JP4622303B2 - Method for producing laminated molded product and laminated molded product - Google Patents

Description

  The production method of the present invention is suitable for, for example, a hot melt molding method. The product manufactured by the manufacturing method of the present invention is suitable for, for example, electrical and electronic parts for waterproofing.

  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, in applications where it is necessary to pack complicated electrical and electronic parts in a small capacity such as a cellular phone, various methods are employed for electrical insulation. In particular, when a resin or the like serving as an electrical insulator is molded into a component having a complicated shape such as a circuit board, a method capable of following the shape is required. For this purpose, a method of reducing the viscosity of the resin during coating is common. A method in which a resin is dissolved in a solvent in advance and impregnated into an electric and electronic component, and then the solvent is evaporated is one of the methods for reducing the viscosity, but when the solvent evaporates, bubbles remain, If an organic solvent is used as the solvent, there are many problems such as a poor working environment.

  So far, two-component epoxy resins have been generally used as proposed in many documents in consideration of durability after resin injection (see, for example, Patent Documents 1 and 2). . In this method, the main agent and the curing agent are mixed at a certain ratio immediately before molding, molded at a low viscosity, heated and stored for several days to accelerate the curing reaction and completely solidify. However, in this method, the adverse effect on the environment is being pointed out by the epoxy resin, it is necessary to precisely adjust the mixing ratio of the two liquids, the usable period before mixing is limited to as short as 1 to 2 months, etc. The problems are known. In addition, since curing requires a curing period of several days, there is also a problem of low productivity. Furthermore, there is a problem that stress due to resin shrinkage after curing concentrates on a weak physical strength part such as a solder part for joining an electric / electronic component and a conductive wire, and the part peels off.

  A hot melt type resin can be used as an injection resin in place of the two-component epoxy resin that has been used with such problems. A hot melt adhesive that only heats and melts the resin in order to reduce the viscosity at the time of injection solves the problems in the working environment of the solvent-containing system and the epoxy resin system. Moreover, since it solidifies only by cooling after injection | pouring and expresses performance, productivity also becomes high. In addition, since a thermoplastic resin is generally used, it is possible to easily recycle the member by heating and melting and removing the resin even after the end of the product life. However, the reason why it has not been a material that can sufficiently replace the two-part epoxy resin while having a high potential as an injection resin is that no suitable material has been proposed.

  For example, ethylene vinyl acetate (EVA), which is relatively inexpensive as a hot melt, has insufficient heat resistance and does not have durability in an environment where electric and electronic parts are used. Therefore, the electrical performance may be deteriorated due to contamination of electrical and electronic parts, which is not suitable. Polyamide that expresses high adhesion to various materials as a single resin is excellent as an injecting resin material due to its low melt viscosity and high resin strength (see, for example, Patent Document 3), but is basically hygroscopic. It is high, and the electrical insulation, which is the most important characteristic, often decreases with time by gradually absorbing moisture from the outside.

  On the other hand, polyester having both high electrical insulation and water resistance is considered to be a very useful material for this application. For example, Patent Document 4 discloses that a polyester having a low melt viscosity and a high strength and elongation is excellent in mold applications. However, polyester resin is excellent in adhesiveness to PVC, etc., but is inferior in adhesiveness to glass epoxy substrates, so that in applications where all dissimilar materials are molded, water can penetrate between the substrate and the resin as a waterproofing application. When the thermal shock test was performed, there was a problem that the electrical insulation was gradually lost.

  As described above, in the prior art, there has not been proposed a manufacturing method that has a complicated shape, in particular, an electric / electronic component made of a different material is injected with resin and sufficiently satisfies various performances.

JP-A-1-75517 ([Claims] and others) JP 2000-239349 A ([Claims] and others) European Patent No. 1052595 (pages 6-8, [Claims] and others) JP 2003-176341 A ([Claims] and others)

  The present invention has been made to solve the above problems, and the object of the present invention is to provide waterproof / electrical insulation / working environment / productivity / durability, etc. for electrical and electronic parts having complicated shapes. It is an object of the present invention to provide a production method and its molded product that sufficiently satisfy various performances.

