JPH05320234A - Plymer-metal composite, production thereof, and solid-surface treatment agent and ultraviolet-intercepting agent the same - Google Patents
Plymer-metal composite, production thereof, and solid-surface treatment agent and ultraviolet-intercepting agent the sameInfo
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- JPH05320234A JPH05320234A JP14986292A JP14986292A JPH05320234A JP H05320234 A JPH05320234 A JP H05320234A JP 14986292 A JP14986292 A JP 14986292A JP 14986292 A JP14986292 A JP 14986292A JP H05320234 A JPH05320234 A JP H05320234A
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- Prior art keywords
- polymer
- metal
- carboxyl group
- metal composite
- solid
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高分子−金属複合体及
びその製造方法、並びにそれを用いた固体表面処理剤及
び紫外線遮蔽剤に係わり、特にカルボキシル基を含有す
る高分子と金属アルコキシドとを複合化した高分子−金
属複合体及びその製造方法、また、複合体中の未反応の
アルコキシド残基と、固体表面上の水酸基との反応を利
用して該複合体を固体表面にコ−テイングすることを特
徴とする固体表面処理剤、及び紫外線遮蔽効果を有する
高分子−金属複合体、または複合体を表面にコーティン
グした紫外線遮蔽剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer-metal composite, a method for producing the same, a solid surface treating agent and an ultraviolet shielding agent using the same, and particularly to a polymer containing a carboxyl group and a metal alkoxide. The polymer-metal composite and the method for producing the same, and the reaction of the unreacted alkoxide residue in the composite with the hydroxyl group on the solid surface is used to coat the composite on the solid surface. The present invention relates to a solid surface-treating agent characterized by being coated with a polymer, a polymer-metal composite having an ultraviolet shielding effect, or an ultraviolet shielding agent having the surface coated with the composite.
【０００２】[0002]
【従来の技術】高分子と金属イオンとの複合体は、接着
性および力学的特性などの物理化学的特性に優れ、各種
包装材料やスポーツ用品等の塗布剤としてに幅広い用途
がある。2. Description of the Related Art A composite of a polymer and a metal ion has excellent physicochemical properties such as adhesiveness and mechanical properties, and has a wide range of applications as a coating material for various packaging materials and sports equipment.
【０００３】また、無機粉体は一般に、表面が親水性で
あり、水に濡れやすく、非水溶媒中での分散性に劣ると
いう欠点があるが、その分散性の改善および表面活性の
抑制という観点から、種々の表面改質法が提案され、粉
体表面に機能性基を導入し、新しい機能を有する改質粉
体が数多く生産されている。Inorganic powders generally have a hydrophilic surface, are easily wetted by water, and have poor dispersibility in a non-aqueous solvent. However, the dispersibility is improved and the surface activity is suppressed. From the viewpoint, various surface modification methods have been proposed, and many modified powders having a new function have been produced by introducing a functional group into the powder surface.
【０００４】しかしながら、これまでに知られているナ
トリウム、亜鉛、鉄などを含有する高分子−金属複合体
は、各種溶媒に対して溶解度が低く、低温・液相で塗布
等の表面処理を行うのは困難である。たとえこれらの複
合体を液相で表面処理したとしても得られる表面皮膜に
は透明性がなく、また接着性が弱いため実用に供するこ
とができない。従って、表面処理には複合体を加熱溶融
して処理する方法をとらざるを得ないが現状である。However, the heretofore known polymer-metal composites containing sodium, zinc, iron and the like have low solubility in various solvents and are subjected to surface treatment such as coating at low temperature and liquid phase. Is difficult. Even if these composites are surface-treated in the liquid phase, the surface coating obtained has no transparency and weak adhesiveness and cannot be put to practical use. Therefore, for the surface treatment, there is no choice but to adopt the method of heating and melting the composite to treat it.
【０００５】また、従来の複合体を用いた粉体の表面改
質にあたっては、同様の理由で粉末状態のまま直接添加
し撹伴混合、あるいは焼成などの方法によってのみ、表
面処理を行うことができる。Further, in the surface modification of the powder using the conventional composite, for the same reason, the surface treatment is carried out only by a method such as directly adding the powder in a powder state, stirring and mixing, or firing. it can.
【０００６】しかし、これらの方法では、例えば有機顔
料や無機顔料を含有させる場合、黄色酸化鉄、紺青のよ
うに熱に弱いものは処理することができない。例えば、
有機顔料の赤色２０２号は８０℃で脱水し、結晶系がα
型からβ型へ変化するとともに色調が変化してしまう。
また、紺青は熱を加えると分解し、１５０℃以上でシア
ンガスを徐々に放出する。However, with these methods, when an organic pigment or an inorganic pigment is contained, for example, yellow iron oxide and dark blue, which are weak to heat, cannot be treated. For example,
Organic pigment red No. 202 was dehydrated at 80 ° C, and the crystal system was α.
The color tone changes as the type changes from β to β.
In addition, dark blue decomposes when heat is applied and gradually releases cyan gas at 150 ° C or higher.
【０００７】一般に、焼き付け処理は、処理温度の高い
ものでは３５０℃で２時間程度、低いものでは１５０℃
で１５〜４０時間程度で行なわれる。このような条件下
では、上記したように紺青は色調変化が起こるのみなら
ず、有毒なシアンガスを放出し、はなはだ危険である。Generally, the baking process is carried out at 350 ° C. for about 2 hours at a high processing temperature and 150 ° C. at a low processing temperature.
