WO2014141892A1 - White pigment for coatings - Google Patents

White pigment for coatings Download PDF

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Publication number
WO2014141892A1
WO2014141892A1 PCT/JP2014/054895 JP2014054895W WO2014141892A1 WO 2014141892 A1 WO2014141892 A1 WO 2014141892A1 JP 2014054895 W JP2014054895 W JP 2014054895W WO 2014141892 A1 WO2014141892 A1 WO 2014141892A1
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Prior art keywords
titanium oxide
kaolin
refractive index
particles
white pigment
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PCT/JP2014/054895
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French (fr)
Japanese (ja)
Inventor
達朗 村上
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水澤化学工業株式会社
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Priority to JP2015505385A priority Critical patent/JP6352242B2/en
Publication of WO2014141892A1 publication Critical patent/WO2014141892A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a white pigment for paint, and more particularly to a white pigment for paint that can be used as a substitute for titanium oxide.
  • Titanium oxide has been widely used as a white pigment for paints because it has a considerably higher refractive index than a resin for paints and thus has a high hiding power. However, since titanium oxide is extremely expensive, an alternative is demanded.
  • Patent Document 1 a powder composition in which various inorganic fine particles are mixed with titanium oxide fine particles is known (for example, Patent Document 1).
  • a powder composition is used as a filler blended in various resins and is not intended for use as a pigment for paints.
  • surface treatment etc. are made
  • an object of the present invention is to provide a white pigment for paint that has a high refractive index of titanium oxide without impairing it and can be used as a substitute for the titanium oxide pigment.
  • the present inventors surprisingly used kaolin ⁇ Al 2 Si 2 O 5 (OH) 4 ⁇ having a considerably lower refractive index than titanium oxide as a main component, By combining this with a small amount of titanium oxide, it was found that an inexpensive white pigment for paints having a refractive index equivalent to that of titanium oxide was obtained, and the present invention was completed.
  • a white pigment for paint which comprises 100 parts by weight of kaolin particles and 25 to 96 parts by weight of titanium oxide particles and has a refractive index of 1.78 or more.
  • the white pigment for paint of the present invention (1) showing a concealment ratio of 95% or more (JIS K 5101-4: 2004); (2) At least a part of the kaolin particles is fired; Is preferred.
  • the white pigment for paints of the present invention has a refractive index in the range of 1.78 or more, particularly 2.72 or less, which is equivalent to the refractive index of titanium oxide (about 2.7), and kaolin particles. Is the subject. Kaolin is a naturally occurring flaky mineral and is therefore very inexpensive. As understood from this, the white pigment for paint of the present invention is extremely useful as a substitute for the titanium oxide white pigment.
  • kaolin is considerably white compared to mica and the like, for example, the whiteness of the liquid dispersed in water is extremely high.
  • the refractive index of kaolin is about 1.6, which is almost the same as the refractive index (about 1.5) of a coating resin (for example, urethane resin), for example. That is, it can be said that kaolin has almost no hiding power when blended in a resin, and it has never been considered at all to use kaolin as a substitute for a titanium oxide white pigment according to conventional common sense.
  • the white pigment for paints of the present invention is composed mainly of kaolin and exhibits a refractive index equivalent to that of titanium oxide.
  • the concealment rate JIS K 5101-4
  • 2004 is 95% or more, the same level as titanium oxide, and does not show the characteristics of kaolin, which is surprising.
  • the main component is kaolin having a refractive index of about 1.6, but a refractive index comparable to that of titanium oxide is obtained because the surface of kaolin particles is covered with a small amount of titanium oxide particles.
  • the white pigment for paint of the present invention reflects the refractive index of titanium oxide.
  • the white pigment for paint according to the present invention is a particle mixture containing kaolin particles and titanium oxide particles, and 25 to 96 parts by mass, particularly 25 to 43 parts by mass of titanium oxide particles with respect to 100 parts by mass of kaolin particles. Include in quantity. If the amount of the titanium oxide particles is less than the above range, the surface of the kaolin particles cannot be sufficiently covered. Therefore, the refractive index is greatly different from that of titanium oxide, and the hiding power when blended with a coating resin is low. It will drop greatly. Moreover, when there is more quantity of a titanium oxide particle than the said range, the cost advantage of a kaolin particle will be impaired and the advantage as a substitute of a titanium oxide will be impaired.
