CN102725323B - 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 - Google Patents
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 Download PDFInfo
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- CN102725323B CN102725323B CN201180007104.XA CN201180007104A CN102725323B CN 102725323 B CN102725323 B CN 102725323B CN 201180007104 A CN201180007104 A CN 201180007104A CN 102725323 B CN102725323 B CN 102725323B
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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'
-
- 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
Abstract
The present invention is a kind of flaky resin composition, its be comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature is the solid-state polyfunctional epoxy resin of less than 70 DEG C and (C) hardener for epoxy resin as the flaky resin composition of required composition, wherein, the mass ratio of described (A)/(B) is 10/90 ~ 30/70.
Description
Technical field
The present invention relates to flaky resin composition, use 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 manufacture method of the electronic devices and components using this composite sheet, electronics, composite sheet.
Background technology
In the past, as the adhesive sheet used in electronic devices and components field, the known adhesive sheet (such as with reference to patent documentation 1) be made up of compositions of thermosetting resin such as composition epoxy resins.But the operability of existing adhesive sheet and intensity are not good, this adhesive sheet is not good to the landfill of bonding region yet.In addition, add man-hour to the electronic devices and components being bonded with existing adhesive sheet, this adhesive sheet is peeled off sometimes, requires to develop the high adhesive sheet of bonding force.
In addition, as adhesive sheet, the prepreg be made up of fiber base material and compositions of thermosetting resin is also used, such as glass epoxide prepreg (such as with reference to patent documentation 2).The operability of prepreg and strength ratio are better, but not good to the landfill of bonding region, and spendable electronic devices and components are also limited.In addition, the manufacture of prepreg generally needs special large-scale coating machine, also needs organic solvent etc.
Disclose following method: cover with as sealing material thermosetting resin, be better epoxy resin form lamellar resin sheet, make it cover to be arranged on the whole surface of the semi-conductor on real estate, then heat, make this lamellar resin sheet softening and make it have viscosity and bounding force, make this lamellar resin sheet bonding with above-mentioned semi-conductor and aforesaid substrate face by this, after heat treated is carried out to it, make above-mentioned softening lamellar resin sheet solidification, by this by above-mentioned encapsulating semiconductor (with reference to patent documentation 3 ~ 5).
The technology that patent documentation 3 ~ 5 is recorded carrys out the technology of seal electronic element, preferably use epoxy resin as the thermosetting resin of sealing material although describe, for other blending composition used in the kind of epoxy resin, sealing material without any record.The cured article that this technology exists sealing resin easily produces the problem of warpage or distortion, during the melt viscosity height of sealing resin, because resin is bad and cause the possibility producing space etc. high to the filling in the thin portion of electronic component.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2002-60720 publication
Patent documentation 2: Japanese Patent Laid-Open 2-102281 publication
Patent documentation 3: Japanese Patent Laid-Open 2003-249510 publication
Patent documentation 4: Japanese Patent Laid-Open 10-125825 publication
Patent documentation 5: Japanese Patent Laid-Open 2003-249510 publication
Summary of the invention
The object of the present invention is to provide a kind of flaky resin composition, this flaky resin composition can manufacture without the need to the large-scale coating apparatus that existing adhesive sheet is such, and with an organic solvent can not manufacture, and the warpage of cured article or distortion few, the sealing etc. of circuit components can be carried out simply.Object of the present invention is also to provide a kind of circuit components using this flaky resin composition.The present invention also aims to provide a kind of use the electronic devices and components of this flaky resin composition sealing method, method of attachment and fixing means.Object of the present invention is also to provide a kind of manufacture method using the composite sheet of this flaky resin composition, the electronic devices and components using this composite sheet, electronics and this composite sheet.
Flaky resin composition of the present invention be comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature is the solid-state polyfunctional epoxy resin of less than 70 DEG C and (C) hardener for epoxy resin as the flaky resin composition of required composition, it is characterized in that, the mass ratio of described (A)/(B) is 10/90 ~ 30/70.
The feature of circuit components of the present invention is, with flaky resin composition of the present invention sealing or bondingly to form.
The sealing method of electronic devices and components of the present invention is the sealing methods carrying out the electronic devices and components be heating and curing after covering with flaky resin composition of the present invention the electronic devices and components be arranged on substrate, it is characterized in that, described electronic devices and components are covered with described flaky resin composition, by the contact part peripheral containment of described electronic devices and components and described substrate, between described electronic devices and components and described substrate, form gap.
The method of attachment of electronic devices and components of the present invention be by have connect with the substrate of the first electrode and the method that is electrically connected via described first electrode and described second electrode of the electronic devices and components with the second electrode be connected, it is characterized in that, comprise the operation be electrically connected with described substrate by described electronic devices and components with flaky resin composition of the present invention.
The fixing means of electronic devices and components of the present invention is methods electronic devices and components being fixed on substrate or framework, it is characterized in that, flaky resin composition of the present invention is arranged so that described substrate or described framework contact with described electronic devices and components, with described flaky resin composition, described substrate or described framework and described electronic devices and components is fixed.
The feature of composite sheet of the present invention is, comprises resin layer and fibrous substrate layer, and described resin layer has flaky resin composition of the present invention, and described fibrous substrate layer is closely sealed to be formed at the interarea of at least one party of described resin layer and to have fiber base material.
The feature of electronic devices and components of the present invention is, comprises electronic devices and components main body and composite sheet of the present invention, on the surface at least partially that described composite sheet is configured in described electronic devices and components main body and by described surface insulation.The feature of electronics of the present invention is, comprises the composite sheet of the present invention of electronic devices and components and the described electronic devices and components of sealing.
The feature of the manufacture method of composite sheet of the present invention is, comprising: the constituent of compositions of thermosetting resin is mixing at the temperature of 50 ~ 110 DEG C, obtains the operation of mixing thing; Described mixing thing be supplied to the one side of fiber base material or described mixing thing is supplied to after between a pair fiber base material, by pressing described mixing thing and described fiber base material and it being configured as integratedly sheet, obtaining the operation of composite sheet.
The simple declaration of accompanying drawing
Fig. 1 is the sectional view of the brief configuration of the first embodiment representing composite sheet.
Fig. 2 is the sectional view of the brief configuration of the second embodiment representing composite sheet.
Fig. 3 is the sectional view of the brief configuration representing existing prepreg.
Fig. 4 is the explanatory view of the first embodiment of the manufacture method that composite sheet is described.
Fig. 5 is the explanatory view of the second embodiment of the manufacture method that composite sheet is described.
Fig. 6 is the explanatory view of the 3rd embodiment of the manufacture method that composite sheet is described.
Fig. 7 is the explanatory view of the 4th embodiment of the manufacture method that composite sheet is described.
Fig. 8 is schematic sectional view, is depicted as an example of the state after representing that the air gap periphery sealing material that formed between substrate and the electronic devices and components of installation is airtight or filling gap.
Fig. 9 is the process picture sheet of the method for attachment for illustration of electronic devices and components.
Figure 10 is the process picture sheet of the method for attachment for illustration of electronic devices and components.
Figure 11 is the process picture sheet of the method for attachment for illustration of electronic devices and components.
Figure 12 is the process picture sheet of the method for attachment for illustration of electronic devices and components.
Figure 13 is the process picture sheet of the method for attachment for illustration of electronic devices and components.
Figure 14 is the front view of the first embodiment of fixing means for illustration of electronic devices and components.
Figure 15 is the side-view of the first embodiment of fixing means for illustration of electronic devices and components.
Figure 16 is the front view of the first embodiment of fixing means for illustration of electronic devices and components.