It takes about 15 to 40 hours. Under such conditions, as described above, dark blue not only causes a change in color tone, but also emits toxic cyan gas, which is extremely dangerous.
【０００８】一方、地上に照射される太陽光には、中紫
外線（２８０〜３２０ｎｍ；ＵＶ−Ｂ）と近紫外線（３
２５〜４００ｎｍ；ＵＶ−Ａ）とが含まれている。これ
らの紫外線は、種々の化学物質の変質、変色などの原因
となる。また、生体に対しても、たとえば、中紫外線
は、皮膚の紅斑水泡等の炎症を引き起こし、近紫外線
は、メラニン生成を促して皮膚の褐色化を生じさせるこ
とが知られている。On the other hand, the sunlight radiated on the ground includes medium ultraviolet rays (280 to 320 nm; UV-B) and near ultraviolet rays (3
25-400 nm; UV-A). These ultraviolet rays cause alteration and discoloration of various chemical substances. It is also known that, for example, medium ultraviolet rays cause inflammation such as erythema vesicles on the skin and near ultraviolet rays promote melanin production to cause browning of the skin.
【０００９】そこで、このような紫外線の化学物質およ
び生体（皮膚）ヘの悪影響に対処するため、従来より紫
外線遮蔽剤を配合した塗料、フィルターおよび日焼け止
め化粧品が知られている。Therefore, in order to cope with such adverse effects of ultraviolet rays on chemical substances and living bodies (skin), paints, filters and sunscreen cosmetics containing an ultraviolet ray shielding agent have been conventionally known.
【００１０】このような用途に用いられる紫外線遮蔽剤
としては、大別すると、ジベンゾイルメタン系、桂皮酸
系、ベンゾフェノン系などの紫外線吸収剤と、酸化亜
鉛、酸化チタンなどの紫外線散乱剤との２種類に分類さ
れる。The ultraviolet shielding agents used for such applications are roughly classified into dibenzoylmethane-based, cinnamic acid-based, and benzophenone-based ultraviolet absorbers and zinc oxide, titanium oxide and other ultraviolet scattering agents. There are two types.
【００１１】しかし、これらの紫外線遮蔽剤は，ＵＶ−
Ａ及びＵＶ−Ｂの紫外線に対する吸収能が不十分であっ
たり、またベンゾフェノン系のように衣類を着色させる
という問題もある。更に、散乱型のものは、粒子の凝集
が起こりまたは使用感が悪化するため、配合できる剤型
が限定されているのが現状である。However, these UV screening agents are
There are problems that A and UV-B have insufficient ability to absorb ultraviolet rays, and that clothes are colored like benzophenone. Further, in the scattering type, aggregation of particles occurs or the feeling of use deteriorates, so that the formulation type that can be blended is currently limited.
【００１２】[0012]
【発明が解決しようとする課題】かかる現状に鑑み、本
発明者は、低温での表面処理等を可能とするべく種々の
溶媒に溶解し、被処理体との付着力が強くまたは／及び
処理後も透明性を有する高分子−金属複合体を提供する
ことを目的とする。In view of the present situation, the present inventor has solved the problem by dissolving in various solvents to enable surface treatment at a low temperature and having a strong adhesion to the object to be treated and / or treatment. It is an object of the present invention to provide a polymer-metal composite that is still transparent.
【００１３】本発明の第２の目的は、上記複合体の製造
方法を提供することを目的とする。更に本発明は固体を
高分子−金属複合体で被覆し、固体に種々の機能をもた
せることが可能な固体表面処理剤を提供することを目的
とする。更に加えて、種々の剤型の化粧料・薬剤等に適
用でき、紫外線遮蔽効果の高い紫外線遮蔽剤を提供する
ことを目的とする。A second object of the present invention is to provide a method for producing the above composite. A further object of the present invention is to provide a solid surface treating agent capable of coating a solid with a polymer-metal composite to give the solid various functions. In addition, it is an object of the present invention to provide an ultraviolet shielding agent which can be applied to various types of cosmetics, medicines and the like and has a high ultraviolet shielding effect.
【００１４】[0014]
【課題を解決するための手段】上記の目的は、カルボキ
シル基を有する高分子と多価金属のアルコキシドにより
形成される高分子−金属複合体及びそれを用いた表面改
質法によって達成することができる。The above objects can be achieved by a polymer-metal composite formed by a polymer having a carboxyl group and a polyvalent metal alkoxide and a surface modification method using the same. it can.
【００１５】即ち、本発明の第１の要旨は、カルボキシ
ル基を有する高分子と、多価金属とからなる高分子−金
属複合体であって、イオン結合により前記多価金属と前
記高分子のカルボキシル基とが結合していることを特徴
とする高分子−金属複合体に存在する。That is, the first gist of the present invention is a polymer-metal composite comprising a polymer having a carboxyl group and a polyvalent metal, wherein the polyvalent metal and the polymer are formed by an ionic bond. It exists in a polymer-metal composite characterized in that it is bound to a carboxyl group.
【００１６】本発明の第２の要旨は、カルボキシル基を
有する高分子と多価金属のアルコキシドを非水溶媒中、
８０℃以下で混合攪拌して高分子−金属複合体を形成す
ることを特徴とする高分子−金属複合体の製造方法に存
在する。The second aspect of the present invention is to provide a polymer having a carboxyl group and a polyvalent metal alkoxide in a non-aqueous solvent,
It exists in a method for producing a polymer-metal composite, which is characterized by forming a polymer-metal composite by mixing and stirring at 80 ° C or lower.
