreg 50 soaks into to fiber base material 51 in order to make compositions of thermosetting resin 52, needs main equipments such as steeping vat, and also needs organic solvent etc.By composite sheet 1 of the present invention; Be formed with the structure of fiber base material layer 3 through driving fit on the interarea that adopts resin layer 2; Can be described below and make, need not main equipment and need not to make product with fiber base material through loaded down with trivial details operation through the method for pushing behind the melts of supplying with the method for pushing behind the fiber base material to the surface of flaky resin compsn or constituting through the constituent material of supplying with to the surface of fiber base material by the flaky resin compsn.
The ratio of the resinous principle in the composite sheet 1 is preferably 65～93 volume %.Reach 65～93 volume % through the ratio that makes resinous principle, can make the bonding force of composite sheet 1 sufficient, and can suppress from the resin of composite sheet 1 ooze out the curing with composite sheet 1 time warpage, anti-separability and anti-fragility are also good.
Promptly; When the ratio of resinous principle is lower than 65 volume %; Because the ratio of resinous principle is few; Therefore 1 pair of composite sheet seals or the insulating bonding region, for example the landfill property of interelectrode recess etc. may be not enough, in the time of possibly can't fully suppressing to be processed into electronic devices and components, peeling off with rimose when particularly cutting take place.On the other hand, when the ratio of resinous principle was higher than 93 volume %, the resin that is attached to the fiber base material surface was many, and the outflow of resin increases, and therefore oozing out beyond bonding region increased, and composite sheet 1 ftractures easily.
The ratio of resinous principle is meant the ratio of the resin combination by volume in the whole composite sheet 1.Here, resin combination is meant the resin combination as the constituent of flaky resin compsn.The ratio of resinous principle [volume %] can be tried to achieve through following formula.
The ratio of resinous principle [volume %]
={ (quality [the g/m of the thickness of composite sheet [μ m]-fiber base material
2Proportion [the g/cm of]/fiber
3])/thickness [μ m] of composite sheet } * 100
For example, to have the thickness of a glasscloth as fiber base material, composite sheet 1 be that the quality of 160 [μ m], glasscloth is 48 [g/m to composite sheet 1
2], the proportion of glass is 2.54 [g/cm
3] time, can be described below and try to achieve.
The ratio of resinous principle [volume %]
={(160[μm]-48[g/m
2]/2.54[g/cm
3])/160[μm]}×100
=88
The thickness of resin layer 2 is preferably 30～500 μ m.Thickness is during less than 30 μ m, and the monomeric operability of flaky resin compsn that for example is used to form resin layer 2 is not good.In addition, composite sheet 1 is adhered to the electronic devices and components element and when processing electronic devices and components, when being processed into electronic devices and components, particularly when cutting, composite sheet 1 may be peeled off from electronic devices and components.On the other hand, during greater than 500 μ m, resin layer 2 ftractures easily, and the slimming of electronic devices and components is also difficult.
The thickness of fiber base material layer 3 is preferably 30～180 μ m.During less than 30 μ m, the monomeric operability of fiber base material that is used to form fiber base material layer 3 is not good.On the other hand, during greater than 180 μ m, be difficult to make resin impregnated to whole fiber base material.
The thickness of composite sheet 1 can be selected suitable thickness according to the thickness of resin layer 2 and fiber base material layer 3 and the purposes of composite sheet 1, is preferably 100～500 μ m usually.
Plasticity number under the normal temperature (25 ℃) of the resin combination of formation resin layer 2 is preferably 60～90.Plasticity number can't suppress the outflow of resin combination less than 60 o'clock, and oozing out outside bonding region increases, and caused the pollution on every side of bad order and bonding region.In addition, plasticity number was greater than 90 o'clock, and the space in the bonding region may increase and take place bonding bad bad with filling.Plasticity number in this specification sheets can be measured with parallel plate plasticity number meter according to the method based on JISK6249.
3 driving fit of fiber base material layer are formed at least one side's of resin layer 2 interarea.Constitute in the fiber base material of fiber base material layer 3; Better be soak into constituent that the flaky resin compsn that constitutes resin layer 2 is arranged at least a portion in its space, be resin combination, good especially is that all spaces are all soaked into the compositions of thermosetting resin that constitutes resin layer 2 is arranged.That is, the fiber base material of formation fiber base material layer 3 better is the surface portion that is configured to be embedded in resin layer 2.
