JPS6327293B2 - - Google Patents
Info
- Publication number
- JPS6327293B2 JPS6327293B2 JP55126488A JP12648880A JPS6327293B2 JP S6327293 B2 JPS6327293 B2 JP S6327293B2 JP 55126488 A JP55126488 A JP 55126488A JP 12648880 A JP12648880 A JP 12648880A JP S6327293 B2 JPS6327293 B2 JP S6327293B2
- Authority
- JP
- Japan
- Prior art keywords
- barium sulfate
- resin
- particle size
- parts
- weight
- 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 116
- 239000002245 particle Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011164 primary particle Substances 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 10
- 239000003973 paint Substances 0.000 description 36
- 239000000049 pigment Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 239000004606 Fillers/Extenders Substances 0.000 description 11
- 238000000635 electron micrograph Methods 0.000 description 11
- 239000008199 coating composition Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 239000004640 Melamine resin Substances 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 7
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 235000010746 mayonnaise Nutrition 0.000 description 4
- 239000008268 mayonnaise Substances 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000001052 yellow pigment Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は樹脂被膜形成性組成物に関し、詳しく
は、塗料組成物、インキ組成物等のように樹脂被
膜を形成するための樹脂組成物に関する。
従来、硫酸バリウムは一般的には硫酸ナトリウ
ム水溶液と硫化バリウム水溶液とを反応させて製
造されているが、このようにして得られる硫酸バ
リウムは、通常、その平均粒径が0.3〜0.8μと大
きく、且つ、その粒径分布も広い。従つて、従来
の硫酸バリウムは一般に隠蔽力が大きいために、
かかる硫酸バリウムを透明顔料又は体質顔料とし
て配合した塗料組成物やインキ組成物において
は、硫酸バリウム粒子の光散乱のために、形成さ
れる乾燥塗膜が、一般に透明性や表面光沢に劣
る。更に、例えば、濃色塗料の場合には、硫酸バ
リウム粒子が光散乱により塗膜を白濁させると共
に、有色顔料自体が分散性に劣るために、二次凝
集を起こしやすく、鮮明で光沢ある濃色の塗膜を
得ることができない。
このために平均粒径が約0.1μの硫酸バリウムを
透明顔料又は体質顔料として配合した樹脂被膜形
成性組成物も提案されているが(特公昭50−
33984号公報)、配合量が増すにつれて塗膜物性、
特に、光沢及び透明性の低下が著しい。
本発明は上記した問題を解決するためになされ
たものであつて、超微細硫酸バリウムを含有する
ために、光沢及び透明性にすぐれる樹脂被膜を与
えることができる樹脂被膜形成性組成物を提供す
ることを目的とする。
本発明による塗膜形成性樹脂組成物は、一次粒
子の平均粒径が0.01〜0.08μであると共に、粒径
0.1μ以下の一次粒子が全体の90%以上を占める粒
径分布を有する超微細硫酸バリウムを含有するこ
とを特徴とする。
本発明において用いる硫酸バリウムは、一次粒
子の平均粒径が0.01〜0.08μであり、しかも、粒
径0.1μ以下の一次粒子数が全体の90%以上、好ま
しくは95%以上を占めるような粒径分布を有する
超微細硫酸バリウムである。
可視光の波長は380〜780nmであるから粒径が
光の半波長以下、即ち0.19μ以下であれば、理論
的には光はその粒子を透過する。本発明において
用いる超微細硫酸バリウムは、上記のように、一
次粒子の平均粒径が0.01〜0.08μであり、且つ、
一次粒子の粒径分布が後に説明するように、実質
的にすべてが光の半波長以下にあるから、樹脂溶
液に一次粒子として分散させた場合に実質的に透
明である。
更に、上記のような硫酸バリウムは、塗料やイ
ンキ組成物のような樹脂組成物中に通常の顔料の
分散条件下に容易に一次粒子に分散するので、か
かる硫酸バリウムを含有する本発明による樹脂被
膜形成性組成物によれば、得られる樹脂被膜は硫
酸バリウムの光散乱に基づく白濁が起こらず、従
つて、これを体質顔料として多量に用いても、極
めて透明で且つ表面光沢のすぐれた樹脂被膜を得