  • the kaolin particles and the titanium oxide particles are used in the amounts as described above, and the surface of the kaolin particles may be coated with the titanium oxide particles. is necessary.
  • kaolin particles and titanium oxide particles are mixed and then mechanically pulverized with a high shear force under dry conditions, for example, dry pulverization using a jet mill, and the amount is about 0.1 to 0.7 ⁇ m.
  • the particle size may be adjusted to the particle size. That is, the coating as described above is realized by rubbing the titanium oxide particles on the surface of the kaolin particles by a high degree of mechanical pulverization. Obtainable.
  • Kaolin particles and titanium oxide particles only exist independently of each other. That is, as shown in a comparative example described later, in this case, only the refractive index of kaolin and the refractive index of titanium oxide are observed.
  • the above surface coating cannot be performed. If the titanium oxide particles are dispersed in water, they aggregate and cannot be used for surface coating of kaolin particles.
  • the kaolin particles described above are collected from nature, and can be used as appropriate after roughly removing the impurities to an appropriate size, but at least a part of the kaolin particles, preferably It is good to use what the whole quantity baked at the temperature of 600 degreeC or more. By such firing, the particle strength can be increased, the surface coating of the titanium oxide particles by mechanical pulverization described above can be performed stably, and the coating resin can be easily blended.
  • the white pigment for paints of the present invention thus obtained can be mixed with a resin in exactly the same manner as the titanium oxide pigment, whereby a white color with an extremely high hiding power can be realized.
  • this white pigment is mainly composed of inexpensive kaolin particles, the cost can be greatly reduced as compared with the titanium oxide pigment, and it is extremely useful as a substitute for the titanium oxide pigment.
  • Example 1 A 2 liter sealed container is charged with 70 g of commercially available kaolin (particle size 0.2 ⁇ m), 70 g of calcined kaolin (particle size 0.8 ⁇ m), and 60 g of titanium oxide (particle size 0.14 ⁇ m), and shaken sufficiently to provide a simple mixture. Got. Subsequently, dry rubbing was performed using a jet mill to obtain a powder sample.
  • Example 2 A powder sample was obtained in the same manner as in Example 1 except that 80 g of commercially available kaolin, 80 g of calcined kaolin, and 40 g of titanium oxide were used.
  • Example 3 A powder sample was obtained in the same manner as in Example 1 except that 51 g of commercially available kaolin, 51 g of calcined kaolin, and 98 g of titanium oxide were used.
  • Example 1 A simple mixture was directly used as a powder sample in the same manner as in Example 1 except that dry rubbing with a jet mill was not performed.
  • Example 2 A powder sample was obtained in the same manner as in Example 1 except that 90 g of commercially available kaolin, 90 g of calcined kaolin and 20 g of titanium oxide were used.
  • the obtained sample was measured by the following method. The results are shown in Tables 1 and 2.
  • surface is a value with respect to 100 mass parts of kaolins.
  • Concealment rate JIS K 5101-4: 2004 Pigment test method-Part 4 Concealment power-Concealment rate test paper method
  • 25 g of powder sample was dispersed in 50 g of clear urethane paint, Applied.
  • the concealment rate was calculated
  • Example 2 As shown in Table 1, the refractive index of Example 1 subjected to dry rubbing greatly exceeded 1.78. As a result, the coating concealment ratio was also high, and the coating film was smooth and glossy.
  • the lower limit of the amount of titanium oxide that can maintain a concealment ratio of 95% or more with a refractive index greatly exceeding 1.78 is 25 parts by mass (Example 2), and the upper limit is 96 parts by mass (Example 3).
  • Example 3 Particularly, in Example 3, 51% of the pigment component was kaolin, but the hiding rate was the same as that of the titanium oxide single paint as a comparative control (Comparative Example 3 in Table 2).
