JPS6090266A - Novel pigment - Google Patents

Abstract

PURPOSE:To provide a novel pigment obtained by the reaction of a phosphoric acid compound with a boric acid compound and a compound of Ca, Sr, Ba, Zn or Al, represented by a specific composition formula, having excellent corrosion protection and adhisivity to metals and high water resistance, and useful also as a mildew-proofing agent and flame-retardant. CONSTITUTION:The objective pigment having the composition of formula (Me is Ca, Sr, Ba, Zn or Al; x, y and n are 0.1-0.9, 0.1-0.9, and 0-2 per 1mol of MeO, respectively) can be produced by reacting (A) a phosphoric acid compound (e.g. tribasic sodium phosphate) with (B) a boric acid compound (e.g. borax) and if necessary, (C) a silicic acid compound (e.g. sodium silicate) and (D) one or more compounds of Ca, Sr, Ba, Zn or Al (e.g. BaS).

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本＠明は、金属に対するすぐ九之防食効果を有し、かっ
防刀為び剤、難燃化剤としても有効な性能ケ有する新規
な頭４＋全提供しＬつとするものでめゐ。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a novel product that has a corrosion-preventing effect on metals and is also effective as an anti-strength agent and a flame retardant. It's okay to provide 4+ all heads and L one.

従来、防食顔料としてばクロム酸系顔料や鉛系顔料が主
として使用されてきたが、クロム及び鉛の毒性が問題と
なり、無心ないし低毒性のり／酸亜鉛、モリブデン酸亜
鉛、モリブデン戚カルクウム、メタホウ酸バリウム等が
使用されてきている。Traditionally, chromic acid pigments and lead pigments have been mainly used as anti-corrosion pigments, but the toxicity of chromium and lead has become a problem, so non-poisonous or low-toxicity glues/zinc acids, zinc molybdate, molybdenum-related calcium, and metaboric acid have been used as anticorrosive pigments. Barium etc. have been used.

しかし、これらにいずれも防食性の点でクロム酸系顔料
と比べて、その効果が不充分である。However, all of these have insufficient anticorrosion effects compared to chromic acid pigments.

本発明者等に、これらの顔料に代わるすぐれた性能を有
する顔料につき種々検討した結果、リン酸化合物及びホ
ウ酸化合物並びに必要に応じてケイ酸化付物と、Ｏａ、
　Ｓｒ、　Ｂａ、ＩＺｏ、Ａｔ　の化＆　、ＷＪ０１種
又は２種以上と全反応させ之、特定開会の組成を有する
生成物を顔料として用いた場合、鉄鋼の防食性、金属板
との密着性及び耐水性にすぐれ、ｍ膜のふくれを防止す
る効果に！時性を有すること全見出し本発明を得た。As a result of various studies by the present inventors on pigments with excellent performance that can replace these pigments, we found that phosphoric acid compounds, boric acid compounds, and if necessary silicic acid adducts, Oa,
When a product having a specific composition of Sr, Ba, IZo, and At is reacted with one or more WJ0 types as a pigment, it improves the corrosion resistance of steel, the adhesion to metal plates, and It has excellent water resistance and is effective in preventing blistering of the M membrane! The present invention has been obtained in a timely manner.

〔防食性能について〕[About anti-corrosion performance]

次に防攻性化について詳しく脱力ｊ６と、アルカリ土類
金属、Ｚｎ及びＡｔ等とリン酸との化−８′吻に、防食
顔料としての性能金持ら、リン酸亜鉛、リン酸アルミ等
が１吏用されているが、その防食Ｉ幾溝としては塗膜中
に存在する水分の影営で化合物の一部が可溶化し、遊離
したリン酸が塗ｊ摸素地の金属面アノード域に生じるＦ
ｅ２＋イオンと反応し、離溶性の沈澱破膜全形成す６７
ζめ、防食効果全保持するといわれている。Next, we will discuss in detail about the anti-aggressive property, and the addition of alkaline earth metals, Zn, At, etc., and phosphoric acid to the proboscis-8', which has a high performance as an anti-corrosion pigment, zinc phosphate, aluminum phosphate, etc. However, due to its anti-corrosion grooves, a part of the compound is solubilized under the influence of moisture present in the coating film, and the liberated phosphoric acid is transferred to the anode area of the metal surface of the coating base. resulting F
Reacts with e2+ ions to form a dissolvable precipitate and a ruptured membrane67
It is said that it retains all of its anticorrosive effects.

又一方、ホウ酸との金属化会・ｉｆｆは、リン酸塩の場
合と同様塗ノ漠中での水分の影嘗にエリロエＭ化し、バ
ッファー作用にエリ素地鉄１Ｍを微アルカリに保ち、安
定な酸化被膜ｒ形成する。又、対イオンとして用いられ
た金属イオン例えばＢａ　等μ塗ｊ摸ビヒクル中の脂肪
酸と金属セッケン金形成し、素地鉄面〜の遁雅脂肪酸の
直接反応全防止するため防食効果を持つと説明されてい
／）。On the other hand, the metallization reaction with boric acid, if, is similar to the case of phosphates, it becomes Eryloe M due to the influence of moisture in the coating, and the buffer action keeps the Erymine base iron 1M slightly alkaline, making it stable. Forms an oxide film. In addition, metal ions used as counterions, such as Ba, form metal soaps with the fatty acids in the coating vehicle, and are said to have an anticorrosion effect because they completely prevent the direct reaction of the fatty acids on the steel surface. attitude/).