Fiber base material both can be that woven cloth also can be a non-woven fabrics, can adopt fiber base material arbitrarily.In addition, its constituent material does not have special qualification yet, can adopt spun glass, aromatic polyamide fibre, cellulosic fibre, trevira etc., and they can use separately or mix more than 2 kinds and use.
Fiber base material better is glasscloth or zellglas, and good especially is glasscloth.The kind of glasscloth does not have special qualification, better is the tabby weave E glasscloth etc. of IPC-EG-140 regulation, the glasscloth of thick 30～180 μ m of 1078 types, 1080 types, 1037 types, 1084 types, 2110 types, 7628 types and so on especially.
[method for making of composite sheet]
Through such method of manufacture, can be manufactured on the composite sheet 1 that driving fit on the interarea of resin layer 2 is formed with fiber base material layer 3 easily.In the above-mentioned method of manufacture, mold release film 4 is conducted to when supplying with mixing thing and fiber base material the one or both sides of mixing thing and fiber base material, can be made into composite sheet 1 with mold release film 4.
The supply mode of mixing thing does not have special qualification, can adopt bulk, sheet, molten.In addition, the shaping of mixing thing and fiber base material both can be carried out through batch mode, also can carry out continuously with thermocompressor or backer roll etc.
The manufacturing of composite sheet 1 is good especially to be following method: after mixing thing is conducted to the one side of fiber base material or is conducted to mixing thing between a pair of fiber base material, make them pass through between a pair of backer roll it to be configured as sheet integratedly.A pair of backer roll better is to adjust the backer roll of crack size therebetween, for example better is that diameter is that 20～60mm, gap size are the backer roll about 5～500 μ m.In addition, being used for incorporate shaping better is in 30～180 ℃ TR, to pass through backer roll with 0.1～5m/ minute speed.Through adopting such temperature and, can obtaining good composite sheet 1 through speed.
Fig. 4 is the brief configuration figure of first embodiment of manufacturing installation and the method for manufacture of expression composite sheet 1.Manufacturing installation 10 for example comprises: the resin combination 5 that will become resin layer 2 is processed feedway 11, the coiling fiber base material of supplying with after the molten 6 and the base material of supplying with this fiber base material 6 with roller 12, coiling mold release film 4 and supply with a pair of mold release film of this mold release film 4 with a pair of guide reel 14 of roller 13, guiding fiber base material 6 and mold release film 4, to a pair of backer roll 15 of fiber base material 6 and mold release film 4 pressurizations etc. by bulk.
In this manufacturing installation 10, between a pair of guide reel 14, supply with a pair of mold release film 4 continuously with roller 13, and between this a pair of guide reel 14, supply with fiber base material 6 with roller 12 continuously from base material from a pair of mold release film.In addition, between a fiber base material 6 and a side's mold release film 4, supply with the resin combination 5 of processing molten by bulk from feedway 11.Make these aliments through between a pair of backer roll 15 again.
Through aforesaid operation, can be made into to be embedded with on the interarea of resin combination 5 and soak into the composite sheet 1 that has resin combination 5 and outermost layer to be provided with mold release film 4 in fiber base material 6 or the fiber base material 6.Particularly a pair of backer roll 15 through adopting the clearance-adjustable size, make the gap of the constituent material of composite sheet 1 through them; Can adjust bury degree or resin combination 5 the soak into degree in fiber base material 6 of fiber base material 6 in resin combination 5, and the integral thickness of sheet material 1 is closed in also adjustable reduction.
Fig. 5 is the brief configuration figure of second embodiment of manufacturing installation and the method for manufacture of expression composite sheet 1.This manufacturing installation 10 is in manufacturing installation shown in Figure 4 10, further to append base material to be provided with the manufacturing installation of a pair of base material with roller 12 with roller 12.A pair of base material is configured to each fiber base material 6 is wound in respectively the part of the periphery of a pair of guide reel 14 with roller 12.
In this manufacturing installation 10, between a pair of guide reel 14, supply with a pair of mold release film 4 continuously with roller 13, and between this a pair of guide reel 14, supply with a pair of fiber base material 6 with roller 12 continuously from a pair of base material from a pair of mold release film.Through aforesaid operation, can be made into the composite sheet 1 that has a pair of fiber base material 6 on two interareas of resin layer 2.
