JPH11140330A - Thermoplastic resin composition, resin molding, and composite molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin compsn. having excellent adhesion to materials other than thermoplastic resins, such as metals or ceramics, and to provide a resin molded article comprising the thermoplastic resin compsn. and a composite molding comprising the resin molding. SOLUTION: This thermoplastic resin compsn. contains a crystalline resin and a noncrystalline resin having a lower glass transition temp. than the m.p. of the crystalline resin in a wt. ratio of (40:60) to (99:1). The thermoplastic resin compsn. is heat treated at a temp. of the glass transition temp. of the crystalline resin to the m.p. of the crystalline resin. The resin molding comprises the thermoplastic resin compsn., and is heat treated under the above temp. conditions. The composite molding comprises: a resin molding comprising a thermoplastic resin compsn. comprised of a crystalline resin and a noncrystalline resin in a wt. ratio of (40:60) to (99:1); and a composite molding constituting member comprising a material different from the resin molding. The composite molded article having been heat treated at a temp. of the glass transition temp. of the noncrystalline resin to the m.p. of the crystalline resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition capable of obtaining a molded article having excellent adhesion to metals and ceramics, a resin molded article made of the thermoplastic resin composition, and a resin molded article. The present invention relates to a composite molded product in which composite molded product constituent members made of other materials are integrally provided.

[0002]

2. Description of the Related Art Generally, electronic elements such as IC elements and light-emitting diodes are made of metal or ceramics, and when left in the air, oxidation or the like occurs due to oxygen or moisture in the air, resulting in surface deterioration. Or dust in the atmosphere may adhere to the surface, or the surface may be damaged by the dust. For these reasons, in order to prevent the deterioration of the surface, the adhesion of dust to the surface, and the damage to the surface, a composite molded product sealed with a resin or the like has been used in the electronic element.

[0003] In the sealing of such an electronic element, an epoxy resin has conventionally been used as a sealing material. However, since the epoxy resin is a thermosetting resin and requires a long curing process, a considerably long time is required for the sealing operation. In addition, after the sealing process, if the epoxy resin is not sufficiently cured, the curing of the uncured portion progresses with time and the entire sealing resin shrinks,
There has been a problem that the electronic element is destroyed by the pressure.

[0004] Recently, studies on encapsulating materials made of thermoplastic resins have been advanced. For example, encapsulating electronic elements using an addition-type copolymer resin of norbornenes and olefins. A method has been proposed (see JP-A-2-31451). However, such a thermoplastic resin is excellent in that it can be sealed in a short time, but has poor adhesion to materials other than the resin such as metal and ceramics. Also,
The coefficient of thermal expansion of a thermoplastic resin is significantly different from the coefficients of thermal expansion of materials other than thermoplastic resins, such as ceramics. Therefore, in a composite molded product having a resin molded product made of a thermoplastic resin and a composite molded product component made of other materials, when subjected to a thermal history due to a temperature change, the resin molded product becomes a composite molded product component. From the film. Therefore, in the gap between the resin molded body and the composite molded product component,
As a result of air entering and coming into contact with the component of the composite molded product, there has been a problem that the surface of the composite component is deteriorated due to oxidation or the like.

In order to solve such a problem, there has been proposed a composite molded product in which an intermediate layer made of a rubber material, a photocurable resin, an electron beam curable resin, or the like is formed on the surface of a component of the composite molded product. (See JP-A-6-91694). However, in such a composite molded article, not only is the adhesion between the resin molded article made of a thermoplastic resin and the composite molded article component insufficient, but also in the production of the composite molded article, In order to form an intermediate layer on the surface, a step of applying a polymer solution or a molten polymer is required, so that there is a problem that high productivity cannot be obtained.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
It is an object of the present invention to provide a thermoplastic resin composition having excellent adhesion to materials other than thermoplastic resins such as metals and ceramics, and a resin molded article made of the thermoplastic resin composition. Another object of the present invention is a composite molded product having a resin molded product made of a thermoplastic resin and a composite molded product component made of another material, wherein the resin molded product and the composite molded product component are provided. An object of the present invention is to provide a composite molded article having excellent adhesion at the interface with the composite molded article and preventing the resin molded article from peeling off from the constituent member of the composite molded article.