ここで直装なことぼ防食効果として要求される項目に（
グ耐水比、耐温水性等防食顔料の溶解度に関係する事項
と塗）漠の密層性、防食性等素地金属面の保護に関係す
る事項とがある。りＵえばホウ酸塩とリン酸塩の防食顔
料系ＶＣ＆いて、Ｂ２Ｏ３／　Ｐ２Ｏ。Here, the items required for the anti-corrosion effect of directly mounted pots are (
There are matters related to the solubility of anticorrosive pigments, such as the water resistance ratio and hot water resistance, and matters related to the protection of the base metal surface, such as the density of coatings and corrosion resistance. For example, borate and phosphate anticorrosive pigment system VC & B2O3/P2O.

０モル比が犬となるところで１吏用すると塗膜の密層性
ぼ向上するが、ホウ酸塩化合物の溶解度が高い１ζめ、
塗膜の耐水性が劣ることとなる。又逆にＢ２Ｏ３／Ｐ２
０．のモル比が小とｆＬ心配台でＩ吏用丁几ば、リン酸
塩化合物の溶解度が小さいことの影褥金受けて、耐水性
に向上するが、密層性に劣ることとなる。If the molar ratio is 0, the layer density of the coating film will be improved, but the solubility of the borate compound is high.
The water resistance of the paint film will be poor. And vice versa, B2O3/P2
0. If the molar ratio of fL is small, the water resistance will be improved due to the influence of the low solubility of the phosphate compound, but the layer density will be poor.

〔発明の溝底と効果の概要〕[Summary of the bottom of the invention and its effects]

本発明者等は新規顔料の探索に当りリン酸塩及びホウ酸
塩のそれぞれの防食性能を保持し、目的に応じてその特
性をより顕著に発揮しつる物質をめて研究した結果、リ
ン酸塩とホウ酸塩の防食顔料を単に混合することなく、
前記原料物質の反応により得られ、これら両成分全特定
割合で含む生成物がこの目的に合致することを見出した
。In searching for new pigments, the present inventors conducted research on substances that maintain the anticorrosive properties of phosphates and borates, and exhibit their properties more markedly depending on the purpose.As a result, phosphoric acid Without simply mixing salt and borate anticorrosive pigments,
It has been found that a product obtained by the reaction of the raw materials mentioned above and containing both of these components in all specified proportions meets this purpose.

本発明に係る第１の顔料と第２の顔料の組成を一括して
示せば次の通りである。The compositions of the first pigment and the second pigment according to the present invention are summarized as follows.

ＭｅＯａ　ｍｐ、ｏ、　ＩＩ　ｙＢ２０．　＠　ｚｓｉ
ｏ、　ａ　ｎＨ２Ｏここに、Ｍｅ　１ｑｏａ、　Ｓｒ、
　Ｅａ％Ｚｎ、　Ａ４に表し、ｘＳｙ、ｚにそれぞれＭ
θＯ１モルに対して、Ｘ　ＨＯ，１〜０．９．７　ｉｌ
（０，１〜０．９、ｚぼｏ〜０．８、ｎは０〜２である
。MeOa mp, o, II yB20. @zsi
o, a nH2O here, Me 1qoa, Sr,
Ea%Zn, expressed on A4, xSy, z respectively M
For 1 mole of θO, X HO, 1 to 0.9.7 il
(0.1-0.9, zbo-0.8, n is 0-2.

この新頭科にホウ酸塩又Ｕ　１７７酸Ｊｌの両金属化会
物のそれぞれのＸ線回折図とは別の新たな回折図？示し
、単なる混付物とに異なること金示している。Does this new head have a new diffraction pattern different from the respective X-ray diffraction patterns of both borate and U 177 acid Jl metallization? It shows that it is different from a mere adulterant.

次に、添付図面に工９、本発明顯、糾と、リン酸」１及
びホウ酸塩の防食性能について比較説明する。Next, with reference to the accompanying drawings, a comparative explanation will be given of the anticorrosion performance of the present invention, phosphoric acid 1, and borate.

図面は、メラミン・アルキド樹脂塗料に、金属がＢａ　
である上記顔料を配分した組成物の耐水性並びに防食性
と、組成物中のリン酸（刈並びにホウ威力のモル比の関
係を説明するグラフであって、○（本発明品）、１（混
合品）に耐水性、Δ（本発明品）、ム（！＃、金品）に
防食性を示している。The drawing shows melamine alkyd resin paint with metal Ba
1 is a graph illustrating the relationship between the water resistance and anticorrosion properties of a composition in which the above-mentioned pigment is distributed and the molar ratio of phosphoric acid and phosphorous power in the composition, ○ (product of the present invention), 1 ( Mixed product) shows water resistance, and Δ (product of the present invention) and Mu (!#, metal product) show corrosion resistance.

試験方法その他の条件は後記のｄＯである。The test method and other conditions are dO described below.

図から明らかなように、本発明顔料に、　Ｂ、Ｏ，／Ｐ
２Ｏ３（ｙ／”　）が０．１〜０．９のｉｉｉ［の略々
全域に亘って、防食性及び耐水性のいずれにｐいても混
合品よりすぐ扛ているが、この優位性灯耐水性において
ｙ／ｘが０．２５〜１．５、防水性にＪｒＶｈてｙ／ｘ
が０．５〜４．０の範囲が荷に顕著で、ｂ心。As is clear from the figure, the pigment of the present invention contains B, O, /P
2O3 (y/") is 0.1 to 0.9, which covers almost the entire range of iii [, both corrosion resistance and water resistance are superior to mixed products, but this superiority y/x is 0.25 to 1.5 for waterproofness, JrVh is y/x for waterproofness.
The range of 0.5 to 4.0 is significant for loads, and the B core.

