JPS6196063A - Manufacture of composite formed body - Google Patents

Abstract

PURPOSE:To obtain the composite formed body integrating firmly a resin base material with ceramics, by spraying ceramics after forming a specific intermediate layer consisting of inorganic filler component and organic binder component on the surface of the resin base material. CONSTITUTION:The intermediate layer having the following thermal conductivity and composed by incorporating the organic filler component of unflat shape to the organic binder component, is previously formed on the resin base material or on the surface layer thereof: the thermal conductivity being >=0.001 cal.cm<-1>.sec<-1>.deg<-1> and satisfying lambda.S>=0.05 in which lambda means the thermal conductivity represented by cal.cm<-1>.sec<-1>.deg<-1> and S means the surface area represented by m<2>/g. Moreover, nickel, diatomaceous earth, iron or the like can be used as the inorganic filler and acrylic resin or the like can be used as the organic binder, the inorganic filler component is incorporated to the intermediate layer by >=15wt%. Succeedingly, the ceramics is sprayed on this intermediate layer to form the firm composite formed body having a ceramics-sprayed film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a composite molded body by thermally spraying ceramics onto a resin base material.

[Conventional technology]

Conventionally, it is well known that a composite molded article having a metal film formed on the surface of a resin base material can be obtained by, for example, a plating method, a vacuum evaporation method, or the like. In this case, the metal film generally lacks hardness, has poor abrasion resistance, and still has problems in terms of chemical resistance, so its range of use is currently limited.

Ceramics have many advantages over these metals, such as extremely high hardness and stability against chemicals. Therefore, composite molded products in which a ceramic film is appropriately formed on the surface of a resin base material are expected to be used in industrial materials and even functional materials, which could not be used in the past. The voice that wishes for the appearance of the body is getting louder.

However, ceramics generally have a high melting point and are brittle. For example, it is difficult to form a film thickness on the surface of a resin base material that can fully utilize the film performance of ceramics.
This is currently considered to be completely impossible [Polymer Digest Mol 35° Late 11, pp. 2-13 (1983)].

In other words, when a ceramic film is deposited on the surface of a resin base material using a thermal spraying method, (1) the coefficient of linear expansion of the resin base material and the sprayed film are significantly different; (2) the ceramic material is melted at a high temperature; (3) Ceramics and resin substrates are thermally deformed or, in extreme cases, melted or thermally decomposed because the ceramics are sprayed directly onto the surface of the resin substrate, which has a low softening point. For various reasons, such as the lack of affinity or chemical bonds found in general organic coating agents, it could not be put to practical use.

In order to solve the above problems, the present inventors conducted intensive studies, and in Japanese Patent Application No. 59-71351, the inventors of the present invention have prepared a material with a thermal conductivity of 0.001 caJ-a on the surface or surface layer of a resin base material in advance.
We have already proposed a method for producing a composite molded body by forming an intermediate layer consisting of an inorganic filler component and an organic binder component of m-'.5ea-'.d@p-' and then thermally spraying the ceramic material.

The present inventors further developed the above-mentioned proposal and conducted various studies in order to form a strong thermally sprayed ceramic coating on the surface of a resin base material, which had been considered completely impossible.
In order to improve the durability of the resin base material and thermal spray coating,
A method for manufacturing an integrated composite molded body has been obtained.

[Means for solving problems]

The gist of the present invention is that the resin base material has a thermal conductivity of 0.001 ear・am-'
・s e c-'・deg-' or more, the thermal conductivity S expressed by formula 7 (%) is the surface area expressed in ml. After forming an intermediate layer, a ceramic is thermally sprayed to produce a composite molded body.

In the present invention, in order to form an intermediate layer on the surface of a resin base material, at this stage, for example, industrial equipment parts having a complicated shape or high dimensional accuracy, such as gears, pulleys, high-speed rollers, and even textile machine parts, are drawn. A major feature is that ceramic spraying can be applied to rollers, take-up rollers, yarn twisting disks, etc. In addition, ceramic spraying
In particular, it is possible to form a ceramic film on the surface of a resin base material that has a complex shape, which was previously impossible, so ceramics can be thermally sprayed onto the surface of a plastic mold used to process plastics for automobile parts, making it heat resistant and wear resistant. It has the characteristic that it can also improve

In the present invention, in order to form a sprayed ceramic coating on the surface of the resin base material, the interface between the resin base material and the sprayed coating has a thermal conductivity of O.
'·deg-' It is necessary that the intermediate layer satisfies the formula 1 formula % formula % above and contains an inorganic filler component whose shape is not flat.

