JPH03106963A - Metal parts insert molded products - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. useful for insert molding of a metal part by compounding a hydrogenated norbornene-based ring-opening polymer and a rubber in a specified ratio. CONSTITUTION:95-60wt.% hydrogenated norbornene-based ring-opening polymer (e.g. a hydrogenated ring-opening polymer of 6-ethyl-1,4:5,8-dimethano-1,4,4 a,5,6,7,8,8a-octahydronaphthalene) is compounded with 5-40wt.% rubber (e.g. styrene-butadiene-styrene block copolymer).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a resin composition containing a hydrogenated norbornene-based ring-opening polymer and rubber, and more particularly, to a resin composition suitable for insert molding of metal parts. A resin composition comprising:
This article relates to a resin composition suitable for use as a hub, which is a component of an optical disk substrate. [Prior Art J] Optical discs are generally made using disk-shaped substrates made of synthetic resin or glass, and read-only discs (R
OM) and optical recording discs (DRAW), which are additional recordable discs that can be written to by the user only once, and rewritable discs that can be erased and written to by the user. By the way, in the case of a DRAW type optical disc, since the board is clamped to the drive using a magnet, it is necessary to attach a metal plate with a hole in the center of the board. When using a synthetic resin substrate, usually instead of directly bonding a metal plate to the synthetic resin substrate, a hub is created in advance by insert molding the metal plate into a synthetic resin disk, and then this is bonded to the resin substrate. Adhesive method is used. For example, in the case of an optical disk whose substrate is polycarbonate resin (PC), a hub made by insert molding a metal plate on the same PC is bonded to the substrate. By the way, recently, it has been reported in Japanese Patent Laid-Open No. 1983-1989 that thermoplastic saturated norbornene polymers, such as hydrogenated norbornene ring-opening polymers and addition type copolymer of norbornene monomer and ethylene, have excellent characteristics as optical disc substrate materials. -26024, JP 64-24826, JP 60-1 68708
No., JP-A-61-115912, JP-A-61-120
It is disclosed in No. 816, etc. However, even if you try to attach a general-purpose PC hub to these norbornene-based polymer disk substrates,
Conventional adhesive methods such as ultraviolet curable adhesives, epoxy adhesives, hot melt adhesives, and ultrasonic adhesives have had the problem of not providing good adhesion. Therefore, the present inventors have found that when a hub made of the same norbornene polymer and a metal plate inserted or shaped is bonded to a norbornene polymer substrate using hot melt adhesive or ultrasonic bonding, the adhesive properties are good. I found out.

However, when trying to create a hub by insert molding a metal plate using a hydrogenated norbornene ring-opening polymer as the norbornene polymer, if the molecular weight of the polymer is small, it may cause problems during molding or due to changes over time after molding. Cracks easily occur in insert molded products. On the other hand, if the molecular weight of the polymer is large, cracks are less likely to occur, but there is a problem that sink marks are more likely to occur in the insert molded product.

[Problem to be solved by the invention]

An object of the present invention is to provide a resin material suitable for insert molding of metal parts.

Another object of the present invention is to provide a resin material that provides an insert molded product with excellent adhesiveness to an optical disk substrate made of a thermoplastic saturated norbornene polymer.

As a result of intensive research to solve the problems of the prior art, the present inventors discovered that a resin composition containing rubber mixed with a hydrogenated norbornene-based ring-opening polymer was developed for use in the insert molding of metal parts. It was discovered that when used for molding, it produces insert molded products that are free from cracks and sink marks during molding, and also has excellent adhesion to thermoplastic saturated norbornene-based polymer substrates. Furthermore, this resin composition can be used as a sealant, coating agent, film, etc.
Various molding. It was discovered that it can be used for various purposes such as products. The present invention has been completed based on these findings.

[Means to solve the problem]

Thus, according to the present invention, a resin composition containing 95 to 60% by weight of a hydrogenated norbornene-based ring-opening polymer and 5 to 40% by weight of rubber is provided.

Hereinafter, the configuration of the present invention will be explained in detail.

(Hydrogenated norbornene-based ring-opening polymer) The hydrogenated norbornene-based ring-opening polymer used in the present invention is a polymer obtained by hydrogenating a ring-opening polymer of a norbornene-based monomer. The hydrogenated product has a number average molecular weight (Mn) of 20,000 to 100 as measured by high performance liquid chromatography.
,000, preferably 30,000 to 60,00
It is a polymer of 0.