  • Comparative Example 1 of Table 2 when the same amount of titanium oxide as in Example 1 was employed and dry rubbing was not performed, particles having a refractive index of 1.55 and 1.78 were used. More than a single particle was observed alone. At this time, agglomeration of the powder sample was observed in the paint, and it was not possible to uniformly apply to the concealment rate test paper, and the concealment rate could not be evaluated. The coating film was greatly impaired in smoothness, did not show gloss, and could not be used as a paint pigment.
  • Comparative Example 2 in Table 2 when the compounding amount of titanium oxide is 11 parts by mass, the refractive index decreases to 1.57, which is almost equivalent to kaolin, even when dry-type rubbing is performed.
  • the factor for improving the refractive index and dispersibility of the kaolin particles is the titanium oxide coating effect on the kaolin surface, and the effectiveness of dry rubbing with a jet mill has been clarified. Further, it was found that the amount of titanium oxide whose refractive index is improved to a level comparable to that of titanium oxide is in the range of 25 to 96 parts by mass.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

Provided is a white pigment for coatings, which still retains a high refractive index of titanium oxide contained therein and can be used as an alternative to a titanium oxide pigment. The white pigment for coatings according to the present invention comprises 100 parts by mass of kaolin particles and 25 to 96 parts by mass of titanium oxide particles, and is characterized by having a refractive index of 1.78 or more.

Description

塗料用白色顔料White pigment for paint
　本発明は、塗料用白色顔料に関するものであり、より詳細には、酸化チタンの代替品となり得る塗料用白色顔料に関する。 The present invention relates to a white pigment for paint, and more particularly to a white pigment for paint that can be used as a substitute for titanium oxide.
　酸化チタンは、塗料用の樹脂と比較して屈折率がかなり高く、従って高い隠ぺい力を有していることから、塗料用の白色顔料として従来から広く使用されている。
　しかしながら、酸化チタンは極めて高価であるため、その代替品が求められている。 Titanium oxide has been widely used as a white pigment for paints because it has a considerably higher refractive index than a resin for paints and thus has a high hiding power.
However, since titanium oxide is extremely expensive, an alternative is demanded.
　一方、酸化チタン微粒子に種々の無機微粒子を混合した粉体組成物が知られている（例えば特許文献１）。
　しかるに、このような粉体組成物は、種々の樹脂に配合するフィラーなどとして使用されるものであり、塗料用の顔料としての使用を目的とするものではない。また、表面処理などがなされているため、白色顔料として使用される酸化チタンの代替品として使用することはできない。表面処理剤によって、酸化チタンの高い屈折率が損なわれてしまうためである。 On the other hand, a powder composition in which various inorganic fine particles are mixed with titanium oxide fine particles is known (for example, Patent Document 1).
However, such a powder composition is used as a filler blended in various resins and is not intended for use as a pigment for paints. Moreover, since surface treatment etc. are made | formed, it cannot use as a substitute of the titanium oxide used as a white pigment. This is because the high refractive index of titanium oxide is impaired by the surface treatment agent.
特開平９－９９２４６号公報JP-A-9-99246
　従って、本発明の目的は、酸化チタンの高い屈折率を損なわずに有しており、酸化チタン顔料の代替品となり得る塗料用白色顔料を提供することにある。 Therefore, an object of the present invention is to provide a white pigment for paint that has a high refractive index of titanium oxide without impairing it and can be used as a substitute for the titanium oxide pigment.
　本発明者等は、酸化チタンの代替品について種々検討した結果、意外にも酸化チタンに比して屈折率のかなり低いカオリン｛Ａｌ２Ｓｉ２Ｏ５（ＯＨ）４｝を主成分として用い、これを少量の酸化チタンと組み合わせることにより、酸化チタンと同等の屈折率を示し且つ安価な塗料用白色顔料が得られることを見出し、本発明を完成させるに至った。 As a result of various investigations on alternatives to titanium oxide, the present inventors surprisingly used kaolin {Al 2 Si 2 O 5 (OH) 4 } having a considerably lower refractive index than titanium oxide as a main component, By combining this with a small amount of titanium oxide, it was found that an inexpensive white pigment for paints having a refractive index equivalent to that of titanium oxide was obtained, and the present invention was completed.
