Composite plate and method for producing same

Abstract

A composite plate has a thickness of 2 mm or less, which is obtained by laminating and closely fixing a zirconia sintered body and a fiber-reinforced plastic with each other, and the thickness ratio of the zirconia sintered body to the fiber-reinforced plastic is 0.01 to 1, and the apparent density of the composite plate is 4.3 g/cm.sup.3 or less. A composite plate has a thickness of 2 mm or less, which is obtained by laminating and closely fixing a zirconia sintered body and a fiber-reinforced plastic with each other, and the maximum roughness depth of the surface of the zirconia sintered body is 50 m or less per 1 cm.sup.2.

Claims

1. A composite plate comprising a laminate including a zirconia sintered body and a fiber-reinforced plastic that are closely fixed to each other by an adhesive, the composite plate having a thickness of 0.624 to 0.966 mm, wherein a ratio of a thickness of the zirconia sintered body to a thickness of the fiber-reinforced plastic is 0.16 to 0.57, the composite plate has an apparent density of 4.3 g/cm.sup.3 or less, and the fiber-reinforced plastic is selected from the group consisting of glass fiber-reinforced plastic and; carbon fiber-reinforced plastic.

2. The composite plate according to claim 1, comprising the laminate including the zirconia sintered body and the fiber-reinforced plastic that are closely fixed to each other with a white adhesive, herein the zirconia sintered body shows a white color with a surface color (L*, a*, b*) in a range where L* is 86 to 94, a* is 1 to +1, and b* is 1 to +1.

3. The composite plate according to claim 1, wherein the zirconia sintered body is zirconia containing 2 to 10 mol % yttria with respect to the zirconia.

4. The composite plate according to claim 1, wherein the zirconia sintered body is zirconia containing at least one type selected from the group consisting of a white pigment, a transition metal oxide, and a color pigment.

5. The composite plate according to claim 1, wherein the zirconia sintered body has a relative density of 97% or more.

6. The composite plate according to claim 1, wherein the zirconia sintered body has a Vickers hardness of 1,000 or more.

7. The composite plate according to claim 1, wherein the composite plate has high impact resistance with a fracture height of 10 cm or more in a test in which a steel ball of 130 g is freely dropped thereon.

8. The composite plate according to claim 1, wherein the composite plate has an apparent density of 0.9 to 4.3 g/cm.sup.3.

9. A composite plate comprising a laminate including a zirconia sintered body and a fiber-reinforced plastic that are closely fixed to each other by an adhesive, the composite plate having a thickness of 0.624 to 0.966 mm, wherein a maximum roughness depth of a surface of the zirconia sintered body is 50 m or less per 1 cm, a ratio of a thickness of the zirconia sintered body to a thickness of the fiber-reinforced plastic is 0.16 to 0.57, the composite plate has an apparent density of 4.3 g/cm.sup.3 or less, and the fiber-reinforced plastic is selected from the group consisting of glass fiber-reinforced plastic and; carbon fiber-reinforced plastic.

10. The composite plate according to claim 9, comprising the laminate including the zirconia sintered body and the fiber-reinforced plastic that are closely fixed to each other with a white adhesive, wherein the zirconia sintered body shows a white color with a surface color (L*, a*, b*) in a range where L* is 86 to 94, a* is 1 to +1, and b* is 1 to +1.

11. A case for a mobile electronic device using the composite plate according to claim 1.

12. A watch component using the composite plate according to claim 1.

13. A method for producing the composite plate according to claim 1, comprising bonding the zirconia sintered body and the fiber-reinforced plastic using an epoxy-based thermosetting adhesive at a temperature of 300 C. or lower.

14. The method for producing the composite plate according to claim 13, wherein the zirconia sintered body is obtained by forming a slurry into a green sheet having a thickness of 1 mm or less, the slurry being prepared by mixing zirconia powder and an organic binder, and sintering the green sheet and the slurry at 1,300 to 1,500 C.

15. A method for producing the composite plate according to claim 9, comprising bonding the zirconia sintered body and the fiber-reinforced plastic using an epoxy-based thermosetting adhesive at a temperature of 300 C. or lower.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a diagram illustrating an external appearance of a zirconia composite plate obtained in Example 4.

(2) FIG. 2 is a micrograph showing the surface of a zirconia composite plate obtained in Example 37 and subjected to scratching treatment.

(3) FIG. 3 is a diagram illustrating the state of a zirconia composite plate obtained in Example 39 and subjected to a nail penetration test.

(4) FIG. 4 is a micrograph showing the surface of an aluminosilicate-based tempered glass used in Comparative Example 5 and subjected to scratching treatment.

(5) FIG. 5 is a diagram illustrating the state of a base material (a white zirconia sintered body) in Comparative Example 6 after a nail penetration test.

(6) FIG. 6 shows a three-dimensional surface shape of a zirconia sintered body used in Example 41.

(7) FIG. 7 shows a three-dimensional surface shape of a zirconia composite plate in Example 41.

(8) FIG. 8 shows a three-dimensional surface shape of a zirconia composite plate in Example 42.

(9) FIG. 9 shows a surface profile of a composite plate in Reference Example 1.

(10) FIG. 10 shows the surface shape of a zirconia sintered body in Reference Example 2.

(11) FIG. 11 is a diagram illustrating a tablet terminal device in a first embodiment.

(12) FIG. 12 is a diagram illustrating a wristwatch in a second embodiment.

DESCRIPTION OF EMBODIMENTS

(13) Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples.

