TW201400546A - Resin composition for encapsulating electric/electronic components, manufacturing method for electric/electronic components and encapsulated body of electric/electronic component - Google Patents

Abstract

The purposes of the present invention are to provide a resin composition for encapsulating electric/electronic components, which has less concern for gelation even if retained in a high temperature condition and has excellent initial adhesive strength for aluminum material and excellent durability of environmental loads such as thermal cycle loading, etc., and to provide an encapsulated body of electric/electronic components using the same. The solving means is a resin composition for encapsulating electric/electronic components, which contains: a crystalline polyester elastomer (A), a phenol-modified alkyl benzene resin (B1), and/or a phenol resin (B2), and a fluororesin (C). Furthermore, the resin composition has a melt viscosity of 5 dPa.s or more and 3000 dPa.s or less, when dried to have a moisture ratio of 0.1% or less, heated to 220 DEG C, subjected to a pressure of 1 Mpa and extruded through a mold having a thickness of 10 mm and a pore diameter of 1.0 mm.

Description

Resin composition for electrical and electronic parts packaging, method of manufacturing electrical and electronic parts, and electrical and electronic parts package

The present invention relates to an electric and electronic component package packaged with a resin composition, a method for producing the same, and a resin composition suitable for the purpose.

Electrical and electronic parts that are widely used in automobiles and electrochemical products are necessary for electrical insulation from the outside in order to achieve their intended use. For example, the electric wires are covered with an electrically insulating resin. Recently, the use of electric and electronic parts having a complicated shape in a small volume such as a mobile phone has proliferated, and various methods have been employed for electrical insulation. In particular, when an electrical and electronic component having a complicated shape such as a circuit board is packaged by a resin that is an electrical insulator, a packaging method that can surely follow the shape of the electrical and electronic component without causing an unfilled portion is required. Therefore, the usual method is to lower the viscosity of the encapsulating resin composition at the time of coating. A hot-melt resin that can be packaged by heating only by melting and melting, and can be cured by cooling after being packaged to form a package, so that productivity is high, and since thermoplastic resin is usually used, it is used as a resin. After the end of the life of the product, the resin can be melted and removed by heating, so that the member can be easily reused.

In addition, as an automobile application, an electronic substrate provided in an engine room or the like often has a heating element, and in order to prevent accumulation of heat, a countermeasure is to provide a heat dissipation plate made of aluminum. Moreover, in order to reduce the weight, the wire harness for automotive use is gradually transferred to the aluminum wire. Under this circumstance, the adhesion to aluminum is required to be increased in the packaging material.

A polyester having high electrical insulating properties and high water resistance is considered to be a very useful material for this purpose. However, generally, the melt viscosity is high, and in order to package a complicated shape, it is necessary to use a high-pressure injection molding of several hundred MPa or more. Therefore, there will be damage to electrical and electronic parts. Patent Document 1 discloses a copolymerization of a specific polytetramethylene glycol. A binder composition for a structure comprising a polyetherester elastomer and an epoxy group having an epoxy group having an average number of at least 1.2 or more in the molecule. The polyester resin used herein has a good initial adhesion, but tends to have high crystallinity. Therefore, when it is changed from an amorphous state to a crystalline state, the strain energy is generated and the adhesion strength is greatly lowered. The tendency is not suitable as a package for electrical and electronic parts.

Patent Documents 2 and 3 propose a packaged hot-melt resin composition having a melt viscosity which can be packaged at a low pressure which does not damage electrical and electronic parts. By the resin composition, a molded article having good initial adhesion can be obtained, and the polyester resin composition can be applied to general electrical and electronic parts. However, for example, if it is repeatedly exposed to a thermal cycle of -40 ° C and 80 ° C for a long period of time, there is a problem that the adhesion strength is largely lowered and the package state cannot be maintained.

Patent Document 4 discloses a resin composition for encapsulating an electric and electronic component in which a crystalline polyester resin, an epoxy resin, and a polyolefin resin are blended. Although this composition has high adhesive strength and high resistance to cold and heat cycle load, there is a problem that if a blend of epoxy propyl groups is retained at a high temperature, gelation or hardening and agglomeration may occur.

Patent Document 5 discloses that a hot-melt adhesive composition blended with a specific polyester resin and a phenol-modified xylene resin is displayed for tin-plated copper and biaxially-oriented polyethylene terephthalate film. Good adhesion. The adhesive composition also has a problem of insufficient adhesion durability at 40 ° C for 40 minutes in automotive use and 30 minutes at 80 ° C for the thermal cycle.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 60-18562

[Patent Document 2] Japanese Patent No. 3553559

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-83918

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-150471

[Patent Document 5] Japanese Patent No. 4389144

As described above, in the conventional art, as a resin composition for electrical and electronic component packaging having a complicated shape, there has not been proposed a person who can sufficiently satisfy all the required performances.

A first object of the present invention is to provide an electric and electronic component package excellent in durability against environmental loads such as a thermal cycle load and the like, and an electric and electronic component package to which the gelation is small, even if it is retained at a high temperature. The manufacturing method of the body and the resin composition for electrical and electronic component packaging. More specifically, the elongation and strength are not greatly reduced even after 1000 cycles of heat-cooling cycles of 30 minutes at -40 ° C for 30 minutes and 80 minutes at 80 ° C, even if the heat and cold cycle load is highly durable. Resin composition for electrical and electronic parts packaging that can be used in the required environment. A second object of the present invention is to provide an electrical and electronic component package excellent in durability against cold-heat cycle load and high-temperature long-term load, and a suitable electrical property, which is excellent in gelation even when it is retained at a high temperature. A method of manufacturing an electronic component package and a resin composition for electrical and electronic component packaging. More specifically, it provides a resin composition for electrical and electronic parts packaging which is elongated even after a heat cycle of 1000 cycles of -40 ° C for 30 minutes and 150 ° C for 30 minutes, or a high temperature and long time load of 150 ° C for 1000 hours. The degree and strength are not greatly reduced, and even in an environment such as a car engine room, which is highly durable for a hot and cold cycle load or a high temperature and long time load, it can cope with it.

In order to achieve the above object, the inventors of the present invention have made an effort to discuss and finally propose the following invention. In other words, the present invention relates to: (1) a resin composition for encapsulating an electric and electronic component, comprising a crystalline polyester elastomer (A), Phenol-modified alkylbenzene resin (B1) and/or phenol resin (B2) and fluororesin (C); dried to a moisture content of 0.1% or less, heated to 220 ° C, applied pressure of 1 MPa, and a pore diameter of 1.0 mm. The melt viscosity of the die with a thickness of 10 mm is 5dPa. s above 3000dPa. s below.

(2) The resin composition for electrical and electronic component encapsulation of (1), wherein the crystalline polyester elastomer (A) is selected from the group consisting of a crystalline polyester resin (A1) obtained by copolymerization of a polyether component, One or two or more of the group consisting of the crystalline polyester resin (A2) obtained by copolymerization of the polycarbonate component and the crystalline polyester resin (A3) obtained by copolymerization of the polylactone component mixture.

(3) The resin composition according to (1) or (2), wherein the phenol-modified alkylbenzene resin (B1) is an alkylphenol-modified alkylbenzene resin, and the hydroxyl value is 100 equivalents/10 ⁶ g the above.

(4) The resin composition according to any one of (1) to (3), wherein the phenol resin (B2) is a novolac type phenol resin, and the valence of the hydroxyl group is 100 equivalents/10 ⁶ g or more.

(5) The resin composition according to any one of (1) to (4), wherein a phenol-modified alkylbenzene resin (B1) is blended with respect to 100 parts by weight of the crystalline polyester-based elastomer (A). The total amount of the phenol resin (B2) is 0.1 to 100 parts by weight, and the fluororesin (C) is 0.1 to 100 parts by weight.

(6) The resin composition for electrical and electronic parts encapsulation according to any one of (1) to (5), wherein the aluminum plate is subjected to 1000 cycles of -40 ° C for 30 minutes and 80 ° C for 30 minutes before and after the heat cycle of the T-type. The peel strength retention rate was 50% or more.