　即ち、本発明によれば、１００質量部のカオリン粒子と、２５～９６質量部の酸化チタン粒子とからなり、屈折率が１．７８以上であることを特徴とする塗料用白色顔料が提供される。
　本発明の塗料用白色顔料においては、
（１）９５％以上の隠ぺい率（ＪＩＳ　Ｋ　５１０１－４：２００４）を示すこと、
（２）前記カオリン粒子の少なくとも一部が焼成されたものであること、
が好ましい。 That is, according to the present invention, there is provided a white pigment for paint, which comprises 100 parts by weight of kaolin particles and 25 to 96 parts by weight of titanium oxide particles and has a refractive index of 1.78 or more. The
In the white pigment for paint of the present invention,
(1) showing a concealment ratio of 95% or more (JIS K 5101-4: 2004);
(2) At least a part of the kaolin particles is fired;
Is preferred.
　本発明の塗料用白色顔料は、屈折率が１．７８以上、特に２．７２以下の範囲にあり、これは、酸化チタンの屈折率（約２．７）と同等であり、しかも、カオリン粒子を主体としている。カオリンは、天然に産出する薄片構造の鉱物であり、従って、極めて安価である。このことから理解されるように、本発明の塗料用白色顔料は、酸化チタン白色顔料の代替品として極めて有用である。 The white pigment for paints of the present invention has a refractive index in the range of 1.78 or more, particularly 2.72 or less, which is equivalent to the refractive index of titanium oxide (about 2.7), and kaolin particles. Is the subject. Kaolin is a naturally occurring flaky mineral and is therefore very inexpensive. As understood from this, the white pigment for paint of the present invention is extremely useful as a substitute for the titanium oxide white pigment.
　ところで、カオリンは、雲母などと比較してかなり白く、例えば水に分散させた液の白色度は極めて高い。しかしながら、カオリンの屈折率は約１．６であり、例えば塗料用樹脂（例えばウレタン樹脂）の屈折率（約１．５）とほぼ同等である。即ち、カオリンは、樹脂に配合したときの隠ぺい力はほとんど無いといってよく、従来の常識では、カオリンを酸化チタン白色顔料の代替に用いることは全く考えられなかったのである。
　しかるに、本発明の塗料用白色顔料は、カオリンを主体としていながら、酸化チタンと同等の屈折率を示し、後述する実施例にも示されているように、その隠ぺい率（ＪＩＳ　Ｋ　５１０１－４：２００４）も９５％以上と酸化チタンと同レベルの高さを示し、カオリンの特性を示さず、これは驚くべきことである。 By the way, kaolin is considerably white compared to mica and the like, for example, the whiteness of the liquid dispersed in water is extremely high. However, the refractive index of kaolin is about 1.6, which is almost the same as the refractive index (about 1.5) of a coating resin (for example, urethane resin), for example. That is, it can be said that kaolin has almost no hiding power when blended in a resin, and it has never been considered at all to use kaolin as a substitute for a titanium oxide white pigment according to conventional common sense.
However, the white pigment for paints of the present invention is composed mainly of kaolin and exhibits a refractive index equivalent to that of titanium oxide. As shown in the examples described later, the concealment rate (JIS K 5101-4) is also shown. : 2004) is 95% or more, the same level as titanium oxide, and does not show the characteristics of kaolin, which is surprising.
　なお、本発明において、屈折率が約１．６のカオリンを主体としていながら、酸化チタンと同程度の屈折率が得られているのは、カオリン粒子の表面が少量の酸化チタン粒子によって被覆されており、この結果、本発明の塗料用白色顔料には、酸化チタンの屈折率が反映されているからである。 In the present invention, the main component is kaolin having a refractive index of about 1.6, but a refractive index comparable to that of titanium oxide is obtained because the surface of kaolin particles is covered with a small amount of titanium oxide particles. As a result, the white pigment for paint of the present invention reflects the refractive index of titanium oxide.