Fig. 6 is the brief configuration figure of the 3rd embodiment of manufacturing installation and the method for manufacture of expression composite sheet 1.This manufacturing installation 10 is identical with the substruction of manufacturing installation 10 shown in Figure 4; But different in the following areas: have sheet material and replace feedway 11 with roller 16, this sheet material with roller 16 be used to reel flaky resin compsn 7 monomer and supply with this sheet material resin combination 7.Thus, can directly supply with flaky resin compsn 7 and make composite sheet 1.
Fig. 7 is the brief configuration figure of the 4th embodiment of manufacturing installation and the method for manufacture of expression composite sheet 1.This manufacturing installation 10 is in manufacturing installation shown in Figure 6 10, further to append base material to be provided with the manufacturing installation of a pair of base material with roller 12 with roller 12.Through aforesaid operation, can be made into the composite sheet 1 that has a pair of fiber base material 6 on two interareas of resin layer 2.
More than; Method to using backer roll 15 to make composite sheet 1 continuously is illustrated; But composite sheet 1 also can be through following method manufacturing: its constituent material with the regulation sequential cascade, is pressurizeed under the condition of the temperature about 50～100 ℃, pressure 0.5～1.5MPa with forming mill.
Then, the application examples to flaky resin compsn 7 of the present invention and composite sheet 1 specifies.Below, be that example describes with flaky resin compsn 7, also can be applied for composite sheet 1 through same method.
[circuit elements device]
For the circuit substrate that electronic devices and components such as semi-conductor, chip-resistance, diode, electrical condenser are installed, through coveing with flaky resin compsn 7 of the present invention and make its thermofixation, can be simply with face seal or covering and process the circuit elements device.Adopt sealing, the covering method of the electronic devices and components of flaky resin compsn 7 of the present invention not to have special qualification, for example can be described below seal, overlapping operation.
For example cover with flaky resin compsn 7 on the circuit substrate of electronic devices and components being equipped with, make its overlay electronic components and parts, be heated to about 80～200 ℃ then, be preferably 100～150 ℃ temperature; Make 7 fluidizations of flaky resin compsn; After making electronic devices and components not fill the position on every side, heating about 0.5～2 hour under 100～180 ℃ the temperature again, making the resin solidification of fluidization; Through above-mentioned simple operation, can obtain circuit elements device of the present invention.In the circuit elements device that obtains as stated, cured article seldom produces warpage or distortion, and the generation of not filling the position around the electronic devices and components is also few.
[sealings of hollow electronic devices and components]
Adopt sheet material resin combination 7 of the present invention, can be easy and carry out the sealing of the electronic devices and components with hollow space of SAW device and so on good yield rate.At first; For example cover and be installed in the electronic devices and components on the substrate with flaky resin compsn 7; Be heated to about 80～150 ℃, be preferably 100～150 ℃ temperature, make 7 fluidizations of flaky resin compsn after, heating under 100～180 ℃ the temperature about 0.5～2 hour again; The flaky resin compsn 7 of fluidization is solidified, thus can be airtight or the gap filled with being formed on gap periphery between electronic devices and components and the substrate.
One of its schematic sectional view is illustrated in Fig. 8 (a)～(e).Among each figure, 7 is the flaky resin compsn, and 31 and 32 is electronic devices and components (31 for example are chip-shaped device, and 32 for example is salient point), and 33 is substrate.Among the present invention, airtight Fig. 8 of being meant (a), (c) or (d) shown in be formed on the state that the gap between electronic devices and components and the substrate is maintained, fill be meant Fig. 8 (b) or (e) shown in resin combination be full of this gap and state that the gap disappears.Utilize flaky resin compsn 7 of the present invention; Through adjusting Heating temperature etc.; Both can fill the gap that is formed between electronic devices and components and the substrate; Also can keep the gap that is formed between electronic devices and components and the substrate, not seal with the state of resin combination and substrate contacts with the electric function portion shown in for example Fig. 8 (d).As element with electric function portion, sensor elements such as piezoelectric elements such as the quartz crystal unit for example of can giving an example, the circuit element that forms high frequency circuit, photo detector etc.
[electrical connections of electronic devices and components]
Use flaky resin compsn 7 of the present invention, can be easy and carry out the electrical connection of electronic devices and components and substrate with good yield rate.Fig. 9～13rd is used to explain the process chart of the method for attachment of electronic devices and components.
At first, for example shown in Figure 9, prepare to be formed with substrate 41 as the terminal pad portion 42 of first electrode.Substrate 41 for example can be had the formations such as metal sheet of MOX by glass substrate, ceramic substrate, resin substrate (BT, PET etc.), glass epoxy substrate (FR-4, FR-5), surface coverage.
