JPWO2014185325A1 - Electrical and electronic component sealing method and sealed body - Google Patents

Abstract

An object of the present invention is to provide a low-pressure insert-sealing method for electrical and electronic parts that can exhibit good adhesion to olefinic resins such as polyethylene and polypropylene, which are difficult-to-adhere materials. A resin composition mainly composed of a crystalline copolyester having a glass transition temperature of 0 ° C. or lower and a melting point of 120 ° C. or higher and 240 ° C. or lower is used. An electrical / electronic component sealing method, wherein the electrical / electronic component is subjected to an atmospheric pressure plasma treatment at the time of insert molding sealing at a temperature of 5 ° C. [Selection figure] None

Description

  The present invention relates to a sealing method and a sealing body by low-pressure insert molding such as electrical and electronic parts.

Olefin-based resins such as polypropylene (PP) and polyethylene (PE) are inexpensive and light, and are widely used in various fields including automobiles and home appliances because of their excellent physical strength, chemical resistance, and heat and heat resistance. . Particularly in recent years, weight reduction has been strongly demanded for improving the fuel efficiency of automobiles, and glass fiber reinforced polypropylene has been widely studied as a substitute for metal. Conventionally, vinyl chloride (vinyl chloride) has been mainly used as a covering material for electric wires used in electric and electronic parts, but in recent years, cross-linked polyethylene-coated electric wires have been widely used from the viewpoint of environmental problems and heat resistance. It has come to be.
However, since these olefin-based resins such as polypropylene and (crosslinked) polyethylene have no polarity, there is no resin having good adhesion to molded articles, electrical and electronic parts, or films using these, for example, In order to form a composite with a metal such as aluminum or stainless steel or a resin such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), it was necessary to make a hole and fix it with a screw.

  On the other hand, electrical and electronic parts used in automobiles and electrical appliances are connected to the outside by electric wires in order to receive external power supply and send electrical signals to the outside. Requires electrical insulation from the outside and is sealed with an insulating resin or the like. In the past, two-component curable epoxy resins and silicone resins have been generally used in consideration of the durability after sealing, but for olefin-based resins such as cross-linked polyethylene-coated electric wires and polypropylene casings, etc. In some cases, the adhesive strength is low, water or the like may enter from the interface between the wire or housing and the sealing material, resulting in poor insulation, and the electrical and electronic components may be destroyed due to shrinkage stress during curing. There was also.

Therefore, in recent years, a hot-melt type resin has been proposed as a sealing resin that replaces the two-component curable epoxy resin. Hot melt resin has a merit that the work efficiency is drastically improved compared to two-part curable epoxy resin because the viscosity is lowered by simply heating and melting and electric and electronic parts can be easily sealed. Polyamide that is low and exhibits high adhesion to various materials is excellent as a resin material for low-pressure injection molding (see, for example, Patent Document 1), but has no adhesion to cross-linked polyethylene and is similar to two-part curable epoxy In addition to water intrusion from the interface between the wire and the sealing material, it may not only cause poor insulation, but basically it is highly hygroscopic so that it can ensure the most important characteristic, electrical insulation. It was often difficult. On the other hand, polyesters with high electrical insulation and water resistance are considered to be very useful materials for this application, but polyesters developed for hot melt adhesives (for example, Patent Document 2) still have adhesive strength to crosslinked polyethylene. Not only may the water resistance and insulation properties be poor, but the melt viscosity is generally high, and injection molding at high pressures of several tens to several hundreds of MPa is required to seal parts with complex shapes. There is a risk of destroying the electrical / electronic component to be sealed. Polyesters developed for molding electrical and electronic parts (for example, Patent Documents 3 and 4) have a low melt viscosity and can be molded at low pressure, and can be sealed without destroying electrical and electronic parts. Adhesive strength to polypropylene or the like has not been improved, water cannot be prevented from entering from the interface of the electric wire, and there has been a major drawback in that the electrical insulation that is the original purpose is hindered.
As a resin composition having improved adhesion to crosslinked polyethylene or polypropylene, a low-pressure molding resin composition mainly composed of an olefin resin has been proposed (for example, Patent Document 5), but the elongation as a resin composition is also proposed. Because of its small size and poor flexibility, it has been difficult to apply it to electric and electronic parts such as electric wires in which bendability is important.

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

JP 2001-24550 A JP 60-18562 A Japanese Patent No. 3553559 JP 2010-150471 A JP 2012-180385 A Japanese Patent No. 5077502 Japanese Patent No. 1557180

  The subject of this invention is providing the sealing method by the low voltage | pressure insert molding of the electrical and electronic component which has favorable adhesiveness with respect to olefin resin, such as a bridge | crosslinking polyethylene covering electric wire and a polypropylene, and a sealing body.

