JP2005146007A - Luminescent pigment and its manufacturing method - Google Patents
Luminescent pigment and its manufacturing method Download PDFInfo
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- JP2005146007A JP2005146007A JP2003381293A JP2003381293A JP2005146007A JP 2005146007 A JP2005146007 A JP 2005146007A JP 2003381293 A JP2003381293 A JP 2003381293A JP 2003381293 A JP2003381293 A JP 2003381293A JP 2005146007 A JP2005146007 A JP 2005146007A
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Description
本発明は、光輝性顔料及びその製造方法に関するものである。 The present invention relates to a luster pigment and a method for producing the same.
従来より、天然マイカ、合成マイカ、鱗片状アルミナ等の鱗片状材料の表面に、酸化チタン層を設けた光輝性顔料が多くの分野で使用されている。これらの従来の光輝性顔料は光輝感が強く、かつ粒子感（キラキラとした光沢感）を有するものであり、パール光沢を付与する顔料として用いられている。 Conventionally, a luster pigment in which a titanium oxide layer is provided on the surface of a scaly material such as natural mica, synthetic mica, or scaly alumina has been used in many fields. These conventional glitter pigments have a strong glitter feeling and a grain feeling (shiny gloss feeling), and are used as pigments imparting pearl luster.
しかしながら、さらに高級感を有する意匠として、シルクのような深みのある落ち着いた緻密な輝きを示す意匠が求められている。このようなシルキー感を付与することができる光輝性顔料として、特許文献１においては、所定の形状の合成フッ素金雲母粒子の上に二酸化チタンなどの金属酸化物を被覆したシルキー光沢顔料が提案されている。
しかしながら、上記特許文献１に提案されたシルキー光沢顔料は、マイカを基材として用い、その表面に酸化チタン層を設けたものであるため、粒子感が強く、高級感がある意匠として従来より求められている良好なシルキー感を呈するものではなかった。 However, the silky luster pigment proposed in Patent Document 1 uses mica as a base material and is provided with a titanium oxide layer on the surface thereof. It did not exhibit a good silky feeling.
本発明は、良好なシルキー感を呈する光輝性顔料及びその製造方法を提供することにある。 An object of the present invention is to provide a luster pigment exhibiting a good silky feeling and a method for producing the same.
本発明に従う第１の局面は、薄片状チタン酸の薄膜が積層されており、薄膜間に空隙が存在していることを特徴としている。従って、このような光輝性顔料を例えば塗料中に配合すると、薄膜間の空隙には塗料中のポリマー成分または空気等の気体が存在することになる。ポリマー成分及び気体は、薄片状チタン酸の薄膜と異なる屈折率を有するものであるので、屈折率の異なる層が積層した構造となり、塗膜にシルキー感のある意匠性を付与することができる。 A first aspect according to the present invention is characterized in that flaky titanic acid thin films are laminated, and voids exist between the thin films. Therefore, when such a luster pigment is blended in a paint, for example, a polymer component in the paint or a gas such as air exists in the gaps between the thin films. Since the polymer component and the gas have a refractive index different from that of the flaky titanic acid thin film, the polymer component and the gas have a structure in which layers having different refractive indexes are laminated, and can impart a silky design to the coating film.
本発明に従う第２の局面は、層状チタン酸の薄膜が積層されており、薄膜間に高分子樹脂が挿入されていることを特徴としている。このような光輝性顔料は、例えば、薄片状チタン酸を高分子樹脂溶液中に分散した塗料を塗膜化し、これを粉砕することによって得ることができる。このようにして得られる光輝性顔料は、薄片状チタン酸の薄膜の表面が高分子樹脂により被覆されている。 A second aspect according to the present invention is characterized in that layered titanic acid thin films are laminated, and a polymer resin is inserted between the thin films. Such a luster pigment can be obtained, for example, by forming a coating film obtained by dispersing flaky titanic acid in a polymer resin solution and pulverizing it. The surface of the flaky titanic acid thin film is coated with a polymer resin in the bright pigment thus obtained.
本発明の第２の局面における光輝性顔料において、薄片状チタン酸の屈折率と高分子樹脂の屈折率は、一般に異なるものであり、このため、屈折率の異なる層が積層した構造を有する光輝性顔料となり、シルキー感を有する光輝性顔料となる。 In the glitter pigment according to the second aspect of the present invention, the refractive index of the flaky titanic acid and the refractive index of the polymer resin are generally different. Therefore, the glitter pigment has a structure in which layers having different refractive indices are laminated. It becomes a glossy pigment having a silky feeling.
