TW201736273A - Particulate laminated material for forming charges on substrate surface and film shaping liquid for forming charges on substrate surface - Google Patents

Particulate laminated material for forming charges on substrate surface and film shaping liquid for forming charges on substrate surface Download PDF

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TW201736273A
TW201736273A TW105143287A TW105143287A TW201736273A TW 201736273 A TW201736273 A TW 201736273A TW 105143287 A TW105143287 A TW 105143287A TW 105143287 A TW105143287 A TW 105143287A TW 201736273 A TW201736273 A TW 201736273A
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substance
substrate
titanium oxide
charge
semiconductor
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Shiro Ogata
Yoshimitsu Matsui
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Sustainable Titania Tech Inc
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B08B17/02—Preventing deposition of fouling or of dust
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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Abstract

The present invention is characterized in that: a particulate laminated material is formed on a substrate surface or in a substrate surface layer to positively and/or negatively charge the substrate surface or the substrate surface layer, in order to cause a contaminating substance from the outside to be electrostatically repelled or adsorbed; and titanium oxide and/or silicon oxide (including a compound of titanium oxide and/or silicon oxide) is interposed as a dielectric material or a semiconductor material in a substance having positive charges and/or a substance having negative charges, in order to efficiently and stably form charges in the particulate laminated material without the charges being distributed unevenly.

Description

基體表面電荷形成用粒子狀積層物及基體表面電荷形成用造膜液Particle-shaped laminate for forming a surface charge of a substrate and a film forming liquid for forming a surface charge of a substrate

本發明係關於如下技術：藉由於基體表面或基體表面層中形成使基體表面帶電之粒子狀積層物，使漂浮於大氣中而對基體造成不良影響之污染物質於基體表面排斥或者於基體表面吸附脫離，又，藉由使污染物質轉變為安全物質，而保護基體表面或者降低污染物質對基體之影響。The present invention relates to a technique in which a particulate layer-like material which charges a surface of a substrate is formed in a surface of a substrate or a surface layer of a substrate, so that a pollutant floating in the atmosphere and adversely affecting the substrate is repelled on the surface of the substrate or adsorbed on the surface of the substrate. Detach, and, by turning pollutants into safe substances, protect the surface of the substrate or reduce the impact of pollutants on the substrate.

於大氣中漂浮有各種各樣之污染物質，該等污染物質對基體之表面或基體表面附近之功能或環境造成影響。如此，作為保護基體免受自外部對基體造成影響之污染物質之影響之代表性技術，可列舉光觸媒技術。 另一方面，申請人於專利文獻1中，揭示有如下技術：藉由於基體表面或基體表面層配置導電體與介電體或半導體之複合體，而於基體表面產生正電荷，使來自外部之污染物質靜電吸附或排斥，藉此保護基體表面。又，申請人於專利文獻2中，揭示有如下技術：藉由於基體表面或基體表面層配置正電荷物質及負電荷物質，使基體表面帶正電及帶負電，而使來自外部之污染物質於基體表面靜電吸附或排斥，藉此保護基體表面。再者，於該技術中，關於由配置於基體表面或基體表面層之正電荷物質及/或負電荷物質所產生之基體表面上之帶電壓，雖如上所述發揮用於保護基體之功能，但例如即使對電子機器之表面實施該技術，亦僅為不損害電子機器自身功能之程度之微弱帶電壓。 於專利文獻1及專利文獻2中，揭示有為了於基體表面或基體表面層配置正電荷物質及/或負電荷物質，可選擇何種物質作為正電荷物質或負電荷物質。又，於上述文獻中，作為將正電荷物質或負電荷物質配置於基體表面或基體表面層之方法之一，揭示有使用具有正電荷物質及/或負電荷物質之造膜液而於基體之表面形成覆膜或層係較為有效之方法。 另一方面，為了藉由使基體表面或基體表面層帶電而有效地發揮使來自外部之污染物質靜電性地排斥或者吸附之功能，要求不僅配置正電荷物質或負電荷物質，而且使電荷不局部化、有效率且穩定地形成於基體表面或基體表面層中。 此處，為了避免形成於基體表面或基體表面層中之電荷之局部化，解決方法之一係於具有導電性之物質間適當地介置用於穩定地形成電荷之介電體或半導體。又，對於以下問題必須加以解決：就功能或成本之方面選擇合適之物質作為該介電體或半導體，進而實現用以使電荷於基體表面或表面層中穩定地形成及固定並發揮功能之電荷物質與介電體或半導體之數量上之平衡，或者於基體表面或基體表面層形成由粒子狀積層物獲得之功能性優異之覆膜或層之方法。 [先前技術文獻] [專利文獻] [專利文獻1]國際公開WO2005/108056號公報 [專利文獻2]國際公開WO2008/013148號公報There are a variety of pollutants floating in the atmosphere that affect the function or environment near the surface of the substrate or near the surface of the substrate. As described above, a photocatalytic technique can be cited as a representative technique for protecting the substrate from contaminants that affect the substrate from the outside. On the other hand, in the patent document 1, the applicant discloses a technique of generating a positive charge on the surface of the substrate by disposing a conductor and a composite of a dielectric or a semiconductor on the surface of the substrate or the surface layer of the substrate, so as to be externally charged. Contaminants are electrostatically adsorbed or repelled, thereby protecting the surface of the substrate. Further, the applicant disclosed in Patent Document 2 that the surface of the substrate is positively charged and negatively charged by the arrangement of the positively-charged substance and the negatively-charged substance on the surface of the substrate or the surface layer of the substrate, so that the pollutants from the outside are The surface of the substrate is electrostatically adsorbed or repelled, thereby protecting the surface of the substrate. Further, in this technique, the band voltage on the surface of the substrate generated by the positively-charged substance and/or the negatively-charged substance disposed on the surface of the substrate or the surface layer of the substrate functions as a function of protecting the substrate as described above. However, for example, even if the technology is implemented on the surface of an electronic device, it is only a weak band voltage that does not impair the function of the electronic device itself. Patent Document 1 and Patent Document 2 disclose that a substance can be selected as a positively-charged substance or a negatively-charged substance in order to dispose a positively-charged substance and/or a negatively-charged substance on the surface of the substrate or the surface layer of the substrate. Further, in the above document, as one of methods for disposing a positively-charged substance or a negatively-charged substance on a surface of a substrate or a surface layer of a substrate, it is disclosed that a film-forming liquid having a positively-charged substance and/or a negatively-charged substance is used in the substrate. A method in which a film or a layer is formed on the surface is effective. On the other hand, in order to effectively exert the function of electrostatically repelling or adsorbing pollutants from the outside by charging the surface of the substrate or the surface layer of the substrate, it is required to dispose not only the positively or negatively charged substances but also the electric charges. It is formed efficiently, stably and stably in the surface of the substrate or in the surface layer of the substrate. Here, in order to avoid localization of charges formed on the surface of the substrate or the surface layer of the substrate, one of the solutions is to appropriately interpose a dielectric or semiconductor for stably forming charges between substances having conductivity. Further, it is necessary to solve the problem that a suitable substance is selected as the dielectric or semiconductor in terms of function or cost, thereby realizing a charge for stably forming and fixing and functioning a charge on a surface or a surface layer of a substrate. A method in which a substance is balanced with a quantity of a dielectric or a semiconductor, or a film or a layer excellent in functionality obtained by a particulate laminate is formed on a surface of a substrate or a surface layer of a substrate. [Prior Art Document] [Patent Document] [Patent Document 1] International Publication No. WO2005/108056 [Patent Document 2] International Publication WO2008/013148

[發明所欲解決之問題] 本發明之目的在於提供一種於藉由使基體表面或基體表面層帶正電及/或帶負電，而使來自外部之污染物質靜電性地排斥或者吸附之基體之保護技術中，使電荷不局部化、有效率且穩定地形成於基體之表面或表面層中之方法。 [解決問題之技術手段] 本發明之基體表面電荷形成用粒子狀積層物之特徵在於：於基體之表面或基體之表面層中，於具有正電荷之物質及/或具有負電荷之物質之間介置作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)。 上述粒子狀積層物之一態樣之特徵在於：其係包含具有正電荷之物質及/或具有負電荷之物質之粒子與包含作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)之粒子相鄰地接合而成。 上述粒子狀積層物之另一態樣之特徵在於：其係接合具有正電荷之物質及/或具有負電荷之物質內包於作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)中而成之膠體粒子而形成。 上述粒子狀積層物之又一態樣之特徵在於：其係具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)以分子等級之複合體之粒子之形式接合而成。 又，本發明之基體表面電荷形成用造膜液之特徵在於含有：具有正電荷之物質及/或具有負電荷之物質、及作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)。 進而，關於上述基體表面電荷形成用造膜液，較佳為上述作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)與上述具有正電荷之物質及/或具有負電荷之物質之比率以固體成分莫耳比計，於使用氧化鈦(包含氧化鈦化合物)之情形時為1：0.01～1：0.3之比率，於使用氧化矽(包含氧化矽之化合物)之情形時為1：0.03～1：2.7之比率，於使用氧化鈦及氧化矽(包含該等之化合物)之情形時為1：0.01～1：0.3之比率。 再者，於上述基體表面電荷形成用粒子狀積層物或基體表面電荷形成用造膜液中， 上述具有正電荷之物質及/或具有負電荷之物質較佳為選自由下述(1)至(6)所組成之群中之至少一種具有正電荷之物質及/或具有負電荷之物質： (1)陽離子 (2)具有正電荷之導電體、具有正電荷之導電體與介電體之複合體、具有正電荷之導電體與半導體之複合體、包含具有正電荷之2種以上之介電體或/及半導體之複合體之任一具有正電荷之導電體或複合體 (3)陰離子 (4)具有負電荷之導電體、具有負電荷之導電體與介電體之複合體、具有負電荷之導電體與半導體之複合體、包含具有負電荷之2種以上之介電體或/及半導體之複合體之任一具有負電荷之導電體或複合體 (5)具有光觸媒功能之物質 (6)氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體。 [發明之效果] 根據本發明，藉由於基體或基體表面層配置具有正電荷之物質及/或具有負電荷之物質使之帶電，能夠使得使基體表面或基體表面層帶正電及/或帶負電之粒子狀積層物在電荷不局部化之情況下有效率且穩定地形成，因此可使來自外部之污染物質靜電性地排斥或者吸附，而有效地保護基體。 又，於本發明中，於具有正電荷之物質及/或具有負電荷之物質中，介置作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)，藉此，能夠於基體表面或基體表面層不使用黏合劑而形成利用粒子狀積層物所得之薄、透明度較高且硬的膜質。 又，根據本發明，藉由使基體表面帶正電及/或帶負電，從而不僅能夠藉由使來自外部之污染物質靜電吸附或反斥而保護基體表面，亦能夠降低由電磁波所引起之基體之氧化劣化。即，關於基體之氧化劣化，其原因係於基體表面或基體中生成1 O2 、・OH等自由基而產生氧化分解反應，但基體之正電荷表面成為使該等自由基穩定之分子。因此，認為基體之氧化劣化得到防止或減少。再者，於基體為金屬製之情形時，能夠減少來自相同之製程之鏽之產生。 進而，根據本發明，藉由使基體表面帶正電、或帶正及負電，能夠去除於基體表面上因加熱而固著之碳化污染物。[Problem to be Solved by the Invention] An object of the present invention is to provide a substrate which electrostatically repels or adsorbs contaminants from the outside by positively and/or negatively charging the surface of the substrate or the surface of the substrate. In the protection technique, a method of making a charge non-localized, efficiently and stably formed on a surface or a surface layer of a substrate. [Technical means for solving the problem] The particulate layered product for forming a surface charge of a substrate of the present invention is characterized in that, between the surface of the substrate or the surface layer of the substrate, between the substance having a positive charge and/or the substance having a negative charge Titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) as a dielectric or semiconductor is interposed. One aspect of the above-mentioned particulate laminate is characterized in that it contains a substance having a positive charge and/or a substance having a negative charge and a titanium oxide and/or yttrium oxide containing a dielectric or a semiconductor (including oxidation The particles of titanium and/or cerium oxide compound are joined adjacently. Another aspect of the above-mentioned particulate laminate is characterized in that it is bonded to a substance having a positive charge and/or a substance having a negative charge is contained in a titanium oxide and/or yttrium oxide as a dielectric or semiconductor (including oxidation It is formed by colloidal particles formed from titanium and/or cerium oxide compounds. A further aspect of the above-mentioned particulate laminate is characterized in that it is a substance having a positive charge and/or a substance having a negative charge and titanium oxide and/or cerium oxide as a dielectric or semiconductor (including titanium oxide and/or Or a compound of cerium oxide) is formed by combining particles of a molecular grade complex. Further, the film forming liquid for forming a surface charge of a substrate of the present invention is characterized by containing a substance having a positive charge and/or a substance having a negative charge, and titanium oxide and/or cerium oxide as a dielectric or semiconductor (including oxidation Titanium and / or cerium oxide compounds). Further, the film forming liquid for forming a surface charge of the substrate is preferably the above-mentioned titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) as a dielectric or semiconductor, and the above-mentioned substance having a positive charge. And/or the ratio of the substance having a negative charge is measured by the molar ratio of the solid component, in the case of using titanium oxide (including the titanium oxide compound), in a ratio of 1:0.01 to 1:0.3, in the case of using cerium oxide (including cerium oxide) In the case of the compound), the ratio is 1:0.03 to 1:2.7, and when titanium oxide and cerium oxide (including the compounds) are used, the ratio is 1:0.01 to 1:0.3. Further, in the film-forming layer for forming a surface charge of a substrate or the film-forming liquid for forming a surface charge of a substrate, the positively charged substance and/or the substance having a negative charge are preferably selected from the following (1) to (6) At least one of the group consisting of a positively charged substance and/or a substance having a negative charge: (1) a cation (2) a positively charged conductor, a positively charged conductor and a dielectric Any one of a complex, a positively charged conductor and a semiconductor, or a positively charged conductor or complex (3) anion comprising a composite of two or more dielectrics having a positive charge or/and a semiconductor. (4) a conductor having a negative charge, a composite of a negatively charged conductor and a dielectric, a composite of a negatively charged conductor and a semiconductor, or a dielectric containing two or more kinds of negative charges or Any of the negatively charged conductors or composites (5) having a photocatalytic function (6) titanium oxide and/or cerium oxide (compounds containing titanium oxide and/or cerium oxide) Electrical or semiconductor. [Effects of the Invention] According to the present invention, the surface of the substrate or the surface layer of the substrate can be positively charged and/or brought about by the fact that the surface layer of the substrate or the substrate is provided with a substance having a positive charge and/or a substance having a negative charge. The negatively charged particulate laminate is efficiently and stably formed without localization of charges, so that the pollutants from the outside can be electrostatically repelled or adsorbed, and the substrate can be effectively protected. Further, in the present invention, titanium oxide and/or cerium oxide (including these compounds) as a dielectric or semiconductor are interposed in a substance having a positive charge and/or a substance having a negative charge, whereby It is possible to form a thin, highly transparent and hard film quality obtained by using a particulate laminate without using a binder on the surface of the substrate or the surface layer of the substrate. Further, according to the present invention, by positively charging and/or negatively charging the surface of the substrate, it is possible to protect the surface of the substrate not only by electrostatically adsorbing or repelling the externally contaminated substance, but also to reduce the substrate caused by the electromagnetic wave. Oxidative degradation. In other words, the oxidative degradation of the substrate is caused by the formation of an oxidative decomposition reaction such as a radical such as 1 O 2 or OH on the surface of the substrate or the substrate, but the positively charged surface of the substrate is a molecule which stabilizes the radicals. Therefore, it is considered that the oxidative degradation of the substrate is prevented or reduced. Furthermore, in the case where the substrate is made of metal, the generation of rust from the same process can be reduced. Further, according to the present invention, by making the surface of the substrate positively charged or positively and negatively charged, it is possible to remove the carbonized contaminants which are fixed by heating on the surface of the substrate.