【００１７】第３の要旨は、カルボキシル基を有する高
分子と多価金属のアルコキシドとを未反応のアルコキシ
基が残る割合で混合した混合物であって、該混合物を表
面に水酸基を有する固体と接触させ、該粉体の水酸基と
前記未反応のアルコキシ基とを反応させることにより、
固体の表面に高分子−金属複合体を形成することを特徴
とする固体表面処理方法に存在する。A third aspect is a mixture in which a polymer having a carboxyl group and a polyvalent metal alkoxide are mixed in such a proportion that an unreacted alkoxy group remains, and the mixture is brought into contact with a solid having a hydroxyl group on the surface. By reacting the hydroxyl group of the powder with the unreacted alkoxy group,
It exists in a solid surface treatment method characterized by forming a polymer-metal complex on the surface of a solid.
【００１８】また、第４の要旨は、上記高分子−金属複
合体を用いることを特徴とする紫外線遮蔽剤に存在す
る。The fourth gist resides in an ultraviolet shielding agent characterized by using the polymer-metal composite.
【００１９】[0019]
【作用】本発明の高分子−金属複合体は、カルボキシル
基を有する高分子と多価金属のアルコキシドを非水溶媒
中で反応させることにより得られ、金属との錯形成後
は、種々の溶媒に対して高い溶解性を示し、透明な粘稠
溶液となる。また、この透明性は乾燥後も維持される。
したがって、液相で種々の物質を表面改質することが可
能となり、従来の含イオン高分子にない優れた加工性を
有する。The polymer-metal complex of the present invention is obtained by reacting a polymer having a carboxyl group with an alkoxide of a polyvalent metal in a non-aqueous solvent, and after forming a complex with a metal, various solvents are used. It has a high solubility in A. and becomes a transparent viscous solution. Also, this transparency is maintained after drying.
Therefore, it becomes possible to modify the surface of various substances in the liquid phase, and it has excellent workability that conventional ionic polymers do not have.
【００２０】また、固体の表面改質においても、通常の
金属アルコキシドの加水分解反応は、室温もしくは８０
℃以下で反応を進行させることができるため、熱的に不
安定な化合物も含有させることができる。しかも本発明
の高分子−金属複合体は、付着性に優れた膜となる。Also, in the surface modification of solids, the usual hydrolysis reaction of metal alkoxide is carried out at room temperature or 80
Since the reaction can proceed at a temperature of not higher than 0 ° C, a thermally unstable compound can be contained. Moreover, the polymer-metal composite of the present invention forms a film having excellent adhesiveness.
【００２１】更に、機能性分子をカルボキシル基を介し
て多価金属に固定化することにより、機能性分子特有の
機能を複合体にもたせることができる。Furthermore, by immobilizing the functional molecule on the polyvalent metal via the carboxyl group, the complex can have a function peculiar to the functional molecule.
【００２２】以下に本発明の構成を詳細に説明する。The structure of the present invention will be described in detail below.
【００２３】本発明で用いられるカルボキシル基を含有
する高分子は、カルボキシル基を有する共重合体である
限り特に限定されるものではなく、ポリマー主鎖に直結
もしくはアルキレン基もしくはアルキレンオキシ基など
のスペーサーを介してカルボキシル基が結合されている
か、もしくはぺンダント基にカルボキシル基を有してい
るか、またはポリマー鎖末端にカルボキシル基を有して
いるものをいう。具体的には、アクリル酸、メタクリル
酸、クロトン酸、マレイン酸、イタコン酸等とその他の
ビニルモノマーとの共重合体、あるいは末端にカルボキ
シル基を有する各種高分子が用いられ、特に側鎖にスペ
ーサーを介してカルボキシル基を含有するビニルポリマ
ーもしくは変性ポリシロキサンが好ましい。カルボキシ
ル基を有するビニルポリマー及び変性シロキサンの構造
の一例をそれぞれ（Ｉ）、（ＩＩ）式に示す。The carboxyl group-containing polymer used in the present invention is not particularly limited as long as it is a copolymer having a carboxyl group, and it is directly linked to the polymer main chain or a spacer such as an alkylene group or an alkyleneoxy group. A carboxyl group is bound to the pendent group, a carboxyl group is contained in the pendent group, or a carboxyl group is contained in the polymer chain terminal. Specifically, copolymers of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and the like with other vinyl monomers, or various polymers having a carboxyl group at the terminal are used, and spacers are particularly used in the side chains. Vinyl polymers or modified polysiloxanes containing carboxyl groups via are preferred. Examples of the structures of the vinyl polymer having a carboxyl group and the modified siloxane are shown in formulas (I) and (II), respectively.
【００２４】 [0024]
【００２５】高分子中のカルボキシル基含量は、特に限
定されるものではないが、カルボキシル基を有する単量
体のモル比として３０％以下が望ましい。３０％を越え
るとイオンによる架橋率が高くなり、各種溶媒に対する
溶解度が低下する。The content of the carboxyl group in the polymer is not particularly limited, but the molar ratio of the monomer having a carboxyl group is preferably 30% or less. If it exceeds 30%, the cross-linking ratio due to ions increases and the solubility in various solvents decreases.