　本発明の塗料用白色顔料は、カオリン粒子と酸化チタン粒子とを含んだ粒子混合物であり、１００質量部のカオリン粒子に対し、酸化チタン粒子を２５～９６質量部、特に２５～４３質量部の量で含む。酸化チタン粒子の量が上記範囲よりも少ないと、カオリン粒子の表面を十分に被覆することができず、従って、屈折率が酸化チタンと大きく異なってしまい、塗料樹脂に配合したときの隠ぺい力が大きく低下してしまう。また、酸化チタン粒子の量が上記範囲よりも多いと、カオリン粒子のコスト的なメリットが損なわれてしまい、酸化チタンの代替としての利点が損なわれてしまう。 The white pigment for paint according to the present invention is a particle mixture containing kaolin particles and titanium oxide particles, and 25 to 96 parts by mass, particularly 25 to 43 parts by mass of titanium oxide particles with respect to 100 parts by mass of kaolin particles. Include in quantity. If the amount of the titanium oxide particles is less than the above range, the surface of the kaolin particles cannot be sufficiently covered. Therefore, the refractive index is greatly different from that of titanium oxide, and the hiding power when blended with a coating resin is low. It will drop greatly. Moreover, when there is more quantity of a titanium oxide particle than the said range, the cost advantage of a kaolin particle will be impaired and the advantage as a substitute of a titanium oxide will be impaired.
　本発明においては、酸化チタンと同等の屈折率を発現させるためには、上記のような量でカオリン粒子と酸化チタン粒子とを使用するとともに、カオリン粒子の表面を酸化チタン粒子で被覆することが必要である。 In the present invention, in order to express a refractive index equivalent to that of titanium oxide, the kaolin particles and the titanium oxide particles are used in the amounts as described above, and the surface of the kaolin particles may be coated with the titanium oxide particles. is necessary.
　このためには、カオリン粒子と酸化チタン粒子とを混合した後、乾式下で高せん断力での機械的粉砕、例えばジェットミルを使用しての乾式粉砕を行って０．１～０．７μｍ程度の粒子径に粒度調整すればよい。即ち、高度の機械的粉砕によってカオリン粒子の表面に酸化チタン粒子を摺擦することによって上記のような被覆を実現し、１．７８以上、特に１．７８～２．７２の範囲の屈折率を得ることができる。 For this purpose, kaolin particles and titanium oxide particles are mixed and then mechanically pulverized with a high shear force under dry conditions, for example, dry pulverization using a jet mill, and the amount is about 0.1 to 0.7 μm. The particle size may be adjusted to the particle size. That is, the coating as described above is realized by rubbing the titanium oxide particles on the surface of the kaolin particles by a high degree of mechanical pulverization. Obtainable.
　例えば、カオリン粒子と酸化チタン粒子とのそれぞれについて予め機械的粉砕し、その後に両者を混合したのでは、これらが再凝集しやすいだけでなく、上記のような表面被覆を行うことができず、カオリン粒子と酸化チタン粒子とがそれぞれ独立に存在しているに過ぎないものとなる。即ち、後述する比較例に示されているように、この場合には、カオリンの屈折率と酸化チタンの屈折率とが観測されるに過ぎない。 For example, when mechanically pulverized in advance for each of kaolin particles and titanium oxide particles, and then mixing both, they are not only easily re-aggregated, but cannot be surface coated as described above, Kaolin particles and titanium oxide particles only exist independently of each other. That is, as shown in a comparative example described later, in this case, only the refractive index of kaolin and the refractive index of titanium oxide are observed.
　また、カオリン粒子と酸化チタン粒子とを湿式粉砕に供した場合にも、上記のような表面被覆を行うことができない。酸化チタン粒子を水に分散させると凝集してしまうため、カオリン粒子の表面被覆など、到底、行うことができない。 Further, even when the kaolin particles and the titanium oxide particles are subjected to wet pulverization, the above surface coating cannot be performed. If the titanium oxide particles are dispersed in water, they aggregate and cannot be used for surface coating of kaolin particles.
