Compositions: coating or plastic – Coating or plastic compositions – Inorganic materials only containing at least one metal atom
Reexamination Certificate
1997-12-19
2001-06-12
Jones, Dwayne C. (Department: 1614)
Compositions: coating or plastic
Coating or plastic compositions
Inorganic materials only containing at least one metal atom
C106S437000, C524S413000, C524S441000, C524S442000, C524S513000, C524S543000, C524S577000, C524S593000, C524S567000, C524S565000
Reexamination Certificate
active
06245140
ABSTRACT:
BACKGROUND ART
1. Field of the Invention
The present invention relates to the manufacture of surface-fluorinated metal oxide particulates. More specifically, the present invention relates to surface-fluorinated metal oxide particulates whose surface affinity being controlled from ‘hydrophilic’ to ‘hydrophobic’ and which has improved stability, water repellent and dispersibility, a process for manufacturing the same and use of the same.
2. Description of the Related Art
Metal oxide particulates are used for a wide variety of applications and useful as raw materials of paints, matting agents for synthetic fibers, printing ink, cosmetics, opal glass, etc. and as coloring agents for rubbers and resins, pigments; and the like.
The surface of a metal oxide particulate is usually covered with a hydroxyl group and exhibits hydrophilicity. Accordingly, when the metal oxide particulates are blend in a resin, a paint or a cosmetic, a large number of surface treatments such as treatment with a higher fatty acid, treatment with an organic silicon compound, silica-alumina treatment and treatment with various coupling agents, are being attempted and practiced so as to improve dispersibility, for example, of titanium oxide. Also, there has been attempted surface treatment of aluminum oxide or silicon oxide with a silylating agent or the like.
These methods all intend to control the hydrophobicity or hydrophilicity or control the surface activity by the substitution-elimination of hydroxyl groups on the surface of a metal oxide particulate.
However, when this metal oxide particulate is added to fluororesin or the like, higher hydrophobicity and higher lipophobicity are demanded and accordingly, it is necessary to form a surface covered with fluorine having a surface energy lower than water or oil.
As the technique for solving this problem, for example, JP-A-59-184263 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) discloses a method of adding sodium fluoride to a suspension slurry of titanium oxide and stirring the mixture. However, according to this method, in the case when titanium oxide is an ultrafine particulate, coagulation in the drying process is intensified and good dispersibility cannot be obtained even if the matters coagulated are crushed. Further, according to this method, the fluorine atom is not bonded directly to the titanium atom and it cannot be said that the titanium oxide surface is fluorinated or modified with fluorine.
JP-A-61-215216 discloses a method of using an organic fluorine compound as a hydrophobicity-imparting substance in the production of hydrophobic spherical titanium oxide particulates. However, also in this case, the titanium oxide surface is substantially not modified with fluorine.
JP-A-3-40919 discloses a method of bringing freon gas into contact with titanium oxide ultrafine particulates and modifying their surface with fluorine at a high temperature of from 200 to 400° C. However, use of the reaction temperature as high as 200° C. or more results in the thermal efficiency which is not always good.
With respect to aluminum oxide and silicon oxide, nothing has been known about the fluorination of the surface of the particulates thereof.
SUMMARY OF THE INVENTION
The present invention is to solve these problems involved in the conventional techniques and provides surface fluorinated metal oxide particulates and a process for manufacturing the same.
Another object of the present invention is to provide a thermoplastic resin composition containing surface-fluorinated titanium oxide particulate pigment as a specific use of surface-fluorinated titanium oxide particulate, for one example of the surface-fluorinated metal oxide particulates described above.
As a result of extensive investigations to solve these problems in the conventional techniques, the present inventors have found that when a metal oxide particulate is reacted with fluorine, there can be obtained a substantially surface-fluorinated metal oxide particulate, which is accordingly water-repellent and oil-repellent.
Also, the present inventors have confirmed that among surface-fluorinated metal oxides, a surface-fluorinated titanium oxide particulate has been improved on light stability, water-repellence, and dispersibility over the conventional titanium oxide particulates and accordingly is particularly suitable for use in thermoplastic resin compositions for photographic resin coating paper such as highly white thin film composed of a thermoplastic resin containing a titanium oxide particulate as a white pigment.
Base on these findings, the present invention provides surface-fluorinated metal oxide particulates, a process for manufacturing the same and a thermoplastic resin composition containing surface-fluorinated titanium oxide particulate pigment as below.
1) A process for manufacturing surface-fluorinated metal oxide particulates, comprising reacting a metal oxide particulate with fluorine.
2) The process for manufacturing surface-fluorinated metal oxide particulates as described in 1) above, wherein a fluorine-containing gas is used which contains fluorine and a diluent gas.
3) The process for manufacturing surface-fluorinated metal oxide particulates as described in 2) above, wherein the diluent gas is nitrogen or argon.
4) The process for manufacturing surface-fluorinated metal oxide particulates as described in any one of 1) to 3) above, wherein at least one of reaction time and gas concentration of raw material fluorine is controlled to obtain a surface-fluorinated metal oxide particulate with a controlled surface-fluorination rate.
5) The process for manufacturing surface-fluorinated metal oxide particulates as described in any one of 1) to 4) above, wherein the metal oxide is titanium oxide.
6) The process for manufacturing surface-fluorinated metal oxide part-culates as described in any one of 1) to 4) above, wherein the metal oxide is aluminum oxide.
7) The process for manufacturing surface-fluorinated metal oxide particulates as described in any one of 1) to 4) above, wherein the metal oxide is silicon oxide.
8) A surface-fluorinated metal oxide particulate.
9) The metal oxide particulate as described in 9) above, wherein the metal oxide particle is obtained by any one of the methods 1) to 7) above and has a substantially fluorinated surface.
10) The metal oxide particulate having a substantially fluorinated surface as described in 8) or 9) above, wherein the metal oxide is aluminum oxide.
11) The metal oxide particulate having a substantially fluorinated surface as described in 8) or 9) above, wherein the metal oxide is silicon oxide.
12) The metal oxide particulate having a substantially fluorinated surface as described in 8) or 9) above, wherein the metal oxide is titanium oxide.
13) A thermoplastic resin composition containing a surface-fluorinated titanium oxide particulate pigment, which is a thermoplastic resin composition containing titanium dioxide pigment for coating on a substrate, wherein the composition comprises the surface-fluorinated titanium oxide particulate pigment as described in 12) above and has a water content of 10 to 1,400 ppm as determined by moisture conditioning 3 g of the composition in an atmosphere of 60 ° C. and relative humidity of 60% for 4 hours, exposing the thus conditioned composition to an air stream of absolute humidity of 0.009 kg H
2
O/kg of dry air at 80 ° C. for 4 hours, degassing the composition at 300° C. for 30 minutes, measuring the moisture content (g) of the composition using a Karl-Fischer moisture meter, and dividing the amount of moisture thus obtained by the surface-fluorinated titanium dioxide content (g).
14) A thermoplastic resin composition containing a surface-fluorinated titanium dioxide particulate pigment as described in 13) above, wherein the composition contains 20 to 80% by weight of the surface-fluorinated titanium dioxide particulate pigment.
15) A thermoplastic resin composition containing a surface-fluorinated titanium dioxide particulate pigment as described in 13) or
Hagihara Hiroyuki
Inoue Chozo
Ito Katsura
Monden Ryuji
Ohira Manabu
Delacroix-Muirheid C.
Jones Dwayne C.
Showa Denko K.K.
Sughrue Mion Zinn Macpeak & Seas, PLLC
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