[0007]

SUMMARY OF THE INVENTION The thermoplastic resin composition of the present invention comprises a crystalline resin and an amorphous resin having a glass transition temperature lower than the melting point of the crystalline resin. A thermoplastic resin composition wherein the weight ratio of the non-crystalline resin to the non-crystalline resin is 40:60 to 99: 1 by weight, and is equal to or higher than the glass transition temperature of the non-crystalline resin and equal to or lower than the melting point of the crystalline resin. The heat treatment is carried out at a temperature of

The resin molded article of the present invention contains a crystalline resin and an amorphous resin having a glass transition temperature lower than the melting point of the crystalline resin. A resin molded product comprising a thermoplastic resin composition having a weight ratio of 40:60 to 99: 1,
The heat treatment is performed at a temperature equal to or higher than the glass transition temperature of the amorphous resin and equal to or lower than the melting point of the crystalline resin.

The composite molded article of the present invention comprises a crystalline resin and an amorphous resin having a glass transition temperature lower than the melting point of the crystalline resin. Composite molding made of a thermoplastic resin composition having a weight ratio of 40:60 to 99: 1 and a material different from the resin molded body provided integrally with the resin molded body And a heat treatment at a temperature not less than the glass transition temperature of the non-crystalline resin and not more than the melting point of the crystalline resin.

[0010]

According to the present invention, a resin molded article made of a specific thermoplastic resin composition is heat-treated at a specific temperature in a state of being integrated with a composite molded article made of other materials. Therefore, the adhesion between the resin molded body and the component of the composite molded article is significantly improved. The reason is presumed as follows. The thermoplastic resin composition constituting the resin molded product has a structure in which a phase formed by a crystalline resin and a phase formed by an amorphous resin are mixed, or a continuous phase formed by a crystalline resin and It has a so-called sea-island structure with a discontinuous phase (dispersed phase) formed by a crystalline resin. The thermoplastic resin composition having such a structure is used for the glass transition temperature (T
g) By performing the heat treatment at a temperature of not less than the melting point (mp) of the crystalline resin and not more than, for example, the non-crystalline resin forming the dispersed phase fluidizes and enters the interface with the composite molded article constituent member, For example, the crystallization of the crystalline resin forming the continuous phase progresses, and the entire resin molded body shrinks. And
The component of the composite molded product is tightened by the pressure due to the contraction of the resin molded product, and as a result, the adhesion between the resin molded product and the component of the composite molded product is improved.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thermoplastic resin composition of the present invention contains a crystalline resin and a non-crystalline resin. Further, the resin molded article of the present invention is made of the thermoplastic resin composition. Further, the composite molded article of the present invention is formed by integrally providing this resin molded article and a composite molded article constituent member made of a material different from the resin molded article.

<Crystalline Resin> Various resins can be used as the crystalline resin constituting the thermoplastic resin composition, and specific examples thereof include polyethylene resin, polypropylene resin, polyarylene sulfide resin, and polyether. Ether ketone resin, nylon 6 resin, nylon 6
6 resin, nylon 46 resin, polyethylene terephthalate resin, polybutylene terephthalate resin, and the like. These resins can be used alone or in combination of two or more.

[0013] Among the above crystalline resins, polyarylene sulfide resins are preferred because of their excellent heat resistance, flame retardancy and dimensional stability. This polyarylene sulfide resin mainly has a structural unit represented by the following general formula (I) in a skeleton.

[0014]

Embedded image In the general formula (I), X represents a divalent aromatic group.