【００２６】本発明に用いられる多価金属アルコキシド
は、特に限定されるものではなく、例えばチタン、鉄、
アルミニウム、ジルコニウム、亜鉛等の多価金属と、例
えばエタノール、イソプロパノール等のアルコールとの
反応により得られる多価金属アルコキシドが用いられ、
特にチタンのイソプロポキシドが好ましい。The polyvalent metal alkoxide used in the present invention is not particularly limited, and examples thereof include titanium, iron,
A polyvalent metal alkoxide obtained by reacting a polyvalent metal such as aluminum, zirconium or zinc with an alcohol such as ethanol or isopropanol is used.
Particularly, titanium isopropoxide is preferable.
【００２７】本発明の固体表面処理剤が対象とする固体
は、常温で固体でありさえすれば、寸法、形状及び材質
は問わない。従って、寸法としては、０．０２μｍ程度
の超微粉体からｍｍのオ−ダ−の粉体、そしてｃｍない
しｍのオ−ダ−又はそれ以上の物体が含まれる。また、
形状としては、粉末状、繊維状、シ−ト状、塊状等が含
まれる。また、１種以上の材料の凝集体、成形体もしく
は造形体、または複合体等も含まれる。更に、材質も任
意である。例えば、無機材料［例えば、金属及びその誘
導体（例えば無機酸化物）、粘土鉱物、セラミック、コ
ンクリ−ト、ガラス］、及び有機材料［生体物質（例え
ば木材、セルロ−ス等の生体高分子あるいは生体低分子
等）、合成物質、有機顔料）等］が含まれる。The solid targeted by the solid surface treating agent of the present invention may be of any size, shape and material as long as it is a solid at room temperature. Therefore, the size includes ultra fine powder of about 0.02 μm to powder of the order of mm, and objects of the order of cm to m or more. Also,
The shape includes powder, fiber, sheet, lump and the like. In addition, an aggregate, a molded body or a molded body of one or more materials, a composite body, and the like are also included. Further, the material is also arbitrary. For example, inorganic materials [for example, metals and their derivatives (for example, inorganic oxides), clay minerals, ceramics, concrete, glass], and organic materials [biomaterials (for example, biopolymers or biomaterials such as wood and cellulose) Low molecular weight compounds), synthetic substances, organic pigments), etc.] are included.
【００２８】前記金属酸化物としては、例えばベリリウ
ム、マグネシウム、アルミニウム、珪素、カルシウム、
バナジウム、バリウム、チタン、クロム、マンガン、
鉄、コバルト、二ツケル、銅亜鉛、ガリウム、インジウ
ム、タリウム、ジルコニウムなど金属及び合金の酸化物
があげられ、これらのうちで、透明性にすぐれた微粒子
シリカ、あるいは微粒子酸化亜鉛が特に好適に適用され
る。また、酸化チタンや酸化亜鉛のように、元来ＵＶ−
Ａ領域に散乱効果を有する酸化物である必要はない。Examples of the metal oxide include beryllium, magnesium, aluminum, silicon, calcium,
Vanadium, barium, titanium, chromium, manganese,
Examples thereof include oxides of metals and alloys such as iron, cobalt, nickel, copper zinc, gallium, indium, thallium, and zirconium. Among these, fine particle silica having excellent transparency or fine particle zinc oxide is particularly preferably applied. To be done. Also, like titanium oxide and zinc oxide, UV-
It does not have to be an oxide having a scattering effect in the A region.
【００２９】また、本発明の固体表明処理剤は、例えば
流体透過材（例えば、モノリス担体または多孔質体）に
適用される。この流体透過材は、例えば、セラミックス
（活性アルミナ、コ−ディエライト等）、メタル（アル
ミニウム合金、鉄、ステンレススチ−ル等）、生体高分
子（セルロ−ス、キチン等）、カ−ボンまたはガラスか
らなる。前記流体透過材は、通常０．０１〜１０００μ
ｍ、好ましくは０．０１〜３００μｍ、更に好ましくは
０．０１〜１０μｍの口径の多数の透過口を備えたもの
であり、形状は一般にシ−ト状、円筒状または板状であ
る。The solid surface treatment agent of the present invention is applied to, for example, a fluid permeable material (for example, a monolith carrier or a porous body). This fluid permeable material is, for example, ceramics (activated alumina, cordierite, etc.), metal (aluminum alloy, iron, stainless steel, etc.), biopolymer (cellulosic, chitin, etc.), carbon or It consists of glass. The fluid permeable material is usually 0.01 to 1000 μm.
m, preferably 0.01 to 300 μm, more preferably 0.01 to 10 μm, and has a large number of permeation ports, and the shape is generally a sheet shape, a cylindrical shape or a plate shape.
