JPH05132569A - Method for bonding molded plastic article and method for sealing electric or electronic part with resin - Google Patents

Abstract

PURPOSE:To improve adhesive strength in bonding molded engineering plastc article to each other or the article to another substance with an adhesive and to improve adhesive strength in sealing an electric or electronic part in a case with a resin. CONSTITUTION:At least one surface-modifying agent selected from the group consisting of an org. epoxy compd., a silane coupling agent, and a titanate coupling agent is deposited at least on the surface to be bonded of a molded glassfiber-contg. engineering plastic article. The surface is then irradiated with ultraviolet rays mainly comprising rays having a wavelength of 300nm or lower, and bonded to another adherend with an adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adhering an engineering plastic molded product and a resin sealing method for electric / electronic parts.

[0002]

2. Description of the Related Art Engineering plastics are classified into general-purpose engineering plastics and super engineering plastics. These materials are used in various fields because of their high mechanical strength. Molded products obtained from engineering plastics include injection molded products, hollow molded products, compression molded products, extrusion molded products (films, sheets, pipes, profile extruded products, extrusion coated products) and the like. Some of these engineering plastic molded products (hereinafter, also simply referred to as molded products) have excellent adhesiveness depending on their types, but in general, it is difficult to bond them with an adhesive. Therefore, when adhering these molded products with a large adhesive strength, appropriate pretreatment is required, and conventionally, sandblast treatment, chromic acid mixture treatment, flame treatment,
Corona discharge treatment, plasma treatment, surface functional group addition treatment,
Surface photografting treatment and the like have been used or studied, but none of them is a satisfactory method. On the other hand, in order to embed and fix electrical / electronic components and other embedded components in the plastic in the plastic case,
BACKGROUND ART A resin sealing method (potting) for electric / electronic components in which a resin in a fluid state is cured and adhered to an inner wall surface of a case in a case accommodating those components is widely used. Even in such a method, many studies have been conducted on how to improve the adhesive strength between the cured resin and the inner wall surface of the plastic case, but satisfactory results have not yet been obtained.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for adhering an engineering plastic molded article with sufficient adhesive strength and simply and without causing a safe pollution problem, a plastic case and a cured resin. It is an object of the present invention to provide a resin sealing method for electric / electronic components for increasing the adhesive strength between the two.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that glass fiber-containing engineering plastic moldings generally have an organic epoxy compound or a silane cup on the surface thereof. It has been found that the presence of a ring agent or a titanate coupling agent, and the surface of the ring agent or the titanate coupling agent, which has been subjected to ultraviolet irradiation treatment, can be adhered with a significantly improved adhesive force by adhering. It has also been found that certain types of specific engineering plastic moldings can be bonded with sufficient adhesive force only by UV irradiation treatment. Furthermore, an organic epoxy compound, a silane coupling agent or a titanate coupling agent is present on the inner wall surface of a case made of glass fiber-containing engineering plastics, and the surface of the case is subjected to ultraviolet irradiation treatment to make a resin for electrical and electronic parts. It has been found that the sealing can improve the adhesive strength between the inner wall surface of the case and the cured resin. Further, it has been found that when a case formed of a certain specific engineering plastic is used, the case and the cured resin can be bonded with sufficient adhesive force only by the ultraviolet irradiation treatment. The present invention has been made based on the above findings.

That is, according to the present invention, when an engineering plastic molded article containing glass fibers is adhered to each other or to another substance, as the molded article, an organic epoxy compound, a silane coupling agent and a titanate coupling are used. Using at least one surface modifier selected from the above-mentioned agents on its surface, and irradiating the surface of the molded product with ultraviolet rays having a wavelength of 300 nm or less as a main wavelength component, the adhesive agent There is provided a method for adhering an engineering plastic molded article, which is characterized by adhering by

According to the present invention, nylon 6, nylon 6,6, nylon 4,6, polyphenylene ether (including modified polyphenylene ether), polyetherimide, polycyclohexanedimethyl terephthalate,
When a molded article of an engineering plastic selected from polysulfone, polyallylsulfone, polyethersulfone and polyetheretherketone is adhered to each other or to another substance, 300
Irradiate ultraviolet rays whose main wavelength component is a wavelength of nm or less,
Provided is a method for adhering an engineering plastic molded article, which comprises adhering with an adhesive.