(14) (Relative Density)

(15) The density of a sample, a collection of five zirconia sintered bodies, was measured using the Archimedes method. The obtained density was used to determine the relative density with respect to the true density. The true densities of sintered bodies obtained by sintering powders used in the following Examples and Comparative Examples are as follows. The true density of a sintered body using a white zirconia powder (3YS20A) is 5.51 g/cm.sup.3. The true density of a sintered body using a black zirconia powder (product name TZ-Black, manufactured by TOSOH Corporation) is 6.06 g/cm.sup.3. The true density of a sintered body using a zirconia powder (product name 3YSE, manufactured by TOSOH Corporation) is 6.09 g/cm.sup.3.

(16) Note that the 3YS20A is a system prepared by adding 20 wt % of alumina to zirconia containing 3 mol % of yttria, the TZ-Black is a system prepared by adding a spinel compound-based black pigment to zirconia containing 3 mol % of yttria, and the 3YSE is a system prepared by adding 0.25 wt % of alumina serving as an auxiliary agent to zirconia containing 3 mol % of yttria.

(17) (Measurement of Impact Strength)

(18) The impact strength of a composite plate was evaluated using a steel ball drop test. A method similar to ISO14368-3 in the specifications of Dimensions of watch glass and test method was used for the steel ball drop test. Specifically, one of the composite plates obtained in the Examples and Comparative Examples was secured to a 5 mm-thick flat aluminum alloy (50 mm52 mm) using a 0.1 mm-thick double-sided tape (product number 4511-100, manufactured by 3M). Then a steel ball of 130 g was freely dropped onto the central position of the composite plate from a given height, and the height that caused the composite plate to break was measured. The impact surface used was a mirror polished surface in which a surface roughness Ra is 0.02 m or less.

(19) (Measurement of Bending Strength)

(20) The bending strength of a composite plate was measured according to biaxial bending strength measurement (ISO/DIS6872). The measurement was performed as follows. The radius of a support was set to 6 mm, and the center of the composite plate was placed on the support with the zirconia surface facing up and the fiber-reinforced plastic surface on the rear side. An indenter was placed such that a load was applied to the center of the zirconia surface. To compute the bending strength, a reduced diameter using a flat plate area was used. The zirconia used had mirror-polished opposite surfaces in which a surface roughness Ra is 0.02 m or less.

(21) (Measurement of Surface Shape)

(22) The surface roughness of a composite plate in a three-dimensional shape measurement was evaluated using Zygo New View 7100. The surface roughness per 1 cm.sup.2 was measured in an area around the center of the test piece. In Comparative Example 1 in which undulations were large, an optical microscope was used to measure focal lengths to thereby measure the surface shape.

(23) (Apparent Density)

(24) An apparent density was computed from the ratio of zirconia to a glass fiber-reinforced resin. In this case, 5.47 g/cm.sup.3 (relative density: 99.3%) was used for the density of the zirconia (3YS20A), and 2.0 g/cm.sup.3 was used for the density of the glass fiber-reinforced plastic.

Examples 1 to 3

(25) A white zirconia powder (product name 3YS20A, manufactured by TOSOH Corporation) was molded at a pressure of 50 MPa using a die press. The obtained compact was further molded using a cold isostatic press (CIP) at a pressure of 200 MPa.

(26) The obtained compact was heated in air at a temperature rising speed of 100 C./h to 1,500 C. and held at 1,500 C. for 2 hours to sinter the compact. The properties of the obtained sintered body are shown in TABLE 3 as a Reference Example. The opposite sides of the obtained sintered body were grounded and polished to obtain a zirconia thin plate having a prescribed thickness. Hv10 in TABLE 3 represents a Vickers hardness measured using an indenter load of 10 kgf.

(27) The surface of the obtained zirconia thin plate and the surface of an epoxy resin-based glass fiber-reinforced plastic (epoxy/glass cloth laminate SL-EC, manufactured by Nitto Shinko Corporation) were washed with acetone. Then an epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) was uniformly applied to a surface to be bonded, and the zirconia thin plate and the glass fiber-reinforced plastic were bonded together under the condition of 120 C. for 30 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. The thicknesses of the respective layers of each of the obtained composite plates are shown in TABLE 1. Each of the obtained composite plates was cut into pieces of 32 mm25 mm. No separation of the adhesive and no chipping of the zirconia due to machining were found, and the workability was high. The properties of the glass fiber-reinforced plastic used are shown in TABLE 4 as a Reference Example. To compute the apparent density, 2.0 g/cm.sup.3 was used as the density of the reinforced plastic.

(28) The results of evaluation of each of the obtained composite plates are shown in TABLE 1. The apparent densities of all the composite plates were 4.3 g/cm.sup.3 or less, and all the composite plates had a Vickers hardness of 1,000 or more. The steel ball drop test was performed in steps of 5 cm. The results were 10 cm or more for all the cases, showing high impact resistance. Another steel ball drop test was performed. Specifically, the steel ball was dropped once from a height of 30 cm and once from a height 50 cm onto an undamaged portion of each tested test piece. The impact resistance was higher than that evaluated in steps of 5 cm. The high value may be because interfacial separation of the adhesive layer caused by the repeated impact test did not occur.

Examples 4 to 10

(29) A white zirconia sintered body (3YS20A) was obtained by the same method as in Example 1. No separation of the adhesive and no chipping of the zirconia due to machining were found, and the workability was high. A photograph of the obtained composite is shown in FIG. 1. One side of the obtained white zirconia sintered body was ground, and the ground side was mirror-polished.

(30) Next, the mirror-polished surface of the zirconia sintered body and the glass fiber-reinforced plastic were bonded together using an epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) under the condition of 120 C. for 30 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. Each of the obtained composite plates was cut into a shape of 32 mm25 mm, and the ceramic side was ground and mirror-polished such that the total thickness of the zirconia sintered body, the adhesive, and the fiber-reinforced plastic was about 0.8 mm.