矢に、第２の発明に、リン酸とホウ酸の系にケイ酸を導
入した顔料である。ＳｉＯ□）グリン酸塩及びホウ酸塩
の金属化置物の水に対する溶解度を梃に１氏ドさせる効
果があるが、逆に防食性能とじては遅効性となるので金
属に対するモル比ｆｍ　０．８以下に制限される。The second invention is a pigment in which silicic acid is introduced into a system of phosphoric acid and boric acid. SiO□) It has the effect of increasing the solubility of metallized phosphates and borates in water by 1 degree, but on the other hand, the anticorrosion performance is slow-acting, so the molar ratio to metal fm 0.8 Limited to:

以上↓す、特に耐水性が要求される塗料系では、溶Ｐ！
６度の小さい防錆顔料が適しており、Ｂ２Ｏ，ｚｐ、ｏ
。Above ↓, especially for paint systems that require water resistance, melt P!
Small anti-rust pigments of 6 degrees are suitable, B2O, zp, o
.

のモル比が０．２５〜１．５で、５ｉｎ２／　ＭｅＯが
０．１５〜０．８の範囲内が望ましい。父、荷に金ｔ４
素地との密着性が要求される塗料系でぼ、適正な溶解度
を有する防錆顔料が適しており、ＢｚＯｓ　／　Ｐ２０
＊のモル比が０．５〜４．０で、ＳｉＯ，／ＭｅＯＱ）
　％　ル比７５Ｅ　Ｏ〜０．４の範囲内が望ましい。It is desirable that the molar ratio of 5in2/MeO is 0.25 to 1.5 and 5in2/MeO is 0.15 to 0.8. Father, gold t4 in the cargo
For paint systems that require good adhesion to the substrate, anti-rust pigments with appropriate solubility are suitable, such as BzOs/P20.
The molar ratio of * is 0.5 to 4.0, SiO, /MeOQ)
% Le ratio is preferably within the range of 75E O to 0.4.

Ｂ、０３／Ｐ、ｏ、が０．１エリ小さくなると、図に示
す通り、防食性においてりン酸、・ケイ酸のバリウム化
合物とホウ酸・ケイ酸のバリウム化−８−物との乾式混
合品と比べて優位性がない。又Ｂｔ”ｓ　／　”２０ｓ
のモル比が９．０エリ大きくなると、耐水性において乾
式混合品と比べて優位性がない。本発明の新規顔料が乾
式混合品と比べて耐水性と防食性とｉＣ２いて丁ぐ几て
いるのｎ　Ｂ２Ｏ３／　Ｐ２Ｏ５のモル比力０．１〜９
．００〆α囲内であり、それ以外でに本発明の目的とす
る良好な耐水性と防食性とを弁用する顔料を得ることは
ほとんど期待できない。As shown in the figure, when B, 03/P, o becomes smaller by 0.1 eri, the dry process of barium compounds of phosphoric acid and silicic acid and barium compounds of boric acid and silicic acid improves corrosion resistance. There is no advantage compared to mixed products. Also Bt"s / "20s
When the molar ratio of 9.0 eri increases, there is no superiority in water resistance compared to dry blended products. The novel pigment of the present invention has better water resistance, anticorrosion properties, and iC2 density compared to dry blended products.
．． 00〆α, and otherwise it is hardly expected to obtain a pigment that exhibits the good water resistance and anticorrosion properties that are the objects of the present invention.

図に。おけゐ拭・倹方法等： （１）用いらｔｌ、定木溶性メラミン・アルキド樹脂ｍ
科の組成及び試験方法ぼ、後記実施列の方法と同じであ
る。In figure. Wiping/saving methods, etc.: (1) Used tl, wood-soluble melamine/alkyd resin m
The composition of the family and the test method are the same as those in the implementation series below.

（２）耐水性試験方法にＪ工５Ｋ５４ＵＯの７．２（耐
水（支）に準拠し、４０℃で５日間浸漬後の塗膜のフク
レｔ−５段階で評価し友。(2) Based on the water resistance test method 7.2 (Water Resistance) of J-K5K54UO, the coating film was evaluated as blistering T-5 after immersion at 40°C for 5 days.

ｌ（全面フクレ）→５（全く７クレなし）（３）防食性
試験方法ぼＪ工５Ｋ５４００の７．８（塩水噴霧試験）
に準拠し、４００時間試験後のクロス部フクレを５段階
で評価した。l (full surface blistering) → 5 (no blisters at all) (3) Corrosion resistance test method 7.8 (salt water spray test) for J Engineering 5K5400
Based on the above, the blistering at the cross section after the 400-hour test was evaluated on a five-grade scale.

ｉ（全ｇフクレ）→５（全＜７クンなし）（４）本発明
の顔料ぼリン酸化せ物としてヘキサメタリン酸ノーダを
用い、実施列ｌの方法に準じて調製し友。原料の添〃口
比率を変えて、グラフのｘ、ｙの比率の顔料を得た。そ
の熟成比率はＢａＯ＋＋　ｘＰ２０．　＊　ｙＢ２０．
　ｍ　Ｏ，２Ｓｉｎ、　ｍ　Ｏ，７Ｈ，Ｏである。i (total g blisters)→5 (total <7 no blisters) (4) Prepared according to the method of Example 1 using hexametaphosphate as the pigment phosphorylated saccharide of the present invention. By changing the additive ratio of raw materials, pigments with the ratio of x and y in the graph were obtained. Its aging ratio is BaO++ x P20. *yB20.
m O,2Sin, m O,7H,O.