Further, according to the present invention, in a method of curing a resin in a fluid state in a plastic case accommodating electric / electronic parts and adhering it to the inner wall surface of the plastic case, the plastic case contains glass fiber. At least one selected from organic epoxy compounds, silane coupling agents and titanate coupling agents.
Electricity characterized by using a kind of surface modifier present on at least the inner wall surface and irradiating the inner wall surface with ultraviolet rays having a wavelength of 300 nm or less as a main wavelength component.
A method of resin sealing an electronic component is provided.

Further, according to the present invention, in a method of curing a resin in a fluid state in a plastic case accommodating electric / electronic parts and adhering the resin to the inner wall surface of the plastic case, nylon 6 is used as the plastic case. , Nylon 6,6, nylon 4,6, polyphenylene ether (including modified polyphenylene ether), polyarylate, polyetherimide, polycyclohexanedimethyl terephthalate, polysulfone,
An engineering plastic selected from polyallylsulfone, polyethersulfone, and polyetheretherketone, characterized in that the inner wall surface is irradiated with ultraviolet rays having a wavelength of 300 nm or less as a main wavelength component Provided is a resin sealing method for electric / electronic parts.

The engineering plastics used in the present invention include polyamide, (PA) (nylon), polyacetal (POM), polycarbonate (PC),
In addition to general-purpose engineering plastics such as polyphenylene ether (including modified polyphenylene ether), polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and ultra high molecular weight polyethylene,
Polysulfone (PSF), Polyethersulfone (PE
S), polyphenylene sulfide, polyarylate (U polymer), polyamideimide, polyetherketone (PEK), polyetheretherketone (PEE)
K), polyimide (PI), super engineering plastics such as liquid crystal polyester, and ABS /
Examples include polymer alloys containing the above engineering plastics such as polycarbonate, polyphenylene ether / nylon 6,6, polyphenylene ether / polystyrene, polybutylene terephthalate / polycarbonate.

In the present invention, a surface modification selected from an organic epoxy compound, a silane coupling agent and a titanate coupling agent is present on at least the surface of the engineering plastic molded article containing glass fiber. As a method for this, (i) a method of mixing a surface modifier into the raw material plastic, (ii) a method of mixing a filler in which the surface modifier is preliminarily supported into the raw material plastic, (iii) molding There is a method of coating the surface of the product with a surface modifier. The content of glass fiber is 5 to 50% by weight, preferably 10 to 40% by weight.
Is.

As the organic epoxy compound, a conventionally known liquid or solid compound having one or a plurality of epoxy groups in the molecule at ordinary temperature is used. Such organic epoxy compounds include various glycidyl ether compounds and glycidyl ester compounds.

As the silane coupling agent, polar groups such as epoxy group, carboxyl group, ester group, acid anhydride group, amino group, halogen (chlorine, bromine, iodine, etc.),
Examples thereof include those containing a vinyl group, a hydroxyl group and the like. These silane coupling agents are well known in the art. Examples of preferable silane coupling agents used in the present invention include those represented by the following general formula. XR-Si (OR ¹ ) ₃ (1) In the above formula, XR- represents a vinyl group, an amino group, an alkylamino group, an epoxyalkyloxy group, an acryloxy group,
A polar group such as a methacryloxy group is shown. On the other hand, the —OR ¹ group represents an alkoxy group such as a methoxy group, an ethoxy group and a 2-methoxyethoxy group.

On the other hand, specific examples of the titanate coupling agent include, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetra Octyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene tatinate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) Examples include phosphite titanate.

