U.S. patent application number 10/560744 was filed with the patent office on 2006-09-14 for titanium oxide-organic polymer conjuction suitable for artificial bone.
Invention is credited to Masakazu Kawashita, Tadashi Kokubo, Takashi Nakamura.
Application Number | 20060204491 10/560744 |
Document ID | / |
Family ID | 36971188 |
Filed Date | 2006-09-14 |
United States Patent
Application |
20060204491 |
Kind Code |
A1 |
Kokubo; Tadashi ; et
al. |
September 14, 2006 |
Titanium oxide-organic polymer conjuction suitable for artificial
bone
Abstract
The titanium oxide-organic polymer composite material for
artificial bone obtained by forming titania gel on the surface of
said base material by titania solution treatment to dip into a
solution of 0.degree. C. to 50.degree. C. temperature for from
several seconds to 1 week obtained by adding a solution consisting
of acidic alcohol and water into alcohol solution of
titaniumtetraalcoxide to a base material composed of a polymer
compound selected from a group consisting of polyolefin, polyester
and nylon, and modifying to a titanium oxide membrane which forms
apatite having similar Ca/P atom ratio to an apatite of mammalian's
bone in supersaturated aqueous solution to apatite or from a body
fluid of mammalian by dipping said base material on the surface of
which titania gel is formed into hot water of 50.degree. C. to
95.degree. C. or solution of room temperature to 95.degree. C. to
which acid is added.
Inventors: |
Kokubo; Tadashi;
(Nagaokakyo-shi, JP) ; Kawashita; Masakazu;
(Nagaokakyo-shi, JP) ; Nakamura; Takashi;
(Kyoto-shi, JP) |
Correspondence
Address: |
HAHN & VOIGHT PLLC
1012 14TH STREET, NW
SUITE 620
WASHINGTON
DC
20005
US
|
Family ID: |
36971188 |
Appl. No.: |
10/560744 |
Filed: |
March 29, 2004 |
PCT Filed: |
March 29, 2004 |
PCT NO: |
PCT/JP04/04406 |
371 Date: |
December 15, 2005 |
Current U.S.
Class: |
424/123 ;
424/617 |
Current CPC
Class: |
A61F 2310/00227
20130101; A61F 2/3094 20130101; A61K 33/24 20130101; A61F 2/28
20130101; A61L 27/446 20130101 |
Class at
Publication: |
424/123 ;
424/617 |
International
Class: |
A61K 35/00 20060101
A61K035/00; A61K 33/24 20060101 A61K033/24 |
Claims
1. A titanium oxide-organic polymer composite material for
artificial bone obtained by forming titania gel on the surface of
said base material by titania solution treatment to dip into a
solution of 0.degree. C. to 50.degree. C. temperature for from
several seconds to 1 week obtained by adding a solution consisting
of acidic alcohol and water into alcohol solution of
titaniumtetraalcoxide to a base material composed of a polymer
compound selected from a group consisting of polyolefin, polyester
and nylon, and modifying to a titanium oxide membrane which forms
apatite having similar Ca/P atom ratio to an apatite of mammalian's
bone in supersaturated aqueous solution to apatite or from a body
fluid of mammalian by dipping said base material on the surface of
which titania gel is formed into hot water of 50.degree. C. to
95.degree. C. or solution of room temperature to 95.degree. C. to
which acid is added.
2. The titanium oxide-organic polymer composite material for
artificial bone of claim 1, wherein titaniumtetraalcoxide is
tetraisopropyltitanate, alcohol is ethanol and acid is inorganic
acid.
3. The titanium oxide-organic polymer composite material for
artificial bone of claim 1, wherein polyolefin is low-density
polyethylene, polyester is polyethyleneterephthalate and nylon is
6-nylon.
4. The titanium oxide-organic polymer composite material for
artificial bone according to claim 1, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
5. A composite for artificial bone prepared by obtaining a titanium
oxide-organic polymer composite material for artificial bone
obtained by forming titania gel on the surface of said base
material by titania solution treatment characterizing dipping into
a solution of 0.degree. C. to 10.degree. C. temperature for from
several seconds to 1 week obtained by adding a solution consisting
of acidic alcohol and water into alcohol solution of
titaniumtetraalcoxide to a base material composed of a polymer
compound selected from a group consisting of polyolefin, polyester
and nylon, and modifying to a titanium oxide membrane which forms
apatite having similar Ca/P atom ratio to an apatite of mammalian's
bone in supersaturated aqueous solution to apatite or from a body
fluid of mammalian by dipping said base material on the surface of
which titania gel is formed into hot water of 50.degree. C. to
95.degree. C. or solution of room temperature to 95.degree. C. to
which acid is added, then forming an apatite by dipping said
composite into supersaturated aqueous solution to apatite.