【００３０】次に、本発明の複合体の製造方法について
詳述する。まず、カルボキシル基を有する共重合体、お
よび多価金属アルコキシドの溶液を調製する。多価金属
アルコキシドは、水の存在下で容易に加水分解するの
で、本発明の高分子−金属アルコキシド複合体の調製に
はべンゼン、トルエン、キシレン、クロロホルム等の非
水溶媒を用いるのが好ましい。用いる溶媒は特に限定さ
れるものではなく、原料の高分子をよく溶解し、しかも
水を含まないものであればよい。次に、共重合体溶液
に、多価金属アルコキシド溶液を攪拌しながら滴下して
均―な混合物を製造する。これによつてカルボキシル基
と多価金属アルコキシドとの反応により、（ＣＯＯ-）n
Ｍn+なるイオン結合による架橋構造が生じる。このよう
な架橋構造を形成した場合でも、本発明の高分子−金属
複合体溶液は、粘度の増大を伴うが透明性は失われず、
固体の析出等は認められない。更に、溶媒を蒸発させた
後も本発明の高分子−金属複合体は透明性を維持する。Next, the method for producing the composite of the present invention will be described in detail. First, a solution of a copolymer having a carboxyl group and a polyvalent metal alkoxide is prepared. Since the polyvalent metal alkoxide is easily hydrolyzed in the presence of water, it is preferable to use a non-aqueous solvent such as benzene, toluene, xylene and chloroform for the preparation of the polymer-metal alkoxide complex of the present invention. .. The solvent used is not particularly limited as long as it can dissolve the raw material polymer well and does not contain water. Next, the polyvalent metal alkoxide solution is added dropwise to the copolymer solution with stirring to produce a uniform mixture. As a result, the reaction of the carboxyl group with the polyvalent metal alkoxide results in (COO − ) n
A crosslinked structure due to an ionic bond of M n + is generated. Even when such a cross-linked structure is formed, the polymer-metal composite solution of the present invention is accompanied by an increase in viscosity but does not lose transparency,
No solid precipitation is observed. Furthermore, the polymer-metal composite of the present invention maintains transparency even after the solvent is evaporated.
【００３１】次に、本発明の機能性高分子を固定した高
分子−金属複合体の製造方法を、多価金属アルコキシド
としてチタンテトライソプロポキシド、機能性分子とし
て紫外線吸収剤である桂皮酸を用いた場合について説明
する。Next, the method for producing a polymer-metal composite having a functional polymer immobilized thereon according to the present invention is carried out by using titanium tetraisopropoxide as a polyvalent metal alkoxide and cinnamic acid as an ultraviolet absorber as a functional molecule. The case of use will be described.
【００３２】まず、桂皮酸のクロロホルム溶液に、チタ
ンテトライソプロポキシドのクロロホルム溶液を加え、
桂皮酸―チタンイオン複合体を調製する。ここに、桂皮
酸とチタンテトライソプロポキシドとのモル比は、３／
１以下とすることが好ましい。First, a chloroform solution of titanium tetraisopropoxide was added to a chloroform solution of cinnamic acid,
A cinnamic acid-titanium ion complex is prepared. Here, the molar ratio of cinnamic acid and titanium tetraisopropoxide is 3 /
It is preferably 1 or less.
【００３３】一方、カルボキシル基を有する高分子のク
ロロホルム溶液を調製し、この溶液中に、桂皮酸−チタ
ンイオン複合体のクロロホルム溶液を、激しく撹伴しな
がら７ 滴下する。滴下開始とともに、系は粘稠となり
複合体の生成が認められる。生じた粘稠溶液をシャーレ
上に流延して自然乾燥することにより、透明な高分子膜
が得られる。さらに溶媒を完全に除去するためにはこの
状態で真空乾燥することが望ましい。On the other hand, a chloroform solution of a polymer having a carboxyl group is prepared, and a chloroform solution of a cinnamic acid-titanium ion complex is added dropwise to this solution 7 with vigorous stirring. The system becomes viscous as the dropping is started, and formation of a complex is observed. A transparent polymer film is obtained by casting the resulting viscous solution on a petri dish and naturally drying. Further, in order to completely remove the solvent, vacuum drying in this state is desirable.
【００３４】このようにして調製した高分子−チタン−
桂皮酸複合体は、透明皮膜であり、放置してもチタンイ
オンのない系で見られるような桂皮酸の析出はなく、透
明性は長時間安定に維持される。Polymer thus prepared--titanium--
The cinnamic acid complex is a transparent film, and even if it is left to stand, there is no precipitation of cinnamic acid as seen in a system without titanium ions, and the transparency is maintained stable for a long time.
【００３５】高分子―金属複合体に固定化される機能性
分子は、カルボキシル基を有するものであれば、特に限
定されるものではなく、例えば紫外線吸収剤としての種
々の桂皮酸誘導体、サリチル酸誘導体、防腐剤としての
安息香酸誘導体、カルボキシル基を有するアミノ酸、ペ
プチド等の各種薬剤等があげられる。The functional molecule immobilized on the polymer-metal complex is not particularly limited as long as it has a carboxyl group. For example, various cinnamic acid derivatives and salicylic acid derivatives as ultraviolet absorbers. Examples include various agents such as benzoic acid derivatives as preservatives, amino acids having a carboxyl group, and peptides.
【００３６】また、高分子中のカルボキシル基含量に対
し過剰の金属アルコキシドを加えた場合には、アルコキ
シド残基が一部イオン結合を形成せずに残存するため、
カツプリング剤として使用することができ、そのアルコ
キシド残基と固体表面上の水酸基との反応を利用するこ
とにより、高分子による固体の表面改質が可能となる。When an excess amount of metal alkoxide is added to the content of carboxyl group in the polymer, some alkoxide residues remain without forming an ionic bond.
It can be used as a coupling agent, and by utilizing the reaction between the alkoxide residue and the hydroxyl group on the solid surface, it becomes possible to modify the surface of the solid with a polymer.
【００３７】例えば、本発明の高分子−金属複合体によ
る粉体の表面処理は、以下の手順をもって行なわれる。For example, the surface treatment of powder with the polymer-metal composite of the present invention is carried out by the following procedure.