In the above general formula (1), the divalent aromatic group represented by X includes p-phenylene group, m-phenylene group, 2,6-naphthalene group, 4,4′-biphenylene group, , P'-bibenzyl groups and those in which these groups have been substituted with nuclei. Among the polyarylene sulfide resins having such a structural unit, a poly-p-phenylene sulfide resin having a nucleus-substituted p-phenylene group is preferable in that it has excellent moldability.

As the polyarylene sulfide resin,
It is preferable to use one containing at least 70 mol% or more of the structural unit represented by the general formula (1) in one molecule. When the content is less than 70 mol%, the polyarylene sulfide resin has low crystallinity or low glass transition temperature, and thus the physical properties of the obtained thermoplastic resin composition May decrease. The polyarylene sulfide resin contains a trivalent or higher valent aromatic group, an aliphatic group, a hetero atom-containing group or the like such as a 1,2,4-bonded phenylene nucleus in a proportion of 30 mol% or less in one molecule. The following can be used.

As the polyarylene sulfide resin, a linear type or a cross-linked type can be used alone or in combination according to the purpose. For example, in the case of producing a resin molded product by injection molding, it is preferable to use a cross-linked polyarylene sulfide resin in order to obtain a molded product with less burrs. On the other hand, in order to reduce the anisotropy of the molding shrinkage of the obtained resin molded article (the property that the shrinkage rate of the molded article in the flow direction of the material differs from the shrinkage rate of the molded article in the direction perpendicular to the flow direction of the material). It is preferable to use a linear type polyarylene sulfide resin.

Further, as the polyarylene sulfide resin, a resin modified with an appropriate functional group (hereinafter, referred to as “polyarylene sulfide resin”)
It is referred to as “modified polyarylene sulfide resin”. ), And a mixture of a modified polyarylene sulfide resin and an unmodified polyarylene sulfide resin. As the modified polyarylene sulfide resin, those modified with a functional group such as an epoxy group, an amino group, a carboxyl group, an acid anhydride group, an oxazoline group, a vinyl group, a (meth) acryl group, and a mercapto group can be used. But, in particular,
Epoxy group-modified polyarylene sulfide resin and amino group-modified polyarylene sulfide resin are preferred. By using a modified polyarylene sulfide resin as a crystalline resin, the functional group of the modified polyarylene sulfide resin reacts with an ester group in a thermoplastic norbornene-based resin used as a non-crystalline resin described below, whereby the modified polyarylene sulfide resin is modified. A block copolymer of a polyarylene sulfide resin and a norbornene-based resin is formed, whereby the compatibility between the two is increased, and the physical properties of the obtained thermoplastic resin composition can be improved. Property can be reduced.

As a crystalline resin, polyarylene sulfite
When using a resin, the polyarylene
The melt viscosity of the FID resin is determined by the thermoplastic resin composition obtained.
From the viewpoint of achieving a balance between the strength and formability of
0 ° C, strain rate 1000 sec ^-1Under the measurement conditions of 1
It is preferably from 100 to 100,000 poise.

<Non-crystalline resin> Various non-crystalline resins can be used as the non-crystalline resin constituting the thermoplastic resin composition. Specific examples thereof include polycarbonate, polystyrene, polyvinyl chloride, and polyvinyl acetate. , Poly (meth) acrylate, polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, and thermoplastic norbornene-based resin. Among these, a thermoplastic norbornene-based resin is preferable from the viewpoint of balancing the strength and moldability of the obtained thermoplastic resin composition.

The thermoplastic norbornene resin has a norbornane skeleton in its repeating unit, and preferably has a norbornane skeleton represented by the following general formulas (II) to (V).

[0022]

Embedded image

(In the general formulas (II) to (V),
R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or a monovalent organic group, which may be the same or different. )

Examples of such a thermoplastic norbornene-based resin include JP-A-60-168708, JP-A-62-252406, and JP-A-62-240240.
No. 7, JP-A-2-133413, JP-A-63
-145324, JP-A-63-264626, JP-A-1-240517, JP-B-57-88.
No. 15 can be cited. Specifically, a polymer obtained by subjecting a monomer comprising a tetracyclododecene derivative represented by the following general formula (VI) to metathesis polymerization, or a tetracyclododecene represented by the following general formula (VI) And a polymer obtained by metathesis polymerization of a mixed monomer comprising an unsaturated cyclic compound copolymerizable therewith (hereinafter, referred to as a “copolymerizable monomer”), and water obtained by hydrogenation. An addition polymer can be mentioned.