(31) The results of evaluation of the obtained composite plates are shown in TABLE 1. The apparent densities of all the composite plates were 4.3 g/cm.sup.3 or less, and all the composite plates had a Vickers hardness of 1,000 or more. The results of the steel ball drop test performed under the same conditions as in Example 1 are shown in TABLE 1. The results of the impact resistance test were 10 cm or more for all the cases, showing high impact resistance.

Examples 11 to 12

(32) Zirconia composite plates were obtained using the same method as in Example 4 except that one of room temperature curable acrylic-based adhesives (G55-03 and NS-700M-20, manufactured by Denki Kagaku Kogyo Kabushiki Kaisha) was used as the adhesive and the adhesive was uniformly applied to a surface to be bonded and cured for bonding at room temperature for a whole day and night with a load uniformly applied to the upper and lower surfaces of the composite plate. The results of evaluation of the obtained composite plates are shown in TABLE 1. The impact resistance was high, i.e., 10 cm or more for all the composite plates.

Examples 13 to 18

(33) Zirconia composite plates were obtained using the same method as in Example 4 except that, before the zirconia plate and the glass fiber-reinforced plastic were bonded together, their surfaces to be bonded were washed with acetone and irradiated with ultraviolet-induced ozone to perform cleaning treatment and then the surfaces subjected to the cleaning treatment were bonded together using an epoxy adhesive. The results of evaluation of the obtained composite plates are shown in TABLE 1. It was found that the composite plates irradiated with ultraviolet-induced ozone showed high impact resistance.

Examples 19 to 25

(34) Each of a zirconia powder (product name 3YSE, manufactured by TOSOH Corporation) and a black zirconia powder (product name TZ-Black, manufactured by TOSOH Corporation) was molded using a die press at a pressure of 50 MPa. Each of the obtained compacts was further molded using a cold isostatic press (CIP) at a pressure of 200 MPa.

(35) Next, to sinter the 3YSE, its temperature was increased to 1,450 C. in air at a temperature rising speed of 100 C./h, and the temperature was held at 1,450 C. for 2 hours. To sinter the TZ-Black, its temperature was increased to 1,400 C. at a temperature rising speed of 100 C./h, and the temperature was held at 1,400 C. for 1 hour. The properties of the obtained sintered bodies are shown in TABLE 3 as Reference Examples. The opposite sides of each of the obtained sintered bodies were ground and mirror-polished to obtain a zirconia thin plate having a prescribed thickness. The obtained zirconia thin plate was bonded to the glass fiber-reinforced plastic using the same method as in Example 4 to obtain a composite plate.

(36) The apparent densities of all the composite plates were 4.3 g/cm.sup.3 or lower, and all the composite plates had a Vickers hardness of 1,000 or more. The results of the steel ball drop test performed under the same conditions as in Example 1 are shown in TABLE 1. The results of the impact resistance test were 10 cm or more for all the cases, showing high impact resistance.

Examples 26 to 31

(37) Zirconia sintered bodies were obtained using one of 3YS20A, 3YSE, and TZ-Black powders. Each of the zirconia sintered bodies was subjected to hot isostatic press (HIP) to obtain a zirconia thin plate, and a composite plate was produced using the zirconia thin plate.

(38) Specifically, the 3YS20A, 3YSE, and TZ-Black sintered bodies were produced according to Examples 4, 19, and 22, respectively, and then subjected to HIP treatment under the conditions of an argon gas atmosphere and 150 MPa. The temperature of the HIP treatment was 1,450 C. for 1 hour for the 3YS20A and 3YSE and was 1,350 C. for 1 hour for the TZ-Black. The sintered bodies subjected to the HIP treatment were subjected to tempering treatment under the condition of 1,000 C. for 1 hour, and composite plates were produced using the same method as in Example 4. After the HIP treatment, the relative densities of all the sintered bodies reached 100%.

(39) The results of the impact resistance test on the obtained composite plates are shown in TABLE 1. It was found that the composite plates using the HIP-treated zirconia sintered bodies showed higher impact resistance.

Examples 32 to 35

(40) Zirconia composite plates were produced using the same method as in Example 1 except that a carbon fiber-reinforced plastic (manufactured by CFD Co., Ltd.) was used. The properties of the carbon fiber-reinforced plastic used are shown in TABLE 4 as a Reference Example. The density of the carbon fiber-reinforced plastic was 1.5 g/cm.sup.3. The results of the steel ball drop test performed on the obtained composite plates in steps of 5 cm are shown in TABLE 1. The results of the impact resistance test were 10 cm or more for all the cases, showing high impact resistance.

Example 36

(41) A composite plate was produced under the same conditions as in Example 4. The thickness of the sintered body was 0.239 mm, the thickness of the glass fiber-reinforced resin was 0.501 mm, and the thickness of the adhesive layer was 31 m. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.48. The apparent density of the composite plate was 3.00 g/cm.sup.3, and its Vickers hardness was 1,430.

(42) A steel ball drop test was performed on the obtained composite plate. Specifically, the evaluation was performed on a region 1 mm away from an end face of the composite toward the center of the test piece. No cracking was observed even when the steel ball was dropped from 15 cm, and the composite plate showed high impact resistant strength even at the edge.

Example 37

(43) A composite plate was produced using the same method as in Example 4. The thickness of the sintered body was 0.210 mm, the thickness of the glass fiber-reinforced resin was 0.510 mm, and the thickness of the adhesive layer was 35 m. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.41. The apparent density of the composite plate was 2.87 g/cm.sup.3, and its Vickers hardness was 1,430.