（５）混合品ぼリン酸・ケイ酸のバリウム化合物力・ら
なゐ顔料と、ホウ酸・ケイ酸υバリウム化合物力・らな
る−顔料とを別々に調製し、乾式で混会してグラフの１
％７の比率に！疋ゐ工うＶＣ調督した。(5) Mixed products: A pigment made from a barium compound of phosphoric acid and silicic acid and a pigment made from a barium compound made of boric acid and silicate are prepared separately, mixed in a dry method, and then graphed. 1
The ratio is 7%! I managed the VC.

（’）　ｙ　ｔ＊・ケイ酸のバリウム化合物の調製方法
）■ヘキサメタリｙｄｌ、ソーダ３８Ｐを水５０５？に
溶解すゐ。(') yt*・Preparation method of barium compound of silicic acid)■ Hexametalyrydl, 38P of soda and 505% of water? It dissolves in.

０１号ケイ酸ソーダ（Ｅｌｌｏ、　３２チ′）金７ｙ−
用意する。No. 01 Sodium Silicate (Ello, 32') Gold 7y-
prepare.

■硫化バリウム溶液（ＢａＳ　１２チ）を２８９？調製
する。■Barium sulfide solution (BaS 12%) at 289? Prepare.

上記（Ｄ■■のそれぞｎの＠銭金５０℃に加温し、これ
らｔ別に用意した圧力容器に同時に添加しながら攪拌し
、反応させる。ついで１３０℃まで昇温し１引き続き６
時間攪拌した。反応液ｔブフナー漏斗で１遇し、このケ
ーキ（Ｉ−純水３８（Ｉ−用いて水洗丁ゐ。ついで水洗
ケーキ全１３０℃で１６時間乾燥し九後、サンプルミル
で粉砕して調製した。Heat each of the above (D■■) to 50℃, stir and react while simultaneously adding them to the pressure vessels prepared separately.Then, raise the temperature to 130℃, 1 successively 6
Stir for hours. The reaction solution was mixed in a Buchner funnel and washed with water using 38 ml of pure water.The washed cake was then dried at 130° C. for 16 hours, and then ground in a sample mill to prepare the cake.

（調製品の組成） （ホウ酸・ケイ酸のバリウム化付物の調製方法）■硼砂
（１０水塩）４４′ｔを水２０６？に溶解する。(Composition of prepared product) (Preparation method of barium adduct of boric acid/silicic acid) ■44't of borax (decahydrate) and 206 ml of water? dissolve in

０１号ケイ酸ソーダ（８ｉ０．３２チ）Ｊ＆ニアを用意
する。Prepare No. 01 Sodium Silicate (8i0.32ch) J & Nia.

■硫化バリウム溶液（Ｂａ８１２％）ｔ−３７５Ｐ＋４
１製する。■Barium sulfide solution (Ba812%) t-375P+4
Make one.

上記■（）０のそれぞれの溶液を５０℃に加温し、これ
らを別に用意した圧力容器に同時に添加しｌ孟がら攪拌
し、反応させる。ついで１３０℃まで昇温し、引き続き
６時間攪拌した。反応銭金ブ７ナー漏斗で１遇し、この
ケーキを純水３Ｂ紫用いて水洗する。ついで水洗ケーキ
を１３０　’Ｃで１６時間乾燥し友後、す／グルミルで
粉砕して調製した。The solutions of (1) and (2) above were heated to 50°C, added simultaneously to a separately prepared pressure vessel, and stirred to react. Then, the temperature was raised to 130°C, and the mixture was continuously stirred for 6 hours. The cake was washed with 3B pure water using a reaction funnel. The washed cake was then dried at 130'C for 16 hours, and then ground in a Su/Glumill.

（調製品の組成） 〔適用分野〕 本発明の新規顔料ａ１防錆顔料として広範囲ｒｌ塗料系
で有効である。例えば溶剤型塗料でぼ、油性系、アルキ
ド系、アミノアルキド系、アクリル系、フェノール系、
エポキシ系、ウレタン系、シリコーン系、ニトロセルロ
ース系、ビニル系、コム系の塗料に使用される。水系塗
料でに、水溶性あるいは水分散型のアルキド系、アクリ
ル系、エポキシエステル系塗料及びエマルション型のア
クリル系あるい（２アクリル・ステノン系塗料に使用さ
れる。その他下地金属金保贋する目的で使用さｔ′Ｌ／
）用途の樹ノ指系Ｖｃに例外ｒｇ　（用いることかでさ
る。防錆類Ｐ＋は、一般に金属用塗料に配合さ几て金属
素地の腐食を防止する鋤さ＋Ｃ丁心が、塗膜性能として
址属素池との密着性が要求される。父、防錆類＋＋を配
合した塗膜の耐水１生金悪化させｙ、（いことも大切で
ある。即ら金属素地との蓄溜性と、塗膜の１叶水性とが
同時に要求され６゜本発明の顔Ｒ’ｅ血科に配合した場
往には、を属素地との密着性及び耐水性ＶＣ′ｒぐれ、
塗膜のふく几金防止する効果に時性を発揮するので、位
属用塗料の防婿力？効果的に高める。(Composition of Preparation Product) [Field of Application] The novel pigment a1 of the present invention is effective as a rust-preventing pigment in a wide range of RL paint systems. For example, solvent-based paints, oil-based, alkyd-based, aminoalkyd-based, acrylic-based, phenolic-based,
Used in epoxy, urethane, silicone, nitrocellulose, vinyl, and comb paints. Used in water-based paints, water-soluble or water-dispersible alkyd, acrylic, and epoxy ester paints, and emulsion-type acrylic or (2) acrylic/stenone paints.Other used for the purpose of protecting base metals. used t'L/
) An exception to the tree-finger type Vc for use. As such, adhesion with the base metal is required.It is also important that the water resistance of the paint film containing anti-corrosion ++ deteriorates the raw metal. When compounded with the face R'e of the present invention, where both the water resistance and the water resistance of the coating film are required at the same time, adhesion to the substrate and water resistance of the paint film are required.
Because it exhibits a timely effect in preventing the buildup of the paint film, is it possible that the paint for the rank has a protective effect? Enhance effectively.

