JP2010150471A - Resin composition for sealing electric and electronic component, method for manufacturing electric and electronic component sealed object, and electric and electronic component sealed object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: an electric and electronic component sealed object excellent in durability under environmental loads such as a cold/hot cycle load, a high temperature/high humidity load and a high temperature load; a method for manufacturing an electric and electronic component sealed object suited to such applications; and a resin composition for sealing electric and electronic components for such applications. <P>SOLUTION: The resin composition for sealing electric and electronic components is formulated with 0.1-50 pts.mass epoxy resin (B) and 0.5-50 pts.mass polyolefin resin (C) to 100 pts.mass crystalline polyester resin (A) and is characterized in that: the melt viscosity is 5-2,000 dPa s when the composition is dried to ≤0.1% moisture content and heated to 220°C and extruded from a die with 1.0 mm hole diameter and 10 mm thickness under 1 MPa pressure; the retention of shear adhesion strength with a polybutylene terephthalate plate containing 30 wt.% glass filler is ≥50% to the initial shear adhesion strength after application of 1,000 cold/hot cycles between 30 minutes at -40°C and 30 minutes at 80°C; and the retention of shear adhesion strength with a glass-epoxy plate is ≥50% to the initial shear adhesion strength after application of 1,000 cold/hot cycles between 30 minutes at -40°C and 30 minutes at 80°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  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.

  Electrical and electronic parts that are widely used in automobiles and electrical appliances must have electrical insulation from the outside in order to achieve their intended purpose. For example, the electric wire is covered with a resin having electrical insulation. In recent years, there has been a rapid increase in applications where it is necessary to pack electrical and electronic parts having a complicated shape in a small capacity, such as a mobile phone, and various methods have been adopted for the electrical insulation. In particular, when an electric / electronic component having a complicated shape, such as a circuit board, is sealed with a resin serving as an electric insulator, a sealing method that reliably follows the shape of the electric / electronic component and does not generate an unfilled portion is required. For this purpose, a method of reducing the viscosity of the sealing resin composition at the time of coating is common. A method in which the sealing resin is dissolved in a solvent in advance to form a solution, impregnated between the electric and electronic parts, and the electric and electronic parts are wrapped, and then the solvent is evaporated is one of the methods for reducing the viscosity of the sealing resin composition. However, there are many problems such as bubbles remaining when the solvent evaporates, and since an organic solvent is used as the solvent, a production facility corresponding to the volatilization of the organic solvent into the working environment is required.

  So far, two-component curable epoxy resins have been generally used in consideration of durability after sealing (for example, see Patent Documents 1 and 2). This is done by mixing the main agent and curing agent immediately before sealing, impregnating the low-viscosity resin composition between the electric and electronic parts and enclosing the electric and electronic parts, and then heating and storing for several days. It promotes and solidifies completely. However, in this method, there is a concern that the liquid epoxy resin may adversely affect the environment. Furthermore, since it is necessary to precisely adjust the mixing ratio of the two liquids, it takes time and cost, and there is a risk of occurrence of defects due to fluctuations in the mixing ratio. Furthermore, the usable period after mixing is 1-2 months. It is limited to short. Furthermore, since curing requires a curing period of several hours to several days, there is a problem that productivity is low. In addition, after curing, there is a problem that stress due to curing shrinkage of the epoxy resin may be concentrated at places where the physical strength is weak, such as solder parts that join electrical and electronic parts and conductors, and the parts may be peeled off. There is also a point.

  As a sealing resin that replaces the two-pack type epoxy resin that has been used with such problems, a hot-melt type resin can be used. A hot melt resin that can be sealed by reducing the viscosity only by heating and melting solves problems in the working environment of the solvent-containing system. Moreover, since the sealing body is formed by solidifying only by cooling after sealing, the productivity is increased. In addition, since a thermoplastic resin is generally used, the member can be easily recycled by heating to melt and remove the resin even after the end of the product life. However, the material suitable for it has not been proposed so far, although it has a high potential as a sealing resin and has not been a material that can sufficiently replace the two-component curable epoxy resin so far. It depends.

  For example, ethylene vinyl acetate (EVA) is widely used at a relatively low cost as a hot melt adhesive. However, the heat resistance is insufficient, and it does not have durability in the environment where electric and electronic parts are used. In addition, various additives are blended in order to develop adhesion. There is a risk that the electrical performance will be reduced by this, which is not suitable. Polyamide that expresses high adhesion to various materials with a single resin is excellent as a resin material for low-pressure injection molding due to its low melt viscosity and high resin strength (see, for example, Patent Document 3), but basically absorbs moisture. In many cases, electrical insulation, which is the most important characteristic, often deteriorates with time by gradually absorbing moisture from the outside.

  On the other hand, polyester that 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 is used at a high pressure of several hundred MPa or higher to seal parts with complex shapes. Therefore, there is a risk of destroying the electric and electronic parts. Patent Document 4 proposes an adhesive using a crystalline polyetherester elastomer and an epoxy resin obtained by reacting polytetramethylene glycol (hereinafter abbreviated as PTMG). The polyester used here Resin has good initial adhesion, but tends to have high crystallinity, and after adhesion, strain energy is generated when changing from an amorphous state to a crystalline state. It was.

  Patent Documents 5 and 6 propose a resin having a melt viscosity optimum for sealing at a low pressure without damaging the parts, and a molded product with good initial adhesion can be obtained. However, for example, if the heat cycle of -40 ° C and 80 ° C is repeated many times or exposed to a high temperature and high humidity environment such as a temperature of 85 ° C and a relative humidity of 85% for a long time, the adhesion strength is greatly reduced and the sealing state is increased. There is a problem that it may not be possible to keep.

  As described above, in the prior art, a material that sufficiently satisfies all required performances has not been proposed as a resin for encapsulating electrical and electronic parts having a complicated shape.

JP-A-1-75517 JP 2000-239349 A JP 2001-24550 A JP 60-18562 A Japanese Patent No. 3553559 JP 2004-83918 A

  An object of the present invention is to provide an electrical / electronic component encapsulant that is excellent in durability against environmental loads such as a cold / heat cycle load, a high-temperature / high-humidity load, and a high-temperature load, It is to provide a resin composition for sealing electric and electronic parts.