(7) The resin composition for electrical and electronic component packaging according to any one of (1) to (6), wherein the initial T-type peel strength of the aluminum plate is 0.5 N/mm or more.

(8) A method of producing an electrical and electronic component package, which comprises heating and kneading the resin composition of any one of (1) to (7), and then having a resin composition temperature of 130 ° C or more and 260 ° C or less and resin composition The resin composition is injected into a mold in which an electric and electronic component is inserted under the condition that the material pressure is 0.1 MPa or more and 10 MPa or less.

(9) An electric and electronic component package which is encapsulated by the resin composition of any one of (1) to (7).

The resin composition for electric and electronic component encapsulation of the present invention is excellent in melt fluidity, and can be used as an electric and electronic component encapsulant even under a low pressure without causing a short shot. In addition, the initial adhesion strength of each member including the aluminum material is excellent, and even after the cooling and heating cycle load, the high adhesion can be maintained, and the high adhesion durability to the cold and heat cycle can be exhibited. Therefore, the electrical and electronic component package packaged by the resin composition for electrical and electronic component packaging of the present invention exhibits durability against a severe environmental load of cold and heat cycles. Moreover, since the resin composition for electrical and electronic component packaging according to the specific embodiment of the present invention is excellent in melt fluidity, it can be used as a sealing material in an electrical and electronic component package, and can be formed even at a low pressure. Insufficient fill occurs. In addition, it is excellent in initial adhesion to various members including aluminum, and can maintain adhesive strength even after passing through a cycle of heat cycle of 1000 cycles of -40 ° C for 30 minutes and 150 ° C for 30 minutes. The thermal cycle is durable, and even after a long period of high temperature of 150 ° C for 1000 hours, the elongation at break can be maintained, and the heat aging resistance can be exhibited. Therefore, the electrical and electronic component package packaged by the resin composition for electrical and electronic component packaging of the present invention can exhibit durability against such severe environmental loads as thermal cycle or high temperature and long-term load.

[Formation of the Invention]

In the electric and electronic component package of the present invention, a resin or a resin composition which is heated and kneaded to impart fluidity can be injected and injected into a mold in which an electric and electronic component is incorporated in a mold at a low pressure of 0.1 to 10 MPa. And manufacturing. The electrical and electronic parts are encapsulated in whole or in part by encapsulation of the injected resin. Compared with conventional high-pressure injection molding used in plastic molding at 40 MPa or higher, since it is carried out at a very low pressure, it is heat-resistant and pressure-resistant even though it is packaged by injection molding. Electrical and electronic parts with limited properties are packaged without breaking Bad. By appropriately selecting the encapsulating resin or the encapsulating resin composition, it is possible to obtain a package having a durability against environmental load such as a cold heat cycle load and a high temperature long time load, even for a metal member such as an aluminum material. body. The details of the embodiments of the invention are described below in order.

The resin composition for electrical and electronic component encapsulation 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). It is dried to a moisture content of 0.1% or less, heated to 220 ° C, a pressure of 1 MPa, and a melt viscosity of 5 dPa when extruded through a die having a hole diameter of 1.0 mm and a thickness of 10 mm. s above 3000dPa. s below. The crystalline polyester elastomer (A) in the present invention is a polyester composed of a chemical structure obtained by polycondensation of a polyvalent carboxylic acid compound and a polyol compound, and has a glass transition temperature of 0 or less and a melting point. It is a polyester of 100 degrees or more. A typical example of the crystalline polyester elastomer (A) in the present invention is a crystal obtained by copolymerizing a crystalline polyester resin (A1) obtained by copolymerizing a polyether component and a polycarbonate component. A crystalline polyester resin (A3) obtained by copolymerizing a polyester resin (A2) and a polylactone component. Further, a carbon number of 10 or more such as a dicarboxylic acid or a hydrogenated dimer acid having 10 or more carbon atoms and/or a dimer diol or a hydrogenated dimer diol is used. The aliphatic polyester and/or the alicyclic diol are copolymerized to introduce a block segment into the polyester resin, and a crystalline polyester elastomer can also be obtained.

A preferred example of the crystalline polyester elastomer (A) used in the present invention is a crystalline polyester resin (A1) obtained by copolymerizing a polyether component. By the copolymerization of the polyether component, the crystalline polyester resin (A1) can be characterized by low melt viscosity, high flexibility, and high adhesion. The polyether component is typically copolymerized with a crystalline polyester resin (A1) using a polyether diol as a raw material. When the total amount of the diol component constituting the crystalline polyester resin (A1) is 100 mol%, the copolymerization ratio of the polyether component is preferably 1 mol% or more, more preferably 5 mol% or more. It is more preferably 10 mol% or more, and particularly 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. If the copolymerization ratio of the polyether component is too low, the melt viscosity becomes high and no The method is formed at a low pressure, or the crystallization speed is fast, and there is a tendency that problems such as insufficient filling occur. Further, when the copolymerization ratio of the polyether component is too high, there is a tendency that problems such as insufficient heat resistance occur. On the other hand, the number average molecular weight of the polyether component is preferably 400 or more, more preferably 800 or more. When the number average molecular weight is too low, flexibility cannot be imparted, and there is a tendency that a stress load on the electronic substrate after encapsulation increases. Further, the number average molecular weight of the polyether component is preferably 5,000 or less, more preferably 3,000 or less. When the number average molecular weight is too high, the compatibility with other components is inferior, and there is a tendency that copolymerization cannot occur. Specific examples of the raw material of the polyether component include polyethylene glycol, polytrimethylene glycol, and polytetramethylene glycol, and the effect of improving the flexibility of the obtained crystalline polyester resin (A1) In terms of the effect of lowering the melt viscosity, it is preferably polytetramethylene glycol.

In the constituent components of the crystalline polyester elastomer (A) used in the present invention, the composition ratio of the aliphatic component and/or the alicyclic component to the aromatic component is adjusted to be used as an engineering plastic. Low-melting viscosity of a general-purpose crystalline polyester resin such as polyethylene terephthalate (hereinafter also referred to as PET) or polybutylene terephthalate (hereinafter also referred to as PBT) It can be used in combination with heat resistance, high temperature and high humidity resistance, and cold and heat cycle resistance comparable to those of the two-liquid epoxy resin. For example, in order to exhibit high heat resistance of 150 ° C or higher, it is suitable for terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, naphthalene dicarboxylic acid and ethylene glycol, naphthalene dicarboxylate. A copolymerized polyester mainly composed of an acid and 1,4-butanediol. In particular, based on the rapid crystallization solidification after forming, the mold release property can be improved and the productivity can be improved as desired. Therefore, it is preferred to crystallize terephthalic acid with 1,4-butanediol and naphthalene. A carboxylic acid and 1,4-butanediol are used as main components.

The acid component constituting the crystalline polyester elastomer (A) preferably contains either or both of terephthalic acid and naphthalene dicarboxylic acid in terms of heat resistance. In addition, when the total amount of the acid components is 100 mol%, the total of terephthalic acid and naphthalene dicarboxylic acid is preferably 65 mol% or more, and more preferably 70 mol% or more. Particularly good is more than 80% by mole. If the total of terephthalic acid and naphthalene dicarboxylic acid is too low, electrical and electronic The heat resistance necessary for the parts may be insufficient.

In addition, as the diol component constituting the crystalline polyester-based elastomer (A), it is preferred to contain both ethylene glycol and 1,4-butanediol in consideration of crystallinity retention during copolymerization. One. Further, when the copolymerization ratio is 100 mol% based on the total amount of the diol components, the total amount of ethylene glycol and 1,4-butanediol is preferably 40 mol% or more, more preferably 45 mol. More than or equal to the ear, particularly preferably 50 mol% or more, and most preferably 55 mol% or more. When the total amount of the ethylene glycol and the 1,4-butanediol is too low, the crystallization rate is lowered, and the mold release property is deteriorated, the molding time is prolonged, and the moldability is impaired, and the crystallinity is insufficient. Insufficient heat resistance.

