Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—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
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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 by lowering viscosity simply by heating and melting solidify and form a sealed body by simply cooling after sealing, so the productivity is high, and the resin is melted and removed by heating. It has excellent characteristics such as easy recycling of the member, and is suitable for sealing electrical and electronic parts.
• 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 polyester resin composition for molding containing a polyester resin having a specific composition and physical properties and an antioxidant, and sealing at a low pressure that does not damage electrical and electronic parts. Is disclosed to be possible. 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.
• Patent Document 2 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. This composition has a high initial adhesion strength to a glass epoxy plate or a polybutylene terephthalate plate containing 30% by weight of a glass filler. A decrease in adhesion strength due to loading at 105 ° C. for 1000 hours is also suppressed.
• An object of the present invention is to provide an electrical / electronic component capable of forming a sealed electrical / electronic component having excellent initial adhesion to an aluminum material, excellent durability against a cold cycle load, and excellent durability against a high-temperature and long-term load.
• An object of the present invention is to provide a sealing resin composition, and to provide a method for producing an electric / electronic component encapsulant using the same and an electric / electronic component encapsulant.
• the present inventors have intensively studied and have proposed the following invention. That is, the present invention (1) Crystalline polyester resin (A), epoxy resin (B) and polyamide resin (C) are contained, dried to a moisture content of 0.1% or less, heated to 220 ° C. and given a pressure of 1 MPa, A resin composition for sealing electrical and electronic parts, having a melt viscosity of 5 dPa ⁇ s to 3000 dPa ⁇ s when extruded from a die having a thickness of 1.0 mm and a thickness of 10 mm.
• a resin composition for sealing electrical and electronic parts having a melt viscosity of 5 dPa ⁇ s to 3000 dPa ⁇ s when extruded from a die having a thickness of 1.0 mm and a thickness of 10 mm.
• a resin composition for sealing electrical and electronic parts (7) The resin composition for sealing electrical and electronic parts according to any one of (1) to (6), wherein the initial T-type peel strength with respect to the aluminum plate is 0.5 N / mm or more.
• the resin composition temperature is 130 ° C. or higher and 260 ° C. or lower in a mold into which an electric / electronic component is inserted.
• a method for producing an encapsulated electrical and electronic component which is injected at an object pressure of 0.1 MPa to 10 MPa.
• the resin composition for encapsulating electrical and electronic parts of the present invention has excellent initial adhesion to an aluminum material, and retains adhesive strength even after 1000 cycles of cooling and heating cycle loading at ⁇ 40 ° C. for 30 minutes and 80 ° C. for 30 minutes. In addition, it exhibits high heat cycle aging durability, and also exhibits high heat aging resistance in which the tensile fracture elongation does not decrease even after a high temperature long time load at 150 ° C. for 1000 hours. For this reason, the electrical and electronic component encapsulated body sealed with the resin composition for encapsulating electrical and electronic components of the present invention exhibits durability against severe environmental loads in a thermal cycle and durability against high-temperature and long-term loads.
• the encapsulated body for electrical and electronic parts of the present invention comprises a resin or a resin composition that is heated and kneaded in a mold in which the electrical and electronic parts are set inside the mold to give fluidity to 0.1 to 10 MPa. It can be manufactured by injecting at low pressure and enclosing and sealing the electrical and electronic parts with a resin or resin composition. In other words, since it is performed at a very low pressure compared to injection molding at a high pressure of 40 MPa or more, which is generally used for molding plastics in the past, it is resistant to heat and pressure while being sealed by an injection molding method. It is possible to seal a limited electric / electronic component without breaking it.
• the resin composition for sealing electrical and electronic parts of the present invention contains a crystalline polyester resin (A), an epoxy resin (B), and a polyamide resin (C), and is dried to a moisture content of 0.1% or less at 220 ° C.
• the melt viscosity is 5 dPa ⁇ s or more and 3000 dPa ⁇ s or less when extruded from a die having a hole diameter of 1.0 mm and a thickness of 10 mm.
• polyether diol is copolymerized, or a hard segment mainly composed of a polyester segment and a soft segment mainly composed of a polycarbonate are bonded by an ester bond. It consists of a chemical structure.
• the polyether diol is copolymerized to exhibit characteristics such as a decrease in melt viscosity, imparting flexibility, and imparting adhesion.
• the copolymerization ratio of the polyether diol is preferably 1 mol% or more, and more preferably 5 mol% or more when the total glycol component constituting the crystalline polyester resin (A) is 100 mol%.