(44) #100 sand paper was placed on the zirconia surface of the composite plate, and an iron-made weight of 3 kg was used to apply a load. The iron-made weight was moved a distance of 30 cm on the sand paper back and forth 5 times to scratch the zirconia surface. The steel ball fracture height was 20 cm and remained unchanged before and after the scratching treatment, and no reduction in impact strength due to the scratching treatment was found. A micrograph of the zirconia surface after the scratching treatment is shown in FIG. 2. The surface roughnesses of the zirconia after the scratching were 0.13 as Ra and 2.73 as Rz, and it was found that the composite plate of the present invention has high resistance to scratching.

Example 38

(45) A 3YS20A composite plate of 32 mm25 mm was produced using the same method as in Example 4, and its bending strength was measured. The thickness of the sintered body was 0.257 mm, the thickness of the glass fiber-reinforced resin was 0.525 mm, and the thickness of the adhesive layer was 19 m. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.49. The apparent density of the composite plate was 3.07 g/cm.sup.3, and its Vickers hardness was 1,430.

(46) The bending strength was high, i.e., 800 MPa. The bending elastic modulus was estimated from the load-displacement curve in the test and found to be about 40 GPa. This value is significantly lower than the elastic modulus of the zirconia (250 GPa).

Example 39

(47) A composite plate prepared by bonding the 3YS20A (32 mm25 mm) to the glass fiber-reinforced plastic using the same method as in Example 4 was subjected to a nail penetration test. The thickness of the sintered body was 0.198 mm, the thickness of the glass fiber-reinforced resin was 0.504 mm, and the thickness of adhesive layer was 45 m. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.39. The apparent density of the composite plate was 2.80 g/cm.sup.3, and its Vickers hardness was 1,430. Cracks did not propagate throughout the composite plate even after penetration of the nail, and a through hole was formed only around the nail. The appearance of the composite plate after the nail penetration test is shown in FIG. 3.

Example 40

(48) 700 g of TZ-3YS powder, 14 g of a commercial polycarboxylate macromolecular dispersant used as a dispersant, 3.5 g of commercial polyethylene glycol mono-para-iso-octylphenyl ether used as an antifoaming agent, 245 g of ethyl acetate and 245 g of n-butyl acetate used as solvents, 49 g of butyral resin (degree of polymerization: about 1,000) powder used as a binder, and 42 g of industrial dioctyl phthalate used as a plasticizer were added to a ball mill and mixed for 48 hours. PET was used as a carrier film, and a green sheet was formed on the carrier film using a doctor blade device and a blade.

(49) The obtained green sheet was placed on a porous alumina setter and sintered with an alumina setter used as a weight placed on the green sheet. During the sintering, temperature was increased from room temperature to 450 C. at a temperature rising speed of 5 C./h and held at 450 C. for 10 hours to perform degreasing. Then the temperature was increased from 450 C. to 1,000 C. at a temperature rising speed of 50 C./h and held at 1,000 C. for 5 hours. Then the temperature was held at 1, 450 C. for two hours to perform sintering. The relative density of the obtained sintered body was 99% or higher.

(50) The obtained sintered body was bonded to a 0.501 mm-thick glass fiber-reinforced plastic of 32 mm25 mm using an epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) in the same manner as in Example 1. The zirconia surface of the bonded composite plate was ground and polished to produce a composite plate.

(51) The thickness of the sintered body was 0.234 mm, and the thickness of the adhesive layer was 32 m. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.47. The apparent density of the composite plate was 3.15 g/cm.sup.3, and its Vickers hardness was 1,430. An impact resistance test was performed using a falling steel ball in the same manner as in Example 1 (in steps of 5 cm). The results showed that the fracture height of the composite plate was 20 cm.

Comparative Example 1

(52) The 3YS20A was used to produce a composite plate using the same method as in Example 1. In this composite plate, the ratio of the thickness of the zirconia sintered body to the thickness of the glass fiber-reinforced plastic was 2.56. The results are shown in TABLE 2. The apparent density of the composite plate was larger than 4.3 g/cm.sup.3.

Comparative Example 2

(53) The 3YS20A was used to produce a plate using the same method as in Example 1. In this plate, the zirconia sintered body and the glass fiber-reinforced plastic were laminated without using the adhesive. Then the plate was subjected to the steel ball drop test, and the results are shown in TABLE 2. When the zirconia sintered body was not bonded to the glass fiber-reinforced plastic but was placed directly thereon, the plate broke at 5 cm, and it was found that the impact resistance characteristics were significantly low.

Comparative Example 3

(54) The 3YS20A was used to produce a composite plate using the same method as in Example 1 except that an ABS resin was used instead of the glass fiber-reinforced plastic. The results of the steel ball drop test on this composite plate are shown in TABLE 2. The composite plate using the ABS resin broke at 5 cm, and it was found that the impact resistance characteristics were significantly low.

Comparative Example 4

(55) A steel ball of 130 g was dropped onto a 0.7 mm-thick aluminosilicate-based tempered glass (32 mm25 mm) at a position 1 mm away from an end face toward the center of the base material. Fracture occurred near the end face at 5 cm.

Comparative Example 5

(56) The surface of an aluminosilicate-based tempered glass (32 mm25 mm, thickness: 0.7 mm) was subjected to scratching treatment using the same method as in Example 23, and impact resistance was evaluated before and after the scratching treatment. The falling steel ball fracture strength was 30 cm before the scratching treatment, and the steel ball fracture height became 10 cm after the scratching treatment. The surface roughnesses after the scratching were 0.8 m as Ra and 6.72 m as Ry. A photograph of the surface of the scratching-treated glass is shown in FIG. 4.

Comparative Example 6

(57) A white zirconia sintered body was produced under the conditions described in Example 1. The opposite sides of the sintered body were polished to obtain a zirconia thin plate having a thickness of 0.2 mm, and a nail penetration test was performed on the zirconia thin plate. In the zirconia thin plate, penetration of the nail caused cracks to propagate over the entire sintered body, and the base material broke into several pieces. The appearance of the base material after the nail penetration test is shown in FIG. 5.