Figure 17 is the front view of the second embodiment of fixing means for illustration of electronic devices and components.
Figure 18 is the side-view of the second embodiment of fixing means for illustration of electronic devices and components.
Figure 19 is the front view of the second embodiment of fixing means for illustration of electronic devices and components.
Figure 20 is the sectional view of the example representing the electronic devices and components main body employing composite sheet.
Figure 21 is the sectional view of the example representing the electronic devices and components employing composite sheet.
Figure 22 is the sectional view of another example representing the electronic devices and components employing composite sheet.
The mode carried out an invention
First, flaky resin composition of the present invention is described.
[flaky resin composition]
Flaky resin composition of the present invention be comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature is the solid-state polyfunctional epoxy resin of less than 70 DEG C and (C) hardener for epoxy resin as the flaky resin composition of required composition, it is characterized in that, the mass ratio of described (A)/(B) is 10/90 ~ 30/70.Flaky resin composition of the present invention is better (D) mineral filler of 10 ~ 80 quality % containing total composition, and is better containing (E) fire retardant.
[(A) composition]
In flaky resin composition of the present invention, use liquid bisphenol type epoxy resin as (A) composition.
As this liquid bisphenol type epoxy resin, as long as have the bisphenol type compounds of the liquid state of more than 2 epoxy group(ing) in 1 molecule, be not particularly limited, such as preferred bisphenol A-type and bisphenol-f type.Wherein, preferred use liquid bisphenol A type epoxy resin, as its concrete example, " エ ピ コ ー ト #807 " (epoxy equivalent (weight) 170) that " DER383 ", japan epoxy resin company (ジ ャ パ Application エ Port キ シ レ ジ Application society) that " R140P " (epoxy equivalent (weight) 188) that Mitsui Chemicals, Inc. (Mitsui Chemicals society) can be used to make, Dow Chemical (ダ ウ ケ ミ カ Le society) make make etc.These liquid bisphenol type epoxy resin can be used alone a kind, also can two or more combinationally use.In the present invention, liquid bisphenol type epoxy resin refers to the bisphenol-type epoxy resin be in a liquid state at 25 DEG C.
[(B) composition]
In flaky resin composition of the present invention, be the solid-state polyfunctional epoxy resin of less than 70 DEG C as (B) composition use softening temperature.As the solid-state polyfunctional epoxy resin that this softening temperature is less than 70 DEG C, the mixture of the aralkyl-type epoxy resin containing bisphenol backbone that such as following formula (1) represents can be exemplified.In following formula (1), m represents the integer of 1 ~ 4.
[changing 1]
Also can exemplify the mixture etc. of the dicyclopentadiene-type epoxy resin that following formula (2) represents.In following formula (2), n represents the integer of 1 ~ 10.
[changing 2]
The softening temperature of these solid-state polyfunctional epoxy resins is the values recorded by following method.
The mensuration > of < softening temperature
According to JISK2207, in the ring of regulation, fill sample, horizontal support is in water-bath or glycerol bath, the ball of regulation is placed in the central authorities of sample, bath temperature is raised with the speed of per minute 5 DEG C, and read temperature when being wrapped in the contacts baseplate of the sample of ball and land, this temperature is softening temperature.
Be the commercial goods of the solid-state polyfunctional epoxy resin of less than 70 DEG C as this softening temperature, " NC3000 (softening temperature 57 DEG C) ", " NC3000H (softening temperature 70 DEG C) " that preferably use Japanese chemical drug company (Japanese chemical drug society) to make etc.
In the present invention, by with (A) liquid bisphenol type epoxy resin and (B) softening temperature being also the solid-state polyfunctional epoxy resin of less than 70 DEG C, namely, by the mixing of different for fusing point two kinds of epoxy resin, the flaky resin composition of behavior demonstrating under room temperature in the form of sheets, be in a liquid state under high temperature can be obtained.
In the present invention, require that the mass ratio of described (A)/(B) is in the scope of 10/90 ~ 30/70.If liquid-state epoxy resin is less than the softening temperature of described scope or solid epoxy resin higher than 70 DEG C, then sheet material cracks or fragment, undesirable.If liquid-state epoxy resin is too low more than the softening temperature of described scope or solid epoxy resin, then not easily form sheet material.Consider from above-mentioned angle, the mass ratio of (A)/(B) more preferably 15/85 ~ 25/75 scope, the lower limit of the softening temperature of solid epoxy resin is generally about 40 DEG C.
[(C) composition]
In flaky resin composition of the present invention, use hardener for epoxy resin as (C) composition.Be not particularly limited as this hardener for epoxy resin, the solidifying agent that can use from the solidifying agent in the past as epoxy resin, the suitable arbitrary solidifying agent of choice for use, can exemplify such as amine, phenol, anhydrides etc.As amine curing agent, can illustrate as Dyhard RU 100, mphenylenediamine, 4 by preference, 4 '-diaminodiphenyl-methane, 4, the aromatic diamine such as 4 '-diaminodiphenylsulfone(DDS), m-xylene diamine etc., as phenol solidifying agent, can illustrate as lacquer resins, cresol novolaks, bisphenol A-type novolac resin, triazine modified linear phenol-aldehyde resin etc. by preference.As acid anhydride type curing agent, the halogen such as aliphatic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride such as the aromatic anhydrides such as alicyclic acid anhydrides, Tetra hydro Phthalic anhydride such as such as methylhexahydrophthalic anhydride, binary aliphatic acid anhydrides (PAPA) acid anhydrides etc. can be exemplified.These solidifying agent can be used alone a kind, also can two or more combinationally use.Angularly consider from the balance of solidified nature and cured resin physical property, the consumption of this hardener for epoxy resin using the equivalent ratio relative to the epoxy resin as described (A) and (B) composition, about being generally 0.5 ~ 1.5 equivalence ratio, selected in the scope of preferably 0.7 ~ 1.3 equivalence ratio.
[any composition: curing catalyst used for epoxy resin]
In flaky resin composition of the present invention, can as required containing curing catalyst used for epoxy resin in the scope not affecting effect of the present invention.Be not particularly limited as this curing catalyst used for epoxy resin, the suitable arbitrary curing catalyst of choice for use the curing catalyst that can use from the curing catalyst in the past as epoxy resin.Such as, the aromatic series dimethyl urea as urea can be exemplified, aliphatics dimethyl urea, 3-(3, 4-dichlorophenyl)-1, 1-dimethyl urea (DCMU), 3-(the chloro-4-aminomethyl phenyl of 3-)-1, 1-dimethyl urea, 2, 4-two (3, 3-dimethyl urea groups) ureas such as toluene, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, glyoxal ethyline, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-phenylimidazole, the imidazolium compoundss such as 2-phenyl-4-methylimidazole, 2, 4, 6-tri-(dimethylamino methyl) phenol, boron trifluoride amine complex, triphenylphosphine etc.These curing catalysts can be used alone a kind, also can two or more combinationally use.Angularly consider from the balance of solidification promotion property and cured resin physical property, the consumption of this curing catalyst used for epoxy resin relative to epoxy resin 100 mass parts as described (A) and (B) composition, about being generally 0.1 ~ 10 mass parts, selected in the scope of preferably 0.4 ~ 5 mass parts.