Here, the thermal conductivity λ is preferably large in order to solidify ceramic droplets to form a film during ceramic spraying and to relieve stress caused by a temperature difference between the sprayed coating and the base material.

In addition, the surface area S is, for example, B, E, T due to a gas adsorption trap.
It is the surface area of an inorganic filler obtained by the . That is, in order to improve the adhesion between the ceramic sprayed coating and the undercoat layer, it is necessary to sufficiently enhance the anchoring effect of the sprayed coating, and for this purpose, it is preferable that the surface area S is large.

Here, if the value of the formula λ°S is smaller than 0.05, for example, even if λ is large, if S is small, the anchoring effect of the sprayed coating will be small, and although the coating can be formed, the impact resistance will be This results in poor impact resistance.

In addition, when λ is small and S is large, it becomes difficult to form a film, and this tendency becomes impractical, especially when the base material is a material with a small λ such as plastics.

Furthermore, even if λ・S is within the range of the present invention, if the filler has a flat shape, the filler will be oriented in the layer direction of the intermediate layer in the present invention, resulting in an anchor effect between the filler and the ceramic film. Therefore, a composite molded article having excellent adhesion, which is the object of the present invention, cannot be obtained.

Therefore, the filler shape is spherical.

It is preferable to have a polygonal shape, a dendritic shape, or a shape with an aspect ratio of 1 or more, but a mixture of these shapes or a shape that is aggregated or fused while maintaining the original shape is also acceptable.

Based on the above study results, the present inventors have found that excellent performance can be obtained by interposing an intermediate layer consisting of an inorganic filler component and an organic binder component at the interface between the resin base material and the thermal spray coating. It is something. This intermediate layer has an affinity with the chemical lamic coating, and the organic binder component mixed with the inorganic filler has the role of alleviating the stress caused by thermal shrinkage that occurs during the formation of the thermal spray coating. A multi-composite body with adhesive strength superior to that obtained by ceramic thermal spraying has now been obtained. For example, when the base material is metal and the sprayed coating is ceramic, as the thickness of the sprayed coating increases, the internal strain of the sprayed coating increases, which inevitably causes natural peeling. Although the limit is several hundred micrometers, the method of the present invention can produce a surprising composite molded article in which the thickness of the sprayed coating can be from several micrometers to several inches.

The method for manufacturing the composite molded article of the umbrella invention is as follows: (1) A thermoplastic resin or a thermosetting resin mixed with an inorganic filler on the surface of a resin base material is dissolved in +a+organic solvent, or dissolved in TBL water. Alternatively, an emulsion-type water-based type, TC+solvent-free type, etc. is coated by a spray method, screen method, dipping method, etc., and it is fixed to the surface of the resin base material, and then ceramic spraying is performed. (2) Resin base material During molding, there are two methods: directly mixing inorganic filler into the surface layer, fixing it, and then performing ceramic spraying to integrate it.

In the present invention, the inorganic filler component has a thermal conductivity of 0.001 cal-am-'・sec-' ・de
7 + -' or more, and a synergistic effect between thermal conductivity and surface area is required. ) is required to satisfy the following.

Specific examples thereof include a complex of two alloys of an inorganic compound generally referred to as a metal, a compound or salt with an oxide, nitride, carbide, or nonmetal, such as evanickel and carbonyl nickel.

Diatomaceous earth, aluminum, copper, iron, tin, zinc, silver.

Platinum, palladium, chromium, carbon, 7
Bismuth, selenium, tellurium, charcoal.

Alumina, silicon carbide, titania, zirconia.

Examples include one or a mixture of two or more of boron nitride, zirconium nitride, tungsten carbide, silicon carbide, magnesium zirconate, asbestos, and the like.