As the filler which carries the surface modifier,
Various conventionally known granular, flat plate, scale, needle, spherical, hollow and fibrous materials are used. Specifically, calcium carbonate, magnesium carbonate, calcium sulfate, calcium silicate, magnesium hydroxide, aluminum hydroxide, clay, diatomaceous earth, talc, alumina, silica, glass powder, iron oxide, metal powder, graphite, silicon carbide. , Silicon nitrogen, boron nitride, aluminum nitride, carbon black, wollastonite, mica, sericite, bilophyllite, metal flakes, graphite, shirasu balloon, perlite, glass fiber, carbon fiber, whiskers, metal fiber, silicon car A bite fiber etc. can be illustrated.

The surface modifier loaded on the filler is the content of the surface modifier contained in the filler, and is usually 0.5 to 30.
% By weight. When the surface modifier is mixed in the plastic, the addition amount is 0.1-2 in the plastic.
It is 0% by weight. When a surface modifier is coated on the surface of a molded article, the surface modifier is dissolved in a solvent that dissolves it, for example, water, ethyl alcohol, acetone, toluene, dimethylformamide, dimethyl sulfoxide, dioxane, etc. to form a solution. The surface of the molded body may be coated with this solution. Further, as a solvent for dissolving the surface modifier, an ultraviolet absorbing solvent described later is particularly preferable. As a coating method, a spray method, a roll coating method, a dipping method, or the like is appropriately used depending on the shape of the molded product. Among the molded products used in the present invention, especially nylon 6, nylon 6,6, nylon 4,
6, polyphenylene ether (including modified polyphenylene ether), polyarylate, polyetherimide,
The one selected from polycyclohexane dimethyl terephthalate, polysulfone, polyallyl sulfone, polyether sulfone and polyether ether ketone is
It has been found that the adhesive can be adhered with a sufficient adhesive force only by the irradiation of ultraviolet rays without the surface modifier treatment. As a matter of course, it is desirable that these molded articles also contain glass fibers or have a surface modifier present on at least the surface thereof in order to further improve the adhesiveness thereof.

The adhesive used in the present invention is basically a curable adhesive, and epoxy, polyurethane and reactive acrylic adhesives are particularly preferable. The epoxy adhesive is mainly composed of an epoxy resin and a curing agent, preferably an amine compound. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin. , Alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, prom-containing epoxy resin, hydrogenated bisphenol A epoxy resin, propylene glycol glycidyl ether, pentaerythritol polyglycidyl ether, etc. Examples thereof include aliphatic epoxy resins and urethane-modified epoxy resins, and these epoxy resins may be used as a mixture of two or more kinds. If necessary, a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and aliphatic alcohol glycidyl ether may be added to reduce the viscosity.

As the amine compound which is a preferable curing agent used in the epoxy resin, for example, aliphatic amines such as diethylenetriamine, triethylenetetramine and diethylaminopropylamine; mensendiamine,
Aliphatic polyamines such as isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine; Aliphatic polyamines containing aromatic rings such as metaxylenediamine; Third
Polyethyleneimine having a primary amine nitrogen in one molecule;
Aromatic polyamines such as metaphenylenediamine, methylenedianiline, and diaminodiphenylsulfone; the above-mentioned aliphatic polyamines, aliphatic polyamines containing aromatic rings, polyamine compounds such as aromatic polyamines, etc., by known modification methods, for example, epoxy compounds Modified polyamines formed by the addition reaction of styrene, Michael addition reaction with acrylonitrile, acrylic acid ester, Mannich reaction with a methylol compound, and the like; 2-methylimidazole, 2
-Ethyl-4 methylimidazole, 1-cyanoethyl-
An imidazole compound such as 2-methylimidazole;
Tertiary amines such as trisdimethylaminophenol;
Examples thereof include tri-2-ethylhexyl acid salt of trisdimethylaminomethylphenol. In addition, commercially available versamide (manufactured by Henken Hakusui), tomide (manufactured by Fuji Kagaku Kogyo), sunmide (manufactured by Sanwa Chemical Industry), laccamide (manufactured by Dainippon Ink and Chemicals), which is mainly produced by the condensation reaction of dimer acid and polyamine. Polyamide polyamine known under the trade name of Further, general-purpose latent curing agents such as dicyandiamide, adipic acid dihydrazide, and isophthalic acid dihydrazide, and those curable at 70 to 80 ° C., for example, JP-A-60-4524 and JP-A-62-26523, It is also possible to use the latent curing agent shown in Kaihei 1-254731.