[0025]

Embedded image

(In the general formula (VI), R ¹ , R ² , R
³ and R ⁴ each represent a hydrogen atom or a monovalent organic group, which may be the same or different. )

The tetracyclo represented by the general formula (VI)
In the dodecene derivative, R¹, R ^Two, R^ThreeAnd R^Four
At least one, preferably only one of them
Is a polar group.
Compatibility with composite molded product components described later
In terms of heat resistance and the heat resistance of the resulting thermoplastic resin composition
preferable.

In such a tetracyclododecene derivative, the polar group is preferably one represented by the following general formula (VII), since a polymer having a high glass transition temperature can be obtained.

[0029]

Embedded image

(In the general formula (VII), R ⁵ represents a hydrocarbon group having 1 to 20 carbon atoms. N is an integer of 0 to 10.)

In the general formula (VII), the hydrocarbon group represented by R ⁵ has 1 to 20 carbon atoms. The greater the number of carbon atoms, the lower the hygroscopicity of the obtained hydrogenated polymer becomes. From the viewpoint of the balance with the glass transition temperature of the obtained hydrogenated polymer, it is preferably a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms. Are preferred, especially a methyl group, an ethyl group,
Preferably, it is a cyclohexyl group.

In the tetracyclododecene derivative represented by the general formula (VI), the compound represented by the general formula (VII)
Has a carbon number of 1 to a carbon atom to which a polar group represented by
Those in which 10 hydrocarbon groups are bonded are preferable in that a polymer having low hygroscopicity can be obtained. In particular, a tetracyclododecene derivative in which the hydrocarbon group is a methyl group or an ethyl group is preferable in that the synthesis is easy, and specifically, 8-methyl-8-methoxycarbonyltetracyclo [4.4 0.12,5 17,10] Dodeca-8
-Ene is preferred.

The polymer obtained by subjecting a monomer comprising the tetracyclododecene derivative represented by the above general formula (VI) or a mixed monomer comprising the monomer and the copolymerizable monomer to metathesis polymerization is obtained. As a method for hydrogenation, for example,
No. 77520, page 4, upper right column, line 12 to page 6, lower right column, line 6 can be used.

The thermoplastic norbornene-based resin thus obtained preferably has an intrinsic viscosity ([η] inh) measured in chloroform at 30 ° C. in the range of 0.3 to 1.5 dl / g. . By using a thermoplastic norbornene-based resin having an intrinsic viscosity ([η] inh) within the above range, the obtained thermoplastic resin composition has a good balance of moldability, heat resistance, and mechanical properties. .

The glass transition temperature (Tg) of the thermoplastic norbornene-based resin is preferably in the range of 100 ° C. to 250 ° C., particularly preferably in the range of 120 ° C. to 200 ° C. When a thermoplastic norbornene resin having a glass transition temperature (Tg) of less than 100 ° C. is used, the resulting thermoplastic resin composition may have low heat resistance. On the other hand, when a thermoplastic norbornene-based resin having a glass transition temperature (Tg) of more than 250 ° C. is used, the resulting thermoplastic resin composition has a high molding temperature. May be discolored, so that it may be difficult to obtain a good quality resin molded article.

The hydrogenation rate of the thermoplastic norbornene resin is preferably at least 50%, more preferably at least 90%, further preferably at least 98%, as measured by 60 MHz, ¹ H-NMR. It is. As the hydrogenation rate increases, a thermoplastic norbornene-based resin having excellent heat and light stability can be obtained. Further, as the thermoplastic norbornene-based resin, it is preferable to use a hydrogenated polymer having a gel content of 5% by weight or less, particularly 1% by weight.