[(D) composition]
In flaky resin composition of the present invention, mineral filler can be contained as (D) composition.Be not particularly limited as this mineral filler, such as, can use the fused silica pulverized through ball mill etc., the spherical silicon dioxide obtained by flame melting, silica-based by the obtained spherical silicon dioxide such as sol-gel method etc.; Aluminum oxide; The metal hydrate such as aluminium hydroxide and magnesium hydroxide; Titanium oxide; The mineral filler that carbon black etc. are conventional.These mineral fillers can be used alone a kind, also can two or more combinationally use.Consider from the angle of operability when manufacturing and charging efficiency, the mass median diameter of this mineral filler is better be in the scope of 4 ~ 30 μm.This mass median diameter is the value recorded by laser diffraction and scattering mode (such as Shimadzu Seisakusho Ltd.'s system, device name: SALD-3100).
Better spherical silicon dioxide as this mineral filler, " FB-959 (mass median diameter: 25 μm) " etc. of such as preferred Denki Kagaku Kogyo kabushiki.The content of this mineral filler is better be 10 ~ 80 quality % relative to resin combination total amount.Here, do not make following composite sheet, when namely fiber base material not being set on flaky resin composition, preferably 50 ~ 80 quality %.When fiber base material is not set, by making content reach more than 50 quality %, when carrying out sealed electronic element with flaky resin composition, cured article can be effectively suppressed to produce warpage or distortion.In addition, by making content reach below 80 quality %, can effectively suppress flaky resin composition to crack or fragment, melting time mobility decline, produce phenomenons such as not filling position around components and parts.On the other hand, when making composite sheet, if content reaches more than 10 quality %, then can suppress the warpage etc. of cured article.In addition, when making composite sheet, by making content reach below 50 quality %, mobility during melting can be improved, suppressing the generation of not filling position, therefore preferably.When using metal hydrate as mineral filler, also play the effect of fire retardant.
[any composition: coupling agent]
In flaky resin composition of the present invention, consider from the angle of fillibility, coupling agent can be contained as required.As coupling agent, silicane, titanate ester, aluminium class etc. can be exemplified, wherein preferred silane coupling agent.As silane coupling agent, particularly preferably use the amino silane compounds such as gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, N-β-(N-vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane and N-β-(N-vinylbenzylaminoethyl)-γ aminopropyltriethoxy silane.The content of this silane coupling agent is about 0.03 ~ 5.0 quality % relative to resin combination total amount, preferably 0.1 ~ 2.5 quality %.
[(E) composition]
In flaky resin composition of the present invention, be better use fire retardant as (E) composition.Be not particularly limited as this fire retardant, such as, can use phosphorus compound, metal hydrate etc.As phosphorus compound, such as, there are (a) phosphazene compound, (b) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivative thereof, (c) phosphate compound, (d) phosphoric ester amides etc.
As described (a) phosphazene compound, be not halogen-containing in fact compound, angularly consider from thermotolerance, wet fastness, flame retardancy, chemical-resistant, preferably use fusing point is the phosphazene compound of more than 80 DEG C.As a specific example, the ring Phosphazene oligomers that following general formula (3) represents can be exemplified.
[changing 3]
In described general formula (3), R
1and R
2separately represent hydrogen atom or not halogen-containing organic group, k represents the integer of 3 ~ 10.In described general formula (3), as R
1and R
2in not halogen-containing organic group, the alkoxyl group of such as carbon number 1 ~ 10, phenoxy group, amino, allyl group etc. can be exemplified.As such phosphazene compound, such as great mound chemical company (great mound chemistry society can be exemplified) " SPB-100 " that make etc.
Described (b) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide has the structure that formula (4) represents.
[changing 4]
In addition, as its derivative, (2,5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound etc. that the such as formula (5) that can exemplify represents.
[changing 5]
The compound that above formula (4) represents can be used as " SANKO-HCA " [Sanko Co., Ltd.'s system, trade(brand)name] obtain, the compound that above formula (5) represents can be used as " SANKO HCA-HQ " [Sanko Co., Ltd.'s system, trade(brand)name] and obtains.As derivative, " SANKO M-Acid-AH " ［ Sanko Co., Ltd.'s system, trade(brand)name ］ is also had commercially to sell.
As described (c) phosphate compound, the such as add-on type phosphoric acid ester such as triphenylphosphate, tricresyl phosphate Biphenyl Ester can be exemplified; The polyphenol such as Resorcinol and the monohydric phenol such as phenol, cresols is used to carry out esterification and the response type phosphoric acid ester " RDP " [the meticulous scientific & technical corporation of aginomoto (monosodium glutamate Off ア イ Application テ Network ノ society) makes, trade(brand)name] etc. that left behind as reactive free group of at least one hydroxyl in this polyphenol; And the condensed type phosphoric acid ester " PX-200 " that free hydroxyl group in response type phosphoric acid ester is esterified [large eight chemical industrial companies (large eight chemical industry societies) make, trade(brand)name] etc.
As described (d) phosphoric ester amides, comprise the coupling scheme of phosphoric acid ester and phosphamide, the phosphoric ester amides etc. recorded in Japanese Patent Laid-Open 2001-139823 publication, Japanese Patent Laid-Open 2000-154277 publication, Japanese Patent Laid-Open 10-175985 publication, Japanese Patent Laid-Open 8-59888 publication, Japanese Patent Laid-Open No. Sho 63-235363 publication can also be used.As preferred phosphoric ester amides, condensed phosphoric acid esters amides can be exemplified.As such phosphoric ester amides, such as N-(two aryloxy phosphinyls) substituted alkylene amine can be exemplified, two ~ tetra-[(two aryloxy phosphinyls) is amino] substituted aromatic compound class, N-(cyclic alkylidene dioxy base phosphinyl) substituted alkylene amine, two ~ tetra-[(cyclic alkylidene dioxy base phosphinyl) is amino] substituted aromatic compound class, N-(ring-type arylidene dioxy base phosphinyl) substituted alkylene amine, two ~ tetra-[(ring-type arylidene dioxy base phosphinyl) is amino] substituted aromatic compound class, 3, two (the N-substituted-amino)-2 of 9-, 4, 8, 10-tetra-oxa--3, 9-bis-phospha spiral shell [5.5]-undecane-3, 9-dioxide class etc.Phosphoric ester amides can be used as trade(brand)name " phosphoric ester amides based flame retardant SP series (such as SP-601, SP-670, SP-703, SP-720 etc.) " [Shikoku Chem's (four countries change into industry) system] and obtains.
On the other hand, as the kind of metal hydrate, aluminium hydroxide, magnesium hydroxide can be used, as aluminum hydroxide compound, preferably use " H42M " that such as Showa electrician company (Showa Electricity work society) makes.
In the present invention, described fire retardant can be used alone a kind, also can two or more combinationally use.Its content depends on the kind of fire retardant, considers from the angle of the balance of flame retardancy and other physical property, relative to resin combination total amount preferably 5 ~ 50 quality %, more preferably 10 ~ 40 quality %, and more preferably 10 ~ 35 quality % further.
[other any composition]
In flaky resin composition of the present invention, as other any composition, in the scope not affecting effect of the present invention, suitably can contain the low-stress agent such as thermoplastic resin of the powder such as silicon rubber and silica gel, silicone modified epoxy resin and resol, MBS and so on; The viscosity reduction degree thinners 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; Wetting property rising agent and the defoamers etc. such as nonionic class tensio-active agent, fluorine class tensio-active agent, silicone oil.
