JPH04164883A - Ceramic conjugate plate - Google Patents

Abstract

PURPOSE:To improve surface fouling resistance and toughness for a long period by providing a thermoplastic resin layer on a ceramic layer. CONSTITUTION:A thermoplastic resin film (e.g. tetrafluoroethylene-based resin) having 2-1000mum thickness is joined onto a ceramic layer, prepared by, as necessary, blending ceramics (e.g. Al2O3) with a 0.01-5PHR colorant (e.g. TiO2), forming the resultant blend and sintering the formed product and having 0.5-10mm thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a ceramic composite, and more particularly to a ceramic composite plate that has excellent long-term surface contamination resistance and excellent toughness.

[Conventional technology]

Traditionally, ceramics are hard materials with superior heat resistance, corrosion resistance, abrasion resistance, and electrical insulation properties compared to metals and plastics, so they are used in ceramics such as tile bricks and roof tiles, and in steelmaking furnaces. refractories such as materials, refractory bricks, refractory insulation materials, IC boards, thermistors, capacitors, piezoelectric materials,
It is widely used in electric/electronic/magnetic materials such as magnetic materials, power reactor materials, high temperature/structural materials such as gears, fans, turbines, cylinders, etc.

However, these ceramics have poor surface smoothness and impact resistance due to their raw materials and manufacturing methods, are easily contaminated, and are easily destroyed, so their uses have been limited.

[Problem to be solved by the invention]

An object of the present invention is to solve the above-mentioned problems that the prior art had, and to provide a novel ceramic composite plate that has been completely unknown heretofore.

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems, and provides a ceramic composite plate characterized by having at least a thermoplastic resin layer and a ceramic layer. The constituent factors of the present invention will be explained in more detail below.

The U thermoplastic resin layer in the present invention is not particularly limited, and any thermoplastic resin may be used, but
For example, Me Gram-H
ill, Inc., published by Modern Plastics Encyclopedia.
Encyclopedia) J Volume 66-11, No. 6
00-643, specifically, fluorine-containing, vinyl, acrylate, urethane, ester, cellulose, styrene, olefin, amide, acetal, and aryl resins. , epoxy type, carbonate type, imide type, and mixtures thereof, among which fluorine-containing type, vinyl type, and acrylic type are preferable, and fluorine-containing type thermoplastic resin is particularly preferable.

The fluorine-containing thermoplastic resin referred to in this application is not particularly limited as long as it is a thermoplastic resin that contains fluorine in its molecular structure, but specifically, for example, These include tetrafluoroethylene resins having individual fluorine atoms, trifluoroethylene resins, difluoroethylene resins, -fluoroethylene resins, and composites of these resins, among others, tetrafluoroethylene resins. and nifsoethylene-based resins are preferred, and tetrafluoroethylene-based resins are more preferred. Here, the tetrafluoroethylene resin is
Specifically, for example, tetrafluoroethylene 41j resin (P
TFE), tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene/hexafluoropropylene/perfluoroalkoxyethylene copolymer (EPE), and tetrafluoroethylene/ethylene copolymer (
ETFE'), among others PFASETFE and E
PE is preferred, especially ETFE. Specifically, ETFE is mainly composed of ethylene and tetrafluoroethylene, and the molar ratio of ethylene/tetrafluoroethylene is generally 40/60 to 60/40), and if necessary, a small amount (usually 10 mol). % or less), and in the present invention, in particular, the molar ratio of ethylene/tetrafluoroethylene is 40/60 to 60/40, preferably 4515
5 to 55/45, and the content of perfluoroalkyl vinyl monomer units represented by the formula % is 0.1 to 10 mol%, preferably 0.
．． An ethylene-tetrafluoroethylene copolymer having a content in the range of 3 to 5 mol% is preferably used. This ethylene-tetrafluoroethylene copolymer is known per se, and can be produced, for example, by the method described in Japanese Patent Publication No. 59-50163. It is also possible to use those commercially available under trade names.

In addition, the above-mentioned trifluoroethylene resin specifically includes, for example, trifluorochloroethylene resin (PCTFE) and trifluorochloroethylene/ethylene copolymer (ECTFE).
etc., and among them, PCTFE is preferable. Specifically, the difluorinated ethylene resin and the -fluorinated ethylene resin are, for example, vinylidene fluoride resin (PVDF) and vinyl fluoride resin (PVC).

In the present invention, there are no particular limitations on the method for setting the thermoplastic resin layer, and for example, a thermoplastic resin film may be first created and then bonded onto a ceramic plate using an adhesive or a hot melting method. Alternatively, it can also be obtained by applying a thermoplastic resin solution onto a ceramic plate and drying it. A coloring agent can be added to these thermoplastic resin layers as necessary.