In order to achieve the above object, the present inventors have intensively studied and have proposed the following invention. That is, the present invention
(1) 0.1 to 50 parts by mass of epoxy resin (B) and 0.5 to 50 parts by mass of polyolefin resin (C) are blended with respect to 100 parts by mass of crystalline polyester resin (A),
Moisture viscosity is 5 dPa · s or more and 2000 dPa · s or less when extruding from a die having a pore diameter of 1.0 mm and a thickness of 10 mm, dried to a moisture content of 0.1% or less and heated to 220 ° C. to give a pressure of 1 MPa.
With respect to the polybutylene terephthalate plate containing 30% by weight of the glass filler, the shear adhesion strength retention ratio with respect to the initial shear adhesion strength after adding 1000 cycles of -40 ° C. for 30 minutes and 80 ° C. for 30 minutes is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after adding 1000 cycles of -40 ° C. for 30 minutes and 80 ° C. for 30 minutes to the glass epoxy plate is 50% or more,
Resin composition for sealing electrical and electronic parts.
(2) The initial shear adhesion strength to a polybutylene terephthalate plate containing 30% by weight of a glass filler is 0.5 MPa or more,
The initial shear adhesion strength to the glass epoxy plate is 0.5 MPa or more,
The resin composition for sealing electrical and electronic parts according to (1).
(3) With respect to the polybutylene terephthalate plate containing 30% by weight of the glass filler, the shear adhesion strength retention rate relative to the initial shear adhesion strength after applying an environmental load of 85 ° C., 85% RH, 1000 hours is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after applying an environmental load of 85 ° C., 85% RH, 1000 hours to the glass epoxy plate is 50% or more.
The resin composition according to (1) or (2).
(4) With respect to polybutylene terephthalate containing 30% by weight of glass filler, the shear adhesion strength retention rate relative to the initial shear adhesion strength after imparting an environmental load of 105 ° C. and 1000 hours is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after imparting an environmental load of 105 ° C. and 1000 hours to the glass epoxy plate is 50% or more.
(1)-The resin composition in any one of (3).
(5) After the resin composition according to any one of (1) to (4) is heated and kneaded, the resin composition temperature is 130 ° C. or higher and 260 ° C. or lower in a mold in which an electric / electronic component is inserted. The manufacturing method of the electrical / electronic component sealing body inject | poured by the pressure of 0.1 MPa or more and 10 MPa or less.
(6) A sealed electrical and electronic part sealed with the resin composition according to any one of (1) to (4).
(7) The crystalline polyester resin (A) is
It contains both or one of terephthalic acid and naphthalenedicarboxylic acid as the acid component, and the total of terephthalic acid and naphthalenedicarboxylic acid is 65 mol% or more when the total amount of the acid components is 100 mol%,
The glycol component contains both or one of 1,4-butanediol and ethylene glycol, and the total of 1,4-butanediol and ethylene glycol is 40 mol% or more when the total amount of glycol components is 100 mol%. is there,
The resin composition according to any one of (1) to (4).
(8) When the crystalline polyester resin (A) is a glycol diol, a polyether diol having a number average molecular weight of 400 to 5000 and a total amount of glycol components of 100 mol% is 1 mol% or more and 50 mol% or less. The resin composition according to any one of (1) to (4) and (7).
(9) any of the density at temperature of 30 ° C. is less than 0.75 g / cm ³ or more 0.91 g / cm ³ of the polyolefin resin (C) (1) ~ (4) and (7) and (8) The resin composition described in 1.
(10) The resin composition according to any one of (1) to (4) and (7) to (9), wherein the polyolefin resin (C) is polyethylene or an α-olefin copolymer.
(11) The resin composition according to any one of (1) to (4) and (7) to (10), wherein the epoxy resin (B) is an epoxy resin having an average of two or more glycidyl groups per molecule. .
(12) The resin composition according to any one of (1) to (4) and (7) to (11), wherein the epoxy resin (B) is a bisphenol type epoxy resin.

  The resin composition for sealing electric and electronic parts of the present invention is used as a sealing material in an electric and electronic part sealing body, thereby forming glass filler-containing polybutylene terephthalate and glass epoxy, which are representative substrates of electric and electronic parts. On the other hand, high adhesion durability against a cold cycle load can be exhibited and insulation can be maintained. In a preferred embodiment of the present invention, high initial adhesion strength, high temperature environmental load, and high durability against high humidity and high temperature environmental load can be exhibited. For this reason, the electrical and electronic component sealing body sealed using the resin composition for sealing an electrical and electronic component of the present invention exhibits durability against severe environmental loads such as a cold cycle, high temperature, and high humidity and high temperature. .

  The encapsulated body for electrical and electronic parts of the present invention comprises a resin or a resin composition, which 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. By appropriately selecting a sealing resin or a sealing resin composition, it is possible to obtain a sealed body having adhesion durability that can withstand environmental loads on various polyester substrates, glass epoxy substrates, metals, and the like. Is. The details of the embodiments of the invention will be sequentially described below.

  In the present invention, by blending the epoxy resin (B) into the sealing resin composition, when initializing electrical and electronic parts, excellent initial adhesion and excellent durability such as adhesion to cold cycle and high humidity high temperature environmental load Characteristics can be imparted. The epoxy resin (B) is a stress relaxation effect due to the crystallization delay of the polyester resin (A), an effect as a compatibilizer of the crystalline polyester resin (A) and the polyolefin resin (C), and a base material by introducing a functional group It is considered that the effect of improving wettability to the skin is exhibited. The compounding quantity of the epoxy resin (B) in this invention is 0.1-50 mass parts with respect to 100 mass parts of polyester resins (A). When the compounding amount of the epoxy resin (B) is less than 0.1 parts by mass, the stress relaxation effect due to the crystallization delay cannot be expressed, and the function as a compatibilizer for the polyolefin resin (C) and the epoxy resin (B) cannot be expressed. Sometimes. Moreover, when 50 mass parts or more of epoxy resins (B) are mix | blended, it is inferior to productivity of a resin composition, and also characteristics, such as the heat resistance of a sealing body, may be inferior.

