JPH07156332A - Tubular product made of synthetic resin - Google Patents

Abstract

PURPOSE:To obtain a tubular product being light in weight and excellent in strength-rigidity, dimensional precision, heat resistance and durability by providing a metal film on the outer surface of the tubular product made of thermoplastic synthetic resin which is molded by injection molding. CONSTITUTION:Thermoplastic synthetic resin such as thermotropic liquid crystal resin being used, a molded article (tubular product) is obtained by injection molding. A metal film is provided thereon by electroless plating, electrolytic plating or others. First the molded article is degreased by an organic solvent or the like and subjected then to conditioning, catalyzing and activating processes and further to the electroless plating. Thereafter the electrolytic plating is applied as occasion demands. As for a metal used for the electroless plating, copper, nickel, chromium or others can be mentioned. The tubular product of the synthetic resin obtained in this way is excellent in dimensional precision, strength, rigidity and heat resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin tubular product coated with a metal film, and more particularly useful for office machines such as copying machines and printing machines, and rolls of industrial machines such as conveyors and heating furnaces. so,
The present invention relates to a synthetic resin tubular product having a metal coating on the outer surface of a thermoplastic synthetic resin tubular product formed by injection molding.

[0002]

2. Description of the Related Art Rolls used in the fields of office equipment and industrial machinery are required to have strength / rigidity, dimensional accuracy, heat resistance, durability, etc., so that metal rolls are currently used. ing. However, in recent years, there has been an increasing demand for weight reduction for these applications. Although it is effective to use a synthetic resin for weight reduction, the synthetic resin is inferior in practical use due to its poor strength / rigidity, dimensional accuracy, heat resistance, durability and the like.

An extrusion molding method is usually used to form a cylindrical material such as a roll by using a synthetic resin. However, in this method, dimensional accuracy (in a cylindrical shape, roundness and wall thickness are uniform). Sex). In addition, in order to improve strength / rigidity and heat resistance, which are insufficient only with synthetic resins, it is effective to add an inorganic filler such as glass fiber or carbon fiber. Is strongly orientated in the flow direction, and the molded product is likely to be longitudinally cracked. Further, such applications often slide with other substances, require durability such as abrasion resistance, and the performance of the synthetic resin is insufficient.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve these problems of the prior art, to use a synthetic resin, to make it lightweight, and to have excellent strength / rigidity, dimensional accuracy, heat resistance and durability. The purpose is to provide an article.

[0005]

Means for Solving the Problems The inventors of the present invention have made various studies in order to achieve the above-mentioned objects, and arrived at the present invention.

That is, the present invention relates to a synthetic resin tubular article characterized in that a metal coating is applied to the outer surface of the thermoplastic synthetic resin tubular article molded by injection molding.

The present invention will be described in more detail below. The tubular article in the present invention is usually a tubular article such as a roll or a pipe, but depending on the application, a tubular article having a triangular or square cross section is also included. This tubular object includes both open ends and closed ends.

There are various thermoplastic synthetic resins used in the present invention. For example, thermotropic liquid crystal resin,
Polyolefin resin such as polyethylene, polypropylene and polybutene, polystyrene resin, polyvinyl chloride resin, aliphatic polyamide resin such as nylon 6 and nylon 66 and aromatic polyamide resin such as polyphthalamide, polycarbonate resin, polyethylene Polyester resins such as terephthalate and polybutylene terephthalate, polyoxymethylene resins, polyphenylene ether resins, polyurethane resins, polysulfone resins, polyether sulfone resins, polyphenylene sulfide resins, polyketone resins, polyarylate resins , Polyimide resin, polyamide-imide resin,
Fluorocarbon resins and the like can be listed.

Among these thermoplastic resins, strength, rigidity,
Thermotropic liquid crystal resin, particularly thermotropic liquid crystal polyester resin, which has excellent dimensional accuracy, heat resistance and good moldability, is most preferable.

The thermotropic liquid crystal resin referred to here is
It is a thermoplastic, meltable polymer that exhibits optical anisotropy when melted. As described above, the polymer exhibiting optical anisotropy when melted has a property that the polymer molecular chains have a regular parallel arrangement in the melted state. The properties of the optically anisotropic molten phase can be confirmed by a usual polarization inspection method using a crossed polarizer.

