WO2012165206A1 - Composition de résine pour un composant électrique/électronique de scellement étanche, procédé de fabrication d'un composant électrique/électronique et corps à composant électrique/électronique scellé de façon étanche - Google Patents

Composition de résine pour un composant électrique/électronique de scellement étanche, procédé de fabrication d'un composant électrique/électronique et corps à composant électrique/électronique scellé de façon étanche Download PDF

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Publication number
WO2012165206A1
WO2012165206A1 PCT/JP2012/062979 JP2012062979W WO2012165206A1 WO 2012165206 A1 WO2012165206 A1 WO 2012165206A1 JP 2012062979 W JP2012062979 W JP 2012062979W WO 2012165206 A1 WO2012165206 A1 WO 2012165206A1
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Prior art keywords
resin
resin composition
phenol
crystalline polyester
sealing
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PCT/JP2012/062979
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English (en)
Japanese (ja)
Inventor
大樹 舩岡
健治 志賀
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東洋紡株式会社
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Publication of WO2012165206A1 publication Critical patent/WO2012165206A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a sealed electric and electronic part sealed with a resin composition, a method for producing the same, and a resin composition suitable for this application.
  • Hot melt resins that can be sealed with reduced viscosity simply by heating and melting solidify and form a sealed body just by cooling after sealing, so that productivity is also high, and in addition, generally thermoplastic resins Therefore, even after the end of the product life, the member can be easily recycled by heating to melt and remove the resin.
  • Polyester which has both high electrical insulation and water resistance, is considered to be a very useful material for this application, but generally has a high melt viscosity and injection at a high pressure of several hundred MPa or more to seal parts with complex shapes. Molding is required, and there is a risk of destroying electrical and electronic parts.
  • Patent Document 1 discloses a structural adhesive composition comprising a specific polytetramethylene glycol copolymer polyether ester elastomer and an epoxy compound having a glycidyl group of at least number average 1.2 or more in the molecule.
  • the polyester resin used here has good initial adhesion, but tends to have high crystallinity, and therefore, after adhesion, strain energy is generated when changing from an amorphous state to a crystalline state. There was a tendency to decrease significantly, and it was inappropriate as a sealing material for electric and electronic parts.
  • Patent Documents 2 and 3 propose hot-melt resin compositions for sealing having a melt viscosity that enables sealing at low pressure without damaging electrical and electronic parts.
  • this resin composition With this resin composition, a molded product with good initial adhesion can be obtained, and the polyester resin composition can be applied to general electric and electronic parts.
  • the adhesion strength is greatly reduced and the sealed state may not be maintained. .
  • Patent Document 4 discloses a resin composition for sealing electrical and electronic parts in which a crystalline polyester resin, an epoxy resin, and a polyolefin resin are blended. Although this composition has high adhesive strength and is strong against a cooling cycle load, there is a problem in that a formulation having a glycidyl group may cause gelation or hardening aggregation when retained at high temperatures.
  • Patent Document 5 shows that a hot melt adhesive composition containing a specific polyester resin and a phenol-modified xylene resin exhibits good adhesion to tin-plated copper and a biaxially stretched polyethylene terephthalate film. Yes.
  • This adhesive composition also has a problem that the durability of adhesion in a cooling / heating cycle such as ⁇ 40 ° C. for 30 minutes and 80 ° C. for 30 minutes as in an automobile application is insufficient.
  • JP 60-18562 A Japanese Patent No. 3553559 JP 2004-83918 A JP 2010-150471 A Patent No. 4389144
  • the first problem of the present invention is to provide an electrical and electronic component sealing body that has less concern about gelation even if it remains at high temperatures, and that is excellent in durability against environmental loads such as a thermal cycle load. It is an object to provide a suitable method for producing an encapsulated body for electric and electronic parts and a resin composition for encapsulating electric and electronic parts. More specifically, the elongation and strength do not drop significantly after 1000 cycles of a cooling cycle of ⁇ 40 ° C. for 30 minutes and 80 ° C. for 30 minutes, and the environment requires high durability against the cooling cycle load. Is to provide a resin composition for sealing electric and electronic parts.
  • the second problem of the present invention is to provide a sealed electrical and electronic component that is less susceptible to gelation even if it remains at a high temperature, and is excellent in durability against a cold cycle load and a high temperature long time load
  • An object of the present invention is to provide a method for producing an encapsulated body for electric and electronic parts and a resin composition for encapsulating electric and electronic parts. More specifically, the elongation and strength are not significantly reduced even after a 1000 cycle load at -40 ° C. for 30 minutes and 150 ° C. for 30 minutes, and a high temperature long time load at 150 ° C.
  • the present inventors have intensively studied and have proposed the following invention. That is, the present invention (1) Crystalline polyester elastomer (A), Phenol-modified alkylbenzene resin (B1) and / or phenol resin (B2), Fluororesin (C), Containing Electricity having a melt viscosity of 5 dPa ⁇ s or more and 3000 dPa ⁇ s or less when dried to a moisture content of 0.1% or less, heated to 220 ° C., applied with a pressure of 1 MPa, and extruded from a die having a pore diameter of 1.0 mm and a thickness of 10 mm. Resin composition for sealing electronic parts.
  • the crystalline polyester elastomer (A) includes a crystalline polyester resin (A1) in which a polyether component is copolymerized, a crystalline polyester resin (A2) in which a polycarbonate component is copolymerized, and a polylactone component.
  • the resin composition for sealing electrical and electronic parts according to (1) which is one or a mixture of two or more selected from the group consisting of polymerized crystalline polyester resin (A3).
  • the total of the phenol-modified alkylbenzene resin (B1) and the phenol resin (B2) is 0.1 to 100 parts by weight and the fluororesin (C) is 0.1 to 100 parts by weight with respect to 100 parts by weight of the crystalline polyester elastomer (A).
  • the resin composition for encapsulating electrical and electronic parts of the present invention is excellent in melt fluidity, and therefore, when used as an electrical and electronic parts sealing material, it can be molded without causing a short shot even at a relatively low pressure. Moreover, it is excellent in the initial adhesion strength to various members including an aluminum material, and maintains a high degree of adhesion even after being subjected to a thermal cycle load, and can exhibit a high level of adhesion durability against a thermal cycle. For this reason, the electrical and electronic component sealing body sealed using the electrical and electronic component sealing resin composition of the present invention exhibits durability against the severe environmental load of the cooling and heating cycle.