以下，一面參照圖式一面說明本發明之實施形態。概要 本案發明人發現：於推進開發藉由於基體表面或基體表面層配置具有正電荷之物質及/或具有負電荷之物質使之帶電，而使來自外部之污染物質靜電性地排斥或者吸附之基體之保護或環境改善方法之過程中，為了使電荷不局部化、有效率且穩定地形成於基體之表面或表面層中，重要的是於基體之表面或表面層中，形成於具有正電荷之物質及/或具有負電荷之物質之間適當地介置用於穩定地形成電荷之介電體或半導體的粒子狀積層物。再者，所謂粒子狀積層物係指包含層狀地排列之粒子狀物質，且形成於基體之表面或表面層之膜或者層。 進而，本案發明人發現：於上述粒子狀積層物中，作為介置於使基體表面或基體表面層帶電之物質間之介電體或半導體，就為成本較低且容易使用之材質方面、具備優異之介電特性或半導體特性方面、及能夠形成無黏合劑膜等功能性優異之方面而言，可選擇氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)。 於申請人揭示之先前技術中，揭示有：作為用於使基體表面或基體表面層帶電之物質，若為帶正電，則使用陽離子、具有正電荷之導電體、具有正電荷之導電體與介電體之複合體、及具有正電荷之導電體與半導體之複合體，若為帶負電，則使用陰離子、具有負電荷之導電體、具有負電荷之導電體與介電體之複合體、具有負電荷之導電體與半導體之複合體、及具有光觸媒功能之物質(上述專利文獻1、專利文獻2等)。申請人進而發現，若使2種以上之介電體或半導體複合，則藉由使用之介電體或半導體之種類而帶正電或帶負電。 另一方面，本案發明人新發現：於使用氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)作為介置於使基體表面或基體表面層帶電之物質間之介電體或半導體之情形時，若使用氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體，代替上述具有正電荷之物質及/或具有負電荷之物質，則藉由該等介電體或半導體之種類，基體表面或基體表面層會帶正電或負電、以及正及負之兩性帶電。 因此，以下，於本案說明書中，雖然將使基體表面或基體表面層帶正電之物質定義為「具有正電荷之物質」，將使基體表面或基體表面層帶負電之物質定義為「具有負電荷之物質」，但於該具有正電荷之物質及具有負電荷之物質中，亦包含「氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體」。該等介電體或半導體具有優異之靜電極化及靜電感應特性，理想的是具備藉由電磁波或熱或光之能量之照射使該等物質內之電荷偶極子變動之特質。 為了使形成於基體表面或基體表面層之膜或層更有效地發揮使來自外部之污染物質靜電性地排斥或者吸附之功能，理想的是於基體表面或表面層形成粒子狀積層物，且於該粒子狀積層物規則地取入經乾燥固化之粒子，而形成有均一且均等之電荷。例如，作為此種粒子狀積層物之較佳例，可列舉以下之(a)～(c)。 (a)具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽分別藉由單粒子進行粒子接合而成之基體表面膜或表面層 (b)藉由於氧化鈦或氧化矽內包具有正電荷之物質及/或具有負電荷之物質而得之膠體粒子進行粒子接合而成之基體表面膜或表面層 (c)具有正電荷之物質及/或具有負電荷之物質與氧化鈦及/或氧化矽以作為分子等級之複合體之鈣鈦礦型或鈣鈦礦型擬晶粒之形式進行粒子接合而成之基體表面膜或表面層 上述形成於基體表面或表面層之粒子狀積層物之粒徑較佳為0.1 nm～100 nm。又，該積層物之層厚無特別限定，較佳為10 nm～1 μm之範圍，更佳為10 nm～100 nm之範圍。關於電荷形成之原理 以下，使用圖5及圖6，主要對如上述(a)所記載之藉由形成於基體表面或基體表面層之粒子狀積層物而對基體表面或者基體表面層賦予正電荷、負電荷、或者正電荷及負電荷之電荷形成之原理進行說明。 圖5(1)、圖5(2)、圖5(3)係模式性表示使用具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)，對基體表面或基體表面層分別賦予正電荷、負電荷、正電荷及負電荷之原理之圖。圖5(1)中，於具有正電荷之導電體之粒子AP與作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)之粒子BB鄰接之狀態下在基體表面或基體表面層形成有膜或層，圖5(2)中，於具有負電荷之導電體之粒子AN與作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)之粒子BB鄰接之狀態下在基體表面或基體表面層形成有膜或層，圖5(3)中，於具有負電荷之導電體之粒子AN與具有正電荷之導電體之粒子AP交替地鄰接於作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)之粒子BB之狀態下在基體表面或基體表面層形成有膜或層。導電體在能夠自由地於內部移動之自由電子為高濃度下存在，藉由激發而使電洞(hole)或負之電子集中於造膜或者形成層之表面，藉此保持正或負之電荷狀態。與導電體相鄰之介電體或半導體因導電體之表面電荷狀態之影響而被介電極化，於與具有正電荷之導電體相鄰之側產生負電荷之狀態，於與具有負電荷之導電體相鄰之側產生正電荷之狀態，於該相對電極側產生相反之電荷之狀態。因此，於形成之粒子狀積層物之表面形成有均一且均等之電荷。 圖6(1)、圖6(2)、圖6(3)係模式性表示使用氧化鈦及氧化矽(包含該等之化合物)除外之介電體或半導體、及作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)，而對基體表面或基體表面層分別賦予正電荷、負電荷、正電荷及負電荷之原理之圖。圖6(1)～(3)中，於氧化鈦及氧化矽(包含該等之化合物)除外之介電體或半導體之粒子CC與作為介電體或半導體之氧化鈦或氧化矽(包含該等之化合物)之粒子BB相鄰之狀態下，於基體表面或基體表面層分別形成有膜或層。於氧化鈦及氧化矽(包含該等之化合物)除外之介電體或半導體中，若形成該物質之電性偶極子迅速與相鄰物質(即，氧化鈦或氧化矽(包含該等之化合物))之經介電極化之表面電荷反應，而使偶極子以與經介電極化之電荷相反之電荷移動，則認為於基體表面或表面層上生成有均一之正或負電荷。圖6(1)、圖6(2)、圖6(3)中，分別表示生成均一之正電荷之態樣、生成均一之負電荷之態樣、生成均一之正電荷及負電荷之態樣。基體表面之造膜方法 接著，關於如段落編號0025所記載之(a)～(c)之各自之基體表面之電荷表面形成方法或造膜方法，於以下之(A)～(C)中加以說明。 (A)利用單粒子之膜之造膜方法 圖1(1)係模式性表示(a)之態樣之於基體S1上之造膜剖面之圖。圖中，著色之圓為具有正電荷之物質及/或具有負電荷之物質之粒子，未著色之圓表示由作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)形成之粒子。即，(a)之態樣係於由氧化鈦及/或氧化矽形成之單粒子之接合中均勻地分散有由具有正電荷之物質及/或具有負電荷之物質形成之單粒子的形態。以下說明基於該形態之粒子狀積層物之造膜方法。 如使用圖5及圖6所說明般，理論上較佳為具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)於成膜上以1：1之比率進行複合化。關於在基體表面或表面層形成此種經複合化之膜或層之方法，可考慮各種方法，並無特別限定。 作為其一例，有使用造膜液之方法。具體而言，預先製造氧化鈦及/或氧化矽(包含該等之化合物)之粒子及具有正電荷之物質及/或具有負電荷之物質之粒子，在此基礎上將該等粒子分散於水或有機介質等中，而製成造膜液。並且，可使用基於將該造膜液塗佈於基體上進行造膜之濕式方式進行之造膜方法。又，亦可使用如下造膜方法，即，使用上述造膜液，藉由基於離子鍍覆或濺鍍等之乾式方式，將造膜液中所包含之微小粉體或離子性微小粒子於基體上造膜。再者，該基體之造膜方法之更詳細說明或關於造膜液之詳細之製造方法之說明於後段進行敍述。 再者，於使用分散於水或有機介質等之造膜液將氧化鈦及/或氧化矽(包含該等之化合物)之粒子與具有正電荷之物質及/或具有負電荷之物質之粒子於基體表面上進行造膜之情形時，關於該等粒子之比率，雖然成膜後之比率如上述所述理論上較佳為1：1，但於考慮造膜液之穩定性之情形時，若以固體成分莫耳比表示氧化鈦及/或氧化矽(包含該等之化合物)與具有正電荷之物質及/或具有負電荷之物質之比率，則於使用氧化鈦(包含氧化鈦化合物)之情形時，較佳為1：0.01～1：0.3之比率，於使用氧化矽(包含氧化矽之化合物)之情形時，較佳為1：0.03～1：2.7之比率，於使用氧化鈦及氧化矽(包含該等之化合物)之情形時，較佳為1：0.01～1：0.3之比率。 (B)利用內包具有正電荷之物質及/或具有負電荷之物質之膠體粒子之膜之造膜方法 圖1(2)係模式性表示(b)之態樣之於基體S1上之造膜剖面之圖。圖中，著色之圓為具有正電荷之物質及/或具有負電荷之物質，未著色之圓表示作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)，藉由接合氧化鈦及/或氧化矽(包含該等之化合物)內包具有正電荷之物質及/或具有負電荷之物質而成之膠體粒子而形成膜。於該形態之膜之造膜時，於使氧化鈦或氧化矽(包含該等之化合物)與具有正電荷之物質及/或具有負電荷之物質進行混合或複合化之步驟中，使用向具有正電荷之物質及/或具有負電荷之物質中添加鹼性劑或酸性劑等使之反應而製作之離子錯合物液中調配有作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)之造膜液，並藉由基於濕式方式或乾式方式之造膜而固著於基體表面，此時，成為氧化鈦及/或氧化矽(包含該等之化合物)內包具有正電荷之物質及/或具有負電荷之物質而成之膠體粒子。即，氧化鈦及/或氧化矽(包含該等之化合物)與具有正電荷之物質及/或具有負電荷之物質藉由乾燥而固體化時，可以膠體粒子之形式使離子一體化而進行積層。 關於上述造膜液中之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)與具有正電荷之物質及/或具有負電荷之物質之複合比，若以固體成分莫耳比表示，則於使用氧化鈦(包含氧化鈦化合物)之情形時，較佳為1：0.01～1：0.3之比率，於使用氧化矽(包含氧化矽之化合物)之情形時，較佳為1：0.03～1：2.7之比率，於使用氧化鈦及氧化矽(包含該等之化合物)之情形時，較佳為1：0.01～1：0.3之比率。 再者，於基體上之造膜較佳為無黏合劑固著，該無黏合劑固著利用的是由作為氧化鈦或氧化矽之自固著化修飾體之過氧基或甲基、或者作為有機矽化合物之矽烷單體或聚矽氧烷聚合物等之H2 O、CO2 之脫離所引起之縮聚反應。 (C)具有正電荷之物質及/或具有負電荷之物質與氧化鈦及/或氧化矽以作為分子等級之複合體之鈣鈦礦型或鈣鈦礦型擬晶粒之形式進行粒子接合而成之膜之造膜方法 圖1(3)係模式性表示(c)之態樣之於基體S1上之造膜剖面之圖。圖中，著色之圓為具有正電荷之物質及/或具有負電荷之物質，未著色之圓表示作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)，由示於外側之圓表示分子等級之粒子於內部取入離子後之結晶構造或擬結晶構造。 於形成氧化鈦或/及氧化矽之Ti分子與O2 分子或O3 分子、或者Si分子與O2 分子或O3 分子於溶液中解離之狀態下，使具有正電荷之物質及/或具有負電荷之物質於分子離子狀態下進行反應，藉由酸性劑、鹼性劑或者電磁波照射等使之固體化，藉此生成複合結晶物。關於進行反應之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)與具有正電荷之物質及/或具有負電荷之物質之複合比，若以固體成分莫耳比表示，則於使用氧化鈦(包含氧化鈦化合物)之情形時，較佳為1：0.01～1：0.3之比率，於使用氧化矽(包含氧化矽之化合物)之情形時，較佳為1：0.03～1：2.7之比率，於使用氧化鈦及氧化矽(包含該等之化合物)之情形時，較佳為1：0.01～1：0.3之比率。 上述複合結晶物具有通常習知之於內部以離子形式取入複合分子之鈣鈦礦型結晶構造或擬結晶構造，就該複合晶粒而言，Ti或Si作為正電荷發揮功能，O2 作為負電荷發揮功能。因此，於該複合晶粒中，藉由內包之離子，能夠選擇性地呈現兩性、正＞負、或負＞正之電荷。 以上，使用圖1，對於將於具有正電荷之物質及/或具有負電荷之物質介置作為介電體或半導體之氧化鈦及或氧化矽(包含該等之化合物)而成之膜於基體表面進行造膜之方法之例進行說明。於使用利用圖1之造膜方法時，不論何種基體均能造膜。 再者，於圖1之(1)、(2)及(3)中，例示出形成於基體表面之粒子狀積層物之粒子之層為1層或2層之例，但為了發揮本發明之功能，理想的是以複數層形成粒子狀積層物。於基體之表面層上之粒子狀積層物之形成 另一方面，圖2表示，於基體之表面層中藉由於具有正電荷之物質及/或具有負電荷之物質中介置作為介電體或半導體之氧化鈦與氧化矽(包含該等之化合物)，可使電荷不局部化、有效率且穩定地形成於基體表面層中之態樣之例。圖2之(1)、(2)、(3)係模式性表示該等態樣之基板剖面之圖式。圖中，著色之圓為具有正電荷之物質及/或具有負電荷之物質之粒子，未著色之圓表示由作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)形成之粒子。 於圖2(1)所示之態樣中，預先形成具有正電荷之物質及或具有負電荷之物質之粒子，且於包含作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)之基板S2之表面層形成該等粒子之層。作為於基體S2形成此種表面層之方法，有將具有正電荷之物質及/或具有負電荷之物質之粒子藉由壓製加工等壓接於基板S2之表面之方法，或於基板S2之製作時將包含具有正電荷之物質及/或具有負電荷之物質之粒子之層於基板S2之表面模鑄成形之方法等。 於圖2(2)所示之態樣中，預先形成氧化鈦及/或氧化矽(包含該等之化合物)之粒子，將該等粒子與具有正電荷之物質及/或具有負電荷之物質之基板S3藉由壓製加工等進行壓接，或於基板S3之製作時進行模鑄成形，藉此能夠製作如圖所示之表面層。 於圖2(3)所示之態樣中，預先於利用硬化前之有機高分子樹脂等形成之片狀或塊狀之基體S4(內部可含有無機成分)形成使作為介電體或半導體之氧化鈦與氧化矽(包含該等之化合物)之粒子介置於具有正電荷之物質及/或具有負電荷之物質之粒子中之層，並對該基體S4照射紫外線之電磁波，或者，將使作為介電體或半導體之氧化鈦與氧化矽(包含該等之化合物)之粒子介置於具有正電荷之物質及/或具有負電荷之物質之粒子而成之層模鑄成形於基體S4，藉此能夠製作如圖所示之表面層。 於圖2(1)及圖2(2)所示之態樣中，並非如圖1(1)所示之具有正電荷之物質及/或具有負電荷之物質之粒子與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)之粒子鄰接地接合之態樣，而是藉由於包含作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)之基板S2之表面側接合具有正電荷之物質及/或具有負電荷之物質之粒子，或者，藉由於具有正電荷之物質及/或具有負電荷之物質之基板S3之表面側接合氧化鈦及/或氧化矽(包含該等之化合物)之粒子，同樣能夠於基板表面形成均一且均等之電荷。 再者，於圖2之(1)、(2)及(3)中例示出形成於基體之表面層中之粒子之層為1層或2層之例，但為了發揮本發明之功能，期望的是形成於基體之表面層中之粒子之層以複數層形成。 接著，對作為組成本案發明之用於表面電荷形成之粒子狀積層膜之具有正電荷之物質及/或具有負電荷之物質、及作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)較佳為何種物質進行詳細說明。作為介電體或半導體之氧化鈦及 / 或氧化矽 介置於具有正電荷之物質及/或具有負電荷之物質中之作為介電體或半導體之氧化鈦及/或氧化矽其介電特性或半導體特性優異，能夠在不使用黏合劑之情況下形成高硬度且高透明性之薄膜。又，就成本之方面而言，亦能夠相對低價地使用。作為介置於具有正電荷之物質及/或具有負電荷之物質中之介電體或半導體，亦可使用氧化鈦或氧化矽之各種氧化物或過氧化物或該等化合物，進而，亦包含以鹼金屬或鹼土金屬為代表之作為第3族之鈧或釔及鑭系元素物質的鑭或鈰、第4族之鋯或鉿等、該等之化合物，亦可使導電性金屬以外之介電體或半導體複合化或共存。具有正電荷之物質及 / 或具有負電荷之物質 關於與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)複合之具有正電荷之物質及/或具有負電荷之物質，只要為能夠對基體表面賦予正電荷或負電荷者，則可使用任意之具有正電荷或負電荷之物質，較佳為選自由以下之(1)至(6)所組成之群中之至少一種具有正電荷之物質及/或具有負電荷之物質。 (1)陽離子 (2)具有正電荷之導電體、具有正電荷之導電體與介電體之複合體、具有正電荷之導電體與半導體之複合體、包含具有正電荷之2種以上之介電體或/及半導體之複合體之任一具有正電荷之導電體或複合體 (3)陰離子 (4)具有負電荷之導電體、具有負電荷之導電體與介電體之複合體、具有負電荷之導電體與半導體之複合體、包含具有負電荷之2種以上之介電體或/及半導體之複合體之任一具有負電荷之導電體或複合體 (5)具有光觸媒功能之物質 (6)氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體 作為(1)～(6)之陽離子、陰離子、具有負電荷或正電荷之導電體、作為光觸媒發揮功能之物質、介電體或半導體，雖然不論為有機物質、無機物質、有機物質與無機物質之複合體等物質之種類均可，但為了能夠於基體表面形成穩定之電荷，進而使污染物靜電吸附或者排斥而保護基體，而可形成基於供照射電磁波或熱或光之能量之基體之使用條件下之電荷，就該方面而言，尤佳為使用金屬或金屬以外之一部分無機物質。再者，關於與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)複合之具有正電荷之物質及/或具有負電荷之物質較佳為主要為金屬，因此，為方便起見，以下，將金屬或金屬以外之一部分無機物質與作為介電體或半導體之氧化鈦(包含氧化鈦之化合物)之複合體稱為金屬摻雜氧化鈦，將金屬或金屬以外之一部分無機物質與作為介電體或半導體之氧化矽(包含氧化矽之化合物)之複合體稱為金屬摻雜氧化矽。 關於與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)複合之金屬，較佳為選自以金、銀、鉑、銅、錳、鎳、鈷、鐵、鋯、鉿為代表之過渡金屬、以鋅或錫為代表之典型金屬、鹼金屬、鹼土金屬、以鑭或鈰為代表之鑭系元素中之金屬元素或無機元素之至少一種，更佳為使2種金屬元素複合。作為複合之金屬元素，尤佳為銀及銅。 又，關於與作為介電體或半導體之氧化鈦及/或氧化矽(包含該等之化合物)複合之金屬以外之無機物質，較佳為矽。關於金屬摻雜氧化鈦 以下，對作為組成本案發明之用於表面電荷形成之粒子狀積層膜之物質所較佳之金屬(包含金屬以外之一部分無機物質)與作為介電體或半導體之氧化鈦(包含氧化鈦之化合物)之組合加以說明。作為與金屬(包含金屬以外之一部分無機物質)複合之作為介電體或半導體之氧化鈦(包含氧化鈦之化合物)，可使用TiO2 、TiO3 、TiO、TiO3 /nH2 O等各種氧化物或過氧化物。尤佳為具有過氧基之過氧化鈦。氧化鈦為非晶型、銳鈦礦型、板鈦礦型、金紅石型之任一種均可，該等亦可混合存在，但較佳為非晶型氧化鈦。其中，使氧化鈦與金屬複合化而成為固體成分之後之氧化鈦呈現銳鈦礦型結晶或銳鈦礦型結晶之前驅物。 在此，對氧化鈦所具有之光觸媒功能與上述金屬摻雜氧化鈦之關係進行說明。其原因在於：若氧化鈦於基體表面發揮光觸媒功能，則根據基體種類之不同，有因光觸媒作用導致基體本身發生分解劣化之虞。氧化鈦中，非晶型氧化鈦及銳鈦礦型結晶前驅物氧化鈦不具有光觸媒功能。另一方面，雖然銳鈦礦型、板鈦礦型及金紅石型氧化鈦具有光觸媒功能，但若使銅、錳、鎳、鈷、鐵或鋅以一定濃度以上與該等氧化鈦複合，則光觸媒功能降低或喪失。再者，非晶型氧化鈦及銳鈦礦型結晶前驅物氧化鈦雖藉由太陽光之加熱等而經時轉化為銳鈦礦型氧化鈦，但若與銅、錳、鎳、鈷、鐵或鋅複合，則銳鈦礦型氧化鈦之光觸媒功能降低。因此，即使為任一型之氧化鈦，摻雜有銅、錳、鎳、鈷、鐵或鋅之鈦氧化物亦可不考慮由光觸媒作用所引起之不良影響。再者，關於摻雜有金、銀、鉑之鈦氧化物，亦包含非晶型氧化鈦轉化為銳鈦礦型氧化鈦之情形在內均具有光觸媒性能，但於摻雜有金、銀、鉑之鈦氧化物中，使正電荷物質以一定濃度以上共存之情形時不顯示光觸媒性能。因此，由於與金、銀、鉑、銅、錳、鎳、鈷、鐵或鋅複合而成之金屬摻雜氧化鈦最終可使光觸媒性能喪失或降低，因此可不考慮由光觸媒作用所產生之不良影響。其中，於使用光觸媒物質作為負電荷物質之情形時，可有效使用藉由光觸媒功能所生成之表面負電荷或負性電荷物。 接著，對上述金屬摻雜氧化鈦之製造方法加以說明。上述金屬摻雜氧化鈦可採用以作為普通二氧化鈦粉末之製造方法之鹽酸法或硫酸法為基礎之製造方法，亦可採用各種液體分散二氧化鈦溶液之製造方法。並且，與氧化鈦複合之金屬或金屬以外之一部分無機物質無論製造階段如何，均能夠與氧化鈦複合化。 以下，一面參照圖3，一面對金屬摻雜氧化鈦之分散液之製造方法之一例加以說明。首先，於將50%四氯化鈦(市售品)經純水稀釋之溶液中，以莫耳比計為1：0.05之比率將於圖3之左側例示之無機物化合物或金屬化合物(具有結晶水之化合物)進行混合。 無機物化合物或金屬化合物可混合複數種。關於四氯化鈦與無機物化合物或金屬化合物之混合比率，以莫耳比計較佳為1：0.01～1：0.3，更佳為1：0.02～1：0.1。向其中滴加25%氨水(市售品)調整至pH7左右，使鈦及無機物或金屬之氫氧化物析出，進行洗淨直至上清液之導電率成為0.9 mS/m以下。於洗淨之氫氧化物中混合濃度為35%之雙氧水，反應數小時後進行超過濾，藉此獲得分散有經複合之無機物質或金屬被修飾之非晶型過氧化鈦之微細粒子之溶液。又，於上述氫氧化物中混合雙氧水使之反應後，加熱並進行超過濾，藉此獲得分散有經複合之無機物質或金屬被修飾之銳鈦礦型過氧化鈦之微細粒子之溶液。 再者，由上述製造方法所得之水性分散液中之過氧化鈦濃度(包含共存之金、銀、鉑、銅、錳、鎳、鈷、鐵、鋅等金屬或無機物之合計量)較佳為0.05～15 wt%，更佳為0.1～5 wt%。 於上述金屬摻雜氧化鈦之製造步驟中，作為用於獲得與氧化鈦(包含其化合物)複合之無機物質或金屬(包含鹼金屬、鹼土金屬)而混合之金、銀、鉑、鎳、鈷、銅、錳、鐵、鋅、鋰、鈉、矽、鉀、鋯、鈰、鉿之化合物之例，可分別列舉以下者。 Au化合物：AuCl、AuCl3 、AuOH、Au(OH)4 、Au2 O、Au2 O3 等 Ag化合物：AgNO3 、AgF、AgClO3 、AgOH、Ag(NH3 )OH、Ag2 SO4 等 Pt化合物：PtCl2 、PtO、Pt(NH3 )Cl2 、PtO2 、PtCl4 、[Pt(OH)6 ]2- 等 Ni化合物：Ni(OH)2 、NiCl2 等 Co化合物：Co(OH)NO3 、Co(OH)2 、CoSO4 、CoCl2 等 Cu化合物：Cu(OH)2 、Cu(NO3 )2 、CuSO4 、CuCl2 、Cu(CH3 COO)2 等 Mn化合物：MnNO4 、MnSO4 、MnCl2 等 Fe化合物：Fe(OH)2 、Fe(OH)3 、FeCl3 等 Zn化合物：Zn(NO3 )2 、ZnSO4 、ZnCl2 等 Li化合物：LiOH、Li2 CO3 、LiCl等 Na化合物：NaOH、NaCl、Na2 CO2 等 Si化合物：SiO2 、SiH4 、SiCl4 等 K化合物：KOH、K2 O、KCl等 Zr化合物：Zr2 O、Zr(OH)2 、ZrCl等 Ce化合物：CeO2 、CeCl2 、Ce(OH)3 等 Hf化合物：HfCl2 、Hf(OH)3 等 再者，除參照圖3說明之金屬摻雜氧化鈦分散液之製造方法以外，亦存在較多使無機物質或金屬與氧化鈦複合化之方法，例如可預先分別製作氧化鈦粒子、與所要複合化之無機物質或金屬之粒子，並分別進行混合。於本案發明中，為了製作金屬摻雜氧化鈦，除上述製法以外，亦有多種製造氧化鈦之微細粒子及其分散溶液之方法，可使用其任意一種方法。關於金屬摻雜氧化矽 以下，對作為組成本案發明之用於表面電荷形成之粒子狀積層膜之物質所較佳之金屬(包含金屬以外之一部分無機物質)與作為介電體或半導體之氧化矽(包含氧化矽之化合物)之組合加以說明。關於與金屬(包含金屬以外之一部分無機物質)複合之作為介電體或半導體之氧化矽(包含氧化矽之化合物)，可使用SiO2 、SiO3 、SiO、SiO3 /nH2 O等各種氧化物或過氧化物。 作為含有氧化矽之材料，市售有多種製品。例如，作為有機材料與無機材料之結合材料(複合材料)，可列舉以下者。 ・賦予複合材料之機械強度之提高或結合性之改良或表面親水性之矽烷偶合劑中，就水解性而言具有甲氧基或乙氧基之水溶性塗佈劑。 ・作為分子內具有有機官能基與烷氧基之低聚物型偶合劑，使各種物質複合化而作為樹脂改質或功能性塗佈劑使用之矽酮低聚物。 ・作為對後述基材之撥水性賦予功能材料使用之具有甲基或長鏈烷基、苯基之烷氧基矽烷或烷氧基氮烷。 ・含有具有有機材料或無機材料之活性氫保護功能之有機矽烷基，藉由控制烷基之反應位置能夠製造有機合成構件之矽烷化劑等。 使用上述含有氧化矽之材料，可製造使金屬複合之表面電荷膜形成用造膜液。以下，使用圖4，對所複合化者為金、銀、鉑、銅、錳、鎳、鈷、鐵、鋅等典型金屬及過渡金屬之情形之金屬摻雜氧化矽之分散液之製作方法之一例加以說明。首先，若於矽酸甲酯中混合醇與純水及特定量之觸媒而進行水解，則製作矽溶膠。將該矽溶膠利用純水進行稀釋。矽溶膠稀釋液中之固體成分濃度較佳為10%～0.2%，更佳為4%～0.85%。將該矽溶膠稀釋液與調整為1%濃度之金屬化合物(具有結晶水之化合物)以相對於二氧化矽之莫耳濃度比計，較佳為以1：0.03～1：2.7之比率、更佳為以1：0.03～1：0.27之比率進行混合。又，氧化矽與鹼金屬及鹼土金屬等之複合化亦相同。 再者，如圖4所示，於上述分散液之製作中，能夠與氧化矽複合之金屬化合物或無機化合物可與製作金屬摻雜氧化鈦時使用之金屬化合物或無機物化合物為相同之物質。關於金屬摻雜氧化鈦及氧化矽 最後，對使金屬與氧化鈦及氧化矽複合化之溶液之製作方法加以說明。首先，對純水以莫耳比計為1：0.5之比率混合四氯化鈦與矽溶膠，並進一步混合金屬化合物(具有結晶水之化合物)。金屬化合物可混合複數種。再者，能夠混合之金屬化合物例如可使用製作金屬摻雜氧化鈦時使用之如圖3所示之金屬化合物。關於四氯化鈦及矽溶膠與金屬化合物之混合比率，以莫耳比計較佳為1：0.01～1：0.3，更佳為1：0.02～1：0.1。於其中滴加調整至25%之氨水，而調整為pH7左右，使鈦、矽及所要複合化之無機物質或金屬之氫氧化物析出。將該析出之氫氧化物於純水中進行洗淨直至上清液之導電率成為0.9 mS/m以下。於洗淨後之氫氧化物中，混合濃度為35%之雙氧水，反應數小時後進行超過濾，藉此獲得分散有與二氧化矽複合之金屬或無機物質被修飾之非晶型過氧化鈦之微細粒子之溶液。 再者，由上述製造方法所得之水性分散液中之過氧化鈦濃度(包含共存之金、銀、鉑、銅、錳、鎳、鈷、鐵、鋅等之金屬或無機物質之合計量)較佳為0.05～15 wt%，更佳為0.1～5 wt%。關於作為介電體或半導體之氧化鈦及 / 或氧化矽 ( 包含該等之化合物 ) 、與氧化鈦及氧化矽除外之介電體及 / 或半導體之組合 如上所述，於作為介置於使基體表面或基體表面層帶電之物質間之介電體或半導體，使用氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)之情形時，若使氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體以1種以上複合，則基體表面帶正電荷或帶負電荷及兩性帶電。為了於基體之表面形成基於該態樣之造膜，可與上述金屬摻雜氧化鈦同樣地使用氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)與氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體複合之分散液。又，作為該分散液之製造方法，與圖3及圖4所示之方法相同。 接著，對基體表面或基體表面層上之用於使基體表面帶電之粒子狀積層物之形成方法，進行更詳細地說明。於基體表面上之電荷形成用造膜方法 圖1(1)係於基體表面形成有規則地取入具有正電荷之物質及/或具有負電荷之物質之粒子及作為介電體或半導體之氧化鈦及/或氧化矽之粒子之粒子狀積層膜之態樣，圖1(2)及圖1(3)係於基體表面形成有由使具有正電荷之物質及/或具有負電荷之物質及作為介電體或半導體之氧化鈦及/或氧化矽複合化而成之粒子所得之粒子狀積層膜之態樣。該等粒子狀積層物之層厚並無特別限定，較佳為10 nm～1 μm之範圍，更佳為10 nm～100 nm之範圍。 上述粒子狀積層物例如可藉由濺鍍、熔射法、離子鍍覆(陰極電弧放電型)、CVD塗佈、電沈積塗佈而形成。又，可藉由進行至少一次如下步驟形成：將基體浸漬於包含具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽之溶液、懸浮液或乳化液中進行浸漬塗佈，或者將上述溶液、懸浮液或乳化液利用噴霧器、滾筒、刷毛、海綿等塗佈於基體上後，進行乾燥而使溶劑或介質揮散之步驟。 具體而言，經過將例如使金、銀、鉑、銅、錳、鎳、鈷、鐵等金屬之金屬複合而成之金屬摻雜非晶型氧化鈦分散液、金屬摻雜氧化矽分散液、該等分散液之混合液塗佈於基體上後進行乾燥之步驟，可於基體上進行圖1所示之造膜。 於上述粒子狀積層物中，為了促進層中之包含具有正電荷之物質或具有負電荷之物質及作為介電體或半導體之氧化鈦及/或氧化矽之固體成分不局部化地分散，進而較佳為使各種界面活性劑或分散劑與具有正電荷之物質及/或具有負電荷之物質共存。界面活性劑或分散劑之調配量可設為具有正電荷之物質及/或具有負電荷之物質之總量之0.001～1.0重量%，較佳為0.1～1.0重量%之範圍。 作為上述界面活性劑或分散劑，可使用各種有機矽化合物作為用於形成均一膜之微粉體、微粒子固定劑。作為有機矽化合物，可使用各種矽烷化合物及各種聚矽氧油、聚矽氧橡膠及聚矽氧樹脂，較佳為分子中具有烷基矽酸酯結構或聚醚結構者，或具有烷基矽酸酯結構與聚醚結構之兩者。關於中間層及被覆層 於上述粒子狀積層物與基體之間可設置中間層，或者於上述粒子狀積層物之表面設置被覆層。該中間層或被覆層例如可使用能夠對基體賦予親水性或疏水性或撥水性或撥油性之各種有機或無機物質。 於中間層及被覆層所可使用之有機或無機物質之中，作為親水性之有機物質，可列舉：聚醚；聚乙烯醇；聚丙烯酸(包含鹼金屬鹽、銨鹽等鹽)、聚甲基丙烯酸(包含鹼金屬鹽、銨鹽等鹽)、聚丙烯酸-聚甲基丙烯酸(包含鹼金屬鹽、銨鹽等鹽)共聚物；聚丙烯醯胺；聚乙烯吡咯啶酮；親水性纖維素類；多糖類等天然親水性高分子化合物等。亦可使用於該等高分子材料中調配玻璃纖維、碳纖維、二氧化矽等無機系介電體並複合化而得者。又，亦可使用塗料作為上述高分子材料。 於中間層及被覆層所可使用之有機或無機物質之中，作為親水性之無機材料，例如可列舉矽烷偶合劑、SiO2 或其他矽化合物。 