JP2002173611A - Surface-modified inorganic particle and coating composition containing the same - Google Patents
Surface-modified inorganic particle and coating composition containing the sameInfo
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- JP2002173611A JP2002173611A JP2000369669A JP2000369669A JP2002173611A JP 2002173611 A JP2002173611 A JP 2002173611A JP 2000369669 A JP2000369669 A JP 2000369669A JP 2000369669 A JP2000369669 A JP 2000369669A JP 2002173611 A JP2002173611 A JP 2002173611A
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- inorganic particles
- calcium carbonate
- modified inorganic
- modified
- weight
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面改質無機粒子
及び該表面改質無機粒子を含有してなる塗料組成物に関
し、更に詳しくは、特に、塗料に色別れ防止、レベリン
グ性、スリップ性、ブロッキング防止性、消泡性等を、
特に、色別れ防止を付与する表面改質無機粒子並びにそ
れを含有してなる塗料組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-modified inorganic particle and a coating composition containing the surface-modified inorganic particle, and more particularly, to prevention of color separation, leveling property and slip property of the coating. , Anti-blocking properties, defoaming properties, etc.
In particular, the present invention relates to surface-modified inorganic particles that provide color separation prevention and a coating composition containing the same.
【０００２】[0002]
【従来の技術及び本発明が解決しようとする課題】従
来、塗料にレベリング性、スリップ性、ブロッキング防
止性、色別れ防止性、消泡性などを付与する目的で有機
珪素化合物からなる塗料添加剤が広く使用されてきた
が、それらは塗料製造時に添加される為に、塗料中にて
体質顔料、着色顔料等の無機粒子を造粒させ、凝集を引
き起こす原因にもなっている。2. Description of the Related Art Conventionally, a coating additive comprising an organosilicon compound has been used for the purpose of imparting leveling properties, slip properties, anti-blocking properties, anti-separation properties, defoaming properties, etc. to coating materials. Although they have been widely used, they are added at the time of the production of paints, so that they cause inorganic particles such as extender pigments and color pigments to be granulated in the paint and cause agglomeration.
【０００３】また、従来より塗料やゴム成形材料、プラ
スチック成形材料等において、増量、軽量、補強、着
色、隠蔽性、防錆性、磁性、難燃性等を目的として各種
脂肪酸、樹脂酸、界面活性剤、高分子分散剤等による無
機粒子の表面改質効果が提案されている。しかし乍ら、
その効果は不十分であり、例えば、塗膜面のザラツキや
光沢の低下、耐水性や耐候性の低下、レベリング性、ス
リップ性、ブロッキング性、色別れ防止性、消泡性など
を改善するには不十分であるという問題点が残されてい
る。[0003] Conventionally, in paints, rubber molding materials, plastic molding materials and the like, various fatty acids, resin acids, interface, etc. have been used for the purpose of increasing the weight, reducing the weight, reinforcing, coloring, concealing, rust-preventing, magnetizing, flame-retarding and the like. The effect of modifying the surface of inorganic particles with an activator, a polymer dispersant or the like has been proposed. However,
The effect is insufficient, for example, to improve the roughness and gloss of the coating film surface, water and weather resistance, leveling, slip, blocking, color separation prevention, defoaming, etc. Is still insufficient.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、上記従来
技術の問題点に鑑み、鋭意研究の結果、有機珪素化合物
を無機粒子に担持させることにより、無機粒子を効果的
に塗料製造時に塗料系内に混合することが出来、同時に
無機粒子自身の溶剤や塗料樹脂との濡れや親和性を向上
させ、その結果、レベリング性、スリップ性、ブロッキ
ング防止性、色別れ防止性、消泡性等を、とりわけ、色
別れ防止性を飛躍的に向上させることができることを見
いだし、本発明を完成するに至った。Means for Solving the Problems In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive studies and found that by supporting an organic silicon compound on inorganic particles, the inorganic particles can be effectively produced at the time of coating production. Can be mixed into the paint system, and at the same time improve the wettability and affinity of the inorganic particles with the solvent and paint resin, resulting in leveling, slip, anti-blocking, anti-separation, defoaming In particular, the present inventors have found that it is possible to dramatically improve the color separation prevention, and have completed the present invention.
【０００５】即ち、本発明の第１（請求項１）は、無機
粒子に有機珪素化合物を担持させたことを特徴とする表
面改質無機粒子を内容とする。[0005] That is, a first aspect of the present invention (claim 1) includes surface-modified inorganic particles characterized in that an organic silicon compound is supported on inorganic particles.
【０００６】本発明の第２（請求項２）は、無機粒子を
有機物で表面処理し、更に、該有機物の表面に有機珪素
化合物を担持させたことを特徴とする表面改質無機粒子
を内容とする。A second aspect (claim 2) of the present invention is to provide a surface-modified inorganic particle characterized in that the surface of the inorganic particle is treated with an organic substance and an organic silicon compound is supported on the surface of the organic substance. And
【０００７】好ましい態様として請求項３は、有機珪素
化合物が下記一般式で示されるシリコーンオイルまたは
変性シリコーンオイルからなる請求項１または２記載の
表面改質無機粒子である。[0007] In a preferred embodiment, claim 3 is the surface-modified inorganic particles according to claim 1 or 2, wherein the organosilicon compound comprises a silicone oil or a modified silicone oil represented by the following general formula.
【０００８】[0008]
【化２】 Embedded image
【０００９】［式中、Ｒ1 は炭素数１〜２０の１価の炭
化水素基、Ｒ2 は炭素数１〜２０の１価の炭化水素基、
−Ｃ6 Ｈ5 、−（ＣＨ2 ）a ＮＨ2 、−（ＣＨ2 ）a Ｓ
Ｈ2 、−（ＣＨ2 ）a ＣＯＯＨ、−（ＣＨ2 ）a −（Ｎ
ＨＣＨ2 ＣＨ2 ）b ＮＨＲ4 （式中、Ｒ4 は水素原子ま
たは炭素数１〜２０の１価の炭化水素基、ａは０〜１０
の整数、ｂは０〜１０の整数）、Ｒ3 はＲ1 、Ｒ2 、水
酸基または炭素数１〜２０のアルコキシ基、−ＣＨ＝Ｃ
ＨＣＨ3 、ｍは０〜３０００の整数、ｎは０〜３０００
の整数、ｍ＋ｎは１〜３０００の整数］Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
-C 6 H 5, - (CH 2) a NH 2, - (CH 2) a S
H 2, - (CH 2) a COOH, - (CH 2) a - (N
HCH 2 CH 2 ) b NHR 4 (wherein R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a is 0 to 10)
, B is an integer of 0 to 10), R 3 is R 1 , R 2 , a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, —CH ＝ C
HCH 3 , m is an integer of 0 to 3000, n is 0 to 3000
And m + n is an integer of 1 to 3000]
【００１０】好ましい態様として請求項４は、有機珪素
化合物の平均分子量Ｍｗが、１００〜１，０００，００
０である請求項１〜３のいずれか１項に記載の表面改質
無機粒子である。In a preferred embodiment, the average molecular weight Mw of the organosilicon compound is from 100 to 1,000,000.
The surface-modified inorganic particles according to any one of claims 1 to 3, which is 0.
【００１１】好ましい態様として請求項５は、有機珪素
化合物の量が、無機粒子に対して０．００１〜３０重量
% である請求項１〜４のいずれか１項に記載の表面改質
無機粒子である。In a preferred embodiment, the amount of the organosilicon compound is 0.001 to 30% by weight with respect to the inorganic particles.
%. The surface-modified inorganic particles according to any one of claims 1 to 4, wherein
【００１２】好ましい態様として請求項６は、有機物
が、アニオン性、カチオン性、ノニオン性等の界面活性
剤、エステル、脂肪酸、樹脂酸から選ばれる少なくとも
１種である請求項１〜５のいずれか１項に記載の表面改
質無機粒子である。In a preferred embodiment, the organic material is at least one selected from anionic, cationic and nonionic surfactants, esters, fatty acids and resin acids. 2. Surface-modified inorganic particles according to item 1.
【００１３】好ましい態様として請求項７は、有機物の
量が、無機粒子に対して０．０１〜３０重量% である請
求項１〜６のいずれか１項に記載の表面改質無機粒子で
ある。In a preferred embodiment, the surface-modified inorganic particles according to any one of claims 1 to 6, wherein the amount of the organic substance is 0.01 to 30% by weight based on the weight of the inorganic particles. .
【００１４】好ましい態様として請求項８は、無機粒子
が、炭酸カルシウム、タルク、クレー、二酸化チタン、
硫酸バリウム、シリカ、水酸化マグネシウムから選ばれ
る少なくとも１種である請求項１〜７のいずれか１項に
記載の表面改質無機粒子である。In a preferred embodiment, the inorganic particles are calcium carbonate, talc, clay, titanium dioxide,
The surface-modified inorganic particles according to any one of claims 1 to 7, which are at least one selected from barium sulfate, silica, and magnesium hydroxide.
【００１５】好ましい態様として請求項９は、無機粒子
が炭酸カルシウムからなる請求項１〜８のいずれか１項
に記載の表面改質無機粒子である。In a preferred aspect, the present invention provides the surface-modified inorganic particles according to any one of claims 1 to 8, wherein the inorganic particles are made of calcium carbonate.
【００１６】好ましい態様として請求項１０は、炭酸カ
ルシウムが合成炭酸カルシウムからなる請求項８または
９記載の表面改質無機粒子である。In a preferred embodiment, the surface-modified inorganic particles according to claim 8 or 9, wherein the calcium carbonate is composed of synthetic calcium carbonate.
【００１７】好ましい態様として請求項１１は、炭酸カ
ルシウムが、合成炭酸カルシウムと重質炭酸カルシウム
の混合物である請求項８〜１０のいずれか１項に記載の
表面改質無機粒子である。In a preferred embodiment, the surface-modified inorganic particles according to any one of claims 8 to 10, wherein the calcium carbonate is a mixture of synthetic calcium carbonate and heavy calcium carbonate.
【００１８】好ましい態様として請求項１２は、合成炭
酸カルシウムと重質炭酸カルシウムの混合物の混合比が
１：９９〜９９：１である請求項１１記載の表面改質無
機粒子である。In a preferred embodiment, the surface-modified inorganic particles according to claim 11, wherein the mixing ratio of the mixture of synthetic calcium carbonate and heavy calcium carbonate is 1:99 to 99: 1.
【００１９】好ましい態様として請求項１３は、合成炭
酸カルシウムが、平均一次粒子径が１０μm 以下の粒子
径を有する合成炭酸カルシウムである請求項１０〜１２
のいずれか１項に記載の表面改質無機粒子である。In a preferred embodiment, the synthetic calcium carbonate is a synthetic calcium carbonate having an average primary particle diameter of 10 μm or less.
The surface-modified inorganic particles according to any one of the above.
【００２０】本発明の第３（請求項１４）は、請求項１
〜１３のいずれか１項に記載の表面改質無機粒子を含有
してなることを特徴とする塗料組成物である。A third aspect (claim 14) of the present invention is claim 1.
A coating composition comprising the surface-modified inorganic particles according to any one of Items 1 to 13.