6. The composite material for artificial bone of claim 5, wherein
titaniumtetraalcoxide is tetraisopropyltitanate, alcohol is ethanol
and acid is inorganic acid.
7. The composite material for artificial bone of claim 5, wherein
titanium oxide-organic polymer for artificial bone is obtained by
using low-density polyethylene as polyolefin,
polyethyleneterephthalate as polyester and 6-nylon as nylon.
8. The titanium oxide-organic polymer composite material for
artificial bone according to claim 5, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
9. The titanium oxide-organic polymer composite material for
artificial bone of claim 2, wherein polyolefin is low-density
polyethylene, polyester is polyethyleneterephthalate and nylon is
6-nylon.
10. The titanium oxide-organic polymer composite material for
artificial bone according to claim 2, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
11. The titanium oxide-organic polymer composite material for
artificial bone according to claim 3, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
12. The titanium oxide-organic polymer composite material for
artificial bone according to claim 9, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
13. The composite material for artificial bone of claim 6, wherein
titanium oxide-organic polymer for artificial bone is obtained by
using low-density polyethylene as polyolefin,
polyethyleneterephthalate as polyester and 6-nylon as nylon.
14. The titanium oxide-organic polymer composite material for
artificial bone according to claim 6, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
15. The titanium oxide-organic polymer composite material for
artificial bone according to claim 7, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
16. The titanium oxide-organic polymer composite material for
artificial bone according to claim 13, wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a titanium oxide-organic
polymer composite material for an artificial bone prepared by using
polyolefin, polyester or polyamide as a substrate, treating the
surface of said substrate by titania solution directory then
dipping it in warm water or solution to which acid is added whose
temperature is from room temperature to 95.degree. C., forming a
titanium oxide membrane having a forming ability of apatite of
similar Ca/P atom ratio as to apatite of mammalian's bone in
supersaturated aqueous solution to apatite or in body fluid of
mammalian.
BACK GROUND OF THE ART
[0002] Researches for a composite materials used for an artificial
bone forming a layer of inorganic material which can form an
apatite layer from a simulated body fluid (SBF), using an organic
polymer containing ester group and/or hydroxyl group which has high
apatite forming ability in a simulated body fluid (SBF), in other
words, being familiar for formation of a layer whose bioactivity is
high, for example, ethylene-vinylalcohol copolymer (hereinafter
shortened to EVOH) possessing strength necessary as a bone on the
surface of the organic polymer, have been carried out
vigorously.
[0003] In said circumference, researches aiming to form easily a
layer having high bioactivity on surface of a base material are
also carried out. Especially, in a case to use an organic polymer
not having a functional group which is advantageous for formation
of a layer of said bioactivity, the formation of an intermediate
layer to which bioactivity is provided is considered to be
necessary. Further, as a composite material which forms said
intermediate layer, a substrate material which is prepared and
denatured by reacting 3-isocianatepropyltriethoxysilane
[OCN(CH.sub.2).sub.3Si(OCH.sub.2H.sub.5).sub.3] (hereinafter
shortened to IPTS) and silica solution is proposed, furthermore,
the treatment of surface by calcium silica solution is
proposed.
[0004] Regarding said prior art, in M. Uchida, H.-M. Kim, T.
Kokubo, S. Fujibayashi, T. Nakamura J. Biomed. Mater. Res., 64A
(2003) 164-170 (Document 1), the fact that Ti--OH group in titania
gel having specific structure, such as anatase, causes formation of
apatite nucleus in short term in SBF is reported. Further, it is
reported that when the surface of said base material is treated by
IPTS and further treated by calcium silicate solution, obtained
specimen forms apatite on the surface in SBF within 2 days,
however, since the formed calcium silicate gel layer dissolves
rapidly in SBF, it is very difficult to control the formation of
apatite on the surface of the specimen. On the contrary, since the
solubility of titania gel to SBF is remarkably small, the titania
gel layer having Ti--OH group is excellent as a bioactivity
layer.