• it is 10 mol% or more, and especially preferably 20 mol% or more. Further, it is preferably 90 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, and particularly preferably 45 mol% or less.
• the copolymerization ratio of the polyether diol is too low, the melt viscosity becomes high, and molding tends not to be performed at a low pressure, or the crystallization speed is high and a short shot tends to occur. Moreover, when the copolymerization ratio of the polyether diol is too high, problems such as insufficient heat resistance tend to occur.
• the number average molecular weight of the polyether diol is preferably 400 or more, and more preferably 800 or more. If the number average molecular weight is too low, flexibility cannot be imparted, and the stress load on the electronic substrate after sealing tends to increase.
• the number average molecular weight of the polyether diol 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 polyether diol include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and the like, and polytetramethylene glycol is most preferable in terms of imparting flexibility and reducing melt viscosity.
• the crystalline polyester resin (A) used in the present invention is widely used as an engineering plastic by adjusting the composition ratio of an aliphatic component and / or an alicyclic component and an aromatic component.
• Low melt viscosity and two-part curable epoxy that are not available in general-purpose crystalline polyester resins such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polybutylene terephthalate (hereinafter sometimes abbreviated as PBT) Heat resistance, high-temperature and high-humidity resistance, cold-heat cycle resistance, and the like comparable to resins can be exhibited. For example, in order to maintain high heat resistance of 150 ° C.
• 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.
• a copolymerized polyester based is suitable.
• mold releasability due to rapid crystallization after molding is a desirable characteristic from the viewpoint of productivity, so terephthalic acid and 1,4-butanediol, naphthalenedicarboxylic acid and 1,4-butanediol, which are rapidly crystallized, are used. It is preferable to use it as a main component.
• the acid component constituting the crystalline polyester resin (A) it is preferable to contain both or one of terephthalic acid and naphthalenedicarboxylic acid from the viewpoint of heat resistance.
• 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 resin (A) contains one or both 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-mentioned 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, -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
• the crystalline polyester resin (A) used in the present invention includes an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as dimer acid or hydrogenated dimer acid, and / or dimer diol or hydrogenated dimer diol.
• an aliphatic and / or alicyclic diol having 10 or more carbon atoms such as a copolymer is copolymerized, the glass transition temperature is lowered while maintaining a high melting point, and the heat resistance of the resin composition of the present invention and adhesion to electric and electronic parts are reduced. In some cases, the compatibility with the sex can be further improved.
• 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
• polytetramethylene glycol 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 or the like (most dimers, trimers, monomers, etc.)
• the hydrogenated dimer acid means a hydrogenated dimer acid with hydrogen added to the unsaturated bond portion thereof.
• 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 crystalline polyester resin (A) used in the present invention may have 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 composed of a polycarbonate segment constituting the crystalline polyester resin (A) 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 copolymerization ratio of the polycarbonate component is preferably 25% by weight or more, more preferably 30% by weight or more when the entire hard segment component constituting the crystalline polyester resin (A) is 100% by weight. 35% by weight or more is particularly preferable.
• the polycarbonate component is preferably an aliphatic polycarbonate component mainly composed of a poly (alkylene carbonate) component.
• 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.
• 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.
• Crystalline polyester segments are 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 (A) used in the present invention, a small amount of an aromatic copolymer component can be used as long as the low melt viscosity is maintained.
• 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 resin (A) is 8000 equivalents / 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 crystalline polyester resin (A) of the present invention, when the total of all acid components and all glycol components of the crystalline polyester resin (A) is 200 mol%, it is 2 mol% or 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.
• the number average molecular weight of the crystalline polyester resin (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 resin (A) used in the present invention is desirably a saturated polyester resin that does not contain an unsaturated group. If it is an unsaturated polyester, there is a possibility that crosslinking occurs at the time of melting, and the melt stability may be inferior.
• the crystalline polyester resin (A) used in the present invention may be a polyester having a branch by copolymerizing a tri- or higher functional polycarboxylic acid such as trimellitic anhydride or trimethylolpropane or a polyol as necessary. There is no problem.
• the resin composition melts quickly at 210 to 240 ° C.
• the upper limit of the melting point of the crystalline polyester resin (A) is preferably 210 ° C. 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.
• the crystalline polyester resin (A) used in the present invention As a method for producing the crystalline polyester resin (A) used in the present invention, a known method can be used.
• the dicarboxylic acid and the diol component are esterified at 150 to 250 ° C., and then the pressure is reduced.
• 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.