【００２１】好ましい態様として請求項１５は、表面改
質無機粒子の含有量が樹脂固形分１００重量部に対して
５〜１５０重量部である請求項１４記載の塗料組成物で
ある。In a preferred embodiment, the coating composition according to the present invention is characterized in that the content of the surface-modified inorganic particles is 5 to 150 parts by weight based on 100 parts by weight of the solid content of the resin.
【００２２】[0022]
【発明の実施の形態】有機珪素化合物は、溶剤の対流現
象、顔料の分散性、あるいは塗膜の表面張力、レベリン
グ性、流動性等に起因している、塗料の色別れ（Floodi
ng）、浮き（Floating）、ゆず肌（Orangepeel）、へこ
み（Crater）等の塗膜欠陥の防止に微量添加することに
より効果がある。しかし、従来の添加方法では塗料製造
時に直接添加されているため、使用する樹脂とのなじみ
が悪く、塗料系内全体に均一に分散混合されない場合が
あった。また、その分散性を改善するために、有機溶媒
である程度希釈してから使用することも考えられるが、
環境問題より有機溶媒の使用量を少なくする昨今の動向
に逆行するものである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Organosilicon compounds are used for the color separation of paint (Floodi) due to the convection phenomenon of a solvent, the dispersibility of a pigment, or the surface tension, leveling property, fluidity, etc. of a coating film.
(ng), floating (Floating), orange peel, orange (Crater), and the like. However, in the conventional addition method, since it is directly added at the time of the production of the paint, the compatibility with the resin to be used is poor, and the dispersion may not be uniformly dispersed and mixed throughout the paint system. In order to improve the dispersibility, it is also conceivable to use it after diluting it to some extent with an organic solvent,
This goes against the recent trend of reducing the amount of organic solvents used due to environmental issues.
【００２３】そこで、本発明者等は塗料に配合される種
種の無機粒子に該有機珪素化合物を担持させることによ
り、過剰な有機溶媒を使用せずに塗料中へ均一に分散さ
せることが出来ることを見いだした。また、本発明の有
機珪素化合物は無機粒子と塗料のビヒクルとの濡れを向
上させ、無機粒子がビヒクル中にて沈降しにくくなって
塗料の保存安定性が向上し、沈降しにくいことから、造
膜時のレベリング性を向上させるとともに、顕著な色別
れ防止機能を発揮することを見いだした。Therefore, the present inventors have found that by supporting the organic silicon compound on various kinds of inorganic particles blended in the paint, the organic silicon compound can be uniformly dispersed in the paint without using an excessive organic solvent. Was found. Further, the organosilicon compound of the present invention improves the wetting of the inorganic particles with the vehicle of the paint, and the inorganic particles hardly settle in the vehicle, thereby improving the storage stability of the paint and hardly settle. It has been found that while improving the leveling property at the time of film formation, a remarkable color separation prevention function is exhibited.
【００２４】本発明に用いられる有機珪素化合物は特に
制限されないが、塗膜の耐擦傷性、耐色落ち性、塗料の
色別れ防止性、浮き防止性、ゆず肌防止性、レベリング
性の向上等の特性を充分に発揮させる点で下記一般式で
示されるシリコーンオイル、変性シリコーンオイルが好
ましい。The organosilicon compound used in the present invention is not particularly limited, but the scratch resistance, discoloration resistance, anti-segregation property of paint, anti-floating property, anti-yuzu skin property, leveling property, etc. of the coating film are improved. The silicone oils and modified silicone oils represented by the following general formulas are preferred from the viewpoint of sufficiently exhibiting the above properties.
【００２５】[0025]
【化３】 Embedded image
【００２６】［式中、Ｒ1 は炭素数１〜２０の１価の炭
化水素基、Ｒ2 は炭素数１〜２０の１価の炭化水素基、
−Ｃ6 Ｈ5 、−（ＣＨ2 ）a ＮＨ2 、−（ＣＨ2 ）a Ｓ
Ｈ2 、−（ＣＨ2 ）a ＣＯＯＨ、−（ＣＨ2 ）a −（Ｎ
ＨＣＨ2 ＣＨ2 ）b ＮＨＲ4 （式中、Ｒ4 は水素原子ま
たは炭素数１〜２０の１価の炭化水素基、ａは０〜１０
の整数、ｂは０〜１０の整数）、Ｒ3 はＲ1 、Ｒ2 、水
酸基または炭素数１〜２０のアルコキシ基、−ＣＨ＝Ｃ
ＨＣＨ3 、ｍは０〜３０００の整数、ｎは０〜３０００
の整数、ｍ＋ｎは１〜３０００の整数］Wherein R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
-C 6 H 5, - (CH 2) a NH 2, - (CH 2) a S
H 2, - (CH 2) a COOH, - (CH 2) a - (N
HCH 2 CH 2 ) b NHR 4 (wherein R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a is 0 to 10)
, B is an integer of 0 to 10), R 3 is R 1 , R 2 , a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, —CH ＝ C
HCH 3 , m is an integer of 0 to 3000, n is 0 to 3000
And m + n is an integer of 1 to 3000]
【００２７】更に好ましくは、上記一般式で示される有
機珪素化合物において、塗料樹脂との結合性を向上さ
せ、溶剤の対流現象、顔料の分散性、あるいは塗膜の表
面張力、レベリング性、流動性等を改善できる点で、式
中Ｒ2 が、−Ｃ6 Ｈ5 、−（ＣＨ2 ）a ＮＨ2 、−（Ｃ
Ｈ2 ）a ＳＨ2 、−（ＣＨ2 ）a ＣＯＯＨ、−（Ｃ
Ｈ2）a −（ＮＨＣＨ2 ＣＨ2 ）b ＮＨＲ4 （式中、Ｒ
4 は水素原子または炭素数１〜２０の１価の炭化水素
基、ａは０〜１０の整数、ｂは０〜１０の整数）、Ｒ3
はＲ1 、Ｒ2 、水酸基または炭素数１〜２０のアルコキ
シ基、−ＣＨ＝ＣＨＣＨ 3 、ｍは０〜３０００の整数、
ｎは０〜３０００の整数、ｍ＋ｎは１〜３０００の整数
の整数である変成シリコーンオイルが好ましい。これら
は、塗料ビヒクルと無機粒子との界面の接着性を増大さ
せるだけでなく、塗料樹脂と化学的に結合することによ
り上記した効果を持続させるばかりでなく、特に、色別
れ防止性及び耐色落ち性を顕著に向上させる効果も併せ
持つので好ましい。More preferably, the compound represented by the above general formula is used.
Silicone compound improves bonding with paint resin
Solvent, convection of the solvent, dispersibility of the pigment, or
In terms of improving surface tension, leveling properties, fluidity, etc., the formula
Middle RTwoIs -C6HFive,-(CHTwo)aNHTwo,-(C
HTwo)aSHTwo,-(CHTwo)aCOOH,-(C
HTwo)a-(NHCHTwoCHTwo)bNHRFour(Where R
FourIs a hydrogen atom or a monovalent hydrocarbon having 1 to 20 carbon atoms
Group, a is an integer of 0 to 10, b is an integer of 0 to 10), RThree
Is R1, RTwo, Hydroxyl or alkoxy having 1 to 20 carbon atoms
Si group, -CH = CHCH Three, M is an integer from 0 to 3000,
n is an integer of 0 to 3000, m + n is an integer of 1 to 3000
Modified silicone oil which is an integer of is preferred. these
Increases the adhesion of the interface between the paint vehicle and the inorganic particles
In addition to chemical bonding with paint resin.
Not only maintain the above effects, but also
It also has the effect of remarkably improving the anti-shearing property and colorfastness.
It is preferable to have.
【００２８】変性シリコーンオイルとして、特に代表的
なものを例示すれば下記のとおりである。 （ａ）水酸基を有するシリコーンとしては、両末端に水
酸基を有するものとして、Ｘ−２２−１６０−ＡＳ、Ｘ
−２２−１６０Ａ、Ｘ−２２−１６０Ｂ、Ｘ−２２−１
６０Ｃ［信越シリコーン株式会社製商品名］、また、片
末端に水酸基を有するものとして、Ｘ−２２−１７０Ｄ
［信越シリコーン株式会社製商品名］、更に、側鎖に水
酸基を有するものとして、ＳＨ３７４６、ＳＦ８４２
８、ＳＨ３７７１、ＢＹ１６−０３６、ＢＹ１６−０２
７、ＢＹ１６−０３８［東レダウコーニング・シリコー
ン株式会社製商品名］等が挙げられる。Particularly typical modified silicone oils are as follows. (A) As a silicone having a hydroxyl group, X-22-160-AS, X
22-160A, X-22-160B, X-22-1
60C [trade name, manufactured by Shin-Etsu Silicone Co., Ltd.] and X-22-170D as having a hydroxyl group at one end.
[Trade name of Shin-Etsu Silicone Co., Ltd.] Further, SH3746, SF842
8, SH3771, BY16-036, BY16-02
7, BY16-038 [trade name of Dow Corning Toray Silicone Co., Ltd.] and the like.
【００２９】（ｂ）アミノ基を有するシリコーンオイル
としては、両末端にアミノ基を有するものとして、Ｘ−
２２−１６１ＡＳ、Ｘ−２２−１６１Ａ、Ｘ−２２−１
６１Ｂ、Ｘ−２２−１６１Ｃ［信越シリコーン株式会社
製商品名］、また、片末端にアミノ基を有するものとし
て、Ｘ−２２−１７１Ｄ［信越シリコーン株式会社製商
品名］、更に、側鎖にアミノ基を有するものとして、Ｂ
Ｙ１６−８２８、ＢＹ１６−８５０，ＢＹ１６−８４１
７、ＢＹ１６−８４９、ＢＹ−１６−８７２［東レダウ
コーニング・シリコーン株式会社製商品名］などが挙げ
られる。(B) As the silicone oil having an amino group, a silicone oil having an amino group at both ends may be selected from X-
22-161AS, X-22-161A, X-22-1
61B, X-22-161C (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.). Further, as one having an amino group at one end, X-22-171D (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.). Having a group, B
Y16-828, BY16-850, BY16-841
7, BY16-849, BY-16-872 [trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.], and the like.
【００３０】（ｃ）グリシジル基を有するシリコーンオ
イルとしては、両末端にグリシジル基を有するものとし
ては、、Ｘ−２２−１６３ＡＳ、Ｘ−２２−１６３Ａ、
Ｘ−２２−１６３Ｂ、Ｘ−２２−１６３Ｃ［信越シリコ
ーン株式会社製商品名］、また、片末端にグリシジル基
を有するものとして、Ｘ−２２−１７３Ｄ［信越シリコ
ーン株式会社製商品名］、更に側鎖にグリシジル基を有
するものとして、ＳＦ８４１３、ＳＦ８４１１［東レダ
ウコーニング・シリコーン株式会社製商品名］等が挙げ
られる。(C) As the silicone oil having a glycidyl group, those having a glycidyl group at both terminals include X-22-163AS, X-22-163A,
X-22-163B and X-22-163C (trade names manufactured by Shin-Etsu Silicone Co., Ltd.), and those having a glycidyl group at one end, X-22-173D (trade names manufactured by Shin-Etsu Silicone Co., Ltd.) Examples of those having a glycidyl group in the chain include SF8413 and SF8411 (trade names of Dow Corning Toray Silicone Co., Ltd.).