With respect to the epoxy resin, in addition to the above main components, if necessary, an inorganic filler such as silica,
Powders such as quartz glass, mica, calcium carbonate, alumina, talc, clay, graphite and carbon black can also be added. Furthermore, in order to improve the curability, known curing accelerators such as phenol, nonylphenol, salicylic acid, and triphenylphosphite can be used. The polyurethane adhesive used in the present invention contains an isocyanate component and a polyol component as basic components, and if necessary, auxiliary components such as a catalyst, a stabilizer, a pigment, a filler, and a tackifier are mixed.

The isocyanate component includes aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and modified products thereof. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, and examples of the alicyclic isocyanate include isophorone diisocyanate. Examples of aromatic isocyanates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) thiophosphate. Examples of the modified isocyanate include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate, trimer, and isophorone diisocyanate trimer.

Examples of the polyol component include low molecular weight polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and trimethylolpropane; polyethylene glycol, polypropylene glycol, polytetra Polyether polyols such as methylene glycol and ethylene oxide / propylene oxide copolymers; polycaprolactone, poly β-methyl-δ-butyrolactone, polyesters from diols and dibasic acids, and the like. Other examples include hydroxyl group-containing liquid polybutadiene, castor oil, polycarbonate diol, and acrylic polyol. As auxiliary components, coupling agents such as silane coupling agents and titanium coupling agents; tackifiers such as terpene resins, phenol resins, terpenes, rosin resins and xylene resins; calcium carbonate,
Examples include fillers and thixotropic agents such as clay, titanium oxide, carbon black, and Aerosil; stabilizers such as ultraviolet absorbers, antioxidants, heat resistance stabilizers, and hydrolysis resistance stabilizers. In the present invention, the urethane-based adhesive can be used in either one-component type or two-component type. Also,
The curing type includes a reaction type by mixing two liquids, a moisture curing type, and a heat curing type.

The reactive acrylic adhesive used in the present invention is a liquid adhesive containing an acrylic monomer or oligomer as a main component, and is hardened by anionic polymerization, radical polymerization or redox polymerization upon adhesion. Various types of reactive acrylic adhesives have been known in the past, for example, an anionic polymerization type instant adhesive containing 2-cyanoacrylic acid ester as a main component,
Redox polymerization type acrylic adhesives (SGA) containing methacrylic acid ester as a main component, radical polymerization type ultraviolet curing adhesives containing polyfunctional acrylic acid ester and polyfunctional methacrylic acid ester as a main component by UV irradiation are available. Can be mentioned.

In the present invention, the surface of the molded product is irradiated with ultraviolet rays prior to the bonding work, but in this case, the irradiation light is
It is a special ultraviolet ray having an irradiation wavelength in the region of 300 nm or less. The action of ultraviolet rays on a molded product varies depending on the wavelength, and a shorter wavelength is more effective. Therefore, 300n
It is desirable that the light energy with a wavelength of m or less, preferably with a wavelength shorter than 254 nm, occupy 85% or more of the total energy, and further, ultraviolet light having a working wavelength near 185 nm is preferable. Therefore, the material of the ultraviolet irradiation lamp is preferably one having a high transmittance of ultraviolet rays having a short wavelength, and synthetic quartz glass having a higher purity than that of naturally occurring quartz glass is preferable. When the surface of the molded product is irradiated with ultraviolet rays, the distance between the molded product and the lamp is about 1 to 50 cm, more preferably 5 to 30 c.
A range of m is preferred. If the irradiation distance is 1 cm or less, the surface of the molded product may be chemically deteriorated due to excessive irradiation. If this distance is 50 cm or more, the irradiation strength may be insufficient and sufficient adhesive force may not be obtained. Irradiation time is arbitrary, but if it is too short, sufficient adhesion may not be obtained, and if it is too long (especially when irradiation distance is short), it may cause excessive irradiation and cause deterioration. Therefore, about 20 seconds to 5 minutes is a realistic processing time.