• 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 resin (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 epoxy resin (B) used in the present invention is an epoxy resin having an average of at least 0.1 or more glycidyl groups in the molecule, preferably in the number average molecular weight range of 450 to 40,000.
• glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolak glycidyl ether, brominated bisphenol A diglycidyl ether, glycidyl ester type such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanate Nurate, glycidylhindantoin, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmetaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisaminomethylcyclohexane, etc.
• epoxidized polybutadiene such as alicyclic or aliphatic epoxides such as epoxidized soybean oil.
• a preferred number average molecular weight of the epoxy resin (C) is 450 to 40,000. If the number average molecular weight of the epoxy resin (C) is too low, the resin composition of the present invention is very easily softened, and the mechanical properties may be inferior.
• the polyamide resin (C) can be easily finely dispersed and mixed with the originally incompatible crystalline polyester resin (A). For this reason, blending the epoxy resin (B) has an effect that a homogeneous resin composition can be easily obtained by a general kneading facility such as a single screw extruder or a twin screw extruder. Demonstrate.
• the polyamide resin (C) used in the present invention is not particularly limited as long as it is a polyamide resin.
• Nylon 4, nylon 6, nylon 7, nylon 11, nylon 12, nylon 66, and other nylon resins, aramid resins, and these Polymers and mixtures can be mentioned as preferred examples.
• an elastomer type polyamide resin obtained by copolymerizing polyether, polycarbonate, aliphatic polyester or the like with these nylon resins is particularly preferable as the polyamide resin (C) used in the present invention.
• Polyester block amide elastomers of VESTAMID (registered trademark) E series sold by Daicel Evonik Co., Ltd. and PEBAX (registered trademark) series sold by Arkema Co., Ltd. are easily available. It is preferable as the polyamide resin (C) of the present invention.
• a polyamide resin having a melting point of 220 ° C. or lower is preferably used, and more preferably 210 ° C. or lower. If the melting point of the polyamide resin (C) 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.
• Component and (C) component are low in compatibility, and cannot be dispersed well as a composition, and the adhesion between the resin composition and the object to be sealed may not be exhibited.
• the melting point of the polyamide resin (C) is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 140 ° C. or higher. If the melting point of the polyamide resin (C) is too low, the heat resistance of the composition may be insufficient.
• the polyamide resin (C) of the present invention preferably has a melt mass flow rate (hereinafter sometimes abbreviated as MFR) measured by ASTM D 3307 at 3 to 200 g / 10 min at 235 ° C. and 1 kg load. If the MFR is low, the adhesion between the resin component having a high melt viscosity and the material to be sealed in the molding conditions of the sealing body of the present invention may be impaired.
• MFR melt mass flow rate
• blending the polyamide resin (C) into the sealing resin composition is superior to the electrical and electronic component sealing body of the present invention, such as improved initial adhesion and adhesion durability against a thermal cycle. Demonstrate the characteristics.
• 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 blending ratio of the component (C) is too low, strain energy relaxation due to crystallization and enthalpy relaxation of the component (A) is small, and the adhesion strength tends to decrease.
• the blending ratio of the component (C) is too high, there is a tendency to deteriorate the adhesion and resin physical properties, and the (A) component and the (C) component cause macro phase separation and break. There is a case where the elongation is lowered and the moldability is adversely affected such that a smooth surface cannot be obtained.
• the sealing resin composition of the present invention does not fall under any of the components (A), (B) and (C) of the present invention, such as polyester, polyamide, polyolefin, polycarbonate, acrylic, ethylene vinyl acetate, etc.
• Other resins, isocyanate compounds, curing agents such as melamine, fillers such as talc and mica, pigments such as carbon black and titanium oxide, flame retardants such as antimony trioxide and brominated polystyrene may be used at all. .
• curing agents such as melamine
• fillers such as talc and mica
• pigments such as carbon black and titanium oxide
• flame retardants such as antimony trioxide and brominated polystyrene
• the component (A) 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 polyester resin (A) itself has excellent adhesion to electrical and electronic parts, adhesion durability, elongation retention, hydrolysis resistance, and water resistance. May decrease.
• 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-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2-methyl- 5-t-butylphenyl) butane
• 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.
• the sealing resin composition of the present invention preferably has a melt viscosity at 220 ° C. of 5 to 3000 dPa ⁇ s, and the types and blending ratios of the components (A), (B), and (C) are appropriate. This can be achieved by adjusting to For example, when the encapsulating resin composition of the present invention comprises the component (A), the component (B), and the component (C), the melt viscosity of the encapsulating resin composition can be estimated by the following equation. The resin composition having an appropriate melt viscosity can be obtained by further fine adjustment as necessary.