【００３１】（ｄ）ビニル基を有するシリコーンオイル
としては、両末端にビニル基を有するものとして、Ｘ−
２２−１６４ＡＳ、Ｘ−２２−１６４Ａ、Ｘ−２２−１
６４Ｂ、Ｘ−２２−１６７Ｃ［信越シリコーン株式会社
製商品名］、また、片末端にビニル基を有するものとし
て、Ｘ−２２−１７４Ｄ［信越シリコーン株式会社製商
品名］等が挙げられる。(D) As the silicone oil having a vinyl group, a silicone oil having a vinyl group at both ends may be X-
22-164AS, X-22-164A, X-22-1
64B, X-22-167C (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.), and those having a vinyl group at one end include X-22-174D (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.).
【００３２】（ｅ）チオール基を有するシリコーンオイ
ルとしては、両末端にチオール基を有するものとして、
Ｘ−２２−１６７ＡＳ、Ｘ−２２−１６７Ａ、Ｘ−２２
−１６７Ｂ、Ｘ−２２−１６７Ｃ［信越シリコーン株式
会社製商品名］、また、片末端にチオール基を有するも
のとして、Ｘ−２２−１７７Ｄ［信越シリコーン株式会
社製商品名］等が挙げられる。(E) As the silicone oil having a thiol group, those having a thiol group at both terminals can be used.
X-22-167AS, X-22-167A, X-22
X-167B and X-22-167C (trade names manufactured by Shin-Etsu Silicone Co., Ltd.), and those having a thiol group at one end include X-22-177D (trade names manufactured by Shin-Etsu Silicone Co., Ltd.).
【００３３】上記シリコーンオイル並びに変性シリコー
ンオイルは、単独で、または２種以上組み合わせて用い
られる。The above silicone oils and modified silicone oils are used alone or in combination of two or more.
【００３４】有機珪素化合物はの分子量は、好ましくは
数平均分子量が１００〜１，０００，０００、より好ま
しくは３００〜５００，０００、更に好ましくは５００
〜３００，０００である。数平均分子量が１００未満で
は、その期待する効果が得にくい場合があり、１，００
０，０００を越えると粘性が高くなり、無機粒子に効率
よく担持させることが出来ず、逆に無機粒子の分散性を
阻害する場合がある。The organic silicon compound has a number average molecular weight of preferably 100 to 1,000,000, more preferably 300 to 500,000, and still more preferably 500.
３００300,000. If the number average molecular weight is less than 100, the expected effect may be hardly obtained.
If it exceeds 000, the viscosity becomes too high to be efficiently carried on the inorganic particles, and on the contrary, the dispersibility of the inorganic particles may be hindered.
【００３５】無機粒子に有機珪素化合物を担持させる量
としては、無機粒子に対して０．００１〜３０重量% の
割合で用いることが好ましく、より好ましくは０．０５
〜２０重量% である。有機珪素化合物が０．００１重量
% 未満では担持させる効果が期待できず、一方、３０重
量% を越えると無機粒子自体の分散性を逆に阻害したり
する場合がある。The amount of the organic silicon compound supported on the inorganic particles is preferably 0.001 to 30% by weight based on the inorganic particles, more preferably 0.05 to 30% by weight.
-20% by weight. 0.001 weight of organic silicon compound
When the amount is less than 30% by weight, the effect of supporting the inorganic particles cannot be expected. On the other hand, when the amount exceeds 30% by weight, the dispersibility of the inorganic particles themselves may be hindered.
【００３６】また、無機粒子に有機珪素化合物を担持さ
せる量としては、担持させる無機粒子の吸油量の８０%
以下が好ましく、より好ましくは７０％以下、更に好ま
しくは５０％以下である。８０% を越えると無機粒子が
有機珪素化合物によりペースト状態に近くなり、ハンド
リングが困難になる傾向がある。The amount of the organosilicon compound supported on the inorganic particles is 80% of the oil absorption of the inorganic particles supported.
The following is preferable, More preferably, it is 70% or less, More preferably, it is 50% or less. If it exceeds 80%, the inorganic particles become close to a paste state due to the organosilicon compound, and handling tends to be difficult.
【００３７】本発明に用いられる無機粒子は、通常塗料
に使用される物なら特に限定されないが、体質顔料とし
ては、例えば、タルク、カオリン、クレー、セリサイ
ト、白雲母、金雲母、紅雲母、合成雲母、バーミキュラ
イト、炭酸マグネシウム、炭酸カルシウム、珪藻土、珪
酸マグネシウム、珪酸カルシウム、珪酸アルミニウム、
シリカ、ヒドロキシアパタイト、ゼオライト、窒化ホウ
素、硫酸バリウム、アルミナ等が挙げられる。The inorganic particles used in the present invention are not particularly limited as long as they are usually used in paints. Examples of extender pigments include talc, kaolin, clay, sericite, muscovite, phlogopite, phlogopite, Synthetic mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate,
Examples include silica, hydroxyapatite, zeolite, boron nitride, barium sulfate, and alumina.
【００３８】複合顔料としては、例えば、酸化チタン−
酸化鉄、酸化チタン−シリカ、セリサイト−酸化チタ
ン、シリカ−酸化セリウム、シリカ−酸化亜鉛、マイカ
−水酸化アルミニウム、マイカ−酸化チタン−シリカ、
マイカ−酸化鉄−シリカ、酸化チタン−酸化鉄−シリ
カ、硫酸バリウム−酸化チタン、硫酸バリウム−酸化亜
鉛、マイカ−硫酸バリウム−酸化チタン、マイカ−硫酸
バリウム−酸化亜鉛等が挙げられる。As the composite pigment, for example, titanium oxide
Iron oxide, titanium oxide-silica, sericite-titanium oxide, silica-cerium oxide, silica-zinc oxide, mica-aluminum hydroxide, mica-titanium oxide-silica,
Mica-iron oxide-silica, titanium oxide-iron oxide-silica, barium sulfate-titanium oxide, barium sulfate-zinc oxide, mica-barium sulfate-titanium oxide, mica-barium sulfate-zinc oxide and the like.
【００３９】白色顔料としては、酸化チタン、酸化亜
鉛、酸化セリウム等がある。着色顔料としては、酸化
鉄、水和酸化鉄、黄土、酸化クロム、水酸化クロム、チ
タン酸コバルト、群青、紺青等が挙げられる。The white pigment includes titanium oxide, zinc oxide, cerium oxide and the like. Examples of the coloring pigment include iron oxide, hydrated iron oxide, loess, chromium oxide, chromium hydroxide, cobalt titanate, ultramarine, navy blue, and the like.
【００４０】パール顔料としては、酸化チタン被覆雲
母、酸化チタン被覆オキシ塩化ビスマス、酸化チタン被
覆タルク、オキシ塩化ビスマス、魚鱗箔、アルミニウム
パウダー等が挙げられる。Examples of the pearl pigment include titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, bismuth oxychloride, fish scale foil, aluminum powder and the like.
【００４１】これらの無機粒子は単独で、または２種以
上組み合わせて用いられる。これらの中でも、多くの塗
料に使用され、安価に入手が可能で粒子径の制御が比較
的容易な体質顔料、白色顔料が好ましい。例えば、炭酸
カルシウム、タルク、カオリン、クレー、二酸化チタ
ン、硫酸バリウム、シリカ、水酸化マグネシウム、炭酸
マグネシウム等が挙げられる。特にそれらのなかでも炭
酸カルシウムが、形状の制御性、コスト、色彩設計に制
約を与えない等の観点から望ましい。These inorganic particles can be used alone or in combination of two or more. Among these, extender pigments and white pigments, which are used in many paints, are available at low cost, and whose particle diameter can be relatively easily controlled, are preferred. Examples include calcium carbonate, talc, kaolin, clay, titanium dioxide, barium sulfate, silica, magnesium hydroxide, magnesium carbonate, and the like. Among them, calcium carbonate is particularly desirable from the viewpoint of controllability of shape, cost, and no restriction on color design.
【００４２】即ち、酸化チタンは、白色顔料として塗料
全般に広く使用されているが、その単価が高いため、汎
用的でなく、硫酸バリウムは比較的平均粒子径が細か
く、分散性が悪く凝集性が強い。また、カオリンやクレ
ー、タルクといった板状粒子は、塗料の隠蔽性を上げた
り、艶消し塗料などに使われているが、それらを配合し
た塗料は色相が悪く、白塗料などには余り適しない場合
がある。That is, although titanium oxide is widely used as a white pigment in paints in general, it is not versatile because of its high unit price, and barium sulfate has a relatively small average particle size, poor dispersibility, and poor cohesiveness. Is strong. In addition, plate-like particles such as kaolin, clay, and talc are used to increase the hiding power of paints and are used in matte paints, but paints containing them have poor hue and are not very suitable for white paints, etc. There are cases.
【００４３】そこで、比較的安価で、粒子径コントロー
ルが容易でかつ粒度分布のシャープなものが得られやす
い無機粒子として、天然に産出される石灰石を乾式もし
くは湿式で粉砕・分級を行い、粒子径をコントロールし
て製造される重質炭酸カルシウムや、石灰石を原料とし
化学的製法により得られる合成炭酸カルシウムが好まし
い。また、合成炭酸カルシウムは、平均一次粒子径が１
０μm 以下の粒子を得るのに適しており、同時に重質炭
酸カルシウムよりも粒度分布のシャープなものが得やす
く、一般的に一次粒子径が細かなものは、それら粒子の
表面活性が高く、水分や有機物との吸着性に富んでお
り、有機珪素化合物を担持させ易い点でも好ましい。更
に、塗装した際の塗膜の強度や光沢等を鑑みた場合、微
細な粒子のほうが塗料設計の自由度が増すと言った点で
も合成炭酸カルシウム（軽質炭酸カルシウムやコロイド
炭酸カルシウム）が好ましい。Therefore, limestone produced naturally is pulverized and classified in a dry or wet process as inorganic particles which are relatively inexpensive, easy to control the particle size and easy to obtain a sharp particle size distribution. Heavy calcium carbonate produced by controlling the concentration of limestone and synthetic calcium carbonate obtained by a chemical production method using limestone as a raw material are preferred. The synthetic calcium carbonate has an average primary particle diameter of 1
It is suitable for obtaining particles of 0 μm or less, and at the same time, it is easy to obtain a particle having a sharper particle size distribution than heavy calcium carbonate. It is also preferable in that it has a high adsorptivity to organic substances and organic substances and is easy to carry an organic silicon compound. Further, in view of the strength and gloss of the coating film at the time of coating, synthetic calcium carbonate (light calcium carbonate or colloidal calcium carbonate) is also preferable in that fine particles increase the degree of freedom in paint design.