If the number average molecular weight (Mn) is larger than the above range, the moldability will be poor and the molded product will tend to have whiskers; if it is smaller than the above range, the mechanical strength will be poor and the metal insert molded product will be prone to cracks.

In addition, from the viewpoint of heat resistance and injection moldability, the hydrogenated material in the present invention has a glass transition temperature (g) of 100°C or higher, preferably 120 to 200°C, more preferably 1
The temperature is preferably 30 to 180°C.

Specific examples of norbornene monomers include norbornene and its alkyl and/or alkylidene substitutes, such as 5-methyl-2-norbornene, 5.6
-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, etc.; dicyclopentadiene,
and alkyl substituted products thereof such as methyl, ethyl, proyl, butyl; dimethanoloctahydronaphthalene, and alkyl and/or alkylidene substituted products thereof;
For example, 6-methyl-1,4:5,8-dimethano-1.
4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4:5,8-dimethano-1.4
, 4a,5,6,7,8,8a-octahyde-naphthalene, 6-ethylidene-1,4:5,8-dimethano-1,
4,4a,5,6,7,8,8a-octahydronaphthalene, etc.; cyclopentadiene trimer-tetramer, e.g.
4,9:5,8-dimethano-3a. 4, 4a, 5, 8,
8a,9,9a-octahydro-IH-penzoindene, 4,l1:5,10:6,9-trimethanol 3a,4
, 4a, 5, 5a, 6, 9, 9a, 10, 10a, 11
, lla-dodecahydro IH-cyclopentaanthracene, and the like; dimethanodehydrobenzoindene, dimethanodecahydrofluorene, and alkyl substituted products thereof. These norbornene monomers may be used alone, or in combination of two or more.

In order to make the desired Tg of the hydrogenated ring-opening polymer 100°C or higher, among these norbornene monomers, tetracyclic or pentacyclic monomers are used, or these are used as the main component, It is preferable to use it in combination with a bicyclic or tricyclic monomer.

In addition, as a copolymerization component, other cycloolefins such as cyclobropene, cyclobutene, cyclopentene, cyclohebutene, cyclooctene, 5,6-dihydrodicyclobentadiene, etc. may be added within a range that does not impair the purpose of the present invention, usually 30% by weight. It can be used within the range of % or less. In addition, a small amount of acyclic olefin (
(Usually, up to 10 mol%) may be used, and among them, α-
Olefins are preferred. Ring-opening polymers of norbornene-based monomers are produced by combining, for example, a titanium component and a monomer using a catalyst system consisting of a transition metal compound such as titanium tetrahalide, an organometallic compound such as an organoaluminium compound, and a tertiary amine. It can be obtained by sequential addition to the reaction system. Of course, catalysts prepared using other catalyst systems may be used as long as they meet the above requirements. Ring-opening polymerization is possible without using a solvent, but it is usually carried out using aromatic hydrocarbons such as benzene, toluene, and xylene.
It is carried out in an inert organic solvent such as an aliphatic hydrocarbon such as hexane or hebutane, an alicyclic hydrocarbon such as cyclohexane, or a halogenated hydrocarbon such as dichloroethane. Further, the polymerization temperature is usually selected from the range of -20°C to 100°C, and the polymerization pressure is selected from the range of 0 to 50 kg/crrr.

The ring-opened polymer of norbornene monomers is then hydrogenated using a well-known hydrogenation catalyst. Any hydrogenation catalyst that is commonly used in the hydrogenation of olefin compounds can be used, such as Wilkinson complex, cobalt acetate/triethylaluminum, nickel acetylacetate/triisobutylaluminum, palladium-carbon, and ruthenium. -Carbon, nickel, diatomaceous earth, etc.