[method for making of flaky resin composition]
The preparation method of flaky resin composition of the present invention is not particularly limited, such as, can as described belowly prepare.First, be the solid-state polyfunctional epoxy resin of less than 70 DEG C by described (A) liquid bisphenol type epoxy resin, (B) softening temperature with high-speed mixer etc., mix (C) hardener for epoxy resin and various any uniform composition of using as required, then use kneader, twin-roll machine, continuous mixing device etc. fully mixing.As melting temperature, preferably about 50 ~ 110 DEG C.By obtain as mentioned above resin combination cooling after, with forming mill about 50 ~ 100 DEG C temperature, pressure 0.5 ~ 1.5MPa condition under pressurize, make flaky resin composition of the present invention.The thickness of flaky resin composition depends on purposes, is generally about 0.1 ~ 2.0mm, preferably 0.1 ~ 1.0mm.
The treatability of this flaky resin composition itself, plasticity are good, and the warpage of cured article or distortion few.By this flaky resin composition, such as, by being layered in post-heating on electronic component, easily electronic devices and components can be sealed, therefore can simplify sealing process, manufacture easily.In addition, can seal when not affecting the function of the electronic component with electric function portion without the need to main equipment, therefore can realize the reduction of manufacturing cost.
[composite sheet]
In flaky resin composition of the present invention, can fiber base material be set on the interarea of its at least one party and make composite sheet.
Fig. 1 is the sectional view of the brief configuration of the first embodiment representing composite sheet, and Fig. 2 is the sectional view of the brief configuration of the second embodiment representing composite sheet.Fig. 3 is the sectional view of the brief configuration representing existing prepreg.
Shown in composite sheet 1 such as Fig. 1 (a) or Fig. 2 (a), closely sealedly on the interarea of one or both of resin layer 2 with flaky resin composition be formed with the fibrous substrate layer 3 with fiber base material.In addition, two interareas of composite sheet 1 are provided with the mold release film 4 be made up of such as polyethylene terephthalate etc.This mold release film 4 is stripped in use, and composite sheet 1 uses so that the state shown in such as Fig. 1 (b) or Fig. 2 (b) is bonding with electronic devices and components element etc., thus makes electronic devices and components.
Composite sheet 1 is closely sealed on the interarea of at least one party of resin layer 2 is formed with fibrous substrate layer 3.By this composite sheet 1, because be formed with fibrous substrate layer 3 on interarea, so operability and good strength, and without the need to main equipment and without the need to can manufacture the product with fiber base material through loaded down with trivial details operation.In addition, for bonding with electronic devices and components element manufacture electronic devices and components time, stripping when can suppress to be processed into electronic devices and components, when particularly cutting and the generation of cracking, can improve the yield rate of electronic devices and components.
Fig. 3 is the sectional view representing existing prepreg 50.The structure of existing prepreg 50 is: have fiber base material 51, and soaking in this fiber base material 51 has compositions of thermosetting resin 52.Existing prepreg 50 soaks into fiber base material 51 to make compositions of thermosetting resin 52, needs the main equipments such as steeping vat, and also needs organic solvent etc.By composite sheet 1 of the present invention, by the closely sealed structure being formed with fibrous substrate layer 3 on the interarea of employing resin layer 2, can as described by carrying out the method that presses or manufactured, without the need to main equipment and without the need to can manufacture the product with fiber base material through loaded down with trivial details operation by the method carrying out pressing after supplying to the surface of fiber base material the melts be made up of the constituent material of flaky resin composition after the surface supply fiber base material of flaky resin composition.
Ratio preferably 65 ~ 93 volume % of the resinous principle in composite sheet 1.By making the ratio of resinous principle reach 65 ~ 93 volume %, the bonding force of composite sheet 1 can be made sufficient, and warpage when can suppress the solidification of oozing out with composite sheet 1 from the resin of composite sheet 1, peel resistance and cracking also good.
Namely, when the ratio of resinous principle is lower than 65 volume %, because the ratio of resinous principle is few, therefore composite sheet 1 may be not enough to the landfill of the bonding region sealed or insulate, such as interelectrode recess etc., stripping when possibly cannot fully suppress to be processed into electronic devices and components, when particularly cutting and the generation of cracking.On the other hand, when the ratio of resinous principle is higher than 93 volume %, the resin being attached to fibrous substrate surface is many, and the outflow of resin increases, and therefore increases to oozing out beyond bonding region, and composite sheet 1 easily ftractures.
The ratio of resinous principle refers to the resin combination ratio by volume in whole composite sheet 1.Here, resin combination refers to the resin combination of the constituent as flaky resin composition.The ratio [volume %] of resinous principle is tried to achieve by following formula.
The ratio [volume %] of resinous principle
={ (quality [the g/m of thickness [μm]-fiber base material of composite sheet
2proportion [the g/cm of]/fiber
3]) thickness [μm] of/composite sheet × 100
Such as, composite sheet 1 has one block of glasscloth as fiber base material, the thickness of composite sheet 1 is 160 [μm], the quality of glasscloth is 48 [g/m
2], the proportion of glass is 2.54 [g/cm
3] time, can as described belowly try to achieve.
The ratio [volume %] of resinous principle
={(160[μm]-48[g/m
2]/2.54[g/cm
3])/160[μm]}×100
=88
The thickness of resin layer 2 preferably 30 ~ 500 μm.When thickness is less than 30 μm, such as, operability for the formation of the monomer of the flaky resin composition of resin layer 2 is not good.In addition, when composite sheet 1 being adhered to electronic devices and components element and making 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, when being greater than 500 μm, resin layer 2 easily ftractures, and the slimming of electronic devices and components is also difficult.
The thickness of fibrous substrate layer 3 preferably 30 ~ 180 μm.When being less than 30 μm, the operability for the formation of the monomer of the fiber base material of fibrous substrate layer 3 is not good.On the other hand, when being greater than 180 μm, be difficult to make resin impregnated to whole fiber base material.
The thickness of composite sheet 1 can select suitable thickness according to resin layer 2 and the thickness of fibrous substrate layer 3 and the purposes of composite sheet 1, preferably 100 ~ 500 μm usually.
Form the plasticity number preferably 60 ~ 90 under the normal temperature (25 DEG C) of the resin combination of resin layer 2.When plasticity number is less than 60, the outflow of resin combination cannot be suppressed, increase to oozing out outside bonding region, cause the pollution around bad order and bonding region.In addition, when plasticity number is greater than 90, the space in bonding region may increase and poor attachment occurs and fills bad.Plasticity number in this specification sheets can measure according to the method parallel plate plasticity number meter based on JISK6249.
The closely sealed interarea being formed at least one party of resin layer 2 of fibrous substrate layer 3.Form in the fiber base material of fibrous substrate layer 3, be better its space at least partially in soak into constituent, the i.e. resin combination of flaky resin composition having and form resin layer 2, particularly preferably the compositions of thermosetting resin having and form resin layer 2 is all soaked in all spaces.That is, the fiber base material forming fibrous substrate layer 3 is better the surface portion being configured to be embedded in resin layer 2.
Fiber base material both can be woven cloth also can be non-woven fabrics, can adopt arbitrary fiber base material.In addition, its constituent material is also not particularly limited, and can adopt glass fibre, aromatic polyamide fibre, cellulosic fibre, trevira etc., and they can be used alone or two or more is used in combination.
Fiber base material is better glasscloth or glassine paper, particularly preferably glasscloth.The kind of glasscloth is not particularly limited, and is better the tabby weave E glasscloth etc. that IPC-EG-140 specifies, the glasscloth of thick 30 ~ 180 μm of 1078 types, 1080 types, 1037 types, 1084 types, 2110 types, 7628 types and so on especially.
[method for making of composite sheet]
Composite sheet 1 such as can manufacture via following operation: the constituent of flaky resin composition is mixing at the temperature of 50 ~ 110 DEG C, obtains the operation of mixing thing; Mixing thing be supplied to the one side of fiber base material or mixing thing is supplied to after between a pair fiber base material, it being configured as integratedly the operation of sheet by mixing thing is pressed on fiber base material.