[0005] Still further, in JP 2002-325834 publication (Document 2),
especially in claims, [0012] and [0013], an invention of a titanium
oxide-organic polymer composite material for an artificial bone
obtained by following process is reported. That is, after forming
titania gel on the surface of a base material substantially
composed of organic polymer, by transforming to a titanium oxide
membrane having activity to form an apatite of Ca/P atomic ratio
same as to an apatite of bone of a mammal from body fluid of a
mammal by treating said titania gel with warm water or aqueous
solution of acid. However, this document reports that, as a polymer
consisting of a base material which can form the titanium oxide
membrane having an activity to form an apatite without forming an
intermediate layer, it is necessary to use a polymer containing
hydroxyl group and/or derivatives thereof, thiol group, aldehyde
group or amino group [0013].
[0006] Therefore, said composite material for an artificial bone is
required to use a polymer having said active group as a polymer to
consist of a base material, or to be treated so as to form an
intermediate layer which makes possible to form a bioactivity
layer.
[0007] The subject of the present invention is to provide a
titanium oxide-organic polymer composite material for an artificial
bone obtained by using a polymer which does not have above
mentioned active group as a material which composes a base material
for an artificial bone, further not forming said intermediate
layer.
[0008] For the purpose to accomplish the subject of the present
invention, an investigation to obtain a titanium oxide-organic
polymer composite material for artificial bone using polyolefin,
especially polyethylene, in particular low-density polyethylene,
polyester, especially polyethyleneterephthalate, nylon, especially
6 nylon, is carried out without forming said intermediate layer,
and combinations of a specimen obtained from materials consisting
of said base material, material for forming bioactive titanium
oxide layer and forming conditions of a titanium oxide-organic
polymer composite material for artificial bone are investigated by
trial and error. As understood from Examples and Comparative
Examples which uses EVOH, which will be illustrated after, an
unexpected result is obtained in a case in which specific material
polymer is used. That is, it is confirmed that a titanium oxide
layer formed on the surface of the base material has high
bioactivity further has high resistance to peeling confirmed by a
peeling test using an adhere tape, and above mentioned subject is
accomplished. Said titanium oxide layer is formed by a process
mentioned in Patent Document 1 which was filed by the inventors of
the present invention by processing a material consisting a base
material by "forming titania gel on the surface of said base
material by titania solution treatment characterizing dipping into
a solution of 0.degree. C. to 50.degree. C. temperature for from
several seconds to 1 week obtained by adding a solution consisting
of acidic alcohol and water into alcohol solution of
titaniumtetraalcoxide, and by dipping said base material on the
surface of which titania gel is formed into hot water of 50.degree.
C. to 95.degree. C. or solution of room temperature to 95.degree.
C. to which acid is added".
DISCLOSURE OF THE INVENTION
[0009] The first one of the present invention is (1) a titanium
oxide-organic polymer composite material for artificial bone
obtained by forming titania gel on the surface of said base
material by titania solution treatment to dip into a solution of
0.degree. C. to 50.degree. C. temperature for from several seconds
to 1 week obtained by adding a solution consisting of acidic
alcohol and water into alcohol solution of titaniumtetraalcoxide to
a base material composed of a polymer compound selected from a
group consisting of polyolefin, polyester and nylon, and modifying
to a titanium oxide membrane which forms apatite having similar
Ca/P atom ratio to an apatite of mammalian's bone in supersaturated
aqueous solution to apatite or from a body fluid of mammalian by
dipping said base material on the surface of which titania gel is
formed into hot water of 50.degree. C. to 95.degree. C. or solution
of room temperature to 95.degree. C. to which acid is added.
Desirably, the first one of the present invention is (2) the
titanium oxide-organic polymer composite material for artificial
bone of (1), wherein titaniumtetraalcoxide is
tetraisopropyltitanate, alcohol is ethanol and acid is inorganic
acid, more desirably the first one of the present invention is (3)
the titanium oxide-organic polymer composite material for
artificial bone of (1) or (2), wherein polyolefin is low-density
polyethylene, polyester is polyethyleneterephthalate and nylon is
6-nylon, further desirably the first one of the present invention
is (4) the titanium oxide-organic polymer composite material for
artificial bone of (1), (2) or (3), wherein the solution for
titania solution treatment is prepared by dipping a solution
composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C., especially, maintaining said
temperature using water with ice.