現在使用されている防４顔料？、防食機能別に分類する
と塩基性防錆顔料、不動態被膜形成防錆顔料、還元性防
錆顔料、金属石ケン杉成防４顔料及び顔料粒子の形状全
利用した防錆顔料とに分けられる。１１基性防錆順科に
は、鉛系（鉛丹、亜酸化鉛、／アナミド鉛、塩基性クロ
ム酸鉛等）やホウ酸系（メタホウ酸バリウム、ホウ酸カ
ルシウム、ボウｒＩ／、岨鉛等）があり、不動態１彼漠
形成防錆顔料にはクロム酸系（クロム葭亜鉛、クロム酸
ストロンチウム等）やモリブデン酸系（モリブデン酸亜
鉛、モリブデン改カルシウム等）、タングステン酸系、
リン酸系（リン酸亜鉛、リン、俊アルミニウム等）や有
機金属１系（有機ニトロ化汁物の唾鉛塩等）があり、還
元性防錆顔料にぼ笠属系（亜鉛末、アルミニウム末等）
や狙＋４７ＪＲ系がある。金属石ケン形成防４頭料にａ
鉛系、アルカリ土類金属系及び唾鉛系が、Ｉｔ）心。顔
料粒子のル伏を利用した防錆顔料には盛母状酸化鉄等か
あ／）。Anti-4 pigments currently used? When classified by anticorrosive function, they are divided into basic anticorrosive pigments, passive film-forming anticorrosive pigments, reducing anticorrosive pigments, metal soap suginasebo 4 pigments, and anticorrosive pigments that utilize all shapes of pigment particles. 11-based rust preventives include lead-based (redium, lead zinc oxide, lead anamide, basic lead chromate, etc.) and boric acid-based (barium metaborate, calcium borate, borium, lead chloride, etc.) etc.), and passive 1 desert-forming rust preventive pigments include chromic acid-based (chromic acid zinc, strontium chromate, etc.), molybdic acid-based (zinc molybdate, molybdenum modified calcium, etc.), tungstic acid-based,
There are phosphoric acid-based pigments (zinc phosphate, phosphorus, shun aluminum, etc.) and organic metal-based pigments (organic nitrated salivary lead salts, etc.). )
There is the Yaai +47 JR series. Metal soap formation prevention 4 to a
Lead-based, alkaline-earth metal-based, and salivary lead-based systems are important. Rust-preventing pigments that utilize the lubricity of pigment particles include iron matrix iron oxide, etc.

本＠明の顔４に、第１にＱ工垣基性防、端顔料としての
効果、即らＯａ、Ｓｒ、及びＢａ等の金属塩が塗膜中で
の水分の影響にエリ９居化し、素地鉄面を微アルカリに
保ち、安定な酸化ｆｆ１模を形成する。The main reason for the appearance of this @ Ming 4 is that the first effect is as a Q-based barrier and as an end pigment, that is, metal salts such as Oa, Sr, and Ba are converted into 9 groups due to the influence of moisture in the coating film. , the base iron surface is kept slightly alkaline to form a stable oxidized ff1 model.

第２にに、Ｃａ、’　Ｅｌｒ、　Ｂａ及びＺｎ　等の金
属は金属石ケン形成防ａ顔料としての機能金持ら、塗膜
ビヒクル中のノ信肪酸と金属石ケン金形成し、遊離脂肪
酸による金属素地面への付着阻害が防止される。第３に
ａ、リン酸及びホウ酸には不動態被膜形成作用があり、
金属面アノード域に生ずるＦｅ”イオンと反応して難溶
性の沈澱′ｆＪＩＬｒ！Ｘ　ｋ形成する効果を有する。Second, metals such as Ca, 'Elr, Ba and Zn have the function of metal soap forming anti-alkaline pigments, and the metal soap gold formation with fatty acids in the coating film vehicle, resulting in the formation of free fatty acids. Adhesion to the metal base surface is prevented. Thirdly, phosphoric acid and boric acid have a passive film forming effect,
It has the effect of reacting with Fe'' ions generated in the metal surface anode region to form a hardly soluble precipitate.

