JPS6225707B2 - - Google Patents
Info
- Publication number
- JPS6225707B2 JPS6225707B2 JP57229842A JP22984282A JPS6225707B2 JP S6225707 B2 JPS6225707 B2 JP S6225707B2 JP 57229842 A JP57229842 A JP 57229842A JP 22984282 A JP22984282 A JP 22984282A JP S6225707 B2 JPS6225707 B2 JP S6225707B2
- Authority
- JP
- Japan
- Prior art keywords
- barium sulfate
- barium
- plate
- aqueous
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 249
- 239000002002 slurry Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052916 barium silicate Inorganic materials 0.000 claims description 22
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 17
- 229960004029 silicic acid Drugs 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001422 barium ion Inorganic materials 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 159000000009 barium salts Chemical group 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 25
- 239000003973 paint Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- -1 sheets Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 241000276425 Xiphophorus maculatus Species 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Description
本発明は表面処理板状硫酸バリウムの製造方法
に関し、詳しくは、樹脂親和性にすぐれ、樹脂成
形品や塗料に充填剤又は体質顔料として配合され
たとき、それら成形品や塗膜の物理的特性、特に
強度や耐摩耗性を改善することができる表面処理
板状硫酸バリウムの製造方法に関する。
硫酸バリウムは一般に塩化バリウム、硫化バリ
ウム、硝酸バリウム等のバリウム塩水溶液に硫酸
塩又は硫酸の水溶液を反応させる水溶液反応によ
つて生成され、このような硫酸バリウムは、一次
粒子が普通、0.3〜2.0μ程度の球状粒子であり、
濾過、水洗後、得られた湿潤キーキを乾燥、粉砕
して、製品として種々の用途に供される。
従来、硫酸バリウムは一般に、シート、フイル
ム、容器、工業部品、装飾品等の樹脂成形品や、
塗料、インキ等の製造等の種々の分野で樹脂系に
配合されて使用されているが、かかる使用は、本
来、硫酸バリウムが化学的、物理的に安定である
特性を利用した体質顔料としての使用であり、製
品の美観を損なわない顔料特性が重要視されてき
ている。従つて、その形状も従来は、立方量密充
填構造をとりやすい球状が最適であるとされてき
ている。
しかしながら、本発明者らは、上記とは異な
り、板状硫酸バリウムを樹脂成形品に配合した場
合、その機械的強度、特に曲げ強度が著しく改善
され、また、塗料に配合した場合、塗膜の耐摩耗
性や耐チツピング性が著しく改善されることを見
出した。このように樹脂成形品や塗膜の性質が改
善される理由は必ずしも明らかではないが、板状
硫酸バリウムが樹脂成形品や塗膜等の樹脂系内で
層状に配向するためであると考えられる。
板状硫酸バリウムはこのような特異な効果を樹
脂系内において発現するが、しかし、一方におい
て、前記したように、硫酸バリウムはその表面が
不活性であるため、樹脂によつては親和性に劣
り、このような樹脂を含有する塗料に使用したと
き、硫酸バリウムが凝集を起こして塗料粘度が高
くなり、必要な塗料性能が得られない場合があ
る。
本発明者らは、上記した種々の問題を解決する
ために鋭意研究した結果、板状硫酸バリウムの不
活性な表面に含水シリカを沈着させて、その表面
を改質することにより、樹脂との親和性にすぐれ
た硫酸バリウムを得ることができ、かくして得ら
れる硫酸バリウムは、樹脂との親和性にすぐれる
のみならず、樹脂系においてその物理的特性を著
しく改善することを見出して本発明に至つたもの
である。
従つて、本発明は、樹脂親和性にすぐれ、樹脂
成形品や塗料に配合した場合に良好な物理的特性
をそれらに与えることができる表面処理板状硫酸
バリウムの製造方法を提供することを目的とす
る。
本発明による表面処理板状硫酸バリウムの製造
方法は、バリウムイオンを含有する板状硫酸バリ
ウムの水スラリーにケイ酸アルカリ水溶液を加え
て板状硫酸バリウムの表面にケイ酸バリウムを生
成させ、次いで、スラリーに鉱酸を加え、上記ケ
イ酸バリウムを含水シリカに分解して板状硫酸バ
リウム表面に沈着させることを特徴とする。
本発明において用いる板状硫酸バリウムは、最
大粒子径において特に制限されるものではない
が、好ましくは、0.2〜20μである。粒子径が20
μを越える場合は、塗料に配合したときに塗膜の
光沢が低下し、また、樹脂成形品に配合したとき
は、肉眼でつぶが認められるようになるので、製
品品質を下げる。0.2μよりも小さい場合は、前
記したような強度等の物性改善の効果が小さくな
る。
上記のような板状硫酸バリウムは、硫化バリウ
ム水溶液と硫酸水溶液とを連続的に反応槽に供給
して反応させる水溶液反応において、PHを３〜６
に制御することにより得られる。生成する板状硫
酸バリウムの粒子径は、硫化バリウムと硫酸水溶
液の濃度及び温度によつても制御することができ
るが、好ましくは、反応槽からの反応液の一部を
反応槽に循環させ、再度反応させることにより調
整される。
本発明の方法においては、上記のように水溶液
反応により硫酸バリウムを生成させ、この水スラ
リーに水溶性バリウム塩、例えば、硫化バリウ
ム、塩化バリウム、硝酸バリウム等を添加、溶解
させて、バリウムイオンを共存させ、これにケイ
酸アルカリ水溶液を加えるのが、作業性の点から
好ましい。しかし、本発明においては、予め調製
された板状硫酸バリウム粉末を水に分散させると
共に、これに上記のような水溶性バリウム塩を溶
解させて、バリウムイオンを含有する硫酸バリウ
ムスラリーを調製し、これにケイ酸アルカリ水溶
液を加えてもよい。
水スラリー中のバリウムイオンの過剰量は、特
に制限されるものではないが、好ましくは、板状
硫酸バリウムに対して、0.02〜５モル％、特に好
ましくは0.1〜１モル％である。硫酸バリウムス
ラリー中のバリウムイオン量が少なすぎるとき
は、ケイ酸アルカリとバリウムイオンとの反応に
基づく硫酸バリウム表面でのケイ酸バリウムの生
成が不十分となり、後続する鉱酸によるケイ酸バ
リウムの加水分解によつて十分な量の含水シリカ
硫酸バリウム表面に沈着しない。一方、バリウム
イオン量が多すぎるときは不経済である。
また、硫酸バリウムの水スラリー中の硫酸バリ