【００３８】まず、高分子−金属複合体を、多価金属ア
ルコキシドのアルコキシ基の一部が未反応で残るよう
に、カルボキシル基を有する高分子とカルボキシル基を
有する機能性分子と多価金属アルコキシドとを調製す
る。該複合体の溶液を粉体を分散した液に滴下し、滴下
終了後も室温で１６時間程度攪拌する。撹伴終了後ろ過
及び／またはエバポレーションにより、固体を回収し溶
媒で洗浄する。さらに５０℃で一昼夜真空乾燥すること
により改質粉体を得ることができる。First, a polymer-metal complex is prepared by polymerizing a polymer having a carboxyl group, a functional molecule having a carboxyl group and a polyvalent metal alkoxide so that a part of the alkoxy groups of the polyvalent metal alkoxide remains unreacted. And prepare. The solution of the composite is added dropwise to the liquid in which the powder is dispersed, and after completion of the addition, the mixture is stirred for about 16 hours at room temperature. After completion of stirring, the solid is recovered by filtration and / or evaporation and washed with a solvent. Further, the modified powder can be obtained by vacuum drying at 50 ° C. for one day.
【００３９】[0039]
【実施例】以下に実施例をあげて本発明を具体的に説明
するが、本発明はこれによつて限定されるものではな
い。The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
【００４０】（実施例１）本発明の高分子−金属複合体
を以下の手順で作製した。Example 1 A polymer-metal composite of the present invention was prepared by the following procedure.
【００４１】カルボキシル基１．３モル％を含有するカ
ルボキシ変性シリコ−ン（分子量２０００）の１０％ト
ルエン溶液中に、チタンテトライソプロポキシド０．２
５モル当量を含む卜ルエン溶液を撹枠しながら滴下す
る。滴下後室温で１６時間攪拌を続けた。得られた粘稠
溶液を石英基板上にキャストし、乾燥して複合体の皮膜
を作製した（試料１）。0.2% of titanium tetraisopropoxide was added to a 10% toluene solution of a carboxy-modified silicone (molecular weight 2000) containing 1.3 mol% of carboxyl groups.
A ruthenium solution containing 5 molar equivalents is added dropwise with stirring. After the dropping, stirring was continued at room temperature for 16 hours. The viscous solution thus obtained was cast on a quartz substrate and dried to form a composite film (Sample 1).
【００４２】また、機能性分子（桂皮酸）を固定した複
合体を次のようにして作製した。A complex having a functional molecule (cinnamic acid) fixed thereon was prepared as follows.
【００４３】前記カルボキシ変性シリコ−ンの１０％ト
ルエン溶液に、チタンテトライソプロポキシド０．５モ
ル当量、桂皮酸０．５モル当量を含むトルエン溶液を撹
粋しながら滴下した。得られた粘稠な液体を試料１と同
様にして皮膜を作製した（試料２）。A toluene solution containing 0.5 molar equivalent of titanium tetraisopropoxide and 0.5 molar equivalent of cinnamic acid was added dropwise to a 10% toluene solution of the carboxy-modified silicone while stirring. A film was formed from the obtained viscous liquid in the same manner as in Sample 1 (Sample 2).
【００４４】また、比較のためカルボキシ変性シリコー
ンだけの皮膜（比較試料１）及びチタンテトライソプロ
ポキシドと桂皮酸からなる皮膜（比較試料２）も同様に
して作製した。For comparison, a film containing only carboxy-modified silicone (Comparative Sample 1) and a film containing titanium tetraisopropoxide and cinnamic acid (Comparative Sample 2) were prepared in the same manner.
【００４５】試料１，２及び比較試料１は、透明な皮膜
となったが、高分子を含まない比較試料２は白く濁り、
均一な膜は得られなかった。The samples 1 and 2 and the comparative sample 1 were transparent films, but the comparative sample 2 containing no polymer was turbid in white.
No uniform film was obtained.
【００４６】試料１，２及び比較試料１の紫外可視吸収
スペクトルを図１に示す。図から明らかなように、カル
ボキシ変性シリコ−ン及びチタンイソテトラプロポキシ
ドだけでは紫外領域に吸収はみられないが、両者の複合
体である試料１のスペクトルには３６０ｎｍに吸収端を
持つバンドが現れることが分かる。即ち、高分子と金属
を複合化することにより得られる複合体が、紫外線吸収
能を持ち紫外線遮蔽剤に適用できることが分かった。The UV-visible absorption spectra of Samples 1 and 2 and Comparative Sample 1 are shown in FIG. As is clear from the figure, absorption is not observed in the ultraviolet region only with carboxy-modified silicone and titanium isotetrapropoxide, but the spectrum of Sample 1 which is a complex of both shows a band having an absorption edge at 360 nm. You can see it appear. That is, it was found that a composite obtained by combining a polymer and a metal has an ultraviolet absorbing ability and can be applied to an ultraviolet shielding agent.
【００４７】更に、紫外線吸収剤である桂皮酸を固定し
た試料２のスペクトルの吸収端は４１０ｎｍにシフト
し、桂皮酸の紫外線吸収効果が観察された。言い換えれ
ば、試料２の複合体には、桂皮酸が固定化されているこ
とを示している。Further, the absorption edge of the spectrum of the sample 2 to which cinnamic acid as an ultraviolet absorber was fixed was shifted to 410 nm, and the ultraviolet absorption effect of cinnamic acid was observed. In other words, it is shown that the cinnamic acid is immobilized in the complex of Sample 2.