Then, shown in figure 10, coating conductive paste 43 in the terminal pad portion 42 of substrate 41.Conductive paste 43 can use with resin as base resin and be added with the conductive paste of conducting particles.Then, shown in figure 11, the area configurations flaky resin compsn 7 that does not form terminal pad portion 42 and conductive paste 43 in substrate 41.
Then, shown in figure 12, prepare electronic devices and components 44.The lower surface of these electronic devices and components 44 is formed with the electrode holder 45 as second electrode.Be formed with metal electrode salient point 46 across shielded metal films such as Cr-Cu, Ti-Pd through plating method on the electrode holder 45.Metal electrode salient point 46 for example can be made up of Au, Ag, Cu.In addition, also can supply with soldering tin material, process the scolding tin salient point, to replace metal electrode salient point 46 through backflow.In this embodiment, conductive paste is arranged in the terminal pad portion 42 of substrate 41, but also can be arranged on the metal electrode salient point 46.
Then, electronic devices and components 44 are configured on the substrate 41, make the position consistency of conductive paste 43 of metal electrode salient point 46 and substrate 41 of electronic devices and components 44, in the temperature that is heated under the pressure of 0～0.1Pa about 80～150 ℃.Then, make conductive paste 43 and 7 fusions simultaneously of flaky resin compsn after, cool off, conductive paste 43 and flaky resin compsn 7 are solidified together.By this, shown in figure 13, substrate 41 and electronic devices and components 44 are that electric connector 47 is electrically connected through the cured article of conductive paste 43 grades, and pass through cured article 8 mechanical connections of flaky resin compsn 7.
As stated, in this embodiment, make conductive paste 43 and flaky resin compsn 7 fusion and curing together, substrate 41 and electronic devices and components 44 be electrically connected and mechanical connections, therefore with compared as long as implement the heating process in a stage in the past.In addition, through above-mentioned heat treated, conductive paste 43 and 7 fluidizations simultaneously of flaky resin compsn, the pressure maximum that therefore puts on electronic devices and components 44 also can only reach 0.1Pa.Therefore, even under the situation of electronic devices and components 44 fragilities, can not destroy electronic devices and components 44 yet.
[electronic devices and components bonding, fixing]
Use flaky resin compsn 7 of the present invention, can not have under the situation of stationary fixture easy and electronic devices and components such as miniaturized electronics are fixed in substrate or framework with good yield rate.Describe through Figure 14～16 and 17～19.
Figure 14～16th is used for explaining the process chart of the method that this embodiment is connected with substrate as the vibrating motor of electronic devices and components.Figure 14 and 16 is the front views that are used to explain the method for attachment of vibrating motor, and Figure 15 is the relevant side-view of the method for attachment of vibrating motor shown in Figure 14.
At first, for example shown in Figure 14 and 15, prepared substrate or framework 51 and vibrating motor 52.Metal sheet that substrate or framework 51 for example have MOX by glass epoxy board or surface coverage etc. constitutes.Vibrating motor 52 for example has motor body 520 and eccentric counterweight 522.Like Figure 14 and shown in Figure 15, the flaky resin compsn 7 that motor body 520 is cut into specified length covers, and substrate or framework 51 are fixed in the contact of the end of flaky resin compsn 7.The contact of 7 pairs of substrates of flaky resin compsn or framework 51 is fixing both can be carried out through the caking agent of regulation, and the 7 partial melting sets of flaky resin compsn are carried out.
In this embodiment, shown in figure 16, through flaky resin compsn 7 is heated; Flaky resin compsn 7 is softening; Softening fusion under across the state of the part of the part of substrate or framework 51 and motor body 520, the part of substrate or framework 51 and the contact part of motor body 520 enlarge along surface separately, curing under this state; Become illustrated cured article 8, thereby can be made into vibration generating arrangement 50.Therefore, can substrate or framework 51 be adhesively fixed with vibrating motor 52 securely.
Figure 17～19th is used for explaining the process chart with another method of attachment of the vibrating motor of this embodiment.Figure 17 and 19 is the front views that are used to explain the method for attachment of vibrating motor, and Figure 18 is the relevant side-view of the method for attachment of vibrating motor shown in Figure 17.