In the present invention, before applying the adhesive,
The surface of the molded product is usually treated with an alcohol-based or mineral-oil-based solvent for the purpose of degreasing, cleaning, etc. It is possible to obtain excellent adhesive strength. As the organic solvent used, one having an ultraviolet absorbing property is preferable. This ultraviolet absorbing solvent may be one in which the solvent itself has an ultraviolet absorbing structure in the dispenser, or one in which an additive having an ultraviolet absorbing structure is dissolved in the solvent. Examples of the former include aromatic hydrocarbon solvents such as benzene, toluene, xylene, decalin and tetralin, carbon tetrachloride, trichloroethylene, tetrachloroethylene, chloroform, trichloroethane, tetrachloroethane, trichlorotrifluoroethane, bromine. There are halogenated hydrocarbon solvents such as benzene and dichlorobenzene, and acrylic acid ester solvents.Examples of the latter include photosensitization of acetophenone derivatives, benzophenone derivatives, benzoin derivatives, diazonium salt derivatives, etc. There are solvents such as aromatic hydrocarbons, halogenated hydrocarbons, acrylic acid esters, and acrylamide in which a sensitizer is dissolved.

As a method of bringing the organic solvent into contact with the surface of the molded article, there are a dipping method, a spraying method, a coating method, and the like.
Further, when the molded product and the solvent are brought into contact with each other, ultrasonic waves can be applied to accelerate the sorption of the solvent on the surface of the molded product. When the solvent is brought into contact with the solvent in the present invention, the solvent may be at room temperature, but the effect is enhanced by heating it. The heating temperature is preferably as high as possible, but if heated excessively, volatilization and evaporation will become severe, so about 30 to 80 ° C. is recommended. Another preferred method for contacting with the solvent is to heat the molded article itself. This makes it possible to minimize the volatilization and evaporation of the solvent. The heating temperature of the molded product is also preferably higher, but if it is too high, the molded product may be deformed or melted.
C. is preferable. Time to contact with solvent is 5 seconds to 20
Minutes, preferably 10 seconds to 5 minutes. If it is 5 seconds or less, a substantial solvent treatment effect cannot be expected, and even if it is contacted for 20 minutes or more, the effect is not improved and it is economically disadvantageous. The method of applying the adhesive to the molded product in the present invention is not limited, and various conventionally known methods are appropriately selected according to the shape of the molded product. As such a coating method, a brush coating method, a spray method,
An immersion method, a roll coating method and the like can be mentioned.

In the resin encapsulation method of the present invention, a plastic case made of glass fiber-containing engineering plastic, in which a surface modifier is present on at least the inner wall surface, and the inner wall surface is irradiated with ultraviolet rays, is used.
Examples of the engineering plastic include the above-mentioned various plastics.

As a method of allowing the surface modifier to be present on the inner wall surface of the case, (i) a method of mixing the surface modifier with the raw material plastic, as in the case of the method for adhering the molded article, (ii) There are a method of mixing a raw material plastic with a filler carrying a surface modifier in advance, and (iii) a method of coating the surface of the case with the surface modifier. Further, as a specific method of irradiating the inside of the case with ultraviolet rays, the method described above can be adopted. Furthermore, before irradiation with ultraviolet rays, the inner wall surface of the case is usually treated with an alcohol-based or mineral oil-based solvent or the like for the purpose of degreasing, cleaning, etc. As in the case, it is preferable to treat with an ultraviolet absorbing organic solvent. Furthermore, in the case of the above-mentioned specific engineering plastic, the mixing of glass fiber and the use of the surface modifier can be omitted.