【００４８】本実施例では、機能性分子として紫外線吸
収効果を有する桂皮酸を用いたが、紫外線吸収効果を有
する分子に限らず、カルボキシル基を有する分子でさえ
あれば複合化して複合体に固定化することが可能であ
り、その分子特有の種々の機能を持たせた透明な複合体
を作製することができる。In this example, cinnamic acid having an ultraviolet absorbing effect was used as the functional molecule, but it is not limited to a molecule having an ultraviolet absorbing effect, and any molecule having a carboxyl group can be complexed and fixed to the complex. It is possible to produce a transparent complex having various functions peculiar to the molecule.
【００４９】（実施例２）カルボキシ基１．３モル％を
含有するカルボキシ変性シリコ−ン（分子量２０００）
の１０％クロロホルム溶液中に、等モルのチタンテトラ
イソプロポキシドを含むクロロホルム溶液を攪拌しなが
ら滴下することにより、透明で粘稠な液体を得た。本溶
液を、シリカＯＸ−５０（日本アエロジル社製）のクロ
ロホルム分散液中に加え、１６時間室温（２５℃）で攪
拌した。反応終了後、固体を吸引ろ過して溶媒から分離
し、５０℃で真空乾燥して、改質粉体を得た。(Example 2) Carboxy modified silicone containing 1.3 mol% of carboxy group (molecular weight 2000)
A chloroform solution containing equimolar amount of titanium tetraisopropoxide was added dropwise to the 10% chloroform solution of 1. under stirring to obtain a transparent viscous liquid. This solution was added to a chloroform dispersion of silica OX-50 (manufactured by Nippon Aerosil Co., Ltd.) and stirred at room temperature (25 ° C.) for 16 hours. After the reaction was completed, the solid was suction-filtered to separate it from the solvent, and vacuum dried at 50 ° C. to obtain a modified powder.
【００５０】得られた粉体及び未処理の粉体をクロロホ
ルム中、２５℃で３時間放置したところ、未処理の粉体
は、即座に凝集・沈降し始めたのに対し、本実施例の粉
体は３時間後でも凝集せず、安定な分散状態を示した。When the obtained powder and the untreated powder were left to stand in chloroform at 25 ° C. for 3 hours, the untreated powder immediately began to aggregate / precipitate. The powder did not aggregate even after 3 hours and showed a stable dispersion state.
【００５１】[0051]
【発明の効果】請求項１の発明により、被処理体との付
着力が強く、表面処理後も透明性を有し、被処理体の外
観を損なわない表面処理剤・塗布剤等を提供することが
可能となる。According to the first aspect of the present invention, there is provided a surface treatment agent / coating agent, etc., which has a strong adhesive force with the object to be treated, is transparent even after the surface treatment, and does not impair the appearance of the object to be treated. It becomes possible.
【００５２】また請求項２の発明により、機能性分子特
有の機能を複合体にもたせることができ、種々の機能を
有する薬剤・化粧料を製造することが可能となる。更
に、液相で処理可能なため、熱的に不安定な物質等も含
有させることも可能となり、紫外線吸収剤、防腐剤、美
白剤等のより広範囲な応用が可能となる。According to the second aspect of the present invention, the complex can be provided with the function peculiar to the functional molecule, and it becomes possible to manufacture a drug or cosmetic having various functions. Further, since it can be treated in the liquid phase, it is possible to contain a thermally unstable substance, etc., and it is possible to apply to a wider range of ultraviolet absorbers, preservatives, whitening agents and the like.
【００５３】請求項５及び６の発明により、高分子−金
属複合体の製造方法を提供することが可能となる。The inventions of claims 5 and 6 make it possible to provide a method for producing a polymer-metal composite.
【００５４】更に請求項７及び８の本発明により、固体
を高分子−金属複合体で被覆し、固体に種々の機能をも
たせることが可能な固体処理剤を提供することが可能と
なる。Furthermore, according to the present invention of claims 7 and 8, it is possible to provide a solid processing agent capable of coating a solid with a polymer-metal composite to give the solid various functions.
【図１】本発明の複合体の紫外可視吸収スペクトル。FIG. 1 is an ultraviolet-visible absorption spectrum of the complex of the present invention.
Claims (9)
属とからなる高分子−金属複合体であって、イオン結合
により前記多価金属と前記高分子のカルボキシル基とが
結合していることを特徴とする高分子−金属複合体。1. A polymer-metal composite comprising a polymer having a carboxyl group and a polyvalent metal, wherein the polyvalent metal and the carboxyl group of the polymer are bound by an ionic bond. A characteristic polymer-metal composite.
該機能性分子のカルボキシル基と前記多価金属とのイオ
ン結合により前記多価金属に固定化されていることを特
徴とする請求項１記載の高分子−金属複合体。2. A functional molecule having a carboxyl group,
The polymer-metal composite according to claim 1, wherein the polymer-metal complex is immobilized on the polyvalent metal by an ionic bond between the carboxyl group of the functional molecule and the polyvalent metal.
はＵＶ−Ｂの紫外光を吸収する機能性分子であることを
特徴とする請求項２記載の高分子−金属複合体。3. The polymer-metal composite according to claim 2, wherein the functional molecule is a functional molecule that absorbs UV light of UV-A and / or UV-B.