薄片状チタン酸の薄膜間に挿入される高分子樹脂の量を制御することにより、薄膜間距離を所定の範囲に制御することができる。 By controlling the amount of the polymer resin inserted between the flaky titanic acid thin films, the distance between the thin films can be controlled within a predetermined range.
本発明の第２の局面において、薄片状チタン酸の薄膜間に挿入する高分子樹脂としては、特に規定されないが、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、ビニル樹脂、尿素樹脂、フッ素樹脂などを用いることができる。 In the second aspect of the present invention, the polymer resin to be inserted between the flaky titanic acid thin films is not particularly defined, but is an acrylic resin, polyurethane resin, epoxy resin, polyester resin, melamine resin, phenol resin, vinyl resin. Urea resin, fluorine resin, or the like can be used.
本発明において用いる薄片状チタン酸は、層状チタン酸塩を酸処理して得られるものであることが好ましい。このような原料の層状チタン酸塩の例としては、レピドクロサイト型Ｋ0.5〜0.7Ｌｉ0.27Ｔｉ1.6Ｏ3.85〜3.95が挙られる。 The flaky titanic acid used in the present invention is preferably obtained by acid treatment of a layered titanate. As an example of such a raw material layered titanate, lepidocrocite type K 0.5 to 0.7 Li 0.27 Ti 1.6 O 3.85 to 3.95 can be mentioned.
また、このような層状チタン酸塩の酸処理条件としては、５重量％スラリーに対し、塩酸を用いてｐＨ１、４０℃とし、１２時間攪拌することが好ましいが、この限りではない。 In addition, the acid treatment conditions for such a layered titanate are preferably set to pH 1 and 40 ° C. using hydrochloric acid with respect to a 5 wt% slurry, and stirred for 12 hours, but this is not restrictive.
本発明の製造方法は、上記本発明の第２の局面に従う光輝性顔料を製造することができる方法であり、薄片状チタン酸を高分子樹脂溶液中に分散して塗料を調製し、該塗料を塗布して塗膜を作製し、該塗膜を粉砕することを特徴としている。 The production method of the present invention is a method capable of producing the luster pigment according to the second aspect of the present invention, wherein a paint is prepared by dispersing flaky titanic acid in a polymer resin solution, and the paint It is characterized in that a coating film is prepared by coating and pulverizing the coating film.
高分子樹脂としては、上記の高分子樹脂を用いることができ、溶液の溶媒としては、高分子樹脂を溶解できるものであればよい。高分子樹脂溶液の濃度としては、特に規定されないが、１重量％〜９０重量％、好ましくは１０重量％〜４０重量％である。 As the polymer resin, the above-described polymer resin can be used, and any solvent can be used as long as it can dissolve the polymer resin. The concentration of the polymer resin solution is not particularly defined, but is 1% to 90% by weight, preferably 10% to 40% by weight.
また、薄片状チタン酸を高分子溶液中に分散する方法としては、ボールミル、ディスパーミル、３本ロールミルなどを用いる方法を挙げることができる。 Examples of a method for dispersing flaky titanic acid in a polymer solution include a method using a ball mill, a disper mill, a three roll mill, and the like.
高分子樹脂溶液中に添加する薄片状チタン酸の量は、薄片状チタン酸の薄膜間に挿入する高分子樹脂の量や、高分子樹脂溶液中の高分子樹脂の濃度などを考慮して適宜選択される。 The amount of flaky titanic acid added to the polymer resin solution is appropriately determined in consideration of the amount of the polymer resin inserted between the flaky titanic acid thin films and the concentration of the polymer resin in the polymer resin solution. Selected.
塗料を塗布する基材としては、塗膜が容易に剥離し得る基材であることが好ましい。このような基材としては、ＰＥＴフィルム、ＰＰフィルムなど、フレキシブルな基材がよい。 The substrate to which the paint is applied is preferably a substrate from which the coating film can be easily peeled off. Such a substrate is preferably a flexible substrate such as a PET film or a PP film.
塗膜を粉砕する方法としては、ディスクミル、ピンミル、ローラミル、ボールミル、振動ボールミル等を用いることができ、さらに乾式気流分級機にて分級する。 As a method for pulverizing the coating film, a disk mill, a pin mill, a roller mill, a ball mill, a vibrating ball mill, or the like can be used, and further, classification is performed with a dry air classifier.