ウムの濃度は50〜150ｇ／が好ましいが、これ
に限定されるものではない。濃度が余りに小さい
ときは、処理液量が過大となつて、処理に手間を
要し、また、余りに大きいときは、水スラリーの
粘度が高くなりすぎて、処理性が悪くなるので好
ましくない。
本発明の方法は、上記のような硫酸バリウムの
水スラリーにケイ酸アルカリを添加し、アルカリ
性下で水スラリー中の過剰のバリウムイオンと反
応させてケイ酸バリウムを生成させ、硫酸バリウ
ム表面に沈着させる。ケイ酸バリウムを安定に生
成させるためには、PHは９以上であることが望ま
しい。ケイ酸アルカリとしては、具体的にはケイ
酸ナトリウム、ケイ酸カリウム等が好ましく用い
られる。ケイ酸アルカリの添加量は、スラリー中
に存在するバリウムイオンとの反応によつて硫酸
バリウム表面上に均一にケイ酸バリウムを沈着さ
せるために、硫酸バリウムに対して、SiO2換算
で0.1〜10重量％、好ましくは0.5〜５重量％であ
る。ケイ酸アルカリ量が余りに少ないときは、硫
酸バリウムの表面に均一に沈着せず、余りに多い
ときは、加水分解した含水シリカが硫酸バリウム
を凝集させ、かくして得られる硫酸バリウムを塗
料に使用した場合、その分散性や光沢性に劣るよ
うになるので好ましくない。
次いで、上記スラリーに鉱酸を加えて、硫酸バ
リウム表面に沈着したケイ酸バリウムを加水分解
し、含水シリカ（SiO2・nH2O）として硫酸バリ
ウム表面に沈着させる。鉱酸としては、塩酸、硝
酸等のように、スラリー中に尚バリウムイオンが
存在しても、水不溶性バリウム塩を生成しないも
のが好ましいが、必要ならば硫酸も用いることが
できる。この加水分解反応はPHが７以下で十分に
起こるので、通常、水スラリーのPHは２〜７の範
囲に調整されるが、好ましくは、得られる硫酸バ
リウムの顔料PHを７±１とするために、そのPHは
６±１とされる。このケイ酸バリウムの加水分解
反応の温度は特に制限されないが、普通、40℃以
上、好ましくは60〜90℃である。
以上のようにして得られる表面処理板状硫酸バ
リウムは、樹脂親和性にすぐれると共に、塗料、
インキ等に配合されたとき、その塗膜の耐摩耗
性、耐チツピング性とをを改善し、また、樹脂成
形品に配合されたとき、その強度、特に曲げ強度
を改善する。
本発明によれば、かかる表面処理した板状硫酸
バリウムを更にシランカツプリング剤にて処理
し、又はアルミニウム、チタン、ジルコニウム、
亜鉛等の金属の含水酸化物を沈着させて、一層、
板状硫酸バリウムの樹脂親和性を高めることがで
きる。
即ち、本発明による表面処理板状硫酸バリウム
の別の製造方法は、バリウムイオンを含有する板
状硫酸バリウムの水スラリーにケイ酸アルカリ水
溶液を加えて板状硫酸バリウムの表面にケイ酸バ
リウムを生成させ、次いで、スラリーに鉱酸を加
え、上記ケイ酸バリウムを含水シリカに分解して
板状硫酸バリウム表面に沈着させ、かくして得た
板状硫酸バリウムをシランカツプリング剤にて処
理することを特徴とする。
含水シリカを沈着させた板状硫酸バリウムをシ
ランカツプリング剤で処理するに際して、硫酸バ
リウムの水スラリーにシランカツプリング剤を添
加混合してもよく、或いは含水シリカを沈着させ
た硫酸バリウムを濾過、水洗、乾燥した後に、シ
ランカツプリング剤と混合してもよいが、作業性
の点からは、硫酸バリウムを前記のように水スラ
リー中で含水シリカを沈着させた後、この水スラ
リーにシランカツプリング剤を添加するのが好ま
しい。いずれにしても、シランカツプリング剤の
添加量は、硫酸バリウムに対して0.01〜２重量
％、好ましくは0.05〜１重量％である。
シランカツプリング剤は既に種々のものが知ら
れており、通常、次の一般式
Ｘ−Si（OR）3
（但し、Ｘはアルキル基、ビニル基、アクリル
基、メタアクリル基、アミノ基、エポキシ基、メ
ルカプト基、ハロゲン等を含む有機基を示し、Ｒ
はアルキル基を示す。）
で表わされ、好ましい具体例として、例えば、ビ
ニルトリメトキシシラン、γ―アニリノプロピル
トリメトキシシラン、メチルトリメトキシシラ
ン、γ―メタアクリロキシプロピルトリメトキシ
シラン、γ―グリシドキシトリメトキシシラン等
を挙げることができる。
板状硫酸バリウムをそのままでシランカツプリ
ング剤で処理しても、硫酸バリウム粒子表面は不
活性であるため、シランカツプリング剤は硫酸バ
リウム上に沈着しないが、本発明によれば、予め
含水シリカを沈着させてあるので、シランカツプ
リング剤が含水シリカの有する水酸基と反応し
て、硫酸バリウム粒子表面に結合され、また、塗
料、樹脂成形品等に配合した場合には、官能基Ｘ
が樹脂と結合を生じ、塗料、樹脂成形品等の機械
的強度を向上させる。
また、本発明による表面処理板状硫酸バリウム
の更に別の製造方法は、バリウムイオンを含有す
る板状硫酸バリウムの水スラリーにケイ酸アルカ
リ水溶液を加えて板状硫酸バリウムの表面にケイ
酸バリウムを生成させ、次いで、スラリーに鉱酸
を加え、上記ケイ酸バリウムを含水シリカに分解
して板状硫酸バリウム表面に沈着させ、かくして
得た板状硫酸バリウムのスラリーに水溶性金属化
合物の水溶液を加えた後、上記金属化合物に応じ
てアルカリ又は酸で中和して、板状硫酸バリウム
の表面に上記金属の含水酸化物を沈着させること
を特徴とする。
この方法において、上記のように硫酸バリウム
の水スラリー中で硫酸バリウムに含水シリカを沈
着させた後、引き続いてこのスラリーを処理する
のが好ましいが、しかし、シリカ沈着させた硫酸
バリウムを一旦濾過、水洗、乾燥し、粉末化した
後、改めてスラリー化して処理することもでき
る。
水スラリー中のシリカ沈着硫酸バリウムの量は
特に制限されないが、通常、30〜300ｇ／の範
囲が適当であり、好ましくは、50〜150ｇ／の
範囲である。硫酸バリウム量が少なすぎるときは
生産性に劣り、多すぎるときは、水スラリーの粘
度が高くなつて、作業性に劣るようになるからで
ある。
この水スラリーに加える水溶性金属化合物の量
は、前記と同様に硫酸バリウム上に均一に含水酸
化物を沈着させるために、硫酸バリウムに対して
その金属の酸化物換算で0.1〜10重量％が好まし
く、特に0.5〜５重量％が好ましい。
上記水溶性金属化合物を分解するためのアルカ
リ又は酸は特に制限されないが、通常、アルカリ
としては水酸化ナトリウム、水酸化カリウム、ア
ンモニア等が、酸としては塩酸、硝酸等が適宜に
用いられ、その量は上記水溶性金属化合物が含水
酸化物を形成するに足る量であり、通常、水スラ
リーのPHが７±１になるように添加される。ま
た、この加水分解反応の温度は特に制限されない
が、通常、40℃以上、好ましくは60〜90℃であ
る。
本発明において、上記水溶性金属化合物は、シ
リカ沈着硫酸バリウムスラリーに水溶液として添
加後、アルカリ又は酸により含水酸化物を形成し
得るものであれば、特に制限されず、前記したア
ルミニウム、チタン、ジルコニウム及び亜鉛のほ
か、種々の金属化合物を用いることができること
は明らかであろう。
例えば、含水アルミナを形成させるためには、
水溶性アルミニウム化合物としてアルミン酸ナト
リウムが好適に用いられる。また、含水酸化チタ
ンを沈着させるためには、例えば硫酸チタニルを
好適に用いることができる。
尚、本発明によれば、より高温加圧下にこの反
応を行なわせることもでき、この場合、含水アル
ミナ等の含水金属酸化物をより安定に硫酸バリウ
ム表面上に沈着させることができる。
シリカ処理をしていない硫酸バリウムの水スラ
リーを用いた場合は、硫酸バリウムがこれら金属
酸化物に対して殆ど親和性を有しないために、含
水酸化物は硫酸バリウム上に沈着することなく独
立に沈殿するので、硫酸バリウムは何ら表面処理