  In the present invention, the compounding of the polyolefin resin (C) with the sealing resin composition has excellent properties such as good adhesion and durability against cold cycle and high temperature hard environmental load when sealing electrical and electronic parts. Demonstrate. The polyolefin resin (C) is considered to exhibit a strain energy relaxation effect by crystallization and enthalpy relaxation of the polyester resin (A). The compounding quantity of polyolefin resin (C) in this invention is 0.5-50 mass parts with respect to 100 weight part of polyester resins (A). When the polyolefin resin (C) is less than 0.5 parts by mass, it is difficult to relax the strain energy by crystallization or enthalpy relaxation of the polyester resin (A), so that the adhesion strength tends to decrease. Moreover, when 50 mass parts or more of polyolefin resin (C) is mix | blended, there exists a tendency for adhesiveness and a resin physical property to fall conversely. In addition, the polyester resin (A) and the polyolefin resin (C) cause macroscopic phase separation, the elongation at break decreases, and the moldability may be adversely affected such that a smooth surface cannot be obtained.

  The sealing resin composition of the present invention includes polyester, polyamide, and polyolefin other than polyester resin (A), epoxy resin (B), and polyolefin resin (C) for the purpose of improving adhesion, flexibility, durability, and the like. , Epoxy, polycarbonate, acrylic, ethylene vinyl acetate, other resins such as phenol, isocyanate compounds, curing agents such as melamine, fillers such as talc and mica, pigments such as carbon black and titanium oxide, antimony trioxide, bromination A flame retardant such as polystyrene may be blended at all. The polyester resin (A) at that time 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 entire composition. When the content of the polyester resin (A) is less than 50% by weight, the polyester resin (A) itself has excellent adhesion to electrical and electronic parts, adhesion durability, elongation retention, hydrolysis resistance, water resistance May decrease.

  Furthermore, when the sealing body of the present invention is exposed to a high temperature and high humidity environment for a long period of time, it is preferable to add an antioxidant. For example, as a hindered phenol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2-methyl- 5-t-butylphenyl) butane, 1,1-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy- Benzenepropanoic acid, pentaerythrityltetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-benzenepropano Icic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4 , 10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) benzene, phosphorus As the system, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecylphosphite, isodecylphenylphosphite , Diphenyl 2-ethylhexyl phosphite, dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2- Til-4-ditridecyl phosphite-5-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, pentaerythritol bis (2,4-di-t-butylphenyl phosphite) ), 2,2′-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, thioether 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) -5-methyl-4,1 -Phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-do Decylthiopropionate) and bis (tridecyl) thiodipropionate, and these can be used alone or in combination. 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.

  In the polyester resin composition of the present invention, the retention rate of the melt viscosity after completion of the heat treatment test at 100 ° C., 121 ° C., 0.2 MPa, saturated water vapor pressure is 70% or more with respect to the melt viscosity before the heat treatment test is conducted. Things are desirable. The heat treatment test here refers to a resin for molding and its composition cut into a 1 cm side cube and processed under conditions of 121 ° C., 0.2 MPa (under saturated water vapor pressure) for 100 hours. The melt viscosity retention after the heat treatment test is preferably 75% or more, more preferably 80% or more, and most preferably 90% or more. There is no limitation on the upper limit, and a value close to 100% is better. If the retention rate of the melt viscosity is less than 70%, durability during use at a high temperature may be lowered. As a method for setting the melt viscosity retention ratio to 70% or more, for example, adopting a composition described later as a preferred composition of the polyester resin (A), or blending an antioxidant into the sealing resin composition. Can be mentioned.

  Low melt viscosity not found in general-purpose crystalline polyester resins such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polybutylene terephthalate (hereinafter sometimes abbreviated as PBT), which are widely used as engineering plastics In order to develop heat resistance, high-temperature and high-humidity resistance, cold-heat cycle resistance, etc. comparable to the two-component curable epoxy resin, in the constituent component of the polyester resin (A), aliphatic and / or alicyclic It is necessary to adjust the composition ratio of the aromatic system. For example, in order to maintain high heat resistance of 150 ° C. or higher, 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. In particular, 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 polyester resin (A) contains either or one of terephthalic acid and naphthalenedicarboxylic acid, and the total amount of terephthalic acid and naphthalenedicarboxylic acid is 65 mol% when the total amount of the acid components is 100 mol%. It is preferably at least 70 mol%, more preferably at least 80 mol%. If it is 60 mol% or less, the heat resistance required for electric and electronic parts may be insufficient.

  Moreover, as a glycol component which comprises a polyester resin (A), it contains both or one of ethylene glycol and 1,4-butanediol, and the total amount of ethylene glycol and 1,4-butanediol is the total amount of glycol components. When it is 100 mol%, it is preferably 40 mol% or more, more preferably 45 mol% or more, particularly preferably 50 mol% or more, and most preferably 55 mol% or more. If it is 40 mol% or less, the crystallization speed is insufficient, the mold releasability is deteriorated, the moldability is deteriorated such as the molding time is prolonged, the crystallinity is also insufficient, and the heat resistance may be insufficient. .

  In the polyester resin (A) of the present application, as a copolymer component for imparting adhesion and the like to the basic composition composed of the above-mentioned acid component and glycol component giving high heat resistance, adipic acid, azelaic acid, sebacic acid, Aliphatic or alicyclic such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, hydrogenated dimer acid Group dicarboxylic acids, 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, die Lene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanedimethanol, tricyclodecane dimethanol, neopentylglycol hydroxypivalate, 1,9-nonanediol, 2-methyl It is preferable to use aliphatic or alicyclic glycols such as octanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, polytetramethylene glycol, and polyoxymethylene glycol.