　本発明において、上述したカオリン粒子は、天然から採取され、適宜、不純物を除いたものを適宜の大きさに粗粉砕したものをそのまま使用することもできるが、少なくともカオリン粒子の一部、好ましくは全量が、６００℃以上の温度で焼成したものを使用するのがよい。このような焼成により、粒子強度を高め、上述した機械的粉砕による酸化チタン粒子の表面被覆を安定に行うことができ、また、塗料用樹脂の配合も容易に行うことができる。 In the present invention, the kaolin particles described above are collected from nature, and can be used as appropriate after roughly removing the impurities to an appropriate size, but at least a part of the kaolin particles, preferably It is good to use what the whole quantity baked at the temperature of 600 degreeC or more. By such firing, the particle strength can be increased, the surface coating of the titanium oxide particles by mechanical pulverization described above can be performed stably, and the coating resin can be easily blended.
　このようにして得られる本発明の塗料用白色顔料として、酸化チタン顔料と全く同様にして樹脂に配合することにより、極めて隠ぺい力の高い白色を実現することができる。しかも、この白色顔料は、安価なカオリン粒子を主体としているため、酸化チタン顔料に比して大幅なコストダウンを図ることができ、酸化チタン顔料の代替品として、極めて有用である。 The white pigment for paints of the present invention thus obtained can be mixed with a resin in exactly the same manner as the titanium oxide pigment, whereby a white color with an extremely high hiding power can be realized. In addition, since this white pigment is mainly composed of inexpensive kaolin particles, the cost can be greatly reduced as compared with the titanium oxide pigment, and it is extremely useful as a substitute for the titanium oxide pigment.
　本発明を次の実験例で説明する。 The present invention will be described in the following experimental example.
　（実施例１）
　２リットルの密閉容器に市販のカオリン（粒子径０．２μｍ）７０ｇ、焼成カオリン（粒子径０．８μｍ）７０ｇ、酸化チタン（粒子径０．１４μｍ）６０ｇを仕込み、十分に振とうさせて単純混合物を得た。次いで、ジェットミルを用いて乾式摺擦を行って粉末試料を得た。 (Example 1)
A 2 liter sealed container is charged with 70 g of commercially available kaolin (particle size 0.2 μm), 70 g of calcined kaolin (particle size 0.8 μm), and 60 g of titanium oxide (particle size 0.14 μm), and shaken sufficiently to provide a simple mixture. Got. Subsequently, dry rubbing was performed using a jet mill to obtain a powder sample.
　（実施例２）
　市販のカオリン８０ｇ、焼成カオリン８０ｇ、酸化チタン４０ｇを用いた以外は実施例１と同様にして粉末試料を得た。 (Example 2)
A powder sample was obtained in the same manner as in Example 1 except that 80 g of commercially available kaolin, 80 g of calcined kaolin, and 40 g of titanium oxide were used.
　（実施例３）
　市販のカオリン５１ｇ、焼成カオリン５１ｇ、酸化チタン９８ｇを用いた以外は実施例１と同様にして粉末試料を得た。 (Example 3)
A powder sample was obtained in the same manner as in Example 1 except that 51 g of commercially available kaolin, 51 g of calcined kaolin, and 98 g of titanium oxide were used.
　（比較例１）
　ジェットミルによる乾式摺擦を行わなかった以外は実施例１と同様にして、単純混合物をそのまま粉末試料とした。 (Comparative Example 1)
A simple mixture was directly used as a powder sample in the same manner as in Example 1 except that dry rubbing with a jet mill was not performed.
　（比較例２）
　市販のカオリン９０ｇ、焼成カオリン９０ｇ、酸化チタン２０ｇを用いた以外は実施例１と同様にして粉末試料を得た。 (Comparative Example 2)
A powder sample was obtained in the same manner as in Example 1 except that 90 g of commercially available kaolin, 90 g of calcined kaolin and 20 g of titanium oxide were used.