されない。しかし、本発明の方法によれば、硫酸
バリウム表面の沈着含水シリカが含水金属酸化物
と結合を生じるためであると考えられるが、含水
金属酸化物が硫酸バリウム表面に均一に強く沈着
し、かくして、極めて樹脂親和性にすぐれる硫酸
バリウムが得られる。また、このように処理され
た硫酸バリウムは、その後の濾過性等の作業性に
もすぐれる。
以上のように、シリカを沈着させた硫酸バリウ
ム、又はこれを更にシランカツプリング剤処理し
た硫酸バリウムや含水アルミナ等を沈着させた硫
酸バリウムは、通常の方法によつて濾過、水洗、
乾燥され、この後、粉砕して製品として使用に供
される。しかし、水溶性樹脂塗料やインキ、コー
テイング紙等への用途には、濾過水洗後の湿潤ケ
ーキのままで使用に供することができる。
以上のようにして、本発明によつて得られる表
面処理硫酸バリウムは、著しく樹脂親和性にすぐ
れると共に、塗料に配合されたとき、その耐摩耗
性や耐チツピング性を改善し、また、樹脂成形品
に配合されたとき、その強度、特に曲げ強度を改
善する。
以下に実施例を挙げて本発明を説明するが、本
発明はこれら実施例により何ら限定されるもので
はない。尚、以下において、部及び％はそれぞれ
重量部及び重量％を示す。
実施例 １
(a) 表面処理硫酸バリウムの製造
撹拌機を備えた容量250の反応槽に濃度125
ｇ／、温度20℃の硫酸水溶液を200／時の割
合で供給すると共に、濃度125ｇ／、温度50℃
の硫化バリウム水溶液を反応槽内のPHが４となる
ように連続的に供給して、硫酸と等モル反応させ
た。このようにして得られた板状硫酸バリウムの
平均粒子寸法は、長さ５μ、幅５μ、厚み0.5μ
であつた。
反応槽から得たこの硫酸バリウムの水スラリー
を五等分し、第一の水スラリーはフイルタープレ
スにて濾過、水洗して、湿潤ケーキを得、これを
乾燥後、衝撃式粉砕機により粉砕して、比較品板
状硫酸バリウム１を得た。
第二のスラリーには、生成硫酸バリウムに対し
て0.5モル％の硫化バリウムを添加溶解させた
後、70℃に加温し、10％ケイ酸ナトリウム水溶液
をSiO2換算で1.0％添加して、ケイ酸バリウムを
硫酸バリウム粒子表面上に生成させた。この後、
塩酸を加えてPHを２として、ケイ酸バリウムを含
水シリカに分解し、30分間熟成した後、30％カ性
ソーダ水溶液を加えてPHを７とした。この後、上
記比較品硫酸バリウム１と同様に、濾過水洗、乾
燥し、粉砕し、本発明品硫酸バリウム１を得た。
第三の水スラリーは、上記本発明品１の製造に
おいて、PHを７とした後、このスラリーにメタク
リロキシプロピルトリメトキシシランを硫酸バリ
ウムに対して0.3％添加し、更に30分間熟成し
た。この後、上記と同様に濾過、水洗、乾燥、粉
砕して、本発明品硫酸バリウム２を得た。
第四の水スラリーは、上記本発明品硫酸バリウ
ム１と同様にして含水シリカを沈着させる処理を
行なつた後、このスラリーに30％カ性ソーダを加
えてPHを6.0に調整し、これに硫酸バリウムに対
して、A12O3換算で1.0％のアルミン酸ナトリウ
ムを添加した後、約10％塩酸水溶液でPHを7.0に
調整して、硫酸バリウム上に含水アルミナを沈着
させた。この後、濾過水洗、乾燥、粉砕して、本
発明品硫酸バリウム３を得た。
比較のために、第五の水スラリーにカ性ソーダ
を加えて、PHを７とし、これに前記と同じシラン
カツプリング剤を同量加えた後、30分間熟成し
た。次いで、同様に濾過、水洗、乾燥、粉砕し
て、比較品硫酸バリウム２を得た。
(b) 樹脂成形品の製造及びその機械的強度の評価
上で得た各板状硫酸バリウム粒子20部とアイソ
タクチツクポリピロピレン樹脂80部とをヘンシエ
ルミキサー中で混合した後、押出機で造粒し、更
に射出成形機にて試験片を作製し、JIS Ｋ 6758
に準じて、機械的強度を測定した。結果を表に示
す。
本発明による硫酸バリウムを含有する樹脂成形
品は、曲げ弾性率及びアイゾツト衝撃値のいずれ
においてもすぐれていることが明らかである。
(c) 塗料の調製及び塗膜の物性評価
ポリエステル樹脂（大日本化学工業(株)製Ｍ―
6003）／メラミン樹脂（大日本化学工業(株)製Ｊ―
820）（固形分比85／15）の樹脂混合液に溶剤ソル
ベツソ＃150／ｎ―ブタノール／ブチルセロソル
ブ（重量比70／20／10）を加え、樹脂固形分50重
量％の樹脂溶液を調製した。
この溶液各100部に、前記本発明品１，２，
３、比較品１又は２の硫酸バリウムをそれぞれ10
部、カーボンブラツク0.7部及び酸化チタン40部
を添加し、分散させて、塗料を調製した。
The present invention relates to a method for producing surface-treated plate-like barium sulfate, and more specifically, it has excellent resin affinity, and when incorporated as a filler or extender into resin molded products or paints, it improves the physical properties of these molded products or paint films. In particular, the present invention relates to a method for producing surface-treated plate-shaped barium sulfate that can improve strength and abrasion resistance. Barium sulfate is generally produced by an aqueous reaction in which an aqueous solution of a barium salt such as barium chloride, barium sulfide, or barium nitrate is reacted with an aqueous solution of sulfate or sulfuric acid, and such barium sulfate usually has primary particles of 0.3 to 2.0. It is a spherical particle of about μ,
After filtration and washing with water, the obtained wet kiki is dried and pulverized to be used as a product for various purposes. Conventionally, barium sulfate is generally used in resin molded products such as sheets, films, containers, industrial parts, and decorative items.