As the resin to be injected into the case, various conventionally known thermosetting resins are used, but epoxy resin, polyurethane resin and reactive acrylic resin are preferable.

[0028]

Industrial Applicability As described above, the present invention is a method of surface-treating an engineering plastic molded product by using a special ultraviolet ray and adhering it with an adhesive. An engineering plastic having a low surface activity, which has been conventionally difficult to adhere to. It is simple and safe for molded products, does not cause pollution problems,
It is possible to bond various materials at a low cost with a strong adhesive force, and to provide an industrially effective bonding method. The molded articles to be the subject of the present invention include injection molded articles, hollow molded articles, compression molded articles, extrusion molded articles (films, sheets,
Pipes, profile extrusion products, extrusion coated products, etc. are included, and the molded products are widely used for industrial materials such as automobile parts and electric parts, as well as building materials, packaging materials, household products, office supplies and the like. Further, in the present invention, the material of the other side of the engineering plastic molded product may be the same type of engineering plastic, and may also be a polyolefin resin molded product, polyurethane or phenol resin, ABS resin, AS resin, aluminum,
Films or plates of metal or alloys such as copper, iron, stainless steel, zinc, etc. or their processed products, or molded products;
Examples include various ceramic molded products, cloth, fibers, paper, wood, and the like.

Further, in the sealed product obtained by the resin sealing method for electric / electronic parts of the present invention, the adhesive strength between the surface of the inner wall of the plastic case and the cured resin inside the case is improved, At the time of use, it is possible to effectively prevent interfacial peeling between the inner surface of the case and the cured resin.

[0030]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. In addition, all parts and% shown below are based on weight.

Example 1 Nylon 4,6 sheet (3.0 × 12.0 × 100 m)
m) was immersed in a solution obtained by dissolving 5 parts of a silane coupling agent in 95 parts of ethanol and then dried at 80 ° C. for 20 minutes to obtain nylon 4,6 coated with the silane coupling agent on the surface. Got a sheet of. As the silane coupling agent, one having the following structural formula was used. Next, this sheet is placed under an ultraviolet irradiation lamp (PL11-1102WS / SUV-41H manufactured by Sen Special Light Source Co., Ltd.), the distance between the light source and the sheet is set to 70 mm, and the irradiation intensity is set to 15 mW / cm ² . Irradiate for 90 seconds. Next, an adhesive was applied to the irradiated sheet, and the two sheets were stuck together with an overlap of 7 mm, pressed as a clip, and heat-treated at 80 ° C. for 1 hour. As the epoxy resin, a two-component epoxy resin adhesive [Araldite AV138 / HV998 manufactured by Nagase Ciba Co., Ltd.
Mixture (weight mixing ratio = 100/40)] was used. The tensile shear adhesive strength at 25 ° C. of the test piece obtained as described above was measured, and the results are shown in Table 1. In addition,
The tensile shear bond strength was measured using an Instron universal tester under the conditions of a crosshead speed of 5 mm / min.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the surface treatment of the silane coupling agent was not performed. The results are shown in Table 1.
Shown in. Example 3 An experiment was conducted in the same manner as in Example 1 except that the nylon 4,6 sheet containing 30% of silane-coupled glass fiber was used. The results are shown in Table 1. Example 4 An experiment was performed in the same manner as in Example 3, except that the surface treatment of the silane coupling agent was not performed. The results are shown in Table 1.
Shown in.

[0033]

[Table 1]

Example 5 An experiment was carried out in the same manner as in Example 1 except that the surface treatment of the silane coupling agent was not carried out and the ultraviolet irradiation time was variously changed. The results are shown in Table 2. Example 6 An experiment was performed in the same manner as in Example 3, except that the surface treatment of the silane coupling agent was not performed and the ultraviolet irradiation time was variously changed. The results are shown in Table 2.