By such manufacture method, the closely sealed composite sheet 1 being formed with fibrous substrate layer 3 on the interarea that can be manufactured on resin layer 2 easily.In above-mentioned manufacture method, by mold release film 4 being supplied to while supplying mixing thing and fiber base material the one or both sides of mixing thing and fiber base material, can be made into the composite sheet 1 with mold release film 4.
The supply mode of mixing thing is not particularly limited, and can adopt bulk, sheet, molten.In addition, the shaping of mixing thing and fiber base material both can be undertaken by batch mode, also can carry out continuously with thermocompressor or backer roll etc.
The manufacture particularly preferably following method of composite sheet 1: mixing thing be supplied to the one side of fiber base material or mixing thing is supplied to after between a pair fiber base material, making them by between a pair backer roll, it is configured as sheet integratedly.A pair backer roll is better the backer roll of its gap size of adjustable, such as, be better diameter be 20 ~ 60mm, gap size is the backer roll of about 5 ~ 500 μm.In addition, the shaping for integration is better pass through backer roll with the speed of 0.1 ~ 5m/ minute in the temperature range of 30 ~ 180 DEG C.By adopting such temperature and Negotiation speed, good composite sheet 1 can be obtained.
Fig. 4 is the brief configuration figure representing the manufacturing installation of composite sheet 1 and the first embodiment of manufacture method.Manufacturing installation 10 such as comprises: the feedway 11 supplied after the resin combination 5 becoming resin layer 2 is made molten by bulk, coiled fiber base material 6 and supply the base material roller 12 of this fiber base material 6, winding mold release film 4 and supply a pair mold release film roller 13 of this mold release film 4, a pair guide reel 14 guiding fiber base material 6 and mold release film 4, a pair backer roll 15 etc. of pressurizeing to fiber base material 6 and mold release film 4.
Feedway 11, base material roller 12, mold release film roller 13 configure accordingly with the stepped construction of composite sheet 1.Such as shown in Fig. 4, be arranged so that the mold release film 4 of fiber base material 6 and a side is wound in a part for the periphery of the guide reel 14 (guide reel 14 on right side) of the side in a pair guide reel 14, the mold release film 4 of the opposing party is wound in a part for the periphery of the guide reel 14 of the opposing party.By adopting such configuration, can form small gap, this gap is used for supplying resin combination 5 between fiber base material 6 and the mold release film 4 of the opposing party.
In this manufacturing installation 10, between a pair guide reel 14, supply a pair mold release film 4 from a pair mold release film roller 13 continuously, and between this pair guide reel 14, supply fiber base material 6 from base material roller 12 continuously.In addition, from feedway 11 to supplying the resin combination 5 being made up molten of bulk between fiber base material 6 and the mold release film 4 of a side.Make these aliments by between a pair backer roll 15 again.
By operation as above, the interarea that can be made into resin combination 5 being embedded with in fiber base material 6 or fiber base material 6 soak into has resin combination 5 and outermost layer is provided with the composite sheet 1 of mold release film 4.Particularly by adopting a pair backer roll 15 of clearance-adjustable size, making the gap of constituent material by them of composite sheet 1, the bury degree of adjustable fiber base material 6 in resin combination 5 or resin combination 5 soak into degree in fiber base material 6, and the integral thickness of also adjustable composite sheet 1.
Fig. 5 is the brief configuration figure representing the manufacturing installation of composite sheet 1 and the second embodiment of manufacture method.This manufacturing installation 10 is the manufacturing installations adding base material roller 12 further and be provided with a pair base material roller 12 in the manufacturing installation 10 shown in Fig. 4.A pair base material roller 12 is configured to the part each fiber base material 6 being wound in respectively the periphery of a pair guide reel 14.
In this manufacturing installation 10, between a pair guide reel 14, supply a pair mold release film 4 from a pair mold release film roller 13 continuously, and between this pair guide reel 14, supply a pair fiber base material 6 from a pair base material roller 12 continuously.By operation as above, two interareas that can be made into resin layer 2 has the composite sheet 1 of a pair fiber base material 6.
Fig. 6 is the brief configuration figure representing the manufacturing installation of composite sheet 1 and the 3rd embodiment of manufacture method.This manufacturing installation 10 is identical with the basic structure of the manufacturing installation 10 shown in Fig. 4, but different in the following areas: to there is sheet material roller 16 to replace feedway 11, this sheet material roller 16 for the flaky resin composition 7 that reels monomer and supply this sheet material resin combination 7.Thus, sheet resin combination 7 can directly be supplied to manufacture composite sheet 1.
Fig. 7 is the brief configuration figure representing the manufacturing installation of composite sheet 1 and the 4th embodiment of manufacture method.This manufacturing installation 10 is the manufacturing installations adding base material roller 12 further and be provided with a pair base material roller 12 in the manufacturing installation 10 shown in Fig. 6.By operation as above, two interareas that can be made into resin layer 2 has the composite sheet 1 of a pair fiber base material 6.
Above, the method using backer roll 15 to manufacture composite sheet 1 is continuously illustrated, but composite sheet 1 also can be manufactured by following method: its constituent material is stacked with regulation order, with forming mill about 50 ~ 100 DEG C temperature, pressure 0.5 ~ 1.5MPa condition under pressurize.
Then, the application examples of flaky resin composition 7 of the present invention and composite sheet 1 is specifically described.Below, be described for flaky resin composition 7, composite sheet 1 is also applied by same method.
[circuit components]
For the circuit substrate being provided with the electronic devices and components such as semi-conductor, chip-resistance, diode, electrical condenser, by coveing with flaky resin composition 7 of the present invention and making its thermofixation, simply face seal or covering can be made circuit components.Adopt the sealing of the electronic devices and components of flaky resin composition 7 of the present invention, covering method be not particularly limited, such as, can as described belowly carry out sealing, overlapping operation.
The circuit substrate being provided with electronic devices and components such as covers with flaky resin composition 7, make its overlay electronic components and parts, then about 80 ~ 200 DEG C, the preferably temperature of 100 ~ 150 DEG C is heated to, make flaky resin composition 7 fluidization, after making not fill position around electronic devices and components, then heat 0.5 ~ 2 hours at the temperature of 100 ~ 180 DEG C, make the resin solidification of fluidization, by above-mentioned simple operation, circuit components of the present invention can be obtained.In the circuit components obtained as mentioned above, cured article seldom produces warpage or distortion, and the generation of not filling position around 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 with the electronic devices and components of hollow space of SAW device and so on good yield rate.First, the electronic devices and components be arranged on substrate are such as covered with flaky resin composition 7, be heated to about 80 ~ 150 DEG C, the preferably temperature of 100 ~ 150 DEG C, after making flaky resin composition 7 fluidization, 0.5 ~ 2 hours is heated again at the temperature of 100 ~ 180 DEG C, the flaky resin composition 7 of fluidization is solidified, thus can be airtight or by gap-fill by the gap periphery be formed between electronic devices and components and substrate.
One of its schematic sectional view is illustrated in Fig. 8 (a) ~ (e).In each figure, 7 is flaky resin composition, and 31 and 32 is electronic devices and components (31 is such as chip-type device, and 32 is such as salient point), and 33 is substrate.In the present invention, be formed in the state that the gap between electronic devices and components and substrate is maintained shown in the airtight Fig. 8 of referring to (a), (c) or (d), fill and refer to that the resin combination shown in Fig. 8 (b) or (e) is full of this gap and state that gap disappears.Utilize flaky resin composition 7 of the present invention, by adjustment Heating temperature etc., both the gap be formed between electronic devices and components and substrate can be filled, also can maintain the gap be formed between electronic devices and components and substrate, not seal with the state of resin combination and substrate contacts with the electric function portion such as shown in Fig. 8 (d).As the element with electric function portion, the piezoelectric elements such as such as quartz crystal unit can be exemplified, form the sensor element etc. such as circuit element, photo detector of high frequency circuit.