Barium sulfate is used as an extender pigment in various fields such as the production of paints and inks, but it is originally used as an extender pigment that takes advantage of the chemical and physical stability of barium sulfate. Pigment properties that do not impair the aesthetic appearance of products are becoming more important. Therefore, it has conventionally been considered that the optimum shape is spherical because it can easily form a cubic close-packed structure. However, in contrast to the above, the present inventors found that when platy barium sulfate was blended into a resin molded product, its mechanical strength, especially the bending strength, was significantly improved, and when it was blended into a paint, the paint film was improved. It has been found that wear resistance and chipping resistance are significantly improved. The reason why the properties of resin molded products and coating films are improved in this way is not necessarily clear, but it is thought to be because the plate-shaped barium sulfate is oriented in layers within the resin system of resin molded products and coating films. . Platy barium sulfate exhibits such a unique effect within the resin system, but on the other hand, as mentioned above, the surface of barium sulfate is inert, so depending on the resin, it may have a low affinity. On the other hand, when used in paints containing such resins, barium sulfate may aggregate, increasing the viscosity of the paint and making it impossible to obtain the required paint performance. As a result of intensive research to solve the various problems described above, the present inventors deposited hydrated silica on the inert surface of plate-shaped barium sulfate and modified the surface, thereby making it possible to bond with resin. It has been discovered that barium sulfate with excellent affinity can be obtained, and that the barium sulfate thus obtained not only has excellent affinity with resins, but also significantly improves the physical properties of resin systems, and has developed the present invention. It has been reached. Therefore, an object of the present invention is to provide a method for producing surface-treated plate-like barium sulfate that has excellent resin affinity and can impart good physical properties to resin molded products or paints when incorporated into them. shall be. The method for producing surface-treated barium sulfate plates according to the present invention includes adding an aqueous alkali silicate solution to an aqueous slurry of barium sulfate plates containing barium ions to generate barium silicate on the surface of the barium sulfate plates, and then The method is characterized in that a mineral acid is added to the slurry to decompose the barium silicate into hydrated silica, which is deposited on the surface of the barium sulfate plate. Although the maximum particle size of the plate-shaped barium sulfate used in the present invention is not particularly limited, it is preferably 0.2 to 20μ. Particle size is 20
If it exceeds μ, the gloss of the coating will decrease when it is blended into a paint, and when it is blended into a resin molded product, cracks will be visible to the naked eye, which will lower the product quality. When it is smaller than 0.2μ, the effect of improving physical properties such as strength as described above becomes small. The plate-shaped barium sulfate as described above is produced by an aqueous solution reaction in which a barium sulfide aqueous solution and a sulfuric acid aqueous solution are continuously supplied to a reaction tank and reacted, with a pH of 3 to 6.