In the crystalline polyester elastomer (A) used in the present invention, adipic acid, sebacic acid, and anthracene may be used in the basic composition composed of the acid component and the diol component to impart high heat resistance. Diacid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylate An aliphatic or alicyclic dicarboxylic acid such as an acid, a dimer acid or a hydrogenated dimer acid; 1,2-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, neopentyl glycol hydroxytrimethyl acetate, 1,9- Decylene glycol, 2-methyloctanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3-propanediol, polytetramethylene glycol, polyoxymethylene glycol When the aliphatic or alicyclic diol is used as a copolymerization component, the adhesion of the resin composition of the present invention may be further improved.

In the crystalline polyester elastomer (A) used in the present invention, an aliphatic or/or alicyclic dicarboxylic acid having 10 or more carbon atoms such as a dimer acid or a hydrogenated dimer acid, and/or Or copolymerization of an aliphatic or/or alicyclic diol having a carbon number of 10 or more, such as a dimer diol or a hydrogenated dimer diol, can maintain a high melting point and lower the glass transition temperature, and can be further improved. The heat resistance of the resin composition of the present invention is compatible with the adhesion to electrical and electronic parts.

Further, an aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms such as a dimer acid or a dimer diol, and/or an aliphatic or alicyclic diol having 10 or more carbon atoms, and poly 4 A block segment formed of an aliphatic component having a relatively high molecular weight represented by a polylactone such as a polyalkylene ether glycol such as methylene glycol or a polycaprolactone is introduced into the crystalline polyester elastomer (A). By the decrease in the glass transition temperature of the crystalline polyester elastomer (A), the durability of the cold cycle can be improved, and the hydrolysis resistance can be improved by the reduction of the ester group concentration, and the durability after molding is When it is important, it is a better policy. The term "cold heat cycle durability" as used herein means that even if the temperature is repeatedly raised and lowered a plurality of times between high temperature and low temperature, it is difficult for the electronic component or the like having a different coefficient of linear expansion to be peeled off from the interface portion of the sealing resin, or the sealing resin is less likely to be cracked. Performance. If the modulus of elasticity of the resin rises remarkably during cooling, peeling and cracking are likely to occur. In order to provide a material resistant to cold and heat cycles, it is preferred that the glass transition temperature is -10 ° C or lower. 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, and it is practically preferable to be -100 ° C or more in terms of adhesion and anti-blocking properties.

Here, the term "dimer acid" refers to an aliphatic or alicyclic dicarboxylic acid (mostly a 2-mer) produced by the polymerization of an unsaturated fatty acid by polymerization or a Diels-Alder reaction, etc., and often contains The number of moles of 3-mer, monomer, etc.); the term "hydrogenated dimer acid" refers to the addition of hydrogen to the unsaturated bond of the dimer acid. Moreover, the dimer diol and the hydrogenated dimer diol mean that the dimer acid or the two carboxyl groups of the hydrogenated dimer acid are reduced to a hydroxyl group. Specific examples of the dimer acid or the dimer diol include ENPOL (registered trademark) or SOBAMOL (registered trademark) of COGNIC Co., Ltd., and PRIPOL of UNICHEMA Co., Ltd., and the like. Further, the term "polylactone" means a polymer or oligomer having a structure obtained by ring-opening polymerization of a lactone such as γ-butyrolactone, δ-valerolactone or ε-caprolactone, for example, DAICEL (share) company's PLACCEL (registered trademark) and so on.

On the other hand, in the crystalline polyester elastomer (A) used in the present invention, only To maintain a low melt viscosity, a small amount of aromatic copolymerization components can also be used. Examples of preferred aromatic copolymerization components include aromatic dicarboxylic acids such as isophthalic acid and phthalic acid, ethylene oxide adducts of bisphenol A, and propylene oxide adducts. Aromatic diols. In particular, by introducing an aliphatic component having a relatively high molecular weight such as a dimer acid or a dimer diol, good mold release property can be obtained by rapid crystallization solidification after molding.

Moreover, in order to provide long-term durability of the electric and electronic component package and to impart hydrolysis resistance against high temperature and high humidity, the upper limit of the ester group concentration of the crystalline polyester elastomer (A) is preferably 8,000 equivalents/10 ⁶ g. A preferred upper limit is 7500 equivalents/10 ⁶ g, more preferably 7,000 equivalents/10 ⁶ g. Further, in order to secure chemical resistance (gasoline, engine oil, alcohol, general-purpose solvent, etc.), the lower limit is preferably 1000 equivalents/10 ⁶ g. A preferred lower limit is 1500 equivalents/10 ⁶ g, more preferably 2,000 equivalents/10 ⁶ g. Here, the ester group concentration per unit system represents the equivalent of the resin 10 ⁶ g, based on the calculated value by the composition ratio of the polyester resin and copolymerized.

An aliphatic or alicyclic dicarboxylic acid having 10 or more carbon atoms and/or an aliphatic having 10 or more carbon atoms such as a dimer acid, a hydrogenated dimer acid, a dimer diol, or a hydrogenated dimer diol Or the alicyclic diol is copolymerized, and the blocky segment is introduced into the polyester resin (A) of the present invention, when the total of the total acid component of the polyester resin (A) and the total diol component is 200 When the ear is %, it is preferably 2 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and most preferably 20 mol% or more. The upper limit is preferably 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less, in terms of handling properties such as heat resistance and adhesion.

A preferred example of the crystalline polyester elastomer (A) used in the present invention is a crystalline polyester resin (A2) obtained by copolymerizing a polycarbonate component. The crystalline polyester resin (A2) is preferably a chemical structure in which a hard segment composed mainly of a polyester segment and a soft segment mainly composed of a polycarbonate segment are bonded by an ester bond. Composition.

The crystalline polyester resin (A2) used in the present invention is mainly composed of a soft segment composed of a polycarbonate segment, and a polycarbonate component, typically by copolymerization of a polycarbonate diol. form. By the copolymerization of the polycarbonate component, it is characterized by low melt viscosity, high flexibility, and high adhesion. When the total amount of the hard segment component constituting the crystalline polyester resin (A2) is 100% by weight, the soft segment is preferably 25% by weight or more, more preferably 30% by weight or more, and particularly preferably 35% by weight. the above. Further, 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. When the copolymerization ratio of the soft segment is too low, the melt viscosity is increased, high pressure is required during molding, and the crystallization rate is fast, and the problem of insufficient filling tends to occur. Further, if the copolymerization ratio of the soft segment is too high, there is a tendency that the heat resistance is insufficient. Further, the polycarbonate component constituting the soft segment is preferably an aliphatic polycarbonate component mainly composed of a poly(alkylene carbonate) component. Here, the term "mainly constituted" means that the poly(alkylene carbonate) component accounts for 50% by weight or more of the aliphatic polycarbonate component, preferably 75% by weight or more, more preferably 90% by weight or more. . Further, as the alkylene group constituting the poly(alkylene carbonate), a linear alkyl group having 4 to 16 carbon atoms and a long alkyl group having a long chain tend to have excellent durability against cold cycle load. For ease of consideration, tetramethylene, pentamethylene, hexamethylene, octamethylene, and hexamethylene are preferred. Further, the alkylene group constituting the poly(alkylene carbonate) may be a copolymerized polycarbonate of a mixture of two or more kinds.

Further, as the hard segment of the crystalline polyester resin (A2) used in the present invention, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polynaphthalene are preferred. A heat-resistant crystalline polyester segment such as ethylene diformate (PEN) or polybutylene naphthalate (PBN). PBT and PBN are preferred. When other crystalline polyester is used, there is a case where heat resistance is insufficient, durability, and low-temperature characteristics are deteriorated.