In order to achieve the above object, the present inventors have intensively studied and have proposed the following invention. That is, this invention relates to the sealing method by the low voltage | pressure insert molding of the electrical / electronic component which used the resin composition shown below and gave the specific easily bonding surface treatment, and a sealing body.
(1) Using a resin composition containing as a main component a crystalline copolyester (A) having a glass transition temperature of 0 ° C. or lower and a melting point of 120 ° C. or higher and 240 ° C. or lower, An electrical / electronic component sealing method, wherein the electrical / electronic component is preliminarily subjected to an atmospheric pressure plasma treatment as an easy-adhesion surface treatment when insert sealing is performed at a temperature of 260 ° C. or lower.
(2) The crystalline copolyester (A) is any one of a crystalline copolyester (A1) obtained by copolymerizing a polyether segment or a crystalline copolyester (A2) obtained by copolymerizing a polycarbonate segment. The method for sealing electrical and electronic parts according to (1), comprising the above.
(3) The method for sealing an electric / electronic component according to (2), wherein the polyether segment copolymerized with the crystalline copolymerized polyester (A1) is 50% by mass or more of the crystalline copolymerized polyester. .
(4) The method for sealing an electric / electronic component according to (2), wherein the polycarbonate segment copolymerized with the crystalline copolymerized polyester (A2) is 50% by mass or more of the crystalline copolymerized polyester. .
(5) When the content of the crystalline copolymer polyester (A) is 100 parts by mass in the resin composition, 5 to 50 parts by mass is the amorphous resin (B), and 5 to 50 parts by mass. The resin composition according to any one of (1) to (4), wherein the resin composition is a polyolefin (C).
(6) The amorphous resin (B) contains at least one of amorphous copolymer polyester (B1), epoxy resin (B2), and phenol-modified alkylbenzene resin (B3). (1) The sealing method of the electric and electronic component in any one of (5).
(7) The method for sealing an electric / electronic component according to any one of (1) to (6), wherein the resin composition has a melt viscosity at 220 ° C. of 150 Pa · s or less.
(8) The method for manufacturing an electrical / electronic component according to any one of (1) to (7), wherein the atmospheric pressure plasma treatment is an atmospheric pressure glow discharge plasma treatment.
(9) The electrical and electronic component sealing method according to (8), wherein the atmospheric pressure glow discharge plasma treatment is a remote atmospheric pressure glow discharge plasma.
(10) The electrical and electronic component sealing method according to any one of (8) and (9), wherein the atmospheric pressure plasma treatment is performed in a nitrogen atmosphere having an oxygen concentration of 5% by volume or less.
(11) A sealed body sealed by the method according to any one of (1) to (10).

  TECHNICAL FIELD The present invention relates to a method for sealing electrical and electronic parts, and has good adhesive strength to polyolefin resins that cannot be secured with conventional polyester resins and polyamide resins such as cross-linked polyethylene-coated electric wires and polypropylene molded products. Thus, the present invention provides a sealing method and a sealing body for electrical and electronic components having good sealing properties, waterproofness, and electrical insulation.

It is a schematic diagram which shows the external appearance and sectional structure of the sealing body sample for moldability evaluation.

Ordinary insert molding is a method in which a resin that has been heated and melted at a high temperature and high pressure is injection-molded with respect to a base material previously set in a mold. For example, in the case of PBT, it is necessary to apply a pressure of about 60 MPa at about 260 ° C.
However, when electric and electronic parts having poor heat resistance and pressure resistance are insert-molded by the above method, the electric and electronic parts may be destroyed by the high temperature and high-pressure resin during injection molding.
For this reason, it is generally necessary to perform insert molding of electrical and electronic parts at low temperatures and low pressures. However, at low temperatures and low pressures, the adhesion between the electrical and electronic parts and the sealing resin is insufficient, and the desired electrical insulation and waterproofing properties are achieved. In many cases, it was not fully demonstrated. Particularly for (olefinic) olefinic resins such as (crosslinked) polyethylene and polypropylene, it is very difficult to ensure the adhesion between the base material and the sealing resin by insert molding at low temperature and low pressure.
Therefore, as a result of intensive studies by the present inventors, the resin composition of the present invention was selected as the sealing resin composition, and the electrical and electronic parts were preliminarily subjected to atmospheric pressure plasma treatment, so that crosslinked polyethylene-coated electric wires and other polypro Various types of electrical and electronic parts such as plastic resin, polyester base materials such as PET and PBT, glass epoxy substrates (glass epoxy cloth cloth cloth cloth cloth cloth cloth) It is possible to obtain a sealed body that can provide good adhesion even with insert molding at low temperature and low pressure with respect to various materials, exhibit high waterproofness, and have durability to withstand environmental loads. I found it. Below, the detail of the form for inventing is demonstrated one by one.

The electrical and electronic component sealing method used in the present invention comprises a resin composition comprising a crystalline copolyester (A) having a glass transition temperature (Tg) of 0 ° C. or lower and a melting point of 120 ° C. or higher and 240 ° C. or lower as a main component. When an electrical and electronic part is insert-sealed and molded at a pressure of 20 MPa or less and a temperature of 260 ° C. or less using an object, it is essential that the electrical and electronic part is previously subjected to atmospheric pressure plasma treatment. In addition, containing as said main component means containing 50 mass% or more with respect to all the resin components in a resin composition.
By using a crystalline copolyester (A) having a glass transition temperature of 0 ° C. or less as a main component as a resin composition, flexibility at a low temperature can be secured, and a crystallinity having a melting point of 120 ° C. or higher and 240 ° C. or lower. Since the copolyester (A) is the main component, the electrical and electronic parts are mainly used near room temperature and have a melting point of Tg or more and a melting point or less. The properties can be maintained, and molding can be performed at a temperature higher than the melting point and lower than 260 ° C.
In the sealing method of the present invention, it is essential that the electrical / electronic component to be insert-sealed is subjected to atmospheric pressure plasma treatment. Due to the atmospheric pressure plasma treatment of electrical and electronic parts, the wettability of the substrate surface such as polypropylene and (crosslinked) polyethylene is greatly improved, and the adhesive strength between the electrical and electronic parts and the sealing resin is dramatically increased. It is possible to ensure electrical insulation and waterproofness of electrical and electronic parts.

  The crystalline copolyester (A) used in the present invention can be obtained, for example, by dehydrating or dealcoholizing an acid component such as a dibasic acid or its anhydride or an alkyl ester with a glycol component.

  Examples of the dibasic acid compound include terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, aromatic dibasic acid such as 1,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, Sebacic acid, dodecanoic acid, dimer acid, hydrogenated dimer acid, dodecenyl succinic anhydride, fumaric acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2- Examples thereof include aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and alicyclic dicarboxylic acids. Of these dibasic acid compounds, terephthalic acid or 1,6-naphthalenedicarboxylic acid is preferably contained in an amount of 50 mol% or more of the total dibasic acid compound from the viewpoints of crystallinity, heat resistance, and hydrolysis resistance. . Furthermore, it is more preferable to contain 60 mol% or more.