Comparative Example 7

(58) A composite plate was produced using a sapphire thin plate instead of the zirconia under the conditions described in Example 1. The thickness of the sapphire was 0.218 mm, and the thickness of the adhesive layer was 45 m. The thickness of the glass fiber-reinforced plastic was 0.527 mm. This composite plate was evaluated using the method described in Example 1. The results showed that the composite plate broke at 5 cm. Since the elastic modulus of the sapphire (elastic modulus: 400 GPa) is higher than that of the zirconia, the ability of the sapphire to deform upon impact is insufficient. Therefore, high tensile stress may occur on the sapphire side.

(59) TABLE-US-00001 TABLE 1 THICKNESS RATIO AP- VICKERS STEEL BALL TYPE OF ZIR- ADHESIVE ZIR- PARENT HARD- FRACTURE HEIGHT ZIR- CONIA FRP LAYER TOTAL CONIA/ DENSITY NESS STEPS OF CONIA mm mm mm mm FRP g/cm.sup.3 Hv10 5 CM (cm) 30 cm 50 cm EXAMPLE 1 3YS20A 0.141 0.511 0.031 0.683 0.28 2.63 1430 15 OK CRACKED EXAMPLE 2 3YS20A 0.171 0.516 0.034 0.721 0.33 2.73 1430 15 OK CRACKED EXAMPLE 3 3YS20A 0.162 0.512 0.014 0.688 0.32 2.78 1430 30 OK CRACKED EXAMPLE 4 3YS20A 0.256 0.524 0.022 0.802 0.49 3.05 1430 20 OK CRACKED EXAMPLE 5 3YS20A 0.271 0.521 0.023 0.815 0.52 3.10 1430 15 OK CRACKED EXAMPLE 6 3YS20A 0.287 0.524 0.013 0.824 0.55 3.18 1430 20 OK OK EXAMPLE 7 3YS20A 0.275 0.518 0.008 0.801 0.53 3.17 1430 15 OK CRACKED EXAMPLE 8 3YS20A 0.247 0.551 0.012 0.810 0.45 3.03 1430 20 OK CRACKED EXAMPLE 9 3YS20A 0.266 0.524 0.009 0.799 0.51 3.13 1430 25 OK OK EXAMPLE 10 3YS20A 0.253 0.519 0.194 0.966 0.49 2.51 1430 20 OK CRACKED EXAMPLE 11 3YS20A 0.298 0.521 0.010 0.829 0.57 3.22 1430 15 CRACKED EXAMPLE 12 3YS20A 0.204 0.563 0.012 0.779 0.36 2.88 1430 20 OK CRACKED EXAMPLE 13 3YS20A 0.266 0.517 0.018 0.801 0.51 3.11 1430 20 OK OK EXAMPLE 14 3YS20A 0.246 0.521 0.018 0.785 0.47 3.04 1430 15 OK OK EXAMPLE 15 3YS20A 0.255 0.517 0.025 0.797 0.49 3.05 1430 20 OK OK EXAMPLE 16 3YS20A 0.278 0.517 0.024 0.819 0.54 3.12 1430 25 OK OK EXAMPLE 17 3YS20A 0.133 0.516 0.021 0.670 0.26 2.63 1430 40 OK OK EXAMPLE 18 3YS20A 0.086 0.525 0.013 0.624 0.16 2.44 1430 50 OK OK EXAMPLE 19 3YSE 0.169 0.521 0.018 0.708 0.32 2.92 1240 50 OK OK EXAMPLE 20 3YSE 0.175 0.522 0.018 0.715 0.34 2.95 1240 50 OK OK EXAMPLE 21 3YSE 0.210 0.523 0.018 0.751 0.40 3.09 1240 40 OK OK EXAMPLE 22 TZ-Black 0.270 0.517 0.021 0.808 0.52 3.28 1240 20 OK OK EXAMPLE 23 TZ-Black 0.238 0.520 0.021 0.779 0.46 3.17 1240 25 OK OK EXAMPLE 24 TZ-Black 0.127 0.665 0.014 0.806 0.19 2.73 1240 50 OK OK EXAMPLE 25 TZ-Black 0.175 0.714 0.017 0.906 0.24 2.94 1240 50 OK OK EXAMPLE 26 3YS20AHIP 0.224 0.521 0.021 0.766 0.43 2.97 1430 50 OK OK EXAMPLE 27 3YS20AHIP 0.214 0.522 0.029 0.765 0.41 2.91 1430 35 OK OK EXAMPLE 28 3YSEHIP 0.179 0.521 0.025 0.725 0.34 2.94 1240 50 OK OK EXAMPLE 29 3YSEHIP 0.188 0.521 0.021 0.730 0.36 2.99 1240 50 OK OK EXAMPLE 30 TZ-BIack 0.132 0.521 0.024 0.677 0.25 2.72 1240 40 OK OK HIP EXAMPLE 31 TZ-Black 0.219 0.52 0.01 0.749 0.42 3.16 1240 50 OK OK HIP EXAMPLE 32 3YS20A 0.155 0.512 0.047 0.714 0.30 2.26 1430 20 EXAMPLE 33 3YS20A 0.154 0.511 0.043 0.708 0.30 2.27 1430 15 EXAMPLE 34 3YS20A 0.154 0.510 0.034 0.698 0.30 2.30 1430 25 EXAMPLE 35 3YS20A 0.154 0.506 0.025 0.665 0.26 2.24 1430 30