於中間層及被覆層所可使用之有機或無機物質之中，作為撥水性之無機系材料，例如可列舉：矽烷系、矽酸鹽系、矽酮系及矽烷複合系、或氟系之撥水劑或者乾燥劑等。尤佳為氟系撥水劑，作為例，可列舉含全氟烷基化合物等含氟化合物或含有含氟化合物之組合物。再者，於在中間層包含對基材表面之吸附性較高之含氟化合物之情形時，未必需要使中間層之撥水劑或乾燥劑之化學成分與基材反應生成化學鍵，或中間層與基材之化學成分彼此交聯。 可用作此種氟系撥水劑之含氟化合物較佳為於分子中含有全氟烷基且分子量為1,000～20,000者，其中，就對基材表面之吸附性優異之方面而言，較佳為全氟烷基磷酸脂、及全氟烷基三甲基銨鹽。 再者，於吸水性基體之情形時，較佳為於基體上預先形成位於上述由正電荷物質及/或負電荷物質與作為介電體或半導體之氧化鈦及/或氧化矽所得之粒子狀積層物之下方的包含矽烷化合物之中間層。該中間層由於大量地含有Si-O鍵，故而可提高由正電荷物質及/或負電荷物質與作為介電體或半導體之氧化鈦及/或氧化矽所得之層之強度或與基體之密接性。又，上述中間層亦具有防止水分對基體之滲入之功能。 作為上述矽烷化合物，可列舉水解性矽烷、其水解物及該等之混合物。又，於該等矽烷化合物中亦可調配各種有機聚矽氧烷。 又，作為中間層之構成材料，亦可使用甲基矽酮樹脂及甲基苯基矽酮樹脂等室溫硬化型矽酮樹脂。 關於上述由具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽所得之粒子狀積層物成分，於中間層及被覆層包含矽烷化合物或矽酮樹脂之情形時，與該等矽烷化合物或矽酮樹脂之混合比(重量比)較佳為1：2～1：0.05之範圍，更佳為1：1～1：0.1之範圍。關於基體 成為本發明之對象之基體之材質並無特別限定，可使用各種親水性或疏水性之無機系基體及有機系基體、或者組合其等者。 作為無機系基體，例如可列舉包含鈉鈣玻璃等透明或不透明玻璃、氧化鋯等金屬氧化物、陶瓷、混凝土、砂漿、石材、金屬等物質之基體。又，作為有機系基體，例如可列舉包含有機樹脂、木材、紙、布等物質之基體。若更具體地例示有機樹脂，例如可列舉：聚乙烯、聚丙烯、聚碳酸酯、丙烯酸系樹脂、PET等聚酯、聚醯胺、聚胺基甲酸酯、ABS樹脂、聚氯乙烯、矽酮、三聚氰胺樹脂、尿素樹脂、矽酮樹脂、氟樹脂、纖維素、環氧改性樹脂等。 成為本發明之對象之基體之形狀並無特別限定，可取立方體、長方體、球形、片形、纖維狀等任意之形狀。再者，基體可為多孔質。基體表面亦可藉由電暈放電處理或紫外線照射處理等而親水性化。作為基體，適合為建築、土木用基板或密封材料、或機器、裝置搬送用機體、顯示畫面等之用途。 本發明能夠利用於要求各種設計性及高防水、防染性能之任意領域，可較佳地用於包含玻璃、金屬、陶瓷、混凝土、木材、石材、高分子樹脂外罩、高分子樹脂片、纖維(衣類、幕簾等)、密封材料等、或該等組合之於建材、空調室外機、廚房設備頂板或庫內、衛生設備、照明器具、汽車、腳踏車、機動二輪車、飛機、火車、船舶等室內外使用之物品或各種機械、電子機器、電視等之面板。本發明尤其適合於建材，使用應用有本案發明之建材所建造之房屋、大廈、道路、隧道等建築物能夠經時發揮高防水、防染效果。 又，本發明亦可應用於空氣淨化裝置(亦包含空調機等)、水淨化裝置(亦包含水罐、水壺等)，對於該等設備之內部使用之裝置或發光元件等暴露於空氣或者水中之基體表面之污染防止或污染之降低能夠發揮效果。進而，對於防止鍋或煎鍋、烹飪器具等之附碳化焦之附著亦有效。 [實施例] 以下，對本發明之實施例加以說明，但本發明不受該等實施例任何限定。 於本發明之實施例中，使用以下之參考例1～參考例9所記載之分散液，製作實施例1～9、實施例11～19及實施例20～23之基板，分別進行與比較例1、2及3之評價。 ・參考例1 氧化鈦(介電體：非晶型過氧化鈦)與具有正電荷之物質(導電體：Cu)之複合體分散液 於將四氯化鈦(大阪鈦技術股份有限公司製造)稀釋液與97%CuCl2 ･2H2 O(氯化銅)(日本化學產業股份有限公司製造)完全地溶解之溶液中，滴加氨水調製為pH7左右而使氫氧化物析出。將該析出之氫氧化物於純水中進行洗淨直至上清液之導電率成為0.9 mS/m以下。接著，於該氫氧化物中混合雙氧水並反應數小時，結果獲得銅被修飾之非晶型過氧化鈦溶液。 ・參考例2 氧化鈦(介電體：非晶型過氧化鈦)與具有正電荷之物質(導電體：Cu與介電體：Zr之複合體)之複合體分散液 於將四氯化鈦(大阪鈦技術股份有限公司製造)稀釋液與97%CuCl2 ･2H2 O(氯化銅)(日本化學產業股份有限公司製造)及氧氯化鋯完全地溶解之溶液中，滴加氨水調製為pH7左右而使氫氧化物析出。將該析出之氫氧化物於純水中進行洗淨直至上清液之導電率成為0.9 mS/m以下。接著，於該氫氧化物中混合雙氧水並反應數小時，結果製作出銅及鋯被修飾之非晶型過氧化鈦溶液。 ・參考例3 氧化矽(半導體：聚矽酸酯)與具有正電荷之物質(導電體：Cu)之複合體分散液 將矽酸甲酯51(三菱化學股份有限公司製造)、甲基改性醇、純水及3%鹽酸進行混合，一面加溫一面攪拌，結果製作聚矽酸酯。進而，將該製作出之聚矽酸酯於純水中調整為固體成分濃度4 wt%，並攪拌混合Cu粉末與35%雙氧水及氨水，結果製作出氧化矽與銅之複合體分散液。 ・參考例4 氧化鈦(介電體：非晶型過氧化鈦)與氧化鈦以外之介電體(Ce：介電體)之複合體分散液(基於該組合之造膜呈負電荷) 於將四氯化鈦(大阪鈦技術股份有限公司製造)稀釋液與CeCl3 ・7H2 O(氯化鈰(III))(三津和化學藥品股份有限公司製造)完全地溶解之溶液中，滴加氨水調製為pH7左右而使氫氧化物析出。將該析出之氫氧化物於純水中進行洗淨直至上清液之導電率成為0.9 mS/m以下。接著，於該氫氧化物中混合雙氧水並反應數小時，結果製作出鈰被修飾之非晶型過氧化鈦溶液。 ・參考例5 氧化鈦(介電體：非晶型過氧化鈦)與具有負電荷之物質(導電體：Sn與介電體：Ce之複合體)之複合體分散液 於將四氯化鈦(大阪鈦技術股份有限公司製造)稀釋液與SnCl2 ･2H2 O(氯化亞錫)(岸田化學股份有限公司製造)及CeCl3 ・7H2 O(氯化鈰(III))(三津和化學藥品股份有限公司製造)完全地溶解之溶液中，滴加氨水調製成pH7左右而使氫氧化物析出。將該析出之氫氧化物於純水中進行洗淨直至上清液之導電率成為0.9 mS/m以下。接著，於該氫氧化物中混合雙氧水並反應數小時，結果製作出錫與鈰被修飾之非晶型過氧化鈦溶液。 ・參考例6 氧化矽(半導體：聚矽酸酯)與具有負電荷之物質(導電體：K)之複合體分散液 將矽酸甲酯51(三菱化學股份有限公司製造)、甲基改性醇、純水及3%鹽酸進行混合，一面加溫一面攪拌，結果製作聚矽酸酯。進而，將該製作出之聚矽酸酯於純水中調整為固體成分濃度4 wt%，並混合KOH(氫氧化鉀)，結果製作出氧化矽與鉀之複合體分散液。 ・參考例7 將參考例1之分散液與參考例4之分散液以體積比1：1混合而成之複合體分散液 將參考例1之分散液(摻雜有銅之非晶型過氧化鈦溶液)與參考例4之分散液(鈰被修飾之非晶型過氧化鈦溶液)以體積比1：1進行混合而製作。 ・參考例8 將參考例2之分散液與參考例5之分散液以體積比1：1混合而成之複合體分散液 將參考例2之分散液(銅與鋯被修飾之非晶型過氧化鈦溶液)與參考例5之分散液(錫與鈰被修飾之非晶型過氧化鈦溶液)以體積比1：1進行混合而製作。 ・參考例9 將參考例3之分散液與參考例5之分散液以體積比1：1混合而成之複合體分散液 將參考例3(氧化矽與銅之複合體分散液)之分散液與參考例5(錫與鈰被修飾之非晶型過氧化鈦溶液)之分散液以體積比1：1進行混合而製作。 實施例1 於市售陶磁器磚(100 mm×100 mm)基板表面用噴槍以10 g/m2 (濕潤狀態)之比率塗佈參考例1之分散液，於200℃下加熱10分鐘而設為實施例1。 實施例2～9 以與實施例1相同之步驟，使用參考例2～參考例9之分散液而製作基板，將所得基板分別設為實施例2～9。 比較例1 將於市售陶磁器磚(100 mm×100 mm)基板表面上未進行新造膜之無造膜基板設為比較例1。 評價1 於實施例1～9及比較例1之磚之表面，塗佈0.007 g/100 cm2 之將作為負電荷染料之含有靛紅之市售紅墨水(PILOTINK股份有限公司製造)稀釋而得之液體，常溫乾燥而製作評價基板。 又，利用相同之程序，將作為正電荷顏料之亞甲基藍試劑溶液塗佈於實施例1～9及比較例1之磚表面而製作評價基板。 對於使用該等負電荷染料及正電荷顏料製作之各評價基板，自紫外線量1300 μw/cm2 之位置照射15 W黑光燈螢光燈(東芝股份有限公司製造)，利用色彩計CR-200(柯尼卡美能達股份有限公司製造)對各電荷表面之脫色率經時評價，並根據各實施例之評價基板之脫色率評價各表面電荷狀態。經時評價之時間之單位為天。 關於實施例1～9及比較例1之各評價基板之經時脫色率，於紅墨水之情形時如表1所示，於亞甲基藍試劑之情形時如表2所示。 [表1] [表2] ＜結果1＞ ・於表1(負染料：靛紅)之經過時間(5.8天)下，藉由靜電反斥而脫色率較高的是具有負電荷表面特性之實施例4～6。與其相反地脫色率較低的是具有正電荷表面特性之實施例1～3。可知具有負電荷表面與正電荷表面之大致中間值之脫色率之實施例7～9具有兩性電荷表面特性。再者，比較例1之無造膜表現出由表面釉藥產生之負電荷特性。 ・於表2(正顏料：亞甲基藍)之經過時間(5.8天)下，藉由靜電反斥而脫色率較高的是具有正電荷表面特性之實施例1～3。與其相反地脫色率較低的是具有負電荷表面特性之實施例4～6。可知具有負電荷表面與正電荷表面之大致中間值之脫色率之實施例7～9具有兩性電荷表面特性。 再者，比較例1之無造膜表現出由磚之表面釉藥產生之負電荷特性。 實施例11～19 於普通浮法玻璃(100 mm×100 mm厚3 mm)基板表面，利用噴槍分別以10 g/m2 (wet狀態)之比率塗佈參考例1～參考例9之分散液，於200℃下加熱10分鐘而設為實施例11～19。 比較例2 將於實施例11～19所使用之普通浮法玻璃基板上不新造膜之無造膜玻璃基板設為比較例2。 評價2 使用關東壤土層沙塵、中東迪拜沙漠沙塵、九州地區火山灰之3種，進行實施例11～19及比較例2之沙塵吸附防污評價。將關東壤土層沙塵、中東迪拜沙漠沙塵、九州地區火山灰分別以1小湯匙地滴下至實施例11～19及比較例2之基板表面，設為評價基板，將該等評價基板立起並輕輕地於台上叩打2次，使用光澤度計IG-331(堀場製作所股份有限公司製造)測定光澤度。然後，求出與滴加沙塵或火山灰之前測得之各實施例及比較例之基板之光澤度之差，藉此根據因附著殘餘引起之光之漫反射率評價抗沙塵吸附之防污性能，並將評價結果(3處之測定平均值)示於下述表3(數值：粉體評價前光澤度－粉體評價後光澤度)。 [表3] ＜結果2＞ 表3揭示以下之結果。 於使用關東壤土粉體之情形時，顯示出作為正電荷表面特性造膜基板之實施例11～13、及作為兩性電荷表面特性造膜之實施例17～19之評價前與評價後之光澤度變化低，對於關東壤土粉體，正或兩性之電荷表面具有防污功能。於使用迪拜沙漠沙塵粉體之情形時之防污功能亦相同。 於使用九州地區火山灰粉體之情形時，顯示出作為負電荷表面特性造膜基板之實施例14～16之評價前與評價後之光澤度變化低，對於火山灰粉體，負電荷表面具有防污功能。相對於此，比較例2之無造膜藍浮法玻璃表面顯示出基於3種粉體附著之光澤度數值。 實施例20 於普通鈉鈣浮法玻璃(100 mm×100 mm厚3 mm)基板表面，利用海綿擠壓法以10 g/m2 之比率塗佈參考例1之分散液，於300℃下加熱10分鐘，設為實施例20。 實施例21 使用參考例4之分散液，藉由與實施例20相同之製作方法製作實施例21。 實施例22 使用參考例5之分散液，藉由與實施例20相同之製作方法製作實施例22。 實施例23 使用參考例7之分散液，藉由與實施例20相同之製作方法製作實施例23。 比較例3 將普通鈉鈣浮法玻璃(100 mm×100 mm厚3 mm)基板上無造膜者設為比較例3。 評價3 於實施例20～23之評價基板及比較例3之基板之上表面，以寬約20mm、長約60mm左右塗佈攪拌有雞蛋之液體與市售之橄欖油之液體，於300℃下加熱30分鐘，固定各碳化聚合物製成各評價基板，藉由使市售面紙吸水擦拭各評價基板表面之方法、及將廚房用海綿之柔軟側潤濕來擦拭各評價基板表面之方法，評價利用該等碳化物之靜電反斥獲得之易去除性。又，關於造膜於各實施例之基板上之表面膜之狀態，目視評價碳化聚合物之去除作業後之表面膜有無擦傷。將其結果示於以下之表4。   [表4] ＜結果3＞ 表4係表示於基體處於被加熱之環境或使用條件下之情形時之由靜電反斥獲得之固著之污染物之去除性能者。 自表4可知，實施例21及實施例22之於加熱前造膜有負電荷膜之評價基板無碳化污染物之吸附，且除去性能優異。 相對於此，於實施例20之於加熱前造膜有正電荷膜之評價基板及比較例3之無造膜基板中，顯示出無法去除固著之碳化污染物。 又，於實施例23之造膜有兩性電荷膜之評價基板中，顯示出實施例20與實施例21之大致中間之碳化污染物之去除性能。 再者，關於各實施例之基板之表面膜之狀態，顯示出即使在碳化聚合物去除作業後亦無擦傷，為能耐受此種環境或作業之硬質之膜。 由此可知，關於利用表面電荷形成之防污技術賦予，無論防污對象物為何種物質，無論造膜基體處於何種使用環境或者使用條件下，均必須考慮電荷來設計對基體表面賦予之電荷之種類。 又，顯示出藉由使用氧化鈦或氧化矽作為介電體及半導體，不僅能夠形成穩定之表面之電荷，而且能夠形成硬質之膜。Hereinafter, embodiments of the present invention will be described with reference to the drawings.summary The inventors of the present invention have found that in order to promote the development of a substrate having a positive charge or a negatively charged substance due to the surface of the substrate or the surface layer of the substrate, the substrate is electrostatically repelled or adsorbed by externally contaminated substances. In the process of protection or environmental improvement, in order to make the charge non-localized, efficiently and stably formed on the surface or surface layer of the substrate, it is important to form a positively charged substance in the surface or surface layer of the substrate. And a particulate layered product in which a negatively charged substance is appropriately interposed between a substance for stably forming a charge or a semiconductor. In addition, the particulate layered product refers to a film or layer formed of a particulate material arranged in a layered manner and formed on the surface or surface layer of the substrate. Further, the inventors of the present invention have found that the dielectric material or semiconductor interposed between the substances for charging the surface of the substrate or the surface layer of the substrate in the particulate layer is a material which is low in cost and easy to use. Titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) may be selected from the viewpoints of excellent dielectric properties, semiconductor characteristics, and excellent functionality such as a non-adhesive film. In the prior art disclosed by the Applicant, it is disclosed that as a substance for charging a surface of a substrate or a surface layer of a substrate, if it is positively charged, a cation, a positively charged conductor, a positively charged conductor and a composite of a dielectric body and a composite of a positively charged conductor and a semiconductor, and if it is negatively charged, an anion, a negatively charged conductor, a negatively charged conductor and a dielectric composite, A composite of a negatively charged conductor and a semiconductor, and a substance having a photocatalytic function (Patent Document 1 and Patent Document 2). The applicant further found that when two or more kinds of dielectric bodies or semiconductors are combined, they are positively or negatively charged by the type of dielectric or semiconductor used. On the other hand, the inventors of the present invention have newly discovered that titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) is used as a dielectric interposed between substances which charge the surface of the substrate or the surface layer of the substrate. In the case of a semiconductor, if a dielectric or semiconductor other than titanium oxide and/or antimony oxide (a compound containing titanium oxide and/or antimony oxide) is used, instead of the above-mentioned substance having a positive charge and/or a substance having a negative charge By the kind of the dielectric or semiconductor, the surface of the substrate or the surface layer of the substrate may be positively or negatively charged, and both positive and negative are charged. Therefore, in the following description, although the substance which is positively charged on the surface of the substrate or the surface layer of the substrate is defined as a "positively charged substance", the substance which is negatively charged on the surface of the substrate or the surface layer of the substrate is defined as "having a negative a substance of a charge, but a substance having a positive charge and a substance having a negative charge also includes a dielectric or semiconductor other than "titanium oxide and/or antimony oxide (a compound containing titanium oxide and/or antimony oxide). "." These dielectric bodies or semiconductors have excellent electrostatic polarization and electrostatic induction characteristics, and it is desirable to have a property of changing the charge dipoles in the substances by irradiation of electromagnetic waves or heat or light. In order to more effectively exert a function of electrostatically repelling or adsorbing contaminants from the outside on the surface of the substrate or the surface layer of the substrate, it is desirable to form a particulate laminate on the surface or surface layer of the substrate, and The particulate laminate is regularly taken into the dried and solidified particles to form a uniform and uniform charge. For example, as a preferable example of such a particulate laminate, the following (a) to (c) are exemplified. (a) a surface film or surface layer of a substrate having a positively charged substance and/or a substance having a negative charge and a titanium oxide and/or cerium oxide as a dielectric or semiconductor, respectively, by particle bonding of a single particle (b) a substrate having a positive charge by a particle surface obtained by particle bonding of colloidal particles obtained by coating a colloidal particle having a positively charged substance and/or a negatively charged substance in titanium oxide or cerium oxide and/or Or a surface film or a surface layer formed by particle bonding of a substance having a negative charge and titanium oxide and/or cerium oxide in the form of a perovskite or perovskite type crystallite as a composite of molecular grades. The particle size of the particulate laminate on the surface of the substrate or the surface layer is preferably from 0.1 nm to 100 nm. Further, the layer thickness of the laminate is not particularly limited, but is preferably in the range of 10 nm to 1 μm, more preferably in the range of 10 nm to 100 nm.About the principle of charge formation Hereinafter, the positive or negative charge or the negative charge is applied to the surface of the substrate or the surface layer of the substrate by using the particulate laminate formed on the surface of the substrate or the surface of the substrate as described in the above (a), as shown in FIG. 5 and FIG. The principle of charge formation of positive and negative charges will be described. 5(1), 5(2), and 5(3) schematically show the use of a substance having a positive charge and/or a substance having a negative charge and a titanium oxide or a cerium oxide as a dielectric or semiconductor (including These compounds) are diagrams that give the principle of positive, negative, positive and negative charges on the surface of the substrate or on the surface layer of the substrate. In Fig. 5 (1), on the surface of the substrate or the surface of the substrate, the particles AP of the positively charged conductor are adjacent to the particles BB of the dielectric or semiconductor titanium oxide or cerium oxide (including the compound). The layer is formed with a film or a layer, and in FIG. 5 (2), the state of the particles AN of the negatively charged conductor and the particles BB of the dielectric or semiconductor titanium oxide or cerium oxide (including the compound) are adjacent to each other. A film or layer is formed on the surface of the substrate or the surface layer of the substrate. In FIG. 5 (3), the particles AN of the negatively charged conductor and the particles AP of the positively charged conductor are alternately adjacent to each other as a dielectric or A film or layer is formed on the surface of the substrate or the surface layer of the substrate in the state of the particles BB of the titanium oxide or the cerium oxide (including the compound) of the semiconductor. The conductor exists at a high concentration of free electrons that can move freely inside, and holes or negative electrons are concentrated on the surface of the film formation or formation layer by excitation, thereby maintaining a positive or negative charge. status. The dielectric or semiconductor adjacent to the conductor is dielectrically polarized by the surface charge state of the conductor, and is in a state of generating a negative charge on the side adjacent to the conductor having a positive charge, and having a negative charge A state in which a positive charge is generated on the side adjacent to the conductor, and a state in which an opposite charge is generated on the opposite electrode side. Therefore, a uniform and uniform charge is formed on the surface of the formed particulate laminate. 