This can be obtained by controlling the The particle size of the plate-shaped barium sulfate to be produced can also be controlled by the concentration and temperature of the barium sulfide and sulfuric acid aqueous solution, but preferably, a part of the reaction liquid from the reaction tank is circulated to the reaction tank, It is adjusted by reacting again. In the method of the present invention, barium sulfate is produced by an aqueous reaction as described above, and a water-soluble barium salt such as barium sulfide, barium chloride, barium nitrate, etc. is added and dissolved in this water slurry to form barium ions. From the viewpoint of workability, it is preferable to allow these to coexist and add an aqueous alkali silicate solution thereto. However, in the present invention, barium sulfate slurry containing barium ions is prepared by dispersing previously prepared plate-shaped barium sulfate powder in water and dissolving the water-soluble barium salt as described above therein. An aqueous alkali silicate solution may be added to this. The excess amount of barium ions in the water slurry is not particularly limited, but is preferably 0.02 to 5 mol %, particularly preferably 0.1 to 1 mol %, based on the plate barium sulfate. When the amount of barium ions in the barium sulfate slurry is too small, the generation of barium silicate on the barium sulfate surface due to the reaction between the alkali silicate and barium ions will be insufficient, and the barium silicate will be hydrated by the subsequent mineral acid. Decomposition does not result in sufficient amounts of hydrated silica barium sulfate being deposited on the surface. On the other hand, when the amount of barium ions is too large, it is uneconomical. Further, the concentration of barium sulfate in the aqueous slurry of barium sulfate is preferably 50 to 150 g, but is not limited to this. If the concentration is too low, the amount of treatment liquid becomes too large, making treatment time-consuming. If the concentration is too large, the viscosity of the water slurry becomes too high, which impairs processability, which is not preferable. In the method of the present invention, an alkali silicate is added to an aqueous slurry of barium sulfate as described above, and is reacted with excess barium ions in the aqueous slurry under alkaline conditions to generate barium silicate, which is deposited on the surface of barium sulfate. let In order to stably produce barium silicate, the pH is preferably 9 or higher. As the alkali silicate, specifically, sodium silicate, potassium silicate, etc. are preferably used. The amount of alkali silicate added is 0.1 to 10 in terms of SiO 2 to barium sulfate in order to uniformly deposit barium silicate on the barium sulfate surface by reaction with barium ions present in the slurry. % by weight, preferably 0.5-5% by weight. If the amount of alkali silicate is too small, it will not be deposited uniformly on the surface of barium sulfate, and if it is too large, the hydrolyzed hydrated silica will aggregate the barium sulfate, and when the barium sulfate obtained in this way is used in paints, This is not preferable because its dispersibility and gloss become poor. Next, a mineral acid is added to the slurry to hydrolyze the barium silicate deposited on the barium sulfate surface, and the barium silicate is deposited as hydrous silica (SiO 2 .nH 2 O) on the barium sulfate surface. Preferably, the mineral acid is one that does not produce water-insoluble barium salts even if barium ions are present in the slurry, such as hydrochloric acid or nitric acid, but sulfuric acid can also be used if necessary. This hydrolysis reaction occurs sufficiently when the pH is 7 or less, so the pH of the water slurry is usually adjusted to a range of 2 to 7, but preferably, the pH of the resulting barium sulfate pigment is adjusted to 7±1. Its pH is assumed to be 6±1. The temperature of this barium silicate hydrolysis reaction is not particularly limited, but is usually 40°C or higher, preferably 60 to 90°C. The surface-treated plate-like barium sulfate obtained in the above manner has excellent resin affinity and can be used in paints,
When blended into ink etc., it improves the abrasion resistance and chipping resistance of the coating film, and when blended into resin molded products, it improves the strength, especially the bending strength. According to the present invention, such surface-treated plate barium sulfate is further treated with a silane coupling agent, or aluminum, titanium, zirconium,
By depositing hydrated oxides of metals such as zinc,
The resin affinity of plate barium sulfate can be improved. That is, another method for producing surface-treated barium sulfate plates according to the present invention involves adding an aqueous alkali silicate solution to an aqueous slurry of barium sulfate plates containing barium ions to form barium silicate on the surface of the barium sulfate plates. Then, mineral acid is added to the slurry to decompose the barium silicate into hydrous silica and deposited on the surface of the plate-shaped barium sulfate, and the plate-shaped barium sulfate thus obtained is treated with a silane coupling agent. shall be. When treating plate-shaped barium sulfate on which hydrated silica has been deposited with a silane coupling agent, the silane coupling agent may be added to and mixed with an aqueous slurry of barium sulfate, or the barium sulfate on which hydrated silica has been deposited may be filtered, After washing with water and drying, it may be mixed with a silane coupling agent, but from the viewpoint of workability, barium sulfate may be mixed with a silane coupling agent after depositing hydrated silica in a water slurry as described above. Preferably, a ring agent is added. In any case, the amount of the silane coupling agent added is 0.01 to 2% by weight, preferably 0.05 to 1% by weight, based on barium sulfate. Various types of silane coupling agents are already known, and they usually have the following general formula : R represents an organic group containing a group, a mercapto group, a halogen, etc.