For example, liquid crystalline polyester, liquid crystalline polyester imide and the like, specifically (all) aromatic polyester, polyester amide, polyester carbonate and the like can be mentioned. A thermotropic liquid crystal polyester resin is preferred, and is included in the category of the polyester of the present invention as long as it contains a plurality of ester bonds in the molecule. A more preferred polyester is an aromatic polyester.

In the thermotropic liquid crystal polyester resin preferably used in the present invention, a part of one polymer chain is composed of a polymer segment forming an anisotropic melt phase, and the remaining part is an anisotropic melt phase. Also included are polymers composed of polymer segments that do not form Also, a composite of a plurality of thermotropic liquid crystal polyester resins is included.

Typical examples of the monomer constituting the thermotropic liquid crystal polyester resin include (a) at least one aromatic dicarboxylic acid, (b) at least one aromatic hydroxycarboxylic acid compound, and (c) aromatic. At least one kind of diol compound, at least one kind of (d) (d ₁ ) aromatic dithiol, (d ₂ ) aromatic thiophenol, (d ₃ ) aromatic thiol carboxylic acid compound,
(E) At least one kind of aromatic hydroxyamine, aromatic diamine compound, etc. may be mentioned.

Although these may be configured independently,
Many are (a) and (c), (a) and (d), (a),
(B) and (c), (a), (b) and (e), or (a), (b), (c) and (e), etc. are combined and configured.

The above-mentioned (a) aromatic dicarboxylic acid type compounds include terephthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid and 2,6-
Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,
4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,
3'-dicarboxylic acid, diphenoxyethane-3,3'-
Aromatic dicarboxylic acids such as dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid,
Examples thereof include alkyl, alkoxy or halogen substitution products of the above aromatic dicarboxylic acids such as dimethyl terephthalic acid, ethyl terephthalic acid, methoxy terephthalic acid and ethoxy terephthalic acid.

Examples of the aromatic hydroxycarboxylic acid compound (b) include aromatic hydroxy such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and 6-hydroxy-1-naphthoic acid. Carboxylic acid or 3-methyl-4-hydroxybenzoic acid, 3,5
-Dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl -2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid,
2-chloro-4-hydroxybenzoic acid, 3-chloro-4
-Hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3
-Bromo-4-hydroxybenzoic acid, 6-hydroxy-
Alkyl, alkoxy or halogen substitution of aromatic hydroxycarboxylic acid such as 5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid The body.

As the aromatic diol (c), 4,4 '
-Dihydroxydiphenyl, 3,3'-dihydroxydiphenyl, 4,4'-dihydroxytriphenyl, hydroquinone, resorcin, 2,6-naphthalenediol, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenoxy) ethane, 3 , 3'-Dihydroxydiphenyl ether, 1,6-naphthalenediole, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane and other aromatic diols or chlorohydroquinone Alkyl, alkoxy or halogen substitution products of aromatic diols such as methyl hydroquinone, t-butyl hydroquinone, phenyl hydroquinone, methoxy hydroquinone, phenoxy hydroquinone, 4-chlororesorcinol and 4-methylresorcinol. That.

Examples of the aromatic dithiol (d ₁ ) include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol and 2,7-naphthalene-dithio. -Ru and the like.

The (d ₂ ) aromatic thiophenol includes
4-mercaptophenol, 3-mercaptophenol
And 6-mercaptophenol and the like.

Examples of the aromatic thiolcarboxylic acid (d ₃ ) include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid and 7-mercapto-2-naphthoic acid.

(E) Aromatic hydroxyamine and aromatic diamine compounds include 4-aminophenol and N-
Methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine,
N, N'-dimethyl-1,4-phenylenediamine, 3
-Aminophenol, 3-methyl-4-aminophen-
2-chloro-4-aminophenol, 4-amino-
1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenylether, 4-amino-4'-hydroxydiphenylmethane,
4-amino-4'-hydroxydiphenyl sulfide,
4,4'-diaminophenyl sulfide (thiodianiline), 4,4 'diaminodiphenyl sulfone, 2,5-
Diaminotoluene, 4,4'-ethylenedianiline,
4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,
4'-diaminodiphenyl ether (oxydianiline) and the like can be mentioned.

The thermotropic liquid crystal polyester resin used in the present invention can be produced from the above-mentioned monomers by various ester forming methods such as a melt acidolysis method and a slurry polymerization method.