6(1), 6(2), and 6(3) schematically show a dielectric or semiconductor other than titanium oxide and antimony oxide (including these compounds), and a dielectric or semiconductor. A graph of the principle of giving positive, negative, positive, and negative charges to the surface of the substrate or the surface layer of the substrate, respectively, of titanium oxide or cerium oxide (comprising such compounds). 6(1) to (3), a dielectric CC or a semiconductor particle CC other than titanium oxide and cerium oxide (including the compound), and titanium oxide or cerium oxide as a dielectric or semiconductor (including the In the state in which the particles BB of the compound (the compound) are adjacent to each other, a film or a layer is formed on the surface of the substrate or the surface layer of the substrate, respectively. In a dielectric or semiconductor other than titanium oxide and cerium oxide (including such compounds), if an electrical dipole of the substance is formed rapidly with an adjacent substance (ie, titanium oxide or cerium oxide (including such compounds) )) The surface charge reaction of the dielectric polarization causes the dipole to move with a charge opposite to the dielectrically charged charge, and it is considered that a uniform positive or negative charge is generated on the surface or surface layer of the substrate. 6(1), 6(2), and 6(3) show the state of generating a uniform positive charge, generating a uniform negative charge, and generating uniform positive and negative charges, respectively. .Film forming method for substrate surface Next, a method of forming a charge surface or a film forming method on the surface of each of the substrates (a) to (c) described in paragraph No. 0025 will be described in the following (A) to (C). (A) Film forming method using a single-particle film Fig. 1 (1) schematically shows a film-forming cross section of the substrate S1 in the form of (a). In the figure, the colored circle is a positively charged substance and/or a negatively charged substance, and the uncolored circle represents titanium oxide and/or cerium oxide (including the compound) as a dielectric or semiconductor. The particles formed. That is, the aspect of (a) is a form in which a single particle formed of a substance having a positive charge and/or a substance having a negative charge is uniformly dispersed in the bonding of a single particle formed of titanium oxide and/or cerium oxide. A film forming method of a particulate laminate according to this embodiment will be described below. As described with reference to FIGS. 5 and 6, it is theoretically preferable to have a positively charged substance and/or a negatively charged substance and a titanium oxide and/or cerium oxide as a dielectric or semiconductor (including such compounds). ) The composite was formed at a ratio of 1:1 on the film formation. Regarding the method of forming such a composite film or layer on the surface or the surface layer of the substrate, various methods are conceivable, and it is not particularly limited. As an example, there is a method of using a film forming liquid. Specifically, particles of titanium oxide and/or cerium oxide (including the compounds) and particles having a positive charge and/or a substance having a negative charge are prepared in advance, and the particles are dispersed in water. Or a film forming solution in an organic medium or the like. Further, a film forming method based on a wet method in which the film forming liquid is applied to a substrate to form a film can be used. Further, it is also possible to use a film forming method in which a fine powder or ionic fine particles contained in a film forming liquid is applied to a substrate by a dry method such as ion plating or sputtering using the film forming solution. Make a film on it. Further, a more detailed description of the film forming method of the substrate or a detailed description of the manufacturing method of the film forming liquid will be described later. Further, the particles of titanium oxide and/or cerium oxide (including the compound) and particles having a positive charge and/or a substance having a negative charge are used in a film forming solution dispersed in water or an organic medium. When the film is formed on the surface of the substrate, the ratio of the particles is preferably 1:1 after the film formation as described above, but in consideration of the stability of the film forming liquid, The ratio of titanium oxide and/or cerium oxide (including such compounds) to a substance having a positive charge and/or a substance having a negative charge is represented by a solid content molar ratio, and titanium oxide (including a titanium oxide compound) is used. In the case, it is preferably a ratio of 1:0.01 to 1:0.3, and in the case of using cerium oxide (a compound containing cerium oxide), it is preferably a ratio of 1:0.03 to 1:2.7, using titanium oxide and oxidizing. In the case of hydrazine (including these compounds), a ratio of 1:0.01 to 1:0.3 is preferred. (B) A film forming method using a film containing a positively charged substance and/or a negatively charged substance, FIG. 1 (2) schematically shows the aspect of (b) on the substrate S1. A diagram of the membrane profile. In the figure, the colored circle is a substance having a positive charge and/or a substance having a negative charge, and the uncolored circle represents titanium oxide and/or yttrium oxide (including the compound) as a dielectric or a semiconductor, by A film is formed by bonding colloidal particles of titanium oxide and/or cerium oxide (including these compounds) containing a positively charged substance and/or a negatively charged substance. In the film formation of the film of this form, in the step of mixing or compositing titanium oxide or cerium oxide (including the compound) with a substance having a positive charge and/or a substance having a negative charge, A positively charged substance and/or a substance having a negative charge is prepared by reacting an alkaline agent or an acidic agent and reacting it to prepare a titanium oxide and/or yttrium oxide as a dielectric or semiconductor. The film-forming liquid containing the compound) is fixed to the surface of the substrate by a film formed by a wet method or a dry method, and at this time, it is made into titanium oxide and/or cerium oxide (including these compounds). A colloidal particle composed of a substance having a positive charge and/or a substance having a negative charge. That is, when titanium oxide and/or cerium oxide (including these compounds) and a substance having a positive charge and/or a substance having a negative charge are solidified by drying, ions may be integrated in the form of colloidal particles to be laminated. . a composite ratio of titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) to a positively charged substance and/or a negatively charged substance in the above film forming liquid, The ratio is preferably from 1:0.01 to 1:0.3 when titanium oxide (including a titanium oxide compound) is used, and is preferably one in the case of using cerium oxide (a compound containing cerium oxide). The ratio of 0.03 to 1:2.7 is preferably a ratio of 1:0.01 to 1:0.3 when titanium oxide and cerium oxide (including these compounds) are used. Further, the film formation on the substrate is preferably a non-adhesive fixing, and the non-adhesive agent is fixed by a peroxy or methyl group as a self-fixing modification of titanium oxide or cerium oxide, or H as a decane monomer or polysiloxane polymer of an organic ruthenium compound2 O, CO2 The polycondensation reaction caused by the detachment. (C) a positively charged substance and/or a substance having a negative charge and a titanium oxide and/or cerium oxide in the form of a perovskite or perovskite type pseudomorphic crystal as a composite of molecular grades Film forming method of the formed film Fig. 1 (3) schematically shows a film forming cross section of the substrate S1 in the form of (c). In the figure, the colored circle is a substance having a positive charge and/or a substance having a negative charge, and the uncolored circle means titanium oxide and/or yttrium oxide (including the compound) as a dielectric or a semiconductor, The circle on the outer side indicates a crystal structure or a pseudocrystal structure in which molecules of a molecular grade are internally taken into ions. Ti molecules and O for forming titanium oxide or/and cerium oxide2 Molecular or O3 Molecule, or Si molecule and O2 Molecular or O3 When the molecule is dissociated in the solution, the positively charged substance and/or the negatively charged substance are reacted in a molecular ion state, and solidified by an acidic agent, an alkaline agent, or electromagnetic wave irradiation. A composite crystal is formed. The composite ratio of the titanium oxide and/or cerium oxide (the compound containing titanium oxide and/or cerium oxide) to the positively charged substance and/or the negatively charged substance is expressed by the molar ratio of the solid component. When titanium oxide (including a titanium oxide compound) is used, it is preferably a ratio of 1:0.01 to 1:0.3, and when cerium oxide (a compound containing cerium oxide) is used, it is preferably 1:0.03. The ratio of 1:2.7 is preferably in the range of 1:0.01 to 1:0.3 when titanium oxide and cerium oxide (including these compounds) are used. The above composite crystal has a perovskite crystal structure or a pseudocrystal structure which is conventionally known to internally take in a composite molecule in an ion form, and in the case of the composite crystal grain, Ti or Si functions as a positive charge, O2 Functions as a negative charge. Therefore, in the composite crystal grains, the amphiphilic, positive>negative, or negative>positive charges can be selectively exhibited by the ions contained therein. As described above, with reference to FIG. 1, a film obtained by interposing a material having a positive charge and/or a substance having a negative charge as a dielectric or a semiconductor, or a ruthenium oxide (including the compound) is formed on the substrate. An example of a method of forming a film on the surface will be described. When the film forming method of Fig. 1 is used, the film can be formed regardless of the substrate. Further, in (1), (2), and (3) of FIG. 1 , the layer of the particles of the particulate laminate formed on the surface of the substrate is exemplified as one layer or two layers, but in order to exhibit the present invention Functionally, it is desirable to form a particulate laminate by a plurality of layers.Formation of a particulate layer on the surface layer of the substrate On the other hand, FIG. 2 shows that titanium oxide and cerium oxide (including these compounds) are interposed as a dielectric or semiconductor by a substance having a positive charge and/or a substance having a negative charge in the surface layer of the substrate. An example in which the charge is not localized, efficiently and stably formed in the surface layer of the substrate. (1), (2), and (3) of Fig. 2 schematically show a pattern of a substrate cross section of the same. In the figure, the colored circle is a positively charged substance and/or a negatively charged substance, and the uncolored circle represents titanium oxide and/or cerium oxide (including the compound) as a dielectric or semiconductor. The particles formed. In the aspect shown in FIG. 2 (1), particles having a positively charged substance and or a substance having a negative charge are formed in advance, and titanium oxide and/or cerium oxide as a dielectric or semiconductor are contained (including the The surface layer of the substrate S2 of the compound) forms a layer of the particles. As a method of forming such a surface layer on the substrate S2, there is a method in which particles having a positively charged substance and/or a substance having a negative charge are pressure-bonded to the surface of the substrate S2 by press working or the like, or a substrate S2 is produced. A method of molding a layer of a positively charged substance and/or a layer of a substance having a negative charge on the surface of the substrate S2, or the like. In the aspect shown in FIG. 2 (2), particles of titanium oxide and/or cerium oxide (including the compounds) are formed in advance, and the particles are positively charged and/or negatively charged. The substrate S3 is pressure-bonded by press working or the like, or is molded at the time of production of the substrate S3, whereby the surface layer as shown in the drawing can be produced. In the aspect shown in Fig. 2 (3), a sheet or a block-shaped substrate S4 (which may contain an inorganic component) formed by an organic polymer resin or the like before curing is formed in advance as a