represents an alkyl group. ) Preferred specific examples include vinyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxytrimethoxysilane, etc. can be mentioned. Even if plate-like barium sulfate is treated as it is with a silane coupling agent, the surface of the barium sulfate particles is inert, so the silane coupling agent will not be deposited on the barium sulfate. However, according to the present invention, hydrated silica is deposited, the silane coupling agent reacts with the hydroxyl group of the hydrated silica and is bonded to the surface of the barium sulfate particles, and when added to paints, resin molded products, etc., the functional group
forms a bond with the resin, improving the mechanical strength of paints, resin molded products, etc. Furthermore, another method for producing surface-treated barium sulfate plates according to the present invention is to add barium silicate to the surface of the barium sulfate plates by adding an aqueous alkali silicate solution to an aqueous slurry of barium sulfate plates containing barium ions. Then, a mineral acid is added to the slurry to decompose the barium silicate into hydrous silica and deposited on the surface of the barium sulfate plate, and an aqueous solution of a water-soluble metal compound is added to the slurry of the barium sulfate plate thus obtained. After that, the metal compound is neutralized with an alkali or an acid depending on the metal compound, and a hydrous oxide of the metal is deposited on the surface of the plate-shaped barium sulfate. In this method, after depositing the hydrated silica on barium sulfate in an aqueous slurry of barium sulfate as described above, it is preferred to subsequently treat this slurry; however, once the silica-deposited barium sulfate is filtered, After washing with water, drying, and pulverizing, it can also be processed by making it into a slurry again. The amount of silica-deposited barium sulfate in the water slurry is not particularly limited, but is usually in the range of 30 to 300 g/, preferably in the range of 50 to 150 g/. This is because when the amount of barium sulfate is too small, productivity is poor, and when it is too large, the viscosity of the water slurry becomes high, resulting in poor workability. The amount of the water-soluble metal compound added to this water slurry is 0.1 to 10% by weight, calculated as the metal oxide based on the barium sulfate, in order to uniformly deposit the hydrated oxide on the barium sulfate as described above. Preferably, 0.5 to 5% by weight is particularly preferred. The alkali or acid for decomposing the above-mentioned water-soluble metal compound is not particularly limited, but the alkali is usually sodium hydroxide, potassium hydroxide, ammonia, etc., and the acid is hydrochloric acid, nitric acid, etc., as appropriate. The amount is sufficient for the water-soluble metal compound to form a hydrous oxide, and is usually added so that the pH of the water slurry is 7±1. Further, the temperature of this hydrolysis reaction is not particularly limited, but is usually 40°C or higher, preferably 60 to 90°C. In the present invention, the water-soluble metal compound is not particularly limited as long as it can form a hydrous oxide with an alkali or acid after being added as an aqueous solution to the silica-deposited barium sulfate slurry, and the above-mentioned aluminum, titanium, zirconium It will be clear that in addition to zinc and zinc, various metal compounds can be used. For example, to form hydrated alumina,
Sodium aluminate is preferably used as the water-soluble aluminum compound. Further, in order to deposit hydrous titanium oxide, for example, titanyl sulfate can be suitably used. According to the present invention, this reaction can also be carried out at a higher temperature and under pressure, and in this case, a hydrated metal oxide such as hydrated alumina can be more stably deposited on the surface of barium sulfate. When using an aqueous slurry of barium sulfate that has not been treated with silica, barium sulfate has almost no affinity for these metal oxides, so the hydrated oxides do not precipitate on the barium sulfate and can stand alone. Barium sulfate does not undergo any surface treatment as it precipitates. However, according to the method of the present invention, the hydrated metal oxide is uniformly and strongly deposited on the barium sulfate surface, which is thought to be because the hydrated silica deposited on the barium sulfate surface forms a bond with the hydrated metal oxide. , barium sulfate with extremely good resin affinity is obtained. Furthermore, barium sulfate treated in this manner has excellent subsequent workability such as filterability. As described above, barium sulfate with silica deposited, barium sulfate treated with a silane coupling agent, barium sulfate with hydrated alumina deposited, etc. can be filtered, washed with water,
It is dried, then ground and used as a product. However, for applications such as water-soluble resin paints, inks, and coated papers, the wet cake after filtration and washing with water can be used as it is. As described above, the surface-treated barium sulfate obtained by the present invention has a remarkable affinity for resins, improves the abrasion resistance and chipping resistance of paints, and improves resin properties. When incorporated into molded products, it improves their strength, especially their bending strength. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the following, parts and % indicate parts by weight and % by weight, respectively. Example 1 (a) Production of surface-treated barium sulfate A reaction vessel with a capacity of 250 and a concentration of 125
Aqueous sulfuric acid solution with a temperature of 20°C is supplied at a rate of 200g/hour, and a concentration of 125g/hour is supplied at a temperature of 50°C.
A barium sulfide aqueous solution was continuously supplied so that the pH in the reaction tank was 4, and equimolar reaction with sulfuric acid was carried out. The average particle size of the plate-shaped barium sulfate thus obtained was 5μ in length, 5μ in width, and 0.5μ in thickness.