図１〜図３は、本発明の光輝性顔料を説明するための模式図である。図１は、本発明の第１の局面に従う薄片状チタン酸を示す模式図である。図１に示すように、薄膜１が積層された構造を有しており、薄膜１間には空隙２が存在している。 1-3 is a schematic diagram for demonstrating the luster pigment of this invention. FIG. 1 is a schematic diagram showing flaky titanic acid according to the first aspect of the present invention. As shown in FIG. 1, the thin film 1 has a laminated structure, and a gap 2 exists between the thin films 1.
図１に示す薄片状チタン酸は、例えば、図３に示す層状チタン酸塩３を酸処理することにより製造することができる。層状チタン酸塩３が層状チタン酸アルカリ塩である場合、酸処理により、層間に存在するアルカリを脱離することにより、図１に示すような薄片状チタン酸とすることができる。 The flaky titanic acid shown in FIG. 1 can be produced, for example, by subjecting the layered titanate 3 shown in FIG. 3 to acid treatment. When the layered titanate 3 is a layered alkali titanate, flaky titanic acid as shown in FIG. 1 can be obtained by removing the alkali present between the layers by acid treatment.
図２は、本発明の第２の局面に従う光輝性顔料を示す模式図である。図２に示すように、薄膜１間には高分子樹脂２が存在しており、この高分子樹脂２により薄膜１間の距離が制御されている。 FIG. 2 is a schematic diagram showing a luster pigment according to the second aspect of the present invention. As shown in FIG. 2, a polymer resin 2 exists between the thin films 1, and the distance between the thin films 1 is controlled by the polymer resin 2.
本発明によれば、良好なシルキー感を付与することができる光輝性顔料とすることができる。 According to this invention, it can be set as the luster pigment which can provide a favorable silky feeling.
以下、本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能なものである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented without departing from the scope of the present invention. .
（実施例１）
〔光輝性顔料（薄片状チタン酸）の調製〕
Ｋ0.5〜0.7Ｌｉ0.27Ｔｉ1.6Ｏ3.85〜3.95の組成式で表される層状チタン酸塩４０ｇを、０．５規定の塩酸６００ｇ中に入れ、４０℃にて１２時間撹拌した。濾過、水洗し、１１０℃で乾燥し、薄片状チタン酸を得た。
(Example 1)
[Preparation of luster pigment (flaky titanic acid)]
40 g of layered titanate represented by a composition formula of K 0.5 to 0.7 Li 0.27 Ti 1.6 O 3.85 to 3.95 was placed in 600 g of 0.5 N hydrochloric acid and stirred at 40 ° C. for 12 hours. Filtration, washing with water and drying at 110 ° C. gave flaky titanic acid.
図４は薄片状チタン酸を示す走査型電子顕微鏡（ＳＥＭ）写真である。図４に示すように、薄片状チタン酸は、薄膜が積層された構造を有しており、薄膜間には空隙が存在している。 FIG. 4 is a scanning electron microscope (SEM) photograph showing flaky titanic acid. As shown in FIG. 4, flaky titanic acid has a structure in which thin films are laminated, and there are voids between the thin films.
〔塗料の調製〕
得られた光輝性顔料を用い、塗料を作製した。塗料の樹脂成分としてポリウレタン樹脂を用い、溶媒（分散媒）として水を用い、４０重量％の樹脂溶液を調製した。この高分子樹脂溶液に、ＰＷＣ１０％となるように光輝性顔料を添加して塗料を作製した。
[Preparation of paint]
A paint was prepared using the resulting bright pigment. A polyurethane resin was used as a resin component of the paint, and water was used as a solvent (dispersion medium) to prepare a 40% by weight resin solution. A glittering pigment was added to this polymer resin solution so that the PWC would be 10% to prepare a coating material.
〔塗膜の作製〕
上記のようにして得られた塗料を、白色塗板の上に乾燥膜厚が２０μｍとなるように塗装し、さらにこの上にクリア塗料（クリア塗料は塗料の調製で用いたものと同じポリウレタン樹脂を用いた）を乾燥膜厚４０μｍとなるように塗装して塗装サンプルを作製した。
[Preparation of coating film]
The paint obtained as described above is applied on a white coated plate so that the dry film thickness is 20 μm, and further a clear paint (the clear paint is the same polyurethane resin used in the preparation of the paint). Used) was coated to a dry film thickness of 40 μm to prepare a coated sample.
（比較例１）
光輝性顔料として、従来のパール顔料であるチタニア被覆マイカ（商品名「イリオジン１２０」、メルク社製）を用いる以外は、上記実施例１と同様にして塗料を作製し、この塗料を用いて塗装サンプルを作製した。
(Comparative Example 1)
A paint was prepared in the same manner as in Example 1 except that titania-coated mica (trade name “Iriodin 120”, manufactured by Merck & Co., Inc.), which is a conventional pearl pigment, was used as the glitter pigment, and this paint was used for coating. A sample was made.