dielectric or a semiconductor. a layer of titanium oxide and cerium oxide (comprising the compound) is interposed in a layer of a positively charged substance and/or a substance having a negative charge, and irradiates the substrate S4 with an electromagnetic wave of ultraviolet rays, or a layer of a titanium oxide of a dielectric or a semiconductor and a particle of a cerium oxide (including the compound), which is interposed between a positively charged substance and/or a substance having a negative charge, is molded on the substrate S4. Thereby, the surface layer as shown in the figure can be produced. In the aspect shown in FIG. 2 (1) and FIG. 2 (2), not the positively charged substance and/or the negatively charged substance particle as shown in FIG. 1 (1) and the dielectric or The titanium oxide of a semiconductor and/or the particles of cerium oxide (including the compound) are adjacently joined, but by containing titanium oxide and/or cerium oxide as a dielectric or semiconductor (including such compounds) The surface side of the substrate S2 is bonded to a substance having a positive charge and/or a substance having a negative charge, or a surface side-bound titanium oxide by a substrate having a positive charge and/or a substance having a negative charge And/or particles of cerium oxide (comprising such compounds) can also form a uniform and uniform charge on the surface of the substrate. Further, in (1), (2), and (3) of FIG. 2, an example in which a layer of particles formed in a surface layer of a substrate is one layer or two layers is exemplified, but in order to exert the function of the present invention, it is desirable The layer of particles formed in the surface layer of the substrate is formed in a plurality of layers. Next, a positively charged substance and/or a negatively charged substance, and a titanium oxide and/or cerium oxide as a dielectric or semiconductor, which are the particulate laminated film for surface charge formation of the invention of the present invention, Which of these compounds is preferably described in detail.Titanium oxide as a dielectric or semiconductor / Oxide The titanium oxide and/or yttrium oxide as a dielectric or semiconductor interposed between a positively charged substance and/or a negatively charged substance are excellent in dielectric properties or semiconductor characteristics, and can be used without using a binder. A film of high hardness and high transparency is formed. Moreover, in terms of cost, it can also be used at relatively low cost. As the dielectric or semiconductor interposed between the substance having a positive charge and/or the substance having a negative charge, various oxides or peroxides of titanium oxide or cerium oxide or the like may be used, and further, An alkali metal or an alkaline earth metal, which is a group 3 or a lanthanum or a lanthanoid element, or a group 4 zirconium or hafnium, etc., or a compound other than a conductive metal. The electric body or semiconductor is composited or coexistent.a substance with a positive charge and / Or a substance with a negative charge A positively charged substance and/or a negatively charged substance which is combined with titanium oxide and/or cerium oxide (including such a compound) as a dielectric or semiconductor, as long as it is capable of imparting a positive charge or a negative to the surface of the substrate. As the charge, any substance having a positive or negative charge may be used, preferably at least one substance having a positive charge selected from the group consisting of (1) to (6) below and/or having a negative charge. Substance. (1) a cation (2) a conductor having a positive charge, a composite of a positively charged conductor and a dielectric, a composite of a positively charged conductor and a semiconductor, and a combination of two or more types having a positive charge Any one of a combination of an electric body or/and a semiconductor having a positive charge or a composite (3) an anion (4) having a negative charge, a negatively charged conductor and a dielectric, having A negatively charged conductor or composite (5) having a photocatalytic function, a composite of a negatively charged conductor and a semiconductor, or a composite of two or more dielectrics or semiconductors having a negative charge (6) A dielectric or a semiconductor other than titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) as a cation, an anion, or a negatively or positively charged conductive of (1) to (6) A substance, a dielectric, or a semiconductor that functions as a photocatalyst may be of a type such as an organic substance, an inorganic substance, a composite of an organic substance and an inorganic substance, but a stable electric power can be formed on the surface of the substrate. Further, the substance is protected by electrostatic adsorption or repulsion of the contaminant, and the charge under the use condition of the substrate for irradiating electromagnetic waves or heat or light can be formed. In this respect, it is particularly preferable to use a metal or a metal. A part of inorganic substances. Further, it is preferable that a substance having a positive charge and a substance having a negative charge which are complexed with titanium oxide and/or cerium oxide (including the compound) as a dielectric or semiconductor are mainly metals, and therefore, For the sake of convenience, a composite of a part of an inorganic substance other than a metal or a metal and a titanium oxide (a compound containing titanium oxide) as a dielectric or a semiconductor is hereinafter referred to as a metal-doped titanium oxide, and a metal or a metal A composite of a part of an inorganic substance and a cerium oxide (a compound containing cerium oxide) as a dielectric or a semiconductor is referred to as a metal-doped cerium oxide. The metal compounded with titanium oxide and/or cerium oxide (including the compound) as a dielectric or semiconductor is preferably selected from the group consisting of gold, silver, platinum, copper, manganese, nickel, cobalt, iron, and zirconium. a transition metal represented by ruthenium, a typical metal represented by zinc or tin, an alkali metal, an alkaline earth metal, a metal element or an inorganic element represented by lanthanum or lanthanum, and more preferably 2 a composite of metal elements. As a composite metal element, silver and copper are particularly preferred. Further, the inorganic substance other than the metal which is a composite of titanium oxide and/or cerium oxide (including these compounds) as a dielectric or semiconductor is preferably ruthenium.About metal doped titanium oxide In the following, a metal (including a part of an inorganic substance other than a metal) and a titanium oxide (a compound containing titanium oxide) as a dielectric or semiconductor are preferable as the material constituting the particulate-shaped laminated film for surface charge formation of the present invention. The combination is explained. As a titanium oxide (a compound containing titanium oxide) which is a dielectric or a semiconductor compounded with a metal (a part of an inorganic substance other than a metal), TiO can be used.2 TiO3 , TiO, TiO3 /nH2 Various oxides or peroxides such as O. It is especially preferred to be a titanium peroxide having a peroxy group. The titanium oxide may be any of an amorphous type, an anatase type, a brookite type, and a rutile type, and these may be mixed, but are preferably amorphous titanium oxide. Among them, the titanium oxide obtained by combining titanium oxide with a metal to form a solid component exhibits an anatase crystal or an anatase crystal precursor. Here, the relationship between the photocatalytic function of the titanium oxide and the metal-doped titanium oxide described above will be described. The reason for this is that if the titanium oxide functions as a photocatalyst on the surface of the substrate, depending on the type of the substrate, the substrate itself may be decomposed and deteriorated due to the photocatalytic action. Among the titanium oxide, the amorphous titanium oxide and the anatase type crystalline precursor titanium oxide do not have a photocatalytic function. On the other hand, although the anatase type, brookite type, and rutile type titanium oxide have a photocatalytic function, if copper, manganese, nickel, cobalt, iron, or zinc is combined with the titanium oxide at a certain concentration or more, The photocatalytic function is reduced or lost. Further, the amorphous titanium oxide and the anatase type crystal precursor titanium oxide are converted into anatase-type titanium oxide by time by heating by sunlight or the like, but if combined with copper, manganese, nickel, cobalt, iron Or zinc composite, the photocatalytic function of anatase titanium oxide is reduced. Therefore, even if it is any type of titanium oxide, the titanium oxide doped with copper, manganese, nickel, cobalt, iron or zinc may not be considered to have an adverse effect caused by the photocatalytic action. Furthermore, the titanium oxide doped with gold, silver or platinum also contains photocatalytic properties including amorphous titanium oxide converted to anatase titanium oxide, but is doped with gold, silver, In the titanium oxide of platinum, when a positively-charged substance coexists at a certain concentration or more, the photocatalytic performance is not exhibited. Therefore, since the metal-doped titanium oxide compounded with gold, silver, platinum, copper, manganese, nickel, cobalt, iron or zinc can eventually lose or reduce the photocatalytic performance, the adverse effects caused by the photocatalytic action can be ignored. . Among them, when a photocatalytic substance is used as a negatively-charged substance, a surface negative charge or a negative charge generated by a photocatalytic function can be effectively used. Next, a method of producing the above-described metal-doped titanium oxide will be described. The metal-doped titanium oxide may be a production method based on a hydrochloric acid method or a sulfuric acid method as a method for producing a conventional titanium oxide powder, or a method for producing various liquid-dispersed titanium oxide solutions. Further, a part of the inorganic substance other than the metal or the metal compounded with the titanium oxide can be combined with the titanium oxide regardless of the production stage. Hereinafter, an example of a method of producing a dispersion of a metal-doped titanium oxide will be described with reference to Fig. 3 . First, an inorganic compound or a metal compound (having crystals) exemplified on the left side of FIG. 3 in a ratio of 1:0.05 in a molar ratio of 50% titanium tetrachloride (commercial product) in a pure water solution The compound of water) is mixed. The inorganic compound or the metal compound may be mixed in plural. The mixing ratio of the titanium tetrachloride to the inorganic compound or the metal compound is preferably from 1:0.01 to 1:0.3, more preferably from 1:0.02 to 1:0.1 in terms of a molar ratio. 25% aqueous ammonia (commercial product) was added dropwise thereto to adjust to pH 7, and titanium, an inorganic substance or a metal hydroxide was precipitated and washed until the conductivity of the supernatant became 0.9 mS/m or less. Mixing 35% of hydrogen peroxide in the washed hydroxide, and performing ultrafiltration after several hours of reaction, thereby obtaining a solution of fine particles of amorphous titanium peroxide dispersed with the composite inorganic substance or metal modified. . Further, after the hydrogen peroxide is mixed with the above-mentioned hydroxide and reacted, the mixture is heated and subjected to ultrafiltration to obtain a solution in which fine particles of the anatase-type titanium peroxide having the composite inorganic substance or metal modified are dispersed. Further, the concentration of titanium peroxide in the aqueous dispersion obtained by the above production method (including the total amount of metal or inorganic substances such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zinc, etc. coexisting) is preferably 0.05 to 15 wt%, more preferably 0.1 to 5 wt%. In the manufacturing step of the above-mentioned metal-doped titanium oxide, gold, silver, platinum, nickel, cobalt mixed for obtaining an inorganic substance or a metal (including an alkali metal or an alkaline earth metal) compounded with titanium oxide (including a compound thereof) Examples of the compounds of copper, manganese, iron, zinc, lithium, sodium, cesium, potassium, zirconium, lanthanum and cerium may be listed below. Au compound: AuCl, AuCl3 , AuOH, Au(OH)4 Au2 O, Au2 O3 Et compound: AgNO3 , AgF, AgClO3 , AgOH, Ag (NH3 )OH, Ag2 SO4 Pt compound: PtCl2 , PtO, Pt (NH3 )Cl2 , PtO2 , PtCl4 , [Pt(OH)6 ]2- Ni compound: Ni(OH)2 NiCl2 Co compound: Co(OH)NO3 Co(OH)2 CoSO4 CoCl2 Etc. Cu compound: Cu(OH)2 , Cu (NO3 )2 CuSO4 CuCl2 , Cu(CH3 COO)2 Etc. Mn compound: MnNO4 MnSO4 MnCl2 Fe compound: Fe(OH)2 ,Fe(OH)3 FeCl3 Etc. Zn compound: Zn (NO3 )2 ZnSO4 ZnCl2 Li compound: LiOH, Li2 CO3 , LiCl, etc. Na compounds: NaOH, NaCl, Na2 CO2 Si compound: SiO2 , SiH4 , SiCl4 K compound: KOH, K2 O, KCl, etc. Zr compound: Zr2 O, Zr(OH)2 , ZrCl, etc. Ce compound: CeO2 CeCl2 , Ce(OH)3 Hf compound: HfCl2 , Hf(OH)3 In addition to the method for producing the metal-doped titanium oxide dispersion described with reference to FIG. 3, there are many methods for compounding an inorganic substance or a metal with titanium oxide. For example, titanium oxide particles can be separately prepared in advance. The composite inorganic material or metal particles are mixed separately. In the invention of the present invention, in order to produce metal-doped titanium oxide, in addition to the above-described production method, there are various methods for producing fine particles of titanium oxide and a dispersion solution thereof, and any of them may be used.About metal doped cerium oxide In the following, a metal (including a part of an inorganic substance other than a metal) which is a substance constituting the particulate charge film for surface charge formation of the present invention and a cerium oxide (a compound containing cerium oxide) as a dielectric or a semiconductor are preferable. The combination is explained. For cerium oxide (a compound containing cerium oxide) which is a dielectric or a semiconductor compounded with a metal (a part of an inorganic substance other than a metal), SiO can be used.2 SiO3 , SiO, SiO3 /nH2 Various oxides or peroxides such as O. As a material containing cerium oxide, various products are commercially available. For example, as a bonding material (composite material) of an organic material and an inorganic material, the following may be mentioned. A water-soluble coating agent having a methoxy group or an ethoxy group in terms of hydrolyzability, in addition to the improvement of the mechanical strength of the composite material or the improvement of the bondability or the surface hydrophilicity of the decane coupling agent.