The glycol component includes ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol. 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl- 1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl- 3′-hydroxypropanoate, 2- (n-butyl) -2-ethyl-1, -Propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol and the like Aliphatic diols such as 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4-hydroxyethoxycyclohexyl) propane Bis (4-hydroxycyclohexyl) methane 2,2-bis (4-hydroxycyclohexyl) propane, 3 (4), 8 (9) - tricyclo [5.2.1.0 ^{2, 6]} alicyclic glycols such as decane dimethanol, or Bisphenol A Aromatic glycols such as ethylene oxide adducts and propylene oxide adducts, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol and the like. Among these, ethylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol and the like are preferably used in an amount of 50 mol% or more of the total glycol component of the crystalline copolymer polyester because it is easy to express crystallinity. .

  Furthermore, in the crystalline copolyester (A) used in the present invention, a part of the dibasic acid component is replaced with a trifunctional or higher carboxylic acid, or a part of the glycol component is replaced with a trifunctional or higher functional polyol. It can be substituted and copolymerized. These tri- or higher functional compounds include trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) and many others. And polyfunctional glycols such as trivalent carboxylic acids and their anhydrides, trimethylolpropane, pentaerythritol, glycerin and polyglycerin. The copolymerization amount of the tri- or higher functional compound is preferably 0 to 5 mol% in all components from the viewpoints of crystallinity and reactivity.

  Further, the crystalline copolymerized polyester (A) used in the present invention can be copolymerized or post-added with glycolic acid, lactones, lactides or (poly) carbonates, or can be post-added or copolymerized with acid anhydrides. .

The crystalline copolyester (A) used in the present invention is any one of a crystalline copolyester (A1) obtained by copolymerizing polyether segments or a crystalline copolyester (A2) obtained by copolymerizing polycarbonate segments. It is preferable to contain the above or to be a mixture of two kinds.

When the ether component is copolymerized with the crystalline copolymerized polyester (A1), characteristics such as low melt viscosity, high flexibility, and high adhesion can be imparted and the glass transition temperature can be lowered. Since the glass transition temperature greatly contributes to the thermal cycle characteristics, it is preferably −10 ° C. or lower, more preferably −20 ° C. or lower.
Examples of the ether component include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol. From the viewpoint of increasing flexibility, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, poly Polyethers such as tetramethylene glycol are preferred. Furthermore, polytetramethylene glycol is desirable from the viewpoint of enhancing crystallinity. The copolymerization ratio of the polyether component is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more when the crystalline copolymer polyester (A1) is 100% by mass. More preferably, it is particularly preferably 60% by mass or more. Moreover, it is preferable that it is 90 mass% or less, it is more preferable that it is 85 mass% or less, and it is still more preferable that it is 80 mass% or less. If the copolymerization ratio of the polyether component is too low, the melt viscosity becomes high and it tends to cause problems such as inability to mold at low pressure, or high crystallization speed and short shot. Moreover, when the copolymerization ratio of the polyether component is too high, problems such as insufficient heat resistance tend to occur. On the other hand, the number average molecular weight of the polyether component is preferably 400 or more, and more preferably 800 or more. If the number average molecular weight is too low, flexibility cannot be imparted, and the stress load on the electronic substrate after sealing tends to increase. Further, the number average molecular weight of the polyether component is preferably 5000 or less, and more preferably 4000 or less. If the number average molecular weight is too high, the compatibility with other components is poor, and there is a tendency to cause a problem that copolymerization is impossible.

On the other hand, the crystalline copolyester (A2) is desirably copolymerized with an aliphatic polycarbonate component. By having an aliphatic polycarbonate bond in the molecule, the heat resistance of the resin can be improved, characteristics such as low melt viscosity, high flexibility, and high adhesion can be exhibited, and further the glass transition temperature can be lowered. . Since the glass transition temperature greatly contributes to the thermal cycle characteristics, it is preferably −10 ° C. or lower, more preferably −20 ° C. or lower.
The aliphatic polycarbonate segment can be formed by copolymerizing an aliphatic polycarbonate component, typically an aliphatic polycarbonate diol. The copolymerization amount of the aliphatic polycarbonate component is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more, based on 100% by mass of the entire crystalline copolyester. It is particularly preferred. Further, it is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less. If the copolymerization ratio of the aliphatic polycarbonate component is too low, there is a tendency that the melt viscosity becomes high and a high pressure is required for molding, and a short shot is likely to occur because of a high crystallization speed. Moreover, when the copolymerization ratio is too high, there is a tendency to cause problems such as insufficient heat resistance. As the alkylene group constituting the aliphatic polycarbonate, a linear alkylene group having 4 to 16 carbon atoms is more preferable, and a longer-chain alkylene group tends to be excellent in durability against cold cycle load. Considering availability, it is preferably a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a nonamethylene group. Moreover, the copolymer type polycarbonate in which the alkylene group which comprises poly (alkylene carbonate) is 2 or more types of mixtures may be sufficient.
The crystalline copolyester in the present invention is a differential scanning calorimeter “DSC220 type” manufactured by Seiko Denshi Kogyo Co., Ltd., and 5 mg of a measurement sample is put in an aluminum pan and sealed with a lid once. Hold the sample at 5 ° C. for 5 minutes at a melting point of 210 ° C. or higher (melting point + 20 ° C.) and then rapidly cool with liquid nitrogen, then from −150 ° C. to 250 ° C. at 20 ° C./min. When measured at a rate of temperature increase, it indicates a melting point.

  In the resin composition of the present invention, when the content of the crystalline copolymer polyester (A) is 100 parts by mass, 5 to 50 parts by mass is the amorphous resin (B), and 5 to 50 parts by mass is the polyolefin. (C) is desirable. By blending these three types of components, it is possible to adjust the crystallization speed during sealing body manufacture and the crystallinity of the sealing resin composition, thereby reducing stress concentration during crystallization. And the adhesion strength to the substrate can be further increased.

  The resin composition used in the present invention preferably contains 5 to 50 parts by mass of the amorphous resin (B). The amorphous resin serves to disperse the polyolefin in the crystalline copolyester. The blending ratio of the amorphous resin is preferably 8 parts by mass or more and 48 parts by mass or less, and more preferably 10 parts by mass or more and 45 parts by mass or less. When the blending amount of the amorphous resin is too small, the dispersion of the olefin resin becomes poor, and when the blending amount is too large, the resin composition may become brittle.