The molecular weight of the thermotropic liquid crystal polyester resin suitable for use in the present invention is about 2
000-200000, preferably about 4000-100
It is 000. The molecular weight can be measured, for example, by measuring the end groups of a compressed film by infrared spectroscopy. Alternatively, GPC, which is a general measurement method involving solution formation, can be used.

Of the thermotropic liquid crystal polyester resins obtained from these monomers, aromatic polyesters or copolyesters which are (co) polymers containing the monomer unit represented by the following general formula (1) as an essential component are preferable. The monomer unit preferably contains about 30 mol% or more. More preferably, it contains about 50 mol% or more.

[0025]

[Chemical 1]

A particularly preferred aromatic polyester of the present invention is a copolyester represented by the following formula (2) having repeating units each having a structure derived from three compounds of p-hydroxybenzoic acid, phthalic acid and biphenol. is there. The repeating unit of the structure derived from the biphenol of the copolyester represented by the following formula (2) is
It may also be a copolyester in which some or all of it is substituted with repeating units derived from dihydroxybenzene. Alternatively, it is a copolyester represented by the following formula (3) having repeating units each having a structure derived from two compounds of p-hydroxybenzoic acid and hydroxynaphthalenecarboxylic acid.

[0027]

[Chemical 2]

[0028]

[Chemical 3]

The thermotropic liquid crystal polyester resin used in the present invention may be used alone, or two or more kinds thereof may be mixed and used. Two or more kinds of these synthetic resins can be used or a mixture of other polymers such as rubber can be used. In this case, it may be preferable to use a compatibilizing agent or the like in order to improve the compatibility of each component. Further, these synthetic resins may be chemically modified before use.

In the present invention, it is more preferable to add an inorganic filler to these synthetic resins. As the inorganic filler, kaolin, clay, talc, mica (muscovite, phlogopite), vermiculite, highly dispersible silicic acid, calcium silicate, feldspar powder, acid clay, wax clay, silica sand,
Cerisite, sillimanite, bentonite, glass flakes, glass powder, glass beads, slate powder, silicates such as silane, glass fiber, carbon fiber, metal fiber, ceramic fiber, holon fiber, barium titanate, calcium carbonate, calcium sulfate. , Magnesium hydroxide, silica, alumina, barium sulfate, barium carbonate, magnesium carbonate, dolomite, titanium oxide, zinc oxide, iron oxide, ferrite, molybdenum sulfide, perlite powder, calcined gypsum, hydrated alumina, alumina, antimony oxide, oxidation Magnesium, titanium oxide, zinc oxide, amorphous silica, quartz powder, flint quartz, silica sand, diatomaceous earth, white carbon, wollastonite, holon nitrite, silicon nitride, carbon black, graphite, wood powder, various whiskers, metal Powder, moth Scan-like carbon and the like.

Among these inorganic fillers, those having a fibrous or acicular shape such as glass fiber, carbon fiber, acicular calcium carbonate, acicular calcium sulfate and various whiskers, that is, an aspect ratio (particle length It is preferable that the value obtained by dividing by the diameter) is high. The aspect ratio is preferably 5 or more,
10 or more is more preferable. This is because the larger the aspect ratio, the higher the effect of improving strength / rigidity, dimensional accuracy, and heat resistance.

These inorganic fillers may be used alone or in combination of two or more. Further, in order to improve the dispersibility in the synthetic resin and the physical properties, a surface treatment agent such as a coupling agent may be used.

In the present invention, the compounding amount of the inorganic filler with respect to the synthetic resin is 5-80 with respect to 100 parts by weight of the synthetic resin.
Parts by weight are preferred. If it is less than 5 parts by weight, the effects of improving strength / rigidity, dimensional accuracy, and heat resistance may not be exhibited, and if it exceeds 80 parts by weight, moldability may be significantly impaired.