  In order to achieve the above object, the present inventors have intensively studied and have proposed the following invention. That is, this invention is the manufacturing method shown below and its molded article.

(1) A method for producing a laminated molded product, wherein an electric / electronic component is wrapped with a resin (A) and further wrapped with a resin (B).

(2) In the method for producing a laminated molded article according to (1), the resin (A) and the resin (B) are injected into a mold at a pressure of 10 to 800 N / cm ² . Production method.

(3) The resin (A) has a melt viscosity at 200 ° C. of 2 dPa · s or more and less than 100 dPa · s, and the resin (B) has a melt viscosity at 200 ° C. of 100 dPa · s or more and less than 1000 dPa · s. The method for producing a laminated molded article according to (1) or (2).

(4) The method for producing a laminated molded product according to any one of (1) to (3), wherein the resin (A) is polyamide and the resin (B) is polyester.

(5) The method for producing a laminated molded article according to (4), wherein dimer acid or hydrogenated dimer acid is copolymerized as an acid component of polyamide.

(6) The method for producing a laminated molded article according to (4) or (5), wherein polyether glycol is copolymerized as a diol component of the polyester.

(7) A laminated molded product produced by the method according to any one of (1) to (6).

  INDUSTRIAL APPLICABILITY The present invention can provide a manufacturing method and a molded product that sufficiently satisfy various performances such as waterproofness, electrical insulation, work environment, productivity, and durability for electric and electronic parts having complicated shapes. For example, it is useful as a molded product of a switch or a sensor having various connectors, harnesses or electronic components, printed circuit boards for automobiles, communications, computers, and home appliances.

“Mold” or “molding” as used in the present invention is a molding method in which a molten resin is injected at 10 to 800 N / cm ² , and is an average of about 4000 N / cm ² that is conventionally used for molding plastics. Compared with injection molding at high pressure, this molding method is performed at a very low pressure. The specific molding method is to inject molten resin into a mold with electric and electronic parts set, and to seal or wrap the parts in order to destroy the sensitive parts. It can be molded without any problems.

  The manufacturing method of the present invention is formed by pouring into a mold in which electric and electronic parts are set. More specifically, the resin (A) is first heated and melted at around 130 to 220 ° C., poured into a mold, and after a certain cooling time, the molded product is removed from the mold, for example, into another mold. The molded product is set, the resin (B) is heated and melted at around 130 to 220 ° C., poured into a mold, and after a certain cooling time, the molded product is removed from the mold to obtain a molded product.

  By manufacturing a molded product with such a manufacturing method, it is possible to give good durability and sufficiently satisfy various performances such as waterproofness, electrical insulation, work environment, productivity and durability. It is possible to provide an electric / electronic component molded body.

  The equipment for producing the molded product is not particularly limited, and examples thereof include Mold-man 8000 manufactured by Cavist, USA, WS102 / MX3006 manufactured by Nordson, Germany, and Dynamelt series manufactured by ITW Dynatec, USA.

The resin (A) in the present invention preferably has a melt viscosity at 200 ° C. of 2 dPa · s or more and less than 100 dPa · s. When the melt viscosity is 100 dPa · s or higher, relatively high pressure is required for injecting the resin into a complicated shape, which may cause component destruction. By using a resin having a melt viscosity of less than 100 dPa · s, preferably less than 50 dPa · s, a molded article having excellent electrical insulation can be obtained at a relatively low pressure of several hundred N / cm ^2. The characteristics of electronic components are not impaired. Further, the melt viscosity at 200 ° C. is preferably low, but considering the adhesiveness and cohesive force of the resin, the lower limit is preferably 2 dPa · s or more, more preferably 5 dPa · s or more, more preferably 10 dPa · s or more. Preferably there is.