  Examples of the amorphous resin (B) include amorphous copolymer polyester, epoxy resin, polyamide, olefin resin, polycarbonate, acrylic resin, ethylene vinyl acetate resin, phenol resin, xylene resin, and phenol-modified alkylbenzene resin. However, preferred amorphous resins include amorphous copolymer polyester (B1), epoxy resin (B2), and phenol-modified alkylbenzene resin (B3).

  Amorphous copolymer polyester (B1) is obtained by dehydration condensation or dealcoholization condensation of an acid component such as a dibasic acid or its anhydride or an alkyl ester and a glycol component in the same manner as the crystalline copolymer polyester (A). The same material as the above-mentioned crystalline copolyester can be used as a raw material, but for example, many raw materials having side chains such as neopentyl glycol and 1,2-propylene glycol are used so as not to have crystallinity, It is necessary to select raw materials that break linearity such as isophthalic acid and orthophthalic acid.

  The epoxy resin (B2) is preferably an epoxy resin having an average of at least 1.1 glycidyl groups in the molecule. 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. Among these, those having good compatibility with the crystalline copolyester resin (A) are particularly preferable in order to exhibit high adhesion. The preferred number average molecular weight of the epoxy resin (B2) 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 phenol-modified alkylbenzene resin (B3) is obtained by modifying an alkylbenzene resin with phenol and / or alkylphenol, and preferably has a number average molecular weight in the range of 450 to 40,000. For example, the phenol-modified alkylbenzene resin (B3) is prepared by reacting an alkylbenzene such as xylene or mesitylene with an aldehyde such as formaldehyde in the presence of an acidic catalyst to produce an alkylbenzene resin, which is then phenols in the presence of an acidic catalyst. And can be produced by reacting with aldehydes. The phenol-modified alkylbenzene resin (B3) is preferably an alkylphenol-modified xylene resin or an alkylphenol-modified mesitylene resin. A xylene resin is a multimer composition having a basic structure in which a xylene structure is crosslinked by a methylene group or an ether bond, and can be typically obtained by heating meta-xylene and formaldehyde in the presence of sulfuric acid. The mesitylene resin is a multimer composition having a basic structure in which the mesitylene structure is cross-linked by a methylene group or an ether bond. Typically, the mesitylene resin can be obtained by heating mesitylene and formaldehyde in the presence of sulfuric acid. Xylene resins and mesitylene resins are typical of alkylbenzene resins. The phenol-modified xylene resin of the present invention preferably has a hydroxyl value of 100 equivalents / 10 ⁶ g or more, more preferably 1000 equivalents / 10 ⁶ g or more, and even more preferably 5000 equivalents / 10 ⁶ g or more. . Also, preferably not more than 20000 equivalents / 10 ⁶ g, more preferably 15000 or less equivalent / 10 ⁶ g. If the hydroxyl value is too low, the adhesion to the aluminum material tends to be poor, and if the hydroxyl value is too high, the water absorption tends to increase and the insulating property tends to decrease. In addition, the hydroxyl value mentioned here is measured by JIS K1557-1: 2007A method.
Of these, those having good compatibility with the crystalline copolyester (A) are particularly preferable in order to exhibit high adhesion. In order to obtain a phenol-modified alkylbenzene resin (B3) having good compatibility with the crystalline copolyester (A), it is preferable that the melt viscosity is close and it has a hydroxyl group.

The resin composition used in the present invention preferably contains 5 to 50 parts by mass of polyolefin (C) when the content of the crystalline copolyester (A) is 100 parts by mass.
Examples of the polyolefin (C) include low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, general-purpose olefins such as high-density polyethylene and polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, An ethylene-propylene-butene copolymer, a polycycloolefin, etc. are mentioned. Further, unsaturated acids such as (meth) acrylic acid esters and (meth) acrylic acids, alkyl esters of unsaturated acids, vinyl acetate, ethylene, propylene, and α-olefin copolymerized can also be used.
As the polyolefin, it is preferable to use a low crystalline polyolefin. The low crystalline polyolefin tends to have a density lower than that of a general polyolefin, and preferably has a density of 0.75 g / cm ³ or more and less than 0.94 g / cm ³ . By using such a low crystalline and low density polyolefin, the polyolefin can be easily finely dispersed and mixed with the originally incompatible crystalline copolyester. A homogeneous resin composition can be obtained with an extruder. In addition, by using low-density polyolefin with low crystallinity, it also works properly to relieve the residual stress generated in the crystalline copolyester during injection molding over time, and as a sealing resin, it has long-term adhesion durability. It exhibits desirable characteristics such as application and reduction of stress generated by environmental load.

  Further, the polyolefin resin (C) may contain polar groups such as a carboxyl group and a glycidyl group.

  Furthermore, the polyolefin (C) of the present invention has a melt mass flow rate (hereinafter sometimes abbreviated as MFR) measured according to JIS K 7210-1999, Condition D (test temperature 190 ° C., nominal load 2.16 kg). It is preferable that it is 100 g / 10min. If the MFR is less than 5, the melt viscosity is too high, the compatibility with the crystalline copolyester may be reduced, and the adhesion may be impaired. If the MFR is 100 or more, the viscosity is low and the adhesive composition is extremely soft. It is easy to do and there exists a possibility that a mechanical physical property may be inferior.