[0010] The second one of the present invention (5) is a composite
for artificial bone prepared by obtaining a titanium oxide-organic
polymer composite material for artificial bone obtained by forming
titania gel on the surface of said base material by titania
solution treatment characterizing dipping into a solution of
0.degree. C. to 10.degree. C. temperature for from several seconds
to 1 week obtained by adding a solution consisting of acidic
alcohol and water into alcohol solution of titaniumtetraalcoxide to
a base material composed of a polymer compound selected from a
group consisting of polyolefin, polyester and nylon, and modifying
to a titanium oxide membrane which forms apatite having similar
Ca/P atom ratio to an apatite of mammalian's bone in supersaturated
aqueous solution to apatite or from a body fluid of mammalian by
dipping said base material on the surface of which titania gel is
formed into hot water of 50.degree. C. to 95.degree. C. or solution
of room temperature to 95.degree. C. to which acid is added, then
forming an apatite by dipping said composite into supersaturated
aqueous solution to apatite, desirably the second one of the
present invention (6) is the composite material for artificial bone
of (5), wherein titaniumtetraalcoxide is tetraisopropyltitanate,
alcohol is ethanol and acid is inorganic acid, more desirably the
first one of the present invention is (7) the composite material
for artificial bone of (5) or (6), wherein titanium oxide-organic
polymer for artificial bone is obtained by using low-density
polyethylene as polyolefin, polyethyleneterephthalate as polyester
and 6-nylon as nylon, further desirably the first one of the
present invention is (8) the titanium oxide-organic polymer
composite material for artificial bone of (5), (6) or (7), wherein
the solution for titania solution treatment is prepared by dipping
a solution composed of acidic alcohol and water to a solution of
titaniumtetraalcoxide and alcohol maintaining the temperature to
0.degree. C. to 10.degree. C.
BRIEF ILLUSTRATION OF THE DRAWING
[0011] FIG. 1 is a drawing to illustrate a process for treatment by
dipping a specimen (S) characterized by fuse adhering a platinum
wire to one corner of a specimen substrate into titania solution
(T.S) and pulling up (P.U) by prescribed speed.
[0012] FIG. 2 is a drawing to illustrate a process which treat a
specimen (T.S.S) treated by the process of FIG. 1 with warm water
(W.W.T).
[0013] FIG. 3 indicates TF-XRD (Thin film X-ray diffraction)
pattern of specimens of polyethylene (PE), polyester (PET), Nylon 6
and ethylene-vinylalcohol copolymer (EVOH, Comparative Example)
base material which are treated by titania solution-warm water of
FIG. 1 then dipped in SBF. .largecircle. is a detected pattern of a
formed apatite, .diamond. is a detected pattern of anatase and/or
brookite structure, .circle-solid. is a detected pattern of PE or
EVOH and .box-solid. is a detected pattern of PET or Nylon.
[0014] FIG. 4 is a FE-SEM (Field Emission Scanning Electron
Microscope) picture showing a specimen treated by titania
solution--warm water of FIG. 1 and apatite formation characteristic
after dipped in SBF (2 days and 7 days).
[0015] FIG. 5 is a FE-SEM (Field Emission Scanning Electron
Microscope) picture of the apatite formed specimen after removing
test by a Scotch Tape.TM..
DESCRIPTION OF THE PREFERRED EMBODYMENT
[0016] The present invention will be illustrated more in
detail.
[0017] A. As a material for substrate, a polymer compound selected
from a group consisting of polyolefin, polyester and Nylon can be
used. In particular, low-density polyethylene (Product of Sumitomo
Kagaku Co., Ltd.), polyethyleneterephthalate (PET, Product of Toyo
Kasei Co., Ltd.) and 6-Nylon (Product of Scientific Polymer
Products Co., Ltd.) can be mentioned as desirable ones. As a
specimen (S) to confirm the usefulness as an artificial bone, a
substrate of 10.times.10.times.1 mm.sup.3 is prepared and used.
[0018] As a base material, any kinds of structural feature such as
block, sheet, fiber, tape, filament or yarn can be used, further, a
secondary processed products of these materials, for example, woven
cloth (including three dimensional woven cloth), non-woven cloth or
sliver can be used and can provide a shape which improve a
characteristic as an artificial bone for reinforce.
B. Titania Treatment to Form a Titania Membrane;
Process for titania treatment is shown in FIG. 1.
[0019] To one corner of a specimen substrate prepared in A, a
platinum code (Pt) is fuse adhered.