  • the resin composition for sealing electric and electronic parts according to a specific embodiment of the present invention is excellent in melt fluidity, when used as a sealing material in an electric and electronic parts sealing body, a short shot is generated even at a relatively low pressure. Can be molded without any problems.
  • it has excellent initial adhesion to various materials including aluminum materials, and has high thermal cycle durability that maintains the adhesive strength even after passing through 1000 cycles of thermal cycle at -40 ° C for 30 minutes and 150 ° C for 30 minutes.
  • it exhibits high heat aging resistance in which the elongation at break is maintained even after a high temperature and long time load at 150 ° C. for 1000 hours.
  • the electrical and electronic component sealing body sealed using the electrical and electronic component sealing resin composition of the present invention exhibits durability against severe environmental loads such as a cooling cycle and a high temperature and long time load.
  • the encapsulated body for electric and electronic parts according to the present invention is a resin or resin composition that is fluidized by heating and kneading at a low pressure of 0.1 to 10 MPa in a mold in which the electric and electronic parts are set inside the mold. It can be manufactured by injection injection.
  • the electric and electronic parts are encapsulated and sealed by the injected resin in whole or in part. Compared to injection molding at a high pressure of 40 MPa or higher, which is generally used for molding plastics in the past, it is performed at a much lower pressure, so it is sealed by injection molding, but limited to heat resistance and pressure resistance. It is possible to seal an electrical / electronic component without breaking it.
  • sealing resin or a sealing resin composition By properly selecting a sealing resin or a sealing resin composition, it has adhesion durability that can withstand environmental loads such as a cold cycle load and a high-temperature long-time load even for metal members such as aluminum materials. A sealing body can be obtained. The details of the embodiments of the invention will be sequentially described below.
  • the resin composition for sealing electric and electronic parts of the present invention contains a crystalline polyester elastomer (A), a phenol-modified alkylbenzene resin (B1) and / or a phenol resin (B2), and a fluororesin (C), and contains moisture.
  • the melt viscosity is 5 dPa ⁇ s or more and 3000 dPa ⁇ s or less when extruding from a die having a pore diameter of 1.0 mm and a thickness of 10 mm by heating to 220 ° C. by drying to a rate of 0.1% or less and applying a pressure of 1 MPa.
  • the crystalline polyester elastomer (A) in the present invention is a polyester having a chemical structure obtained by polycondensation of a polycarboxylic acid compound and a polyhydric alcohol compound, having a glass transition temperature of 0 ° C. or less and a melting point. It is polyester which is 100 degree
  • Typical examples of the crystalline polyester elastomer (A) in the present invention include a crystalline polyester resin (A1) in which a polyether component is copolymerized and a crystalline polyester resin (A2) in which a polycarbonate component is copolymerized. And a crystalline polyester resin (A3) in which a polylactone component is copolymerized.
  • aliphatic dicarboxylic acids having 10 or more carbon atoms such as dimer acid and hydrogenated dimer acid and / or aliphatic and / or alicyclic diols having 10 or more carbon atoms such as dimer diol and hydrogenated dimer diol.
  • a crystalline polyester elastomer can also be obtained by copolymerizing and introducing block-like segments into the polyester resin.
  • Preferred examples of the crystalline polyester elastomer (A) used in the present invention include a crystalline polyester resin (A1) in which a polyether component is copolymerized.
  • a polyether component By copolymerizing the polyether component, characteristics such as low melt viscosity, high flexibility, and high adhesion are imparted to the crystalline polyester resin (A1).
  • the polyether component is typically copolymerized with the crystalline polyester resin (A1) using polyether diol as a raw material.
  • the copolymerization ratio of the polyether component is preferably 1 mol% or more, and more preferably 5 mol% or more when the entire glycol component constituting the crystalline polyester resin (A1) is 100 mol%.
  • the number average molecular weight of the polyether component is preferably 400 or more, and more preferably 800 or more.
  • the number average molecular weight of the polyether component is preferably 5000 or less, and more preferably 3000 or less. If the number average molecular weight is too high, the compatibility with other components is poor, and there is a tendency to cause a problem that copolymerization is impossible.
  • Specific examples of the raw material of the polyether component include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. The effect of increasing the flexibility of the resulting crystalline polyester resin (A1), melting Polytetramethylene glycol is most preferable in terms of the effect of lowering the viscosity.
  • the crystalline polyester elastomer (A) used in the present invention by adjusting the composition ratio of the aliphatic component and / or the alicyclic component and the aromatic component, it is widely used as an engineering plastic.
  • Low melt viscosity and two-component curing not found in general-purpose crystalline polyester resins such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polybutylene terephthalate (hereinafter sometimes abbreviated as PBT). It is possible to achieve both heat resistance, high-temperature and high-humidity resistance, cold-heat cycle resistance, and the like comparable to the type epoxy resin.
  • terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, naphthalene dicarboxylic acid and ethylene glycol, naphthalene dicarboxylic acid and 1,4-butanediol are used to exhibit high heat resistance of 150 ° C. or higher.
  • a copolymerized polyester based is suitable.
  • rapid crystal solidification after molding improves mold releasability and is a desirable characteristic from the viewpoint of productivity improvement. Therefore, terephthalic acid and 1,4-butanediol, naphthalenedicarboxylic acid and 1,4- It is preferable that butanediol is the main component.
  • the copolymerization ratio is preferably 65 mol% or more, more preferably 70 mol% or more, especially 80 mol% or more when the total amount of terephthalic acid and naphthalenedicarboxylic acid is 100 mol%. It is preferable that If the total of terephthalic acid and naphthalenedicarboxylic acid is too low, the heat resistance required for electrical and electronic parts may be insufficient.
  • the glycol component constituting the crystalline polyester elastomer (A) contains both or one of ethylene glycol and 1,4-butanediol from the viewpoint of maintaining crystallinity during copolymerization.