従って、従来からの塩基性防錆顔料、不動態被膜形成防
錆顔料及び金属石ケン形成防錆顔料、例えばクロム酸系
、鉛系、リン酸系、モリブデン酸系、タングステン酸系
、ホウ酸系及び有機金属塩系防錆顔料が１吏用されてい
るａ科系において、それらの防Ｏ１１顔料と同様の１更
用方法にて、本発明の顔料全単独ないし曲の防錆顔料と
併用して使用することが＝を１能であり、又峨元性防錆
顔料及び顔料粒子の形状を利用した防錆顔料が１吏用さ
れている塗料系においても、それらと弁用して一防錆効
果を上げることができる。Therefore, conventional basic anticorrosive pigments, passive film-forming anticorrosive pigments and metal soap-forming anticorrosive pigments, such as chromic acid, lead, phosphoric acid, molybdic acid, tungstic acid, and boric acid-based In family A systems in which organic metal salt-based rust-preventing pigments are used, the pigments of the present invention can be used alone or in combination with rust-preventing pigments in the same way as those for those O11 pigments. In addition, it can be used in combination with anti-rust pigments and anti-rust pigments that utilize the shape of pigment particles in paint systems that use them. It can improve the rust effect.

尚、本発明の頓科は白色であるのでクロム酸系顔料と異
なり、塗料を任意に着色できることも特長の一つである
。Incidentally, since the pigment of the present invention is white, one of its features is that, unlike chromic acid pigments, the paint can be colored arbitrarily.

〔離燃効果〕[Separation effect]

本発明の″ｔｒ規顔料は難燃剤として、グラスチック、
ゴム、ｍ科及び繊維に配合されて有効である。The "tr" pigment of the present invention can be used as a flame retardant, such as glasstic,
It is effective when blended with rubber, rubber, and fibers.

例えばプラスチックでに塩化ビニル系、ポリエステル系
、ポリオレフィン系、ポリスチレン系、エポキシ系、フ
ェノール系及びアクリロニトリル・ブタジェン・スチレ
ン樹脂（ＡＢＳ）等に使用式れゐ。For example, it can be used for plastics such as vinyl chloride, polyester, polyolefin, polystyrene, epoxy, phenol, and acrylonitrile butadiene styrene resin (ABS).

ゴムでＨ，塩化ゴム、ハイパロン、塩臭化ポリエチレン
ゴム、エチレン・グロビレンゴム及ヒ二トリル・フ゛タ
ジエンゴム等に１史用される。In rubber, it has been used in H, chlorinated rubber, Hypalon, chlorobrominated polyethylene rubber, ethylene/globylene rubber, and nitrile/phytadiene rubber.

塗料でＩζ、塩化ゴム系、塩化ビニル系、アルキド系、
油性系、フェノール系及びエボギシ系ｍ科等に使用さ几
ゐ。Paints include Iζ, chlorinated rubber, vinyl chloride, alkyd,
Used for oil-based, phenol-based, and elegance-based products.

繊維でに、ポリ塩化ビニル系、ポリアミド系、ポリニス
デル系、ポリオレフィン系、ポリアクリルニトリル系、
ポリビニルアルコール系繊維等に使用される。Fibers include polyvinyl chloride, polyamide, polynisder, polyolefin, polyacrylonitrile,
Used for polyvinyl alcohol fibers, etc.

その他禰燃性を要求される用途のプラスチック、ゴム、
塗料及び繊維に例外ｒｘ、　＜用い／）ｃとができる。Plastics, rubber, etc. for other uses that require flammability,
An exception is made for paints and textiles.

本発明の新規顔料に、従来刀・らのホウ酸系難燃ｊｌＪ
　（ホウ砂、ホウ酸、ホウ酸亜鉛、メタポウ酸バリウム
等）と同様ｒｌ緬燃機能を有する。即ら本発明の顔料と
塩素系難燃剤（塩化パラフィン等）と全併用することに
より、可燃物の表面金被覆する機能を有する。The new pigment of the present invention has been added to the conventional boric acid flame retardant
It has the same RL function as (borax, boric acid, zinc borate, barium metaborate, etc.). That is, by using the pigment of the present invention in combination with a chlorinated flame retardant (chlorinated paraffin, etc.), it has the function of coating the surface of combustible materials with gold.

燃焼時には、塩素系難燃剤が分解して発生する塩化水素
ガスによって、本発明の顔料が分解してホウ酸を生じ、
これが可燃物の表面金被覆して酸素をしゃ断し燃焼を防
ぐのである。During combustion, the pigment of the present invention is decomposed by hydrogen chloride gas generated by the decomposition of the chlorine-based flame retardant, producing boric acid.
This coats the surface of combustible materials with gold to cut off oxygen and prevent combustion.

更に三酸化アンチモン全併用する場汗ニ、＃燃効釆がエ
リ有効に発揮されるので、不うと一！Ａｖ順料と三酸化
アンチモノと塩素系難燃剤とθ組合せて使用することが
望ましい。In addition, if antimony trioxide is used in combination, the combustion effect will be effectively demonstrated, so it will be the best! It is desirable to use Av additive, antimono trioxide, and chlorine-based flame retardant in combination.

〔防かび効果〕[Mold-proofing effect]

本発明の新規顔料に防がび剤として、塗料、プラスチッ
ク、ゴム、接着剤、繊維、紙及びセメント等に配合され
て有効である。The novel pigment of the present invention is effective when incorporated into paints, plastics, rubber, adhesives, fibers, paper, cement, etc. as a fungicide.