[0035]

[Table 2]

Example 7 In Example 1, except that a sheet of polycyclohexanedimethylene terephthalate was used in place of the sheet of nylon 4,6, the surface treatment of the silane coupling agent was not performed, and the irradiation time was variously changed. Conducted an experiment in the same manner. The results are shown in Table 3.

[0037]

[Table 3]

Example 8 A sample having the same dimensions as in Example 1 was prepared from various engineering plastic sheets, and the tensile shear bond strength was measured in the same manner as in Example 1 using this sample. The results are shown in Table 4. In this case, the same ultraviolet lamp as in Example 1 was used, and the conditions for ultraviolet irradiation were: irradiation distance 70 mm, irradiation time 90 seconds, irradiation intensity 15
mW / cm ² was adopted. In Table 4, the plastic marked with * contains 30% of glass fiber treated with a silane coupling agent.

[0039]

[Table 4- (1)]

[0040]

[Table 4- (2)]

Example 9 An experiment was conducted in the same manner as in Example 8 except that the engineering plastics shown in Table 5 were used. However, in this case, UVR-200F / UVB-200F manufactured by Sen Special Light Source Co., Ltd. was used as the ultraviolet lamp, and the irradiation conditions were an irradiation distance of 27 mm, an irradiation time of 90 seconds, and an irradiation intensity of 15 mW / cm ² . The results are shown in Table 5. In Table 5, the plastic marked with * contains 30% by weight of glass fiber treated with a silane coupling agent.

[0042]

[Table 5]

Example 10 In Example 1, nylon 4,6 containing 30% of glass fiber surface-treated with a silane coupling agent was used, and a titanate coupling agent (inpropyltriisostearoyl) was used instead of the silane coupling agent. The same experiment was performed except that titanate) was used. The tensile shear bond strength in this case was 105 kg / cm ² . Example 11 An experiment was performed in the same manner as in Example 10, except that inpropyl tris (dioctyl pyrophosphate) titanate) was used as the titanate coupling agent. In this case, the tensile shear bond strength is 110 kg / cm.
^{Was 2} . Example 12 In Example 10, as a titanate coupling agent, tetraoctyl bis (ditridecyl phosphite) was used.
The same experiment was performed except that titanate) was used.
The tensile shear bond strength in this case was 100 kg / cm ² .

Example 13 A 5% methyl ethyl ketone solution of an organic epoxy compound (butanediol diglycidyl ether) was applied to the surface of a sheet of nylon 4,6 (3.0 × 12.0 × 100 mm) containing 30% of glass fiber. After applying thinly, 80 ℃
And dried for 2 minutes. Next, this nylon 4,6 sheet was treated with an ultraviolet lamp (PL11-11 manufactured by Sen Special Light Source Co., Ltd.).
02WS / SUV-41H), the distance between the light source and the sheet is 70 mm, and the irradiation intensity is 5.0 mW / cm ^2.
Irradiation was performed for 90 seconds under the above condition. Next, using this irradiation sheet, the tensile shear strength was measured in the same manner as in Example 1, and a result of 131 kg / cm ² was obtained.

Example 14 An experiment was conducted in the same manner as in Example 13 except that phenylglycidyl ether was used as the organic epoxy compound. The tensile shear strength in this case is 120 kg / c
It was m ² . Example 15 In Example 13, as the organic epoxy compound, 2-
The experiment was conducted in the same manner except that ethylhexyl glycidyl ether was used. The tensile shear strength in this case is 12
It was 5 kg / cm ² . Example 16 An experiment was conducted in the same manner as in Example 13 except that the silane coupling agent shown in Example 1 was used instead of the organic epoxy compound. The tensile shear strength in this case is 1
It was 26 kg / cm ² .