The organic binder component as used in the present invention refers to ordinary thermoplastic resins such as acrylic resins, vinyl acetate resins, epoxy resins, ester m resins, urethane resins, alkyd resins, etc., ordinary thermosetting resins such as acrylic/melamine resins,
Acrylic/urethane resins, curing agent-containing epoxy resins, and the like can be used, and are not particularly limited. The intermediate layer of the present invention is formed by blending the organic binder component and the inorganic filler component, but its usage conditions are as follows:
It may be in any form, such as a solvent type dissolved in an organic solvent, a water type dissolved in water or in an emulsion type, or a non-solvent type. Further, in order to stabilize these conditions and maintain the uniformity of the intermediate layer, a dispersion stabilizer, an anti-settling agent, a thixotropic agent, etc. may be added.

In the present invention, the mixing ratio of the inorganic filler and the resin is
Although it may be selected freely depending on the conditions of the method of forming the intermediate layer, it is preferable that the inorganic filler component accounts for 15% by weight or more, and if it is less than 15% by weight, the effect of the present invention will be weakened.
Environmental resistance.

A composite molded article with good impact resistance cannot be obtained.

The resin base material referred to in the present invention may be either thermoplastic or thermosetting resin, such as polyester.

polyamide, polyethylene, polypropylene.

polyvinyl chloride, polycarbonate, polyvinyl fluoride,
Examples include polyacetal, polymethyl methacrylate, epoxy, melamine, phenol, polyimide, ABS resin, and the like. Furthermore, fiber-reinforced resins containing fibrous materials are also included.These fibrous materials include glass slag, carbon, and boron.

Steel, inorganic fibers such as silicon carbide, polyester,
Examples include organic fibers such as polyamide, aramid, polypropylene, linen, and cotton. These fibrous materials are used in the form of short fibers, long fibers, aligned sheets, nonwoven fabric sheets, knitted woven fabrics, and the like.

In the present invention, a composition consisting of the above-mentioned inorganic filler component and organic binder component is applied onto these resin base materials in the respective shapes, for example, the base material is plate-like.

Depending on the shape, such as a hollow shape or a shape with complex irregularities, spraying methods, screen coating methods, dipping methods, etc. are applied as appropriate. In this case, in order to improve the adhesion with the resin base material, it is preferable to use the same type of organic binder component as the base material as much as possible. In this case, the intermediate layer is necessarily formed of an inorganic filler component on the surface of the resin base material.

Heating, pressure, and other bonding conditions vary depending on the physicochemical properties of the various base materials.

The invention is not limited to this.

The thickness of the intermediate layer is also not particularly limited, but it is preferably 10 μm or more in view of the particle size of the thermal spray material.

The present invention has the above features: (Thus, an intermediate layer consisting of an inorganic filler component and an organic binder component is formed on the surface or surface layer portion of a resin base material.

Next, the ceramics referred to in the present invention are thermally sprayed, and the ceramics herein are ceramics that are thermally sprayed onto ordinary metal substrates, such as aluminal titania, alumina, and titania.

Chromium oxide, nickel oxide, cobalt oxide, zirconia, magnesium zirconate, Schinel.

Oxides such as cesium oxide, tungsten carbide, silicon carbide, chromium carbide.

Nitrides such as titanium nitride, silicon, zirconium nitride, and boron nitride.

Methods for thermally spraying ceramics on a substrate having an intermediate layer formed on the surface or surface layer of the resin substrate of the present invention, which refers to a single carbide or a mixture thereof, are plasma jet thermal spraying and arc thermal spraying.

Methods such as hot wire thermal spraying can be selected, but due to the high melting point of ceramics, they are often insufficient as a heat source, and plasma jet thermal spraying provides an excellent thermal spray coating as a method that can be efficiently sprayed in a short time. This is preferable in that it can be done.