Like Figure 17, shown in 18, at substrate or framework 51 laminated flaky resin compsn 7 is arranged, configuration vibrating motor 52 on this flaky resin compsn 7.Then; Shown in figure 19, be heating and curing through making flaky resin compsn 7, during fusion before curing; Deadweight because of vibrating motor 52; Its part is embedded in the fused flaky resin compsn 7, and vibrating motor 52 around on lift, with roomy face maintain vibrating motor 52 around.Then, the cured article 8 through flaky resin compsn 7 is adhesively fixed.
Through this embodiment; With substrate or framework 51 with motor body 520, be that vibrating motor 52 is configured to contact with the flaky resin compsn 7 that is disposed at therebetween respectively; Flaky resin compsn 7 is heating and curing and fixes, thereby constitute vibration generating arrangement 10.Flaky resin compsn 7 is thinner than elastomericss such as rubber, and flaky resin compsn 7 is heating and curing, so the part of vibrating motor 52 is embedded in the fused flaky resin compsn 7.
Therefore; With fix the situation of vibrating motor and compare through being configured in the intravital elastomerics of frame that is used to dispose vibrating motor through the situation that metal holder fixes vibrating motor, need not loaded down with trivial details operation can be easy and at an easy rate vibrating motor is fixed in substrate or framework.
[electronic devices and components, electronics]
Example for the electronic devices and components element that uses in the manufacturing of electronic devices and components shown in Figure 20.Electronic devices and components element 61 for example comprise element body 62 and with surperficial 2 external connection electrode 63 that are provided with of this element body 62 separated from one anotherly.For example, the interelectrode distance of 2 external connection electrode 63 is 2.0mm, and electrode height is 0.3mm.Flaky resin compsn 7 for example is used for 2 insulation between the external connection electrode 63.The insulation of adopting flaky resin compsn 7 to carry out for example can be described below and carry out.
That is, between 2 external connection electrode 63, cover with flaky resin compsn 7.Then, be heated to about 80～200 ℃, be preferably 100～150 ℃ temperature, make 7 fluidizations of flaky resin compsn.Heating about 0.5～2 hour under 100～180 ℃ the temperature again, the flaky resin compsn 7 of fluidization is solidified.Through aforesaid operation, like Figure 21, shown in 22, flaky resin compsn 7 capable of using (cured article) is with suitably covering, insulate between the external connection electrode 63, thus electron gain components and parts 64.At this moment, replace flaky resin compsn 7, can easily obtain the product that has an even surface shown in Figure 22 through using composite sheet 1.
Embodiment
Then, the present invention will be described in more detail through embodiment, but the present invention is not limited to these examples.Each characteristic in each example is tried to achieve according to the method shown in following.
< flaky resin compsn >
(1) gel time
According to the test tube method of JISC2105, in 100 ℃ oil bath, measure the flaky resin compsn and become the required time of gel.
(2) sheet material characteristic
Estimate according to following criterion.
Zero: at room temperature soft, do not crack and fragment, and be not in a liquid state.
△: at room temperature soft, be not in a liquid state, but crack or fragment.
*: can't process sheet material.
(3) flowability during fusion
The square chip of 2mm that is arranged on the FR-4 substrate is sealed with sheet-like composition, confirm landfill property through range estimation.Condition of cure is 100 ℃, 2 hours.Estimate according to following criterion.
Zero: good.
*: do not fill the position around the components and parts.
(4) melt viscosity
Measure (100 ℃) with rheometer (rheology science (Rhenemetric Scientific) corporate system).
< cured article >
(5) second-order transition temperature
Be warming up to 200 ℃ (10 ℃/minute of heat-up rates) with TMA/SS150 (Seiko Electronics Co., Ltd (セ イ コ one イ Application ス Star メ Application Star society) system) from room temperature, measure second-order transition temperature.
(6) flame retardancy
With UL94 is the condition evaluating flame retardancy of benchmark with test film thickness 1.6mm.
(7) warpage
(30mm * 20mm) is carried on the FR-4 substrate of thick 0.3mm, and (45mm * 30mm) solidified 2 hours in 100 ℃, measured the height of four jiaos of substrates after solidifying, with the index of its MV as warpage with sheet-like composition.
[embodiment 1～9 and comparative example 1～3]
Each raw material that proportioning shown in the table 1 is formed drops into kneader, mixes 1 hour in 70 ℃, is modulated into each resin combination.Then, each resin combination is cooled to 30 ℃ respectively after, with forming mill press molding under 70 ℃, the condition of 1.0MPa, process the sheet material of thick 0.5mm, process each flaky resin compsn.