・An oxime ketone oligomer which is used as a resin-modified or functional coating agent as a oligomer-type coupling agent having an organic functional group and an alkoxy group in the molecule and which is compounded with various materials.・Alkoxy alkane or alkoxyazane having a methyl group or a long-chain alkyl group or a phenyl group used as a water-repellent imparting functional material for a substrate to be described later.・Organic decyl group containing an active hydrogen protecting function of an organic material or an inorganic material, and a sulfonating agent for an organic synthesis member can be produced by controlling the reaction site of the alkyl group. By using the above-mentioned material containing cerium oxide, a film forming liquid for forming a surface charge film which is a metal composite can be produced. Hereinafter, a method for producing a metal-doped cerium oxide dispersion in the case where the composite is a typical metal such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, or zinc, and a transition metal, using FIG. An example will be explained. First, if the alcohol is mixed with pure water and a specific amount of a catalyst in methyl decanoate to carry out hydrolysis, a cerium sol is produced. The cerium sol was diluted with pure water. The solid content concentration in the bismuth sol diluent is preferably from 10% to 0.2%, more preferably from 4% to 0.85%. The cerium sol diluent and the metal compound (the compound having crystal water) adjusted to a concentration of 1% are preferably in a ratio of 1:0.03 to 1:2.7 with respect to the molar concentration ratio of cerium oxide. Preferably, the mixture is mixed at a ratio of 1:0.03 to 1:0.27. Further, the combination of cerium oxide and alkali metal and alkaline earth metal is also the same. Further, as shown in FIG. 4, in the production of the dispersion liquid, the metal compound or inorganic compound which can be combined with cerium oxide can be the same as the metal compound or the inorganic compound used in the production of the metal-doped titanium oxide.About metal doped titanium oxide and antimony oxide Finally, a method of producing a solution in which a metal is combined with titanium oxide and cerium oxide will be described. First, titanium tetrachloride and a ruthenium sol are mixed in a ratio of pure water of 1:0.5 in terms of a molar ratio, and a metal compound (a compound having water of crystallization) is further mixed. The metal compound may be mixed in plural. Further, as the metal compound which can be mixed, for example, a metal compound as shown in FIG. 3 which is used for producing a metal-doped titanium oxide can be used. The mixing ratio of titanium tetrachloride and cerium sol to the metal compound is preferably from 1:0.01 to 1:0.3, more preferably from 1:0.02 to 1:0.1 in terms of a molar ratio. Ammonia water adjusted to 25% is added dropwise thereto, and adjusted to a pH of about 7, to precipitate titanium, cerium, and an inorganic substance or a metal hydroxide to be composited. The precipitated hydroxide was washed in pure water until the conductivity of the supernatant became 0.9 mS/m or less. The washed hydroxide is mixed with a concentration of 35% hydrogen peroxide, and after several hours of reaction, ultrafiltration is carried out, thereby obtaining amorphous titanium peroxide dispersed with a metal or inorganic substance compounded with cerium oxide. a solution of fine particles. Further, the concentration of titanium peroxide in the aqueous dispersion obtained by the above production method (including the total amount of metal or inorganic substances such as gold, silver, platinum, copper, manganese, nickel, cobalt, iron, zinc, etc. coexisting) Preferably, it is 0.05 to 15 wt%, more preferably 0.1 to 5 wt%.About titanium oxide as a dielectric or semiconductor / Oxide ( Containing such compounds ) Dielectrics other than titanium oxide and antimony oxide / Or a combination of semiconductors As described above, when titanium oxide and/or cerium oxide (compound containing titanium oxide and/or cerium oxide) is used as a dielectric or semiconductor interposed between substances for charging a surface of a substrate or a surface layer of a substrate When a dielectric or a semiconductor other than titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) is compounded in one or more types, the surface of the substrate is positively charged or negatively charged and amphoteric charged. In order to form a film based on the surface of the substrate, titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) and titanium oxide and/or may be used in the same manner as the metal-doped titanium oxide. A dispersion of a dielectric or semiconductor compound other than cerium oxide (a compound containing titanium oxide and/or cerium oxide). Further, the method for producing the dispersion is the same as the method shown in Figs. 3 and 4 . Next, a method of forming a particulate laminate for charging the surface of the substrate on the surface of the substrate or the surface layer of the substrate will be described in more detail.Film forming method for forming charges on the surface of a substrate Fig. 1(1) is a particle shape in which particles having a positively charged substance and/or a substance having a negative charge are regularly formed on a surface of a substrate, and particles of titanium oxide and/or cerium oxide as a dielectric or semiconductor are formed. In the aspect of the laminated film, FIG. 1 (2) and FIG. 1 (3) are formed on the surface of the substrate with a substance having a positive charge and/or a substance having a negative charge and titanium oxide as a dielectric or semiconductor and/or Or the aspect of the particulate laminated film obtained by the composite of cerium oxide. The layer thickness of the particulate laminate is not particularly limited, but is preferably in the range of 10 nm to 1 μm, and more preferably in the range of 10 nm to 100 nm. The particulate laminate can be formed, for example, by sputtering, a spray method, ion plating (cathode arc discharge type), CVD coating, or electrodeposition coating. Further, it may be formed by performing at least one of the following steps: immersing the substrate in a solution containing a substance having a positive charge and/or a substance having a negative charge and a solution or suspension of titanium oxide and/or cerium oxide as a dielectric or semiconductor. Alternatively, the emulsion may be subjected to dip coating, or the solution, the suspension or the emulsion may be applied to the substrate by means of a spray, a roller, a bristles, a sponge or the like, followed by drying to volatilize the solvent or the medium. Specifically, the metal-doped amorphous titanium oxide dispersion, the metal-doped cerium oxide dispersion, and the like, which are obtained by combining a metal such as gold, silver, platinum, copper, manganese, nickel, cobalt, or iron, The mixture of the dispersions is applied to a substrate and then dried, and the film formation shown in Fig. 1 can be carried out on the substrate. In the above-mentioned particulate laminate, in order to promote a material containing a positively charged substance or a negatively charged substance in the layer and a solid component of titanium oxide and/or cerium oxide as a dielectric or semiconductor, it is not locally dispersed, and further It is preferred to have various surfactants or dispersants coexist with a substance having a positive charge and/or a substance having a negative charge. The blending amount of the surfactant or the dispersing agent may be 0.001 to 1.0% by weight, preferably 0.1 to 1.0% by weight, based on the total amount of the positively charged substance and/or the negatively charged substance. As the above surfactant or dispersant, various organic ruthenium compounds can be used as the fine powder or fine particle fixing agent for forming a uniform film. As the organic ruthenium compound, various decane compounds and various polyoxoxime oils, polyoxyxylene rubbers, and polyoxyxylene resins can be used, and those having an alkyl phthalate structure or a polyether structure in a molecule or having an alkyl hydrazine are preferable. Both the acid ester structure and the polyether structure.About the intermediate layer and the coating layer An intermediate layer may be provided between the particulate laminate and the substrate, or a coating layer may be provided on the surface of the particulate laminate. As the intermediate layer or the coating layer, for example, various organic or inorganic substances capable of imparting hydrophilicity or hydrophobicity or water repellency or oil repellency to the substrate can be used. Among the organic or inorganic substances usable in the intermediate layer and the coating layer, examples of the hydrophilic organic substance include a polyether, a polyvinyl alcohol, a polyacrylic acid (including an alkali metal salt, an ammonium salt, etc.), and a polymethyl group. Acrylic acid (including alkali metal salt, ammonium salt, etc.), polyacrylic acid-polymethacrylic acid (including alkali metal salt, ammonium salt, etc.) copolymer; polypropylene decylamine; polyvinylpyrrolidone; hydrophilic cellulose Natural hydrophilic polymer compounds such as polysaccharides. It is also possible to use an inorganic dielectric material such as glass fiber, carbon fiber or cerium oxide in the polymer material and to combine them. Further, a coating material may be used as the above polymer material. Among the organic or inorganic substances which can be used for the intermediate layer and the coating layer, examples of the hydrophilic inorganic material include a decane coupling agent and SiO.2 Or other bismuth compounds. Among the organic or inorganic substances which can be used for the intermediate layer and the coating layer, examples of the water-repellent inorganic material include a decane-based, a citrate-based, an anthrone-based and a decane-based compound, or a fluorine-based one. Aqueous or desiccant. In particular, a fluorine-based water repellent agent is used, and examples thereof include a fluorine-containing compound such as a perfluoroalkyl compound or a composition containing a fluorine-containing compound. Furthermore, in the case where the intermediate layer contains a fluorine-containing compound having a high adsorption property to the surface of the substrate, it is not necessary to react the chemical composition of the water-repellent agent or the desiccant of the intermediate layer with the substrate to form a chemical bond, or an intermediate layer. The chemical components with the substrate are crosslinked to each other. The fluorine-containing compound which can be used as such a fluorine-based water repellent is preferably one having a perfluoroalkyl group in the molecule and having a molecular weight of from 1,000 to 20,000, wherein the adsorption property on the surface of the substrate is excellent. Preferably, it is a perfluoroalkyl phosphate and a perfluoroalkyltrimethylammonium salt. Further, in the case of a water-absorptive substrate, it is preferred to form a particle shape of the above-mentioned positively-charged substance and/or negatively-charged substance and titanium oxide and/or cerium oxide as a dielectric or semiconductor on the substrate. An intermediate layer containing a decane compound below the laminate. Since the intermediate layer contains a large amount of Si-O bonds, the strength of the layer obtained by the positively-charged substance and/or the negatively-charged substance and the titanium oxide and/or yttrium oxide as the dielectric or semiconductor can be improved or the substrate is adhered to the substrate. Sex. Further, the intermediate layer also has a function of preventing penetration of moisture into the substrate. Examples of the decane compound include