The resin (B) in the present invention preferably has a melt viscosity at 200 ° C. of 100 dPa · s or more and less than 1000 dPa · s. When the melt viscosity is higher than 1000 dPa · s, high resin cohesive strength and durability can be obtained. However, since a considerably high pressure is required, the parts are destroyed despite being protected by the resin (A). May occur. By using a resin having a melt viscosity of less than 1000 dPa · s, preferably less than 500 dPa · s, a molded article having excellent electrical insulation can be obtained at a relatively low pressure of several hundred N / cm ^2. The characteristics of electronic components are not impaired. The melt viscosity at 200 ° C. is preferably low, but the resin that comes to the outermost shell needs the mechanical strength, impact resistance, and cohesive strength of the resin, and considering these, the lower limit is 100 dPa · s or more. Desirably, more preferably 200 dPa · s or more, and more preferably 500 dPa · s or more.

Here, the melt viscosity at 200 ° C. is a value measured as follows. Using a sample dried to a moisture content of 0.1% or less, a resin heated and stabilized at 200 ° C. with a flow tester (model No. CFT-500C) manufactured by Shimadzu Corporation, and having a thickness of 10 mm having a pore diameter of 1.0 mm The viscosity when passing through a die of 98 N / cm ² is measured.

  The type of resin used in the present invention is not particularly limited in both (A) and (B), but it is preferable to use polyolefin, polyamide, or polyester.

(A) Polyamide, (B) Polyamide (A) Polyamide, (B) Polyolefin (A) Polyamide, (B) Polyester (A) Polyester, (B) Polyamide (A) Polyester, (B) Polyolefin (A ) Polyester, (B) Polyester (A) Polyolefin, (B) Polyamide (A) Polyolefin, (B) Polyester (A) Polyolefin, and (B) Polyolefin are preferred in order to exert the effect.

  Since the adhesion / adhesion characteristics differ depending on the type of component mounted on the electric / electronic component and the type of resin, it is preferable to use the combination as appropriate.

  For example, when a covered electric wire such as polypropylene or polyethylene is mounted on an electric / electronic component, it is preferable to use polyolefin or polyamide in (A). Moreover, when a polyvinyl chloride coated wire is mounted, it is preferable to use polyamide or polyester. In view of the cohesive strength of the resin, polyamide is particularly preferred.

  For example, when electrical and electronic parts are required to have durability such as chemical resistance and water resistance, particularly when there is a possibility of contact with gasoline or alcohol chemicals, it is preferable to use polyester for (B). Polyester is particularly preferred in view of general chemical resistance.

  In the case where a polyamide resin is used in the present invention, examples of the dicarboxylic acids include acids having 2 to 22 carbon atoms, specifically, dimer acid, hydrogenated dimer acid, oxalic acid, malonic acid, (anhydrous). Succinic acid, (anhydrous) maleic acid, glutaric acid, adipic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 1,3- or 1,4-cyclohexane Examples include dicarboxylic acid, 1,18-octadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to contain dimer acid, hydrogenated dimer acid, and sebacic acid in an amount of 20 to 90 mol% of the acid component. In particular, dimer acid or hydrogenated dimer acid containing 40 to 90 mol% of the acid component is preferable for achieving both water resistance and adhesiveness.

  Although it does not restrict | limit especially as a dimer acid, After superposing | polymerizing tall oil fatty acid, beef tallow fatty acid, soybean oil fatty acid, etc., the polymeric fatty acid etc. which are obtained by removing a monomeric acid by distillation are mentioned. Examples of commercially available products include “Prepol 1013” manufactured by Unikema Corporation and “DA-200” manufactured by Harima Chemicals. These may be used alone or in combination of two or more.

  Although it does not specifically limit as hydrogenated dimer acid, As an acid component at the time of obtaining polyamide, it is good also considering dimer acid at least partially hydrogenated beforehand as a raw material, or said dimer acid and organic amine. After polymerization, the resulting polymer may be hydrogenated.