<Thermoplastic resin composition and resin molded article>
The thermoplastic resin composition of the present invention contains the crystalline resin and the non-crystalline resin, and a phase formed by the crystalline resin and a phase formed by the non-crystalline resin are mixed. Or the non-crystalline resin is present as a non-continuous phase in a continuous phase formed by the crystalline resin. As the non-crystalline resin, a resin whose glass transition temperature (Tg) is lower than the melting point (mp) of the crystalline resin is used.

The ratio of the crystalline resin to the non-crystalline resin in the thermoplastic resin composition is from 40:60 to 99:
1, preferably 50:50 to 99: 1, particularly preferably 55:45 to 90:10. If the proportion of the non-crystalline resin is too small, the resulting thermoplastic resin composition tends to have insufficient adhesion to other materials such as metals and ceramics, while the proportion of the non-crystalline resin Is too large, in the obtained thermoplastic resin composition, since the crystalline resin is present as a discontinuous phase in the continuous phase formed by the non-crystalline resin, the obtained resin molded product is , May be deformed by the heat treatment described below.

The thermoplastic resin composition of the present invention contains a compatibilizer in order to increase the compatibility between an amorphous resin such as a thermoplastic norbornene resin and a crystalline resin such as a polyarylene sulfide resin. be able to. The use ratio of such a compatibilizer is usually 0.1 to 20 parts by weight based on 100 parts by weight of the total of the crystalline resin and the non-crystalline resin. As a specific example of the compatibilizer, JP-A-6-3062
No. 87, page 5, left column, line 31 to page 5, right column, line 44, an olefin unit and a carboxyl group,
A polymer having a multilayer structure composed of a vinyl (co) polymer comprising a unit derived from at least one vinyl compound selected from an acid anhydride group, an oxazoline group and an epoxy group can be exemplified.

Further, the thermoplastic resin composition of the present invention comprises:
A known antioxidant can be added as needed. Specific examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-
3,3'-di-t-butyl-5,5'-dimethylphenylmethane, tetrakis [methylene-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl-benzene, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-dioxy-3,
3′-di-t-butyl-5,5′-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10
-Tetraoxyspiro [5,5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-
t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4)
-Methylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite.

Further, the thermoplastic resin composition of the present invention includes:
If necessary, an ultraviolet absorber, a stabilizer, an antistatic agent, a flame retardant, an elastomer for improving impact resistance, and the like can be added. Specific examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2,2′-dihydroxy-4
-Methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2'-dihydroxy-4'-m-octoxyphenyl) benzotriazole and the like.

Further, the thermoplastic resin composition of the present invention comprises:
For the purpose of improving moldability and processability, a plasticizer, a softener, and the like can be added. Specific examples of the softener include:
C5 resin, C9 resin, C5 / C9 mixed resin, cyclopentadiene resin, vinyl-substituted aromatic compound polymer resin, olefin / vinyl-substituted aromatic compound copolymer resin, cyclopentadiene compound Examples thereof include those made of a copolymer resin of a vinyl-substituted aromatic compound or a hydrocarbon resin such as a hydrogenated product of the resin.

The thermoplastic resin composition of the present invention can be prepared by using a kneader such as a single screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Can be produced by kneading the above-mentioned various additives used according to the above.
To show a specific example of a method for producing a thermoplastic resin composition,
(1) A method in which a crystalline resin, an amorphous resin, and various additives used as necessary are mixed by a mixer, and then melt-kneaded at 240 to 360 ° C. using an extruder to granulate; A) a method of melting and kneading a crystalline resin, an amorphous resin, and various additives used as needed by a direct molding machine to form a pellet, (3) using a twin-screw extruder,
A method of kneading a crystalline resin and a non-crystalline resin and adding various additives afterwards to form a pellet.