  In the present invention, blending a polyolefin into a sealing resin composition exhibits excellent characteristics such as good initial adhesion and adhesion durability against environmental loads such as a cooling and heating cycle when sealing an electric / electronic component. The polyolefin is present in an island state in the resin composition, and is considered to play a role of relieving stress when the crystalline copolymerized polyester in the sea state undergoes crystallization shrinkage. The blending amount of the polyolefin (C) in the present invention is preferably 5 parts by mass or more and more preferably 10 parts by mass or more when the content of the crystalline copolyester (A) is 100 parts by mass. Preferably, it is 15 parts by mass or more. Moreover, it is preferable that it is 50 mass parts or less, It is more preferable that it is 45 mass parts or less, It is still more preferable that it is 40 mass parts or less. If the blending ratio of the polyolefin (C) is too low, it is difficult to relieve strain energy due to crystallization of the crystalline copolyester or enthalpy relaxation, so that the adhesion strength tends to decrease. Also, when the blending ratio of polyolefin (C) is too high, there is a tendency to deteriorate the adhesion and resin physical properties, and the crystalline copolyester and polyolefin cause macro phase separation and break elongation. In some cases, the moldability is adversely affected and the smoothness of the surface cannot be obtained.

  The resin composition used in the present invention preferably has a melt viscosity at 220 ° C. of 150 Pa · s or less from the viewpoint of moldability. The pressure is preferably 130 Pa · s or less, more preferably 120 Pa · s or less. If the melt viscosity exceeds 150 Pa · s, the melt viscosity becomes too high at a temperature that does not damage electrical and electronic parts, and in order to ensure good moldability, the temperature and pressure must be increased during molding, Damage to electrical and electronic parts. In order to reduce the melt viscosity to 150 Pa · s or less, it is important to lower the melt viscosity of the crystalline copolymer polyester (A) occupying the largest volume as the composition, and the melt viscosity of the crystalline copolymer polyester is 150 Pa · s. It is desirable that it is s or less.

  Moreover, it is preferable to add antioxidant to the resin composition of this invention. Preferred antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, amine antioxidants, etc., but one or more of these may be used in combination. can do. In particular, the combined use of a hindered phenolic antioxidant and another antioxidant is effective. Further, it is desirable to add a stabilizer such as a heat aging inhibitor, a copper damage inhibitor, an antistatic agent, a light resistance stabilizer, and an ultraviolet absorber. In particular, it is desirable to use a phenolic antioxidant containing a phosphorus atom in the molecule from the viewpoint of efficient radical capture.

  Examples of hindered phenolic antioxidants and stabilizers include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy). -2-methyl-5-tert-butylphenyl) butane, 1,1-bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3- (1,1-dimethylethyl) -4-hydroxy -5-methyl-benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propio Roxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl -4'-hydroxybenzyl) benzene, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, N, N'-hexane-1,6diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5,5 '5 "-hexa-tert-butyl-a, a', a"-(mesitylene-2,4,6triyl) tri-p-cresol, diethyl [[3,5-bis [1,1-dimethylethyl -4-hydroxyphenyl] methyl] phosphate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2'3-bis [[3- [3,5-di-ter-butyl-4- Hydroxyphenyl] propionyl]] propionohydrazide, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2 , 4-8,10-tetraoxaspiro [5 · 5] undecane and the like.

  Examples of phosphorus antioxidants and stabilizers include 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tri (monononylphenyl) phosphite, triphenoxyphosphine, isodecyl Phosphite, isodecylphenyl phosphite, diphenyl 2-ethylhexyl phosphite, dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5 t-butylphenyl) butane, tris (2,4-di-tert-butylphenyl) phosphite, pen Erythritol bis (2,4-di-tert-butylphenyl phosphite), 2,2′-methylene bis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite, bis [2,4-bis [1,1-dimethylethyl] -6-methylphenyl] ethyl ester phosphorous acid, 6- [3- (3-tert- Butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] -dioxaphosphine, tetrakis (2,4 -Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite, and the like.

Examples of sulfur-based antioxidants and stabilizers include 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-dodecylthiopropionate), bis (tridecyl) thiodipropionate, didodecyl -3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipropionate, 4,6-bis (octylthiomethyl) -o-cresol, 4,4-thiobis (3-methyl-6) -Tert-butylphenol) and the like.
4,4′-bis (α, α-dimethylbenzyl) diphenylamine and 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] as amine antioxidants and stabilizers ] Propionyl]] propionohydrazide, N, N′-di-2naphthyl-p-phenylenediamine, N-phenyl-N′-4,4′-thiobis (2-t-butyl-5-methylphenol), 2 , 2-bis [3- (dodecylthio) propanoyloxymethyl] -1,3-propanediol bis [3- (dodecylthio) propionate] and the like.

  The addition amount of the antioxidant is preferably 0.1% by weight or more and 5% by weight or less based on the entire resin composition. If it is less than 0.1% by weight, the effect of preventing thermal deterioration may be poor. If it exceeds 5% by weight, the adhesion may be adversely affected.

  The resin composition of the present invention may contain a filler such as talc or mica, a pigment such as carbon black or titanium oxide, a flame retardant such as antimony trioxide or brominated polystyrene, or a crystal nucleating agent.

  A tackifier such as rosin and terpene can be blended in the resin composition of the present invention, which may improve the adhesion. As a compounding quantity, less than 40 weight% of the whole resin composition is desirable.

  The sealing method of this invention can manufacture a sealing body, for example by arrange | positioning the board | substrate which mounted the electrical and electronic component in a metal mold | die, and extruding the molten body of the resin composition of this invention in a metal mold | die. . More specifically, for example, when a screw type hot melt applicator is used, the resin composition is heated and melted at 160 to 260 ° C., and the molten resin composition is extruded and injected into a mold through a nozzle. Then, after a predetermined cooling time, the melt of the composition is solidified, and then the molded product is removed from the mold to obtain an encapsulated electrical / electronic component.

  Although it does not specifically limit as an applicator apparatus for hot-melt shaping | molding processes, For example, Nordson ST2 and semi-automatic hot-melt uniaxial extrusion molding machine EMC-18F9 by Imoto Seisakusho etc. are mentioned as a screw type. A generally used injection molding machine can also be used, but care must be taken to keep the injection pressure low so as not to damage the electrical and electronic parts to be sealed.

  In the sealing method of the present invention, when an electric / electronic component is insert-molded, the resin composition is melted to 260 ° C. or less using a heated screw, and molded at a low pressure of 10 MPa or less to damage the electronic component. It is desirable in that it is difficult to give. More preferably, it is desirable to mold at 240 ° C. or less and 5 MPa or less.