  Examples of the dimer acid that has been previously hydrogenated include commercially available products such as “Pripole 1009” manufactured by Unikema Co., “Enpol 1008” manufactured by Cognis. Further, dimer acid that has not been hydrogenated may be used by hydrogenation.

  Moreover, you may use together monocarboxylic acid as a raw material as a structural unit derived from an acid component as needed. Examples thereof include acids having 1 to 26 carbon atoms. Specifically, for example, propionic acid, acetic acid, caprylic acid (octanoic acid), stearic acid, oleic acid, rosin (resin acid), benzoic acid, naphthoic acid Etc. These may be used alone or in combination of two or more.

  In addition, examples of the diamine used in the polyamide in the present invention include various diamines having 2 to 20 carbon atoms, such as aliphatic, alicyclic, and aromatic. Ethylenediamine, 1,3-propanediamine, 1,2-diaminopropane, menthanediamine, isophoronediamine, tetraethylenediamine, hexamethylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-methylenebis (cyclohexylamine), Examples include isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,4-bis- (2′-aminoethyl) benzene, piperazine, and N-ethylaminopiperazine. . Among these, those containing 10 to 90 mol% of ethylenediamine, hexamethylenediamine and piperazine in the diamine component are particularly preferable from the viewpoint of heat resistance. These may be used alone or in combination of two or more.

  Further, in order to mold the polyamide without causing thermal degradation as much as possible, rapid melting at about 210 ° C. is required, so the upper limit of the softening point is preferably 200 ° C. Preferably it is 190 degreeC, More preferably, it is 180 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, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, particularly preferably 140 ° C. or higher, and most preferably 150 ° C. or higher.

  Lowering the glass transition temperature improves the thermal cycle durability, so this is a more preferable measure when durability after resin injection is important. The term “cooling cycle durability” as used herein refers to the performance of raising or lowering the temperature between a high temperature and a low temperature many times so that the resin does not peel off or crack at the interface with electronic components having different linear expansion coefficients. . When the elastic modulus of the resin increases during cooling, peeling and cracking are likely to occur. In order to provide a material that can withstand the cooling and heating cycle, the glass transition temperature is preferably 20 ° C. or lower. More preferably, it is 5 degrees C or less, More preferably, it is -10 degrees C or less, Most preferably, it is -20 degrees C or less. Although a minimum is not specifically limited, -100 degreeC or more is realistic when adhesiveness and blocking resistance are considered.

  When the polyester resin is used in the present invention, the dicarboxylic acid and / or its ester-forming derivative may be terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′. -Diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,2-cyclohexanedicarboxylic acid, oxalic acid, dodecanedioic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dicarboxylic acid such as dimer acid and / or ester-forming derivatives thereof. These may be used alone or in combination of two or more. From the viewpoint of improving durability, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferably used, and preferably 60 mol% or more of the total dicarboxylic acid component. Is preferably at least 70 mol%, particularly preferably at least 80 mol%.

  Examples of the aliphatic diol and / or ester-forming derivative thereof used in the polyester of the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,2-butane. Diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol 2,2,4-trimethyl-1,3-pentanediol, cyclohexanedimethanol, neopentylhydroxypivalate, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogenated bisphenol A ethylene oxide Adducts and propylene oxide adducts, 1,9-nonanediol, 2-methyloctanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecane dimethanol, poly Examples include ether glycol and ester derivatives thereof. These may be used alone or in combination of two or more.

  Among the above aliphatic diols, it is preferable to use polyether glycol in order to improve the thermal cycle durability described later. The polyether glycol is preferably 1 mol% or more of the total glycol component in the polyester resin, more preferably 5 mol%, more preferably 10 mol%, and most preferably 20 mol% or more. If it is less than 1 mol%, the low temperature characteristics may be inferior. The upper limit is 80 mol% or less, preferably 70 mol% or less, more preferably 60 mol% or less in consideration of handling properties such as heat resistance and blocking.