The evaluation result of each characteristic of each example is shown in table 1.For example SP57 ℃ of expression softening temperature of the solid epoxy resin next door record in the table 1.
Each composition that uses is described below.
1. liquid-state epoxy resin
(1) R140P: the bisphenol A type epoxy resin of Mitsui Chemicals corporate system (number-average molecular weight: 380, epoxy equivalent (weight): 190)
(2) DER383J: the bisphenol A type epoxy resin of Dow Chemical's system (epoxy equivalent (weight): 190)
(3) エ ピ コ ー ト #807: the bisphenol f type epoxy resin of japan epoxy resin corporate system (epoxy equivalent (weight): 160～175)
2. solid epoxy resin
(1) NC3000: the multifunctional type epoxy resin that contains the bis-phenol skeleton of Japanese chemical drug corporate system (epoxy equivalent (weight): 285, softening temperature: 57 ℃)
(2) NC3000H: the bis-phenol matrix type epoxy resin of Japanese chemical drug corporate system (epoxy equivalent (weight): 290, softening temperature: 70 ℃)
(3) YDCN704: Dongdu changes into the cresols line style phenol aldehyde type epoxy resin (epoxy equivalent (weight): 210, softening temperature: 90 ℃) of corporate system
3. solidifying agent
(1) DICY: the Dyhard RU 100 of Japanese carbide company (Japanese カ one バ イ De society) system
(2) EH-4370S: the modified aliphatic polyamine of rising sun electrification company (A D E K A society) system
4. curing catalyst
U-CAT3502T: the aromatic series dimethyl urea of Sang Apuluo company (サ Application ア プ ロ society) system
5. mineral filler
FB-959: the spherical silicon dioxide of Denki Kagaku Kogyo kabushiki's system (mass median diameter: 25 μ m)
6. fire retardant
(1) phosphazene compound [R in the said general formula (3) of SPB-100: Da mound chemical company system
1And R
2Be phenyl, k is more than 3]
(2) H42M: the white lake (particle diameter: 1.5 μ m) of clear and electrician's corporate system
When using white lake as fire retardant, its incorporation is calculated in mineral filler.
[table 1]
Can know that by table 1 projects of the flowability when the sheet material characteristic of embodiment, fusion, flame retardancy, warpage are good basically.Relative with it; The product of not use (A) the liquid bisphenol type epoxy resin that comparative example 1 is such and (A) liquid bisphenol type epoxy resin of comparative example 2 and (B) softening temperature are that the mass ratio (A)/(B) of the solid-state polyfunctional epoxy resin below 70 ℃ is poor in the sheet material characteristic of 10/90～30/70 extraneous product, and the flowability of comparative example 3 such softening temperatures when being higher than 70 ℃ the fusion of product is poor.
The possibility of utilizing on the industry
Flaky resin compsn of the present invention need not the such large-scale coating apparatus of existing adhesive sheet and can make, and with an organic solvent can not make, and the warpage of cured article or distortion are few, can carry out the sealing of circuit elements device etc. simply.Such flaky resin compsn is suitable for manufacturing, the sealing of electronic devices and components, the connection and fixing of circuit elements device.In addition, flaky resin compsn of the present invention is fit to process composite sheet and the manufacturing that is used for electronic devices and components.
The explanation of symbol
1 ... Composite sheet; 2 ... Resin layer; 3 ... The fiber base material layer; 4 ... Mold release film; 5 ... Resin combination; 6 ... Fiber base material; 7 ... The flaky resin compsn; 8 ... Cured article; 10 ... Manufacturing installation; 11 ... Feedway; 12 ... Base material is used roller; 13 ... Mold release film is used roller; 14 ... Guide reel; 15 ... Backer roll; 31; 32 ... Electronic devices and components; 33 ... Substrate; 41 ... Substrate; 42 ... Terminal pad portion; 43 ... Conductive paste; 44 ... Electronic devices and components; 45 ... Electrode holder; 46 ... The metal electrode salient point; 47 ... Electric connector; 51 ... Substrate or framework; 52 ... Vibrating motor
Claims (18)
1. flaky resin compsn, it is that to comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature be that solid-state polyfunctional epoxy resin below 70 ℃ is characterized in that as the flaky resin compsn of essential composition with (C) hardener for epoxy resin,
The mass ratio of said (A)/(B) is 10/90～30/70.