The hydrogenation reaction is carried out in a homogeneous or heterogeneous system depending on the type of catalyst, under a hydrogen pressure of 1 to 200 atmospheres, and at a temperature of 0 to 2.50°C. The hydrogenation rate is set to 90% or more, preferably 95% or more, and particularly preferably 99% or more from the viewpoint of heat deterioration resistance and light deterioration resistance. (Rubber) The rubber used in the present invention may be raw rubber (raw rubber), vulcanized rubber (elastomer), thermoplastic elastomer, etc., and may be a homopolymer or a copolymer. Also,
It may also be a blend of the above rubber components or a blend containing other resins. Examples of such rubber types include inbrene rubber (IR), trans-isobrene rubber, high cis-butadiene rubber (high cis-BR), low cis-butadiene rubber (low cis-BR), and emulsion polymerized styrene-butadiene rubber. E-SBR, solution polymerized styrene-butadiene rubber (E-SBR), solution polymerized styrene-butadiene rubber (
S-SBR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), carboxylated nitrile rubber, nitrile rubber/vinyl chloride resin blends (NBR/PvC Blends), nitrile rubber/E
PDM blends (NBR/EPDM Blends)
, butyl rubber (IIR), halogenated butyl rubber (X-IIR), ethylene-brobylene rubber (EPM
), ethylene-propylene-diene rubber (EPDM),
Ethylene-vinyl acetate rubber (EVA). acrylic rubber,
Ethylene-acrylic rubber, chlorosulfonated polyethylene (CSM). Chlorinated polyethylene, shrimp chlorohydrin rubber, shrimp chlorohydrin-ethylene oxide rubber,
Polyether urethane rubber, polyester urethane rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, fluorinated silicone rubber, vinylidene fluoride rubber, ethylene-tetrafluoride-propylene rubber, styrene-butadiene- Styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isobrene-styrene block copolymer (SIS), thermoplastic elastomer (boristyrene, polyolefin, polyurethane, Polyester, polyamide, 1,2-polybutadiene, ethylene-vinyl acetate, polyvinyl chloride,
Fluororubber, trans-bolyisoprene, various thermoplastic elastomers based on chlorinated polyethylene), norbornene polymers, etc. (Resin composition) The blending ratio of each component in the resin composition of the present invention is 95 to 60% by weight, preferably 90 to 70% by weight, more preferably 90 to 8% by weight of hydrogenated norbornene ring-opening polymer.
0% by weight and 5-40% by weight of rubber, preferably 10-3%
0% by weight. More preferably 10 to 20% by weight (total 1
00% by weight). The blending ratio of norbornene-based ring-opening polymer hydrogenated material is 95%.
If the molecular weight of the hydrogen additive is relatively small, cracks may easily occur in the resin part of insert molded metal parts, and if the molecular weight is relatively large, cracks may occur during molding. is likely to occur. In other words, the effect of incorporating the rubber component is not fully expressed.

The blending ratio of norbornene-based ring-opening polymer hydrogenated material is 60%.
If the weight percentage is insufficient, the heat resistance of the molded article of the resin composition will decrease, making it unsuitable as an insert molded article for metal parts. Additionally, additives such as stabilizers, pigments, colorants, and fillers may be added if desired. Examples of the blending method include a method of kneading each component, and a method of dynamically vulcanizing a portion of the rubber while kneading the raw material rubber and the hydrogenated norbornene ring-opening polymer.

Examples of the mixing method include a method of mechanically melt-kneading while heating to 200° C. or higher using a batch mixer (Brabender, Labo Blast Mill, Kneader, etc.) or a screw extruder.

As a molding method for the resin composition, general melt processing methods such as extrusion molding and injection molding can be applied.
It is formed into films, sheets, filaments, and various other molded products. The resin composition of the present invention is particularly useful as a material for insert-molded metal parts, and is particularly suitable for use in hubs used in optical disk substrates made of thermoplastic saturated norbornene polymers. The use of the resin composition of the present invention is not limited to insert molded metal parts, but can be used, for example, as a semiconductor encapsulant,
Capacitor encapsulants, wire coatings, flexible optical fiber coatings, optical fiber joints, circuit boards,
It can be used for various purposes such as electromagnetic shielding materials, conductive films, photoelectric conversion elements, various cases, and medical equipment.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1] 6-ethyl-1.4:5,8-dimethano-1,4.4a,5,6 as norbornene ring-opening polymer hydrogenated product
, 7, 8, 8a Hydrogenated ring-opening polymer of one-year-old tahydronaphthalene (ETD: ethyltetracyclododecene) [number average molecular weight (Mn) 38,000, hydrogenation rate almost 100%, Tg = 142 °C] to the hydrogenated product,
Each rubber was produced using a twin-screw extruder at the compounding ratio shown in Table 1.
Each pellet (resin composition) was created by melt-kneading at 0°C.

As the metal plate, a SUS metal disc with a diameter of 22 mm, a thickness of 0.5 mm, and a hole with a diameter of 4 mm in the center is used, and this is placed in a mold in advance, and each of the above-mentioned pellets is injection molded. The diameter is 25 mm and the thickness is 2 m.
We created a disc-shaped metal insert molded product (hub for optical disc) with a diameter of 1.2 m. The resulting metal insert molded product was visually inspected after molding and after 10 heat cycle tests (8 hours per cycle) at -20°C and 80°C to determine whether there were any abnormalities in appearance or the occurrence of cracks. The presence or absence of molding shrinkage and the presence or absence of whiskers during molding were observed.