  Polyether glycols include polyethylene glycol, polypropylene glycol, poly 1,2-propylene glycol, poly 2-methyl-1,3-propylene glycol, poly (tetramethylene glycol-neopentyl glycol) copolymer, ethylene oxide and propylene oxide. Examples thereof include a block or random copolymer, a random copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, and a block or random copolymer of ethylene oxide and tetrahydrofuran. These may be used alone or in combination of two or more.

  The number average molecular weight of the polyether 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, Preferably it is 4000, Most preferably, it is 3000. When the number average molecular weight of the polyether 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.

  Further, in order to mold without causing thermal degradation of the polyester as much as possible, rapid melting at about 210 ° C. is required, so the upper limit of the softening point is preferably 200 ° C. Preferably it is 190 degreeC, More preferably, it is 180 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, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, particularly preferably 140 ° C. or higher, and most preferably 150 ° C. or higher.

  Lowering the glass transition temperature improves the thermal cycle durability, so this is a more preferable measure when durability after resin injection is important. The term “cooling cycle durability” as used herein refers to the performance of raising or lowering the temperature between a high temperature and a low temperature many times so that the resin does not peel off or crack at the interface with electronic components having different linear expansion coefficients. . When the elastic modulus of the resin increases during cooling, peeling and cracking are likely to occur. In order to provide a material that can withstand the cooling and heating cycle, the glass transition temperature is preferably 20 ° C. or lower. More preferably, it is 5 degrees C or less, More preferably, it is -10 degrees C or less, Most preferably, it is -20 degrees C or less. Although a minimum is not specifically limited, -100 degreeC or more is realistic when adhesiveness and blocking resistance are considered.

  As the polyester resin in the present invention, a mixture of two or more kinds of polyester resins may be used, and in particular, a polyester resin in which the above range is allowed is preferable.

  Furthermore, you may add antioxidant to resin (A) and (B) in this invention. Examples include hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, amine antioxidants, and the like. These may be used alone or in combination of two or more. The addition amount is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the resin. If it is less than 0.1 parts by weight, the effect of preventing thermal deterioration may be poor. If it exceeds 5 parts by weight, the adhesion may be adversely affected.

  Examples of hindered phenolic antioxidants that can be blended in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di. -T-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6 '-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-tert-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-dioxy t-butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, triphenol, 2, 2'-ethylidenebis (4,6-di-t-butylphenol), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2 ' -Oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (3 ', 5'-di-t-butyl-4'-hydroxy Ben ) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic ahydr triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. These may be used alone or in combination of two or more.

  Examples of the sulfur-based antioxidant that can be blended in the present invention include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodiuropionate, and distearyl-3,3′-thiodipropionate. Lauryl stearyl-3,3′-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol-tetra (β-lauryl-thiopropionate) ester, and the like. These may be used alone or in combination of two or more.

  Examples of the phosphorus-based antioxidant that can be blended in the present invention include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4′-butylidene- Bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) butane, Tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphanite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phospha Tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene diphosphonite, triphenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite , Trioctadecyl phosphite, trinonyl phenyl phosphite, tridodecyl trithiophosphite and the like. These may be used alone or in combination of two or more.

  Examples of amine antioxidants that can be blended in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, and phenothiazine. N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine, N, N′-bis (1,4-dimethyl- Pentyl) -p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, amines such as 4,4′-bis (4-α, α-dimethyl-benzyl) diphenylamine and their derivatives, and amines and aldehydes Reaction product, reaction product of amine and ketone It can be mentioned from things. These may be used alone or in combination of two or more.

  Further, a light stabilizer may be added to the resin in the present invention. Examples include hindered amine, benzophenone, benzotriazole, triazole, nickel, and salicyl light stabilizers, and these may be used alone or in combination of two or more. The addition amount is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the resin. If it is less than 0.1 parts by weight, the weather resistance may be poor. If it exceeds 5 parts by weight, the adhesion may be adversely affected.