[electrical connections of electronic devices and components]
Use flaky resin composition 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 ~ 13 are process picture sheets of the method for attachment for illustration of electronic devices and components.
First, such as, shown in Fig. 9, prepare the substrate 41 in the terminal pad portion 42 be formed with as the first electrode.Substrate 41 such as can have the metal sheet etc. of metal oxide to form by glass substrate, ceramic substrate, resin substrate (BT, PET etc.), glass epoxy substrate (FR-4, FR-5), surface coverage.
Then, as shown in Figure 10, applying conductive thickener 43 in the terminal pad portion 42 of substrate 41.Conductive paste 43 can use using resin as base resin and be added with the conductive paste of conducting particles.Then, as shown in figure 11, the area configurations flaky resin composition 7 not forming terminal pad portion 42 and conductive paste 43 in substrate 41.
Then, as shown in figure 12, electronic devices and components 44 are prepared.The lower surface of these electronic devices and components 44 is formed with the electrode holder 45 as the second electrode.Electrode holder 45 is formed with metal electrode salient point 46 across shielded metal films such as Cr-Cu, Ti-Pd by electrochemical plating.Metal electrode salient point 46 such as can be made up of Au, Ag, Cu.In addition, also can be used for soldering tin material, make scolding tin salient point, to replace metal electrode salient point 46 by backflow.In present embodiment, conductive paste is arranged in the terminal pad portion 42 of substrate 41, but also can be arranged on metal electrode salient point 46.
Then, electronic devices and components 44 are configured on substrate 41, make the position consistency of the metal electrode salient point 46 of electronic devices and components 44 and the conductive paste 43 of substrate 41, the temperature about heating under pressure to 80 ~ 150 of 0 ~ 0.1Pa DEG C.Then, after making conductive paste 43 and flaky resin composition 7 melting simultaneously, cool, conductive paste 43 is solidified together with flaky resin composition 7.By this, as shown in figure 13, substrate 41 and electronic devices and components 44 are electrically connected by the cured article of conductive paste 43 etc. and electric connector 47, and are mechanically connected by the cured article 8 of flaky resin composition 7.
As mentioned above, in present embodiment, make conductive paste 43 melting and solidification together with flaky resin composition 7, substrate 41 and electronic devices and components 44 be electrically connected and be mechanically connected, if therefore compared with the past enforcement a stage heating process.In addition, by above-mentioned heat treated, the fluidization simultaneously of conductive paste 43 and flaky resin composition 7, therefore puts on that the pressure of electronic devices and components 44 is maximum also can only reach 0.1Pa.Therefore, even if when electronic devices and components 44 fragility, also electronic devices and components 44 can not be destroyed.
[electronic devices and components bonding, fixing]
Use flaky resin composition 7 of the present invention, can be easy and with good yield rate, the electronic devices and components such as miniaturized electronics are fixed on substrate or framework when there is no stationary fixture.Be described by Figure 14 ~ 16 and 17 ~ 19.
Figure 14 ~ 16 are the process picture sheets for illustration of the method will be connected with substrate as the vibrating motor of electronic devices and components in present embodiment.Figure 14 and 16 is front views of the method for attachment for illustration of vibrating motor, and Figure 15 is the relevant side-view of the method for attachment of the vibrating motor shown in Figure 14.
First, such as, shown in Figure 14 and 15, prepared substrate or framework 51 and vibrating motor 52.Substrate or framework 51 such as have the metal sheet etc. of metal oxide to form by glass epoxy board or surface coverage.Vibrating motor 52 such as has motor body 520 and eccentric counterweight 522.As shown in Figure 14 and Figure 15, the flaky resin composition 7 that motor body 520 is cut into specified length covers, and the ends contact of flaky resin composition 7 is fixed on substrate or framework 51.The contact of flaky resin composition 7 pairs of substrates or framework 51 is fixed and both can be undertaken by the caking agent of regulation, and the set of flaky resin composition 7 partial melting also can be made to carry out.
In present embodiment, as shown in figure 16, by heating flaky resin composition 7, flaky resin composition 7 softens, softening melting under the state across a part for substrate or framework 51 and a part for motor body 520, a part for substrate or framework 51 and the contact part of motor body 520 expand along respective surface, solidify in this condition, become illustrated cured article 8, thus can be made into vibration generating arrangement 50.Therefore, substrate or framework 51 and vibrating motor 52 can be adhesively fixed securely.
Figure 17 ~ 19 are the process picture sheets for illustration of another method of attachment by the vibrating motor in present embodiment.Figure 17 and 19 is front views of the method for attachment for illustration of vibrating motor, and Figure 18 is the relevant side-view of the method for attachment of the vibrating motor shown in Figure 17.
As shown in Figure 17,18, substrate or framework 51 are laminated with flaky resin composition 7, this flaky resin composition 7 configures vibrating motor 52.Then, as shown in figure 19, be heating and curing by making flaky resin composition 7, during melting before curing, because of the deadweight of vibrating motor 52, its part is embedded in the flaky resin composition 7 of melting, and the surrounding of vibrating motor 52 lifts, and maintains vibrating motor 52 around with roomy face.Then, be adhesively fixed by the cured article 8 of flaky resin composition 7.
Pass through present embodiment, substrate or framework 51 are configured to contact with the flaky resin composition 7 be configured at therebetween respectively with motor body 520, i.e. vibrating motor 52, make flaky resin composition 7 be heating and curing and fix, thus form vibration generating arrangement 10.Flaky resin composition 7 is thinner than elastomericss such as rubber, and makes flaky resin composition 7 be heating and curing in the present embodiment, and therefore a part for vibrating motor 52 is embedded in the flaky resin composition 7 of melting.
Therefore, with by being configured in compared with the situation fixing vibrating motor for the elastomerics configured in the framework of vibrating motor and the situation being fixed vibrating motor by metal holder, can be easy and at an easy rate vibrating motor is fixed on substrate or framework without the need to loaded down with trivial details operation.
[electronic devices and components, electronics]
This surface insulation, for being adhered to the surface of electronic devices and components element, is manufactured electronic devices and components by flaky resin composition 7 of the present invention.In addition, the sealing of these electronic devices and components, such as muffling electronic devices and components, is manufactured electronics by flaky resin composition 7 of the present invention.Be not particularly limited as electronic devices and components, such as semiconductor element, resistor, diode, electrical condenser can be exemplified.In addition, as electronic devices and components, the hollow devices such as acoustic surface wave device (SAW device), quartz crystal device, high-frequency element, acceleration transducer can be exemplified.
Figure 20 shows that an example of the electronic devices and components element used in the manufacture of electronic devices and components.Electronic devices and components element 61 such as comprise element body 62 and with 2 external connection electrode 63 arranging of ground separated from one another, the surface of this element body 62.Such as, the interelectrode distance of 2 external connection electrode 63 is 2.0mm, and electrode height is 0.3mm.Flaky resin composition 7 is such as the insulation between 2 external connection electrode 63.The insulation adopting flaky resin composition 7 to carry out such as can as described belowly be carried out.