Table 1 shows the blending ratio and observation results for each ingredient. In addition, these metal insert molded products (hubs) were attached to an optical disk substrate made of a hydrogenated compound of the ETD polymer mentioned above with an adhesive (bond hot melt adhesive Mu-102 manufactured by Konishi Corporation).
When the adhesive was bonded using the adhesive, it showed good adhesion and did not peel off even in a peel test with a positive load of 10 kg.
[Comparative Example] For comparison, metal insert molded products were prepared in the same manner as in the Examples, using three types of ETDs with different molecular weights and without a rubber component, and evaluated in the same manner. The results are summarized in Table 1.

In addition, the three types of ETD are as follows: ■Number average molecular weight (Mn)2 5. O O O, hydrogenation rate approximately 100%, Tg = 134°C, ■ number average molecular weight (Mn) 38,000, hydrogenation rate approximately 100%, Tg = 142°C, ■ number average molecular weight (Mn) 80,000, The hydrogenation rate was almost 100%, and Tg = 144°C. (Left below) [Example 2] Instead of the ETD polymer hydrogenated product, ■6-methyl-1,4:5,8-dimethano-1,4,4
a,5,6,7,8,8a-octahydronaphthalene (
MTD: copolymer of methyltetracyclododecene) and dicyclobentadiene (DCP) (MTD/DCP=
80/20, molar ratio) hydrogenated product [number average molecular weight (M
n) 38,000, hydrogenation rate almost 100%, Tg=1
31℃], ■ Cobolimer of ETD and DCP (ETD/
DCP=80/20, molar ratio) hydrogenated product [number average molecular weight (Mn) 38,000, hydrogenation rate almost 100%,
Tg=131℃], ■ Cobolimer of ETD and norbornene (NB) (ET
D/NB=90/10, molar ratio) hydrogenated product [number average molecular weight (Mn) 38,000, hydrogenation rate approximately ioo
%, Tg = 130°C], ■ Hydrogenated copolymer of ETD and ethylidenenorbornene (ENB) (ETD/ENB = 90/10, molar ratio) [number average molecular weight (Mn) 38.000, hydrogenation rate Almost 100%, Tg=130° C.] was used in the same manner as in Example 1, and each rubber was compounded at the compounding ratio shown in Table 2 to produce a metal insert molded product.

Table 2 shows the appearance of the metal insert or shaped product and the results of the heat cycle test. In addition, when these metal insert molded products were adhered to an optical disk substrate made of a hydrogenated ETD polymer using an adhesive in the same manner as in Example 1, they showed good adhesion and peeling under a positive load of 10 kg. It did not peel off during the test.

(The following is a blank space) The rubber components used in Examples 1 and 2 are as follows. SESB: Shell, Clayton G-165
2εPDM: manufactured by Sumitomo Chemical Co., Ltd., S-BLEN 512-FE
PM: Manufactured by Mitsui Petrochemical Co., Ltd., EPM-0045SBR
: Manufactured by Nippon Zeon Co., Ltd., Nipol NS-300 Engineering R: Manufactured by Nippon Zeon Co., Ltd., Nipol IR-2207CR :
Manufactured by Tosoh Corporation, Skybren R-22NBR: Manufactured by Nippon Zeon Corporation, Nipol DN-200NBR/PV
C Blends: Nipol 1230JNNBR/E manufactured by Nippon Zeon Co., Ltd.
PDM Blends: Made by Japan Synthetic Rubber Co., Ltd., JSR-NE SIS: Made by Nippon Zeon Co., Ltd., Quintac 3435 Hydrogenated NBR: Made by Nippon Zeon Co., Ltd., Zetpol-2020
(The following is a blank space) [Effects of the Invention] According to the present invention, when used for insert molding of metal parts, cracks and whiskers during molding are prevented, and moreover, it has excellent adhesiveness to a thermoplastic saturated norbornene-based polymer optical disk substrate. A resin composition is provided that provides a molded insert.

The resin composition of the present invention is also useful as a sealant, a coating, a film, and various other molded products.

Claims (1)

[Claims] (1) Norbornene-based ring-opening polymer hydrogenated product 95-60
% by weight and 5 to 40% by weight of rubber.