（比較例２）
光輝性顔料として、従来のパール顔料であるチタニア被覆アルミナ（商品名「シラリック」、メルク社製）を用いる以外は、上記実施例１と同様にして塗料を作製し、この塗料を用いて塗装サンプルを作製した。
(Comparative Example 2)
A paint was prepared in the same manner as in Example 1 except that titania-coated alumina (trade name “Silary”, manufactured by Merck & Co., Inc.), which is a conventional pearl pigment, was used as the glitter pigment, and a paint sample was prepared using this paint. Was made.
〔塗膜の評価〕
上記の実施例１、比較例１及び２のそれぞれの塗装サンプルについて、白色度、光輝感、及びシルキー感を評価した。
[Evaluation of coating film]
About each coating sample of said Example 1 and Comparative Examples 1 and 2, whiteness, a glittering feeling, and a silky feeling were evaluated.
白色度については、色彩色度計（ミノルタ社製「ＣＲ−３００」）を用いて、ｂ値を測定した。ｂ値の値に応じて、以下のようにして評価した。
△；ｂ値が３以上
○；ｂ値が２未満
About whiteness, b value was measured using the color chromaticity meter ("CR-300" by Minolta Co., Ltd.). Depending on the value of b, the evaluation was performed as follows.
Δ: b value is 3 or more ○; b value is less than 2
光輝感については、以下の基準で評価した。
◎：非常に高い輝度を有する
○：やや高い輝度を有する
The glitter was evaluated according to the following criteria.
◎: Very high brightness ○: Slightly high brightness
シルキー感については、以下の基準で評価した。
○：絹のような意匠性を有する
△：わずかに絹のような意匠性を有する
×：絹の意匠が全くない
評価結果を表１に示す。
The silky feeling was evaluated according to the following criteria.
○: Has a design like silk Δ: Has a design like a little silk ×: No silk design The evaluation results are shown in Table 1.
（実施例２）
〔光輝性顔料の調製〕
Ｋ0.5〜0.7Ｌｉ0.27Ｔｉ1.6Ｏ3.85〜3.95の組成式で表される層状チタン酸塩４０ｇを、０．５規定の塩酸６００ｇ中に入れ、４０℃にて１２時間撹拌した。濾過、水洗した後、１８００ｇの脱イオン交換水に分散させ、これに、ｎ−プロピルアミン２７ｇを脱イオン交換水６００ｇに希釈した溶液を添加した。４０℃で２時間撹拌した後、０．５規定の塩酸をｐＨ１になるまで滴下した。さらに濾過、水洗し、１１０℃で乾燥し、薄片状チタン酸を得た。得られた薄片状チタン酸を、ＰＷＣ６０％となるように高分子樹脂溶液中に添加し混合した。高分子樹脂としてはポリウレタン塗料を用い、溶媒（分散媒）として水を用い、４０重量％のエマルジョンを調製した。
(Example 2)
(Preparation of glitter pigment)
40 g of layered titanate represented by a composition formula of K 0.5 to 0.7 Li 0.27 Ti 1.6 O 3.85 to 3.95 was placed in 600 g of 0.5 N hydrochloric acid and stirred at 40 ° C. for 12 hours. After filtering and washing with water, it was dispersed in 1800 g of deionized water, and a solution obtained by diluting 27 g of n-propylamine in 600 g of deionized water was added thereto. After stirring at 40 ° C. for 2 hours, 0.5 N hydrochloric acid was added dropwise until the pH reached 1. Furthermore, it filtered, washed with water, and dried at 110 degreeC, and flaky titanic acid was obtained. The obtained flaky titanic acid was added and mixed in the polymer resin solution so that the PWC was 60%. A polyurethane paint was used as the polymer resin, and water was used as the solvent (dispersion medium) to prepare a 40% by weight emulsion.
得られた塗料をＰＥＴフィルムの上に、乾燥膜厚が２０μｍとなるように塗布し、乾燥して、塗膜を得た。図５は、この塗膜の断面を示す走査型電子顕微鏡（ＳＥＭ）写真である。図５においては、観察しやすいように酸素プラズマを１時間照射することにより樹脂を除去している。白く見える部分が薄片状チタン酸の薄膜であり、黒く見える部分が樹脂の存在していた部分である。 The obtained coating material was applied onto a PET film so that the dry film thickness was 20 μm and dried to obtain a coating film. FIG. 5 is a scanning electron microscope (SEM) photograph showing a cross section of the coating film. In FIG. 5, the resin is removed by irradiating with oxygen plasma for 1 hour for easy observation. The part that appears white is a flaky titanic acid thin film, and the part that appears black is the part where the resin was present.