  • the copolymerization ratio is preferably 40 mol% or more, more preferably 45 mol% or more, particularly preferably 45 mol% or more when the total amount of ethylene glycol and 1,4-butanediol is 100 mol% of the total amount of glycol components. 50 mol% or more is preferable, and most preferably 55 mol% or more.
  • the basic composition comprising the above acid component and glycol component giving high heat resistance has adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid.
  • Aliphatic or alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, hydrogenated dimer acid, 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol , 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol , Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanedimethanol, tricyclodecane dimethanol, neopentylglycol hydroxypivalate, 1,9-nonane
  • the crystalline polyester elastomer (A) used in the present invention includes an aliphatic and / or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer acid and hydrogenated dimer acid, and / or dimer diol, water.
  • an aliphatic and / or alicyclic diol having 10 or more carbon atoms such as an additive dimer diol is copolymerized, the glass transition temperature is lowered while maintaining a high melting point, and the heat resistance and electrical / electronic component of the resin composition of the present invention are reduced. In some cases, it is possible to further improve the compatibility of the adhesion to the surface.
  • dimer acid, aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer diol and / or aliphatic or alicyclic diol having 10 or more carbon atoms
  • polyalkylene such as polytetramethylene glycol
  • the term “cooling cycle durability” as used herein means that even if the temperature is raised and lowered repeatedly between high and low temperatures, peeling of the interface part between the electronic component having a different linear expansion coefficient and the sealing resin, or cracking of the sealing resin It is performance that is hard to occur. If the elastic modulus of the resin is significantly increased during cooling, peeling or cracking is likely to occur.
  • the glass transition temperature is preferably ⁇ 10 ° C. or lower in order to provide a material that can withstand the cooling and heating cycle. More preferably, it is ⁇ 20 ° C. or less, more preferably ⁇ 40 ° C. or less, and most preferably ⁇ 50 ° C. or less.
  • the lower limit is not particularly limited, but a temperature of ⁇ 100 ° C. or more is realistic in consideration of adhesion and blocking resistance.
  • the dimer acid is an aliphatic or alicyclic dicarboxylic acid produced by dimerization of an unsaturated fatty acid by polymerization or Diels-Alder reaction (most of the dimer, trimer, monomer, etc.).
  • the hydrogenated dimer acid refers to one obtained by adding hydrogen to the unsaturated bond portion of the dimer acid.
  • the dimer diol and hydrogenated dimer diol are those obtained by reducing the two carboxyl groups of the dimer acid or the hydrogenated dimer acid to hydroxyl groups. Specific examples of the dimer acid or dimer diol include Copolis' Enpol (registered trademark) or Sobamol (registered trademark) and Unikema's Prepol.
  • the polylactone is a polymer or oligomer having a structure obtained by ring-opening polymerization of a lactone such as ⁇ -butyrolactone, ⁇ -valerolactone, or ⁇ -caprolactone. Is mentioned.
  • an aromatic copolymer component in the crystalline polyester elastomer (A) used in the present invention, a small amount of an aromatic copolymer component can be used as long as it has a low melt viscosity.
  • Preferred examples of the aromatic copolymer component include aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, and aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A.
  • aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid
  • aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A.
  • an aliphatic component having a relatively high molecular weight such as dimer acid or dimer diol
  • the upper limit of the ester group concentration of the crystalline polyester-based elastomer (A) is 8000 equivalents in order to provide hydrolysis resistance that can withstand high temperature and high humidity in providing long-term durability to the encapsulated electrical and electronic parts.
  • / 10 6 g is desirable.
  • a preferable upper limit is 7500 equivalent / 10 ⁇ 6 > g, More preferably, it is 7000 equivalent / 10 ⁇ 6 > g.
  • the lower limit is desirably 1000 equivalents / 10 6 g.
  • a preferred lower limit is 1500 equivalents / 10 6 g, more preferably 2000 equivalents / 10 6 g.
  • the unit of ester group concentration is represented by the number of equivalents per 10 6 g of resin, and is a value calculated from the composition of the polyester resin and its copolymerization ratio.
  • the block-like segment is introduced into the polyester resin (A) of the present invention, it is preferably 2 mol% or more when the total of all the acid components and all glycol components of the polyester resin (A) is 200 mol%. More preferably, it is 5 mol% or more, more preferably 10 mol% or more, and most preferably 20 mol% or more.
  • the upper limit is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less in consideration of handling properties such as heat resistance and blocking.
  • Preferred examples of the crystalline polyester elastomer (A) used in the present invention include a crystalline polyester resin (A2) in which a polycarbonate component is copolymerized.
  • the crystalline polyester resin (A2) preferably has a chemical structure in which a hard segment mainly composed of a polyester segment and a soft segment mainly composed of a polycarbonate segment are bonded by an ester bond.
  • the soft segment mainly comprising a polycarbonate segment constituting the crystalline polyester resin (A2) used in the present invention can be formed by copolymerizing a polycarbonate component, typically a polycarbonate diol. Due to the copolymerization of the polycarbonate component, characteristics such as low melt viscosity, high flexibility, and high adhesion are exhibited.
  • the soft segment is preferably 25% by weight or more, more preferably 30% by weight or more, and 35% by weight. The above is particularly preferable.
  • the soft segment is preferably 75% by weight or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less.
  • the polycarbonate component constituting the soft segment is preferably an aliphatic polycarbonate component mainly composed of a poly (alkylene carbonate) component.
  • “mainly” means that the poly (alkylene carbonate) component occupies 50% by weight or more of the aliphatic polycarbonate component, more preferably 75% by weight or more, and more preferably 90% by weight or more. preferable.
  • the alkylene group constituting the poly (alkylene carbonate) is more preferably a linear alkylene group having 4 to 16 carbon atoms, and a longer chain alkylene group tends to be excellent in durability against cold cycle load. Considering availability, it is preferably a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a nonamethylene group.
  • the copolymer type polycarbonate in which the alkylene group which comprises poly (alkylene carbonate) is 2 or more types of mixtures may be sufficient.
  • heat resistance such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • a crystalline polyester segment is preferred. More preferred are PBT and PBN. When other crystalline polyesters are used, heat resistance may be insufficient, durability, and low temperature characteristics may deteriorate.
  • an aromatic copolymer component in the crystalline polyester resin (A2) used in the present invention, a small amount of an aromatic copolymer component can be used as long as it is within a range that maintains a low melt viscosity.