ることができるのである。濃色の有色塗料に体質
顔料として用いれば、そのすぐれた透明性のゆえ
に、鮮明な色調の被膜が得られる。特に、有色有
機顔料は濃色顔料としてよく用いられるが、これ
らは一般にビヒクルへの分散性が良好でなく、更
に、従来の硫酸バリウムを体質顔料として用いた
場合には、その光散乱のために塗膜が白味を帯び
るので、到底、鮮明で光沢ある濃色樹脂被膜を得
ることができないが、本発明による樹脂被膜形成
性組成物によれば、透明性のみならず、そのすぐ
れた分散性のために、有色有機顔料の分散助剤と
しても作用し、かくして、従来に比較して色調が
鮮明で光沢ある濃色の樹脂被膜を得ることができ
るのである。
本発明の樹脂被膜形成性組成物は、用いる樹脂
において特に制限されないが、例えば、アルキド
樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂、
不飽和ポリエステル樹脂、フエノール樹脂、ウレ
タン樹脂、熱硬化性アクリル樹脂等の熱硬化性樹
脂や、熱可塑性樹脂アクリル樹脂を好ましく用い
ることができる。樹脂被膜形成性組成物における
硫酸バリウムの添加量は、樹脂組成物の用途、樹
脂の種類等によつて適宜に選ばれ、特に制限され
るものではない。例えば、アルキド樹脂−メラミ
ン樹脂塗料において、樹脂100重量部について160
重量部の前記超微細硫酸バリウムを添加しても、
樹脂のみの塗膜と実質的に同じ透明な塗膜を形成
する。尚、塗料、印刷インキ等の製造において、
硫酸バリウムの添加は、このような技術分野で知
られている通常の方法によればよく、特に制限さ
れない。勿論、他の体質顔料や適宜の添加剤と併
用してもよく、また、樹脂中に予め分散しておい
てもよい。
また、本発明の超微細硫酸バリウムを含有する
塗料、インキ等の樹脂被膜形成性組成物は非ニユ
ートン粘性を示す。従つて、塗料、インキ等の流
動性を改善し、問題となることが多い所謂「垂
れ」を防いで、塗膜の肉もちを良好にすると共
に、前記したように、顔料の分散性を高めてその
沈降を防止するので、作業性にすぐれた樹脂組成
物を得ることができる。
本発明による樹脂被膜形成性組成物において用
いる超微細硫酸バリウムは、一般に、硫化バリウ
ム水溶液と硫酸水溶液とを硫化バリウム濃度が過
剰となるように制御しつつ、連続的に反応槽に導
き、効果的な撹拌の下に極めて短時間反応させ
て、反応系における生成硫酸バリウムの粒子成長
を抑制することによつて得られる。従つて、反応
槽としては例えばポンプが有利に用いられる。
本発明による樹脂被膜形成性組成物において用
いる硫酸バリウムは、以上のように、従来より知
られている通常の硫酸バリウムに比較して、一次
粒子の平均粒径が小さく、且つ、粒径分布も狭い
ので、体質顔料又は透明顔料として用いた場合
に、透明性や光沢、平滑性が著しくすぐれる塗膜
を与え、また、分散助剤としても作用するので、
例えば、有色有機顔料をヒビクルによく分散させ
て、鮮明で且つ光沢にすぐれる樹脂被膜を形成す
ることができる。
以下に実施例を挙げて、本発明による樹脂被膜
形成性組成物を説明するが、本発明はこれら実施
例によつて何ら限定されるものではない。
実施例 1
(1) 超微細硫酸バリウムの製造
吸込口径1.5インチ、吐出口径1インチ、内
容積850c.c.、インペラー回転数2380rpmのニツ
ソワーマンポンプ(太平洋金属(株)製)を反応槽
として用い、このポンプに濃度110g/、温
度20℃の硫酸水溶液を700/時の一定割合に
て吸込ませると共に、ポンプ吐出液の硫化バリ
ウム濃度が6g/となるように、濃度120
g/、温度50℃の硫化バリウム水溶液をその
吸込量を制御しつつポンプに吸込ませ、平均滞
留時間0.17秒、平均反応率92%にてポンプから
吐出させた。
ポンプ吐出液を二分し、一方をフイルタープ
レスにて濾過水洗後、得られたケーキを水中に
高速撹拌して500g/のスラリーとし、スプ
レードライヤーにて乾燥した。
比較のために、特公昭50−33984号公報に記
載された方法に従つて微細硫酸バリウムを製造
した。即ち、1.4モル/の硫酸ナトリウム水
溶液1を50℃の温度で5容量の反応槽に仕
込み、この中にヘキサメタリン酸ナトリウム
3.3gを添加、溶解させた。この混合溶液を撹
拌しつつ、これに0.8モル/の硫化バリウム
水溶液1.75を滴下し、50℃の温度で1時間反
応させた。滴下終了後、更に30分間撹拌した。
得られたスラリーをフイルタープレスにて濾過
水洗し、含水ケーキを100℃の温度で24時間乾
燥後、粉砕して比較用微細硫酸バリウムを得
た。
以上のようにして得た超微細硫酸バリウム及
び比較用硫酸バリウムのそれぞれ300個の粒子
について、10万倍の電子顕微鏡写真により、定
方向の粒径を測定して粒径分布を求めた。結果
を第1表に示す。尚、例えば、粒径が0.02μと
は、実際の粒径が0.015μ以上、0.025μ未満の粒
径である。また、第1図に上記超微細硫酸バリ
ウムの粒径分布を実線で、比較用硫酸バリウム
の粒径分布を破線でそれぞれグラフ化して示
す。
第2図及び第3図はそれぞれ超微細硫酸バリ
ウム及び比較用硫酸バリウムの上記電子顕微鏡
写真である。第4図には、以下に比較用微細炭
酸カルシウムと称する炭酸カルシウムの電子顕
微鏡写真を併せて示す。比較用微細炭酸カルシ
ウムの平均粒径は0.08μである。
第1表から明らかなように、本発明において
用いる超微細硫酸バリウムは、一次粒子の平均
粒径が0.05μであり、粒径0.1μ以下の粒子が全
体の96.0%を占めている。一方、比較用硫酸バ
リウムは一次粒子の平均粒径が0.1μであり、粒
径0.1μ以下の粒子は全体の64.5%にすぎない。
(2) 塗料組成物の調製
焼付型アルキド樹脂(ベツコゾールJ−524、
非揮発分60%、大日本インキ化学工業(株)製)
18.