On the other hand, in the crystalline polyester resin (A2) used in the present invention, a small amount of an aromatic copolymer component may be used as long as the low melt viscosity is maintained. Examples of preferred aromatic copolymerization components include aromatic dicarboxylic acids such as isophthalic acid and phthalic acid, ethylene oxide adducts of bisphenol A, and epoxy resins. An aromatic diol such as a propane adduct. On the other hand, by introducing an aliphatic component having a relatively high molecular weight such as a dimer acid or a dimer diol, a good mold release property can be obtained by rapid crystallization solidification after molding.

The crystalline polyester resin (A2) used in the present invention is an aliphatic or fat having 10 or more carbon atoms such as a dimer acid, a hydrogenated dimer acid, a dimer diol, or a hydrogenated dimer diol. The cyclodicarboxylic acid and/or the aliphatic or alicyclic diol having 10 or more carbon atoms are copolymerized, and the blocky segment is introduced into the polyester resin (A) of the present invention, and the polyester resin (A) is used. When the total of all the acid components and all the diol components is 200 mol%, it is preferably 2 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and most preferably 20 More than Mole. The upper limit is preferably 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less, in terms of handling properties such as heat resistance and adhesion.

The number average molecular weight of the crystalline polyester elastomer (A) used in the present invention is preferably 3,000 or more, preferably 5,000 or more, more preferably 7,000 or more. Further, the upper limit of the number average molecular weight is preferably 50,000 or less, more preferably 40,000 or less, still more preferably 30,000 or less. When the number average molecular weight is less than 3,000, the hydrolysis resistance of the resin composition for encapsulation and the elongation retention property under high temperature and high humidity are insufficient, and if it exceeds 50,000, the melt viscosity at 220 ° C may become high.

The crystalline polyester-based elastomer (A) used in the present invention is preferably a saturated polyester resin containing no unsaturated group. In the case of an unsaturated polyester containing a high concentration of an unsaturated group, crosslinking may occur during melting, and the melt stability may be deteriorated. Moreover, the crystalline polyester elastomer (A) used in the present invention may be contained if the amount of the unsaturated group is extremely small.

Further, in the crystalline polyester elastomer (A) used in the present invention, a trifunctional or higher polycarboxylic acid such as trimellitic anhydride or trimethylolpropane or a polyhydric alcohol may be copolymerized as needed. There are branched polyesters.

The phenol-modified alkylbenzene resin (B1) used in the resin composition of the present invention preferably has a number average molecular weight of 450 to 40,000 in order to modify the alkylbenzene resin with phenol and/or alkylphenol. By. The production of the phenol-modified alkylbenzene resin (B1) can be carried out, for example, by reacting an alkylbenzene such as xylene or 1,3,5-trimethylbenzene with an aldehyde such as formaldehyde in the presence of an acidic catalyst. An alkylbenzene resin is produced and then produced by reacting with a phenol and an aldehyde in the presence of an acidic catalyst. The phenol-modified alkylbenzene resin (B1) is preferably an alkylphenol-modified xylene resin or an alkylphenol-modified 1,3,5-trimethylbenzene resin. A polymer composition of a basic structure in which a xylene resin-based xylene structure is crosslinked by a methylene group or an ether bond can be usually obtained by heating m-xylene and formaldehyde in the presence of sulfuric acid. The 1,3,5-trimethylbenzene resin is a polymer structure of a basic structure in which a 1,3,5-trimethylbenzene structure is crosslinked by a methylene group or an ether bond, and is typically made by making 1,3 , 5-trimethylbenzene and formaldehyde are obtained by heating in the presence of sulfuric acid. The xylene resin and the 1,3,5-trimethylbenzene resin are typical of alkylbenzene resins. Further, the phenol-modified alkylbenzene resin (B1) of the present invention preferably has a hydroxyl value of 100 equivalents/10 ⁶ g or more, preferably 1,000 equivalents/10 ⁶ g or more, more preferably 5,000 equivalents/10 ⁶ g or more. . Further, it is preferably 20,000 equivalents/10 ⁶ g or less, more preferably 15,000 equivalents/10 ⁶ g or less. When the valence of the hydroxy group is too low, the adhesion to the aluminum material tends to be deteriorated. When the valence of the hydroxy group is too high, the water absorbing property is high and the insulating property tends to be lowered. Here, the hydroxyl value referred to herein is measured by the method of JIS K 1557-1:2007A.

The phenol resin (B2) used in the resin composition of the present invention is a resin obtained by a reaction of a phenol and an aldehyde, and may be a novolac type phenol resin or a cresol type phenol resin, and is preferably a phenol resin. The number average molecular weight is in the range of 450 to 40,000. Examples of the phenol which can be used as a starting material for the phenol resin include o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-di. a bifunctional phenol such as cresol; a trifunctional phenol such as phenol, m-cresol, m-ethylphenol, 3,5-xylenol or m-methoxyphenol; and 4 such as bisphenol A and bisphenol F One type of these various phenols or two or more types may be used in combination. In addition, as the formaldehyde to be used for the production of the phenol resin, one type of formaldehyde, trioxane or trioxane may be used, or two or more types may be used in combination. Further, a phenol-modified resin such as a phenol aralkyl group or a phenol-modified xylene resin may be mentioned. Among these, in order to exhibit high adhesion, it is particularly preferable that the crystalline polyester elastomer (A) has good compatibility. In order to obtain a phenol resin having good compatibility with the crystalline polyester elastomer (A), it is preferred that the melt viscosity is close to that of the phenol resin. Further, 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, still more preferably 1,000 equivalents/10 ⁶ g or more. Further, it is preferably 10,000 equivalents/10 ⁶ g or less, more preferably 5,000 equivalents/10 ⁶ g or less. When the hydroxyl value is too low, the adhesion to the aluminum material tends to be inferior, and if the hydroxyl value is too high, the water absorbability is high and the insulating property tends to be lowered. Here, the hydroxyl value referred to herein is measured by the method of JIS K 1557-1:2007A.

In the present invention, by blending a phenol-modified alkylbenzene resin (B1) and/or a phenol resin (B2) in a resin composition for encapsulation, a good initial adhesion can be imparted when encapsulating an electric and electronic component. Sexuality and adhesion to the hot and cold cycle. The phenol-modified alkylbenzene resin (B1) and/or the phenol resin (B2) are used as a crystalline polyester resin (A) to exhibit a stress relaxation effect due to retardation of crystallization of the crystalline polyester resin (A). The effect of the dispersing aid with the fluororesin (C) and the effect of improving the wettability of the substrate by the introduction of the functional group. The blending amount of the phenol-modified alkylbenzene resin (B1) and/or the phenol resin (B2) in the present invention is preferably 0.1 part by weight or more based on 100 parts by mass of the crystalline polyester resin (A). It is preferably 1 part by weight or more, and 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, still more preferably 20 parts by weight or less. When the blending ratio of the phenol-modified alkylbenzene resin (B1) and/or the phenol resin (B2) is too low, the stress relieving effect by retarding crystallization may not be exhibited, and the fluororesin (C) and The action as a dispersing aid of the crystalline polyester resin (A) may not be exhibited. Further, if the blending ratio of the phenol-modified alkylbenzene resin (B1) and/or the phenol resin (B2) is too high, the productivity of the resin composition is poor, and further, the flexibility property of the package may be deteriorated. situation.

The fluororesin (C) used in the present invention means a part or all of hydrogen derived from polyolefin. A structure in which a portion substituted with fluorine or a part of hydrogen of a polyolefin is substituted with fluorine and the other portion is substituted with a perfluoroalkyl ether group. Specific examples of the fluororesin (C) used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene- Ethylene copolymer and polychlorotrifluoroethylene. Among them, in view of dispersibility and the like, it is preferred to copolymerize ethylene or propylene and have a low melting point. Further, it may be a type modified with maleic acid or the like.