That is, between 2 external connection electrode 63, flaky resin composition 7 is coverd with.Then, be heated to about 80 ~ 200 DEG C, the preferably temperature of 100 ~ 150 DEG C, make flaky resin composition 7 fluidization.At the temperature of 100 ~ 180 DEG C, heat 0.5 ~ 2 hours again, the flaky resin composition 7 of fluidization is solidified.By operation as above, as shown in Figure 21,22, flaky resin composition 7 (cured article) can be utilized suitably to cover between external connection electrode 63, to insulate, thus obtain electronic devices and components 64.Now, by using composite sheet 1 to replace flaky resin composition 7, the product that surface shown in Figure 22 is smooth can easily be obtained.
Embodiment
Then, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these examples.Each characteristic in each example is tried to achieve according to method shown below.
< flaky resin composition >
(1) gel time
According to the test tube method of JISC2105, in the oil bath of 100 DEG C, measure flaky resin composition become time needed for gel.
(2) sheet material characteristic
Evaluate 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, is not in a liquid state, but cracks or fragment.
×: cannot sheet material be made.
(3) mobility during melting
Chip sheet-like composition square for the 2mm be arranged on FR-4 substrate is sealed, confirms landfill by range estimation.Condition of cure is 100 DEG C, 2 hours.Evaluate according to following criterion.
Zero: good.
×: do not fill position around components and parts.
(4) melt viscosity
(100 DEG C) are measured with rheometer (stream change science (Rhenemetric Scientific) Inc.).
< cured article >
(5) second-order transition temperature
With TMA/SS150 (Seiko Electronics Co., Ltd (セ イ コ mono-イ Application ス ツメンツ society) system) from room temperature to 200 DEG C (heat-up rate 10 DEG C/min), measure second-order transition temperature.
(6) flame retardancy
Be that benchmark is with the condition evaluating flame retardancy of test film thickness 1.6mm with UL94.
(7) warpage
Sheet-like composition (30mm × 20mm) is carried on the FR-4 substrate (45mm × 30mm) of thick 0.3mm, in 100 DEG C of solidifications 2 hours, measures the height of the substrate corner after solidification, using the index of its mean value as warpage.
[embodiment 1 ~ 9 and comparative example 1 ~ 3]
Each raw material of the proportioning composition shown in table 1 is dropped into kneader, is uniformly mixed 1 hour in 70 DEG C, is modulated into each resin combination.Then, after each resin combination is cooled to 30 DEG C respectively, with forming mill at 70 DEG C, press molding under the condition of 1.0MPa, makes the sheet material of thick 0.5mm, make each flaky resin composition.
The evaluation result of each characteristic of each example is shown in table 1.The such as SP57 DEG C of expression softening temperature that solid epoxy resin side in table 1 is recorded.
The each composition used is as described below.
1. liquid-state epoxy resin
(1) R140P: bisphenol A type epoxy resin (number-average molecular weight: 380, the epoxy equivalent (weight): 190) of Mitsui Chemicals, Inc.
(2) DER383J: the bisphenol A type epoxy resin (epoxy equivalent (weight): 190) of Dow Chemical
(3) エ ピ コ ー ト #807: the bisphenol f type epoxy resin (epoxy equivalent (weight): 160 ~ 175) of japan epoxy resin Inc.
2. solid epoxy resin
(1) NC3000: the multifunctional type epoxy resin (epoxy equivalent (weight): 285, softening temperature: 57 DEG C) containing bisphenol backbone of Japanese chemical drug Inc.
(2) NC3000H: the bisphenol backbone type epoxy resin (epoxy equivalent (weight): 290, softening temperature: 70 DEG C) of Japanese chemical drug Inc.
(3) YDCN704: Dongdu changes into the cresol novolac type epoxy resin (epoxy equivalent (weight): 210, softening temperature: 90 DEG C) of Inc.
3. solidifying agent
(1) DICY: the Dyhard RU 100 that Japanese carbide company (Japanese カ mono-バ イ De society) makes
(2) EH-4370S: the modified aliphatic polyamine that rising sun electrification company (A D E K A society) is made
4. curing catalyst
The aromatic series dimethyl urea that U-CAT3502T: Sang Apuluo company (サ Application ア プ ロ society) makes
5. mineral filler
FB-959: the spherical silicon dioxide (mass median diameter: 25 μm) of Denki Kagaku Kogyo kabushiki
6. fire retardant
(1) phosphazene compound [R in described general formula (3) of SPB-100: great mound chemical company
1and R
2be phenyl, k is more than 3]
(2) H42M: the aluminium hydroxide (particle diameter: 1.5 μm) of Showa electrician Inc.
When using aluminium hydroxide as fire retardant, its incorporation is calculated in mineral filler.
[table 1]
As shown in Table 1, embodiment sheet material characteristic, melting time mobility, flame retardancy, warpage projects substantially good.In contrast, what comparative example 1 was such do not use (A) liquid bisphenol type epoxy resin of the product of (A) liquid bisphenol type epoxy resin and comparative example 2 and (B) softening temperature are that mass ratio (A)/(B) of the solid-state polyfunctional epoxy resin of less than 70 DEG C is poor in the sheet material characteristic of the extraneous product of 10/90 ~ 30/70, and the poor fluidity during melting of the such softening temperature of comparative example 3 higher than the product of 70 DEG C.
The possibility that industry utilizes
Flaky resin composition of the present invention can manufacture without the need to the large-scale coating apparatus that existing adhesive sheet is such, and with an organic solvent can not manufacture, and the warpage of cured article or distortion few, the sealing etc. of circuit components can be carried out simply.Such flaky resin composition is suitable for the manufacture of circuit components, sealing, the connection of electronic devices and components and fixes.In addition, flaky resin composition of the present invention is applicable to making composite sheet and for the manufacture of electronic devices and components.
The explanation of symbol
1 ... composite sheet, 2 ... resin layer, 3 ... fibrous substrate layer, 4 ... mold release film, 5 ... resin combination, 6 ... fiber base material, 7 ... flaky resin composition, 8 ... cured article, 10 ... manufacturing installation, 11 ... feedway, 12 ... base material roller, 13 ... mold release film 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 ... metal electrode salient point, 47 ... electric connector, 51 ... substrate or framework, 52 ... vibrating motor
Claims (18)
1. a flaky resin composition, its be comprise (A) liquid bisphenol type epoxy resin, (B) softening temperature is solid-state polyfunctional epoxy resin, (C) hardener for epoxy resin of less than 70 DEG C, (D) mineral filler and (E) fire retardant be as the flaky resin composition of required composition, it is characterized in that
The mass ratio of described (A)/(B) is 10/90 ~ 30/70, and the content of described (D) mineral filler is 50 ~ 80 quality % relative to resin combination total amount.
2. flaky resin composition as claimed in claim 1, is characterized in that, described (B) is the mixture of the aralkyl-type epoxy resin containing bisphenol backbone that following formula (1) represents;
[changing 1]
In formula, m represents the integer of 1 ~ 4.
3. flaky resin composition as claimed in claim 1, is characterized in that, described (D) mineral filler to be mass median diameter be spherical silicon dioxide of 4 ~ 30 μm.
4. flaky resin composition as claimed in claim 1, is characterized in that, comprise phosphazene compound as described (E) fire retardant.
5. a circuit components, is characterized in that, with flaky resin composition according to claim 1 sealing or bondingly to form.
6. a sealing method for electronic devices and components, it is the sealing method carrying out the electronic devices and components be heating and curing after covering with flaky resin composition according to claim 1 the electronic devices and components be arranged on substrate, it is characterized in that,
Cover described electronic devices and components with described flaky resin composition, by the contact part peripheral containment of described electronic devices and components and described substrate, between described electronic devices and components and described substrate, form gap.