The present invention relates to a resin film-forming composition, and more particularly to a resin composition for forming a resin film, such as a coating composition or an ink composition. Conventionally, barium sulfate is generally produced by reacting an aqueous sodium sulfate solution with an aqueous barium sulfide solution, but the barium sulfate obtained in this way usually has a large average particle size of 0.3 to 0.8μ. , and its particle size distribution is wide. Therefore, conventional barium sulfate generally has a large hiding power, so
In coating compositions and ink compositions containing such barium sulfate as a transparent pigment or extender pigment, the formed dried coating film is generally inferior in transparency and surface gloss due to light scattering of barium sulfate particles. Furthermore, in the case of dark-colored paints, for example, barium sulfate particles cause the paint film to become cloudy due to light scattering, and the colored pigments themselves have poor dispersibility, so secondary aggregation is likely to occur, resulting in clear, glossy dark colors. It is not possible to obtain a coating film of For this purpose, a resin film-forming composition containing barium sulfate with an average particle size of about 0.1μ as a transparent pigment or an extender has been proposed.
33984), as the amount of the compound increases, the physical properties of the coating film decrease,
In particular, the decrease in gloss and transparency is significant. The present invention has been made to solve the above problems, and provides a resin film-forming composition that can provide a resin film with excellent gloss and transparency because it contains ultrafine barium sulfate. The purpose is to The film-forming resin composition according to the present invention has primary particles having an average particle size of 0.01 to 0.08μ, and a particle size of
It is characterized by containing ultrafine barium sulfate with a particle size distribution in which primary particles of 0.1μ or less account for 90% or more of the total. The barium sulfate used in the present invention has a primary particle average particle size of 0.01 to 0.08μ, and the number of primary particles with a particle size of 0.1μ or less accounts for 90% or more, preferably 95% or more of the total. It is ultrafine barium sulfate with a diameter distribution. Since the wavelength of visible light is 380 to 780 nm, theoretically, if the particle size is less than a half wavelength of light, that is, less than 0.19μ, light will pass through the particle. As mentioned above, the ultrafine barium sulfate used in the present invention has an average primary particle diameter of 0.01 to 0.08μ, and
As will be explained later, since the particle size distribution of the primary particles is substantially all within a half wavelength of light, the primary particles are substantially transparent when dispersed as primary particles in a resin solution. Furthermore, since barium sulfate as described above is easily dispersed into primary particles under normal pigment dispersion conditions in resin compositions such as paint and ink compositions, the resin according to the present invention containing such barium sulfate According to the film-forming composition, the resulting resin film does not become cloudy due to light scattering of barium sulfate, and therefore, even when it is used in large quantities as an extender pigment, the resin film is extremely transparent and has excellent surface gloss. A coating can be obtained. When used as an extender pigment in dark colored paints, a film with a clear tone can be obtained due to its excellent transparency. In particular, colored organic pigments are often used as dark pigments, but they generally do not have good dispersibility in vehicles, and furthermore, when conventional barium sulfate is used as an extender pigment, its light scattering Since the coating film has a whitish tinge, it is impossible to obtain a clear and glossy dark resin coating, but the resin coating forming composition according to the present invention not only has transparency but also has excellent dispersibility. Therefore, it also acts as a dispersion aid for colored organic pigments, making it possible to obtain a deep-colored resin coating with a clearer and glossier color tone than in the past. The resin film-forming composition of the present invention is not particularly limited in the resin used, but examples include alkyd resins, melamine resins, urea resins, epoxy resins,
Thermosetting resins such as unsaturated polyester resins, phenolic resins, urethane resins, thermosetting acrylic resins, and thermoplastic acrylic resins can be preferably used. The amount of barium sulfate added to the resin film-forming composition is appropriately selected depending on the use of the resin composition, the type of resin, etc., and is not particularly limited. For example, in an alkyd resin-melamine resin paint, 160 parts by weight for 100 parts by weight of resin.