Further, the fluororesin (C) of the present invention is preferably a fluororesin having a melting point of 220 ° C or less, more preferably 210 ° C or less. When the melting point of the fluororesin is too high, when the package is produced by the resin composition of the present invention, the melt viscosity of the resin composition is greatly increased, and there is a concern that low pressure molding is difficult, and (A) component and ( The compatibility of the component C) is low, and the adhesion between the resin composition and the packaged article cannot be exhibited.

Further, the fluororesin (C) of the present invention preferably has a melt mass flow rate (hereinafter also abbreviated as MFR) as measured by ASTM D 3307 of 20 to 100 g/10 minutes. The low MFR system is synonymous with high melt viscosity, and the decrease in compatibility between the component (A) and the component (C) may impair the adhesion between the resin composition and the packaged article. The high MFR system is synonymous with a low melt viscosity, and there is a concern that the resin composition is extremely soft and the mechanical properties of the package are poor.

In the present invention, the fluororesin (C) is blended in the resin composition for encapsulation for the purpose of exhibiting excellent properties of initial adhesion and adhesion durability to cold and heat cycles during encapsulation of electric and electronic parts. It is considered that the component (C) can relax the crystallization or enthalpy of the component (A) and exhibit the effect of strain energy relaxation. In the present invention, the blending amount of the component (C) is preferably 0.5 part by weight or more, more preferably 3 parts by weight or more, still more preferably 5 parts by weight or more based on 100 parts by weight of the component (A). Further, it is preferably 50 parts by mass or less, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less. When the blending ratio of the component (C) is too low, the effect of alleviating the strain energy due to crystallization or heat relaxation of the component (A) tends to be small, and the adhesion strength tends to decrease. Also, in (C) If the blending ratio is too high, the adhesion and the physical properties of the resin tend to decrease, and the (A) component and the (C) component undergo a giant phase separation, resulting in a decrease in elongation at break. When a smooth surface or the like is not obtained, there is a case where the formability is adversely affected.

The resin composition for encapsulation of the present invention is blended with the crystalline polyester elastomer (A), the phenol-modified alkylbenzene resin (B1), the phenol resin (B2), and the fluororesin (C) of the present invention. Any other resin such as polyester, polyamide, polyolefin, polycarbonate, acrylic or ethylene vinyl acetate, a hardener such as an isocyanate compound or melamine, or a filler such as talc or mica, A pigment such as carbon black or titanium dioxide, a flame retardant such as antimony trioxide or brominated polystyrene may also be used. By blending these components, adhesion, flexibility, durability, and the like can be improved. In this case, the crystalline polyester elastomer (A) is preferably contained in an amount of 50% by weight or more, more preferably 60% by weight or more, and still more preferably 70% by weight or more based on the total of the resin composition of the present invention. When the content of the crystalline polyester elastomer (A) is less than 50% by weight, the crystalline polyester elastomer (A) itself has excellent adhesion to an electric and electronic component, adhesion durability, and elongation. Degree retention, hydrolysis resistance, and water resistance are reduced.

When the package of the present invention is exposed to a high temperature and high humidity environment for a long period of time, it is preferred to add an antioxidant. For example, 1,3,5-glycol (3,5-di-tri-butyl-4-hydroxybenzyl)isocyanate as a hindered phenol system, 1,1,3-tri(4) -hydroxy-2-methyl-5-tributylphenyl)butane, 1,1-bis(3-tert-butyl-6-methyl-4-hydroxyphenyl)butane, 3,5 - bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid, pentaerythritol-anthracene (3,5-di-tri-butyl-4-hydroxyphenyl)propionate, 3- (1,1-dimethylethyl)-4-hydroxy-5-methyl-phenylpropionic acid, 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-) 4-hydroxy-5-methylphenyl)propanyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-trimethyl-2 , 4,6-paran (3',5'-di-tertiary butyl-4'-hydroxybenzyl)benzene; as a phosphorus-based 3,9-bis(p-nonylphenoxy)-2,4 ,8,10-tetraoxa-3,9-diphosphorus [5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9 -Diphosphorus snail [5.5] ten Mono-, tris(monodecylphenyl)phosphite, triphenylphosphine oxide, isodecylphosphite, isodecylphenylphosphite, diphenyl 2-ethylhexylphosphite, two Nonylphenyl bis(nonylphenyl) ester phosphorous acid, 1,1,3-gin (2-methyl-4-bistridecyl phosphite-5-tributylphenyl) butane , ginseng (2,4-di-tertiary butylphenyl) phosphite, pentaerythritol bis(2,4-di-tertiary butyl phenyl phosphite), 2,2'-methylene bis ( 4,6-di-tertiary butylphenyl)2-ethylhexyl phosphite, bis(2,6-di-tri-butyl-4-methylphenyl)pentaerythritol diphosphite; as sulfur Ether 4,4'-thiobis[2-tert-butyl-5-methylphenol] bis[3-(dodecylthio)propionate], thiobis[2-(1,1- Dimethylethyl)-5-methyl-4,1-phenylene]bis[3-(tetradecylsulfanyl)-propionate], pentaerythritol bismuth (3-n-dodecyl thiopropionic acid) Ester), bis(tridecyl)thiodipropionate. These can be used alone or in combination. The amount of addition is preferably 0.1% by weight or more and 5% by weight or less based on the entire resin composition for encapsulation. If it is less than 0.1% by weight, the thermal deterioration prevention effect is lacking. When it exceeds 5% by weight, the adhesion may be adversely affected.

The method of determining the composition and the composition ratio of the polyester resin is, for example, ¹ H-NMR or ¹³ C-NMR measured by dissolving the polyester resin in a solvent such as heavy chloroform, and borrowing from the methanol solution of the polyester resin. The amount of the measurement by gel permeation chromatography (hereinafter also abbreviated as methanol solution-GC method) and the like. In the present invention, when the crystalline polyester elastomer (A) is dissolved and a solvent suitable for ¹ H-NMR measurement is used, the composition and composition ratio are determined by ¹ H-NMR. In the case where there is no suitable solvent or in the case where the composition ratio cannot be determined by the ¹ H-NMR measurement, the ¹³ C-NMR or the methanolysis-GC method is employed or used in combination.

As a method for producing the crystalline polyester elastomer (A) of the present invention, a known method can be employed. For example, the dicarboxylic acid and the diol component are subjected to an esterification reaction at 150 to 250 ° C, and then decompressed. The desired polyester resin can be obtained by performing polycondensation at 230 to 300 °C. Or by using a derivative such as a dimethyl ester of the above dicarboxylic acid and a diol component to carry out a transesterification reaction at 150 to 250 ° C, and then performing polycondensation at 230 to 300 ° C under reduced pressure. The desired polyester resin is obtained.

The resin composition for encapsulation of the present invention preferably has a melt viscosity of from 5 to 3000 dPa at 220 ° C. s, the type and blending ratio of the crystalline polyester elastomer (A), the phenol-modified alkylbenzene resin (B1) and/or the phenol resin (B2), and the fluororesin (C) can be appropriately adjusted. And reached. For example, increasing the copolymerization ratio of the polyether diol copolymerized with the crystalline polyester elastomer (A) or lowering the molecular weight of the crystalline polyester elastomer (A) tends to lower the resin composition of the present invention. The effect of the melt viscosity of the object and the increase in the molecular weight of the crystalline polyester elastomer (A) tend to increase the melt viscosity of the resin composition of the present invention. Here, the melt viscosity at 220 ° C is a value measured as follows. In other words, the resin composition for encapsulation is dried to a moisture content of 0.1% or less, and then a resin composition for encapsulation which is stabilized at 220 ° C by a FLOW TESTER (model CET-500C) manufactured by Shimadzu Corporation, 98 N is used. The pressure of /cm ² was measured by the viscosity of the mold having a thickness of 1.0 mm and a thickness of 10 mm. If it becomes 3000dPa. A high melt viscosity of s or higher can provide high resin aggregating power and durability. However, when a component having a complicated shape is packaged, it is necessary to form a high-pressure injection molding, so that the component may be broken. By using 2000dPa. Below s, preferably 1000dPa. The resin composition for encapsulation of the melt viscosity of s or less can obtain a molded component having excellent electrical insulation properties at a relatively low injection pressure of 0.1 to 100 MPa without impairing the characteristics of the electric and electronic component. Moreover, in terms of the injection operation of the resin composition for encapsulation, the melt viscosity at 220 ° C is preferably lower, but the adhesion and cohesive force of the resin composition are considered, and the lower limit is preferably 5 dPa. Above s, more preferably 10dPa. More preferably s above 50dPa. Above s, the best is 100dPa. s above.