2. flaky resin compsn as claimed in claim 1 is characterized in that, said (B) is the mixture of the aralkyl-type epoxy resin that contains the bis-phenol skeleton of following formula (1) expression;
[changing 1]
In the formula, m representes 1～4 integer.
3. flaky resin compsn as claimed in claim 1 is characterized in that, also containing with respect to total composition is that (D) mass median diameter of 10～80 quality % is the spherical silicon dioxide of 4～30 μ m.
4. flaky resin compsn as claimed in claim 1 is characterized in that, also contains the phosphazene compound as (E) fire retardant.
5. a circuit elements device is characterized in that, with described flaky resin compsn sealing of claim 1 or bonding forming.
6. the sealing method of electronic devices and components, it is to cover the sealing method that is installed in the electronic devices and components that are heating and curing behind the electronic devices and components on the substrate with the described flaky resin compsn of claim 1, it is characterized in that,
Cover said electronic devices and components with said flaky resin compsn, airtight around the contact part with said electronic devices and components and said substrate, between said electronic devices and components and said substrate, form the gap.
7. the sealing method of electronic devices and components as claimed in claim 6 is characterized in that, after making said mobileization of flaky resin compsn under 80～150 ℃, heats 0.5～2 hour down at 100～180 ℃ again, and the said flaky resin compsn of fluidization is solidified.
8. the method for attachment of electronic devices and components, its be with the substrate with first electrode that connects usefulness and electronic devices and components with second electrode that is connected usefulness via said first electrode and the method that said second electrode electricity is connected, it is characterized in that,
Comprise the operation that said electronic devices and components is electrically connected with said substrate with the described flaky resin compsn of claim 1.
9. the method for attachment of electronic devices and components as claimed in claim 8 is characterized in that, comprising:
The operation of configuration conductive paste on said first electrode of said substrate;
The operation of the said flaky resin compsn of configuration in the zone of said first electrode of not forming of said substrate;
Said electronic devices and components are carried on said substrate; Make said second electrode contact with said first electrode of said substrate; Said conductive paste and said flaky resin compsn are heating and curing simultaneously, the operation that said electronic devices and components are electrically connected with said substrate.
10. the fixing means of electronic devices and components, it is the method that electronic devices and components is fixed in substrate or framework, it is characterized in that,
The described flaky resin compsn of claim 1 is arranged such that said substrate or said framework contact with said electronic devices and components, said substrate or said framework and said electronic devices and components is fixed with said flaky resin compsn.
11. the fixing means of electronic devices and components as claimed in claim 10; It is characterized in that; Cover said electronic devices and components top with said flaky resin compsn, make its curing, said substrate or said framework and said electronic devices and components are adhesively fixed through thermoplastic or heating and melting.
12. the fixing means of electronic devices and components as claimed in claim 10; It is characterized in that; Said flaky resin compsn is put the electronic devices and components lift-launch face in said substrate or said framework; After carrying said electronic devices and components on the said flaky resin compsn, through thermoplastic or heating and melting said flaky resin compsn is heating and curing, said substrate or said framework and said electronic devices and components are adhesively fixed.
13. composite sheet; It is characterized in that; Comprise resin layer and fiber base material layer, said resin layer has the described flaky resin compsn of claim 1, the driving fit of said fiber base material layer be formed at said resin layer at least one side interarea and have fiber base material.
14. composite sheet as claimed in claim 13 is characterized in that, the ratio of the resinous principle in the said composite sheet is 65～93 volume %.
15. composite sheet as claimed in claim 13 is characterized in that, said fiber base material is to be selected from inorganic fibre base material and organic fibre base material at least a kind.
16. electronic devices and components is characterized in that, comprise the described composite sheet of electronic devices and components main body and claim 13, said composite sheet is configured on the surface of at least a portion of said electronic devices and components main body and with said surface insulation.
17. an electronics is characterized in that, comprises the described composite sheet of claim 13 of electronic devices and components and the said electronic devices and components of sealing.