(60) TABLE-US-00002 TABLE 2 STEEL BALL THICKNESS FRACTURE ABS ADHESIVE RATIO APPARENT VICKERS HEIGHT ZIRCONIA FRP RESIN LAYER TOTAL ZIRCONIA/ DENSITY HARDNESS STEPS OF mm mm mm mm mm FRP g/cm.sup.3 Hv10 5 CM (cm) COMPARATIVE 1.306 0.511 0.043 1.860 2.56 4.39 1430 10 EXAMPLE 1 COMPARATIVE 0.201 0.506 0.707 0.40 2.99 1430 5 EXAMPLE 2 COMPARATIVE 0.316 1.020 0.022 1.358 2.02 1430 5 EXAMPLE 3

(61) TABLE-US-00003 TABLE 3 REFERENCE EXAMPLE FRACTURE RELATIVE DIELECTRIC SIN- RELA- BENDING TOUGHNESS VICKERS ELASTIC PERMITTIVITY LOSS TANGENT TYPE OF TERING TIVE STRENGTH VALUE HARDNESS MODULUS ROOM TEMPER- ROOM TEMPER- ZIR- TEMPER- DENSITY DENSITY JISR1601 JISR1607 JISR1610 JISR1602 ATURE, 1 GHz ATURE, 1 GHz CONIA ATURE g/cm.sup.3 % MPa Mpam.sup.0.5 Hv10 GPa 3YS20A 1500 5.473 99.3 1300 4.7 1430 250 28.4 0.0003 C. - 2 h 3YSE 1450 6.073 99.8 1400 4.7 1240 200 36.6 0.0022 C. - 2 h TZ-Black 1400 5.993 99.0 1199 5.1 1240 200 37.5 0.0053 C. - 1 h

(62) TABLE-US-00004 TABLE 4 REFERENCE EXAMPLE RELATIVE DIELECTRIC PERMITTIVITY LOSS TANGENT ELASTIC BENDING ROOM ROOM DENSITY MODULUS STRENGTH TEMPERATURE, TEMPERATURE, g/cm.sup.3 Gpa MPa 1 MHz 1 MHz GLASS FIBER- 2.0 10 400 5.0 0.010 REINFORCED PLASTIC CARBON FIBER- 1.5 80 1300 REINFORCED PLASTIC

Example 41

(63) 700 g of TZ-3YS-E (manufactured by TOSOH Corporation) powder, 14 g of a commercial polycarboxylate macromolecular dispersant used as a dispersant, 3.5 g of commercial polyethylene glycol mono-para-iso-octylphenyl ether used as an antifoaming agent, 245 g of ethyl acetate and 245 g of n-butyl acetate used as solvents, 49 g of butyral resin (degree of polymerization: about 1,000) powder used as a binder, and 42 g of industrial dioctyl phthalate used as a plasticizer were added to a ball mill and mixed for 48 hours. Polyethylene terephthalate (PET) was used as a carrier film, and a green sheet was formed on the carrier film using a doctor blade device and a blade.

(64) The obtained green sheet was placed on a porous alumina setter and sintered with an alumina setter used as a weight placed on the green sheet. During the sintering, temperature was increased from room temperature to 450 C. at a temperature rising speed of 5 C./h and held at 450 C. for 10 hours to perform degreasing. Then the temperature was increased from 450 C. to 1,000 C. at a temperature rising speed of 50 C./h and held at 1,000 C. for 5 hours. Then the temperature was held at 1,450 C. for two hours to perform sintering. The density of the obtained zirconia sintered body was 6.085 g/cm.sup.3, and its relative density was 99.9% or higher.

(65) The obtained zirconia sintered body (thickness: about 0.5 mm) was cut into 32 mm25 mm, and the cut piece was machined to a thickness of 0.321 mm using a surface grinding and a mirror polishing machine. To remove residual stress due to machining, the machining was performed on the upper and lower surfaces under the same conditions. The surface grinding was performed using a #140 grindstone. If the grinding speed is high, significant residual stress occurs, causing warpage. Therefore, the grinding was performed at low grinding speed. After the upper and lower surfaces were ground under the same conditions, mirror polishing was performed.

(66) The mirror polishing was performed on the upper and lower surfaces under the same conditions using TegraForce (Marumoto Struers K. K.) with 9 m, 6 m, and 1 m diamond grains. The polishing conditions for the 9 m and 6 m grains were a time of 10 minutes and a pressure of 3.5 N/cm.sup.2, and the polishing conditions for the 1 m grains were a time of 10 minutes and a pressure of 2.8 N/cm.sup.2. The thickness of the obtained sintered body was 0.250 mm. The zirconia sintered body was flat with a maximum surface roughness of 1.381 m per 1 cm.sup.2.

(67) The surface of the obtained zirconia sintered body thin plate and the surface of an epoxy resin-based glass fiber-reinforced plastic (epoxy/glass cloth laminate SL-EC, manufactured by Nitto Shinko Corporation) were washed with acetone. Then an epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) was uniformly applied to a surface to be bonded, and the zirconia sintered body thin plate and the glass fiber-reinforced plastic were bonded together under the condition of 120 C. for 30 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. The obtained composite plate was cut into pieces of 32 mm x 25 mm. No separation of the adhesive and no chipping of the zirconia due to machining were found, and the workability was high. To compute the apparent density, 2.0 g/cm.sup.3 was used as the density of the reinforced plastic.

(68) The thickness of the produced composite plate was 0.900 mm. The thickness of the sintered body was 0.321 mm, the thickness of the adhesive layer was 49 m, and the thickness of the fiber-reinforced plastic was 0.530 mm. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.61. The apparent density of the composite plate was 3.35 g/cm.sup.3, and its Vickers hardness was 1,240. The maximum roughness of the surface of the obtained composite plate was 14.651 m per 1 cm.sup.2, and the obtained composite plate was a flat plate with small reflected image distortion and had high designability.