Even if part by weight of the ultrafine barium sulfate is added,
Forms a transparent coating film that is substantially the same as a resin-only coating. In addition, in the manufacture of paints, printing inks, etc.
The addition of barium sulfate may be carried out by any conventional method known in this technical field, and is not particularly limited. Of course, it may be used in combination with other extender pigments or appropriate additives, or may be dispersed in the resin in advance. Furthermore, the composition for forming resin films such as paints and inks containing ultrafine barium sulfate of the present invention exhibits non-Newtonian viscosity. Therefore, it improves the fluidity of paints, inks, etc., prevents the so-called "sagging" that often causes problems, improves the durability of the paint film, and, as mentioned above, improves the dispersibility of pigments. Since sedimentation is prevented, a resin composition with excellent workability can be obtained. Generally, the ultrafine barium sulfate used in the resin film-forming composition of the present invention is produced by continuously introducing an aqueous barium sulfide solution and an aqueous sulfuric acid solution into a reaction tank while controlling the barium sulfide concentration to be excessive. It is obtained by reacting for a very short period of time under thorough stirring to suppress the particle growth of barium sulfate produced in the reaction system. Therefore, for example, a pump is advantageously used as the reaction tank. As described above, the barium sulfate used in the resin film-forming composition of the present invention has a smaller average primary particle size and a smaller particle size distribution than conventional barium sulfate. Since it is narrow, when used as an extender pigment or a transparent pigment, it provides a coating film with outstanding transparency, gloss, and smoothness, and also acts as a dispersion aid.
For example, a colored organic pigment can be well dispersed in a vehicle to form a clear resin film with excellent gloss. The resin film-forming composition according to the present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 (1) Production of ultrafine barium sulfate A Nitsuso Warman pump (manufactured by Taiheiyo Kinzoku Co., Ltd.) with a suction port diameter of 1.5 inches, a discharge port diameter of 1 inch, an internal volume of 850 c.c., and an impeller rotation speed of 2380 rpm was used as a reaction tank. , This pump sucks in a sulfuric acid aqueous solution with a concentration of 110 g/hour and a temperature of 20°C at a constant rate of 700 g/hour, and a concentration of 120 g/hour so that the barium sulfide concentration of the pump discharge liquid is 6 g/hour.
g/, a barium sulfide aqueous solution at a temperature of 50° C. was sucked into the pump while controlling its suction amount, and was discharged from the pump at an average residence time of 0.17 seconds and an average reaction rate of 92%. The pump discharge liquid was divided into two parts, one of which was filtered using a filter press and washed with water.The resulting cake was stirred in water at high speed to form a slurry of 500 g/ml, which was dried using a spray dryer. For comparison, fine barium sulfate was produced according to the method described in Japanese Patent Publication No. 50-33984. That is, 1.4 mol of sodium sulfate aqueous solution 1 was charged into a 5-volume reaction tank at a temperature of 50°C, and sodium hexametaphosphate was added to the reactor.
3.3g was added and dissolved. While stirring this mixed solution, 1.75% of a 0.8 mol/barium sulfide aqueous solution was added dropwise, and the mixture was reacted at a temperature of 50° C. for 1 hour. After the addition was completed, the mixture was stirred for an additional 30 minutes.
The obtained slurry was filtered and washed with water using a filter press, and the water-containing cake was dried at a temperature of 100° C. for 24 hours and then ground to obtain fine barium sulfate for comparison. For each of the 300 particles of ultrafine barium sulfate and comparative barium sulfate obtained as described above, the particle size in a certain direction was determined using an electron micrograph at a magnification of 100,000 times to determine the particle size distribution. The results are shown in Table 1. Note that, for example, the particle size of 0.02μ means that the actual particle size is 0.015μ or more and less than 0.025μ. Further, in FIG. 1, the particle size distribution of the ultrafine barium sulfate is plotted as a solid line, and the particle size distribution of the comparative barium sulfate is plotted as a broken line. FIGS. 2 and 3 are electron micrographs of ultrafine barium sulfate and comparative barium sulfate, respectively. FIG. 4 also shows an electron micrograph of calcium carbonate, hereinafter referred to as comparative fine calcium carbonate. The average particle size of the comparative fine calcium carbonate is 0.08μ. As is clear from Table 1, the average primary particle size of the ultrafine barium sulfate used in the present invention is 0.05 μm, and particles with a particle size of 0.1 μm or less account for 96.0% of the total. On the other hand, the comparative barium sulfate has an average primary particle size of 0.1μ, and only 64.5% of the total particles have a particle size of 0.1μ or less. (2) Preparation of coating composition Baking type alkyd resin (Betsukosol J-524,
60% non-volatile content, manufactured by Dainippon Ink & Chemicals Co., Ltd.)