  In the sealing method of the present invention, it is essential to subject the electric / electronic component to atmospheric pressure plasma treatment before insert molding the electric / electronic component. By performing atmospheric pressure plasma treatment, the adhesive strength between the base material and the resin composition, particularly the olefin base material and the resin composition, can be improved, and the reliability of waterproofness and electrical insulation can be improved. it can.

  As an atmospheric pressure plasma treatment method, glow discharge plasma or arc discharge plasma can be used, but glow discharge plasma is preferable in consideration of damage to electric and electronic parts.

  As glow discharge plasma, direct processing (a method in which the object to be processed is placed directly in the discharge space (between the electrodes) and direct plasma processing) and remote processing (a method in which the object to be processed is placed away from the discharge space (between the electrodes) There is a method of spraying active species generated in space), but remote processing is more preferable in consideration of damage to electric and electronic parts.

A rare gas such as argon or helium can be used as the atmosphere for the atmospheric pressure plasma treatment, or treatment in nitrogen or air is possible, but in consideration of running costs, treatment in nitrogen or air Is preferred.
On the other hand, in the treatment in air, since ozone is generated, treatment in nitrogen or an atmosphere in which oxygen is added to 5% by volume or less is preferable.

  Regarding the atmospheric pressure plasma treatment conditions, the optimum conditions differ depending on whether glow discharge plasma or arc discharge plasma is used, and whether direct treatment or remote treatment method is used. For example, remote treatment glow discharge manufactured by Sekisui Chemical Co., Ltd. When a plasma irradiator (AP-T05-S320 type) is used, the applied voltage is preferably 200 to 250V, and more preferably 220 to 240V. If the applied voltage is too high, the electrode may be destroyed, and if the applied voltage is too low, the treatment effect is lowered. The input power is preferably 750 to 850 W, and more preferably 780 to 820 W. If the input power is too high, the electrode may be destroyed, and if the input power is too low, the treatment effect is low. The treatment distance (distance between the head and the substrate) is preferably 1 to 20 mm, more preferably 1 to 10 mm, and even more preferably 1 to 6 mm. If the processing distance is too large, the processing effect is lowered. The processing speed is preferably 100 to 5000 mm / min, more preferably 100 to 2000 mm / min, and still more preferably 100 to 1000 mm / min. If the processing speed is too high, the processing effect is lowered. On the other hand, if the processing speed is slow, it takes time to perform processing, leading to an increase in cost. The number of times of processing is preferably 2 times or more. However, it should be noted that increasing the number of times of processing as well as the processing speed leads to an increase in cost.

<< Easy Adhesive Surface Treatment Method >>

<Atmospheric pressure plasma treatment>
-Machine stand: Sekisui Chemical Co., Ltd. atmospheric pressure plasma surface treatment equipment
AP-T05-S320 type (remote head type)
・ Applied voltage: 240V
・ Processing speed: 1000 mm / min ・ Gap: Between the highest part of the substrate to be treated and the electrode = 2 mm
・ Processing gas: Nitrogen gas 130L / min

(1) Cross-linked polyethylene-coated electric wire The PVC sheath of the cross-linked polyethylene-coated electric wire “600V CV” manufactured by Sumiden Hitachi Cable Co., Ltd. is peeled off to expose the cross-linked polyethylene-coated portion (6.3 mmφ) to a length of 50 mm. It cut and left still on a processing stand, and the surface of this bridge | crosslinking polyethylene covering electric wire was surface-treated once using the atmospheric pressure plasma processing machine. Next, the cross-linked polyethylene-coated electric wire was rotated 90 ° clockwise along the circumference and similarly surface-treated.
Furthermore, after rotating 90 degrees right and performing the process, it rotated 90 degrees right again and processed.
As a result, the surface of the cross-linked polyethylene-coated electric wire was surface-treated four times in total every 90 °.
(2) Polypropylene plate A commercially available polypropylene plate (manufactured by Mutual Riken Glass Co., Ltd., thickness: 2 mm) is cut into 20 mm × 100 mm, and left on a processing table, and the surface of the polypropylene plate is subjected to atmospheric pressure plasma treatment 1 I went twice.
(3) PBT plate In place of the polypropylene plate in (2) above, the surface treatment is performed in the same manner as in (2) above except that polybutylene terephthalate resin (EMC730 manufactured by Toyobo Co., Ltd.) containing 30% by mass of glass fiber is used. went.

<< Evaluation Method for Resin, Resin Composition and Molded Body >>

<Measurement of melt viscosity>
Using a flow tester CFT-500C manufactured by Shimadzu Corporation
Test temperature: 220 ° C
Preheating time: 180 seconds Test weight: 10 kgf
Die hole diameter: 1mm
Die length: 10mm
The melt viscosity when the resin composition was extruded was measured.

<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 220 ° C. for 5 minutes, and completely melt the sample. Then, it was quenched with liquid nitrogen, and then measured from -150 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min. The inflection point temperature of the obtained curve was the glass transition temperature, and the endothermic peak temperature was the melting point.

<Formability evaluation>
The cross-linked polyethylene-coated portion at one end of the cross-linked polyethylene-coated electric wire that has been subjected to atmospheric pressure plasma treatment by the above method has a molded diameter of 10 mm, a contact length between the electric wire and the molded resin of 20 mm, and a length of only the molded resin. The resin composition was molded so as to have a cylindrical shape with a length of 30 mm, and a sealed body sample was obtained. A schematic diagram of a sealed sample is shown in FIG. The resin composition was molded using a semi-automatic hot-melt single-screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd., the melting point of the crystalline copolymer polyester in the resin composition + 40 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, and a holding pressure. The pressure time was 10 seconds.
Evaluation criteria ○: Completely filled with no sink marks.
Δ: Filled without short shot, but there is a sink.
X: There is a short shot.