　（比較例３）
　酸化チタン単独で、そのまま粉末試料とした。 (Comparative Example 3)
Titanium oxide alone was used as a powder sample.
　得られた試料について、以下の方法で測定を行った。結果を表１及び表２に示す。尚、表中の酸化チタン質量部の値は、カオリン１００質量部に対する値である。 The obtained sample was measured by the following method. The results are shown in Tables 1 and 2. In addition, the value of the titanium oxide mass part in a table | surface is a value with respect to 100 mass parts of kaolins.
（１）粒子径
　Ｍａｌｖｅｒｎ社製Ｍａｓｔｅｒｓｉｚｅｒ３０００を使用し、粉末試料を水に分散させ、レーザ回折散乱法で測定した体積基準での中位径（Ｄ５０）から粒子径を求めた。 (1) Particle size Using a Mastersizer 3000 manufactured by Malvern, a powder sample was dispersed in water, and the particle size was determined from the median diameter (D 50 ) on a volume basis measured by a laser diffraction scattering method.
（２）屈折率
　予め、アッベ屈折計を用いて、α－ブロムナフタレン（屈折率１．６６）及びケロシン（屈折率１．４５）を所定の割合で混合して、屈折率既知の浸液を調製した。併せて、屈折率１．７８の浸液として、島津デバイス製造製の接触液（屈折液　ｎｄ　１．７８）を用いた。次いで、Ｌａｒｓｅｎの油浸法に従って、微量の粉末試料をスライドガラス上に採り、屈折率既知の浸液を１滴加えて、カバーガラスをかけ、浸液を十分浸漬させた後、光学顕微鏡でベッケ線の移動を観察して屈折率を求めた。 (2) Refractive index In advance, using an Abbe refractometer, α-bromonaphthalene (refractive index 1.66) and kerosene (refractive index 1.45) are mixed at a predetermined ratio to obtain an immersion liquid with a known refractive index. Prepared. In addition, a contact liquid (refractive liquid nd 1.78) manufactured by Shimadzu Device Manufacturing Co., Ltd. was used as the immersion liquid having a refractive index of 1.78. Next, according to Larsen's oil immersion method, a small amount of powder sample is taken on a slide glass, a drop of immersion liquid with a known refractive index is added, a cover glass is applied, and the immersion liquid is sufficiently immersed, and then the optical microscope is used to check the Becke. The refractive index was determined by observing the movement of the line.
（３）隠ぺい率
　ＪＩＳ　Ｋ　５１０１－４：２００４　顔料試験方法－第４部：隠ぺい力－隠ぺい率試験紙法に準拠して、粉末試料２５ｇをクリアウレタン塗料５０ｇに分散させ、隠ぺい率試験紙に塗布した。次いで、日本電色工業製ＣｏｌｏｒＭｅｔｅｒＺＥ２０００を用いて、隠ぺい率試験紙の白色部と黒色部との明度比から隠ぺい率を求めた。 (3) Concealment rate JIS K 5101-4: 2004 Pigment test method-Part 4: Concealment power-Concealment rate test paper method In accordance with the paper test method, 25 g of powder sample was dispersed in 50 g of clear urethane paint, Applied. Subsequently, the concealment rate was calculated | required from the brightness ratio of the white part of a concealment rate test paper, and a black part using Nippon Denshoku Industries ColorMeterZE2000.