It was hot. This water slurry of barium sulfate obtained from the reaction tank was divided into five equal parts, and the first water slurry was filtered with a filter press and washed with water to obtain a wet cake, which was dried and pulverized with an impact pulverizer. A comparison product, plate-shaped barium sulfate 1, was obtained. To the second slurry, 0.5 mol% of barium sulfide was added and dissolved based on the barium sulfate produced, then heated to 70°C, and 1.0% of a 10% sodium silicate aqueous solution was added in terms of SiO 2 . Barium silicate was formed on the surface of barium sulfate particles. After this,
Hydrochloric acid was added to adjust the pH to 2, barium silicate was decomposed into hydrated silica, and after aging for 30 minutes, a 30% caustic soda aqueous solution was added to adjust the pH to 7. Thereafter, in the same manner as the comparative barium sulfate 1, it was filtered, washed with water, dried, and pulverized to obtain the barium sulfate 1 of the present invention. For the third water slurry, the pH was adjusted to 7 in the production of the above-mentioned product 1 of the present invention, then 0.3% methacryloxypropyltrimethoxysilane was added to barium sulfate, and the slurry was further aged for 30 minutes. Thereafter, the product was filtered, washed with water, dried, and pulverized in the same manner as above to obtain barium sulfate 2, a product of the present invention. The fourth water slurry was treated to deposit hydrated silica in the same manner as the barium sulfate 1 of the present invention, and then 30% caustic soda was added to this slurry to adjust the pH to 6.0. After adding 1.0% sodium aluminate in terms of A1 2 O 3 to barium sulfate, the pH was adjusted to 7.0 with an approximately 10% aqueous hydrochloric acid solution, and hydrated alumina was deposited on the barium sulfate. Thereafter, the product was filtered, washed with water, dried, and pulverized to obtain barium sulfate 3, a product of the present invention. For comparison, caustic soda was added to the fifth water slurry to adjust the pH to 7, and the same amount of the same silane coupling agent as above was added thereto, followed by aging for 30 minutes. Next, it was similarly filtered, washed with water, dried, and pulverized to obtain comparative barium sulfate 2. (b) Production of resin molded products and evaluation of their mechanical strength After mixing 20 parts of each of the plate-shaped barium sulfate particles obtained above and 80 parts of isotactic polypropylene resin in a Henschel mixer, the mixture was mixed with an extruder. granulate, and then use an injection molding machine to make test pieces, JIS K 6758
Mechanical strength was measured according to . The results are shown in the table. It is clear that the resin molded article containing barium sulfate according to the present invention is excellent in both flexural modulus and Izod impact value. (c) Preparation of paint and evaluation of physical properties of paint film Polyester resin (M- manufactured by Dainippon Chemical Co., Ltd.)
6003)/Melamine resin (manufactured by Dainippon Chemical Co., Ltd. J-
Solvetsuso #150/n-butanol/butyl cellosolve (weight ratio 70/20/10) was added to a resin mixture of 820) (solid content ratio 85/15) to prepare a resin solution with a resin solid content of 50% by weight. To 100 parts each of this solution, the above-mentioned products 1, 2,
3. Comparative product 1 or 2 barium sulfate 10 each
0.7 parts of carbon black and 40 parts of titanium oxide were added and dispersed to prepare a paint.
【表】
この塗料をスプレー粘度に調整し、寸法70×
150×0.6mmのリン酸亜鉛処理軟鋼板に乾燥膜厚が
30μとなるようにスプレー塗装し、160℃で30分
間加熱して焼き付け、ポリエステル樹脂塗膜を形
成した。この塗膜の機械的強度をJIS Ｚ 2247
（Ａ法）によるエリクセン試験及びJIS Ｋ 5400
―6.13（Ｂ法）による耐衝撃性試験にて調べた。
本発明による硫酸バリウムを含有する塗料は、
いずれも酸化チタンを含有する塗料とほぼ同等若
しくはそれ以上の強度及び硬度を有する塗膜を与
えることが明らかである。これに対して、比較品
硫酸バリウムを含有する塗料は上記の物性のいず
れにおいても劣ることが明らかである。[Table] Adjust this paint to a spray viscosity and measure 70 x
Dry film thickness on 150 x 0.6 mm zinc phosphate treated mild steel plate
It was spray coated to a thickness of 30μ and baked at 160°C for 30 minutes to form a polyester resin coating. The mechanical strength of this coating film is determined by JIS Z 2247.
(Method A) Erichsen test and JIS K 5400
- Investigated by impact resistance test according to 6.13 (Method B). The paint containing barium sulfate according to the invention is
It is clear that both of them provide coating films with strength and hardness that are approximately equal to or greater than those of coatings containing titanium oxide. On the other hand, it is clear that the comparison paint containing barium sulfate is inferior in all of the above physical properties.
Claims (1)
せる水溶液反応において、PHを３〜６に制御して
板状硫酸バリウムを生成させ、この板状硫酸バリ
ウムを含む水スラリーに水溶性バリウム塩を溶解
させてバリウムイオンを共存させ、この水スラリ
ーにケイ酸アルカリ水溶液を加えて板状硫酸バリ
ウムの表面にケイ酸バリウムを生成させ、次い
で、スラリーに鉱酸を加え、上記ケイ酸バリウム
を含水シリカに分解して板状硫酸バリウム表面に
沈着させることを特徴とする表面処理板状硫酸バ
リウムの製造方法。 ２ 硫化バリウム水溶液と硫酸水溶液とを反応さ
せる水溶液反応において、PHを３〜６に制御して
板状硫酸バリウムを生成させ、この板状硫酸バリ
ウムを含む水スラリーに水溶性バリウム塩を溶解
させてバリウムイオンを共存させ、この水スラリ
ーにケイ酸アルカリ水溶液を加えて板状硫酸バリ
ウムの表面にケイ酸バリウムを生成させ、次い
で、スラリーに鉱酸を加え、上記ケイ酸バリウム
を含水シリカに分解して板状硫酸バリウム表面に
沈着させ、かくして得た板状硫酸バリウムをシラ
ンカツプリング剤にて処理することを特徴とする
表面処理板状硫酸バリウムの製造方法。 ３ 硫化バリウム水溶液と硫酸水溶液とを反応さ
せる水溶液反応において、PHを３〜６に制御して
板状硫酸バリウムを生成させ、この板状硫酸バリ
ウムを含む水スラリーに水溶性バリウム塩を溶解
させてバリウムイオンを共存させ、この水スラリ
ーにケイ酸アルカリ水溶液を加えて板状硫酸バリ
ウムの表面にケイ酸バリウムを生成させ、次い
で、スラリーに鉱酸を加え、上記ケイ酸バリウム
を含水シリカに分解して板状硫酸バリウム表面に
沈着させ、かくして得た板状硫酸バリウムのスラ