18. the method for manufacture of a composite sheet is characterized in that, comprising:
The constituent of the described flaky resin compsn of claim 1 is mixing under 50～110 ℃ temperature, obtain the operation of mixing thing;
With said mixing thing be conducted to fiber base material one side or be conducted to said mixing thing between a pair of fiber base material after, through said mixing thing is pressed on said fiber base material and it is configured as sheet integratedly, obtain the operation of composite sheet.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-120879 | 2010-05-26 | ||
| JP2010120879A JP2011246596A (en) | 2010-05-26 | 2010-05-26 | Sheet-like resin composition and circuit component sealed by using the same |
| JP2010-195054 | 2010-08-31 | ||
| JP2010195054A JP2012054363A (en) | 2010-08-31 | 2010-08-31 | Sealing method of electronic component |
| JP2010-286338 | 2010-12-22 | ||
| JP2010286338A JP2012134383A (en) | 2010-12-22 | 2010-12-22 | Method for connection of electronic component |
| JP2010-292219 | 2010-12-28 | ||
| JP2010292219A JP2012139616A (en) | 2010-12-28 | 2010-12-28 | Method for fixing vibration motor, and vibration generator |
| JP2011-114314 | 2011-05-23 | ||
| JP2011114314A JP2012240348A (en) | 2011-05-23 | 2011-05-23 | Composite sheet, method for manufacturing the composite sheet, electronic component, and electronic instrument |
| PCT/JP2011/002891 WO2011148620A1 (en) | 2010-05-26 | 2011-05-24 | Sheet-like resin composition, circuit component using the sheet-like resin composition, method for sealing electronic component, method for connecting electronic component, method for affixing electronic component, composite sheet, electronic component using the composite sheet, electronic device, and method for producing composite sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102725323A true CN102725323A (en) | 2012-10-10 |
| CN102725323B CN102725323B (en) | 2015-08-19 |
Family
ID=45003620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180007104.XA Expired - Fee Related CN102725323B (en) | 2010-05-26 | 2011-05-24 | Flaky resin composition, use the manufacture method of the sealing method of the circuit components of this flaky resin composition, electronic devices and components, method of attachment and fixing means and composite sheet, the electronic devices and components using this composite sheet, electronics, composite sheet |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20130079311A (en) |
| CN (1) | CN102725323B (en) |
| WO (1) | WO2011148620A1 (en) |
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| CN105027266A (en) * | 2013-03-04 | 2015-11-04 | 日东电工株式会社 | Semiconductor device production method, sheet-shaped resin composition, dicing tape-integrated sheet-shaped resin composition |
| CN105074905A (en) * | 2013-03-28 | 2015-11-18 | 日东电工株式会社 | Resin sheet for electronic device sealing and production method for electronic device package |
| CN105938817A (en) * | 2015-03-03 | 2016-09-14 | 日东电工株式会社 | Hollow electronic device sealing sheet and manufacturing method of the same |
| CN106046677A (en) * | 2016-05-27 | 2016-10-26 | 江苏兆鋆新材料股份有限公司 | Epoxy resin and carbon fiber prepreg with storage stability and method for preparing epoxy resin and carbon fiber prepreg |
| CN108463321A (en) * | 2016-01-15 | 2018-08-28 | 日立化成株式会社 | The manufacturing method of prepreg, printed wiring board, semiconductor package body and printed wiring board |
| CN110776719A (en) * | 2019-10-18 | 2020-02-11 | 合肥工业大学 | Method for dispersing nano inorganic particle filler in solid epoxy resin |
| CN112745742A (en) * | 2019-10-31 | 2021-05-04 | 三菱电机株式会社 | Thermosetting resin composition, sheet-type insulating varnish, method for producing same, electrical device, and rotating electrical machine |
| CN109624351B (en) * | 2018-11-21 | 2021-11-23 | 长安大学 | Preparation method of pre-impregnated fiber bundles for three-dimensional weaving |
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| JP7493933B2 (en) * | 2019-12-17 | 2024-06-03 | 日東電工株式会社 | Manufacturing method of magnetic sheet |
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| CN105027266A (en) * | 2013-03-04 | 2015-11-04 | 日东电工株式会社 | Semiconductor device production method, sheet-shaped resin composition, dicing tape-integrated sheet-shaped resin composition |
| CN105074905A (en) * | 2013-03-28 | 2015-11-18 | 日东电工株式会社 | Resin sheet for electronic device sealing and production method for electronic device package |
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| CN109624351B (en) * | 2018-11-21 | 2021-11-23 | 长安大学 | Preparation method of pre-impregnated fiber bundles for three-dimensional weaving |
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| CN112745742A (en) * | 2019-10-31 | 2021-05-04 | 三菱电机株式会社 | Thermosetting resin composition, sheet-type insulating varnish, method for producing same, electrical device, and rotating electrical machine |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20130079311A (en) | 2013-07-10 |
| WO2011148620A1 (en) | 2011-12-01 |
| CN102725323B (en) | 2015-08-19 |
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