[0020] Titania solution is prepared by following process, that is,
to a solution containing Ti(OiC.sub.3H.sub.7).sub.4(TiPT) and half
amount of C.sub.2H.sub.5OH, which is maintained at the temperature
between 0.degree. C. and 10.degree. C., adds solution containing
residue half amount of C.sub.2H.sub.5OH, HNO.sub.3 and H.sub.2O by
dropping it slowly under the condition to maintain the temperature
to 0.degree. C. to 10.degree. C., for example, by cooling with ice.
Ratio of materials is as follows; Ti(OiC.sub.3H.sub.7).sub.4:
H.sub.2O:C.sub.2H.sub.5OH: HNO.sub.3=1.0:0.1-10:1-100:0.01-10 (by
molar ratio)
[0021] Said specimen is dipped in the prepared titania solution at
0.degree. C. to 50.degree. C., for example, at 25.degree. C., for
from several seconds to one week, for example, 24 hours. After
that, the specimen is pulled up by pulling up speed of 0.1-10
cm/minute, for example, 2 cm/minute. The specimen is dried at the
temperature from 30.degree. C. to 150.degree. C. in a dryer (in
air, product of YAMATO Co., Ltd., DK-600) for 24 hours.
C. Treatment to Provide Apatite Forming Ability to a Titania Gel
Layer Prepared in the Process B.
[0022] This treatment is to form a titania membrane possessing
Ti--OH group in fine crystal of anatase or brookite by treating
titania gel with warm water or acid aqueous solution, and is
desirable to be carried out under acidic condition of pH lower than
7 and/or term of 1 hour to 1 month and/or temperature of 30.degree.
C. to 120.degree. C., especially in warm water of 50.degree. C. to
95.degree. C., or solution of room temperature to 95.degree. C. to
which acid is added. That is, it is important to select and combine
said conditions.
A case for treatment using HCl aqueous solution as an inorganic
acid solution is indicated (FIG. 2). For example, the specimen
treated by the process B is treated by dipping in 0.1M HCl aqueous
solution at 80.degree. C. for 8 days.
D. Treatment by Titania Solution
Surface structure change of various polymers which are treated by
titania solution and warm water is analyzed using various measuring
instruments mentioned below.
1. Field Emission Scanning Electron Microscope (FE-SEM); Product of
Hitachi Seisakusho Co., Ltd., S-4700.
2. Energy Dispersive X-ray Spectrometer (EDX); Product of Horiba
Seisakusho Co., Ltd., EMAX-7000
3. X-ray Photoeletron Spectroscope (XPS: MT-5500, product of
ULVAC-PHI Co., Ltd.)
4. Thin-Film X Ray Diffractometer (TF-XRD: RINT2500, Product of
Rigaku Co., Ltd.)
5. Measurement of adhesive strength of Titania Thin Film;
Measurement of adhesive strength of apatite formed on the surface
of substrate using a Scotch Tape.TM. which is a product of Sumitomo
3M.
E. Test of Apatite Forming Ability by Dipping in Simulated Body
Fluid (SBF);
[0023] Specimen is dipped in 30 ml of SBF adjusted to pH 7.40 and
temperature of 36.5.degree. C., for various terms, wherein longest
is 7 days. The specimen is picked out from said solution and washed
by ultra pure water, then dried up at room temperature.
[0024] One example of aqueous solution which is supersaturated to
apatite (simulated body fluid: SBF, having inorganic ion
concentration nearly equal to human's plasma [T. Kokubo, H.
Kushitani, S. Sakka, T. Kitsugi and T. Yamamuro, "Solutions able to
reproduce in vivo surface-structure changes in bioactive
glass-ceramic A-W", J. Biomed, Mater. Res. 24, 721-734 (1996)]) is
shown in Table 1. TABLE-US-00001 TABLE 1 concentration/mM simulated
body fluid plasma ion pH 7.40 pH 7.20-7.40 Na.sup.+ 142 142 K.sup.+
5.0 5.0 Mg.sup.2+ 1.5 1.5 Ca.sup.2+ 2.5 2.5 Cl.sup.- 148.8 103.8
HCO.sub.3.sup.- 4.2 27.0 HPO.sub.4.sup.2- 1.0 1.0 SO.sub.4.sup.2-
0.5 0.5
EXAMPLE
[0025] The present invention will be illustrated more in detail
according to Examples. These Examples are intending to make the
present invention more clear and not restricting the scope of
claims of the present invention.