  In addition, aliphatic or alicyclic dicarboxylic acids having 10 or more carbon atoms such as dimer acid and hydrogenated dimer acid and derivatives thereof, or aliphatic and / or fats having 10 or more carbon atoms such as dimer diol and hydrogenated dimer diol. Copolymerization of a cyclic diol can lower the glass transition temperature while maintaining a high melting point. Therefore, from the viewpoint of achieving both the heat resistance of the polyester resin and the adhesion to electrical and electronic parts, these are copolymerizations. It is preferably contained as a dicarboxylic acid component or a diol component. In addition, the derivative | guide_body of aliphatic and / or alicyclic dicarboxylic acid means what is a derivative | guide_body of carboxylic acid and can become a copolymerization component, for example, ester, acid chloride, etc.

  Here, the dimer acid is an aliphatic or alicyclic dicarboxylic acid produced by dimerization of unsaturated fatty acid by polymerization or Diels-Alder reaction or the like (most dimers, trimers, monomers, etc. The hydrogenated dimer acid is obtained by adding hydrogen to the unsaturated bond portion of the dimer acid. The dimer diol and hydrogenated dimer diol are those obtained by reducing the two carboxyl groups of the dimer acid or the hydrogenated dimer acid to hydroxyl groups. Examples of the dimer acid or dimer diol include ENPOL (registered trademark) or Sobamol (registered trademark) manufactured by Cognis Co., Ltd.

  Also, a small amount of an aromatic copolymer component can be used as long as it is within the range that maintains a low melt viscosity. Preferred examples of the aromatic copolymer component include aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, and aromatic glycols such as ethylene oxide adduct and propylene oxide adduct of bisphenol A. In particular, from the viewpoint of mold releasability, it is preferable to introduce an aliphatic component having a relatively high molecular weight such as dimer acid, dimer diol, or polytetramethylene glycol, which exhibits quick crystallization after molding.

  Moreover, when a block segment represented by a relatively high molecular weight aliphatic component such as dimer acid, dimer diol, or polytetramethylene glycol is introduced, the glass transition temperature of the polyester resin (A) is lowered. Therefore, when the durability after molding is important, the cooling cycle durability is improved, and the hydrolysis resistance is improved by reducing the ester group concentration. 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. In order to provide a material that can withstand the cooling and heating cycle, the glass transition temperature is preferably −10 ° C. or lower. More preferably, it is -20 degrees C or less, More preferably, it is -40 degrees C or less, Most preferably, it is -50 degrees C or less. Although a minimum is not specifically limited, -100 degreeC or more is realistic when adhesiveness and blocking resistance are considered.

In addition, the upper limit of the ester group concentration of the polyester resin (A) is 8000 equivalents / 10 ^{6 in} order to provide hydrolysis resistance that can withstand high temperature and high humidity in providing long-term durability to the sealed electrical and electronic parts. g is desirable. A preferable upper limit is 7500 equivalent / 10 < ⁶ > g, More preferably, it is 7000 equivalent / 10 < ⁶ > g. Moreover, in order to ensure chemical resistance (gasoline, engine oil, alcohol, general-purpose solvent, etc.), 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. Here, 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.

  In introducing a blocky polymer, dimer acid, hydrogenated dimer acid, dimer diol, hydrogenated dimer diol, and polytetramethylene glycol are 200 mol% in total of all acid components and all glycol components of polyester resin (A). Is preferably 2 mol% or more, more preferably 5 mol% or more, more preferably 10 mol% or more, and most preferably 20 mol% or more. The upper limit is 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less in consideration of handling properties such as heat resistance and blocking. The number average molecular weight of polytetramethylene glycol is preferably 400 or more, more preferably 500 or more, still more preferably 600 or more, particularly preferably 700 or more, and the upper limit is preferably 10,000, more preferably 6000, More preferably, it is 4000, Most preferably, it is 3000. When the number average molecular weight of polytetramethylene glycol is less than 400, the thermal cycle durability and hydrolysis resistance may be lowered. On the other hand, if it exceeds 10,000, the compatibility with the polyester portion is lowered, and it may be difficult to copolymerize in a block form.

  The number average molecular weight of the polyester resin (A) of the present invention is preferably 3000 or more, more preferably 5000 or more, and still more 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 polyester resin (A) of 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.

  In addition, the polyester resin (A) of the present invention may be copolymerized with a polycarboxylic acid such as trimellitic anhydride or trimethylolpropane or a polyol as necessary.

Examples of the method for determining the composition and composition ratio of the polyester resin include ¹ H-NMR and ¹³ C-NMR in which the polyester resin is dissolved in a solvent such as deuterated chloroform and measurement by gas chromatography which is measured after methanolysis of the polyester resin. (Hereafter, it may be abbreviated as methanolysis-GC method). In the present invention, when the polyester resin (A) can be dissolved and there is a solvent suitable for ¹ H-NMR measurement, the composition and composition ratio are determined by ¹ H-NMR. When there is no suitable solvent or when the composition ratio cannot be specified only by ¹ H-NMR measurement, ¹³ C-NMR or methanolysis-GC method is adopted or used in combination.

  As a method for producing the crystalline polyester resin (A) of the present invention, a known method can be used. For example, the above-mentioned dicarboxylic acid and diol components are esterified at 150 to 250 ° C. and then reduced in pressure while being reduced in pressure. A target polyester resin can be obtained by polycondensation at ˜300 ° C. Alternatively, the target polyester resin is obtained by transcondensation at 230 ° C. to 300 ° C. under reduced pressure after a transesterification reaction at 150 ° C. to 250 ° C. using a derivative such as dimethyl ester of dicarboxylic acid and a diol component. be able to.

Polyolefin resin used in the present invention (C) is preferably a density less than 0.75 g / cm ³ or more 0.91 g / cm ^3. By using such ultra-low density polyolefin, the polyolefin resin (C) can be easily finely dispersed and mixed with the originally incompatible polyester resin (A). Thus, a homogeneous resin composition can be obtained. In addition, since it has low density and low crystallinity, it also works properly to relieve the residual stress at the time of injection molding occurring in the crystalline polyester resin (A) over time, and provides long-term adhesion durability as a sealing resin. It exhibits favorable characteristics such as reduction of stress caused by environmental load. As the polyolefin resin (C) having such characteristics, polyethylene and ethylene copolymers are particularly preferable because they are readily available, inexpensive, and do not adversely affect the adhesion to metals and films. Specifically, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, ethylene propylene elastomer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate-maleic anhydride Terpolymer, ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate-methacryl Examples thereof include glycidyl acid terpolymers.