リーに水溶性金属化合物の水溶液を加えた後、上
記金属化合物に応じてアルカリ又は酸で中和し
て、板状硫酸バリウムの表面に上記金属の含水酸
化物を沈着させることを特徴とする表面処理板状
硫酸バリウムの製造方法。[Scope of Claims] 1. In an aqueous reaction in which an aqueous barium sulfide solution and an aqueous sulfuric acid solution are reacted, the pH is controlled to 3 to 6 to produce plate-shaped barium sulfate, and the aqueous slurry containing the plate-shaped barium sulfate is Barium salt is dissolved to coexist with barium ions, and an aqueous alkali silicate solution is added to this water slurry to generate barium silicate on the surface of the plate-like barium sulfate.Next, mineral acid is added to the slurry, and the above barium silicate is dissolved. 1. A method for producing surface-treated plate-like barium sulfate, which comprises decomposing hydrated silica into hydrated silica and depositing it on the surface of plate-like barium sulfate. 2. In an aqueous reaction in which an aqueous barium sulfide solution and an aqueous sulfuric acid solution are reacted, the pH is controlled to 3 to 6 to produce plate-shaped barium sulfate, and a water-soluble barium salt is dissolved in the aqueous slurry containing this plate-shaped barium sulfate. Barium ions are allowed to coexist, and an aqueous alkali silicate solution is added to this water slurry to generate barium silicate on the surface of the plate-shaped barium sulfate.Next, mineral acid is added to the slurry to decompose the barium silicate into hydrated silica. A method for producing surface-treated plate-like barium sulfate, which comprises depositing the plate-like barium sulfate on the surface of the plate-like barium sulfate, and treating the plate-like barium sulfate thus obtained with a silane coupling agent. 3. In an aqueous reaction in which an aqueous barium sulfide solution and an aqueous sulfuric acid solution are reacted, the pH is controlled to 3 to 6 to produce plate-shaped barium sulfate, and a water-soluble barium salt is dissolved in the aqueous slurry containing this plate-shaped barium sulfate. Barium ions are allowed to coexist, and an aqueous alkali silicate solution is added to this water slurry to generate barium silicate on the surface of the plate-shaped barium sulfate.Next, mineral acid is added to the slurry to decompose the barium silicate into hydrated silica. After adding an aqueous solution of a water-soluble metal compound to the thus obtained slurry of plate-shaped barium sulfate, the slurry is neutralized with an alkali or acid depending on the metal compound to form plate-shaped barium sulfate. A method for producing surface-treated plate-like barium sulfate, which comprises depositing a hydrous oxide of the metal on the surface of the barium sulfate.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22984282A JPS59122553A (en) | 1982-12-28 | 1982-12-28 | Preparation of surface-treated plate barium sulfate |
| US06/486,962 US4505755A (en) | 1982-12-28 | 1983-04-20 | Method of producing surface-treated barium sulfate |
| GB08334361A GB2134094B (en) | 1982-12-28 | 1983-12-23 | A method of producing surface-treated barium sulfate and a resin composition including the same |
| DE19833348108 DE3348108C2 (en) | 1982-12-28 | 1983-12-27 | |
| DE19833347191 DE3347191A1 (en) | 1982-12-28 | 1983-12-27 | METHOD FOR THE PRODUCTION OF SURFACE-TREATED BARIUM SULFATE AND A RESIN COMPOSITION CONTAINING THIS BARIUM SULFATE |
| US06/688,153 US4551497A (en) | 1982-12-28 | 1984-12-31 | Method of producing surface-treated barium sulfate |
| GB08613141A GB2174999B (en) | 1982-12-28 | 1986-05-30 | Resin composition comprising barium sulphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22984282A JPS59122553A (en) | 1982-12-28 | 1982-12-28 | Preparation of surface-treated plate barium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59122553A JPS59122553A (en) | 1984-07-16 |
| JPS6225707B2 true JPS6225707B2 (en) | 1987-06-04 |
Family
ID=16898532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22984282A Granted JPS59122553A (en) | 1982-12-28 | 1982-12-28 | Preparation of surface-treated plate barium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59122553A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043781A (en) * | 2005-07-18 | 2008-05-19 | 작스트레벤 케미 게젤샤후트밋트베슈렝크테르하후트웅 | Preparation containing barium sulfate |
| JP5292809B2 (en) | 2005-12-16 | 2013-09-18 | 堺化学工業株式会社 | Ultrafine barium sulfate, aqueous coating composition and aqueous ink composition |
| JP5159599B2 (en) * | 2008-12-26 | 2013-03-06 | 日揮触媒化成株式会社 | Thermoplastic resin composition and film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2346188A (en) * | 1940-10-08 | 1944-04-11 | Nat Lead Co | Pigment and method of preparing same |
| JPS5253794A (en) * | 1975-10-30 | 1977-04-30 | Nippon Chem Ind Co Ltd:The | Prepartion of barium sulfate |
| JPS555548A (en) * | 1978-06-28 | 1980-01-16 | Matsushita Electric Ind Co Ltd | Signal control circuit |
-
1982
- 1982-12-28 JP JP22984282A patent/JPS59122553A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2346188A (en) * | 1940-10-08 | 1944-04-11 | Nat Lead Co | Pigment and method of preparing same |
| JPS5253794A (en) * | 1975-10-30 | 1977-04-30 | Nippon Chem Ind Co Ltd:The | Prepartion of barium sulfate |
| JPS555548A (en) * | 1978-06-28 | 1980-01-16 | Matsushita Electric Ind Co Ltd | Signal control circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59122553A (en) | 1984-07-16 |
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