Here, the "colorant" used in the present invention is a colorant added and mixed into the fluorinated resin film,
Although not particularly limited, examples include white coloring, red coloring, vermillion coloring, yellow coloring, greenish blue coloring, purple coloring, and black coloring agents. More specifically, white colorants include, for example, zinc oxide (ZnO), titanium oxide (Tie
), lithopone (ZnS+Ba5O4), zinc sulfide (
Examples of red colorants include cadmium red (CdS+Cd5e), antimony red (2Sb,
S, -S b, O, ), irgazine red, perylene red, vermilion colorants include, for example, iron oxide-based [F
e, O, + (Feo)), chrome vermilion (P
bCrO, -PbMoO4, Pb5O4), amber colorants (Fe20.+MnO, +Mn, O,), yellow colorants include, for example, chrome yellow colorants (PbCrO,
), zinc yellow type (ZnCrO, l), barium chromate type (BaCrO4), cadmium yellow type (CdS),
Titanium yellow type (TiO=-NiO・SbO,),
Ocher type (Fe.

0, S i O, A I20. ), Green colorants include phthalocyanine, chrome green (
Cobalt green type (CoOZnOMg)
O), cerulean blue (Coo-nSn02・mM
go), blue colorants include ultramarine (3NaA
l-5io, ・Na, S, ), dark blue (Fe4(Fe(
CN), )m-nH20), Cobalt Blue (Coo
-nA 1,0. ), cyanine blue colorants, and purple colorants such as cobalt purple [C,, (PO,),)
, cobalt purple [Co, (A s O4) O], dioxazine violet, and black colorants such as carbon black, iron black, aniline block, and cyanine black.

The amount of these colorants added is not particularly limited,
Any one may be used, but in terms of radiation, it is 0.01 to 5 PHR, preferably 0.2 to 3 PHR, more preferably 0.3 to 5 PHR.
It is 2PHR.

Further, the thickness of the thermoplastic resin layer is not particularly limited, but is 2 to 1000 μm, preferably 10 μm.
-250μ, more preferably 30-1ooμ.

Moreover, if necessary, it is also possible to print on the front and/or back surfaces of the film and the surface of the ceramic plate laminated on the thermoplastic resin to improve decoration and functionality.

In addition, "ceramics" in the present invention is not particularly limited, but includes, for example, "Ceramic Engineering Handbook", edited by Japan Ceramics Association, April IO, 1989, published by Gihodo Publishing, 1st edition, 1st edition. , among which oxide ceramics and non-oxide ceramics are preferred. Oxide ceramics include, for example, alumina (AI, O,), magnesia (MgO,
), glass, clay, silicone (ZrO, ), etc., among which AI, O, and the like are preferred. Examples of non-oxide ceramics include aluminum nitride (AIN), silicon carbide (SiC), and silicon nitride (StsNa), with AIN and silicon carbide being preferred.

The thickness of the ceramic layer is not particularly limited and is generally 0.5 to 10 mm, preferably 2 to 8a+n+, and more preferably 3 to 6 mm. Furthermore, it is also possible to improve physical properties such as heat insulation and heat retention by making the ceramic layer have a crab-comb structure, a corrugated core like cardboard, or a foamed material.

Furthermore, although ceramic is a highly hard material with excellent thermal resistance, corrosion resistance, abrasion resistance, and electrical insulation, it is inferior in impact strength and stretching strength, so it is necessary for the ceramic layer in the present invention. Depending on the requirements, fibers can be used as reinforcement.

The fiber material is not particularly regulated, but for example, the above-mentioned document "Ceramic Engineering Handbook" No. 23
Among the fibers described on pages 03 to 2313, carbon fibers,
Examples include glass/ceramic fibers, oxide fibers, non-oxide fibers, and whiskers made of SiC, etc., with carbon fibers and SiC whiskers being particularly preferred.

Furthermore, the composite plate of the present invention has the thermoplastic resin layer and the ceramic layer, and it is important that these are substantially joined, and the entire surface is not necessarily completely bonded and bonded.
It does not need to be bonded and may simply be supported on the surface depending on the purpose, but radiationally, thermal fusion with an adhesive or thermoplastic film, or furthermore, a thermoplastic resin solution can be used. It is desirable that the entire surface be bonded and bonded by coating or the like. The adhesive used in this case, the bonding method, the hot melt bonding method, the plastic resin solution and the coating method are not particularly limited, and conventionally used ones can be used.

The thus obtained composite plate of the present invention has better heat resistance, corrosion resistance, abrasion resistance, and
Due to its excellent physical properties such as electrical insulation and impact resistance, it can be used, for example, as outdoor signage and road sign materials, as well as on the exterior and interior walls of buildings, as well as ceiling and floor materials, fire walls, sinks, bathtubs, and their interior wall materials. , interior walls of clean rooms and computer-related buildings,
It is widely used for ceilings, flooring, chemical reaction equipment materials, etc., and its contribution to the industry is extremely large.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but it goes without saying that the present invention should not be limited to the examples.