<Evaluation of adhesive strength>
(1) Pair-crosslinked polyethylene-coated electric wire Gripping A part and B part (see FIG. 1) of the sealed sample used for the above-described moldability evaluation, using Shimadzu Corporation tensile tester Autograph AG-IS By pulling up and down, the adhesive strength between the cross-linked polyethylene and the sealing resin composition was measured at a pulling rate of 50 mm / min in an environment of 23 ° C. and 60% Rh.
(2) Polypropylene plate Using semi-automatic hot melt uniaxial extrusion molding machine EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd. so that the resin thickness after molding on the treated surface of the polypropylene plate subjected to the above atmospheric pressure plasma treatment becomes 2 mm. Molding was performed at a melting point of the crystalline copolymer polyester in the resin composition + 40 ° C., a molding pressure of 3 MPa, a holding pressure of 3 MPa, and a holding time of 10 seconds. The 90 ° peel strength of the obtained sample was measured using a tensile tester Autograph AG-IS manufactured by Shimadzu Corporation under an environment of 23 ° C. and 60% Rh at a pulling rate of 50 mm / min.
(3) Anti-PBT plate A sample was prepared in the same manner as in (2) above, except that a polybutylene terephthalate resin containing 30% by mass of glass fiber (EMC730 manufactured by Toyobo Co., Ltd.) was used instead of the polypropylene plate in (2) above. Prepared and measured the adhesive strength.

<< Example >>
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.

Production Example of Crystalline Copolyester (a) 166 parts by mass of terephthalic acid, 180 parts by mass of 1,4-butylene glycol, and tetrabutyl titanate in a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation. 25 mass parts was added and esterification reaction was performed at 170-220 degreeC 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 hindered phenol antioxidant “Irganox 1330” (manufactured by BASF Japan Ltd.) While 0.5 part by mass was added and the temperature was raised to 245 ° C., the pressure in the system was slowly reduced to 665 Pa at 245 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 60 minutes to obtain a crystalline copolyester (a). The melting point of this crystalline copolyester (a) was 160 ° C., and the melt viscosity at 220 ° C. was 25 Pa · s. As a result of NMR analysis, the polyether content was 61% by mass.

Production Example of Crystalline Copolyester (b) In the same manner as in the above crystalline copolyester (a), a crystalline copolyester resin (b) was obtained by changing the acid component and the glycol component. The properties of the resin are shown in Table 1.

TPA: terephthalic acid NDCA: 1,6-naphthalenedicarboxylic acid BD: 1,4-butylene glycol PTMG1000: polytetramethylene glycol (number average molecular weight 1000)
PTMG2000: polytetramethylene glycol (number average molecular weight 2000)

Production Example of Crystalline Copolyester (c) <Synthesis Example of PBT>
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow cooler, 88 parts by mass of terephthalic acid, 70 parts by mass of 1,4-butylene glycol and 0.1 part by mass of tetrabutyl titanate were added, and 170-220 ° C. for 1 hour. An esterification reaction was performed. Subsequently, while the temperature of the reaction system was raised from 220 ° C. to 250 ° C., the pressure inside the system was slowly reduced to 500 Pa over 70 minutes. Further, a polycondensation reaction was performed at 130 Pa or less for 70 minutes to obtain PBT. The number average molecular weight of the obtained PBT was 20000.
<Synthesis example of aliphatic polycarbonate diol>
100 parts by mass of polyhexamethylene carbonate diol (Duranol T6002, manufactured by Asahi Kasei Chemicals Co., Ltd., molecular weight 2000) and 9.6 parts by mass of diphenyl carbonate were respectively charged in a reaction vessel and reacted at a temperature of 205 ° C. and 130 Pa. After 2 hours, the contents were cooled to obtain an aliphatic polycarbonate diol. The number average molecular weight of the obtained polycarbonate diol was 13,000.
<Synthesis Example of Crystalline Copolyester (c)>
After mixing 100 parts by mass of the polybutylene terephthalate (PBT) and 150 parts by mass of the aliphatic polycarbonate diol, stirring at 230 ° C. to 245 ° C. and 130 Pa for 1 hour, and confirming that the mixture became transparent, The contents were taken out and cooled after stirring at normal pressure for 10 minutes under a nitrogen stream. The melting point of the obtained resin was 200 ° C., and as a result of NMR analysis, the polycarbonate ratio was 60% by mass.

Production Example of Amorphous Copolyester (d) 83 parts by mass of terephthalic acid, 83 parts by mass of isophthalic acid, 50 parts by mass of ethylene glycol, neopentyl, in a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation. 83 parts by mass of glycol and 0.25 parts by mass of tetrabutyl titanate were added, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, the temperature was raised to 230 ° C., while the pressure in the system was slowly reduced to 665 Pa at 230 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain an amorphous polyester resin (D). The amorphous polyester resin (d) had a glass transition point of 60 ° C., a melt viscosity at 220 ° C. of 2 Pa · s, and no melting point was observed.

Production Example 1 of Resin Composition
As a crystalline copolymer polyester, 100 parts by mass of a crystalline copolymer polyester (a), 10 parts by mass of an amorphous copolymer polyester (d) as an amorphous resin, and Polypropylene Novatec manufactured by Nippon Polypro Co., Ltd. as a polyolefin 20 parts by mass of PP BC08F, 0.5 parts by mass of IRGANOX 1010 manufactured by BASF Japan KK as an antioxidant, 0.5 parts by mass of Sumilizer GP manufactured by Sumitomo Chemical Co., Ltd., carbon manufactured by Dainichi Seika Kogyo Co., Ltd. Resin composition 1 was obtained by adding 0.5 mass part of black masterbatch PP-RM MK1510 and melt-kneading at 195 degreeC using a twin-screw extruder.

Production Examples of Resin Compositions 2 to 5 Resin compositions 2 to 5 were obtained in the same manner as in Production Example of Resin Composition 1 according to the combinations in Table 2. The melt kneading temperature was the melting point of the crystalline copolymer polyester used + 30 ° C.