In the present invention, an injection molding method is used to obtain a tubular product. Although an ordinary injection molding machine can be used, it is necessary to devise a mold in order to obtain a molded product with high dimensional accuracy. A cylindrical molded product (cylindrical object) as shown in Fig. 1
A case of molding 1 using the mold shown in FIGS. 2A and 2B will be described as an example. The basic structure of the mold is a main mold 2 (2a, 2b) that forms the outer surface of a cylindrical object, a columnar body 3 (cylinder if it is a cylinder) that forms the inner surface, and a resin introduction part (sprue 4, runner 5, It consists of a gate 6).
The main mold 2 is usually two molds 2 that open and close left and right or top and bottom.
It is composed of a and 2b and is closed at the time of injection molding and open at the time of taking out a molded product. However, in this case, a trace of the line (referred to as a parting line) remains on the molded product at the mating portion of both molds, which may cause trouble depending on the application. In such a case, it is preferable to use a mold whose main mold is an integral structure. In this case, the molded product is taken out in the longitudinal direction of the tubular product.

The columnar body 3 is inserted into the cavity of the main mold at the time of injection molding, and after injection and cooling are completed, the columnar body 3 is removed from the molded product together with the molded product, and is removed from the molded product in a separate step. There is a method of removing the molded product after injection and cooling, and then removing the molded product. When the columnar body 3 is not firmly fixed at the time of injection, a molded product with good dimensional accuracy cannot be obtained. For this purpose, the main mold opening / closing mechanism is used to grasp the end or both ends of the columnar body. It is possible to take measures such as adopting such a structure or fitting a ring on the columnar body and moving this ring with the inflow of resin to prevent the columnar body from shaking.

Resin introduction part (sprue 4, runner 5,
The gate 6) may basically have a normal shape, but it is necessary to select a structure suitable for this molded product. Figure 2
A gate that flows in from the entire circumference of the cylindrical object, such as the disk gate illustrated in FIG. 3, is suitable because no weld occurs.

There are various methods for applying the metal coating used in the present invention. Specifically, methods such as electroless plating (chemical plating), electrolytic plating, sputtering, and vapor deposition are common. Among these, in the case of the above-mentioned applications where durability is required, the electrolytic plating method or the electroless plating method that forms a relatively strong coating film is preferable, and the electrolytic plating method is the most preferable.

For the plating step, a conventionally known plastic plating method can be adopted. Generally, a molded product is first degreased with an organic solvent, a surfactant or the like. Usually, this is followed by etching with a concentrated solution of sodium hydroxide or sulfuric acid.

Next, electroless plating is performed through each of the conditioning, catalyst application and activation steps. After that, electrolytic plating is performed if necessary. Copper, nickel, chromium and the like are generally used as the metal used in the electroless plating, and among them, nickel, chromium and the like are preferable for applications requiring slidability. There are many kinds of metals used for electrolytic plating, such as copper, nickel, chromium, gold, silver,
Examples thereof include tin-lead alloys. The thickness of the plated metal layer formed by the plastic plating method is generally 200Å to 1000
It is in the range of μm.

The sputtering method is, for example, 1 × 10 ⁻³ to
In a high vacuum of 2 × 10 ⁻⁴ Torr, a high voltage of, for example, 10,000 V or more is applied between the positive and negative electrodes to generate glow discharge, thereby scattering the cathode metal, and the scattered metal is a synthetic resin. It is deposited on the surface of a flexible molded product to form a metal film. Coexistence of an inert gas such as argon is also performed. There are various target metals, and in addition to copper, gold, chromium, aluminum, etc., a coating film of an oxide of a metal such as tin oxide or indium oxide can be formed.

The vapor deposition method includes a vacuum vapor deposition method and a chemical vapor deposition method. The vacuum deposition method is, for example, 1 × 10 ⁻³ to 1 × 10 ⁻⁴ Tor.
A metal film is formed on the surface of a molded body by heating a vapor deposition material under a high vacuum of about r and depositing a metal again on the surface of a molded article which is the surface of a substrate. used.

In the chemical vapor deposition method, a metal or a metal oxide is vaporized and sent to a reaction chamber, and a metal or a metal oxide is deposited on the surface of a molded product in a state close to a thermodynamic equilibrium state to form a film of these. Is the way to do it. Examples of the substance that precipitates include metals such as boron, oxides such as silica and alumina, carbides such as silicon carbide, and nitrides such as silicon nitride.

In addition, it is also possible to use an ion plating method or the like in which the evaporated particles of the base material from the evaporation source are ionized in plasma under high vacuum and the ions are attached to perform coating. As a method of generating plasma, there are a direct current excitation method of applying a direct current electric field and a high frequency excitation method of applying a high frequency electric field. Either method can be adopted.