【００４４】無機粒子に有機珪素化合物を担持させる方
法としては、乾式／湿式の表面処理を挙げることが出来
るが、特にこれらに限定されるものではない。乾式処理
を行うには、無機粒子を高速攪拌機（ヘンシェルミキサ
ー、スーパーミキサー等）等に投入し、高速攪拌を行い
ながら該有機珪素化合物を滴下あるいはスプレーにて添
加し、均一になるように攪拌処理を行う。この際、該有
機珪素化合物は、必要に応じて水もしくは有機溶剤にて
希釈して使用しても差し支えない。また、攪拌処理後に
乾燥を行ってもよい。湿式処理方法としては、無機粒子
を水または有機溶剤に分散させてスラリー化を行い、該
有機珪素化合物を投入した後に、公知の方法にて脱水乾
燥を行い、粉体とすることが出来る。Examples of the method for supporting the organic silicon compound on the inorganic particles include dry / wet surface treatments, but are not particularly limited thereto. In order to carry out the dry treatment, the inorganic particles are put into a high-speed stirrer (Henschel mixer, super mixer, etc.) and the organic silicon compound is added dropwise or sprayed while stirring at a high speed, and the mixture is stirred uniformly. I do. At this time, the organic silicon compound may be used after being diluted with water or an organic solvent, if necessary. Further, drying may be performed after the stirring treatment. As a wet treatment method, a slurry can be obtained by dispersing inorganic particles in water or an organic solvent, and after adding the organosilicon compound, dehydration and drying can be performed by a known method to obtain a powder.
【００４５】無機粒子として合成炭酸カルシウムを使用
する際、該合成炭酸カルシウムは、水スラリー中にて合
成を行い、所望の粒子径に調整した後に有機珪素化合物
で表面処理を行い、公知の方法にて脱水乾燥を行うこと
により得ればよい。しかし、有機珪素化合物の多くは水
に不溶性であるため脱水濾液中のＣＯＤが高くなり環境
に影響を与える場合があり、好ましくは、粉体にて乾式
処理を行うのがよい。この際に、該有機珪素化合物は、
そのままで添加してもよいが、必要に応じて予め有機溶
剤に溶解させればよい。なお、溶剤としては、有機珪素
化合物を溶解するものであれば制限されないが、トルエ
ン、キシレン等の芳香族炭化水素溶剤、ｎ−ヘキサン、
ミネラルスピリッツ等の脂肪族炭化水素溶剤等が例示さ
れる。When synthetic calcium carbonate is used as the inorganic particles, the synthetic calcium carbonate is synthesized in a water slurry, adjusted to a desired particle size, and then subjected to a surface treatment with an organosilicon compound. May be obtained by performing dehydration drying. However, since many organic silicon compounds are insoluble in water, the COD in the dehydrated filtrate may increase, which may affect the environment. Preferably, the powder is subjected to dry treatment. At this time, the organosilicon compound is
Although it may be added as it is, it may be dissolved in an organic solvent in advance as needed. The solvent is not limited as long as it can dissolve the organosilicon compound, but aromatic solvents such as toluene and xylene, n-hexane,
Examples thereof include aliphatic hydrocarbon solvents such as mineral spirits.
【００４６】乾式処理を行うには、例えば、高速攪拌機
（ヘンシェルミキサー、スーパーミキサー等）に合成炭
酸カルシウムと有機珪素化合物とを投入し高速攪拌を行
うが、合成炭酸カルシウムに限らず分散された微粉は、
粉立ちが激しく処理時の作業性が悪い場合がある。この
ため、空気透過式比表面積から換算した平均粒子径が比
較的大きな（好ましくは０．５〜５０μm 、より好まし
くは１〜２０μm ）無機粒子を混合させることにより、
比較的粒子径の小さな粒子からなる合成炭酸カルシウム
の流動性を改善することができるので好ましい。更に、
合成炭酸カルシウムをベースに処理を行う場合、混合す
る無機粒子は、同組成からなり、比較的平均粒子径が大
きな重質炭酸カルシウム（天然石灰石を粉砕分級して得
られる）を使用するのが好ましい。In order to carry out the dry treatment, for example, synthetic calcium carbonate and an organic silicon compound are charged into a high-speed stirrer (Henschel mixer, super mixer, etc.) and high-speed stirring is performed. Is
There is a case where workability at the time of processing is poor due to severe dusting. Therefore, by mixing inorganic particles having a relatively large average particle diameter (preferably 0.5 to 50 μm, more preferably 1 to 20 μm) calculated from the air-permeation specific surface area,
It is preferable because the fluidity of synthetic calcium carbonate composed of particles having a relatively small particle diameter can be improved. Furthermore,
When processing is performed based on synthetic calcium carbonate, it is preferable to use heavy calcium carbonate (obtained by pulverizing and classifying natural limestone) in which inorganic particles to be mixed have the same composition and a relatively large average particle size. .
【００４７】前述の重質炭酸カルシウムと合成炭酸カル
シウムの混合比は、塗料設計に応じて自由に選択すれば
よく、使用する有機珪素化合物の量や種類によっても自
由に選択すればよい。例えば、高光沢の塗料を設計する
場合、比較平均粒子径の大きな粒子を混合させると高光
沢を発揮しない場合があるのでその混合量は出来るだけ
抑える方がよく、逆に艶消し塗料や厚塗りの塗料を設計
する場合は、比較的粒子径の大きな粒子の混合量を多め
に配合すればよい。合成炭酸カルシウムと重質炭酸カル
シウムの混合比は、好ましくは１：９９〜９９：１、よ
り好ましくは１０：９０〜９０：１０、更に好ましくは
２０：８０〜８０：２０である。合成炭酸カルシウムの
配合量が１よりも少ないと、担持させる有機珪素化合物
が分離しやすくなる場合があり好ましくない。逆に９９
を越えると、前述の粉立ちが激しくなり作業性が悪くな
り効率が低下する場合がある。The mixing ratio of the above-mentioned heavy calcium carbonate and synthetic calcium carbonate may be freely selected according to the paint design, and may be freely selected depending on the amount and type of the organic silicon compound used. For example, when designing a high-gloss paint, mixing high-gloss particles with a relatively large average particle size may not produce high gloss, so it is better to reduce the amount of the mixture as much as possible. When designing the paint of the above, it is only necessary to mix a relatively large amount of particles having a relatively large particle diameter. The mixing ratio of synthetic calcium carbonate and heavy calcium carbonate is preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20. If the amount of the synthetic calcium carbonate is less than 1, the organosilicon compound to be supported may be easily separated, which is not preferable. Conversely 99
If the ratio exceeds the above range, the above-mentioned dusting may become severe, the workability may deteriorate, and the efficiency may decrease.
【００４８】本発明に使用する合成炭酸カルシウムは、
走査型電子顕微鏡から観測した平均一次粒子径が１０μ
m 以下が好ましく、より好ましくは５μm 以下、更に好
ましくは０．５μm 以下である。１０μm を越えると高
光沢の塗膜が得られなかったり、塗料の貯蔵時に沈殿を
生じたりする場合がある。この場合、軽質炭酸カルシウ
ムのような紡錘状粒子の場合、その平均粒子径は投影面
積を円換算から求めた直径を平均一次粒子径とする。The synthetic calcium carbonate used in the present invention is:
Average primary particle size of 10μ observed from a scanning electron microscope
m, preferably 5 μm or less, more preferably 0.5 μm or less. If the thickness exceeds 10 μm, a high gloss coating film may not be obtained, or precipitation may occur during storage of the paint. In this case, in the case of spindle-shaped particles such as light calcium carbonate, the average particle diameter is defined as the diameter obtained by converting the projected area from a circle to the average primary particle diameter.
【００４９】本発明に使用する炭酸カルシウムの吸油量
（ml／１００ｇ）は、１０〜１００ml／１００ｇが好ま
しく、より好ましくは１５〜７５ml／１００ｇ、更に好
ましくは２０〜５０ml／１００ｇである。１０ml／１０
０ｇ未満では有機珪素化合物が充分に担持されない場合
があり、逆に１００ml／１００ｇを越えると、塗料中に
おいて有機珪素化合物が炭酸カルシウムに担持されたま
まになり、その効果を充分に発揮できない場合がある。The oil absorption (ml / 100 g) of the calcium carbonate used in the present invention is preferably from 10 to 100 ml / 100 g, more preferably from 15 to 75 ml / 100 g, even more preferably from 20 to 50 ml / 100 g. 10ml / 10
If the amount is less than 0 g, the organosilicon compound may not be sufficiently supported. On the other hand, if it exceeds 100 ml / 100 g, the organosilicon compound may remain supported on the calcium carbonate in the paint, and the effect may not be sufficiently exerted. is there.
【００５０】本発明においては、無機粒子は、アニオン
性、カチオン性、ノニオン性等の界面活性剤、エステ
ル、脂肪酸、樹脂酸等の有機物のうち少なくとも１種で
あらかじめ表面処理したものが好ましい。即ち、無機粒
子の多くは、その表面活性が乏しく、有機珪素化合物と
の付着力が乏しい場合がある。従って、無機粒子に有機
珪素化合物を単純に担持させただけでは、有機珪素化合
物は無機粒子に単に付着しているだけにすぎない。一般
に、無機粒子は輸送コストや保管を考えた場合、粉体と
して取り扱われる為、単に付着しているだけの場合は、
粉体から有機珪素化合物が分離したりする場合があり、
より強固に無機粒子に担持させるのが好ましい。無機粒
子を前述のアニオン性、カチオン性、ノニオン性等の界
面活性剤、エステル、脂肪酸、樹脂酸等の有機物のうち
少なくとも１種以上であらかじめ表面処理することによ
り、無機粒子と有機珪素化合物との親和性が向上し、無
機粒子に有機珪素化合物を強固に付着させることができ
る。また、前述のシリコーンオイル、変性シリコーンオ
イルの場合は、その構造式内に含有する反応性基（官能
基）と前述のアニオン性、カチオン性、ノニオン性等の
界面活性剤、エステル、脂肪酸、樹脂酸等の有機物との
親和性がよいため、より強固に担持される点でも好まし
い。In the present invention, the inorganic particles are preferably those which have been surface-treated in advance with at least one of anionic, cationic, nonionic and other surfactants, and organic substances such as esters, fatty acids and resin acids. That is, many of the inorganic particles have poor surface activity and may have poor adhesion to the organosilicon compound. Therefore, simply supporting the organic silicon compound on the inorganic particles merely causes the organic silicon compound to adhere to the inorganic particles. In general, inorganic particles are handled as powder when considering transportation costs and storage, so if they are just attached,
The organic silicon compound may be separated from the powder,
It is preferable that the inorganic particles are more firmly supported. By previously surface-treating the inorganic particles with at least one of anionic, cationic, nonionic and other surfactants, esters, fatty acids, and organic substances such as resin acids, the inorganic particles and the organosilicon compound The affinity is improved, and the organic silicon compound can be firmly attached to the inorganic particles. In the case of the aforementioned silicone oil or modified silicone oil, the reactive group (functional group) contained in the structural formula and the aforementioned anionic, cationic, nonionic or other surfactant, ester, fatty acid, resin Since it has good affinity with organic substances such as acids, it is also preferable in that it is more firmly supported.