  Examples of the hindered amine light stabilizer that can be blended in the present invention include polycondensates with dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine oxalate, poly [[ 6- (1,1,3,3-tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imyl] Bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1, 2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4- Piperidyl) Polycondensation product of Samethylenediamine and 1,2-dibromoethane, poly [(N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4-monophorino -1,3,5-triazine-2,6-diyl) -bis (3,3,5,5-tetramitylpiperazinone)], tris (2,2,6,6-tetramethyl-4-piperidyl) ) -Dodecyl-1,2,3,4-butanetetracarboxylate, tris (1,2,2,6,6-pentamethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6 , 6-Pentamethylpiperidine-4- L) amino-1,3,5-triazin-2-yl) amino} undecane, 1- [2- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 , 6-Tetromethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6- And pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate. These may be used alone or in combination of two or more.

  Examples of the benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers that can be blended in the present invention include 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, p-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2- (2′-hydroxy-3 ′, 5′-di-t-amyl-phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzylphenyl) Benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobena Zotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzothiazole, 2,5-bis- [5′-t-butylbenzoxazolyl- (2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphoric acid monoethyl ester) nickel salt, 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid-bis A mixture of 85-90% anilide and 10-15% 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyl oxalic acid-bis-anilide, 2- [2-hydroxy-3 , 5-Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2′-ethyloxazalic acid bisanilide, 2- [2′-hydroxy-5 '-Methyl-3'-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxy Examples include light stabilizers such as benzophenone and phenyl salicylate. These may be used alone or in combination of two or more.

  Further, a flame retardant may be added to the resin in the present invention. For example, triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis (2,6-xylenyl) phosphate, 2-ethylhexyl Phosphate, dimethylmethyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate Phosphorus flame retardants such as phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus, ammonium polyphosphate, phosphazene, cyclophosphazene, triazine, Nitrogen flame retardants such as mincyanurate, succinoguanamine, ethylene dimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, melam sulfate Metal salt flame retardant such as potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide imide metal salt, polystyrene sulfonate alkali metal salt, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, Hydrated metal flame retardants such as basic magnesium carbonate, zirconium hydroxide, tin hydroxide, silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide , Cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, etc. Inorganic flame retardant, silicone flame retardant such as silicone powder, tetrabromobisphenol A (TBA), tetrabromobisphenol S (TBS), bis (dibromopropyl) tetrabromobisphenol A ether, TBA epoxy, TBA ethyl ether oligomer, TBA Bis (2,3-dibromopropyl ether), TBA (allyl ether), TBA bis (2-hydroxyethyl ether), TBA carbonate oligomer, TBS bis (2,3-dibromopropyl ether), hexabro Benzene, tetrabromophthalic anhydride, decabromodiphenyl oxide, tris (tribromophenoxy) triazine, bis (pentabromophenyl) ethane, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane, brominated phenoxy, ethylenebis Examples include flame retardants having a halogen-substituted phenyl group such as (tetrabromophthal) imide, brominated diphenyl oxide, and brominated polystyrene. These may be used alone or in combination of two or more. The addition amount is preferably 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin. If it is less than 1 part by weight, the flame retardancy is inferior, and if it exceeds 50 parts by weight, the adhesion may be adversely affected.

  You may mix | blend pigments, such as fillers, such as talc, clay, mica, asbestos, glass fiber, montmorillonite, aluminum nitride, and mica, carbon black, and titanium oxide with the resin in this invention.

  Examples of the molded product in the present invention include examples, but the present invention is not limited to the examples. For example, automobiles, ships, airplanes, communications, computers, various sensors for home appliances, control units, connectors, harnesses, or molded products of printed circuit boards on which electronic components are mounted.

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

  The softening point was measured with an automatic softening point measuring instrument manufactured by Meitec Co., Ltd. at a temperature rising rate of 5 ° C./min.