The thermoplastic resin composition of the present invention thus obtained is molded by a suitable means to form a resin molded body, and then subjected to heat treatment. The heat treatment temperature is not lower than the glass transition temperature (Tg) of the amorphous resin in the thermoplastic resin composition and the melting point (mp) of the crystalline resin.
The temperature is in the following range, and is appropriately set in relation to the heat treatment time. If the heat treatment temperature is lower than the glass transition temperature (Tg) of the non-crystalline resin, the adhesion to the composite molded article component described below will be insufficient, while the heat treatment temperature will be lower than that of the crystalline resin. When the melting point (mp) is exceeded, the resin molded body is melted and thermally deformed. The heating method is not particularly limited, but a method of heating by solder dip, solder reflow, autoclave, or the like can be used.

<Composite molded component> The composite molded component used in the composite molded product of the present invention is not particularly limited as long as it does not melt or deform at the molding temperature of the thermoplastic resin composition described above. Although not limited, those made of materials other than resins, for example, those made of metals such as gold, silver, copper, platinum, aluminum and their alloys, silicon oxide, aluminum oxide, those made of ceramics such as silicon, made of metal What has a part and a part which consists of ceramics can be used. Further, the composite molded component may be an electronic element such as a light emitting diode, a diode, a transistor, and an integrated circuit.

<Composite Molded Article> The composite molded article of the present invention is an intermediate composite comprising a resin molded article made of the above thermoplastic composition and a composite molded article member integrally provided with the resin molded article. And heat-treating this intermediate composite. The method for producing the above-mentioned intermediate composite is not particularly limited. For example, (1) a method of integrally molding a thermoplastic resin composition and a component of a composite molded product,
After producing a resin molded body made of a thermoplastic resin composition,
A method of adhering a component of a composite molded article to the resin molded article by an appropriate means may be used.

In the case of producing an intermediate composite by the above method (1), it is preferable to prepare a composite molded article component having a desired shape before performing the integral molding. In addition, as means for integrally molding,
There is no particular limitation, and it can be appropriately selected according to the purpose. For example, when the component of the composite molded product is an electronic element having a lead wire or a lead frame, an injection molding method, a transfer molding method, a compression molding method,
A method such as a dipping method can be used.

In the case of using the injection molding method or the transfer molding method, a plurality of composite molded component members made of, for example, electronic elements are mounted in a mold, and the mold is closed in this state. Then, the thermoplastic resin composition is poured into the mixture and cooled, and then the mold is opened to take out the composite molded body. In this method, if necessary, an adhesive or a coupling agent may be applied in advance to the surfaces of the leads and lead frames of the electronic elements constituting the composite molded component. As such adhesives and coupling agents, generally used known ones can be used, and specific examples thereof include epoxy adhesives, polyimide adhesives, silane coupling agents, and titanate coupling agents. Agents and the like.

By subjecting the thus obtained intermediate composite to a heat treatment, the molded article of the present invention of the present invention is obtained. The conditions for this heat treatment are the same as those for the above-described heat treatment of the thermoplastic resin composition. The composite molded product thus obtained is, for example, a lead-through mounted product and a surface mounted product, specifically, an IC element, an LSI element, a VLSI
Element, hybrid IC element, transistor, diode, triode, capacitor, resistor, resistor network, thyristor, chip inductor, transformer, motor, LC filter, connector, coil, varistor, transducer, crystal oscillator, fuse,
It is suitable as a mounted product such as a current sensor, a power supply, a switch, a relay, a sensor, a Hall element, a surge absorber, an arrester, a pin grid array, a photocoupler, or a composite mounted product thereof.

[0050]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. The following were used as the non-crystalline resin and the crystalline resin.