Example A (Preparation of Ceramic Composite Board) Example 1 An alumina ceramic substrate with a thickness of 1 cm was prepared by sintering alumina particles with a particle size of 3 μm at a temperature of 1600°C.
After being treated in a 10% aqueous hydrofluoric acid solution at 20° C. for 5 minutes, it was washed with water and dried.

The surface roughness Rz of this alumina plate was 20 prn.

Commercially available ethylene-tetrafluoroethylene copolymer resin (
ETFE; Afron C0P manufactured by Asahi Glass) under temperature condition 32
An ETFE film with a thickness of 60 pm was produced by melt extrusion at 0°C. The melt flow index of this ETFE resin was 4.

The above surface-treated alumina substrate was heat-treated at 350° C. for 10 minutes, and then thermally bonded to an ETFE film using a pair of 5-inch rolls. The crimp force at this time is 120kg/c
It was mt. (7) ETFE heat-fused alumina plate,
Further, heat treatment was performed at 320° C. for 10 minutes to obtain an ETFE laminated alumina plate (2).

Example 2゜In the method of Example 1, a PFA film was used instead of the ETFE film, heat treatment was performed at 360°C, and post-heat treatment 3
A PFA laminated alumina plate (2) was obtained at 80°C.

Example 3 In Example 1, the back side of the ETFE film was corona treated to have a wettability index of 40 dynes, and then printed using a vinylidene fluoride screen printing ink. This printed film was dried at 120° C. for 30 minutes to obtain a vinylidene fluoride film with a thickness of 10 μm. A printed ETFE laminated alumina board (■) was obtained with the printed side facing inside.

Example 4 A quartz glass plate with a thickness of 211 m1 was treated on one side with a 10% hydrofluoric acid aqueous solution at 20°C for 5 minutes, and then washed with water.
It was dried.

This surface-treated quartz glass plate was subjected to ET using the method described in Example 1.
An FE laminated quartz glass plate ■ was obtained.

Example 5゜In the method of Example 4, a quartz glass plate was
After the surface was roughened using 0 mesh 7 random powder, it was treated with hydrofluoric acid to obtain an ETFE laminated quartz glass plate (2).

Comparative Examples 1-2 In Examples 1 and 4, only alumina and quartz glass were used without laminating an ETFE film.

Comparative Example 3゜In Comparative Example 1, a vinyl chloride plate (
Plate thickness III+1) was used.

Comparative Example 4 In Example 1, a vinylidene fluoride paint was applied to the alumina plate without laminating the ETFE film to obtain a ceramic composite board having a vinylidene fluoride resin layer (layer thickness 40μ). .

Example B (Evaluation of Ceramic Composite Board) The physical properties of each ceramic composite board prepared in Example A were tested and evaluated as shown in Table-1, and the results are shown in Table-1.

The test method and basic evaluation of the results were as follows.

(1) Test method 1 A width of 100 mm and a thickness of 12 mm is placed above a 100 AO square test piece.
mm.

A silicone sealant (Toshiba Silicone Tosseal 380) was applied to a size of 12a+m in height, and exposed outdoors for 3 months on a test stand at an angle of 30°.

After exposure, wipe the dirt twice with alcohol-soaked gauze and evaluate the appearance.

<Evaluation criteria> 0 No difference from the original plate can be seen.

○ Slightly dirty.

△ Dirt can be identified.

X: There is a lot of dirt remaining.

(2) Test method: 2° A board is allowed to fall horizontally from a height of 2 m.
Determine appearance.

Evaluation criteria 0 No damage or deformation.

○ There is damage that is less than 10% of the total area, but it does not scatter.

△ There is damage of less than 10% of the total area and it scatters.

× The whole thing is scattered.

(3) Test method 3 The heat resistance temperature is defined as the temperature at which the appearance does not change after being treated at the specified temperature for 2 hours.

(4) Test method 4 60° gloss was actually measured in accordance with JIS Z-8741.

Claims (1)

[Claims] 1. A ceramic composite plate comprising at least a thermoplastic resin layer and a ceramic layer. 2. The ceramic composite plate according to claim 1, wherein the thermoplastic resin is a fluorine-containing resin. 3. The ceramic composite plate according to claim 1, wherein the thermoplastic resin layer has a thickness of 2 to 1000 μm. 4. The ceramic composite plate according to claim 1, wherein the ceramic is alumina. 5. The ceramic composite plate according to claim 1, wherein the ceramic layer has a thickness of 0.5 to 10 mm. 6. The ceramic composite plate according to claims 1 to 5, wherein the ceramic is a fiber-reinforced ceramic. 7. The ceramic composite plate according to claim 6, wherein the fibers are carbon fibers.