hydrolyzable decane, a hydrolyzate thereof, and a mixture thereof. Further, various organopolyoxanes may be formulated in the decane compounds. Further, as a constituent material of the intermediate layer, a room temperature curing type fluorenone resin such as a methyl ketone resin or a methyl phenyl fluorenone resin may be used. The particulate layered component obtained from the positively charged substance and/or the negatively charged substance and the titanium oxide and/or cerium oxide as the dielectric or semiconductor contains a decane compound or ruthenium in the intermediate layer and the coating layer. In the case of a ketone resin, the mixing ratio (weight ratio) to the decane compound or fluorenone resin is preferably in the range of 1:2 to 1:0.05, more preferably in the range of 1:1 to 1:0.1.About the substrate The material of the substrate to be the object of the present invention is not particularly limited, and various hydrophilic or hydrophobic inorganic substrates and organic substrates may be used, or a combination thereof may be used. Examples of the inorganic base material include a transparent or opaque glass such as soda lime glass, a metal oxide such as zirconia, a base material such as ceramics, concrete, mortar, stone, or metal. Further, examples of the organic base material include a base material containing an organic resin, wood, paper, cloth, or the like. More specifically, examples of the organic resin include polyethylene, polypropylene, polycarbonate, acrylic resin, polyester such as PET, polyamine, polyurethane, ABS resin, polyvinyl chloride, and hydrazine. Ketone, melamine resin, urea resin, fluorenone resin, fluororesin, cellulose, epoxy modified resin, and the like. The shape of the substrate to be the object of the present invention is not particularly limited, and may be any shape such as a cube, a rectangular parallelepiped, a sphere, a sheet, or a fiber. Furthermore, the substrate can be porous. The surface of the substrate can also be rendered hydrophilic by corona discharge treatment or ultraviolet irradiation treatment. The substrate is suitably used for construction, civil engineering substrates or sealing materials, or for equipment, device transport, display screens, and the like. The invention can be utilized in any field requiring various design properties and high waterproof and anti-dyeing properties, and can be preferably used for glass, metal, ceramic, concrete, wood, stone, polymer resin cover, polymer resin sheet, fiber. (clothing, curtains, etc.), sealing materials, etc., or such combinations in building materials, air conditioner outdoor units, kitchen equipment roofs or warehouses, sanitary equipment, lighting fixtures, automobiles, bicycles, motorcycles, airplanes, trains, ships, etc. Articles for indoor and outdoor use or various mechanical, electronic, television, etc. panels. The invention is particularly suitable for building materials, and the buildings, buildings, roads, tunnels and the like constructed by the building materials using the invention of the present invention can exert high waterproof and anti-dyeing effects over time. Furthermore, the present invention can also be applied to an air purifying device (including an air conditioner or the like), a water purifying device (including a water tank, a kettle, etc.), and the device or the light-emitting element used for internal use of the device is exposed to air or water. The prevention of contamination or the reduction of contamination on the surface of the substrate can exert an effect. Further, it is also effective for preventing adhesion of carbonized coke in a pan, a frying pan, a cooking utensil, or the like. [Examples] Hereinafter, examples of the invention will be described, but the invention is not limited by the examples. In the examples of the present invention, the substrates of Examples 1 to 9, Examples 11 to 19, and Examples 20 to 23 were produced using the dispersions described in Reference Examples 1 to 9 below, and were respectively subjected to comparative examples. Evaluation of 1, 2 and 3. - Reference Example 1 A composite dispersion of titanium oxide (dielectric: amorphous titanium peroxide) and a positively charged substance (conductor: Cu) in titanium tetrachloride (manufactured by Osaka Titanium Technology Co., Ltd.) Diluent with 97% CuCl2 ・2H2 In the solution in which O (copper chloride) (manufactured by Nippon Chemical Industry Co., Ltd.) was completely dissolved, ammonia water was added dropwise to prepare a pH of about 7, and the hydroxide was precipitated. The precipitated hydroxide was washed in pure water until the conductivity of the supernatant became 0.9 mS/m or less. Next, hydrogen peroxide was mixed with the hydroxide and reacted for several hours to obtain a copper-modified amorphous titanium peroxide solution. - Reference Example 2 A composite dispersion of titanium oxide (dielectric: amorphous titanium peroxide) and a positively charged substance (conductor: Cu and dielectric: Zr complex) in titanium tetrachloride (Manufactured by Osaka Titanium Technology Co., Ltd.) Diluent and 97% CuCl2 ・2H2 In a solution in which O (copper chloride) (manufactured by Nippon Chemical Industry Co., Ltd.) and zirconium oxychloride are completely dissolved, ammonia water is added dropwise to prepare a pH of about 7, and a hydroxide is precipitated. The precipitated hydroxide was washed in pure water until the conductivity of the supernatant became 0.9 mS/m or less. Next, hydrogen peroxide was mixed with the hydroxide and reacted for several hours to prepare a solution of amorphous titanium peroxide having a modified copper and zirconium. - Reference Example 3 A complex dispersion of cerium oxide (semiconductor: polyphthalate) and a substance having a positive charge (conductor: Cu), methyl decanoate 51 (manufactured by Mitsubishi Chemical Corporation), methyl modification The mixture was mixed with alcohol, pure water and 3% hydrochloric acid, and while stirring, the polyphthalate was produced. Furthermore, the produced polyphthalate was adjusted to a solid concentration of 4 wt% in pure water, and Cu powder and 35% of hydrogen peroxide and ammonia water were stirred and mixed, and a composite dispersion of cerium oxide and copper was produced. - Reference Example 4 A composite dispersion of a titanium oxide (dielectric: amorphous titanium peroxide) and a dielectric (Ce: dielectric) other than titanium oxide (a negative charge based on the combination of the film formation) Diluting titanium tetrachloride (made by Osaka Titanium Technology Co., Ltd.) with CeCl3 ・7H2 In a solution in which O (cerium (III) chloride (manufactured by Sanjin and Chemical Co., Ltd.) was completely dissolved, ammonia water was added dropwise to prepare a pH of about 7, and the hydroxide was precipitated. The precipitated hydroxide was washed in pure water until the conductivity of the supernatant became 0.9 mS/m or less. Next, hydrogen peroxide was mixed with the hydroxide and reacted for several hours to obtain a solution of the amorphous titanium peroxide having a modified cerium. - Reference Example 5 A composite dispersion of titanium oxide (dielectric: amorphous titanium peroxide) and a substance having a negative charge (conductor: a combination of Sn and dielectric: Ce) in titanium tetrachloride (Manufactured by Osaka Titanium Technology Co., Ltd.) Diluent and SnCl2 ・2H2 O (stannous chloride) (manufactured by Kishida Chemical Co., Ltd.) and CeCl3 ・7H2 In a solution in which O (cerium (III) chloride (manufactured by Sanjin and Chemicals Co., Ltd.) is completely dissolved, ammonia water is added dropwise to prepare a pH of about 7, and a hydroxide is precipitated. The precipitated hydroxide was washed in pure water until the conductivity of the supernatant became 0.9 mS/m or less. Next, hydrogen peroxide was mixed with the hydroxide and reacted for several hours to prepare an amorphous titanium peroxide solution in which tin and cerium were modified. - Reference Example 6 A complex dispersion of cerium oxide (semiconductor: polyphthalate) and a substance having a negative charge (conductor: K), methyl decanoate 51 (manufactured by Mitsubishi Chemical Corporation), methyl modification The mixture was mixed with alcohol, pure water and 3% hydrochloric acid, and while stirring, the polyphthalate was produced. Furthermore, the produced polyphthalate was adjusted to a solid concentration of 4 wt% in pure water, and KOH (potassium hydroxide) was mixed to prepare a composite dispersion of cerium oxide and potassium. - Reference Example 7 The dispersion of Reference Example 1 was prepared by mixing the dispersion of Reference Example 1 with the dispersion of Reference Example 4 in a volume ratio of 1:1 (the amorphous liquid doped with copper) The titanium solution) was prepared by mixing the dispersion of Reference Example 4 (a modified amorphous titanium peroxide solution) at a volume ratio of 1:1. - Reference Example 8 The dispersion of Reference Example 2 was prepared by mixing the dispersion of Reference Example 2 with the dispersion of Reference Example 5 in a volume ratio of 1:1. The dispersion of Reference Example 2 (copper and zirconium modified amorphous type) The titanium oxide solution) was prepared by mixing the dispersion liquid of Reference Example 5 (a tin-niobium-modified amorphous titanium peroxide solution) at a volume ratio of 1:1. - Reference Example 9 A dispersion of the composite dispersion of the dispersion liquid of Reference Example 3 and the dispersion liquid of Reference Example 5 in a volume ratio of 1:1 was used as a dispersion of Reference Example 3 (complex dispersion of cerium oxide and copper) The dispersion liquid of Reference Example 5 (amorphous titanium peroxide solution modified with tin and antimony) was mixed at a volume ratio of 1:1. Example 1 Using a spray gun at a surface of 10 g/m on a commercially available ceramic tile (100 mm × 100 mm) substrate surface2 The ratio of the (wet state) was applied to the dispersion of Reference Example 1, and the mixture was heated at 200 ° C for 10 minutes to give Example 1. Examples 2 to 9 In the same manner as in Example 1, the substrates were prepared using the dispersions of Reference Examples 2 to 9 and the obtained substrates were designated as Examples 2 to 9, respectively. Comparative Example 1 A non-film-forming substrate on which a new film was not formed on the surface of a commercially available ceramic tile (100 mm × 100 mm) was used as Comparative Example 1. Evaluation 1 On the surfaces of the bricks of Examples 1 to 9 and Comparative Example 1, coated with 0.007 g/100 cm2 The liquid obtained by diluting a commercially available red ink (manufactured by PILOTINK Co., Ltd.) containing a negatively charged dye was dried at room temperature to prepare an evaluation substrate. Further, a methylene blue reagent solution as a positively charged pigment was applied to the surface of the bricks of Examples 1 to 9 and Comparative Example 1 by the same procedure to prepare an evaluation substrate. For each evaluation substrate fabricated using these negatively charged dyes and positively charged pigments, the amount of ultraviolet light is 1300 μw/cm.2 The position is irradiated with a 15 W black light fluorescent lamp (manufactured by Toshiba Co., Ltd.), and the decoloring rate of each charge surface is evaluated with time using a color meter CR-200 (manufactured by Konica Minolta Co., Ltd.), and according to each implementation For example, the decolorization rate of the substrate was evaluated to evaluate the state of each surface charge. The unit of time for evaluation over time is days. The time-dependent decolorization ratio of each of the evaluation substrates of Examples 1 to 9 and Comparative Example 1 is shown in Table 1 in the case of red ink and Table 2 in the case of methylene blue reagent. [Table 1] [Table 2] <Result 1> ・ In the elapsed time (5.8 days) of Table 1 (negative dye: blush), Examples 4 to 6 having a negatively charged surface characteristic were obtained by the electrostatic repulsion and having a high decolorization rate. Conversely, the lower the decolorization rate is Examples 1 to 3 having positively charged surface characteristics. It is understood that Examples 7 to 9 having a decolorization ratio of a substantially intermediate value of a negatively charged surface and a positively charged surface have an amphoteric charge surface characteristic. Further, the non-film forming of Comparative Example 1 exhibited a negative charge characteristic produced by the surface glaze. - In the elapsed time (5.8 days) of Table 2 (positive pigment: methylene blue), Examples 1 to 3 having positive surface characteristics were found to have a high decolorization rate by electrostatic reversion. Conversely, the lower the decolorization rate is Examples 4 to 6 having negatively charged surface characteristics. It is understood that Examples 7 to 9 having a decolorization ratio of a substantially intermediate value of a negatively charged surface and a positively charged surface have an amphoteric charge surface characteristic. Further, the non-film forming of Comparative Example 1 exhibited the negative charge characteristics produced by the surface glaze of the brick. Examples 11 to 19 on the surface of a common float glass (100 mm × 100 mm thick and 3 mm) substrate, using a spray gun of 10 g/m2 The ratio of (wet state) was applied to the dispersion liquids of Reference Examples 1 to 9 