  The polyolefin resin (C) preferably contains no polar group capable of reacting with the polyester resin (A) such as a carboxyl group or a glycidyl group. If a polar group is present, the compatibility with the polyester resin (A) changes, and the strain energy during crystallization of the polyester resin (A) may not be alleviated. Generally, a polyolefin having a polar group tends to have a higher compatibility with a polyester resin than a polyolefin having no polar group. However, in the present invention, when the compatibility is higher, the adhesion deterioration with time tends to increase. .

  The epoxy resin (B) used in the resin composition of the present invention is an epoxy resin having an average of at least 1.1 or more glycidyl groups in the molecule, preferably in the number average molecular weight range of 450 to 40,000. For example, 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. Glycidylamine or 3,4-epoxy B hexyl methyl carboxylate, epoxidized polybutadiene, such as alicyclic or aliphatic epoxides such as epoxidized soybean oil. Of these, those having good compatibility with the polyester resin (A) are particularly preferable in order to exhibit high adhesion. The preferred number average molecular weight of the epoxy resin (C) is 450 to 40,000. If the number average molecular weight is less than 450, the adhesive composition is very soft, and the mechanical properties may be inferior. If it is 40000 or more, the compatibility with the polyester resin (A) is lowered and the adhesion may be impaired. is there.

The sealing resin composition of the present invention preferably has a melt viscosity at 220 ° C. of 5 to 4000 dPa · s. Here, the melt viscosity at 220 ° C. is a value measured as follows. That is, the sealing resin composition was dried to a moisture content of 0.1% or less, and then heated and stabilized at 220 ° C. 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 hole diameter of 1.0 mm is passed at a pressure of 98 N / cm ² . When the melt viscosity is 4000 dPa · s or higher, high resin cohesive strength and durability can be obtained, but high-pressure injection molding is required when sealing to parts with complex shapes, so the parts can be destroyed. May occur. By using a sealing resin composition having a melt viscosity of 1000 dPa · s or less, preferably 500 dPa · s or less, a molded part excellent in electrical insulation can be obtained at a relatively low injection pressure of 0.1 to 100 MPa. As a result, the characteristics of the electric and electronic parts are not impaired. Further, from the viewpoint of the operation of injecting the sealing resin composition, it is preferable that the melt viscosity at 220 ° C. is low, but considering the adhesiveness and cohesive force of the resin composition, the lower limit is preferably 5 dPa · s or more, and more preferably Is preferably 10 dPa · s or more, more preferably 50 dPa · s or more, and most preferably 100 dPa · s or more.

  Further, in order to mold without causing thermal degradation of the polyester resin (A) as much as possible, rapid melting at 210 to 240 ° C. is required. Therefore, the upper limit of the melting point of the polyester resin (A) is 210 ° C. desirable. Preferably, it is 200 degreeC, More preferably, it is 190 degreeC. The lower limit is preferably 5 to 10 ° C. higher than the heat resistant temperature required for the corresponding application. Considering handling at normal temperature and normal heat resistance, it is 70 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly preferably 140 ° C. or higher, and most preferably 150 ° C. or higher.

  In the present invention, the adhesion strength between a specific member and the sealing resin composition is obtained by preparing a measurement sample piece in which two plate-like members are bonded with the sealing resin composition, and measuring the shear fracture strength thereof. Determine by doing. The method for preparing the test specimen for measurement and the method for measuring the shear fracture strength are performed according to the methods described in the examples described later.

  The encapsulating resin composition of the present invention is molded by pouring into a mold in which electric and electronic parts are set. More specifically, in the case of using a screw type hot melt molding process applicator, it is heated and melted at around 130 to 220 ° C., injected into a mold through an injection nozzle, and then molded after a certain cooling time. A molded object can be obtained by removing the object from the mold.

  The type of the applicator for hot melt molding is not particularly limited, and examples thereof include ST2 manufactured by Nordson, Germany, and a vertical extrusion molding machine manufactured by Imoto Seisakusho.

  In order to describe the present invention in more detail, examples and comparative examples are given below, but the present invention is not limited to the examples. In addition, each measured value described in the Example and the comparative example was measured by the following method.

<Measurement of melting point and glass transition temperature>
Using a differential scanning calorimeter “DSC220” manufactured by Seiko Denshi Kogyo Co., Ltd., put 5 mg of a sample into an aluminum pan, seal it with a lid, hold it at 250 ° C. for 5 minutes, and then quench with liquid nitrogen. Thereafter, the temperature was measured from −150 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min. The inflection point of the obtained curve was defined as the glass transition temperature, and the endothermic peak as the melting point.

<Measurement of 10-point average roughness>
Using a surf test 600 manufactured by Mitutoyo Co., Ltd., the measurement length was measured at 5 mm for each of five locations on the surfaces of the base materials 4 and 5 that were in contact with the sealing resin composition, and according to JIS B 0601-1994, The point surface roughness was calculated. The stylus used for the measurement had the following specifications.
Stylus tip material: Diamond Stylus tip shape: 90 ° cone Stylus tip radius of curvature: 2 μm