• increasing the copolymerization ratio of the polyether diol copolymerized with the component (A) or decreasing the molecular weight of the component (A) decreases the melt viscosity of the component (A), and the resin of the present invention. It acts in the direction of lowering the melt viscosity of the composition.
• the melt viscosity of the sealing resin composition of the present invention 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. with a flow tester (model number CFT-500C) manufactured by Shimadzu Corporation. Is a measured value of viscosity when a 10 mm thick die having a 1.0 mm hole diameter is passed through at a pressure of 1 MPa. When the melt viscosity is higher than 3000 dPa ⁇ s, high resin cohesive strength and durability can be obtained. However, when sealing to a component having a complicated shape, high-pressure injection molding is required, so that it is sealed. May cause destruction of parts.
• 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 adhesion strength between the specific member and the sealing resin composition is obtained by preparing a measurement sample piece obtained by bonding the sealing resin composition by molding on a single plate-like member. Determination is made by measuring T-type peel strength.
• the method for preparing the test specimen for measurement and the method for measuring the T-type peel strength are performed according to the methods described in the examples described later.
• the electrical and electronic component sealing body of the present invention can be manufactured by melting and injecting the resin composition of the present invention into a mold into which electrical and electronic components are inserted. More specifically, in the case of using a screw type hot melt molding process applicator, it is heated and melted at around 200 to 280 ° C., injected into a mold through an injection nozzle, and after a certain cooling time, it is molded. An object can be removed from the mold to obtain an electrical / electronic component sealing body.
• the temperature and pressure at the time of pouring the resin composition are more preferably a temperature of 130 ° C. or higher and 260 ° C. or lower and a pressure of 0.1 MPa or higher and 10 MPa or lower.
• 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.
• 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.
• T-type peel strength retention is a value defined by the following mathematical formula.
• T-type peel strength retention rate 80% or more B: T-type peel strength retention rate less than 80% 70% or more ⁇ : T-type peel strength retention rate less than 70% 50% or more
• X T-type peel strength retention rate 50 %Less than
• 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. Molded. The gate position was the center of a 100 mm ⁇ 100 mm surface. Molding conditions: molding resin temperature 220 ° C., molding pressure 3 MPa, holding pressure 3 MPa, cooling time 15 seconds, discharge rotation 50%.
• Evaluation criteria A Completely filled with no burrs or sink marks. ⁇ : Although completely filled, some burrs are generated. ⁇ : Filled without short shot, but there is a sink. X: There is a short shot.
• Polyester Resin A 100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 20,000 as a hard segment component and 67 parts by mass of an aliphatic polycarbonate diol A as a soft segment component are obtained at 230 ° C. to 245 ° C. under 130 Pa. It stirred for 1 hour and it confirmed that resin became transparent. Thereafter, the contents were taken out and cooled. Next, 0.3 part of Lasmit LG and 0.3 part of Irganox 1010 were added and kneaded at 250 ° C. to obtain a polyester resin A.
• PBT polybutylene terephthalate
• polyester resin A the types and blending amounts of the hard segment component and the soft segment component were changed to obtain polyester resins B to E and H.
• the compositions and physical properties of the polyester resins B to E are shown in Table 1.
• Polyester Resin 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-naphthalene 0.25% by weight of tetrabutyl titanate with respect to the total weight of dicarboxylic acid and 1,4-butanediol was charged, and esterification was performed at 170 to 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.
• polyester resin G Similar to the production example of polyester resin F, except that 2,6-naphthalenedicarboxylic acid was changed to terephthalic acid to obtain polyester resin G.
• the composition and physical properties of the polyester resin composition G are shown in Table 1.
• 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 I.
• This polyester resin I had a melting point of 165 ° C. and a melt viscosity of 500 dPa ⁇ s.
• Polyester resins J to L were obtained in the same manner as in the production examples of polyester resin I except that the raw material composition was changed and polyester resins were produced.
• the compositions and physical properties of the polyester resins J to L are shown in Table 2.
• PBT polybutylene terephthalate
• PBN polybutylene naphthalate
• TPA terephthalic acid
• NDC naphthalenedicarboxylic acid
• BD 1,4-butanediol
• PTMG1000 polytetramethylene ether glycol (number average molecular weight 1000)
• PTMG2000 poly Tetramethylene ether glycol (number average molecular weight 2000)
• PCL polycaprolactone (number average molecular weight 2000)
• polyamide resins and epoxy resins used in Tables 3 to 6 are as follows.