  Glass transition temperature: Using a differential scanning calorimeter “DSC220 type” manufactured by Seiko Denshi Kogyo Co., Ltd., put 5 mg of measurement sample into an aluminum pan, seal with a lid, hold once at 250 ° C. for 5 minutes, and remove the sample. After being completely melted, it was quenched with liquid nitrogen and then measured from −150 ° C. to 250 ° C. at a temperature increase rate of 20 ° C./min. The inflection point of the obtained curve was taken as the glass transition temperature.

  Melt viscosity: Made of Shimadzu Corporation, flow tester (CFT-500C type), a resin sample dried to a moisture content of 0.1% or less was charged into a cylinder at the center of a heated body set at 200 ° C., and 1 minute elapsed after filling. After that, a load (98 N) was applied to the sample through the plunger, the molten sample was pushed out from the die (hole diameter: 1.0 mm, thickness: 10 mm) at the bottom of the cylinder, and the distance and time of descent of the plunger were recorded. The melt viscosity was calculated.

[Production example of polyamide resin]
In a reaction vessel equipped with a stirrer, a thermometer, a condenser for distillation, and a nitrogen introduction tube, 400 parts by weight of hydrogenated dimer acid “Prepol 1013” (manufactured by Unikema), 61 parts by weight of sebacic acid, 42 parts by weight of ethylenediamine, 22 parts by weight of 1,2-diaminopropane was added, the temperature was raised to 230 ° C. over 2 hours, 3 parts by weight of hindered phenol antioxidant “Irganox 1010” (manufactured by Ciba Geigy) was added, and polyamide ( a) was obtained. The polyamide (a) had a softening point of 160 ° C. and a melt viscosity of 25 dPa · s.

  The polyamide resins (b) and (c) were synthesized by the same method as the polyamide resin (a). The respective compositions and physical property values are shown in Table 1.

[Production example of polyester resin]
166 parts by weight of terephthalic acid, 180 parts by weight of 1,4-butanediol, and 0.25 parts by weight of tetrabutyl titanate were added to a reaction vessel equipped with a stirrer, a thermometer, and a condenser for distillation. The esterification reaction was performed for 2 hours. After completion of the esterification reaction, 300 parts by weight of polytetramethylene glycol “PTMG1000” (manufactured by Mitsubishi Chemical Corporation) having a number average molecular weight of 1000 and 0.5% of hindered phenol antioxidant “Irganox 1330” (manufactured by Ciba Geigy Corporation) are added. While adding parts by weight, the temperature was raised to 255 ° C., while the pressure in the system was slowly reduced to 665 Pa at 255 ° C. over 60 minutes. Further, a polycondensation reaction was performed at 133 Pa or less for 30 minutes to obtain a polyester (a). The softening point of this polyester (a) was 173 ° C., and the melt viscosity was 100 dPa · s.

  The polyester resins (b) to (e) were synthesized by the same method as the polyester resin (a). The respective compositions and physical property values are shown in Table 2.

Abbreviations in the table are as follows.
PTMG1000: polytetramethylene glycol (number average molecular weight 1000, manufactured by Mitsubishi Chemical Corporation), PTMG2000: polytetramethylene glycol (number average molecular weight 2000, manufactured by Mitsubishi Chemical Corporation)

[Example 1]
Using the polyamide resin and the polyester resin produced as described above, a laminate molded product was produced with the combinations shown in Table 3. The resin was melted in advance, and an applicator “WS102 / MX3006” manufactured by Nordson was used.

  When manufacturing the laminated molded product, a 20 mm × 15 mm circuit board soldered with two PVC lead wires was used as an electrical / electronic component for protection. For injection of the resin (A), an aluminum mold (I) for resin injection having an inner size of 25 mm × 20 mm × 5 mm was used. For the injection of the resin (B), an aluminum mold (II) for resin injection having an inner size of 30 mm × 25 mm × 10 mm was used.