18.
【表】
2重量部とメラミン樹脂(スーパーベツカミン
J−820、非揮発分50%、大日本インキ化学工
業(株)製)9.3重量部とからなる混合ワニス(ア
ルキド樹脂/メラミン樹脂固形分比7/3)に
キシレン5.1重量部及び上記(1)で得た超微細硫
酸バリウム25重量部を添加、分散させ、顔料容
積濃度30%の透明塗料を得た。これに上記ワニ
スを加えて、顔料容積濃度が20%及び10%の塗
料を得た。比較のために、上記超微細硫酸バリ
ウムの代わりに前記比較用硫酸バリウム25重量
部及び前記比較用炭酸カルシウム15.8重量部を
それぞれ用いて塗料を調製した。
このようにして得た透明塗料をそれぞれガラス
板上に6ミルのアプリケーターを用いて並列塗布
し、常温で乾燥後、140℃の温度で20分間焼付け、
膜厚68μの塗膜を形成した。この塗膜についてグ
ロスメーターにて20゜/20゜鏡面反射率を測定し、
塗膜の表面光沢を評価し、また、垂直光線の透過
率をハンター系L値にて測定し、塗膜の透明度を
評価した。結果を第2表及び第3表に示す。
上表から明らかなように、超微細硫酸バリウム
を含有する本発明の透明塗料組成物によれば、顔
料容積濃度が30%(樹脂100重量部当り160重量
部)に至つても、得られる塗膜の表面光沢[Table] Mixed varnish (alkyd resin/melamine resin solid content ratio 7/3), 5.1 parts by weight of xylene and 25 parts by weight of the ultrafine barium sulfate obtained in (1) above were added and dispersed to obtain a transparent paint with a pigment volume concentration of 30%. The above varnish was added to this to obtain paints with pigment volume concentrations of 20% and 10%. For comparison, paints were prepared using 25 parts by weight of the comparative barium sulfate and 15.8 parts by weight of the comparative calcium carbonate in place of the ultrafine barium sulfate. The transparent paints obtained in this way were applied in parallel on a glass plate using a 6 mil applicator, dried at room temperature, and then baked at a temperature of 140°C for 20 minutes.
A coating film with a thickness of 68μ was formed. The 20°/20° specular reflectance of this coating was measured using a gloss meter.
The surface gloss of the coating film was evaluated, and the perpendicular light transmittance was measured using the Hunter system L value to evaluate the transparency of the coating film. The results are shown in Tables 2 and 3. As is clear from the above table, according to the transparent coating composition of the present invention containing ultrafine barium sulfate, even when the pigment volume concentration reaches 30% (160 parts by weight per 100 parts by weight of resin), the resulting coating is Film surface gloss
【表】【table】
【表】
及び透明度は樹脂単独の塗膜と殆ど変わらない。
一方、比較用硫酸バリウム及び炭酸カルシウムの
場合は、添加量の増加に伴う光沢及び透明度の低
下が顕著である。
実施例 2
(1) カラーベースの調製
第4表に示すように、焼付型アルキド樹脂
(ベツコゾールJ−524、前出)33.3重量部とキ
シレン20重量部に黄色顔料(Hostaperm
Yellow H3G、ヘキスト社製)20重量部と種々
の体質顔料(第6表に後出)を市販マヨネーズ
瓶に秤量した。これに径2mmのアルミナビーズ
240gを加え、ペイントコンデイシヨナーで1
時間分散後、更にアルキド樹脂(ベツコゾール
J−524、前出)44.5重量部とメラミン樹脂