  • Preferred examples of the aromatic copolymer component include aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, and aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A.
  • aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid
  • aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A.
  • an aliphatic component having a relatively high molecular weight such as dimer acid or dimer diol, good mold releasability may be obtained by rapid solidification after molding.
  • an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer acid, hydrogenated dimer acid, dimer diol, hydrogenated dimer diol and / or carbon.
  • the total of all acid components and all glycol components of the polyester resin (A) is calculated.
  • it is 200 mol%, it is preferably 2 mol% or more, more preferably 5 mol% or more, more preferably 10 mol% or more, and most preferably 20 mol% or more.
  • the upper limit is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less in consideration of handling properties such as heat resistance and blocking.
  • the number average molecular weight of the crystalline polyester elastomer (A) used in the present invention is preferably 3000 or more, more preferably 5000 or more, and further preferably 7000 or more.
  • the upper limit of the number average molecular weight is preferably 50000 or less, more preferably 40000 or less, and still more preferably 30000 or less. If the number average molecular weight is less than 3000, the sealing resin composition may be insufficient in hydrolysis resistance and high elongation at high temperature and high humidity. If it exceeds 50,000, the melt viscosity at 220 ° C. May be higher.
  • the crystalline polyester elastomer (A) used in the present invention is preferably a saturated polyester resin containing no unsaturated group. If the unsaturated polyester contains an unsaturated group at a high concentration, there is a possibility that crosslinking occurs at the time of melting, and the melt stability may be inferior. Further, the crystalline polyester elastomer (A) used in the present invention may contain an unsaturated group in a very small amount.
  • the crystalline polyester elastomer (A) used in the present invention is copolymerized with a trifunctional or higher polycarboxylic acid such as trimellitic anhydride or trimethylolpropane or a polyol, if necessary, and has a branched polyester. It does not matter.
  • the phenol-modified alkylbenzene resin (B1) used in the resin composition of the present invention is a product obtained by modifying an alkylbenzene resin with phenol and / or alkylphenol, and preferably has a number average molecular weight in the range of 450 to 40,000.
  • the phenol-modified alkylbenzene resin (B1) is prepared by reacting an alkylbenzene such as xylene or mesitylene with an aldehyde such as formaldehyde in the presence of an acidic catalyst to produce an alkylbenzene resin, which is then phenols in the presence of an acidic catalyst. And can be produced by reacting with aldehydes.
  • the phenol-modified alkylbenzene resin (B1) is preferably an alkylphenol-modified xylene resin or an alkylphenol-modified mesitylene resin.
  • a xylene resin is a multimer composition having a basic structure in which a xylene structure is crosslinked by a methylene group or an ether bond, and can be typically obtained by heating meta-xylene and formaldehyde in the presence of sulfuric acid.
  • the mesitylene resin is a multimer composition having a basic structure in which the mesitylene structure is cross-linked by a methylene group or an ether bond. Typically, the mesitylene resin can be obtained by heating mesitylene and formaldehyde in the presence of sulfuric acid.
  • Xylene resins and mesitylene resins are typical of alkylbenzene resins.
  • the phenol-modified alkylbenzene resin (B1) of the present invention preferably has a hydroxyl value of 100 equivalents / 10 6 g or more, more preferably 1000 equivalents / 10 6 g or more, and 5000 equivalents / 10 6 g or more. Is more preferable. Also, preferably not more than 20000 equivalents / 10 6 g, more preferably 15000 or less equivalent / 10 6 g. If the hydroxyl value is too low, the adhesion to the aluminum material tends to be poor, and if the hydroxyl value is too high, the water absorption tends to increase and the insulating property tends to decrease.
  • the hydroxyl value referred to here is measured by the JIS K1557-1: 2007A method.
  • the phenol resin (B2) used in the resin composition of the present invention is a resin obtained by the reaction of phenols and aldehydes, and may be a novolak type phenol resin or a cresol type phenol resin, and has a number average molecular weight of 450 to 40,000. Those within the range are preferred.
  • Phenols that can be used as starting materials for phenol resins include bifunctional compounds such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol and 2,5-xylenol.
  • Trifunctional phenols such as phenol, phenol, m-cresol, m-ethylphenol, 3,5-xylenol and m-methoxyphenol, tetrafunctional phenols such as bisphenol A and bisphenol F, and these various phenols 1 type, or 2 or more types combined use can be mentioned.
  • formaldehyde used for manufacture of a phenol resin 1 type, or 2 or more types, such as formaldehyde, paraformaldehyde, a trioxane, can be used together.
  • Other examples include phenol-modified resins such as phenol aralkyl and phenol-modified xylene resins.
  • the phenol resin (B2) of the present invention preferably has a hydroxyl value of 100 equivalents / 10 6 g or more, more preferably 500 equivalents / 10 6 g or more, and 1000 equivalents / 10 6 g or more. Is more preferable. Further, preferably 10000 or less equivalent / 10 6 g, more preferably not more than 5000 equivalents / 10 6 g.
  • the hydroxyl value referred to here is measured by the JIS K1557-1: 2007A method.
  • the sealing resin composition by blending the phenol-modified alkylbenzene resin (B1) and / or the phenolic resin (B2) into the sealing resin composition, good initial adhesion and adhesion to a thermal cycle when sealing an electric / electronic component. Excellent properties such as durability can be imparted.
  • the phenol-modified alkylbenzene resin (B1) and / or the phenol resin (B2) is a stress relaxation effect due to a crystallization delay of the crystalline polyester resin (A), and a dispersion aid for the crystalline polyester resin (A) and the fluororesin (C). It is considered that the effect of improving the wettability to the base material by introducing the functional group is further exhibited.
  • the blending amount of the phenol-modified alkylbenzene resin (B1) and / or phenol resin (B2) in the present invention is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the crystalline polyester resin (A). More preferably, it is more preferably 3 parts by weight or more. Further, it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and further preferably 20 parts by weight or less.
  • the blending ratio of the phenol-modified alkylbenzene resin (B1) and / or the phenol resin (B2) is too low, the stress relaxation effect due to crystallization delay may not be exhibited, and the fluororesin (C) crystallinity and the polyester resin (A ) May not be expressed as a dispersion aid.