金丹でに、溶剤型塗料及び水系塗料に使用できる。溶剤
型塗料としてぼアクリル系、アルキド系、油性系、セル
ロース系、エポキシ系及びウレタン系塗料等、水系塗料
でに酢酸ビニル系、アクリル系、スチレ／φブタジェン
系及びアルキド系塗料等に使用できる。Golden red can be used in solvent-based paints and water-based paints. It can be used as solvent-based paints such as acrylic, alkyd, oil-based, cellulose-based, epoxy and urethane-based paints, and as water-based paints such as vinyl acetate-based, acrylic-based, styrene/φ-butadiene and alkyd-based paints.

ゴムでｔｑ、　天ｆｉゴム、スチレン−ブタジェンゴム
、イングＶ／ゴム、ブタジェンゴム等に使用で＠ゐ。It can be used for rubber such as TQ, Tenfi rubber, styrene-butadiene rubber, Ing V/rubber, butadiene rubber, etc.

接着剤では、でんぷん、カゼイン、ｎ酸ビニル系、ゴム
系、セルロース系、ポリエステル系、エポキシ系、ウレ
タン系、フェノール系接層剤等に使用できる。Adhesives that can be used include starch, casein, vinyl n-acid, rubber, cellulose, polyester, epoxy, urethane, and phenol adhesives.

その他防かび性全要求さｔ′Ｌる用途の塗料、プラｘチ
ツｙ、−ｔム、接層ｆＮＪ、繊維、紙及びセメント等に
例外なく用いることができる。It can be used without exception in paints, plastics, adhesive layers, fibers, paper, cement, etc., which require all mold resistance.

近年、防〃為び剤の毒性が問題とされ、有機水銀化合・
吻（酢酸フェニル水銀４）、有機錫化ト勿（ピストリブ
トル錫オキサイド等）及びペンタクロロフェノール等毒
性の強い防かび剤（グ使用が１１ｉＩＩ限されてきてお
り、毒性の弱い防かび剤、例えば有機窒素イオウ系、キ
ノン系、サリチル酸系、有機銅系、イミダシリン系、グ
ロロニトリル系及びホウ酸系防かび剤等が使用されてい
る。In recent years, the toxicity of anti-fouling agents has become a problem, and organic mercury compounds and
The use of highly toxic fungicides (eg, phenylmercury acetate), organic tinned compounds (such as pistributol tin oxide), and pentachlorophenol has been limited, and the use of less toxic fungicides, such as organic Nitrogen-sulfur-based, quinone-based, salicylic acid-based, organic copper-based, imidacillin-based, gloronitrile-based, and boric acid-based fungicides are used.

本発明の顔料に、従来のホウ酸系防かび剤（ホウ砂、メ
タホウ酸／＜　ＩＪウム等）と同様な防かび機能金有し
、毒性の弱い防刃・び剤として広い用途に使用できる。The pigment of the present invention has the same anti-fungal properties as conventional boric acid-based anti-fungal agents (borax, metaboric acid/<IJium, etc.), and can be used in a wide range of applications as a mildly toxic blade and anti-fungal agent. .

即ら、塗料、プラスチック、ゴム、接層剤、繊維、紙及
びセメント等にＥ配合されると、各組成物中に存在する
水分の＃響で一部ｄｆ溶化して弱アルカリ性となる機能
と、ホウ酸イオンの酸化　索抑制機能との相乗作用に工
って有効な防かび性を示すのである。That is, when E is added to paints, plastics, rubber, adhesives, fibers, paper, cement, etc., it has the function of becoming weakly alkaline by partially dissolving DF due to the presence of water in each composition. It exhibits effective anti-fungal properties due to its synergistic effect with the oxidation inhibition function of borate ions.

ホウ砂は水溶解性が大きく、起片した組成°吻の耐水性
を悪くし、防刃・び効果も持続性金持たないが、本発明
の顔４＋は水溶解性金４正に調整で＠るので組成物の耐
水性を悪くすることなく、助力・び効果も長期間にわ之
って持続させることができる。Borax has a high water solubility, and its fragmented composition impairs the water resistance of the proboscis, and does not have a long-lasting anti-cutting effect, but the face 4+ of the present invention can be adjusted to the water-soluble gold 4 positive. Because of this, the water-resistance of the composition is not deteriorated, and the aiding and strengthening effects can be maintained for a long period of time.

従って、本発明の顔料を単独ないし曲の防〃・び剤と併
用して使用することにエリ、長期間にわたりて防かび効
果を持続させることができる。；〔製造方法〕 次に本発明の新規顔料の＃！遣方法についで説明する。Therefore, when the pigment of the present invention is used alone or in combination with a mold-preventing agent, the mold-preventing effect can be maintained over a long period of time. ; [Manufacturing method] Next, #! of the new pigment of the present invention. I will explain how to send it.

原料にＦ記の４種類である。There are four types of raw materials listed in F.

■　Ｏａ、　Ｓｒ、　Ｂａ、　Ｚｎ、　ｋｌ　の化合物
は各金属の水溶性化置物が望ましい。例えば硫化物、塩
化吻、硝酸塩、＃酸塩、１Ｉｉｌｆ酸塩等である。更に
金属単体、金属酸化物あるいに金属炭酸塩で、リン酸化
合物とポウ酸化合物との水溶液と反応性１ｎ−るもので
も良い。■ Compounds of Oa, Sr, Ba, Zn, and kl are preferably water-solubilizing compounds of each metal. For example, sulfides, chlorides, nitrates, #acids, 1Iilfates, etc. Further, it may be an elemental metal, a metal oxide, or a metal carbonate, which is reactive with an aqueous solution of a phosphoric acid compound and a porous acid compound.