  After injecting the resin, the molded product was released without any shape defect, and the state of molding on the circuit board was observed, and the continuity test of the board components was performed. As a result, durability tests such as waterproofness were performed on the molded articles having good results by the following method.

(1) Waterproofness The molded product was immersed in water, and the retention rate of circuit resistance was measured. It shows that it is suitable as an insulating material of an electric / electronic component, so that a retention rate is large.
(2) The sample was left for 100 hours and 500 hours at 80 ° C. and 95% RH at high temperature and high humidity, and the retention rate of the circuit resistance was measured.
(3) Gasoline resistance It was immersed in regular gasoline at 50 ° C. for 1 hour, 24 hours, and 100 hours, and appearance shape confirmation and circuit resistance retention were measured.
(4) Thermal shock resistance thermal shock tester “TSE-11” (manufactured by Espec Corp.) was used, (a) “0 ° C. × 1 hour⇔80 ° C. × 1 hour”, (b) “−40 ° C. × 1” Three cycles of 1000 cycles of “time ⇔100 ° C. × 1 hour” and (c) “−60 ° C. × 1 hour⇔120 ° C. × 1 hour” were performed, and appearance shape confirmation and circuit resistance retention were measured.
These results are summarized in Table 3.

Example 2-7], [Comparative Example 1-5]
Molding was performed in the same manner as in Example 1 and evaluated. However, when only one kind of resin was used as a comparative example, the mold (I) was not used, and the resin was injected only with the mold (II). The results are also shown in Table 3.

  As is apparent from Table 3, it can be seen that the laminated molded product of the resin (A) and the resin (B) produced by the method of the present invention has excellent characteristics in high temperature and high humidity, gasoline resistance, and thermal shock resistance.

  INDUSTRIAL APPLICABILITY The present invention can provide a manufacturing method and a molded product that sufficiently satisfy various performances such as waterproofness, electrical insulation, work environment, productivity, and durability for electric and electronic parts having complicated shapes. For example, it is useful as a molded product of a switch or a sensor having various connectors, harnesses or electronic components, printed circuit boards for automobiles, communications, computers, and home appliances.

Claims (9)

The electrical / electronic component is encapsulated with a polyamide resin (A) having a melt viscosity at 200 ° C. of 2 dPa · s or more and less than 50 dPa · s and copolymerizing dimer acid or hydrogenated dimer acid as an acid component. A method for producing a laminated molded article, wherein the melt viscosity at 200 ° C. is 200 dPa · s or more and less than 1000 dPa · s, and is encapsulated with a polyester resin (B) copolymerized with polyether glycol as a diol component . 2. The method for producing a laminated molded product according to claim 1, wherein the resin (A) and the resin (B) are injected into the mold at a pressure of 10 to 800 N / cm < ² >.   The method for producing a laminated molded article according to claim 1 or 2, wherein the polyamide resin (A) contains dimer acid or hydrogenated dimer acid in an amount of 40 to 90 mol% of the acid component.   The manufacturing method of the laminated molded product in any one of Claims 1-3 in which the said polyamide resin (A) contains 10-90 mol% of diamine components with ethylenediamine, hexamethylenediamine, and piperazine.   The method for producing a laminated molded article according to any one of claims 1 to 4, wherein the polyester resin (B) contains terephthalic acid, isophthalic acid, and 2,6-naphthalenecarboxylic acid in an amount of 80 mol% or more of the total dicarboxylic acid component.   The method for producing a laminated molded product according to any one of claims 1 to 5, wherein the polyester resin (B) contains polyether glycol in an amount of 1 mol% to 80 mol% of all glycol components.   The method for producing a laminated molded article according to any one of claims 1 to 6, wherein the polyamide resin (A) has a softening point of 70C to 200C and a glass transition temperature of -100C to 20C.   The method for producing a laminated molded article according to any one of claims 1 to 7, wherein the polyester resin (B) has a softening point of 70C to 200C and a glass transition temperature of -100C to 20C. Laminated molded article was prepared by the method of any of claims 1-8.