Moreover, the thermal spraying conditions can be easily achieved by a method of ceramic thermal spraying on a normal metal base material. By interposing an intermediate layer at the interface between the thermal spray coating and the surface of the resin base material, the heat of the ceramic thermal spray droplets is radiated uniformly and rapidly, and an affinity is developed between the droplets and the intermediate layer. Therefore, it is possible to produce a composite molded article having good initial adhesion, environmental resistance and trapping impact resistance. Above all, it has become possible to spray ceramics onto resin substrates, which was considered impossible in the past, and its industrial value can be said to be extremely large.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

In the examples, parts mean parts by weight.

Example 1 40 parts of epoxy resin (Epicote 834, manufactured by Yuka Shell Co., Ltd.), imidazole compound (Curezol 2PZ)
-CN (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2 parts of each inorganic filler shown in Table 1, and 70 parts of methyl isobutyl ketone were kneaded to obtain an intermediate layer composition.

The intermediate layer composition was spray coated onto various resin substrates that had been previously sandblasted to a thickness of approximately 100 μm, and heat treated at 80° C. for 2 hours to harden the intermediate layer.

Next, ceramics were sprayed onto the base material under the following conditions.

Thermal spraying material: Alumina carrier gas with a particle size of 10 to 44μ; Mixed gas device consisting of 90 parts of nitrogen and 10 parts of hydrogen; Model 7MB manufactured by Metco Co., Ltd. Thermal spraying distance: 150as The performance evaluation results of various composite molded bodies obtained by this method are shown below. 1
Shown in the table.

The height of the fall at which an abnormality was observed (cm).

As is clear from Table 1, it can be seen that the method of the present invention not only makes it possible to spray ceramics onto resin substrates, but also greatly improves performance.

Example 2 The resin base material was a satin fabric with 8 carbon fibers, and epoxy resin (Epicoat 828, Yuka Shell) was used as the matrix resin.
Each base material was prepared by using a laminate having a thickness of 2 mm and a fiber volume content of 50 Mo1% impregnated with the following inorganic filler (manufactured by Co., Ltd.) and thermoset.

Table 2 In this case, these inorganic fillers are prepared by kneading the above-mentioned epoxy resin in a ratio of 2,001 parts by weight and 100 parts by weight, applying this to a thickness of 100 to 150 μm, heating and pressurizing, and adding inorganic fillers to the surface layer. An intermediate layer containing the components was formed.

Furthermore, these were treated with alumina of particle size #150 at a pressure of 2 k.
After sandblasting for 2 minutes at g/♂, alumina/titania (60:40) with an average particle size of 20 μm was applied using a 7MB plasma jet device manufactured by Daiichi Metco Co., Ltd.
Spraying distance 150 m, arc voltage 75v, current 500A,
Plasma spraying was performed using argon-hydrogen gas. The obtained composite molded product exhibited the performance shown in Table 3.

Table 3 As is clear from Table 3, λ is the thermal conductivity of the inorganic filler, and S is the inorganic filler that satisfies the surface area.Excellent properties were obtained by interposing an inorganic filler as an intermediate layer. .

〔Effect of the invention〕

This method forms an intermediate layer consisting of a certain inorganic filler component and an organic binder component, and then thermally sprays ceramics to firmly integrate the resin base material and ceramics, unlike conventional thermal spraying consisting only of resin and ceramics. It becomes possible to produce a composite molded body with durability and strong surface properties not found in composite molded bodies.

Claims (1)

[Claims] 1. On the surface or surface portion of the resin base material, the thermal conductivity is 0.
001cal・cm＾-＾1・sec＾-＾1・deg
＾-＾1 or more, the formula λ・S≧0.05 (However, λ is cal・cm＾-＾1・sec＾-＾1・
After forming an intermediate layer consisting of an inorganic filler component and an organic binder component that satisfies the following (the thermal conductivity S expressed as deg^-^1 and the surface area expressed as m^2/g) and is not flat in shape, , a method for producing a composite molded body, characterized by thermally spraying ceramics. 2. 15% by weight of inorganic filler component on the surface of the resin base material
The method for producing a composite molded article according to claim 1, wherein an intermediate layer is formed by coating the organic binder composition containing the above. 3. The method for producing a composite molded article according to claim 1, wherein an intermediate layer containing 15% by weight or more of an inorganic filler component is formed on at least the surface portion of the resin base material.