  • the productivity of the resin composition may be inferior, and the flexibility characteristics as a sealing body may be inferior.
  • the fluororesin (C) used in the present invention has a structure in which part or all of the hydrogen in the polyolefin is substituted with fluorine, or part of the hydrogen in the polyolefin is fluorine and the other part is perfluoroalkyl. It consists of a structure substituted with an ether group.
  • Specific examples of the fluororesin (C) used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer. Mention may be made of coalescence and polychlorotrifluoroethylene. Among these, in consideration of dispersibility, ethylene and propylene are copolymerized and a low melting point is preferable. Further, it may be a type modified with maleic acid or the like.
  • the fluororesin (C) of the present invention is preferably a fluororesin having a melting point of 220 ° C. or lower, more preferably 210 ° C. or lower. If the melting point of the fluororesin is too high, the melt viscosity of the resin composition may greatly increase when a sealing body is produced with the resin composition of the present invention, and low-pressure molding may become difficult. There is a possibility that the compatibility between the component (C) is low and the adhesion between the resin composition and the object to be sealed cannot be expressed.
  • the fluororesin (C) of the present invention preferably has a melt mass flow rate (hereinafter sometimes abbreviated as MFR) measured by ASTM D 3307 of 20 to 100 g / 10 minutes.
  • MFR melt mass flow rate
  • a low MFR is synonymous with a high melt viscosity, and the compatibility between the component (A) and the component (C) is lowered, and the adhesion between the resin composition part and the object to be sealed may be impaired.
  • a high MFR is synonymous with a low melt viscosity, and the resin composition is very soft, and the mechanical properties of the encapsulant may be inferior.
  • blending the fluororesin (C) with the sealing resin composition exhibits excellent characteristics such as initial adhesion and improved adhesion durability against a thermal cycle when sealing electrical and electronic parts.
  • the component (C) is considered to exhibit an effect of relaxing strain energy due to crystallization and enthalpy relaxation of the component (A).
  • the amount of component (C) in the present invention is preferably 0.5 parts by weight or more, more preferably 3 parts by weight or more, with respect to 100 parts by weight of component (A), and 5 parts by weight or more. More preferably.
  • the sealing resin composition of the present invention does not correspond to any of the crystalline polyester elastomer (A), the phenol-modified alkylbenzene resin (B1), the phenol resin (B2), and the fluororesin (C) of the present invention.
  • Other resins such as polyester, polyamide, polyolefin, polycarbonate, acrylic, ethylene vinyl acetate, curing agents such as isocyanate compounds and melamine, fillers such as talc and mica, pigments such as carbon black and titanium oxide, antimony trioxide, A flame retardant such as brominated polystyrene may be blended at all. By blending these components, adhesion, flexibility, durability and the like may be improved.
  • the crystalline polyester elastomer (A) at that time is preferably contained in an amount of 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more based on the entire resin composition of the present invention. .
  • the content of the crystalline polyester elastomer (A) is less than 50% by weight, the crystalline polyester elastomer (A) itself has excellent adhesion to electrical and electronic parts, adhesion durability, elongation retention, resistance to resistance. Hydrolysis and water resistance may be reduced.
  • an antioxidant for example, as a hindered phenol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2-methyl- 5-t-butylphenyl) butane, 1,1-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy- Benzenepropanoic acid, pentaerythrityltetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-benzenepropano Icic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-
  • the addition amount is preferably 0.1% by weight or more and 5% by weight or less with respect to the whole sealing resin composition. If it is less than 0.1% by weight, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by weight, the adhesion may be adversely affected.
  • Examples of the method for determining the composition and composition ratio of the polyester resin include 1 H-NMR and 13 C-NMR, which are measured by dissolving the polyester resin in a solvent such as deuterated chloroform, and quantification by gas chromatography which is measured after the methanolysis of the polyester resin. (Hereinafter, it may be abbreviated as methanolysis-GC method).
  • methanolysis-GC method when there is a solvent that can dissolve the crystalline polyester elastomer (A) and is suitable for 1 H-NMR measurement, the composition and composition ratio are determined by 1 H-NMR.
  • 13 C-NMR or methanolysis-GC method is adopted or used in combination.
  • the dicarboxylic acid and the diol component are esterified at 150 to 250 ° C., and then reduced in pressure.
  • the target polyester resin can be obtained by polycondensation at 230 to 300 ° C.
  • the target polyester resin is obtained by performing a transesterification reaction at 150 ° C. to 250 ° C. using a derivative such as dimethyl ester of the above dicarboxylic acid and a diol component, and then performing polycondensation at 230 ° C. to 300 ° C. under reduced pressure. be able to.
  • the sealing resin composition of the present invention preferably has a melt viscosity of 5 to 3000 dPa ⁇ s at 220 ° C., and is a crystalline polyester elastomer (A), a phenol-modified alkylbenzene resin (B1) and / or a phenol resin ( This can be achieved by appropriately adjusting the type and blending ratio of B2) and the fluororesin (C).
  • melt viscosity at 220 ° C. is a value measured as follows. That is, the sealing resin composition was dried to a moisture content of 0.1% or less, and then heated and stabilized at 220 ° C.
  • melt viscosity when a 10 mm thick die having a hole diameter of 1.0 mm is passed at a pressure of 98 N / cm 2 .
  • melt viscosity 3000 dPa ⁇ s or higher, high resin cohesive strength and durability can be obtained, but high-pressure injection molding is required when sealing to parts with complex shapes, so the parts can be destroyed. May occur.
  • a sealing resin composition having a melt viscosity of 2000 dPa ⁇ s or less, preferably 1000 dPa ⁇ s or less, a molded part having excellent electrical insulation can be obtained at a relatively low injection pressure of 0.1 to 100 MPa.
  • the melt viscosity at 220 ° C. is low, but considering the adhesiveness and cohesive force of the resin composition, the lower limit is preferably 5 dPa ⁇ s or more, and more preferably Is 10 dPa ⁇ s or more, more preferably 50 dPa ⁇ s or more, and most preferably 100 dPa ⁇ s or more.
  • the upper limit of the melting point of the polyester resin (A) is 210 ° C. is desirable. More preferably, it is 200 degreeC.