（４）光沢度
　Ｇａｒｄｎｅｒ社製ｍｉｃｒｏ－ＴＲＩ－ｇｌｏｓｓを用いて、隠ぺい率測定に用いた試験紙の６０度光沢を測定した。 (4) Glossiness Using a micro-TRI-gloss manufactured by Gardner, the 60-degree glossiness of the test paper used for the hiding ratio measurement was measured.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示すように、乾式摺擦を行った実施例１の屈折率は１．７８を大きく超えており、結果として塗料の隠ぺい率も高く、塗膜は平滑で光沢が認められた。屈折率が１．７８を大きく超えて、隠ぺい率９５％以上を維持できる酸化チタン配合量の下限は２５質量部であり（実施例２）、上限は９６質量部であった（実施例３）。特に、実施例３は顔料成分の５１％がカオリンでありながら、比較対照とした酸化チタン単独塗料（表２の比較例３）と同等の隠ぺい率を示した。
　しかしながら、表２の比較例１が示すように、実施例１と同じ酸化チタンの配合量を採用しても乾式摺擦を行わなかった場合には、屈折率１．５５の粒子と１．７８を超える粒子がそれぞれ単独で観測された。このとき、塗料中では粉末試料の凝集が認められ、隠ぺい率試験紙に対して均一な塗布ができず、隠ぺい率の評価を行えなかった。塗膜は平滑性が大きく損なわれており、光沢も認められず、塗料用顔料として使用できるものではなかった。
　また、表２の比較例２が示すように、酸化チタンの配合量が１１質量部の場合、乾式摺擦を行っても、屈折率はカオリンとほぼ同等の１．５７まで低下し、隠ぺい率も９５％を大きく下回る８８．３％であった。
　以上の結果から、カオリン粒子の屈折率および分散性向上要因は、カオリン表面に対する酸化チタン被覆効果であり、ジェットミルによる乾式摺擦の有効性が明らかとなった。さらに、酸化チタンに匹敵する程度まで屈折率が向上する酸化チタンの配合量は２５～９６質量部の範囲であることが見出された。 As shown in Table 1, the refractive index of Example 1 subjected to dry rubbing greatly exceeded 1.78. As a result, the coating concealment ratio was also high, and the coating film was smooth and glossy. The lower limit of the amount of titanium oxide that can maintain a concealment ratio of 95% or more with a refractive index greatly exceeding 1.78 is 25 parts by mass (Example 2), and the upper limit is 96 parts by mass (Example 3). . Particularly, in Example 3, 51% of the pigment component was kaolin, but the hiding rate was the same as that of the titanium oxide single paint as a comparative control (Comparative Example 3 in Table 2).
However, as shown in Comparative Example 1 of Table 2, when the same amount of titanium oxide as in Example 1 was employed and dry rubbing was not performed, particles having a refractive index of 1.55 and 1.78 were used. More than a single particle was observed alone. At this time, agglomeration of the powder sample was observed in the paint, and it was not possible to uniformly apply to the concealment rate test paper, and the concealment rate could not be evaluated. The coating film was greatly impaired in smoothness, did not show gloss, and could not be used as a paint pigment.
In addition, as shown in Comparative Example 2 in Table 2, when the compounding amount of titanium oxide is 11 parts by mass, the refractive index decreases to 1.57, which is almost equivalent to kaolin, even when dry-type rubbing is performed. Was 88.3%, significantly lower than 95%.
From the above results, the factor for improving the refractive index and dispersibility of the kaolin particles is the titanium oxide coating effect on the kaolin surface, and the effectiveness of dry rubbing with a jet mill has been clarified. Further, it was found that the amount of titanium oxide whose refractive index is improved to a level comparable to that of titanium oxide is in the range of 25 to 96 parts by mass.

Claims (3)

  1. 　１００質量部のカオリン粒子と、２５～９６質量部の酸化チタン粒子とからなり、屈折率が１．７８以上であることを特徴とする塗料用白色顔料。 A white pigment for paint comprising 100 parts by weight of kaolin particles and 25 to 96 parts by weight of titanium oxide particles, and having a refractive index of 1.78 or more.
  2. 　９５％以上の隠ぺい率（ＪＩＳ　Ｋ　５１０１－４：２００４）を示す請求項１に記載の塗料用白色顔料。 The white pigment for paint according to claim 1, which exhibits a concealment ratio of 95% or more (JIS K 5101-4: 2004).
  3. 　前記カオリン粒子の少なくとも一部が焼成されたものである、請求項１に記載の塗料用白色顔料。 The white pigment for paint according to claim 1, wherein at least a part of the kaolin particles is fired.
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CN105038327A (en) * 2014-11-26 2015-11-11 安徽池州博源非金属矿研发中心有限公司 Preparation method of dolomite composite titanium dioxide

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