【００５１】アニオン性の界面活性剤としては、ポリオ
キシエチレンアルキルエーテル硫酸等で例示されるアル
キルエーテル硫酸、ポリオキシエチレンアルキルエーテ
ル燐酸等で例示されるアルキルエーテル燐酸、ポリオキ
シエチレンアルキルフェニルエーテル硫酸等で例示され
るアルキルアリールエーテル硫酸、ポリオキシエチレン
アルキルフェニルエーテル燐酸等で例示されるアルキル
アリールエーテル燐酸、ポリオキシアルキル硫酸エステ
ル等で例示されるアルキル硫酸エステル、ポリオキシア
ルキル燐酸エステル等で例示されるアルキル燐酸エステ
ル、ポリオキシアルキルフェニル硫酸エステル等で例示
されるアルキルアリール硫酸エステル、ポリオキシアル
キルフェニル燐酸エステル等で例示されるアルキルアリ
ール燐酸エステル、脂肪酸アルキロールアミドの硫酸エ
ステル等で例示されるアルキルアミド硫酸エステル、ポ
リオキシエチレンアルキルスルホン酸等で例示されるア
ルキルスルホン酸、アルキルベンゼンスルホン酸、アル
キルナフタレンスルホン酸、スルホコハク酸、ジアルキ
ルスルホコハク酸エステル等で例示されるスルホコハク
酸エステル、α−オレフインスルホン酸、Ｎ−アシルス
ルホン酸及び／又はそれらのアルカリ金属、アルカリ土
類金属塩等の陰イオン性界面活性剤、α、β不飽和モノ
カルボン酸、α、β不飽和ジカルボン酸、メタアクリル
酸アルキルエステル、アルコキシ基を有する（メタ）ア
クリルエーテル、シクロヘキシル基を有する（メタ）ア
クリレート、α、βモノエチレン性不飽和ヒドロキシエ
ステル、ポリアルキレングリコールモノ（メタ）アクリ
レート、ビニルエステル、ビニル系芳香族、不飽和ニト
リル、不飽和ジカルボン酸エステル、ビニルエーテル、
共役ジエン、鎖状オレフイン、環状オレフイン、スルホ
基含有単量体等からなる共重合物等で例示させる陰イオ
ン性高分子分散剤及びそれらのアルカリ金属、アルカリ
土類金属、アンモニウム等による部分もしくは完全中和
された塩等が挙げられる。Examples of the anionic surfactant include alkyl ether sulfuric acid exemplified by polyoxyethylene alkyl ether sulfuric acid, alkyl ether phosphoric acid exemplified by polyoxyethylene alkyl ether phosphoric acid, etc., and polyoxyethylene alkylphenyl ether sulfuric acid. Examples of the alkylaryl ether sulfates exemplified by the above, such as alkylaryl ether phosphoric acid exemplified by the polyoxyethylene alkylphenyl ether phosphoric acid and the like, alkyl sulfates exemplified by the polyoxyalkyl sulfate and the like, exemplified by the polyoxyalkyl phosphates and the like Alkyl aryl sulfates exemplified by alkyl phosphates, polyoxyalkylphenyl sulfates, etc. Alkyl aryl phosphates exemplified by polyoxyalkylphenyl phosphates, etc. Alkyl amide sulfates such as fatty acid alkylolamide sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, sulfonasuccinic acids, and dialkyl sulfosuccinic esters such as polyoxyethylene alkylsulfonic acids. Illustrative anionic surfactants such as sulfosuccinates, α-olefinsulfonic acid, N-acylsulfonic acid and / or their alkali metal and alkaline earth metal salts, α, β unsaturated monocarboxylic acids, α , Β-unsaturated dicarboxylic acid, alkyl methacrylate, (meth) acryl ether having an alkoxy group, (meth) acrylate having a cyclohexyl group, α, β monoethylenically unsaturated hydroxy ester, polyalkylene glycol mono ( Meth) acrylates, vinyl esters, vinyl aromatics, unsaturated nitriles, unsaturated dicarboxylic esters, vinyl ethers,
Anionic polymer dispersants exemplified by copolymers of conjugated dienes, chain olefins, cyclic olefins, sulfo group-containing monomers, etc., and their partial or complete alkali metal, alkaline earth metal, ammonium, etc. And neutralized salts.
【００５２】カチオン性の界面活性剤としては、ステア
リルアミンアセテート、ステアリルアミン塩酸塩などの
脂肪族アミン塩、ラウリルトリメチルアンモニウムクロ
ライド、ステアリルトリメチルアンモニウムクロライド
などの脂肪族４級アンモニウム塩、アルキルベンジルジ
メチルアンモニウムクロライドなどの芳香族４級アンモ
ニウム塩、複素環４級アンモニウム物等の陽イオン性界
面活性剤、アミノ基（第１アミン基）、イミノ基（第２
アミン基）、第３アミン基、第４アンモニウム基、ヒド
ラジノ基等の極性基を有する陽イオン性高分子系分散
剤、それらの極性基を有する単量体と共重合可能な単量
体、例えばα、β不飽和モノカルボン酸、α、β不飽和
ジカルボン酸、メタアクリル酸アルキルエステル、アル
コキシ基を有する（メタ）アクリルエーテル、シクロヘ
キシル基を有する（メタ）アクリレート、α、βモノエ
チレン性不飽和ヒドロキシエステル、ポリアルキレング
リコールモノ（メタ）アクリレート、ビニルエステル、
ビニル系芳香族、不飽和ニトリル、不飽和ジカルボン酸
エステル、ビニルエーテル、共役ジエン、鎖状オレフイ
ン、環状オレフイン、スルホ基含有単量体等の単量体と
の共重合物及びそれらのアルカリ金属、アルカリ土類金
属、アンモニウム等により部分もしくは完全中和された
塩等が挙げられる。Examples of the cationic surfactant include aliphatic amine salts such as stearylamine acetate and stearylamine hydrochloride; aliphatic quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride; and alkylbenzyldimethylammonium chloride. Quaternary ammonium salts such as aromatic quaternary ammonium salts, heterocyclic quaternary ammonium compounds and the like, amino groups (primary amine groups), imino groups (secondary
Amine group), tertiary amine group, quaternary ammonium group, cationic polymer dispersant having a polar group such as hydrazino group, a monomer copolymerizable with a monomer having such a polar group, for example, α, β unsaturated monocarboxylic acid, α, β unsaturated dicarboxylic acid, alkyl methacrylate, (meth) acryl ether having an alkoxy group, (meth) acrylate having a cyclohexyl group, α, β monoethylenically unsaturated Hydroxy ester, polyalkylene glycol mono (meth) acrylate, vinyl ester,
Copolymers with monomers such as vinyl aromatics, unsaturated nitriles, unsaturated dicarboxylic esters, vinyl ethers, conjugated dienes, chain olefins, cyclic olefins, sulfo group-containing monomers, and their alkali metals and alkalis Salts partially or completely neutralized with an earth metal, ammonium or the like can be mentioned.
【００５３】ノニオン性の界面活性剤としては、カルボ
キシベタイン、スルホベタイン等で例示されるベタイ
ン、アミノカルボン酸、イミダゾリン誘導体が例として
挙げられる。Examples of the nonionic surfactant include betaines exemplified by carboxybetaine and sulfobetaine, aminocarboxylic acids, and imidazoline derivatives.
【００５４】また、エステルとしては、ポリオキシエチ
レンアルキルエーテル等で例示されるアルキルエーテ
ル、ポリオキシエチレンノニルフェニルエーテル等で例
示されるアルキルアリルエーテル、ポリオキシエチレン
オレエート等で例示されるアルキルエステル、ポリオキ
シエチレンアルキルアミン等で例示されるアルキルアミ
ン、ソルビタンラウレート等で例示されるソルビタン誘
導体、多環フェニルエーテル、脂肪酸エステル等で例示
される非イオン系界面活性剤、並びに高分子系分散剤、
及びそれらのアルカリ金属、アルカリ土類金属、アンモ
ニウム等により部分もしくは完全中和された塩等が挙げ
られる。Examples of the ester include alkyl ethers such as polyoxyethylene alkyl ether, alkyl allyl ethers such as polyoxyethylene nonylphenyl ether, and alkyl esters such as polyoxyethylene oleate. Alkylamines exemplified by polyoxyethylene alkylamines and the like, sorbitan derivatives exemplified by sorbitan laurate and the like, polycyclic phenyl ethers, nonionic surfactants exemplified by fatty acid esters and the like, and polymer dispersants,
And salts thereof partially or completely neutralized with alkali metals, alkaline earth metals, ammonium and the like.
【００５５】また、脂肪酸、樹脂酸としては、ラウリル
酸、パルミチン酸、オレイン酸、リノール酸、ステアリ
ン酸、ベヘン酸等に例示される飽和、不飽和の脂肪酸、
アビエチン酸、ネオアビエチン酸、安息香酸、桂皮酸等
に例示される脂環族、芳香族の樹脂酸、及び／又は、こ
れら酸のエステル類、アルカリ金属、アルカリ土類金
属、アンモニウム、アミン等から選ばれる１種以上の塩
類などが挙げられる。Examples of the fatty acids and resin acids include saturated and unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, linoleic acid, stearic acid, and behenic acid.
Alicyclic and aromatic resin acids exemplified by abietic acid, neoabietic acid, benzoic acid, cinnamic acid, and / or esters of these acids, alkali metals, alkaline earth metals, ammonium, amines, etc. One or more selected salts are exemplified.
【００５６】上記有機物の量は、無機粒子に対して０．
０１〜３０重量％が好ましく、より好ましくは０．０５
〜２０重量％、更に好ましくは０．１〜１０重量％であ
る。０．０１重量％未満では前処理効果が充分でなく、
一方、３０重量％を超えると無機粒子に対して有機物が
過剰となり、無機粒子の凝集体を作り易くなるため好ま
しくない場合がある。尚、無機粒子として合成炭酸カル
シウムを使用する場合は、合成された水スラリー中で表
面処理することが好ましい。The amount of the organic substance is 0.1 to the inorganic particles.
It is preferably from 0.01 to 30% by weight, more preferably from 0.05 to 30% by weight.
-20% by weight, more preferably 0.1-10% by weight. If less than 0.01% by weight, the pretreatment effect is not sufficient,
On the other hand, if the content exceeds 30% by weight, the amount of organic substances becomes excessive with respect to the inorganic particles, and it is easy to form an aggregate of the inorganic particles. In addition, when using synthetic calcium carbonate as inorganic particles, it is preferable to perform a surface treatment in the synthesized water slurry.
【００５７】上記の如くして得られる表面改質無機粒子
を配合する塗料として、油性塗料、ニトロセルロース塗
料、アルキッド塗料、アミノアルキッド塗料、ビニル樹
脂塗料、アクリル樹脂塗料、エポキシ樹脂塗料、ポリエ
ステル樹脂塗料、塩化ゴム系塗料等の１種あるいは２種
以上を含有する塗料が挙げられる。また、塗料は、その
用い方によって、溶剤系塗料、水系塗料、紫外線硬化型
のアクリル樹脂、エポキシ樹脂、ビニル樹脂等からなる
紫外線硬化型塗料、ポリアミド、ポリエステル、アクリ
ル樹脂、オレフィン樹脂、ポリエーテル樹脂、塩化ビニ
ル樹脂等の熱可塑性樹脂、エポキシ硬化型ポリエステル
樹脂等からなる粉体塗料等の任意のものであってよい
が、特に、溶剤系塗料や水系塗料に適している。Examples of paints containing the surface-modified inorganic particles obtained as described above include oil paints, nitrocellulose paints, alkyd paints, amino alkyd paints, vinyl resin paints, acrylic resin paints, epoxy resin paints, and polyester resin paints. And one or more paints such as chlorinated rubber paints. Depending on the method of use, the paint may be a solvent-based paint, a water-based paint, an ultraviolet-curable acrylic resin, an epoxy resin, an ultraviolet-curable paint composed of a vinyl resin, a polyamide, a polyester, an acrylic resin, an olefin resin, a polyether resin. It may be any material such as a powder coating made of a thermoplastic resin such as a vinyl chloride resin, or an epoxy-curable polyester resin, and is particularly suitable for a solvent-based coating or a water-based coating.