In addition, in order to mold the crystalline polyester elastomer (A) as much as possible without undergoing thermal deterioration, it is required to rapidly melt at 210 to 240 ° C. Therefore, the upper limit of the melting point of the polyester resin (A) is preferably 210 ° C. More preferably 200 ° C. The lower limit may be 5 to 10 ° C or more higher than the heat resistance temperature required for the intended use. The operability at normal temperature and the usual heat resistance are preferably 70 ° C or higher, more preferably 100 ° C or higher, still more preferably 120 ° C or higher, particularly preferably 140 ° C or higher, and most preferably 150 ° C or higher.

In the present invention, the adhesion strength between the specific member and the resin composition for encapsulation is determined by adhering two sheet-like members to a sample for measurement using a resin composition for encapsulation, and measuring the shear failure strength. The method for producing the test piece for measurement and the method for measuring the shear failure strength are carried out according to the method described in the examples below.

The resin composition for encapsulation of the present invention is typically formed by injecting it into a mold for mounting electrical and electronic parts. For example, a resin composition of a crystalline polyester resin (A1) obtained by copolymerizing a crystalline polyester elastomer (A)-based polyether component is a screw type hot melt forming machine. It is heated and melted at about 130 to 220 ° C, injected into the mold through an injection nozzle, and after a specific cooling time, the molded product is removed from the mold to obtain a molded product. The appropriate temperature for the heating and melting of the resin composition varies depending on the resin composition. For example, the crystalline polyester elastomer (A) is a resin composition of a crystalline polyester resin (A2) obtained by copolymerizing a polycarbonate component. In the case of the material, the above heating and melting temperature is preferably set to about 200 to 280 °C.

The type of the hot-melt forming machine is not particularly limited, and examples thereof include ST2 manufactured by Nordson Corporation and vertical extrusion molding machine IMC-18F9 manufactured by Imoto Seiki Co., Ltd., and the like.

[Examples]

In order to explain the present invention in more detail, the examples and comparative examples are given below, but the present invention is not limited to the examples. Moreover, each measurement value described in the examples and the comparative examples is measured by the method described later. Moreover, "normal temperature and normal humidity" means an environment having a temperature of about 23 ° C and a relative humidity of about 65%.

<Measurement of melting point and glass transition temperature>

Using a differential scanning calorimeter "DSC220" manufactured by SEIKO Electronics Co., Ltd., 5 mg of the measurement sample was placed in an aluminum pan, and the lid was tightly closed to seal it. After holding at 250 ° C for 5 minutes, the liquid nitrogen was rushed. After cooling, it was measured from -150 ° C to 250 ° C at a temperature elevation rate of 20 ° C / min. To get the recursion of the curve The point is taken as the glass transition temperature, and the endothermic peak is used as the melting point.

<<Evaluation method of initial adhesion and durability of hot and cold cycle>> <Close strength test> Method for preparing adhesion strength test piece

A 0.5 mm thick aluminum plate (A5052 manufactured by TP Technik Co., Ltd.) was cut into a size of 70 mm × 70 mm, and the surface was wiped with acetone to remove the oil. Then, this aluminum plate was fixed in a mold for forming a flat plate (inner mold size: 100 mm in width × 100 mm in length × 5 mm in thickness), and a transparent tape having a width of 10 mm was adhered to one side of the aluminum plate. Then, a screw-type hot-melt forming machine (the vertical low-pressure extrusion molding machine IMC-18F9 manufactured by Imoto Seisakusho Co., Ltd.) was used, and a resin composition for encapsulation was injected from a gate provided at a center of a surface of 100 mm × 100 mm to carry out molding. The molding conditions were as follows: 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 setting of 50% (maximum discharge as 100%). The molded product was released from the mold, and cut into strips having a width of 20 mm each having a transparent tape bonding portion to obtain an adhesion strength test piece.

Initial adhesion evaluation

The adhesion test piece was stored in an environment of 23 ° C and a relative humidity of 50% for 3 hours or more and 100 hours or less. Then, the aluminum plate was peeled off from the resin by a transparent tape bonding portion, and the T-peel strength was measured. The stretching speed was set at 50 mm/min.

Evaluation criteria AAA: T-peel strength 2.0N/mm or more

AA: T-type peel strength is less than 2.0N/mm, 1.0N/mm or more

A: T-type peel strength is less than 1.0N/mm, 0.5N/mm or more

B: T-peel strength is less than 0.5N/mm

Cold and heat cycle test I

The adhesion strength test piece prepared by the same method as the evaluator for initial adhesion was placed in a single cycle at -40 ° C for 30 minutes, followed by 80 ° C for 30 minutes. The environmental load of 1000 cycles was applied, and then the T-peel strength was measured after standing overnight at normal temperature and humidity. Calculate the following mathematical formula (1) The defined T-peel strength retention ratio I is expressed by the following evaluation criteria.

Evaluation criteria AAA: T-type peel strength retention rate I is 80% or more

AA: T-type peel strength retention rate I is less than 80%, 70% or more

A: T-type peel strength retention rate I is less than 70%, 50% or more

B: T-type peel strength retention rate I is less than 50%

Cold and heat cycle test II

The adhesion strength test piece prepared by the same method as that used for the evaluation of the initial adhesion was applied as a single cycle in an environment of -40 ° C for 30 minutes and then at 150 ° C for 30 minutes. The environmental load was circulated, and then the T-peel strength was measured after standing overnight at normal temperature and humidity. The T-peel strength retention ratio II defined by the following formula (2) was calculated and expressed by the following evaluation criteria.

Evaluation criteria AAA: T-type peel strength retention rate II is 80% or more

AA: T-type peel strength retention rate II is less than 80%, 70% or more

A: T-type peel strength retention rate II is less than 70%, 50% or more

B: T-type peel strength retention rate II is less than 50%

<Melt characteristics test> Method for evaluating melt viscosity of resin and resin composition for encapsulation

FLOW TESTER (CFT-500C type) manufactured by Shimadzu Corporation was used to fill a cylinder having a moisture content of 0.1% or less or a resin composition for encapsulation at a center of a heating body set at 220 ° C, and 1 minute after filling. Thereafter, a load was applied to the sample through a plunger, and at a pressure of 1 MPa, the molten sample was extruded from a mold at the bottom of the cylinder (aperture: 1.0 mm, thickness: 10 mm), and the falling distance and the drop of the push plug were recorded. Time, calculate the melt viscosity.

Low pressure formability evaluation method

A flat-plate molding die was used as a low-pressure molding machine IMC-18F9 manufactured by a well-prepared machine for hot-melt forming processing, and formed into a flat plate (100 mm × 100 mm × 10 mm) made of a resin composition for encapsulation. The flat plate was visually observed, and the presence or absence of burrs, sink marks, and insufficient filling was expressed by the following evaluation criteria. Further, the gate position was set to the center of the surface of 100 mm × 100 mm, and the molding conditions were set to 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 and no dents.

AA: Although completely filled, it produces a number of burrs.

A: Although the filling is in a state of no filling, there is a dent.

B: There is insufficient filling.