(69) The steel ball drop test was performed in steps of 5 cm. The results were 40 cm, showing high impact resistance. Another steel ball drop test was performed. Specifically, the steel ball was dropped once from a height of 50 cm onto an undamaged portion of the tested test piece. No cracks occurred, and the impact resistance was higher than that evaluated in steps of 5 cm. The higher value may be because interfacial separation of the adhesive layer caused by the repeated impact test did not occur.

(70) FIG. 6 shows the three-dimensional surface shape of the zirconia sintered body used in Example 41, and the surface shape after gradation processing is shown. The surface has a substantially flat planar shape within the area of 10.52 mm10.43 mm. In the figure, a slope extending from the left rear corner toward the right front corner can be seen. The difference in level is 1.38053 m calculated by subtracting0.56810 m from 0.81243 m, and points a, b, and c each represent an average level.

(71) FIG. 7 shows the three-dimensional surface shape of the zirconia composite plate in Example 41, and the surface shape after gradation processing similar to that in FIG. 6 is shown. Within the area of 10.52 mm10.43 mm, a convex shape with a low front side, a low rear side, and a high central portion can be seen. The difference in level is 14.65204 m calculated by subtracting 10.50475 m from 4.14729 m, and points a, b, and c each represent an average level.

Example 42

(72) FIG. 8 shows the three-dimensional surface shape of a zirconia composite plate in Example 42, and the surface shape after gradation processing similar to that in FIG. 6 is shown. Within the area of 10.52 mm10.43 mm, a substantially flat shape in which the right side is slightly low and the central portion on the left side is high can be seen. The difference in level is 11.10684 m calculated by subtracting 2.47014 m from 8.63670 m, and points a, b, and c each represent an average level.

(73) A black zirconia powder (product name TZ-Black, manufactured by TOSOH Corporation) was molded using a die press at a pressure of 50 MPa. The compact was further molded using a cold isostatic press (CIP) at a pressure of 200 MPa. The obtained compact was heated in air at a temperature rising speed of 100 C./h to a sintering temperature of 1,400 C. and held for 1 hour to sinter the compact. The opposite surfaces of the obtained zirconia sintered body were ground and polished to obtain a zirconia plate having a thickness of about 1 mm. The density of the obtained zirconia sintered body was 5.993 g/cm.sup.3, and its relative density was 99.0%. 6.053 g/cm.sup.3 was used as the true density of the black zirconia sintered body.

(74) The surface of the obtained zirconia sintered body thin plate and the surface of a glass fiber-reinforced plastic (epoxy/glass cloth laminate SL-EC, manufactured by Nitto Shinko Corporation) were washed with acetone. Then an epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) was uniformly applied to a surface to be bonded, and the zirconia sintered body thin plate and the glass fiber-reinforced plastic were bonded together under the condition of 120 C. for 30 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. The thicknesses of the respective layers in the obtained composite plate are shown in TABLE 1. The obtained composite plate was cut into a piece of 32 mm25 mm. The zirconia side of the cut composite plate was ground and polished to finally obtain a composite plate of about 0.8 mm. The grinding and polishing were performed under the conditions selected such that residual stress generated was as small as possible. No separation of the adhesive and no chipping of the zirconia due to machining were found, and the workability was high. To compute the apparent density, 2.0 g/cm.sup.3 was used as the density of the reinforced plastic.

(75) The thickness of the produced composite plate was 0.817 mm. The thickness of the zirconia sintered body was 0.270 mm, the thickness of the adhesive layer was 37 m, and the thickness of the fiber-reinforced plastic was 0.510 mm. The ratio of the thickness of the zirconia sintered body to the thickness of the fiber-reinforced plastic was 0.53. The apparent density of the composite plate was 3.23 g/cm.sup.3, and its Vickers hardness was 1, 240. The maximum roughness depth of the surface of the obtained composite plate was 11.107 m per 1 cm.sup.2, and the obtained composite plate was a flat plate with small reflected image distortion and had high designability.

(76) The steel ball drop test was performed in steps of 5 cm. The results were 40 cm, showing high impact resistance. Another steel ball drop test was performed. Specifically, the steel ball was dropped once from a height of 50 cm onto an undamaged portion of the tested test piece. No cracks occurred, and the impact resistance was higher than that evaluated in steps of 5 cm. The higher value may be because interfacial separation of the adhesive layer caused by the repeated impact test did not occur.

Reference Example 1

(77) FIG. 9 shows a surface profile of a composite plate in Reference Example 1. The horizontal axis represents the distance from an edge of the composite plate, and the vertical axis represents the level of the surface. As can be seen from FIG. 9, as the distance from the edge increases, the level of the surface decreases, becomes lower than a reference point (0), and further decreases.

(78) A zirconia composite plate with large surface roughness was produced using the same method as in Example 42. The zirconia composite plate was produced under such grinding and polishing conditions that residual stress remained in the machined product. The produced zirconia composite plate has low designability because an image reflected from the zirconia was distorted. The surface shape of the composite plate was measured under an optical microscope, and the maximum roughness depth of the surface per 1 cm.sup.2 was found to be about 72 m. FIG. 4 shows the two-dimensional data of the surface profile with the largest roughness depth.

Reference Example 2

(79) FIG. 10 shows the surface shape of a zirconia sintered body in Reference Example 2, and the surface shape after gradation processing similar to that in FIG. 6 is shown. Within the area of 10.52 mm10.43 mm, a shape in which the central portion is lowest and the level increases toward the four corners can be seen. The difference in level is 7.0228 m calculated by subtracting 2.70643 m from 4.31637 m, and points a, b, and c each represent an average level.