【００５８】水系塗料用樹脂としては、アルキド系、ア
クリル系、酢酸ビニル系、ウレタン系、シリコーン系、
フッ素系、ステレン系、メラミン系、エポキシ系等の一
般塗料用樹脂、アルキド系、アミン系、スチレン−アリ
ルアルコール系、アミノアルキド系、ポリブタジエン系
等の一般塗料用水溶性樹脂、エマルジョン樹脂と水溶性
樹脂とをブレンドした塗料用ディスパージョン樹脂、架
橋型水可溶性樹脂を乳化剤としたディスパージョン樹
脂、アクリルハイドロゾル等から適宜選択することがで
き、また、これら樹脂成分を２種以上組み合わせて使用
することも可能である。Examples of the water-based paint resin include alkyd, acrylic, vinyl acetate, urethane, silicone, and the like.
Resin for general paint such as fluorine, sterene, melamine, epoxy, etc., water-soluble resin for general paint such as alkyd, amine, styrene-allyl alcohol, aminoalkyd, polybutadiene, emulsion resin and water-soluble resin Can be appropriately selected from a dispersion resin for coatings, a dispersion resin using a cross-linkable water-soluble resin as an emulsifier, an acrylic hydrosol, and the like, and a combination of two or more of these resin components can also be used. It is.
【００５９】塗料組成物中における樹脂分濃度は、適宜
調整すればよいが、溶剤系塗料、水性塗料の場合は、通
常、５〜７５重量％、好ましくは１０〜７０重量％の範
囲が適当である。また、本発明の表面改質無機粒子の含
有量は、無機顔料の含有量としては特に限定されるもの
ではないが、好ましくは樹脂固形分１００重量部に対し
て５〜１５０重量部であり、より好ましくは１０〜８０
重量部である。含有量が５重量部未満では、期待される
効果が発現しにくく、コスト的にも不利であり、一方、
含有が１５０重量部を越えると得られる塗料において、
塗装時のハンドリングが著しく悪くなったり著しく光沢
が低下する場合がある。The concentration of the resin component in the coating composition may be appropriately adjusted. In the case of a solvent-based coating or a water-based coating, it is usually in the range of 5 to 75% by weight, preferably 10 to 70% by weight. is there. The content of the surface-modified inorganic particles of the present invention is not particularly limited as the content of the inorganic pigment, but is preferably 5 to 150 parts by weight based on 100 parts by weight of the resin solid content. More preferably 10 to 80
Parts by weight. If the content is less than 5 parts by weight, the expected effect is hardly exhibited and the cost is disadvantageous.
In the paint obtained when the content exceeds 150 parts by weight,
The handling at the time of painting may be significantly deteriorated or the gloss may be significantly reduced.
【００６０】また上記塗料組成物をつくる場合、塗料用
着色顔料及びその他の体質顔料、消泡剤、非粘着剤、湿
潤剤、分散剤、硬化促進剤、防腐剤、防カビ剤、造膜助
剤、凍結防止剤等、この分野で通常使用される添加剤の
１種又は２種以上を必要に応じて、本発明の塗料組成物
中に添加することができる。When the above coating composition is prepared, a coloring pigment for coating and other extender pigments, an antifoaming agent, a non-adhesive, a wetting agent, a dispersing agent, a curing accelerator, a preservative, a fungicide, a film-forming aid. One or more additives commonly used in this field, such as an agent and an antifreezing agent, can be added to the coating composition of the present invention as needed.
【００６１】[0061]
【実施例】以下，実施例，比較例を挙げて本発明をより
詳細に説明するが，本発明はこれらにより何ら制約を受
けるものではない．尚、表１及び表２中、略称はそれぞ
れ下記の物質を表す。 重炭：重質炭酸カルシウム 軽炭：軽質炭酸カルシウム コロイド：コロイド炭酸カルシウムEXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited by these. In Tables 1 and 2, abbreviations represent the following substances, respectively. Heavy coal: Heavy calcium carbonate Light coal: Light calcium carbonate Colloid: Colloidal calcium carbonate
【００６２】実施例１〜２５（表面改質無機粒子） （Ａ）無機粒子の作成・準備 無機粒子１ 比重１．０７の石灰乳を１５℃に調整し、水酸化カルシ
ウム１kgあたり３０リットル／分の炭酸ガス（内２５％
ＣＯ2 ）を導通し炭酸化反応を行い、系のｐＨが８．０
となったときに炭酸化反応を停止し、５０℃、ｐＨ１
０．２で１５時間攪拌し、系の粘度が２３００ｃp に達
したとき、再び炭酸ガスを導通して系のｐＨを６．８と
した。これにより凝集体粒子の極めて少なく、電子顕微
鏡写真より測定した平均１次粒子径が０．１μm の炭酸
カルシウムからなる水スラリーを得た。その後、常法に
従い脱水、乾燥、仕上げ解砕を行い、上記粒子径を有す
る合成炭酸カルシウム（コロイド炭酸カルシウム）を得
た。Examples 1 to 25 (Surface Modified Inorganic Particles) (A) Preparation and Preparation of Inorganic Particles Inorganic particles 1 Lime milk having a specific gravity of 1.07 was adjusted to 15 ° C., and 30 liters / minute per 1 kg of calcium hydroxide. Carbon dioxide (of which 25%
CO 2 ) was conducted to carry out a carbonation reaction, and the pH of the system was adjusted to 8.0.
At which time the carbonation reaction was stopped at 50 ° C., pH 1
The mixture was stirred at 0.2 for 15 hours. When the viscosity of the system reached 2300 cp, carbon dioxide gas was passed again to adjust the pH of the system to 6.8. As a result, an aqueous slurry of calcium carbonate having an extremely small amount of aggregated particles and having an average primary particle diameter of 0.1 μm as measured from an electron micrograph was obtained. Thereafter, dehydration, drying and finish crushing were performed according to a conventional method to obtain a synthetic calcium carbonate (colloidal calcium carbonate) having the above particle diameter.
【００６３】無機粒子２ 比重１．１０の石灰乳を２０℃に調整し、水酸化カルシ
ウム１kgあたり３０リットル／分の炭酸ガス（内２５％
ＣＯ2 ）を導通し炭酸化反応を行い、系のｐＨが７．０
となったときに炭酸化反応を停止した。これにより、電
子顕微鏡写真より測定したところ長径が2.0 〜4.0 μm
、短径が0.8 〜1.0 μm の紡錘状粒子（平均粒子径2.0
μm ）からなる水スラリーを得た。その後、常法に従
い脱水、乾燥、仕上げ解砕を行い、上記粒子径を有する
合成炭酸カルシウム（軽質炭酸カルシウム）粉末を得
た。Inorganic particles 2 Lime milk having a specific gravity of 1.10 was adjusted to 20 ° C., and carbon dioxide gas (30% / min.
CO 2 ) was conducted to carry out a carbonation reaction, and the pH of the system was 7.0.
When it became, the carbonation reaction was stopped. As a result, when measured from an electron micrograph, the major axis was 2.0 to 4.0 μm.
, Spindle-shaped particles with a short diameter of 0.8 to 1.0 μm (average particle diameter 2.0
μm). Thereafter, dehydration, drying, and final disintegration were performed according to a conventional method to obtain a synthetic calcium carbonate (light calcium carbonate) powder having the above particle diameter.
【００６４】無機粒子３〜６ 無機粒子にカオリンクレー（平均粒子径2.8 μm ）（無
機粒子３）、タルク（平均粒子径7.0 μm ）（無機粒子
４）、酸化チタン（平均粒子径０．２μm ）（無機粒子
５）、重質炭酸カルシウム（平均粒子径７．０μm ）
（無機粒子６）を用いた。Inorganic particles 3 to 6 Inorganic particles include kaolin clay (average particle size 2.8 μm) (inorganic particles 3), talc (average particle size 7.0 μm) (inorganic particles 4), and titanium oxide (average particle size 0.2 μm). (Inorganic particles 5), heavy calcium carbonate (average particle diameter 7.0 μm)
(Inorganic particles 6) were used.
【００６５】無機粒子（前処理）７〜１０ 上記無機粒子１のスラリーに、脂肪酸石鹸（無機粒子
７）、樹脂酸石鹸（無機粒子８）、脂肪酸エステル／ド
デシルベンゼンスルホン酸ナトリウム（無機粒子９）、
ポリアクリル酸と脂肪酸エステルの共重合物（ポリアク
リル酸１００：脂肪酸エステル１０、分子量10,000）の
アンモニウム塩（無機粒子１０）の各濃度を１０％に調
整した水溶液を投入し３０min 間攪拌した後、常法に従
い脱水・乾燥、仕上げ解砕し、上記各有機物３重量％
（対炭酸カルシウム）で表面処理された合成炭酸カルシ
ウム（コロイド炭酸カルシウム）を得た。Inorganic Particles (Pretreatment) 7 to 10 Into the slurry of the inorganic particles 1 are added a fatty acid soap (inorganic particles 7), a resin acid soap (inorganic particles 8), a fatty acid ester / sodium dodecylbenzenesulfonate (inorganic particles 9). ,
An aqueous solution in which each concentration of ammonium salt (inorganic particles 10) of a copolymer of polyacrylic acid and fatty acid ester (polyacrylic acid 100: fatty acid ester 10, molecular weight 10,000) was adjusted to 10% was added and stirred for 30 minutes. Dehydrate, dry, finish and disintegrate according to the usual method, 3% by weight of each of the above organic substances
Synthetic calcium carbonate (colloidal calcium carbonate) surface-treated with (to calcium carbonate) was obtained.
【００６６】（Ｂ）有機珪素化合物担持粒子の作成 無機粒子１〜１０を高速攪拌機カワタ製スーパーミキサ
ーに投入し、表１記載の有機珪素化合物並びに添加量を
投入し約３０分間乾式処理し、表１に示すように、有機
珪素化合物が担持された表面改質無機粒子を得た。(B) Preparation of Organic Silicon Compound-Supported Particles Inorganic particles 1 to 10 were charged into a high-speed stirrer Kawata Supermixer, and the organic silicon compound and the amount of addition shown in Table 1 were charged and dry-processed for about 30 minutes. As shown in FIG. 1, surface-modified inorganic particles carrying an organosilicon compound were obtained.
【００６７】[0067]
【表１】 [Table 1]
【００６８】実施例２６〜５０（塗料組成物） 上記実施例１〜２５で得られた表面改質無機粒子を使用
し、下記の配合及び作成方法に基づいてアクリルウレタ
ン塗料組成物を作成した。この評価結果を表２に示す。Examples 26 to 50 (Coating Composition) Using the surface-modified inorganic particles obtained in the above Examples 1 to 25, acrylic urethane coating compositions were prepared based on the following formulation and preparation method. Table 2 shows the evaluation results.