  • the lower limit is preferably 5 to 10 ° C. higher than the heat-resistant temperature required for the corresponding application. Considering handling at normal temperature and normal heat resistance, it is 70 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly preferably 140 ° C. or higher, and most preferably 150 ° C. or higher.
  • the adhesion strength between a specific member and the sealing resin composition is obtained by preparing a measurement sample piece in which two plate-like members are bonded with the sealing resin composition, and measuring the shear fracture strength thereof. Determine by doing.
  • the method for preparing the test specimen for measurement and the method for measuring the shear fracture strength are performed according to the methods described in the examples described later.
  • the sealing resin composition of the present invention is typically molded by pouring it into a mold in which electric and electronic parts are set.
  • a resin composition in which a crystalline polyester elastomer (A) is a crystalline polyester resin (A1) in which a polyether component is copolymerized is obtained at 130 to 220 ° C. using a screw type hot melt molding process applicator. It can be heated and melted before and after, injected into a mold through an injection nozzle, and after a certain cooling time, the molded product can be removed from the mold to obtain a molded product.
  • An appropriate temperature for heating and melting the resin composition varies depending on the resin composition.
  • the resin composition is a crystalline polyester resin (A2) in which the crystalline polyester elastomer (A) is copolymerized with a polycarbonate component.
  • the heating and melting temperature is preferably about 200 to 280 ° C.
  • the type of the applicator for hot melt molding processing is not particularly limited, and examples thereof include Nordson ST2 and Imoto Seisakusho IMC-18F9.
  • the normal temperature and normal humidity refers to an environment having a temperature of about 23 ° C. and a relative humidity of about 65%.
  • a sealing resin composition is injected from a gate provided at the center of a 100 mm ⁇ 100 mm surface, and molding is performed. went.
  • the molding conditions were a molding resin temperature of 220 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, a cooling time of 15 seconds, and a discharge rotation set to 50% (maximum discharge was set to 100%).
  • the molded product was released from the mold and cut into a strip shape with a width of 20 mm each having a cellophane tape-attached portion to obtain an adhesion strength test piece.
  • Thermal cycle test I The environmental load of 1000 cycles, where one cycle consists of an adhesion strength test piece prepared in the same way as the initial adhesion was evaluated for 30 minutes at ⁇ 40 ° C. and then at 80 ° C. for 30 minutes. And then allowed to stand at room temperature and humidity for a day and night, and then measured for T-type peel strength.
  • the T-type peel strength retention I defined by the following formula (1) was calculated and displayed according to the following evaluation criteria.
  • T-type peel strength retention I is 80% or more AA: T-type peel strength retention I is less than 80% 70% or more A: T-type peel strength retention I is less than 70% 50% or more B: T Mold peel strength retention I is less than 50%
  • Thermal cycle test II An environmental load of 1000 cycles, where one cycle is an adhesion strength test piece prepared in the same way as the initial adhesion was evaluated and placed in an environment at ⁇ 40 ° C. for 30 minutes and then at 150 ° C. for 30 minutes. And then allowed to stand at room temperature and humidity for a day and night, and then measured for T-type peel strength.
  • the T-type peel strength retention rate II defined by the following mathematical formula (2) was calculated and displayed according to the following evaluation criteria.
  • T-type peel strength retention II is 80% or more AA: T-type peel strength retention II is less than 80% 70% or more A: T-type peel strength retention II is less than 70% 50% or more B: T Mold peel strength retention II is less than 50%
  • Low pressure moldability evaluation method A flat plate (100 mm x 100 mm x 10 mm) made of a resin composition for sealing using a flat mold and a low pressure molding applicator IMC-18F9 manufactured by Imoto Seisakusho as an applicator for hot melt molding. After molding, the flat plate after mold release was visually observed, and the presence or absence of burrs, sink marks and short shots was displayed according to the following evaluation criteria.
  • the gate position was the center of a 100 mm ⁇ 100 mm surface, and the molding conditions were a molding resin temperature of 220 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, a cooling time of 15 seconds, and a discharge rotation of 50%.
  • Evaluation Criteria AAA Completely filled with no burrs or sink marks. AA: Filled completely, but some burrs are generated. A: Filled without a short shot, but with sink marks. B: There is a short shot.
  • dumbbell and the tensile breaking elongation was measured according to the measuring method of JIS K6251, and the value was defined as “initial tensile breaking elongation”.
  • the dumbbell prepared in the same manner was treated in a 150 ° C. atmosphere for 1000 hours and left standing at room temperature and humidity for one day and night, and then the tensile elongation at break was measured in the same manner.
  • the tensile elongation at break after the test ”.
  • the tensile elongation at break was calculated according to the following formula 2 and displayed according to the following evaluation criteria.
  • Evaluation criteria AAA Tensile rupture elongation retention ratio 65% or more AA: Tensile rupture elongation retention ratio less than 65% 50% or more A: Tensile rupture elongation retention ratio less than 50% 30% or more B: Tensile rupture elongation retention ratio 30 %Less than
  • TPA terephthalic acid
  • NDC naphthalene dicarboxylic acid
  • BD 1,4-butanediol
  • PTMG1000 polytetramethylene ether glycol (number average molecular weight 1000)
  • PTMG2000 Polytetramethylene ether glycol (number average molecular weight 2000)
  • PCL polycaprolactone (number average molecular weight 850)
  • PBT Polybutylene terephthalate
  • PBN Polybutylene naphthalate Fluororesin A: NEOFLON EFEP RP-4020, manufactured by Daikin Industries, Ltd., melting point 155 to 170 ° C., MFR 25 to 50 g / 10 min.
  • Fluororesin B NEOFLON EFEP RP-5000, manufactured by Daikin Industries, Ltd., melting point 190-200 ° C., MFR 20-30 g / 10 minutes
  • Fluororesin C NEOFLON PFA AP-202, manufactured by Daikin Industries, Ltd., melting point 298 ° C. MFR 3.3 g / 10 min.
  • Phenol-modified alkylbenzene resin A Nikanol HP-150, manufactured by Fudou Co., Ltd., phenol-modified xylene resin, hydroxyl value 3035 equivalent / 10 6 g.