The thickness of the film formed by the sputtering method, the vapor deposition method or the ion plating method is generally about 200Å to 1000Å.

In this manner, a lightweight synthetic resin tubular product having excellent strength / rigidity, dimensional accuracy, heat resistance and durability can be obtained.

[0046]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 A thermotropic liquid crystal polyester resin having repeating constitutional units respectively derived from p-hydroxybenzoic acid / terephthalic acid / biphenol / isophthalic acid was prepared (optically using a polarizing microscope equipped with a hot stage). When the anisotropy was observed, it showed optical anisotropy in the molten state at 340 ° C or higher).

45 parts by weight of glass fiber (made by Asahi Fiber Glass, trade name: Mild G
F MF20JH1-20, L = 200 μm, D = 10
μm and aspect ratio 20) were mixed and kneaded and granulated using a twin-screw extruder to obtain a composition.

About this composition, a cylindrical molded article as shown in FIG. 1 (cylindrical length 30 cm, outer shape 2 cm, thickness 2 m)
m) was injection molded using the mold of FIG. As the molding machine, IS-80 (trade name) manufactured by Toshiba Machine Co., Ltd. was used.

This molded product was subjected to an etching treatment in an aqueous KOH solution of 800 g / l at 70 ° C. for 40 minutes. After washing this with water, electroless copper plating was performed under the conditions described together with the following chemicals (both trade names, manufactured by Okuno Chemical Industries Co., Ltd.).

Conditioning: Conditioner SP (150 ml / l, 40 ° C., 40 minutes) Catalyst application: Catalyst C (40 ml / l, 23 ° C.,
4 minutes) Activation: Sulfuric acid (100 ml / l, 40 ° C, 4 minutes) Electroless copper plating: OPC-Kapper H (23 ° C, 10
Minutes)

This was immersed in a plating bath containing nickel sulfate and nickel chloride as main components, and electrolytic plating was carried out by a usual method to form a nickel layer having a thickness of 60 μm.

Example 2 A composition prepared by adding 50 parts by weight of calcium carbonate (average particle size 5 μm) to 100 parts by weight of the same thermotropic liquid crystal polyester resin as in Example 1 was used.
A molded product having the same shape as was molded. This molded product was subjected to an etching treatment for 10 minutes in a 300 g / l KOH aqueous solution heated to 50 ° C. while applying ultrasonic waves. After washing this with water, electroless plating of copper and electrolytic plating of nickel were performed in the same manner as in Example 1.

[0054]

EFFECT OF THE INVENTION Since the synthetic resin tubular article of the present invention is molded by injection molding using a thermoplastic synthetic resin, it has good dimensional accuracy, is lightweight and is inexpensive. In particular, the one using a thermotropic liquid crystal polyester resin is characterized by excellent strength / rigidity and heat resistance and extremely high dimensional accuracy. Further, in the present invention, since the metal coating is formed on the surface of the cylindrical object, the slidability and durability of the surface are good. In particular, nickel and chromium electrolytically plated ones have more structural strength.
The rigidity is improved.

Since the synthetic resin tubular product of the present invention has many features as described above, it can be used for office machines such as copying machines and printing machines, and rolls of industrial machines such as conveyors and heating furnaces. It is useful.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a thermoplastic synthetic resin tubular article used in the present invention.

2A and 2B are a top view and a cross-sectional view of a mold used for manufacturing a thermoplastic synthetic resin tubular product.

[Explanation of symbols]

1: Cylindrical object made of thermoplastic synthetic resin, 2a, 2b: Mold,
3: columnar body, 4: sprue, 5: runner, 6: gate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area B29L 23:00

Claims (5)

[Claims] 1. A synthetic resin tubular article, characterized in that a metal coating is applied to the outer surface of a thermoplastic synthetic resin tubular article formed by injection molding. 2. The synthetic resin cylinder according to claim 1, wherein the metal coating is applied by electrolytic plating or electroless plating. 3. The tubular product made of synthetic resin according to claim 1, wherein the thermoplastic synthetic resin is a thermotropic liquid crystal resin. 4. The synthetic resin tubular article according to claim 1, wherein the thermoplastic synthetic resin is a composition containing an inorganic filler. 5. The synthetic resin cylinder according to claim 4, wherein the aspect ratio of the inorganic filler is 5 or more.