(スーパーベツカミンJ−820、前出)40重量部
とからなる混合ワニスを加え、15分間混合し
て、アルキド樹脂/メラミン樹脂固形分比7/
3、黄色有機顔料を樹脂100重量部当り30重量
部を含有する有色カラーベース(イ)〜(リ)を調製し
た。
(2) 白ベースの調製
アルキド樹脂(ベツコゾールJ−524、前出)
100重量部、メラミン樹脂(スーパーベツカミ
ンJ−820、前出)51重量部及びキシレン28重
量部からなる混合ワニス327重量部に二酸化チ
タン25重量部と径0.15mmのガラスビーズ60重量
部とを加え、この配合物を100ml容量のマヨネ
ーズ瓶に秤量し、ペイントコンデイシヨナーに
て30分間分散させて、白ベースを調製した。
(3) 塗料の調製
上記のカラーベースと白ベースと混合ワニス
とを第5表に示す配合にて市販マヨネーズ瓶に
秤量し、ペイントコンデイシヨナーで15分間混
合して種々の体質顔料組成を有する有色塗料を
得た。
(4) 塗膜物性の評価
前記有色カラーベースと上記(3)で得た有色塗
料をそれぞれ6ミルのアプリケーターでガラス
板上に塗布し、常温で乾燥後、140℃の温度で
20分間焼付けた。この乾燥塗膜の20゜/20゜鏡面
反射率から光沢を評価した。結果をカラーベー
スについて第6表に、塗料について第7表に示
す。本発明の有色塗料組成物によれば、有色の
塗膜光沢の改善が顕著である。
即ち、第6表及び第7表に示すように、本発
明の有色塗料組成物によれば、体質顔料として
超微細硫酸バリウムを含有するために、その含
量が増加するにつれて塗膜光沢が、これを含有
しない場合に比べて、増大している。これに対
して、比較用硫酸バリウムを含有する塗料組成
物によれば、これを含有しない場合に比べて、
塗膜光沢をほぼ同等に保つにすぎない。更に、
従来の通常の市販の硫酸バリウムや炭酸カルシ
ウム、カオリン等を体質顔料として含有する塗
料によれば、含量の増加に伴う塗膜光沢の低下
が著しい。
次に、本発明において用いる超微細硫酸バリウ
ムの分散助剤としての作用を電子顕微鏡写真によ
つて説明する。
第5図は前記黄色顔料(5000倍)を示す。顔料
粒子が凝集していることが認められる。第6図は
第6表において超微細硫酸バリウムの含有量が30
重量部である塗料組成物(5000倍)を示し、第7
図はこの塗料組成物を更に拡大して示す(20000
倍)。超微細硫酸バリウムが顔料の周囲に付着し
て、顔料の分散性を高めていることが認められ
る。
第8図は比較用硫酸バリウムと顔料とを等量比
で含有する塗料組成物(5000倍)を示し、第9図
は更にこれを拡大して示す(20000倍)。硫酸バリ
ウム及び顔料が凝集していることが認められる。
実施例 3
焼付型アクリル樹脂(アクリデイツクA−405、
非揮発分50%、大日本インキ化学工業(株)製)98.0
重量部とメラミン樹脂(スーパーベツカミンJ−
820、前出)42.0重量部とからなる混合ワニス
(アクリル樹脂/メラミン樹脂固形分比7/3)
にキシレン24.5重量部及び実施例1で得た超微細
硫酸バリウム70重量部を市販マヨネーズ瓶に秤量
し、径1.5mmのガラスビーズ330gを加え、ペイン
トコンデイシヨナーで1時間分散させて塗料を得
た。
比較のために、超微細硫酸バリウムの代わりに
前記比較用硫酸バリウム、比較用炭酸カルシウム
及び市販ホワイトカーボンをそれぞれ用い、上記
と同様にして塗料を得た。但し、ホワイトカーボ
ンについては、上記条件では粘度が高くなりすぎ
て、塗料化が困難であつたので、樹脂100重量部
当りの配合量を20重量部とした。
このようにして調製したそれぞれの塗料につい
て、塗料粘度を測定した。非ニユートン粘性は、
回転粘度計においてそのローターを一定とし、1
分当りの回転数が6rpm及び60rpmのときの粘度
(cps)をそれぞれ測定し、この比をチキソトロピ
ー性(以下、TFと称する。)として評価した。
また、各塗料をそれぞれガラス板上に6ミルの
アプリケーターを用いて塗布し、実施例1と同様
にして塗膜を形成し、この塗膜について実施例1
と同様にして表面光沢及び透明度を評価した。結
果を第8表に示す。[Table] and transparency are almost the same as coatings made of resin alone.
On the other hand, in the case of comparative barium sulfate and calcium carbonate, the gloss and transparency decreased significantly as the amount added increased. Example 2 (1) Preparation of color base As shown in Table 4, yellow pigment (Hostaperm
Yellow H3G (manufactured by Hoechst) and various extender pigments (listed later in Table 6) were weighed into a commercially available mayonnaise bottle. Add to this alumina beads with a diameter of 2 mm.