and heated at 200 ° C for 10 minutes to give Examples 11 to 19. Comparative Example 2 A non-film-forming glass substrate which was not newly formed on the ordinary float glass substrate used in Examples 11 to 19 was designated as Comparative Example 2. Evaluation 2 Sand dust adsorption and antifouling evaluations of Examples 11 to 19 and Comparative Example 2 were carried out using three types of dust in the Kanto loam layer, Dubai desert sand dust in the Middle East, and volcanic ash in the Kyushu area. The surface dust of the Kanto loam, the dust of the desert in the Middle East, and the volcanic ash of the Kyushu area were dropped to the surface of the substrates of Examples 11 to 19 and Comparative Example 2, respectively, and used as evaluation substrates, and the evaluation substrates were raised. The gloss was measured by gently rubbing twice on the table and using a gloss meter IG-331 (manufactured by Horiba, Ltd.). Then, the difference in gloss between the substrates of the respective examples and the comparative examples measured before the addition of dust or volcanic ash was determined, thereby evaluating the antifouling against the dust adsorption according to the diffuse reflectance of the light due to the adhesion residual. The results of the evaluation and the evaluation results (average measured at three places) are shown in Table 3 below (value: gloss before powder evaluation - gloss after powder evaluation). [table 3] <Result 2> Table 3 reveals the following results. In the case of using the Kanto loam powder, Examples 11 to 13 which are film-forming substrates of positive charge surface characteristics, and glosses before and after evaluation of Examples 17 to 19 which are films of amphoteric charge surface characteristics were exhibited. The change is low. For the Kanto loam powder, the positive or gender-charged surface has antifouling function. The antifouling function is also the same when using Dubai desert dust powder. In the case of using the volcanic ash powder in the Kyushu region, the changes in gloss before and after the evaluation of Examples 14 to 16 which are film-forming substrates having negative charge surface characteristics were low, and for the volcanic ash powder, the negative-charged surface was stain-resistant. Features. On the other hand, the surface of the non-film-forming blue float glass of Comparative Example 2 showed a glossiness value based on the adhesion of the three kinds of powders. Example 20 On the surface of a common soda lime float glass (100 mm × 100 mm thick 3 mm) substrate, using a sponge extrusion method at 10 g/m2 The ratio of the dispersion of Reference Example 1 was applied and heated at 300 ° C for 10 minutes to prepare Example 20. Example 21 Example 21 was produced by the same production method as in Example 20, using the dispersion liquid of Reference Example 4. Example 22 Example 22 was produced by the same production method as in Example 20, using the dispersion liquid of Reference Example 5. Example 23 Example 23 was produced by the same production method as in Example 20, using the dispersion liquid of Reference Example 7. Comparative Example 3 A non-film-forming person on a common soda lime float glass (100 mm × 100 mm thick 3 mm) substrate was designated as Comparative Example 3. Evaluation 3 On the upper surface of the substrate of Examples 20 to 23 and the substrate of Comparative Example 3, a liquid of a stirred egg liquid and a commercially available olive oil were applied at a width of about 20 mm and a length of about 60 mm at 300 ° C. After heating for 30 minutes, each of the carbonized polymers was fixed to prepare each evaluation substrate, and the method of wiping the surface of each of the evaluation substrates by water-absorbent surface paper and the method of wiping the soft side of the kitchen sponge to wipe the surface of each evaluation substrate were performed. The ease of removal obtained by electrostatic repulsion of the carbides was evaluated. Further, regarding the state of the surface film formed on the substrate of each of the examples, the surface film after the removal of the carbonized polymer was visually evaluated for the presence or absence of scratches. The results are shown in Table 4 below. [Table 4] <Result 3> Table 4 shows the removal performance of the viscous contaminant obtained by electrostatic repelling when the substrate was in a heated environment or use condition. As is apparent from Table 4, in Comparative Example 21 and Example 22, the evaluation of the substrate having a negative charge film before heating was carried out without adsorption of carbonized contaminants, and the removal performance was excellent. On the other hand, in the evaluation substrate of Example 20 in which a positively-charged film was formed before heating and the non-film-formed substrate of Comparative Example 3, it was revealed that the fixed carbonized contaminant could not be removed. Further, in the evaluation substrate of the film having the amphoteric charge film of Example 23, the removal performance of the carbonized contaminant substantially in the middle of Example 20 and Example 21 was exhibited. Further, the state of the surface film of the substrate of each of the examples showed a film which was hard to withstand such an environment or work even if it was not scratched even after the carbonized polymer removal operation. Therefore, it is understood that the antifouling technique by surface charge formation imparts charge to the surface of the substrate regardless of the environment in which the film-forming substrate is used or the conditions of use, regardless of the substance to be used for the object to be treated. The type. Further, it has been shown that by using titanium oxide or cerium oxide as a dielectric and a semiconductor, it is possible to form not only a stable surface charge but also a hard film.

S1‧‧‧基體
S2‧‧‧基體/基板
S3‧‧‧基板
S4‧‧‧基體S1‧‧‧ substrate
S2‧‧‧ base/substrate
S3‧‧‧ substrate
S4‧‧‧ substrate

圖1(1)～(3)係模式性表示本案發明之基體表面電荷形成用粒子狀積層物之造膜剖面之例之圖。 圖2(1)～(3)係模式性表示將本案發明之基體表面電荷形成用粒子狀積層物形成於基體表面層之態樣之剖面之圖。 圖3係表示金屬摻雜氧化鈦之分散液之製作方法之一例之圖。 圖4係表示金屬摻雜氧化矽之分散液之製作方法之一例之圖。 圖5(1)～(3)係模式性表示對基體表面或基體表面層賦予電荷之原理之圖。 圖6(1)～(3)係模式性表示對基體表面或基體表面層賦予電荷之原理之圖。1(1) to (3) are diagrams schematically showing an example of a film formation cross section of a particulate layered product for forming a surface charge of a substrate according to the present invention. 2(1) to (3) are diagrams schematically showing a cross section of a surface layer for forming a surface charge of a substrate according to the present invention in a surface layer of a substrate. Fig. 3 is a view showing an example of a method for producing a metal-doped titanium oxide dispersion. Fig. 4 is a view showing an example of a method of producing a metal-doped cerium oxide dispersion. 5(1) to (3) schematically show the principle of imparting electric charge to the surface of the substrate or the surface layer of the substrate. 6(1) to (3) schematically show the principle of imparting electric charge to the surface of the substrate or the surface layer of the substrate.

無no

Claims (8)

一種基體表面電荷形成用粒子狀積層物，其特徵在於：於基體之表面或基體之表面層，於具有正電荷之物質及/或具有負電荷之物質中，介置作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)。A particle-like laminate for forming a surface charge of a substrate, characterized in that a surface of a substrate or a surface layer of a substrate is interposed as a dielectric or a semiconductor in a substance having a positive charge and/or a substance having a negative charge; Titanium oxide and/or cerium oxide (compound containing titanium oxide and/or cerium oxide). 如請求項1之基體表面電荷形成用粒子狀積層物，其中上述粒子狀積層物係包含具有正電荷之物質及/或具有負電荷之物質之粒子與包含作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)之粒子相鄰地接合而成。The particle-like laminate for forming a surface charge of a substrate according to claim 1, wherein the particulate laminate comprises particles having a positive charge and/or a substance having a negative charge, and titanium oxide containing a dielectric or a semiconductor / or particles of cerium oxide (compound containing titanium oxide and / or cerium oxide) are joined adjacently. 如請求項1之基體表面形成用電荷粒子狀積層物，其中上述粒子狀積層物係接合具有正電荷之物質及/或具有負電荷之物質內包於作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)中而成之膠體粒子而形成。The charge particle-like laminate formed on the surface of the substrate of claim 1, wherein the particulate laminate is bonded to a positively charged substance and/or a negatively charged substance is encapsulated in a titanium oxide and/or a dielectric or a semiconductor. Or a colloidal particle formed by cerium oxide (a compound containing titanium oxide and/or cerium oxide). 如請求項1之基體表面電荷形成用粒子狀積層物，其中上述粒子狀積層物係具有正電荷之物質及/或具有負電荷之物質與作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)以分子等級之複合體之粒子之形式接合而成。The particulate-like laminate for forming a surface charge of a substrate according to claim 1, wherein the particulate-formed layer has a positively charged substance and/or a substance having a negative charge and titanium oxide and/or cerium oxide as a dielectric or semiconductor. (Compound containing titanium oxide and/or cerium oxide) is formed by combining particles of a molecular grade composite. 一種基體表面電荷形成用造膜液，其含有：具有正電荷之物質及/或具有負電荷之物質、及作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)。A film forming liquid for forming a surface charge of a substrate, comprising: a substance having a positive charge and/or a substance having a negative charge, and titanium oxide and/or cerium oxide (including titanium oxide and/or oxidation) as a dielectric or semiconductor矽 compound). 如請求項5之基體表面電荷形成用造膜液，其中上述作為介電體或半導體之氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)與上述具有正電荷之物質及/或具有負電荷之物質之比率以固體成分莫耳比計，於使用氧化鈦(包含氧化鈦化合物)之情形時為1：0.01～1：0.3之比率，於使用氧化矽(包含氧化矽之化合物)之情形時為1：0.03～1：2.7之比率，於使用氧化鈦及氧化矽(包含該等之化合物)之情形時為1：0.01～1：0.3之比率。The film forming liquid for forming a surface charge of a substrate according to claim 5, wherein the titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide) as the dielectric or semiconductor and the positively charged substance and / The ratio of the substance having a negative charge is measured by the ratio of the molar ratio of the solid component to the ratio of 1:0.01 to 1:0.3 in the case of using titanium oxide (including the titanium oxide compound), and the use of cerium oxide (including cerium oxide) In the case of the compound), the ratio is 1:0.03 to 1:2.7, and when titanium oxide and cerium oxide (including the compounds) are used, the ratio is 1:0.01 to 1:0.3. 如請求項1至4中任一項之基體表面電荷形成用粒子狀積層物，其中上述具有正電荷之物質及/或具有負電荷之物質係選自由下述(1)至(6)所組成之群中之至少一種具有正電荷之物質及/或具有負電荷之物質： (1)陽離子 (2)具有正電荷之導電體、具有正電荷之導電體與介電體之複合體、具有正電荷之導電體與半導體之複合體、包含具有正電荷之2種以上之介電體或/及半導體之複合體之任一具有正電荷之導電體或複合體 (3)陰離子 (4)具有負電荷之導電體、具有負電荷之導電體與介電體之複合體、具有負電荷之導電體與半導體之複合體、包含具有負電荷之2種以上之介電體或/及半導體之複合體之任一具有負電荷之導電體或複合體 (5)具有光觸媒功能之物質 (6)氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體。The particulate layered product for forming a surface charge of a substrate according to any one of claims 1 to 4, wherein the substance having a positive charge and/or the substance having a negative charge is selected from the group consisting of (1) to (6) below. At least one of a group having a positive charge and/or a substance having a negative charge: (1) a cation (2) a positively charged conductor, a positively charged conductor and a dielectric composite, having a positive A conductor having a positive charge or a composite (3) anion (4) having a complex of a charge conductor and a semiconductor, or a composite containing two or more dielectrics having a positive charge or/and a semiconductor a conductor of a charge, a composite of a negatively charged conductor and a dielectric, a composite of a negatively charged conductor and a semiconductor, and a composite of two or more dielectrics having a negative charge or/and a semiconductor Any of the negatively charged conductors or composites (5) having a photocatalytic function (6) a dielectric or a semiconductor other than titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide). 如請求項5或6之基體表面電荷形成用造膜液，其中上述具有正電荷之物質及/或具有負電荷之物質係選自由下述(1)至(6)所組成之群中之至少一種具有正電荷之物質及/或具有負電荷之物質： (1)陽離子 (2)具有正電荷之導電體、具有正電荷之導電體與介電體之複合體、具有正電荷之導電體與半導體之複合體、包含具有正電荷之2種以上之介電體或/及半導體之複合體之任一具有正電荷之導電體或複合體 (3)陰離子 (4)具有負電荷之導電體、具有負電荷之導電體與介電體之複合體、具有負電荷之導電體與半導體之複合體、包含具有負電荷之2種以上之介電體或/及半導體之複合體之任一具有負電荷之導電體或複合體 (5)具有光觸媒功能之物質 (6)氧化鈦及/或氧化矽(包含氧化鈦及/或氧化矽之化合物)除外之介電體或半導體。The film-forming liquid for forming a surface charge of a substrate according to claim 5, wherein the substance having a positive charge and/or the substance having a negative charge is at least selected from the group consisting of the following (1) to (6). A substance having a positive charge and/or a substance having a negative charge: (1) a cation (2) a positively charged conductor, a positively charged conductor and a dielectric composite, a positively charged conductor and a semiconductor composite, a conductor having a positive charge or a composite of two or more semiconductors having a positive charge; (3) an anion (4) having a negative charge; Any of a composite of a negatively charged conductor and a dielectric, a composite of a negatively charged conductor and a semiconductor, or a composite of two or more dielectrics having a negative charge or/and a semiconductor The charge conductor or composite (5) has a photocatalytic function (6) a dielectric or a semiconductor other than titanium oxide and/or cerium oxide (a compound containing titanium oxide and/or cerium oxide).
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