<Adhesion strength test>
Preparation method of adhesion strength test piece Base material 4 (width 25 mm × length 48 mm × thickness 2 mm), base material 5 (width 25 mm × length 2 mm) made of PBT containing 30% by weight of glass filler (hereinafter sometimes abbreviated as GPBT) 70 mm × 2 mm in thickness) was placed together with the spacer 3 on a mold 1 for flat plate molding (mold inner surface dimensions: width 100 mm × length 100 mm × thickness 5 mm). Next, a sealing resin composition was injected from the gate 2 using a screw type hot melt molding applicator (Imoto Seisakusho type low pressure extrusion molding machine), and injection molding was performed. The injection 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 an injection speed of 50%. 1 to 3 are schematic views of a cross section of the mold 1, showing a state at the time when injection of the sealing resin composition is completed, and a cross section taken along the line AA 'in FIG. 1 is shown in FIG. The B ′ cross section corresponds to FIG. 1, and the CC ′ cross section of FIGS. The molded product was released, and the sealing resin composition other than the overlapping portion of the flat plate 4 and the flat plate 5 was cut off to obtain an adhesion strength test piece. Hereinafter, this test piece is referred to as a GPBT adhesion test piece. The GPBT adhesion test piece has a structure in which an overlapping portion (width 25 mm × length 18 mm) between GPBT plates is filled and bonded with a sealing resin composition having a thickness of 1 mm, and the adhesion between the GPBT plate and the resin composition is taken. The area is 25 × 18 = 450 mm ² . In addition, the GPBT board used here used the thing in the range whose 1-point average roughness of the adhesion part surface is 1-5 micrometers.

  Nikkan Kogyo FR-4 glass epoxy plate NIKAPLEX was used as the base materials 4 and 5, and the others were the same as the GPBT adhesion test piece, and a glass epoxy adhesion test piece (hereinafter sometimes abbreviated as GE adhesion test piece). Obtained. Hereinafter, when simply referred to as an adhesion test piece, it refers to a GPBT adhesion test piece and / or a GE adhesion test piece. In addition, the glass epoxy board used here used the thing in the range whose 10-point average roughness of the adhesion part surface is 0.5-3 micrometers.

Evaluation of mold releasability The state of releasing the adhesion test piece from the mold was evaluated according to the following criteria.
Evaluation criteria A: The adhesion test piece could be taken out without being caught at all.
○: Some catching occurs on the runner part, but the adhesion test piece
The mold could be released without cracking.
Δ: There is resistance when releasing the adhesion test piece from the mold, and the surface of the adhesion test piece
Dries out, but you can take out the adhesion test piece without cracking.
I was able to.
×: The adhesion test piece could not be released from the mold or adhered when released
The test piece was cracked.

Evaluation of initial adhesion After leaving the adhesion test piece in an atmosphere of 23 ° C. and 50% RH for 3 hours or more and 100 hours or less, applying tensile force in the longitudinal direction of the test piece to add shearing force Was measured. The pulling speed was 50 mm / min. The strength at the time of destruction per adhesion area (450 mm ² ) was defined as shear adhesion strength.
Evaluation criteria A: Shear adhesion strength 1.5 MPa or more
○: Shear adhesion strength less than 1.5 MPa 1.0 MPa or more
Δ: Shear adhesion strength less than 1.0 MPa 0.5 MPa or more
X: Shear adhesion strength less than 0.5 MPa

Environmental load resistance test As an environmental load resistance test, a cold cycle test, a high temperature test, and a high humidity high temperature test were conducted. After applying an environmental load to the adhesion test piece, the adhesion was evaluated by the same method as the evaluation of initial adhesion, and the shear adhesion strength retention rate defined below was calculated.

Evaluation criteria A: Shear adhesion strength retention 80% or more
○: Shear adhesion strength retention rate of less than 80% and 70% or more
Δ: Shear adhesion strength retention less than 70% and 50% or more
X: Shear adhesion strength retention of less than 50%

Cooling cycle test With respect to the adhesion test piece prepared in the same manner as the initial adhesion was evaluated, 1000 cycles of 1 cycle consisting of 30 minutes at −40 ° C. and then 30 minutes at 80 ° C. An environmental load was applied, and then the shear adhesion strength was measured to calculate the shear adhesion retention rate.

High-Temperature Test An adhesion test piece prepared in the same manner as the initial adhesion was evaluated was subjected to an environmental load at 105 ° C. for 1000 hours, and then the adhesion strength was measured to calculate the adhesion retention rate.

High humidity high temperature test Adhesion test piece prepared in the same manner as the initial adhesion was evaluated was subjected to an environmental load of 1000 hours at 85 ° C. and 85% relative humidity, and then the adhesion strength was measured to maintain the adhesion. The rate was calculated.

<Melting property test>
Evaluation Method of Melt Viscosity of Resin and Encapsulating Resin Composition Using a flow tester (CFT-500C type) manufactured by Shimadzu Corporation, dried to a moisture content of 0.1% or less in a central cylinder of a heating body set at 220 ° C. The resin or sealing resin composition was filled, and after 1 minute from filling, a load was applied to the sample through a plunger, and the pressure was 1 MPa, from the die at the bottom of the cylinder (hole diameter: 1.0 mm, thickness: 10 mm) The melted sample was extruded, the plunger descending distance and descending time were recorded, and the melt viscosity was calculated.

Low Pressure Formability Evaluation Method A flat plate (100 mm × 100 mm × 10 mm) made of a sealing resin composition was molded using Nordson ST-2 as an applicator for hot melt molding using a flat plate mold. 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, injection speed 50% Evaluation criteria ○: Completely filled, no sink.
Δ: Filled without short shot, but there is a sink.
X: There is a short shot.

<Insulation test>
Method of making insulating test piece High pressure injection molding a cylindrical molded part 12 of 6 mm diameter and 50 mm length made of PBT coaxially with the central part of a conductive rod 11 of 1.5 mm diameter and 100 mm length made of stainless steel Molded by the method (see FIG. 4A). Next, the cylindrical molded part 13 made of the sealing resin composition was molded by a low-pressure injection molding method so as to overlap with the cylindrical molded part 12 made of PBT in the axial direction (FIG. 4B). reference). Low-pressure injection molding uses a low-pressure vertical extrusion molding machine manufactured by Imoto Seisakusho as an applicator for hot melt molding, molding with 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 an injection speed of 50%. Conducted under conditions. A material obtained by cutting off the gate portion from the molded body thus obtained is hereinafter referred to as an insulating test piece 21.