7. the sealing method of electronic devices and components as claimed in claim 6, is characterized in that, after making described flaky resin combined stream automation, then heats 0.5 ~ 2 hour at 100 ~ 180 DEG C at 80 ~ 150 DEG C, makes the described flaky resin composition solidification of fluidization.
8. a method of attachment for electronic devices and components, its be by have connect with the substrate of the first electrode and the method that is electrically connected via described first electrode and described second electrode of the electronic devices and components with the second electrode be connected, it is characterized in that,
Comprise the operation be electrically connected with described substrate by described electronic devices and components with flaky resin composition according to claim 1.
9. the method for attachment of electronic devices and components as claimed in claim 8, is characterized in that, comprising:
Described first electrode of described substrate configures the operation of conductive paste;
The operation of described flaky resin composition is configured in the region not forming described first electrode of described substrate;
Described electronic devices and components are carried on the substrate, make described first electrode contact of described second electrode and described substrate, described conductive paste and described flaky resin composition are heating and curing, by the operation that described electronic devices and components are electrically connected with described substrate simultaneously.
10. a fixing means for electronic devices and components, it is method electronic devices and components being fixed on substrate or framework, it is characterized in that,
Flaky resin composition according to claim 1 is arranged so that described substrate or described framework contact with described electronic devices and components, with described flaky resin composition, described substrate or described framework and described electronic devices and components is fixed.
The fixing means of 11. electronic devices and components as claimed in claim 10, it is characterized in that, cover above described electronic devices and components with described flaky resin composition, make it solidify by thermoplastic or heating and melting, described substrate or described framework and described electronic devices and components are adhesively fixed.
The fixing means of 12. electronic devices and components as claimed in claim 10, it is characterized in that, by the electronic devices and components mounting surface of described flaky resin composition placing in described substrate or described framework, after described flaky resin composition carries described electronic devices and components, by thermoplastic or heating and melting, described flaky resin composition is heating and curing, described substrate or described framework and described electronic devices and components are adhesively fixed.
13. 1 kinds of composite sheets, it is characterized in that, comprise resin layer and fibrous substrate layer, described resin layer has flaky resin composition according to claim 1, and described fibrous substrate layer is closely sealed to be formed at the interarea of at least one party of described resin layer and to have fiber base material.
14. composite sheets as claimed in claim 13, is characterized in that, the ratio of the resinous principle in described composite sheet is 65 ~ 93 volume %.
15. composite sheets as claimed in claim 13, is characterized in that, described fiber base material is at least a kind that is selected from inorganic fiber substrates and organic fibre base material.
16. 1 kinds of electronic devices and components, is characterized in that, comprise electronic devices and components main body and composite sheet according to claim 13, on the surface at least partially that described composite sheet is configured in described electronic devices and components main body and by described surface insulation.
17. 1 kinds of electronicss, is characterized in that, comprise the composite sheet according to claim 13 of electronic devices and components and the described electronic devices and components of sealing.
The manufacture method of 18. 1 kinds of composite sheets, is characterized in that, comprising:
The constituent of flaky resin composition according to claim 1 is mixing at the temperature of 50 ~ 110 DEG C, obtain the operation of mixing thing;
Described mixing thing be supplied to the one side of fiber base material or described mixing thing is supplied to after between a pair fiber base material, it being configured as integratedly sheet by described mixing thing is pressed on described fiber base material, obtaining the operation of composite sheet.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010120879A JP2011246596A (en) | 2010-05-26 | 2010-05-26 | Sheet-like resin composition and circuit component sealed by using the same |
| JP2010-120879 | 2010-05-26 | ||
| JP2010-195054 | 2010-08-31 | ||
| JP2010195054A JP2012054363A (en) | 2010-08-31 | 2010-08-31 | Sealing method of electronic component |
| JP2010286338A JP2012134383A (en) | 2010-12-22 | 2010-12-22 | Method for connection of electronic component |
| JP2010-286338 | 2010-12-22 | ||
| JP2010-292219 | 2010-12-28 | ||
| JP2010292219A JP2012139616A (en) | 2010-12-28 | 2010-12-28 | Method for fixing vibration motor, and vibration generator |
| JP2011114314A JP2012240348A (en) | 2011-05-23 | 2011-05-23 | Composite sheet, method for manufacturing the composite sheet, electronic component, and electronic instrument |
| JP2011-114314 | 2011-05-23 | ||
| 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 CN102725323A (en) | 2012-10-10 |
| CN102725323B true 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) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP5735030B2 (en) * | 2013-03-28 | 2015-06-17 | 日東電工株式会社 | Resin sheet for sealing electronic device and method for manufacturing electronic device package |
| JP6422370B2 (en) * | 2015-03-03 | 2018-11-14 | 日東電工株式会社 | Hollow type electronic device sealing sheet and method for manufacturing hollow type electronic device package |
| US10856423B2 (en) * | 2016-01-15 | 2020-12-01 | Showa Denko Materials Co., Ltd. | Prepreg, printed circuit board, semiconductor package, and method for producing printed circuit board |
| CN106046677B (en) * | 2016-05-27 | 2019-03-29 | 江苏兆鋆新材料股份有限公司 | A kind of epoxy resin carbon fiber prepreg of shelf-stable and preparation method thereof |
| CN109624351B (en) * | 2018-11-21 | 2021-11-23 | 长安大学 | Preparation method of pre-impregnated fiber bundles for three-dimensional weaving |
| 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 |
| JP6914309B2 (en) * | 2019-10-31 | 2021-08-04 | 三菱電機株式会社 | Sheet type insulating varnish and its manufacturing method, electrical equipment, and rotary electric machine |
| JP2021097136A (en) * | 2019-12-17 | 2021-06-24 | 日東電工株式会社 | Manufacturing method of magnetic sheet |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005105159A (en) * | 2003-09-30 | 2005-04-21 | Sumitomo Bakelite Co Ltd | Resin composition, coverlay, and flexible printed circuit board |
| JP4667753B2 (en) * | 2004-02-13 | 2011-04-13 | 新日鐵化学株式会社 | Epoxy resin production method, epoxy resin composition and cured product |
| JP2006124434A (en) * | 2004-10-26 | 2006-05-18 | Matsushita Electric Works Ltd | Epoxy resin-inorganic material composite sheet and molded article |
| JP2006332150A (en) * | 2005-05-24 | 2006-12-07 | Sumitomo Bakelite Co Ltd | Resin composition for coverlay film, coverlay film, and flexible printed circuit board using the same |
| JP2007238769A (en) * | 2006-03-08 | 2007-09-20 | Sumitomo Bakelite Co Ltd | Resin composition, resin film, cover-lay film and flexible printed circuit board |
| CN101522747B (en) * | 2006-08-17 | 2012-07-04 | 日本化药株式会社 | Modified liquid epoxy resin, epoxy resin composition using the same, and cured product thereof |
| WO2010061980A1 (en) * | 2008-11-28 | 2010-06-03 | 味の素株式会社 | Resin composition |
-
2011
- 2011-05-24 WO PCT/JP2011/002891 patent/WO2011148620A1/en active Application Filing
- 2011-05-24 KR KR1020127017351A patent/KR20130079311A/en not_active Application Discontinuation
- 2011-05-24 CN CN201180007104.XA patent/CN102725323B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102725323A (en) | 2012-10-10 |
| WO2011148620A1 (en) | 2011-12-01 |
| KR20130079311A (en) | 2013-07-10 |
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