<High temperature long-term load test> (Evaluation of heat aging resistance)

The screw-type hot-melt forming machine (the vertical low-pressure extrusion molding machine IMC-18F9 manufactured by Imoto Seisakusho Co., Ltd.) was molded into a resin composition of 100 mm × 100 mm in the center of the surface, and was molded to a thickness of 2 mm. Tablet. 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 setting of 50% (maximum discharge was 100%). The obtained flat plate was punched to prepare a dumbbell body of JIS No. 3, and the tensile elongation at break was measured in accordance with the measurement method of JIS K6251, and this value was referred to as "initial tensile elongation at break". In addition, the dumbbell body prepared in the same manner is processed at a temperature of 150 ° C for 1000 small In the case of standing at room temperature and normal humidity for one day and night, the tensile elongation at break was measured in the same manner, and this value was taken as "the tensile elongation at break after the load test at 150 ° C for 1,000 hours". The tensile elongation at break retention ratio was calculated according to the following Mathematical Formula 3, and was expressed by the following evaluation criteria.

Evaluation criteria AAA: tensile elongation at break retention rate of 65% or more

AA: Tensile elongation at break is less than 65%, 50% or more

A: Tensile elongation at break is less than 50%, 30% or more

B: Tensile elongation at break is less than 30%

The abbreviations of the compounds and/or residues used in the examples and comparative examples of the present invention are shown below.

TPA: terephthalic acid

NDC: naphthalene dicarboxylic acid

BD: 1,4-butanediol

PTMG1000: polymethylene ether glycol (quantitative average molecular weight 1000)

PTMG2000: Polymethylene ether glycol (quantitative average molecular weight 2000)

PCL: polycaprolactone (quantitative molecular weight 850)

PBT: polybutylene terephthalate

PBN: polybutylene naphthalate

Fluoro Resin A: NEOFREON EFEP RP-4020, manufactured by Daikin Industries Co., Ltd., melting point 155~170°C, MFR25~50g/10 min.

Fluoro Resin B: NEOFREON EFEP RP-5000, Daikin Industries Co., Ltd., melting point 190~200°C, MFR20~30g/10 min

Fluoro Resin C: NEOFREON PFA AP-202, manufactured by Daikin Industries Co., Ltd., melting point 298 ° C, MFR 3.3 g/10 min.

Phenol-modified alkylbenzene resin A: NIKANOL HP-150, manufactured by FUDOW Co., Ltd., phenol-modified xylene resin, and hydroxyl group number: 3035 equivalents/10 ⁶ g.

Phenol-modified alkylbenzene resin B: NIKANOL HP-100, manufactured by FUDOW Co., Ltd., phenol-modified xylene resin, and having a hydroxyl group of 2,500 equivalents/10 ⁶ g.

Phenol-modified alkylbenzene resin C: NIKANOL L5, manufactured by FUDOW Co., Ltd., phenol-modified xylene resin (EO addition molding), and hydroxyl group 625 equivalent/10 ⁶ g.

Phenol Resin A: CKM 2400 Showa Polymer Co., Ltd., a novolac type phenol resin, and a hydroxyl group value of 9000 equivalents/10 ⁶ g.

Phenol resin B: EP4020 Asahi Organic Materials Co., Ltd., cresol novolac type phenol resin, hydroxyl group 9250 equivalent/10 ⁶ g.

Production example of polyester resin I-A

In a reactor equipped with a stirrer, a thermometer, and a distilling cooler, 1,4-butanediol is added to 100 mol% of terephthalic acid when the total amount of the diol components is 100 mol%. 60 mol% amount. Then, when the total amount of the tetrabutyl titanate is 100 parts by mass, 0.25 parts by mass is added, and the esterification reaction is carried out at 170 to 220 ° C for 2 hours. After completion of the esterification reaction, a polytetramethylene glycol "PTMG1000" (manufactured by Mitsubishi Chemical Corporation) having a weight average molecular weight of 1000 in a residual amount of 40 mol% was placed, and a hindered phenol-based antioxidant "IRGANOX 1330" (Ciba) was placed. 0.5 parts by mass of the company, the temperature was raised to 255 ° C, and the inside of the system was gradually reduced in pressure, and it was 255 ° C and 665 Pa in 60 minutes. Then, the polycondensation reaction was further carried out at 133 Pa or less for 30 minutes to obtain a polyester resin I-A. The polyester resin I-A has a melting point of 165 ° C and a melt viscosity of 500 dPa. s.

Production example of polyester resin I-B~D

In the same manner as in the production example of the polyester resin I-A, the reaction was carried out by changing the kind and ratio of the raw materials to obtain a polyester resin I-B to D. The composition and physical properties of these polyester resins I-B to D are shown in Table 1.

[Table 1]

Manufacturing Example of Resin Compositions I-1 to 16 for Electrical and Electronic Component Packaging

The resin composition I-1 for electric and electronic component encapsulation is obtained by uniformly mixing the polyester resin I-A by 100 parts by mass, the fluororesin A 20 parts by mass, and the epoxy resin A by 10 parts by mass, and then using a biaxial extrusion machine. It was obtained by melt-kneading at a temperature of 220 °C. The polyester resin compositions I-2 to 16 were prepared by the same method as the polyester resin composition I-1 except that the blending component and the ratio were changed. The compositions are shown in Tables 2 and 3.

Example I-1

The resin composition for encapsulation I-1 was used as a resin composition for encapsulation, and the melting property, the initial adhesion, and the thermal cycle load durability were evaluated. The resin composition has a melt viscosity of 1769 dPa. s is a good melting property. The initial T-peel strength was 1.5 MPa, and 1.0 MPa after the hot and cold cycle test, which showed a high adhesion strength retention rate in all the items, which was a good result. The results are shown in Table 2.

Example I-2~9

The encapsulating resin composition I-2~9 is used as a resin composition for encapsulation, The same procedure as in Example I-1 was carried out to evaluate the melting characteristics, the initial adhesion, and the durability of the cooling and heating cycle load. The evaluation results are shown in Tables 2 to 3.

Comparative Example I-1

The encapsulating resin composition I-10 was used as the encapsulating resin composition, and the melting property, the initial adhesion, and the thermal cycle load durability were evaluated in the same manner as in Example I-1. The resin composition has a melt viscosity of 2169dPa. s is a moldable range, but the initial T-peel strength is 0.4 MPa, and after the hot and cold cycle test is 0.3 MPa, which fails to satisfy the necessary characteristics, and is a bad one. The evaluation results are shown in Table 4.

Comparative Example I-2

The encapsulating resin composition I-11 was used as the encapsulating resin composition, and the melting characteristics, the initial adhesion, and the thermal cycle load durability were evaluated in the same manner as in Example I-1. The resin composition has a melt viscosity of 292 dPa. s, which is a moldable range, but the initial T-type peel strength is 1.1 MPa, and after the hot and cold cycle test is 0.2 MPa, which fails to satisfy the necessary characteristics, and is a poor one. The evaluation results are shown in Table 4.

Comparative Example I-3~7

The encapsulating resin compositions I-12 to 16 were used as the encapsulating resin composition, and the melting characteristics, the initial adhesion, and the thermal cycle load durability were evaluated in the same manner as in Example I-1. The evaluation results are shown in Table 4.

Production example of aliphatic polycarbonate diol A

100 parts by mass of poly(hexamethylene carbonate) diol (number average molecular weight: 2000) and 9.6 parts by mass of diphenyl carbonate were placed in a reaction vessel, and the mixture was reacted at a temperature of 205 ° C and 130 Pa. After 2 hours, the content was cooled, and the resulting polymer was taken out to obtain an aliphatic polycarbonate diol A. The aliphatic polycarbonate diol A has a number average molecular weight of 13,000.

Production example of aliphatic polycarbonate diol B

In the production example of the aliphatic polycarbonate diol A, the poly(hexamethylene carbonate) diol is changed to poly (tetramethylene carbonate) diol (the number average molecular weight is 2,000), and the others are the same. An aliphatic polycarbonate diol B is obtained. The aliphatic polycarbonate diol B has a number average molecular weight of 13,000.