上記の塗膜を、ボールミルにより粉砕し、気流分級機により分級して、光輝性顔料を得た。 The coating film was pulverized with a ball mill and classified with an airflow classifier to obtain a luster pigment.
〔塗料の調製〕
上記のようにして得られた光輝性顔料を用い、実施例１と同様にして塗料を作製し、この塗料を用いて実施例１と同様にして塗装サンプルを作製した。
[Preparation of paint]
A paint was prepared in the same manner as in Example 1 using the bright pigment obtained as described above, and a paint sample was prepared in the same manner as in Example 1 using this paint.
〔塗膜の評価〕
得られた実施例２の塗装サンプルについて、実施例１と同様にして白色度、光輝感、及びシルキー感を評価した。評価結果を表２に示す。なお、表２においては、比較例１及び比較例２の評価結果も併せて示している。
[Evaluation of coating film]
The resulting painted sample of Example 2 was evaluated for whiteness, glitter, and silky feeling in the same manner as in Example 1. The evaluation results are shown in Table 2. In Table 2, the evaluation results of Comparative Example 1 and Comparative Example 2 are also shown.
１…薄膜
２…空隙
３…層状チタン酸塩
４…高分子樹脂
DESCRIPTION OF SYMBOLS 1 ... Thin film 2 ... Air gap 3 ... Layered titanate 4 ... Polymer resin
Claims (7)
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| JP2003381293A JP4653947B2 (en) | 2003-11-11 | 2003-11-11 | Bright pigment and method for producing the same |
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| JP2003381293A JP4653947B2 (en) | 2003-11-11 | 2003-11-11 | Bright pigment and method for producing the same |
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| JP2005146007A true JP2005146007A (en) | 2005-06-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023680A1 (en) * | 2005-08-25 | 2007-03-01 | Otsuka Chemical Co., Ltd. | Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom |
| JP2012241072A (en) * | 2011-05-18 | 2012-12-10 | Toyota Central R&D Labs Inc | Photoluminescent coating composition, photoluminescent resin film, and laminated coating film |
| JP2015007173A (en) * | 2013-06-25 | 2015-01-15 | トヨタ自動車株式会社 | Photoluminescent coating composition, photoluminescent coating film and laminated coating film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212211A (en) * | 1997-01-29 | 1998-08-11 | Natl Inst For Res In Inorg Mater | Cosmetic material |
| JP2001270022A (en) * | 2000-03-24 | 2001-10-02 | National Institute For Materials Science | Titania ultrathin film and method of manufacture it |
| WO2003016218A1 (en) * | 2001-08-20 | 2003-02-27 | Otsuka Chemical Co., Ltd. | Layered titanic acid, lamellar titanic acid, lamellar titanium oxide and method for producing lamellar titanic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212211A (en) * | 1997-01-29 | 1998-08-11 | Natl Inst For Res In Inorg Mater | Cosmetic material |
| JP2001270022A (en) * | 2000-03-24 | 2001-10-02 | National Institute For Materials Science | Titania ultrathin film and method of manufacture it |
| WO2003016218A1 (en) * | 2001-08-20 | 2003-02-27 | Otsuka Chemical Co., Ltd. | Layered titanic acid, lamellar titanic acid, lamellar titanium oxide and method for producing lamellar titanic acid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023680A1 (en) * | 2005-08-25 | 2007-03-01 | Otsuka Chemical Co., Ltd. | Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom |
| JP2007055859A (en) * | 2005-08-25 | 2007-03-08 | Otsuka Chemical Co Ltd | Flake-like titanate having polymerizable functional group, its suspension liquid and coating film of the same |
| US8343455B2 (en) | 2005-08-25 | 2013-01-01 | Otsuka Chemical Co., Ltd. | Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom |
| KR101305654B1 (en) | 2005-08-25 | 2013-09-09 | 오츠카 가가쿠 가부시키가이샤 | Flaky titanic acid having polymerizable functional groups, suspension of the same, and coating films made therefrom |
| JP2012241072A (en) * | 2011-05-18 | 2012-12-10 | Toyota Central R&D Labs Inc | Photoluminescent coating composition, photoluminescent resin film, and laminated coating film |
| JP2015007173A (en) * | 2013-06-25 | 2015-01-15 | トヨタ自動車株式会社 | Photoluminescent coating composition, photoluminescent coating film and laminated coating film |
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| JP4653947B2 (en) | 2011-03-16 |
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