Add 240g and apply 1 with paint conditioner
After time dispersion, a mixed varnish consisting of 44.5 parts by weight of alkyd resin (Betsukosol J-524, supra) and 40 parts by weight of melamine resin (Super Betsukamine J-820, supra) was added and mixed for 15 minutes. Alkyd resin/melamine resin solid content ratio 7/
3. Colored color bases (a) to (li) containing 30 parts by weight of a yellow organic pigment per 100 parts by weight of resin were prepared. (2) Preparation of white base Alkyd resin (Betsukosol J-524, mentioned above)
25 parts by weight of titanium dioxide and 60 parts by weight of glass beads with a diameter of 0.15 mm are added to 327 parts by weight of a mixed varnish consisting of 100 parts by weight, 51 parts by weight of melamine resin (Supervetsucomin J-820, mentioned above) and 28 parts by weight of xylene. In addition, this mixture was weighed into a 100 ml mayonnaise bottle and dispersed in a paint conditioner for 30 minutes to prepare a white base. (3) Preparation of Paint The color base, white base, and mixed varnish described above were weighed in the formulation shown in Table 5 into a commercially available mayonnaise bottle, and mixed for 15 minutes with a paint conditioner to prepare colored paints having various extender pigment compositions. Got the paint. (4) Evaluation of physical properties of paint film The colored color base and the colored paint obtained in (3) above were each applied onto a glass plate using a 6 mil applicator, dried at room temperature, and then heated at 140°C.
Bake for 20 minutes. The gloss of this dried coating film was evaluated from the 20°/20° specular reflectance. The results are shown in Table 6 for the color base and in Table 7 for the paint. According to the colored coating composition of the present invention, the gloss of a colored coating film is significantly improved. That is, as shown in Tables 6 and 7, since the colored paint composition of the present invention contains ultrafine barium sulfate as an extender pigment, the gloss of the paint film decreases as the content increases. It is increased compared to the case where it does not contain. On the other hand, according to the paint composition containing comparative barium sulfate, compared to the case not containing barium sulfate,
It merely maintains the gloss of the coating film at approximately the same level. Furthermore,
According to conventional, commercially available paints containing barium sulfate, calcium carbonate, kaolin, etc. as extender pigments, the gloss of the paint film decreases significantly as the content increases. Next, the action of ultrafine barium sulfate used in the present invention as a dispersion aid will be explained using electron micrographs. Figure 5 shows the yellow pigment (5000x magnification). It is observed that the pigment particles are aggregated. Figure 6 shows that the content of ultrafine barium sulfate is 30 in Table 6.
Indicates the coating composition in parts by weight (5000 times), and the seventh
The figure shows this coating composition further enlarged (20000
times). It is observed that ultrafine barium sulfate adheres around the pigment and improves the dispersibility of the pigment. FIG. 8 shows a comparative coating composition containing barium sulfate and pigment in an equal ratio (5,000 times), and FIG. 9 shows it further enlarged (20,000 times). It is observed that barium sulfate and pigment are aggregated. Example 3 Baking type acrylic resin (acrylic A-405,
Non-volatile content 50%, manufactured by Dainippon Ink & Chemicals Co., Ltd.) 98.0
Weight parts and melamine resin (Supervecamine J-
820, supra) 42.0 parts by weight (acrylic resin/melamine resin solid content ratio 7/3)
Weighed 24.5 parts by weight of xylene and 70 parts by weight of the ultrafine barium sulfate obtained in Example 1 into a commercially available mayonnaise bottle, added 330 g of glass beads with a diameter of 1.5 mm, and dispersed with a paint conditioner for 1 hour to obtain a paint. Ta. For comparison, paints were obtained in the same manner as above, using the comparative barium sulfate, comparative calcium carbonate, and commercially available white carbon instead of the ultrafine barium sulfate. However, the viscosity of white carbon was too high under the above conditions, making it difficult to form into a paint, so the amount of white carbon added was 20 parts by weight per 100 parts by weight of resin. The paint viscosity of each paint thus prepared was measured. Non-Newtonian viscosity is
In a rotational viscometer, the rotor is constant and 1
The viscosity (cps) was measured at rotation speeds of 6 rpm and 60 rpm, respectively, and this ratio was evaluated as thixotropy (hereinafter referred to as TF). In addition, each paint was applied onto a glass plate using a 6 mil applicator, and a coating film was formed in the same manner as in Example 1.
Surface gloss and transparency were evaluated in the same manner as above. The results are shown in Table 8.
【表】【table】
【表】【table】
【表】
量部当りの重量部を示す。
[Table] Shows parts by weight per part.
【表】【table】
【表】
(注) 平均粒径は第6表と同じ。
[Table] (Note) Average particle size is the same as Table 6.