とカルボキシル基を有する第２の単量体とからなる共重
合体であり，該共重合体中の前記第２の単量体のモル比
は３０％以下であることを特徴とする請求項１乃至３の
いずれか１項に記載の高分子−金属複合体。4. The polymer is a copolymer comprising at least a first monomer and a second monomer having a carboxyl group, and the second monomer in the copolymer. The polymer-metal composite according to any one of claims 1 to 3, wherein the molar ratio is 30% or less.
属のアルコキシドを非水溶媒中において、８０℃以下で
混合攪拌して高分子−金属複合体を形成することを特徴
とする請求項１記載の高分子−金属複合体の製造方法。5. The polymer-metal complex is formed by mixing and stirring a polymer having a carboxyl group and an alkoxide of a polyvalent metal at 80 ° C. or less in a non-aqueous solvent. 1. A method for producing a polymer-metal composite.
き、（カルボキシル基を有する機能性分子）／（前記多
価金属のアルコキシド）のモル比が（ｎ−１）以下の範
囲で、前記カルボキシル基を有する機能性分子を加える
ことを特徴とする請求項５記載の高分子−金属複合体の
製造方法。6. When the ionic valence of the polyvalent metal is n, the molar ratio of (functional molecule having a carboxyl group) / (alkoxide of the polyvalent metal) is (n-1) or less. The method for producing a polymer-metal composite according to claim 5, wherein the functional molecule having the carboxyl group is added.
属のアルコキシドとを未反応のアルコキシ基が残る割合
で混合した混合物であって、該混合物を表面に水酸基を
有する固体と接触させ、該固体表面の水酸基と前記未反
応のアルコキシ基とを反応させることにより、固体の表
面に高分子−金属複合体を形成することを特徴とする固
体表面処理剤。7. A mixture in which a polymer having a carboxyl group and a polyvalent metal alkoxide are mixed in such a proportion that an unreacted alkoxy group remains, and the mixture is brought into contact with a solid having a hydroxyl group on the surface thereof. A solid surface treating agent characterized by forming a polymer-metal complex on the surface of a solid by reacting a hydroxyl group on the surface with the unreacted alkoxy group.
残る割合で、カルボキシル基を有する機能性高分子で加
えたことを特徴とする高分子−金属複合体による請求項
７記載の固体表面処理剤。8. The solid surface treatment according to claim 7, wherein the polymer-metal composite is characterized in that a functional polymer having a carboxyl group is added to the mixture in a proportion that an unreacted alkoxy group remains. Agent.
高分子−金属複合体を用いたことを特徴とする紫外線遮
蔽剤。9. An ultraviolet shielding agent comprising the polymer-metal composite according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14986292A JP3199332B2 (en) | 1992-05-18 | 1992-05-18 | Polymer-metal composite, method for producing the same, solid surface treatment agent and ultraviolet shielding agent using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14986292A JP3199332B2 (en) | 1992-05-18 | 1992-05-18 | Polymer-metal composite, method for producing the same, solid surface treatment agent and ultraviolet shielding agent using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320234A true JPH05320234A (en) | 1993-12-03 |
| JP3199332B2 JP3199332B2 (en) | 2001-08-20 |
Family
ID=15484281
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14986292A Expired - Lifetime JP3199332B2 (en) | 1992-05-18 | 1992-05-18 | Polymer-metal composite, method for producing the same, solid surface treatment agent and ultraviolet shielding agent using the same |
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| Country | Link |
|---|---|
| JP (1) | JP3199332B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009022621A1 (en) * | 2007-08-10 | 2009-02-19 | Shiseido Company Ltd. | Surface treatment agent, surface-treated powder and cosmetic preparation |
| WO2009085894A1 (en) * | 2007-12-21 | 2009-07-09 | Dow Corning Corporation | Ionomeric silicone thermoplastic elastomers |
| KR20210041869A (en) * | 2019-10-08 | 2021-04-16 | 주식회사 윤도건설 | Bondability improving agent for rapid hardening repair and reinforcement mortar, Rapid hardening repair and reinforcement mortar using the same and Method of repair and reinforcement of concrete structure using the same |
-
1992
- 1992-05-18 JP JP14986292A patent/JP3199332B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009022621A1 (en) * | 2007-08-10 | 2009-02-19 | Shiseido Company Ltd. | Surface treatment agent, surface-treated powder and cosmetic preparation |
| JP5564256B2 (en) * | 2007-08-10 | 2014-07-30 | 株式会社 資生堂 | Surface treatment agent for powder, surface treatment powder and cosmetics |
| WO2009085894A1 (en) * | 2007-12-21 | 2009-07-09 | Dow Corning Corporation | Ionomeric silicone thermoplastic elastomers |
| JP2011508021A (en) * | 2007-12-21 | 2011-03-10 | ダウ・コーニング・コーポレイション | Ionomer silicone thermoplastic elastomer |
| US8329156B2 (en) | 2007-12-21 | 2012-12-11 | Dow Corning Corporation | Ionomeric silicone thermoplastic elastomers |
| US8808680B2 (en) | 2007-12-21 | 2014-08-19 | Dow Corning Corporation | Ionomeric silicone thermoplastic elastomers |
| KR20210041869A (en) * | 2019-10-08 | 2021-04-16 | 주식회사 윤도건설 | Bondability improving agent for rapid hardening repair and reinforcement mortar, Rapid hardening repair and reinforcement mortar using the same and Method of repair and reinforcement of concrete structure using the same |
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