• Polyamide resin A PEBAX (registered trademark) MX1205, manufactured by Arkema Co., Ltd., polyether block amide, melting point 147 ° C., MFR 7 g / 10 min.
• Polyamide resin B PEBAX (registered trademark) 4033, manufactured by Arkema Co., Ltd., polyether block amide, melting point 160 ° C., MFR 5 g / 10 min.
• Polyamide resin C Gramide (registered trademark) T-661, manufactured by Toyobo Co., Ltd., nylon 66, melting point 260 ° C.
• Polyamide resin D nylon MXD6, manufactured by Mitsubishi Gas Chemical Company, nylon 6, melting point 240 ° C.
• Epoxy resin A JER1007, manufactured by Mitsubishi Chemical Corporation, bisphenol type epoxy resin.
• Epoxy resin B UG4070, manufactured by Toagosei Co., Ltd., a polyfunctional epoxy resin.
• Epoxy resin C EX-145, manufactured by Nagase ChemteX Corporation, monoepoxy resin.
• Example 1 100 parts by weight of polyester resin A, 20 parts by weight of polyamide resin A, and 20 parts by weight of epoxy resin A are uniformly mixed, and then melt-kneaded at a die temperature of 220 to 270 ° C. using a twin screw extruder to obtain a resin composition Product 1 was obtained.
• Table 3 shows the composition of the resin composition 1 and the evaluation results.
• ⁇ melting characteristic test> it was 1899 dPa * s and favorable melting characteristics.
• ⁇ Adhesion Strength Test> the initial adhesion strength is as good as 2.2 MPa.
• ⁇ Cooling Cycle Load Durability Test> the T-type peel strength after the cold-heat cycle test is 1.9 MPa, and the T-type peel strength retention is 86. % And good.
• the tensile elongation at break was as good as 65%.
• Comparative Examples 1 and 2 are examples in which a crystalline polyester resin in which a polytetramethylene glycol component is copolymerized is used instead of the crystalline polyester resin (A) in which a polycarbonate component is copolymerized.
• the initial adhesion strength was 2.5 MPa in ⁇ Adhesion Strength Test>
• the T-type peel strength after the thermal cycle test was 1.9 MPa, which was excellent in initial adhesion and thermal cycle durability.
• the melt viscosity was as good as 1970 dPa ⁇ s, but in the ⁇ high temperature long-term load durability test>, the elongation retention was as poor as 10%.
• Comparative Example 3 is an example where the polyamide resin (C) was not used.
• the ⁇ melting property test> had a favorable result of 490 dPa ⁇ s, and the initial adhesion strength was good at 2.1 MPa in the ⁇ adhesion strength test>, but after the cooling and heating cycle test, it became 0.1 MPa. With bad results.
• Comparative Example 4 is an example where the type of polyamide resin (C) is polyamide resin C and the epoxy resin (B) uses epoxy resin B.
• the ⁇ melting characteristic test> was 5182 dPa ⁇ s, which was a defective result that was difficult to mold.
• Comparative Example 5 is an example where the epoxy resin (B) was not used. In Comparative Example 5, ⁇ initial adhesion> was slightly inferior and ⁇ cooling cycle load durability> was significantly inferior.
• Comparative Example 6 it was 2964 dPa ⁇ s in the ⁇ melting characteristic test>, which was a moldable range, but in the ⁇ adhesion strength test>, the initial adhesion strength to the aluminum plate was 0.2 MPa, and after the cooling / heating cycle test, it was 0. It became defective because it did not meet the required characteristics of 0 MPa.
• Comparative Example 7 is a moldable range at 202 dPa ⁇ s in ⁇ Melting Characteristic Test>.
• ⁇ Adhesion Strength Test> the initial adhesion strength of the aluminum plate adhesion test piece is 1.6 MPa, and 0 after the thermal cycle test. The pressure was 0.0 MPa, and the required characteristics were not satisfied, resulting in a failure.
• the resin composition for encapsulating electrical and electronic parts of the present invention is excellent in initial adhesion strength to an aluminum material when used as a sealant for encapsulating electrical and electronic parts, and has high adhesion durability even after being subjected to a thermal cycle load. Demonstrate and useful.
• the electrical and electronic component encapsulant of the present invention is useful because it exhibits durability against severe environmental loads in a cooling and heating cycle.
• the electrical and electronic component sealing body of the present invention is useful as, for example, automobiles, communications, computers, various connectors for household appliances, harnesses or electronic components, switches having a printed circuit board, and molded products of sensors.

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