<Non-crystalline resin> Non-crystalline resin (A-1): 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12, 5.17,
10] -3-Dodecene (250 parts), 1-hexene (41 parts), and toluene (750 parts) were charged into a nitrogen-purged reaction vessel and heated to 60 ° C. To this solution were added 0.62 parts of a toluene solution of triethylaluminum (concentration: 1.5 mol / l) and a tungsten (VI) chloride solution (t-butyl alcohol and denatured) modified with a mixture of t-butyl alcohol and methyl alcohol. The molar ratio of methyl alcohol to tungsten is 0.35: 0.3:
1, concentration 0.05 mol / l) and 3.7 parts,
The solution was heated with stirring at 80 ° C. for 3 hours to obtain a ring-opened polymer solution. The polymerization conversion in this polymerization reaction was 97%, and the intrinsic viscosity (ηinh
) Was 0.45. This ring-opened polymer solution 4000
Part, RuHCl (CO) [P (C6H5) 3] 30.
Forty-eight parts were charged into an autoclave, and the ring-opening polymer was reacted under stirring under the conditions of a hydrogen gas pressure of 100 kg / cm 2, a reaction temperature of 165 ° C., and a reaction time of 3 hours. After cooling the obtained reaction solution, the pressure in the autoclave was released to obtain a hydrogenated polymer solution. The obtained hydrogenated polymer is poured into a large amount of methanol, and the hydrogenated polymer is solidified to obtain a non-crystalline thermoplastic norbornene having a hydrogenation rate of 99.5% and a glass transition temperature (Tg) of 168 ° C. A system resin was obtained. This thermoplastic norbornene-based resin is referred to as an amorphous resin (A-1).

Non-crystalline resin (A-2): polycarbonate resin [glass transition temperature (Tg) 140 ° C.]

<Crystalline Resin> Crystalline resin (B-1): polyphenylene sulfide resin (melting point (mp) 290 ° C.) Crystalline resin (B-2): polybutylene terephthalate resin (melting point (mp) 224 ° C.) <Compatibilizer>"MODIPAA4101" (manufactured by NOF Corporation)

<Example 1> Amorphous resin (A-1) 35
Part and 65 parts of the crystalline resin (B-1) were melt-kneaded with a twin-screw extruder under the condition of a cylinder temperature of 300 ° C. to prepare a pellet-shaped thermoplastic resin composition. An LSI element is mounted in a mold of an injection molding machine, and the obtained thermoplastic resin composition is injection-molded using the injection molding machine at a mold temperature of 100 ° C. and an injection temperature of 310 ° C. Then, an intermediate composite comprising a resin molded product made of a thermoplastic resin composition and a composite molded product component made of an LSI element provided integrally with the resin molded product was manufactured. The obtained intermediate composite was subjected to a preheating treatment at 180 ° C. for 2 minutes using a solder reflow “Reflow Checker RC-8” (manufactured by Malcolm), and then 235 ° C. (surface of the molded product). Temperature) for 20 seconds, followed by natural cooling. As described above,
A total of 20 composite molded articles were manufactured.

[Adhesion Test of Resin Molded Body and Component of Composite Molded Article] The obtained composite molded article was immersed in water dyed with red ink, at a pressure of 5 kgf / cm ² and a temperature of 80.
After immersion at 30 ° C. for 30 hours, the state of penetration of water into the interface between the lead frame of the LSI element and the resin molded product in the composite molded product was visually inspected. Excellent. Table 1 shows the results.

<Examples 2 to 5> In the same manner as in Example 1 except that a thermoplastic resin composition was prepared according to the composition shown in Table 1, and the conditions of the main heat treatment of the intermediate composite were changed according to Table 1. Twenty composite molded products were manufactured, and an adhesion test between the resin molded product and the component of the composite molded product was performed. Table 1 shows the results.

<Comparative Example 1> Twenty composite molded articles were manufactured in the same manner as in Example 1 except that the preliminary heat treatment and the main heat treatment were not performed. An adhesion test was performed. Table 1 shows the results.

Comparative Example 2 Twenty composite molded articles were manufactured in the same manner as in Example 1 except that the preheating treatment was not performed and the conditions of the main heating treatment were changed to 150 ° C. and 30 seconds. An adhesion test between the resin molded article and the component of the composite molded article was performed. Table 1 shows the results.