  • Phenol-modified alkylbenzene resin B Nikanol HP-100, manufactured by Fudou Co., Ltd., phenol-modified xylene resin, hydroxyl value 2500 equivalent / 10 6 g.
  • Phenol-modified alkylbenzene resin C Nikanol L5, manufactured by Fudou Co., Ltd., phenol-modified xylene resin (EO addition type), hydroxyl value 625 equivalent / 10 6 g.
  • Phenol resin A CKM2400 Showa Highpolymer Co., Ltd., novolac type phenol resin, hydroxyl value 9000 equivalent / 10 6 g.
  • Phenol resin B EP4020 manufactured by Asahi Organic Materials Co., Ltd., cresol novolac type phenol resin, hydroxyl value 9250 equivalent / 10 6 g.
  • polyester resin IA 1,4-butanediol when the total amount of glycol components is 100 mol% with respect to 100 mol% of terephthalic acid in a reaction vessel equipped with a stirrer, thermometer, and condenser for distillation Charge 60 mol%. Thereafter, when the total amount of tetrabutyl titanate was 100 parts by mass, 0.25 part by mass was added, and the esterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, the remaining 40 mol% of polytetramethylene glycol “PTMG1000” (Mitsubishi Chemical Co., Ltd.) having a number average molecular weight of 1000 was charged.
  • PTMG1000 polytetramethylene glycol
  • hindered phenol antioxidant “Irganox 1330” (Ciba Geigy Corp.) was added to 0.5 parts by mass, and the temperature was raised to 255 ° C., while the pressure in the system was slowly reduced to 665 Pa at 255 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain a polyester resin IA.
  • This polyester resin IA had a melting point of 165 ° C. and a melt viscosity of 500 dPa ⁇ s.
  • Polyester Resins IB to D were obtained in the same manner as in Production Examples of Polyester Resin IA, except that the types and ratios of raw materials were changed.
  • the compositions and physical properties of these polyester resins IBD are shown in Table 1.
  • Resin Composition I-1 for sealing electrical and electronic parts is composed of 100 parts by weight of polyester resin IA, 20 parts by weight of fluororesin A, and epoxy resin A. After uniformly mixing 10 parts by mass, it was obtained by melt-kneading at a die temperature of 220 ° C. using a twin screw extruder. Polyester resin compositions I-2 to 16 were prepared in the same manner as polyester resin composition I-1, except that the blending components and ratios were changed. The respective compositions are shown in Tables 2 and 3.
  • Example I-1 The sealing resin composition I-1 was used as the sealing resin composition, and the melt characteristics, initial adhesion, and cooling cycle load durability were evaluated.
  • the melt viscosity of the resin composition was 1769 dPa ⁇ s, which was a good melting property.
  • the initial T-type peel strength was 1.5 MPa, and after the thermal cycle test, 1.0 MPa, which was a good result showing high adhesion strength retention in all items. The results are shown in Table 2.
  • Examples I-2 to 9 Using the sealing resin compositions I-2 to 9 as the sealing resin composition, the melting characteristics, initial adhesion, and cooling cycle load durability were evaluated in the same manner as in Example I-1. The evaluation results are shown in Tables 2 to 3.
  • Example I-1 The sealing resin composition I-10 was used as the sealing resin composition, and the melting characteristics, initial adhesion, and cooling cycle load durability were evaluated in the same manner as in Example I-1.
  • the resin composition melt viscosity was 2169 dPa ⁇ s, which was within the moldable range, but the initial T-type peel strength was 0.4 MPa, and after the thermal cycle test, 0.3 MPa, which was poor and did not satisfy the required characteristics.
  • the evaluation results are shown in Table 4.
  • Comparative Example I-2 Using the sealing resin composition I-11 as the sealing resin composition, the melting characteristics, the initial adhesion, and the cooling cycle load durability were evaluated in the same manner as in Example I-1.
  • the melt viscosity of the resin composition was 292 dPa ⁇ s, which was a moldable range, the initial T-type peel strength was 1.1 MPa, and 0.2 MPa after the cooling / heating cycle test.
  • the evaluation results are shown in Table 4.
  • Comparative Examples I-3 to 7 Using the sealing resin compositions I-12 to 16 as the sealing resin composition, the melting characteristics, the initial adhesion, and the cold cycle load durability were evaluated in the same manner as in Example I-1. The evaluation results are shown in Table 4.
  • Polyester Resin Composition II-A 100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 20,000 as a hard segment component and 150 parts by mass of aliphatic polycarbonate diol A as a soft segment component are 230 ° C. to 245 ° C. The mixture was stirred at 130 Pa for 1 hour to confirm that the resin became transparent. Thereafter, 60 ppm of phenylphosphonic acid as a phosphorus atom was added under a nitrogen stream and stirred for 10 minutes under slightly reduced pressure (> 300 Pa), and then the contents were taken out and cooled.
  • PBT polybutylene terephthalate
  • the polyester resin composition A was mainly composed of a crystalline polyester resin having a terminal vinyl group 13 eq / ton.
  • Polyester Resin Composition F In a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation, 100 mol parts of 2,6-naphthalenedicarboxylic acid, 75 mol parts of 1,4-butanediol, 2,6 -0.25% by weight of tetrabutyl titanate with respect to the total weight of naphthalenedicarboxylic acid and 1,4-butanediol was charged, and the esterification reaction was carried out at 170-220 ° C for 2 hours.
  • polyester resin F After completion of the esterification reaction, 25 mol parts of polytetramethylene glycol “PTMG1000” (Mitsubishi Chemical Co., Ltd.) having a number average molecular weight of 1000 and 0.5% of hindered phenol antioxidant “Irganox 1330” (Ciba Geigy Co., Ltd.) were added. The weight was charged and the temperature was raised to 250 ° C., while the pressure in the system was slowly reduced to 665 Pa at 250 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain a polyester resin F. This polyester resin composition F had a melting point of 190 ° C. and a melt viscosity of 500 dPa ⁇ s.
  • Resin Composition G was obtained in the same manner as in Production Example of Polyester Resin Composition F except that 2,6-naphthalenedicarboxylic acid was changed to terephthalic acid.
  • Table 5 shows the composition and physical properties of the polyester resin composition G.