Production example of 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 an aliphatic polycarbonate diol A of a soft segment component at 230 ° C to 245 ° C, 130 Pa The mixture was stirred for 1 hour, and it was confirmed that the resin had become transparent. Then, under a nitrogen stream, phenylphosphonic acid was added at 60 ppm in terms of phosphorus atom, and after stirring under a slight reduced pressure (>300 Pa) for 10 minutes, the content was taken out and cooled. Next, 0.3 part of Rasmit LG and 0.3 part of Irganox 1010 were added, and kneading was carried out at 250 ° C to obtain a polyester resin composition II-A. The polyester resin composition II-A is mainly composed of a crystalline polyester resin having a terminal vinyl group of 13 eq/ton.

Production example of polyester resin composition II-B~E

In the same manner as in the production example of the polyester resin composition II-A, the type and blending amount of the hard segment component and the soft segment component were changed to obtain a polyester resin composition II-B to E. The composition and physical properties of the polyester resin composition II-B to E are shown in Table 5.

Production example of polyester resin composition F

In a reactor equipped with a stirrer, a thermometer, and a cooler for distillation, 100 parts of 2,6-naphthalenedicarboxylic acid, 75 parts of 1,4-butanediol, and 2,6 are placed. The tetrabutyl titanate was 0.25% by weight based on the total weight of the naphthalene dicarboxylic acid and the 1,4-butanediol, and the esterification reaction was carried out at 170 to 220 ° C for 2 hours. After completion of the esterification reaction, a polytetramethylene glycol "PTMG1000" (manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 1,000, and a hindered phenolic antioxidant "IRGANOX 1330" (manufactured by Ciba Specialty Chemicals Co., Ltd.) were placed. At 0.5% by weight, the temperature was raised to 250 ° C. On the other hand, the inside of the system was gradually depressurized, and it was made into 250 ° C and 665 Pa in 60 minutes. Next, a polycondensation reaction was further carried out for 30 minutes at 133 Pa or less to obtain a polyester resin F. This polyester tree The fat composition F has a melting point of 190 ° C and a melt viscosity of 500 dPa. s.

Production example of polyester resin composition G

The same procedure as in the production example of the polyester resin composition F was carried out, except that 2,6-naphthalenedicarboxylic acid was changed to terephthalic acid to obtain a resin composition G. The composition and physical properties of the polyester resin composition G are shown in Table 5.

Example II-1

100 parts by mass of the polyester resin composition A, 20 parts by mass of the fluororesin A, and 10 parts by mass of the epoxy resin A are uniformly mixed, and then melt-kneaded at a mold temperature of 220 ° C to 240 ° C by a biaxial extruder. Resin composition 1 for electrical and electronic parts packaging. The melting characteristics, the initial adhesion, the thermal cycle durability, and the heat aging resistance of the resin composition 1 for electrical and electronic component encapsulation were evaluated by a method described above. The resin composition has a melt viscosity of 1923dPa. s is a good melting property. The initial T-peel strength was 1.4 MPa, 1.0 MPa after the thermal cycle test, and the T-peel strength retention was 71%. Further, the tensile elongation at break after the high-temperature long-term load test was maintained at 70%. The evaluation results are shown in Table 6.

Example II-2~12, Comparative Example II-1~5

In the same manner as in Example II-1, the blending was changed to Tables 6 to 8, and resin compositions II-2 to 17 for electrical and electronic component encapsulation were produced and evaluated. Evaluation result In Table 6 to Table 8.

In Comparative Example II-1, the initial T-peel strength was 2.1 MPa, and after the thermal cycle test was 1.5 MPa, the initial adhesion and the thermal cycle durability were excellent, and the resin composition melt viscosity was 1920 Pa. s, showing good results, but the elongation retention after high temperature long-term load test was 30%, which was a bad one. The evaluation results are shown in Table 8.

In Comparative Example II-2, the initial T-type peel strength was 2.2 MPa, and after the hot and cold cycle test was 1.2 MPa, and the adhesion result was excellent. However, the elongation retention rate of the high-temperature long-term load test was 35%, which was a bad one. The evaluation results are shown in Table 8.

Production example of polyester resin III-A~C

The same procedure as in the production example of the polyester resin I-A was carried out, but the type and ratio of the raw materials were changed to obtain a polyester resin III-A to C. The composition and physical properties of these polyester resins III-A to C are shown in Table 9.

Example III-1~3, Comparative Example III-1~3

In the same manner as in Example I-1, except that the blending was changed as shown in Table 10, resin compositions III-1 to 16 for electric and electronic component encapsulation were produced and evaluated. The evaluation results are shown in Table 10.

[Industrial availability]

The resin composition for electrical and electronic component encapsulation of the present invention is excellent in melt fluidity and initial adhesion strength to an aluminum material, and exhibits high adhesion durability even after a heat and cold cycle load. Further, the resin composition for electric and electronic component encapsulation according to the specific embodiment of the present invention can further maintain the bonding strength after a thermal cycle load of 1000 cycles of -40 ° C for 30 minutes and 80 ° C or 150 ° C for 30 minutes. It exhibits a high degree of heat and cold cycle durability, and after a long period of high temperature of 150 ° C for 1000 hours, it also maintains elongation at break and exhibits high heat aging resistance. Therefore, the resin composition for electric and electronic component encapsulation of the present invention and the package packaged therewith are in an electrical and electronic component package which may be exposed to severe environmental loads such as a cold cycle or a high temperature and long-term load, for example, As a connector for various types of automobiles, communications, computers, and home appliances, wire harnesses or electronic parts, with printed substrates It is very useful to mold molded parts of sensors and inductors.

Claims (9)

A resin composition for encapsulating an electric and electronic component, comprising a crystalline polyester elastomer (A), a phenol-modified alkyl benzene resin (B1), and/or a phenol resin (B2), and a fluororesin (C); It has a moisture content of 0.1% or less, a heating rate of 220 ° C, a pressure of 1 MPa, and a melt viscosity of 5 dPa when extruded through a die having a hole diameter of 1.0 mm and a thickness of 10 mm. s above 3000dPa. s below. The resin composition for electrical and electronic component encapsulation according to the first aspect of the invention, wherein the crystalline polyester elastomer (A) is selected from the group consisting of a crystalline polyester resin (A1) obtained by copolymerization of a polyether component, One or a mixture of two or more of the group consisting of a crystalline polyester resin (A2) obtained by copolymerization of a polycarbonate component and a crystalline polyester resin (A3) obtained by copolymerization of a polylactone component . The resin composition according to claim 1 or 2, wherein the phenol-modified alkylbenzene resin (B1) is an alkylphenol-modified alkylbenzene resin, and the hydroxyl value is 100 equivalents/10 ⁶ g or more. The resin composition according to any one of claims 1 to 3, wherein the phenol resin (B2) is a novolac type phenol resin, and the valence of the hydroxyl group is 100 equivalents/10 ⁶ g or more. The phenol-modified alkyl benzene resin (B1) is blended with respect to 100 parts by weight of the above-mentioned crystalline polyester-based elastomer (A), in a resin composition according to any one of the above-mentioned claims. The total amount of the phenol resin (B2) is 0.1 to 100 parts by weight, and the fluororesin (C) is 0.1 to 100 parts by weight. The resin composition for electrical and electronic parts packaging according to any one of claims 1 to 5, wherein the aluminum plate is subjected to 1000 cycles of -40 ° C for 30 minutes and 80 ° C for 30 minutes before and after the T-type stripping. The strength retention rate is 50% or more. The resin composition for electrical and electronic component encapsulation according to any one of claims 1 to 6, wherein the initial T-peel strength to the aluminum plate is 0.5 N/mm or more. A method for producing an electrical and electronic component package, wherein the resin composition temperature of the resin composition is 130 ° C or more after heating and kneading the resin composition for electrical and electronic component packaging according to any one of claims 1 to 7. When the resin composition pressure is not more than ° C and the pressure is 0.1 MPa or more and 10 MPa or less, the resin composition is injected into a mold into which an electric and electronic component is inserted. An electric and electronic component package, which is encapsulated by a resin composition for electrical and electronic component packaging according to any one of claims 1 to 7.