Example 1
[0026] Preparation of Specimen;
[0027] Organic polymer substrates are prepared by press molding at
90 kgf/cm.sup.2 pressure for 10 minutes at adequate temperature for
each resin, namely, 180.degree. C. for polyethylene (PE),
270.degree. C. for polyetyleneterephathalate (PET), 230.degree. C.
for Nylon 6 (N-6) and 210.degree. C. for ethylene-vinylalcohol
copolymer (EVOH) of Comparative Example.
[0028] Materials shown in Table 2 are used for the preparation of
titania solution.
[0029] Solution containing TiPT (3.8687 g) and half weight of
C.sub.2H.sub.5OH (2.9 g) are prepared, and solution consisting of
residue half weight of C.sub.2H.sub.5OH (2.9 g), water (0.2450 g)
and nitric acid (0.0858 g) is added to said solution by cooling
with ice to 0-10.degree. C. so as to hydrolysis and a titania gel
solution is prepared.
[0030] Each specimens prepared by press molding are subjected to
titania solution treatment by dipped in 10 g of titania gel
solution kept at 25.degree. C. for 24 hours. After dipped,
specimens are pulled out by 2 cm/minute speed and dried in a dryer
at 80.degree. C. for 1 day and above mentioned press molding is
carried out and titania solution treated specimens (S) are
prepared. TABLE-US-00002 TABLE 2 Molar ratio of each component at
the preparation of titania solution Ti(OiC.sub.3H.sub.7).sub.4
(TiPT) H.sub.2O C.sub.2H.sub.5OH NHO.sub.3 1.0 1.0 9.25 0.1
[0031] For the purpose to provide an apatite forming ability to a
titania gel layer of prepared titania solution treated specimens,
said titania solution treated specimens are dipped into 10 mL of
0.1M hydrochloric acid aqueous solution at 80.degree. C. for 8 days
and transformed said titania gel layer to a titanium oxide layer
having an apatite layer forming ability by contact with
supersaturated aqueous solution to apatite.
[0032] In FIG. 3, thin film X ray diffraction pattern of PE, PET,
EVOH and Nylon-6, which are treated by titania solution and treated
by followed warm water treatment without silane coupling agent
treatment (SC), and are dipped in said SBF for 8 days are shown. In
the case of PE, by titania-warm water treatment, peak belonging to
anatase and/or brookite can be observed. After 7 days from SBF
dipping, a peak belonging to apatite is observed in all
specimens.
[0033] In FIG. 4, FE-SEM pictures of PE, PET, EVOH and Nylon-6
which are treated by titania solution and treated by followed warm
water treatment without SC treatment and are dipped into SBF for 2
or 7 days are shown. A thin layer is formed by titania-warm water
solution treatment. By EDS measurement, it becomes clear that this
layer contains titanium. Accordingly, it is understood that a
titania layer can be formed on the surface of specimen by directly
carrying out titania-warm water treatment without SC treatment.
After 2 days from SBF dipping, almost uniform apatite layer is
formed on the surface of PE, PET and Nylon-6, however, on the
surface of EVOH apatite layer is not formed. After 7 days from the
dipping, apatite is formed on the surface of EVOH too, however the
amount of it is very few.
[0034] In FIG. 5, FE-SEM pictures of the surface of specimens after
removing test by a Scotch Tape.TM. are shown. In cases of PE, PET
and Nylon-6, apatite is not removed by the removing test, while in
a case of EVOH, apatite is removed from the substrate.
POSSIBILITY FOR THE INDUSTRIAL APPLICABILITY
[0035] The titanium oxide-organic polymer composite material of the
present invention is to provide an artificial bone material which
has apatite forming ability on the surface of a base material and
is excellent in bonding strength between titanium oxide membrane
and base material, which is prepared by using polyolefin, polyester
or nylon as a base material, carrying out a treatment by titania
solution which forms titania gel on the surface of the base
material, which is developed by the inventors of the present
invention, and a dipping treatment of said formed titania gel in
warm water of 50.degree. C. to 95.degree. C., or solution of room
temperature to 95.degree. C. to which acid is added, or
transforming said formed titania gel to titanium oxide membrane
having forming ability of apatite of similar Ca/P atom ratio as to
apatite of mammalian's bone in supersaturated aqueous solution to
apatite or in body fluid of mammalian without treating the surface
of base material by previous treatment such as SC treatment. That
is, the present invention has an industrial applicability.
* * * * *