【００６９】 （塗料配合） 「白塗料」 （ミルベース） ａ．アクリル・ウレタン樹脂（固形分６０％） １８．８３重量部 ｂ．キシレン ３８．３ 〃 ｃ．酸化チタン（「ＣＲ−５０」石渡産業） ４５．０ 〃 ｄ．無機粒子 別表２に記載 ｅ．ガラスビーズ １６０．０ 〃(Paint Formulation) “White Paint” (Mill Base) a. Acrylic / urethane resin (solid content 60%) 18.83 parts by weight b. Xylene 38.3〃 c. Titanium oxide (“CR-50” Ishiwatari Sangyo) 45.0〃 d. Inorganic particles listed in Appendix 2 e. Glass beads 160.0 mm
【００７０】（塗料作成方法）上記配合物を１リットル
容器中にて６cmφのディゾルバー羽根にて３０００rpm
で３０分間分散・混合しミルベースを作成した。混練後
該ミルベース１００重量部に対してアクリル・ウレタン
樹脂７５．７重量部を加え、レッドダウンを行い白塗料
とした。(Method of preparing paint) The above-mentioned composition was placed in a 1-liter container at 3000 rpm with a 6 cmφ dissolver blade.
For 30 minutes to prepare a mill base. After kneading, 75.7 parts by weight of an acrylic urethane resin was added to 100 parts by weight of the mill base, and red down was performed to obtain a white paint.
【００７１】「黒塗料」顔料として上記配合の酸化チタ
ン４５重量部の代わりにカーボンブラック粉末２０重量
部を用いた以外は同様にして黒塗料を作成した。Black paint A black paint was prepared in the same manner except that 20 parts by weight of carbon black powder was used as the pigment instead of 45 parts by weight of the titanium oxide compounded as described above.
【００７２】（色別れ）白塗料と黒塗料を７：３の重量
比で約１０分間混合し、試験用灰色塗料を作成した。そ
の後、ブリキ板に刷毛にて塗り広げ、その塗面上に同一
の塗料を、塗布直後と塗布１分後にそれぞれ１滴ずつ数
カ所に滴下し、色別れ性を目視確認し、以下の評価方法
で評価した。塗布した直後は、無機粒子がよく混合分散
されているので色別れがないが、塗布１分後では、塗面
が半乾きで顔料の分散性が悪ければ無機粒子の沈降が早
く、色別れとなる。 ◎ ：色別れがなく、塗布直後の部分と大差なし。 ○ ：僅かに色別れがあるが、塗布直後の部分と比べ僅
かに黒っぽい。 △ ：多少色別れがあり、塗布直後の部分と比べ若干黒
みを帯びている。 × ：ほとんどの滴下箇所で色別れがあり、塗布直後部
分と比べかなり黒みを帯びている。 ××：はっきりと色別れがあり、塗布直後の部分よりか
なり黒く、黒塗料単独と大差ないぐらい黒い。(Color Separation) A white paint and a black paint were mixed at a weight ratio of 7: 3 for about 10 minutes to prepare a test gray paint. After that, the same paint is applied to the tinplate by brushing, and the same paint is dropped on the coated surface one drop at a time immediately after the application and one minute after the application, and the color-separation property is visually checked. evaluated. Immediately after application, there is no color separation because the inorganic particles are well mixed and dispersed, but after 1 minute of application, if the coating surface is semi-dry and the dispersibility of the pigment is poor, the sedimentation of the inorganic particles is fast, and color separation Become. ◎: There is no color separation and there is not much difference from the part immediately after application. ：: Slight color separation, but slightly darker than the portion immediately after application. Δ: There is some color separation, and it is slightly darker than the portion immediately after coating. ×: Color separation is observed at most of the dripping spots, which are considerably darker than those immediately after the application. XX: There is a clear color separation, considerably blacker than the part immediately after application, and black that is not much different from the black paint alone.
【００７３】（耐色落ち性）前述で作成した灰色塗料
を、ＡＢＳ樹脂板上に、乾燥膜厚が５０μm になるよう
に塗布し、６０℃で３０分間の乾燥硬化を行った。次い
で、室温に１週間放置したものにて、下記の方法で耐色
落ち性試験評価を行った。 ラビングテスター；ＡＢＯ型［大平理化工業株式会社］
を用い、フェルト（１０×５０×１０mm）をガーゼ（１
００×１５０mm）でくるんでなる試験片を所定の場所へ
設定後、ここへ５kgの荷重をかけ、塗板上を１００回擦
って、ガーゼへの着色状態を目視より判定した。 ◎ ：ガーゼに、全く色が付かない。 ○ ：ガーゼに僅かに色が付く。 △ ：ガーゼに色が付く。 × ：ガーゼに色が付き、塗膜面もくぼみができる。 ××：ガーゼに色が付き、塗膜自体が剥がれる。(Discoloration resistance) The above-prepared gray paint was applied on an ABS resin plate so as to have a dry film thickness of 50 μm, and was dried and cured at 60 ° C. for 30 minutes. Then, after leaving at room temperature for one week, a color fading resistance test was evaluated by the following method. Loving tester: ABO type [Ohira Rika Kogyo Co., Ltd.]
Using a gauze (1 × 10 × 50 × 10 mm)
(00 × 150 mm), a test piece consisting of a wrap was set in a predetermined place, a load of 5 kg was applied thereto, the coated plate was rubbed 100 times, and the state of coloring on the gauze was visually determined. ◎: The gauze has no color at all. : The gauze is slightly colored. Δ: Gauze is colored. X: The gauze is colored, and the coating film surface is dented. XX: The gauze is colored and the coating film is peeled off.
【００７４】（貯蔵安定性）前述で作成した灰色塗料
を、２００mlの塗料缶に入れて、５０℃にて１２時間放
置した後２０℃にて１２時間放置し、これを１サイクル
として７サイクル繰り返した後に、沈殿物の有無を目視
にて確認し評価した。 ◎ ：全く沈殿物がない。 ○ ：僅かに沈殿物が確認できたが、攪拌すれば消え
る。 △ ：沈殿物が少量確認できたが、強攪拌すると消え
る。 × ：やや堅い沈殿物があり、強攪拌してもツブが残
る。 ××：かなり堅い沈殿物があり、強攪拌してもツブが多
数残る。(Storage stability) The above-prepared gray paint was placed in a 200 ml paint can, left at 50 ° C. for 12 hours, left at 20 ° C. for 12 hours, and this cycle was repeated for 7 cycles. After that, the presence or absence of the precipitate was visually confirmed and evaluated. ◎: There is no precipitate at all. : A precipitate was slightly observed, but disappeared with stirring. Δ: A small amount of precipitate was confirmed, but disappeared when vigorously stirred. ×: There is a slightly hard precipitate, and a grit remains even after strong stirring. XX: There is a considerably hard precipitate, and many lumps remain even after strong stirring.
【００７５】（作業性）塗料作成時の無機粒子（粉体）
の状態を観察評価した。 ◎ ：全く粉立ちがなく、粉体の流動性も良い。 ○ ：僅かに粉立ちがあるが、作業に差し支えない。 △ ：投入初期は粉立ちがあるが、しばらくすると塗料
系内に均一になじむ。 × ：粉立ちがあり容易に塗料に入り込まない。また粉
体がべたつき壁面に大量に付着する。 ××：粉立ちが激しく、塗料液面に最後まで浮遊し、容
器壁面にも大量に付着する。(Workability) Inorganic particles (powder) during paint preparation
Was evaluated by observation. ◎: There is no powder at all, and the powder has good fluidity. ：: There is a slight dusting, but it does not hinder the work. Δ: There is dusting in the initial stage of introduction, but after a while, it blends uniformly into the paint system. ×: Powdery and not easily penetrated into paint. Also, a large amount of powder adheres to the sticky wall surface. XX: Intense dusting, floating to the end of the coating liquid level, and adhered to the container wall in large quantities.
【００７６】（耐候性）前述で作成した灰色塗料にて、
塗料作成１日後にＡＢＳ樹脂板上に乾燥膜厚が５０μm
になるように塗布したものを２枚用意し、６０℃で３０
分間の乾燥硬化を行った。その後、１枚は恒温恒湿（２
０℃、５０％）雰囲気中にて保管し、もう一枚は１ヶ月
間の屋外暴露試験を行い、６ヶ月後にそれら２枚を比較
し評価を行った。 ◎ ：塗膜面に全く差が見られず、塗膜面をさわっても
白粉（チョーキング）がない。 ○ ：若干塗膜面の光沢が低下しているが、白粉（チョ
ーキング）はない。 △ ：塗膜面が曇っており、白粉がある。 × ：塗膜面が光沢を失い若干ざらついており、白粉が
ある。 ××：塗膜面がざらついており、白粉もかなりある。(Weather resistance) Using the gray paint prepared above,
One day after the paint is prepared, the dry film thickness is 50 μm on the ABS resin plate.
Prepare two sheets that have been coated so that
For a minute. After that, one sheet is kept at constant temperature and humidity (2
(0 ° C., 50%) was stored in an atmosphere, and the other was subjected to a one-month outdoor exposure test, and after six months, the two were compared and evaluated. ◎: No difference was observed on the coating surface, and no white powder (chalking) was found even when touching the coating surface. : The gloss of the coating film surface is slightly lowered, but there is no white powder (chalking). Δ: The coating film surface is cloudy and there is white powder. ×: The coating film surface has lost its luster and is slightly rough, and there is white powder. XX: The surface of the coating film is rough, and there is considerable white powder.
【００７７】比較例１ 上記無機粒子６（重質炭酸カルシウム：平均粒子径７．
０μm ）を用いた他は実施例２６〜５０と同様に操作及
び評価した。結果を表２に示す。Comparative Example 1 The above inorganic particles 6 (heavy calcium carbonate: average particle diameter of 7.
The operation and evaluation were performed in the same manner as in Examples 26 to 50 except that 0 μm) was used. Table 2 shows the results.
【００７８】比較例２ 上記無機粒子２（合成炭酸カルシウム：軽質炭酸カルシ
ウム）を用いた他は実施例２６〜５０と同様に操作及び
評価した。結果を表２に示す。Comparative Example 2 The operation and evaluation were performed in the same manner as in Examples 26 to 50, except that the inorganic particles 2 (synthetic calcium carbonate: light calcium carbonate) were used. Table 2 shows the results.
【００７９】比較例３ シリコーンオイルを上記無機粒子６（重質炭酸カルシウ
ム：平均粒子径７．０μm ）と別々に添加した他は実施
例２６〜５０と同様に操作及び評価した。結果を表２に
示す。Comparative Example 3 The operation and evaluation were performed in the same manner as in Examples 26 to 50, except that the silicone oil was separately added to the inorganic particles 6 (heavy calcium carbonate: average particle diameter 7.0 μm). Table 2 shows the results.