Polyolefin P1: Novatec PP BC08F (Nippon Polypro Co., Ltd. polypropylene)
P2: Excellen VL EUL731 (Special ethylene elastomer manufactured by Sumitomo Chemical Co., Ltd.)
Epoxy resin: JER1007 (Bisphenol type epoxy resin manufactured by Mitsubishi Chemical Corporation)
Stabilizer, etc. I-1010: IRGANOX 1010 (manufactured by BASF Japan Ltd.)
S-GP: Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)
Colorant MK1510: PP-RM MK1510 (carbon black masterbatch manufactured by Dainichi Seika Kogyo Co., Ltd.)

Example 1
Using the resin composition 1 as the resin composition for sealing, using a semi-automatic hot-melt single-screw extruder EMC-18F9 manufactured by Imoto Seisakusho Co., Ltd. When the moldability was evaluated, it was good with no shorts or sink marks. Next, the adhesive strength between the crosslinked polyethylene of the sample subjected to the moldability evaluation and the resin composition was measured and found to be 150N. Similarly, Table 3 shows the results of measuring the adhesion strength to a base material made of polypropylene and PBT that has been previously subjected to atmospheric pressure plasma treatment.

Examples 2-5
Table 3 shows the results of measuring moldability and adhesive strength in the same manner as in Example 1 using resin compositions 2 to 5 as the sealing resin composition.

Comparative Examples 1-5
Table 3 shows the results obtained by measuring the formability and adhesive strength of the crosslinked polyethylene-coated electric wire, polypropylene, and PBT that were not subjected to any surface treatment (not subjected to atmospheric pressure plasma treatment) in the same manner as in the Examples.

Comparative Examples 6-10
The formability and adhesive strength of crosslinked polyethylene-coated electric wires, polypropylene, and PBT subjected to UV irradiation as an easy-adhesion surface treatment were measured in the same manner as in the examples. The results are shown in Table 3.
UV irradiation conditions Machine stand: GS Yuasa Corporation
UV SYSTEM KCCT88
Processing conditions: 1000 mJ / cm ²

Examples 1 to 5 satisfy the scope of the claims, and are excellent in moldability and adhesive strength to cross-linked polyethylene, polypropylene, and PBT.
In addition, the system (Examples 1-3) which mix | blended the amorphous resin and polyolefin as a resin composition was compared with the system (Examples 4 and 5) which did not mix | blend these, but the adhesive strength with respect to crosslinked polyethylene and propylene Is high.
On the other hand, all of Comparative Examples 1 to 5 which have not been subjected to any easy-adhesion surface treatment have low adhesion strength to crosslinked polyethylene and propylene. Moreover, the adhesive strength with respect to crosslinked polyethylene and a polypropylene is low like Comparative Examples 1-5 which performed UV irradiation as easy-adhesion surface treatment, as well as Comparative Examples 1-5 which did not perform easy-adhesion surface treatment.
From these points, it can be seen that by combining the resin composition used in the present invention and the atmospheric pressure plasma treatment, the adhesive strength to olefins such as crosslinked polyethylene and propylene is drastically improved.

  The method for sealing electrical and electronic parts using the resin composition resin composition of the present invention is extremely effective for improving the adhesive strength to crosslinked polyethylene, polypropylene, etc., and waterproof and dustproof electrical and electronic parts having complicated shapes. It is useful as a molding material. The sealing method and the sealing body of the present invention are useful as sealing molding resins for, for example, various connectors for automobiles, communication, computers, home appliances, harnesses or electronic components, printed circuit boards, sensors, and the like. .

11: Conductive wire 12: Cross-linked polyethylene coating 13: Sealing resin composition

Claims (11)

  Using a resin composition containing, as a main component, a crystalline copolyester (A) having a glass transition temperature of 0 ° C. or lower and a melting point of 120 ° C. or higher and 240 ° C. or lower, a pressure of 20 MPa or lower and 260 ° C. or lower An electrical and electronic component sealing method, wherein the electrical and electronic component is preliminarily subjected to atmospheric pressure plasma treatment as an easy-adhesion surface treatment when insert sealing molding is performed at a temperature of 5 ° C.   The crystalline copolymer polyester (A) contains at least one of a crystalline copolymer polyester (A1) obtained by copolymerizing a polyether segment or a crystalline copolymer polyester (A2) obtained by copolymerization of a polycarbonate segment. The method for sealing electrical and electronic parts according to claim 1, wherein:   The method for sealing an electric / electronic component according to claim 2, wherein the polyether segment copolymerized with the crystalline copolymerized polyester (A1) is 50% by mass or more of the crystalline copolymerized polyester. The method for sealing an electrical / electronic component according to claim 2, wherein the polycarbonate segment copolymerized with the crystalline copolymerized polyester (A2) is 50% by mass or more of the crystalline copolymerized polyester.   When the resin composition has a content of the crystalline copolymer polyester (A) of 100 parts by mass, 5 to 50 parts by mass is the amorphous resin (B), and 5 to 50 parts by mass is polyolefin ( It is C), The sealing method of the electric and electronic components in any one of Claims 1-4 characterized by the above-mentioned. The amorphous resin (B) contains at least one of amorphous copolymer polyester (B1), epoxy resin (B2), and phenol-modified alkylbenzene resin (B3). Item 6. A method for sealing an electric / electronic component according to any one of Items 1 to 5. The method for sealing an electric / electronic component according to claim 1, wherein the resin composition has a melt viscosity at 220 ° C. of 150 Pa · s or less.   The method for sealing an electric / electronic component according to claim 1, wherein the atmospheric pressure plasma treatment is an atmospheric pressure glow discharge plasma treatment.   9. The method for sealing electrical and electronic parts according to claim 8, wherein the atmospheric pressure glow discharge plasma treatment is a remote atmospheric pressure glow discharge plasma treatment.   10. The method for sealing an electric / electronic component according to claim 8, wherein the atmospheric pressure plasma treatment is performed in a nitrogen atmosphere having an oxygen concentration of 5% by volume or less.   The sealing body sealed by the method in any one of Claims 1-10.