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[Procedure amendment]

[Submission date] June 5, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that glass fiber-containing engineering plastic moldings generally have an organic epoxy compound or a silane cup on the surface thereof. It has been found that the presence of a ring agent or a titanate coupling agent, and the surface of the ring agent or the titanate coupling agent, which has been subjected to ultraviolet irradiation treatment, can be adhered with a significantly improved adhesive force by adhering. It has also been found that certain types of specific engineering plastic moldings can be bonded with sufficient adhesive force only by UV irradiation treatment. Furthermore, an organic epoxy compound, a silane coupling agent or a titanate coupling agent is present on the inner wall surface of a case made of glass fiber-containing engineering plastics, and the surface of the case is subjected to ultraviolet irradiation treatment to make a resin for electrical and electronic parts. It has been found that the sealing can improve the adhesive strength between the inner wall surface of the case and the cured resin. Further, it has been found that when a case molded of a certain kind of specific engineering plastic is used, the case and the cured resin can be bonded with sufficient adhesive force only by the ultraviolet irradiation treatment. The present invention has been made based on the above findings.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

Example 13 A 5% methyl ethyl ketone solution of an organic epoxy compound (butanediol diglycidyl ether) was applied to the surface of a sheet of nylon 4,6 (3.0 × 12.0 × 100 mm) containing 30% of glass fiber. After applying thinly, 80 ℃
And dried for 20 minutes . Next, this nylon 4,6 sheet was treated with an ultraviolet lamp (PL11-1 manufactured by Sen Special Light Source Co., Ltd.).
102WS / SUV-41H), the distance between the light source and the sheet is 70 mm, and the irradiation intensity is 15.0 mW / c.
Irradiation was performed for 90 seconds under the condition of m ² . Next, using this irradiation sheet, the tensile shear strength was measured in the same manner as in Example 1, and a result of 131 kg / cm ² was obtained.

Claims (6)

[Claims] 1. An engineering plastic molded article containing glass fibers, which is selected from an organic epoxy compound, a silane coupling agent and a titanate coupling agent when the molded article is adhered to each other or to another substance. Using at least one surface modifier present on at least the surface, and irradiating the surface of the molded article with ultraviolet rays having a wavelength component of 300 nm or less as a main wavelength component, and bonding with an adhesive Adhesion method for engineering plastic molded products. 2. The method according to claim 1, wherein the surface modifier is mixed and dispersed in the molded article. 3. The method according to claim 1, wherein the surface modifier is mixed and dispersed in the molded article while being preliminarily supported by a filler. 4. Nylon 6, nylon 6,6, nylon 4,6, polyphenylene ether (including modified polyphenylene ether), polyarylate, polyetherimide, polycyclohexanedimethyl terephthalate, polysulfone, polyallylsulfone, polyethersulfone. When a molded product of an engineering plastic selected from phon and polyether ether ketone is adhered to each other or to another substance, the surface of the molded product is 300 nm.
A method for adhering an engineering plastic molded article, which comprises irradiating ultraviolet rays having the following wavelengths as main wavelength components and adhering them with an adhesive. 5. A method of curing a resin in a fluid state in a plastic case accommodating an electric / electronic component and adhering the resin to an inner wall surface of the plastic case, wherein the plastic case is made of an engineering plastic containing glass fiber, And, at least one surface modifier selected from an organic epoxy compound, a silane coupling agent and a titanate coupling agent is present on at least the inner wall surface, and the inner wall surface is provided with 300 n.
A resin encapsulation method for electric / electronic parts, characterized by using a material irradiated with ultraviolet rays having a wavelength of m or less as a main wavelength component. 6. A method of curing a resin in a fluid state in a plastic case accommodating an electric / electronic component and adhering it to an inner wall surface of the plastic case, wherein the plastic case is nylon 6, nylon 6, or the like.
6, selected from nylon 4,6, polyphenylene ether (including modified polyphenylene ether), polyarylate, polyetherimide, polycyclohexanedimethyl terephthalate, polysulfone, polyallylsulfone, polyethersulfone and polyetheretherketone. A method for resin encapsulation of electric / electronic parts, which is made of engineering plastic and whose inner wall surface is irradiated with ultraviolet rays having a wavelength of 300 nm or less as a main wavelength component.