【００８０】[0080]
【表２】 [Table 2]
【００８１】[0081]
【発明の効果】叙上のとおり、本発明の表面改質無機粒
子は、例えば、塗料に使用した場合は、塗料に色別れ防
止、レベリング性、スリップ性、ブロッキング防止性、
消泡性等を付与することができる。また、本発明の表面
改質無機粒子は、熱可塑性樹脂や熱硬化性樹脂に添加し
て、これらの樹脂にスリップ性やブロッキング防止性を
付与することができる。As described above, when the surface-modified inorganic particles of the present invention are used in, for example, a paint, the paint has color separation prevention, leveling properties, slip properties, blocking prevention properties,
Defoaming properties and the like can be provided. In addition, the surface-modified inorganic particles of the present invention can be added to a thermoplastic resin or a thermosetting resin to impart a slip property or an anti-blocking property to these resins.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤原 敏男 兵庫県明石市魚住町西岡1455番地 丸尾カ ルシウム株式会社内 Ｆターム(参考） 4J037 AA05 AA09 AA10 AA11 AA15 AA16 AA17 AA18 AA19 AA21 AA22 AA24 AA25 AA26 AA27 CB09 CB16 CB21 CB22 CC25 CC28 DD24 EE04 EE28 EE43 EE44 FF03 FF15 FF18 FF23 4J038 BA081 CA021 CA131 CB001 CC021 CD021 CE011 CF021 CG141 DA161 DB001 DD001 DD121 DF001 DG031 DL031 KA08 MA09 MA10 NA01 NA10 NA24 PA18 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshio Fujiwara 1455 Nishioka, Uozumi-cho, Akashi-shi, Hyogo F-term (reference) 4C037 AA05 AA09 AA10 AA11 AA15 AA16 AA17 AA18 AA19 AA21 AA22 AA26 A27 CB09 CB16 CB21 CB22 CC25 CC28 DD24 EE04 EE28 EE43 EE44 FF03 FF15 FF18 FF23 4J038 BA081 CA021 CA131 CB001 CC021 CD021 CE011 CF021 CG141 DA161 DB001 DD001 DD121 DF001 DG031 DL031 KA08 MA09 NA10
Claims (15)
ことを特徴とする表面改質無機粒子。1. Surface-modified inorganic particles, wherein an organic silicon compound is supported on the inorganic particles.
該有機物の表面に有機珪素化合物を担持させたことを特
徴とする表面改質無機粒子。2. Surface treatment of inorganic particles with an organic substance,
Surface-modified inorganic particles, wherein an organic silicon compound is supported on the surface of the organic substance.
るシリコーンオイルまたは変性シリコーンオイルからな
る請求項１または２記載の表面改質無機粒子。 【化１】 ［式中、Ｒ1 は炭素数１〜２０の１価の炭化水素基、Ｒ
2 は炭素数１〜２０の１価の炭化水素基、−Ｃ6 Ｈ5 、
−（ＣＨ2 ）a ＮＨ2 、−（ＣＨ2 ）a ＳＨ2 、−（Ｃ
Ｈ2 ）a ＣＯＯＨ、−（ＣＨ2 ）a −（ＮＨＣＨ2 ＣＨ
2 ）b ＮＨＲ4 （式中、Ｒ4 は水素原子または炭素数１
〜２０の１価の炭化水素基、ａは０〜１０の整数、ｂは
０〜１０の整数）、Ｒ3 はＲ1 、Ｒ2 、水酸基または炭
素数１〜２０のアルコキシ基、−ＣＨ＝ＣＨＣＨ3 、ｍ
は０〜３０００の整数、ｎは０〜３０００の整数、ｍ＋
ｎは１〜３０００の整数］3. The surface-modified inorganic particles according to claim 1, wherein the organosilicon compound comprises a silicone oil or a modified silicone oil represented by the following general formula. Embedded image [Wherein, R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, -C 6 H 5,
-(CH 2 ) a NH 2 ,-(CH 2 ) a SH 2 ,-(C
H 2) a COOH, - ( CH 2) a - (NHCH 2 CH
2 ) b NHR 4 (wherein R 4 is a hydrogen atom or carbon atom 1)
A is an integer of 0 to 10, b is an integer of 0 to 10), R 3 is R 1 , R 2 , a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, -CH = CHCH 3 , m
Is an integer of 0 to 3000, n is an integer of 0 to 3000, m +
n is an integer of 1 to 3000]
００〜１，０００，０００である請求項１〜３のいずれ
か１項に記載の表面改質無機粒子。4. An organosilicon compound having an average molecular weight Mw of 1
The surface-modified inorganic particles according to any one of claims 1 to 3, wherein the number is from 00 to 1,000,000.
て０．００１〜３０重量% である請求項１〜４のいずれ
か１項に記載の表面改質無機粒子。5. The surface-modified inorganic particles according to claim 1, wherein the amount of the organosilicon compound is 0.001 to 30% by weight based on the weight of the inorganic particles.
ニオン性等の界面活性剤、エステル、脂肪酸、樹脂酸か
ら選ばれる少なくとも１種である請求項１〜５のいずれ
か１項に記載の表面改質無機粒子。6. The surface according to claim 1, wherein the organic substance is at least one selected from anionic, cationic, nonionic and other surfactants, esters, fatty acids, and resin acids. Modified inorganic particles.
１〜３０重量% である請求項１〜６のいずれか１項に記
載の表面改質無機粒子。7. The amount of the organic substance is 0.0% with respect to the inorganic particles.
The surface-modified inorganic particles according to any one of claims 1 to 6, wherein the content is 1 to 30% by weight.
クレー、二酸化チタン、硫酸バリウム、シリカ、水酸化
マグネシウムから選ばれる少なくとも１種である請求項
１〜７のいずれか１項に記載の表面改質無機粒子。8. The method according to claim 1, wherein the inorganic particles are calcium carbonate, talc,
The surface-modified inorganic particles according to any one of claims 1 to 7, which is at least one selected from clay, titanium dioxide, barium sulfate, silica, and magnesium hydroxide.
項１〜８のいずれか１項に記載の表面改質無機粒子。9. The surface-modified inorganic particles according to claim 1, wherein the inorganic particles are made of calcium carbonate.
からなる請求項８または９記載の表面改質無機粒子。10. The surface-modified inorganic particles according to claim 8, wherein the calcium carbonate is composed of synthetic calcium carbonate.
ムと重質炭酸カルシウムの混合物である請求項８〜１０
のいずれか１項に記載の表面改質無機粒子。11. The calcium carbonate according to claim 8, wherein the calcium carbonate is a mixture of synthetic calcium carbonate and heavy calcium carbonate.
The surface-modified inorganic particles according to any one of the above.
ウムの混合物の混合比が１：９９〜９９：１である請求
項１１記載の表面改質無機粒子。12. The surface-modified inorganic particles according to claim 11, wherein the mixture ratio of the mixture of synthetic calcium carbonate and heavy calcium carbonate is 1:99 to 99: 1.
径が１０μm 以下の粒子径を有する合成炭酸カルシウム
である請求項１０〜１２のいずれか１項に記載の表面改
質無機粒子。13. The surface-modified inorganic particles according to claim 10, wherein the synthetic calcium carbonate is a synthetic calcium carbonate having an average primary particle diameter of 10 μm or less.
の表面改質無機粒子を含有してなることを特徴とする塗
料組成物。14. A coating composition comprising the surface-modified inorganic particles according to claim 1. Description:
分１００重量部に対して５〜１５０重量部である請求項
１４記載の塗料組成物。15. The coating composition according to claim 14, wherein the content of the surface-modified inorganic particles is 5 to 150 parts by weight based on 100 parts by weight of the resin solid content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000369669A JP3652240B2 (en) | 2000-12-05 | 2000-12-05 | Surface-modified calcium carbonate particles for coating materials and coating compositions containing the particles |
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| JP2000369669A JP3652240B2 (en) | 2000-12-05 | 2000-12-05 | Surface-modified calcium carbonate particles for coating materials and coating compositions containing the particles |
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| JP2004315546A (en) * | 2003-02-25 | 2004-11-11 | Dainippon Printing Co Ltd | Ultraviolet curable overprint varnish composition |
| JP2005272610A (en) * | 2004-03-24 | 2005-10-06 | Honda Motor Co Ltd | Coating composition for one-coat coating |
| WO2006064821A1 (en) * | 2004-12-13 | 2006-06-22 | Shiseido Co., Ltd. | Modified powder and cosmetic composition using same |
| WO2007077673A1 (en) * | 2005-12-28 | 2007-07-12 | Agc Si-Teck Co., Ltd. | Water-repellent inorganic powder and process for production thereof |
| JP2011079908A (en) * | 2009-10-05 | 2011-04-21 | Aica Kogyo Co Ltd | Coating composition and construction method |
| JP2014169389A (en) * | 2013-03-04 | 2014-09-18 | Fujikura Ltd | Flame retardant and method for manufacturing flame-retardant resin composition using the same |
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| JP2019510122A (en) * | 2016-02-02 | 2019-04-11 | クローノス インターナショナル インコーポレイテッドＫｒｏｎｏｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ， Ｉｎｃ． | Manufacture of matte paint and printing ink |
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| CN115504497A (en) * | 2022-10-09 | 2022-12-23 | 陕西安东兴阳岗石科技有限公司 | Preparation method and application of low-oil-absorption-value nano calcium carbonate |
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| JP2004315546A (en) * | 2003-02-25 | 2004-11-11 | Dainippon Printing Co Ltd | Ultraviolet curable overprint varnish composition |
| JP2005272610A (en) * | 2004-03-24 | 2005-10-06 | Honda Motor Co Ltd | Coating composition for one-coat coating |
| KR101224339B1 (en) * | 2004-12-13 | 2013-01-18 | 가부시키가이샤 시세이도 | Modified powder and cosmetic composition using same |
| WO2006064821A1 (en) * | 2004-12-13 | 2006-06-22 | Shiseido Co., Ltd. | Modified powder and cosmetic composition using same |
| JPWO2006064821A1 (en) * | 2004-12-13 | 2008-06-12 | 株式会社資生堂 | Modified powder and cosmetics using the same |
| CN101076313B (en) * | 2004-12-13 | 2010-06-16 | 株式会社资生堂 | Modified powder and cosmetic composition using same |
| WO2007077673A1 (en) * | 2005-12-28 | 2007-07-12 | Agc Si-Teck Co., Ltd. | Water-repellent inorganic powder and process for production thereof |
| JP5095418B2 (en) * | 2005-12-28 | 2012-12-12 | Ａｇｃエスアイテック株式会社 | Water repellent inorganic powder |
| JP2011079908A (en) * | 2009-10-05 | 2011-04-21 | Aica Kogyo Co Ltd | Coating composition and construction method |
| JP2014169389A (en) * | 2013-03-04 | 2014-09-18 | Fujikura Ltd | Flame retardant and method for manufacturing flame-retardant resin composition using the same |
| EP3192839A1 (en) | 2016-01-14 | 2017-07-19 | Omya International AG | Alkoxysilane treatment of a calcium carbonate-comprising material |
| US11225578B2 (en) | 2016-01-14 | 2022-01-18 | Omya International Ag | Alkoxysilane treatment of a calcium carbonate-comprising material |
| JP2019510122A (en) * | 2016-02-02 | 2019-04-11 | クローノス インターナショナル インコーポレイテッドＫｒｏｎｏｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ， Ｉｎｃ． | Manufacture of matte paint and printing ink |
| WO2020230650A1 (en) * | 2019-05-10 | 2020-11-19 | テイカ株式会社 | Composite surface-treated inorganic powder and method for producing same, oil-based dispersion and cosmetic including said inorganic powder |
| CN115504497A (en) * | 2022-10-09 | 2022-12-23 | 陕西安东兴阳岗石科技有限公司 | Preparation method and application of low-oil-absorption-value nano calcium carbonate |
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