Insulating evaluation method A conductive rod 22 made of stainless steel having a diameter of 1.5 mm and a length of 100 mm and an insulating test piece 21 are made of glass so that both the conductive rods are in an insulating state and are substantially parallel and spaced at a distance of 95 to 105 mm. Glass container until the conductive rod exposed portion of the insulating test piece 21 is not submerged, and the cylindrical molded portion 13 made of the sealing resin composition is completely submerged. A tap water with a water temperature of 25 ° C. was poured into the tank. After leaving still for 30 minutes, the DC electric resistance value between the conductive bar and the conductive bar 22 of the insulating test piece 21 was measured. When the resistance value was 100 MΩ or more, it was determined that the insulation was maintained, and when it was 100 MΩ or less, the insulation was poor. This test was performed on 100 insulating test pieces and evaluated according to the following criteria.
Evaluation criteria ○: 0 insulation defects
Δ: Insulation failure 1 to less than 5
×: 5 or more insulation defects

Evaluation of mold releasability The state when the insulating test piece was released from the mold was evaluated according to the following criteria.
Evaluation criteria A: The insulation test piece could be taken out without being caught at all.
○: Slightly caught on the runner part,
The mold could be released without causing cracks.
Δ: There is resistance when the insulating test piece is released from the mold, and the surface of the insulating test piece
Slightly wrinkles, but remove the insulation test piece without cracking.
I was able to put it out.
×: The insulating test piece could not be released from the mold, or was disconnected when released.
The edge test piece was cracked.

Production Example of Polyester Resin 166 parts by mass of terephthalic acid, 180 parts by mass of 1,4-butanediol, 0.25 parts by mass of tetrabutyl titanate are added in a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation. The esterification reaction was carried out at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, 300 parts by mass of polytetramethylene glycol “PTMG1000” (Mitsubishi Chemical Co., Ltd.) having a number average molecular weight of 1000 and 0.5% of hindered phenolic antioxidant “Irganox 1330” (Ciba Geigy Co., Ltd.) were added. While mass parts were charged and the temperature was raised to 255 ° C., 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 A. The melting point of this polyester resin A was 165 ° C., and the melt viscosity was 250 dPa · s.

Polyester resins B to H were synthesized by the same method as polyester resin A. The respective compositions and physical property values are shown in Table 1.

Abbreviations in the table are as follows.
TPA: terephthalic acid, NDC: naphthalene dicarboxylic acid, IPA: isophthalic acid, DIA: hydrogenated dimer acid, BD: 1,4-butanediol, PTMG1000: polytetramethylene ether glycol (number average molecular weight 1000), PTMG2000: polytetra Methylene ether glycol (number average molecular weight 2000)

Production Example of Resin Composition for Encapsulating Electrical and Electronic Components Resin composition 1 for encapsulating electrical and electronic components was uniformly mixed with 100 parts by mass of polyester resin A, 20 parts by mass of polyolefin resin A, and 10 parts by mass of epoxy resin A. Thereafter, it was obtained by melt-kneading at a die temperature of 220 ° C. using a twin screw extruder. Polyester resin compositions 2 to 26 were prepared in the same manner as polyester resin composition 1. Each composition and physical-property value were shown to Tables 2-7.

Polyolefin A: Excellen VL EUL731, manufactured by Sumitomo Chemical Co., Ltd., α-olefin copolymerized ultra-low density polyethylene, density 0.90.
Polyolefin B: Admer SF-600, manufactured by Mitsui Chemicals, Inc., adhesive polyolefin, density 0.88.
Polyolefin C: Hi-Zex 2100J, manufactured by Mitsui Chemicals, high density polyethylene, density 0.93.
Epoxy A: JER1007, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol type epoxy resin.
Epoxy B: UG4070, manufactured by Toagosei Co., Ltd., polyfunctional epoxy resin.
Epoxy C: EX-145, manufactured by Nagase ChemteX Corporation, monoepoxy resin.

Example 1
Using the sealing resin composition 1 as the sealing resin composition, <melting property test>, <adhesion strength test>, and <insulation test> were performed. In <melting characteristic test>, it was a favorable melting characteristic of 394 dPa · s. In <Adhesion Strength Test>, for the GPBT adhesion test piece, the initial adhesion strength is 1.2 MPa, after the cooling cycle test is 1.0 MPa, after the high temperature test is 1.1 MPa, after the high humidity high temperature test is 1.0 MPa, the GE adhesion test piece. The initial adhesion strength was 1.2 MPa, 1.1 MPa after the thermal cycle test, 1.1 MPa after the high temperature test, and 0.9 MPa after the high humidity high temperature test. Good results showing high adhesion strength retention in all items It became. Also, in the <insulation test>, the insulation property was maintained for all the samples. The mold releasability was also very good. The evaluation results are shown in Table 2.

Examples 2-13
Using the sealing resin compositions 2 to 13 as the sealing resin composition, a <melting characteristic test>, <adhesion strength test>, and <insulation test> were performed in the same manner as in Example 1. The evaluation results are shown in Tables 2-4.

Comparative Example 1
Using the sealing resin composition 14 as the sealing resin composition, a <melting characteristic test>, <adhesion strength test>, and <insulation test> were performed in the same manner as in Example 1. In <melting characteristic test>, it is 1832 dPa · s, which is a moldable range. In <adhesion strength test>, the initial adhesion strength of the GPBT adhesion test piece is 1.1 MPa, and after the cooling cycle test, 1.1 MPa, left at high temperature. After 1.0MPa and 0.8MPa after high humidity and high temperature test, the required properties are satisfied. However, the initial adhesion strength of the GE adhesion test piece is 1.0MPa, 0.1MPa after the thermal cycle test, 0.1MPa after high temperature standing, It became 0.1 MPa after the wet high temperature test, and the adhesion strength retention after environmental load was low for the GE adhesion test piece, which was outside the scope of the claims. Moreover, in the <insulation test>, insulation failure occurred frequently for all items, resulting in failure.

Comparative Examples 2-13
Using the sealing resin compositions 15 to 26 as the sealing resin composition, <melting characteristic test>, <adhesion strength test>, and <insulation test> were performed in the same manner as in Example 1. The evaluation results are shown in Tables 5-7.