(80) The surface roughness image shown is an image of a bulk zirconia sintered body (thickness: 1 mm) produced using the same procedure as in Example 42. The maximum roughness depth of the surface per 1 cm.sup.2 was 7.0228 m. An image reflected from the surface of the sintered body was not distorted, and high designability was obtained.

Example 43

(81) A white zirconia powder (product name 3YS20A, manufactured by TOSOH Corporation) was molded at a pressure of 50 MPa using a die press. The obtained compact was further molded using a cold isostatic press (CIP) at a pressure of 200 MPa.

(82) The obtained compact was heated in air at a temperature rising speed of 100 C./h to 1,500 C. and held at 1,500 C. for 2 hours to sinter the compact. The opposite sides of the obtained zirconia sintered body were grounded and polished to obtain a zirconia thin plate having a prescribed thickness.

(83) The surface of the obtained zirconia thin plate and the surface of an epoxy resin-based glass fiber-reinforced plastic (epoxy/glass cloth laminate SL-EC, manufactured by Nitto Shinko Corporation) were washed with acetone. Then an epoxy-based thermosetting resin (product number AW136H, manufactured by Nagase ChemteX Corporation) was uniformly applied to a surface to be bonded, and the zirconia thin plate and the glass fiber-reinforced plastic were bonded together under the condition of 100 C. for 10 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. The thicknesses of the respective layers of the obtained composite plate are shown in TABLE 5.

(84) The results of evaluation of the obtained composite plate are shown in TABLE 5. The steel ball drop test was performed in steps of 5 cm, and the results showed that the impact resistance was high, i.e., 15 cm.

(85) A color difference meter was used to measure the lightness index L* and chromaticness indexes a* and b* in the color (L*, a*, b*) of the surface. The lightness index L* was higher than that in Reference Example 3, and the obtained composite plate had a better white color.

(86) The total light transmittance was measured using a haze meter. The total light transmittance was lower than that in Reference Example 1. This showed that transmission of light was prevented and the white color was improved.

Reference Example 3

(87) A white zirconia sintered body (3YS20A) was obtained using the same method as in Example 43. No separation of the adhesive and no chipping of the zirconia due to machining were found, and the workability was high. Then the mirror-polished surface of the zirconia sintered body and the glass fiber-reinforced plastic were bonded together using a black epoxy-based thermosetting resin (product number XN1245SR, manufactured by Nagase ChemteX Corporation) under the condition of 120 C. for 30 minutes with a load uniformly applied to the upper and lower surfaces of the composite plate. The ceramic surface of the obtained composite plate was ground and mirror-polished such that the total thickness of the zirconia, the adhesive, and the fiber-reinforced plastic was 0.8 mm.

(88) The steel ball drop test was performed in steps of 5 cm using the same method as in Example 43. The results showed that the impact resistance was high, i.e., 25 cm.

(89) The lightness index L* and chromaticness indexes a* and b* in the color (L*, a*, b*) of the surface were measured using the same method as in Example 43. The lightness index was lower than that in Example 43, and the color of the black adhesive was visible, so that the white color deteriorated.

Comparative Example 8

(90) A white zirconia sintered body (3YS20A) was obtained in the same method as in Example 43. Grinding and polishing were performed to obtain a flat 1 mm zirconia sintered body.

(91) The steel ball drop test was performed in steps of 5 cm using the same method as in Example 43. The results showed that the impact resistance was low, i.e., 5 cm.

(92) The lightness index L* and chromaticness indexes a* and b* in the CIE1976 L*a*b* color space were measured using the same method as in Example 43. In Example 43, the white color was higher than that in Reference Example 3. It was found that the color in Example 43 was close to the color of bulk zirconia (only a zirconia sintered body having a thickness of 1 mm or more, not a composite plate).

(93) TABLE-US-00005 TABLE 5 STEEL BALL LIGHT- CHROMAT- TOTAL LIGHT FRACTURE THICKNESS [mm] APPARENT NESS ICNESS TRANSMIT- HEIGHT ZIR- ADHESIVE DENSITY INDEX INDEX TANCE STEPS OF ADHESIVE CONIA FRP LAYER TOTAL g/cm.sup.3 L* a* b* [%] 5 CM EXAMPLE 43 AW136H 0.219 0.522 0.004 0.745 3.01 86.12 0.51 0.6 4.1 15 cm REFERENCE XN1245SR 0.208 0.528 0.014 0.750 2.93 82.37 0.31 0.58 11.3 25 cm EXAMPLE 3 COMPARATIVE BULK 1.0 1.0 5.47 94.40 0.37 0.98 1.4 5 cm EXAMPLE 8 ZIRCONIA

First Embodiment

(94) FIG. 11 is a diagram showing a tablet terminal device in a first embodiment.

(95) In this embodiment, a case 2, which is an exterior component of the tablet terminal device 1 serving as a mobile electronic device, is formed from a composite plate in any of the above Examples. The mobile electronic device is not limited to the tablet terminal device and may be any of mobile phones, smartphones, etc.

Second Embodiment

(96) FIG. 12 is a diagram showing a wristwatch in a second embodiment.

(97) In this embodiment, a watch case 4 which is a watch component (exterior component) of the wristwatch 3 serving as the watch is formed from a composite plate in any of the above Examples. The watch is not limited to the wristwatch and may be any of pocket watches, stopwatches, etc.

INDUSTRIAL APPLICABILITY

(98) The composite plate including a zirconia sintered body and a fiber-reinforced plastic according to the present invention is lightweight and has impact resistance and scratch resistance. Therefore, the composite plate can preferably be used for small and thin components of mobile electronic devices and watch components.

REFERENCE SIGNS LIST

(99) 1 tablet terminal device 2 case 3 wristwatch 4 watch component (watch case)