  • Example II-1 100 parts by mass of polyester resin composition A, 20 parts by mass of fluororesin A, and 10 parts by mass of epoxy resin A are uniformly mixed, and then melt-kneaded at a die temperature of 220 ° C. to 240 ° C. using a twin-screw extruder.
  • a sealing resin composition 1 was obtained.
  • the resin composition had a melt viscosity of 1923 dPa ⁇ s and good melt characteristics.
  • the initial T-type peel strength was 1.4 MPa, after the thermal cycle test, 1.0 MPa, and the T-type peel strength retention was 71%. Further, the tensile fracture elongation retention after the high temperature long time load test was 70%.
  • Table 6 The evaluation results are shown in Table 6.
  • Polyester Resins III-A to C were obtained in the same manner as in the production example of Polyester Resin IA, except that the types and ratios of raw materials were changed. Table 9 shows the compositions and physical properties of these polyester resins III-A to C.
  • the resin composition for sealing electric and electronic parts of the present invention is excellent in melt fluidity and initial adhesion strength to an aluminum material, and also exhibits high adhesion durability even after being subjected to a cooling / heating cycle load.
  • the resin composition for sealing an electric / electronic part according to a specific embodiment of the present invention further has an adhesive strength after being subjected to a 1000 cycle cooling / heating cycle load of ⁇ 40 ° C. for 30 minutes and 80 ° C. or 150 ° C. for 30 minutes. It exhibits a high degree of thermal cycle durability that is maintained, and also exhibits a high degree of heat aging resistance in which the elongation at break is maintained even after high-temperature and long-term loading at 150 ° C. for 1000 hours.
  • the resin composition for encapsulating electrical and electronic parts of the present invention and the sealed body sealed thereby can seal electrical and electronic parts that may be exposed to severe environmental loads such as a thermal cycle and a high temperature and long time load.
  • it is useful as a molded product of a switch or a sensor having various types of connectors, harnesses or electronic components, printed circuit boards, and sensors for automobiles, communications, computers, and home appliances.

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Abstract

L'invention concerne une composition de résine pour le scellement étanche d'un composant électrique/électronique, la composition de résine étant moins sujette à gélifier même si elle est laissée dans un environnement à température élevée, tout en ayant une excellente force adhésive initiale sur un matériau d'aluminium et une excellente durabilité à l'encontre d'une charge de cycles thermiques et autres charges environnementales. L'invention concerne également un corps à composant électrique/électronique scellé de façon étanche, dans lequel la composition de résine est utilisée. La composition de résine pour le scellement étanche d'un composant électrique/électronique comprend un élastomère polyester cristallin (A), une résine d'alkylbenzène modifiée par phénol (B1) et/ou une résine phénolique (B2) et une résine fluorée (C); et présente une viscosité à l'état fondu de 5 dPa.s ou plus et de 3000 dPa.s ou moins lorsqu'elle est séchée à une humidité de 0,1 % ou moins, chauffée à 220°C, soumise à une pression de 1 MPa et extrudée à travers une filière ayant une épaisseur de 10 même et un diamètre d'orifice de 1,0 mm.
PCT/JP2012/062979 2011-05-31 2012-05-22 Composition de résine pour un composant électrique/électronique de scellement étanche, procédé de fabrication d'un composant électrique/électronique et corps à composant électrique/électronique scellé de façon étanche WO2012165206A1 (fr)

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Citations (9)

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JPH09249800A (ja) * 1996-03-18 1997-09-22 Teijin Ltd 難燃性樹脂組成物
JPH1121434A (ja) * 1997-07-04 1999-01-26 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH11255965A (ja) * 1998-03-10 1999-09-21 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物の製造方法
WO2000011109A1 (fr) * 1998-08-24 2000-03-02 Nippon Chemical Industrial Co., Ltd. Composition ignifuge et composition de resine ignifuge
JP2003176341A (ja) * 2001-09-18 2003-06-24 Toyobo Co Ltd モールディング用ポリエステル樹脂、樹脂組成物及びそれを用いた成型品
JP2003327940A (ja) * 2002-05-16 2003-11-19 Toyobo Co Ltd 接着剤組成物
JP2004083918A (ja) * 2001-09-18 2004-03-18 Toyobo Co Ltd モールディング用ポリエステル樹脂、樹脂組成物及びそれを用いた成型品
JP2004123864A (ja) * 2002-10-01 2004-04-22 Dainippon Ink & Chem Inc 難燃性熱可塑性樹脂組成物
JP2011505400A (ja) * 2007-12-03 2011-02-24 ビーエーエスエフ ソシエタス・ヨーロピア ２−（４，６−ビス−ビフェニル−４−イル−１，３，５−トリアジン−２−イル）−５−（２−エチル−（ｎ）−ヘキシルオキシ）フェノールの結晶形

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09249800A (ja) * 1996-03-18 1997-09-22 Teijin Ltd 難燃性樹脂組成物
JPH1121434A (ja) * 1997-07-04 1999-01-26 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
JPH11255965A (ja) * 1998-03-10 1999-09-21 Yokohama Rubber Co Ltd:The 熱可塑性エラストマー組成物の製造方法
WO2000011109A1 (fr) * 1998-08-24 2000-03-02 Nippon Chemical Industrial Co., Ltd. Composition ignifuge et composition de resine ignifuge
JP2003176341A (ja) * 2001-09-18 2003-06-24 Toyobo Co Ltd モールディング用ポリエステル樹脂、樹脂組成物及びそれを用いた成型品
JP2004083918A (ja) * 2001-09-18 2004-03-18 Toyobo Co Ltd モールディング用ポリエステル樹脂、樹脂組成物及びそれを用いた成型品
JP2003327940A (ja) * 2002-05-16 2003-11-19 Toyobo Co Ltd 接着剤組成物
JP2004123864A (ja) * 2002-10-01 2004-04-22 Dainippon Ink & Chem Inc 難燃性熱可塑性樹脂組成物
JP2011505400A (ja) * 2007-12-03 2011-02-24 ビーエーエスエフ ソシエタス・ヨーロピア ２−（４，６−ビス−ビフェニル−４−イル−１，３，５−トリアジン−２−イル）−５−（２−エチル−（ｎ）−ヘキシルオキシ）フェノールの結晶形

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