  Examples 1 to 13 satisfy the claims, and the results of the melt property test, the adhesion strength test, and the insulation test are good. On the other hand, Comparative Example 1 has a low shear adhesion strength retention rate against GE, which is outside the scope of the present invention. Since Comparative Examples 2, 4, and 5 do not contain a polyolefin resin, they are out of the scope of the present invention, the deterioration of the adhesion performance after the environmental test is large, and the mold releasability is also poor. Since Comparative Examples 3, 6, and 7 do not contain an epoxy resin, they are out of the scope of the present invention, and the adhesion performance after the environmental test is greatly reduced. Since Comparative Examples 8 and 9 do not contain an epoxy resin and a polyolefin resin, they are out of the scope of the present invention, and the adhesion after a high-humidity high-temperature test is lowered. In Comparative Examples 10 and 11, the compounding ratio of the polyolefin resin is outside the range of claim 1, and therefore the adhesion is very poor. Comparative Examples 12 and 13 have a low shear adhesion retention ratio against GPBT and a shear adhesion retention ratio against GE, which are outside the scope of the present invention.

The polyester resin and resin composition of the present invention can provide materials that sufficiently satisfy various performances for molding electric and electronic parts having complex shapes, such as automobiles, communications, computers, and various household appliances. It is useful as a molded product of a connector, a harness, or an electronic component, a switch having a printed circuit board, or a sensor.

It is a schematic diagram which shows the preparation method of the test piece for an adhesion strength test. It is a schematic diagram which shows the preparation method of the test piece for an adhesion strength test. It is a schematic diagram which shows the preparation method of the test piece for an adhesion strength test. It is a schematic diagram which shows the preparation method of the test piece for insulation tests. It is a schematic diagram of the insulation evaluation method of the test piece for insulation tests.

Explanation of symbols

1: Mold
2: Gate
3: Spacer
4, 5: Base material
6: Resin composition
11: Conductive rod
12: GPBT cylindrical molded part
13: Cylindrical molded part made of resin composition for sealing 21: Insulating test piece
22: Conductive rod
23: Glass container 24: Water surface

Claims (12)

0.1 to 50 parts by mass of epoxy resin (B) and 0.5 to 50 parts by mass of polyolefin resin (C) are blended with respect to 100 parts by mass of crystalline polyester resin (A),
Moisture viscosity is 5 dPa · s or more and 2000 dPa · s or less when extruding from a die having a pore diameter of 1.0 mm and a thickness of 10 mm, dried to a moisture content of 0.1% or less and heated to 220 ° C. to give a pressure of 1 MPa.
With respect to the polybutylene terephthalate plate containing 30% by weight of the glass filler, the shear adhesion strength retention ratio with respect to the initial shear adhesion strength after adding 1000 cycles of -40 ° C. for 30 minutes and 80 ° C. for 30 minutes is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after adding 1000 cycles of -40 ° C. for 30 minutes and 80 ° C. for 30 minutes to the glass epoxy plate is 50% or more,
Resin composition for sealing electrical and electronic parts. The initial shear adhesion strength to the polybutylene terephthalate plate containing 30% by weight of glass filler is 0.5 MPa or more,
The initial shear adhesion strength to the glass epoxy plate is 0.5 MPa or more,
The resin composition for electrical and electronic component sealing according to claim 1. With respect to the polybutylene terephthalate plate containing 30% by weight of the glass filler, the shear adhesion strength retention with respect to the initial shear adhesion strength after giving an environmental load of 85 ° C., 85% RH, 1000 hours is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after applying an environmental load of 85 ° C., 85% RH, 1000 hours to the glass epoxy plate is 50% or more.
The resin composition according to claim 1 or 2. With respect to polybutylene terephthalate containing 30% by weight of glass filler, the shear adhesion strength retention ratio relative to the initial shear adhesion strength after imparting an environmental load of 105 ° C. and 1000 hours is 50% or more,
The shear adhesion strength retention with respect to the initial shear adhesion strength after imparting an environmental load of 105 ° C. and 1000 hours to the glass epoxy plate is 50% or more.
The resin composition in any one of Claims 1-3.   After the resin composition according to any one of claims 1 to 4 is heated and kneaded, the resin composition temperature is 130 ° C or higher and 260 ° C or lower and the resin composition pressure is 0.1 MPa or higher in the mold in which the electric and electronic parts are inserted. The manufacturing method of the electrical and electronic component sealing body inject | poured at 10 Mpa or less.   An electrical / electronic component sealing body sealed with the resin composition according to claim 1. The crystalline polyester resin (A) is
It contains both or one of terephthalic acid and naphthalenedicarboxylic acid as the acid component, and the total of terephthalic acid and naphthalenedicarboxylic acid is 65 mol% or more when the total amount of the acid components is 100 mol%,
The glycol component contains both or one of 1,4-butanediol and ethylene glycol, and the total of 1,4-butanediol and ethylene glycol is 40 mol% or more when the total amount of glycol components is 100 mol%. is there,
The resin composition in any one of Claims 1-4.   The crystalline polyester resin (A) contains, as a glycol component, a polyether diol having a number average molecular weight of 400 to 5000, 1 mol% or more and 50 mol% or less when the total amount of glycol components is 100 mol%. Item 8. The resin composition according to any one of Items 1 to 4 and 7. The resin composition according to any one of claims 1～4,7 and 8 Density at temperature 30 ° C. is less than 0.75 g / cm ³ or more 0.91 g / cm ³ of the polyolefin resin (C).   The resin composition according to any one of claims 1 to 4 and 7 to 9, wherein the polyolefin resin (C) is polyethylene or an α-olefin copolymer.   The resin composition according to any one of claims 1 to 4 and 7 to 10, wherein the epoxy resin (B) is an epoxy resin having an average of 2 or more glycidyl groups per molecule.   The resin composition according to any one of claims 1 to 4 and 7 to 11, wherein the epoxy resin (B) is a bisphenol type epoxy resin.