Comparative Example 3 Composite molding was carried out in the same manner as in Example 1 except that a thermoplastic resin composition was prepared according to the composition shown in Table 1 and the conditions of the main heat treatment of the intermediate composite were changed according to Table 1. Twenty products were manufactured, and an adhesion test between the resin molded product and the component of the composite molded product was performed. Table 1 shows the results
Shown in

[0060]

[Table 1]

As is clear from Table 1, according to the composite molded articles of Examples 1 to 5, the interface between the resin molded article composed of the thermoplastic resin composition and the composite molded article composed of the LSI element is excellent. It was confirmed that good adhesion was obtained. In contrast, Comparative Example 1 did not perform the main heat treatment, so 18 defective products were generated (defective product ratio: 90%). Comparative Example 2 was that the heat treatment temperature in the main heat treatment was non-crystalline resin. Since the glass transition temperature is lower than the glass transition temperature of Example 1, 12 defectives were generated (a defective rate of 60%). In Comparative Example 3, 20 defectives were generated because the proportion of the amorphous resin was too small. (100% defective product rate), in each case, sufficient adhesion could not be obtained at the interface between the resin molded product and the composite component.

<Comparative Example 4> This heating treatment was carried out at 300 ° C for 3 hours.
A composite molded article was manufactured in the same manner as in Example 1 except that the test was performed at 0 seconds. The resin molded article of the composite molded article was deformed during the main heat treatment, and thus could be subjected to an adhesion test. Did not.

Comparative Example 5 Non-crystalline resin (A-1)
A composite molded article was manufactured in the same manner as in Example 1 except that the crystalline resin (B-1) was changed to 20 parts and the crystalline resin (B-1) was changed to 20 parts. And thus could not be subjected to the adhesion test.

[0064]

Industrial Applicability The thermoplastic resin composition and resin-formed body of the present invention have excellent adhesion to materials other than thermoplastic resins such as metals and ceramics. Therefore, it is suitable as a thermoplastic resin composition for composite molded articles and a resin molded article. The composite molded article of the present invention has excellent adhesion at the interface between the resin molded article and the component of the composite molded article, and does not peel off the resin molded article from the component of the composite molded article. Therefore, by using an electronic element as a component of the composite molded product, a mounted product having high reliability without performance degradation due to moisture even under high humidity can be obtained.

Claims (4)

[Claims] 1. A crystalline resin comprising a crystalline resin and a non-crystalline resin having a glass transition temperature lower than the melting point of the crystalline resin, wherein the ratio of the crystalline resin to the non-crystalline resin is 40% by weight. : A thermoplastic resin composition of 60 to 99: 1, wherein the thermoplastic resin composition is heat-treated at a temperature not lower than the glass transition temperature of the non-crystalline resin and not higher than the melting point of the crystalline resin. Resin composition. 2. A composition comprising a crystalline resin and an amorphous resin having a glass transition temperature lower than the melting point of the crystalline resin, wherein the ratio of the crystalline resin to the amorphous resin is 40% by weight. : A resin molded article comprising a thermoplastic resin composition of 60 to 99: 1, wherein the heat treatment is performed at a temperature equal to or higher than the glass transition temperature of the non-crystalline resin and equal to or lower than the melting point of the crystalline resin. Characterized resin molded product. 3. A crystalline resin and a non-crystalline resin having a glass transition temperature lower than the melting point of the crystalline resin, wherein the ratio of the crystalline resin to the non-crystalline resin is 40% by weight. : A resin molded article made of a thermoplastic resin composition of 60 to 99: 1, and a composite molded article constituent member made of a material different from the resin molded article provided integrally with the resin molded article. A composite molded product, which is heat-treated at a temperature equal to or higher than the glass transition temperature of the amorphous resin and equal to or lower than the melting point of the crystalline resin. 4. The composite molded article according to claim 3, wherein the component of the composite molded article is an electronic element.