【表】
上表から明らかなように、超微細硫酸バリウム
を配合してなる塗料組成物は、比較用硫酸バリウ
ムや比較用炭酸カルシウムを配合した塗料組成物
に比較して著しく高いチキソトロピー性を示し、
一方においてその塗膜の光沢と透明度も著しくす
ぐれている。市販ホワイトカーボンは比較的高い
チキソトロピー性を示すが、塗膜の光沢の低下が
著しい。[Table] As is clear from the above table, the coating composition containing ultrafine barium sulfate exhibits significantly higher thixotropy than the coating composition containing comparative barium sulfate or comparative calcium carbonate. ,
On the other hand, the gloss and transparency of the coating film are also outstanding. Although commercially available white carbon exhibits relatively high thixotropy, the gloss of the coating film is significantly reduced.
第1図は本発明及び比較用硫酸バリウムの粒径
分布を示すグラフ、第2図、第3図及び第4図は
それぞれ本発明及び比較用硫酸バリウム並びに比
較用炭酸カルシウムの電子顕微鏡写真(倍率10万
倍)、第5図は実施例2において用いた黄色顔料
を示す電子顕微鏡写真(倍率5000倍)、第6図は
第6表において超微細硫酸バリウムの含有量が30
重量部である塗料組成物の電子顕微鏡写真(倍率
5000倍)、第7図はこれを拡大した電子顕微鏡写
真(倍率20000倍)、第8図は比較用硫酸バリウム
と上記顔料とを等量比で含有する塗料組成物の電
子顕微鏡写真(倍率5000倍)、第9図はこれを拡
大した電子顕微鏡写真(倍率20000倍)である。
Figure 1 is a graph showing the particle size distribution of barium sulfate of the present invention and comparative barium sulfate, and Figures 2, 3, and 4 are electron micrographs (magnification 100,000 times), Figure 5 is an electron micrograph (5000 times magnification) showing the yellow pigment used in Example 2, and Figure 6 is an electron micrograph showing the yellow pigment used in Example 2 (magnification: 5000 times).
Electron micrograph of paint composition in parts by weight (magnification
5000x), Figure 7 is an enlarged electron micrograph (20000x magnification), and Figure 8 is an electron micrograph of a paint composition containing comparative barium sulfate and the above pigment in an equal ratio (5000x magnification). Figure 9 is an enlarged electron micrograph (magnification: 20,000 times).
Claims (1)
共に、粒径0.1μ以下の一次粒子が全体の90%以上
を占める粒径分布を有する超微細硫酸バリウムを
含有することを特徴とする樹脂被膜形成性組成
物。1. A resin containing ultrafine barium sulfate having an average primary particle size of 0.01 to 0.08μ and a particle size distribution in which primary particles with a particle size of 0.1μ or less account for 90% or more of the total. Film-forming composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55126488A JPS5751119A (en) | 1980-09-11 | 1980-09-11 | Ultrafine barium sulfate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55126488A JPS5751119A (en) | 1980-09-11 | 1980-09-11 | Ultrafine barium sulfate |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14595181A Division JPS57145031A (en) | 1981-09-16 | 1981-09-16 | Preparation of barium sulfate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5751119A JPS5751119A (en) | 1982-03-25 |
JPS6327293B2 true JPS6327293B2 (en) | 1988-06-02 |
Family
ID=14936439
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP55126488A Granted JPS5751119A (en) | 1980-09-11 | 1980-09-11 | Ultrafine barium sulfate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5751119A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS581761A (en) * | 1981-06-27 | 1983-01-07 | Nippon Paint Co Ltd | Coating composition |
DE10005685A1 (en) * | 2000-02-09 | 2001-08-23 | Sachtleben Chemie Gmbh | Barium sulfate, process for its preparation and its use |
DE10357115A1 (en) * | 2003-12-06 | 2005-07-07 | Solvay Barium Strontium Gmbh | Epoxy resin with increased impact resistance and elongation at break |
DE102005025719A1 (en) | 2005-06-04 | 2006-12-07 | Solvay Infra Bad Hönningen GmbH | Process for producing a dispersion of deagglomerated barium sulfate in plastics or plastic precursors |
EP1975126B2 (en) | 2005-12-16 | 2016-10-26 | Sakai Chemical Industry Co., Ltd. | Ultrafine barium sulfate particle, water-based coating composition, and water-based ink composition |
CN101475200B (en) * | 2009-01-06 | 2012-02-29 | 重庆科昌科技有限公司 | Preparation of subsphaeroidal barium sulfate by sulfuric acid process and use in copper foil substrate |
CN109133139A (en) * | 2017-06-16 | 2019-01-04 | 南风化工集团股份有限公司 | A method of sub-micro nano-barium sulfate is prepared using pump type reaction |
-
1980
- 1980-09-11 JP JP55126488A patent/JPS5751119A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5751119A (en) | 1982-03-25 |
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