■　りン酸化会物μ正すン識、縮合リンＩ設あるいに正
リン酸、ａ曾すン酸のカリタム又はナトリウム塩である
。■ Phosphate compounds are the potassium or sodium salts of condensed phosphorus, orthophosphoric acid, and phosphoric acid.

■　ホウ酸化・汁物ａホウ酸あるいはホウｒ朦のカリウ
ム又ぼナトリウム塩である。■Boric acid/soup a It is boric acid or potassium or sodium salt of boric acid.

■　ケイ酸化合物にケイ酸あるいにケイ酸のカリウム又
にナトリウム塩である。■ Silicic acid compounds include silicic acid and potassium or sodium salts of silicic acid.

上記■■■■又μ■■■それぞれの水溶液又はＩ罎濁液
を用意し、別に用意した容器に同時に添加しながら攪拌
し、反応させる同時反応方式あるいば別の方法として■
■〔■〕と■■〔■〕とを別々に反応させた後、両反応
液を混合する門別反応混仕方式がある。A simultaneous reaction method in which an aqueous solution or I suspension of each of the above ■■■■ and μ■■■ is prepared and simultaneously added to a separately prepared container while stirring to react, or another method is
There is a reaction mixing method in which ■[■] and ■■[■] are reacted separately and then both reaction solutions are mixed.

反応時の温度及び′ａ度μ特に限定するものでぼないが
、工業的生産でに１００℃以下、好ましくは２０′Ｃ〜
７０℃で、できるだけ高ｄ度、好ましくに各原料水溶液
の飽和濃度に近い濃度が有利である。The temperature during the reaction and 'a degree μ' are not particularly limited, but in industrial production it is 100°C or less, preferably 20'C~
At 70° C., it is advantageous to have as high a degree of d as possible, preferably a concentration close to the saturation concentration of each raw material aqueous solution.

上記同時反応方式あるいぼ個別反応混合方式によって得
られたスラリー全圧力容器に入れ１００℃〜２００℃の
温度で１時間以−ヒ、好ましくぼ４時間程度、竜拌しな
がら水熱・“匙理紫ｆ／）。あるいぼ初めから圧力容器
中で混甘し１００Ｃ〜２００℃の温度で水熱処理上行う
こともできる。The entire slurry obtained by the above simultaneous reaction method or individual reaction mixing method is placed in a pressure vessel and heated at a temperature of 100°C to 200°C for 1 hour or more, preferably about 4 hours, while stirring. Violet f/).It is also possible to mix the plant from the beginning in a pressure vessel and perform hydrothermal treatment at a temperature of 100C to 200C.

次いで得ら′ｎｆｃ反応生成物全通常の方法でｆ過水洗
を行う。水洗度についてｒｓ、Ｐ液比抵抗が略一定にな
るまで行うことが適当である。水洗したケーキをｌ　２
０　Ｃ以上の温度、好ましくは１２０Ｃ〜３００℃で乾
燥し友後粉砕して本＠明の顔料全製造する。The NFC reaction product obtained is then washed with water in a conventional manner. Regarding the degree of water washing, it is appropriate to carry out the washing until the specific resistance of the P liquid becomes approximately constant. 2 l of washed cake
It is dried at a temperature of 0 C or higher, preferably 120 C to 300 C, and then ground to produce the entire pigment.

〔実施例〕〔Example〕

以下実施例によって本発明を説明する〇実施Ｍ　１ ■　リン酸三ナトリウム（１２水塩）７７５’ｅ水１７
３Ｆに溶解する。The present invention will be explained below with reference to examples.
Dissolve in 3F.

■　硼砂（１０水塩）４４ｔを水２０６９−に溶解する
。■ Dissolve 44 tons of borax (10 hydrate salt) in 2069 kg of water.

■　１号ケイ酸ソーダ（５ｉｎ２３２％）金１４を用意
する。■ Prepare No. 1 sodium silicate (5in 232%) Gold 14.

■　硫化バリウム溶液（Ｂａ５Ｌ２チ）　ｆ’ｌ　ｓ　
ＯｐＨｆｌ＃する。■ Barium sulfide solution (Ba5L2) f'l s
OpHfl#.

と記■■■■のそ几ぞれの溶故金５０℃に加温し、これ
らを別に用意した圧力容器に同時に添加しながら攪拌し
反応させる。ついで１３０℃まで昇温し、引き、続き６
峙ｌｉＪ］攪拌した。反応液をブ７ナーロートで１遇し
、このケーキを純水３ｎｔ−用いて水洗丁ゐ。ついで水
洗ケーキを１３０℃で１６４間乾燥し之後、サンプルミ
ルで粉砕して顔料（ｉ−４友。Heat each of the molten metals described in ■■■■ to 50°C, and add them simultaneously to a separately prepared pressure vessel while stirring and reacting. Then, raise the temperature to 130℃, lower it, and continue 6
] Stirred. The reaction solution was filtered once through a 7-nerat funnel, and the cake was washed with 3 nt of pure water. The washed cake was then dried at 130°C for 164 hours, and then ground in a sample mill to form a pigment (i-4 friend).

この顔料の組成を表１に示し、更に防食性試験の結果を
表２−？６に示す。２ 実施列２ ■　リン酸三ナトリウム（１２水塩）７７ｙ−を水１７
３ｙ−にン容解する。The composition of this pigment is shown in Table 1, and the results of the corrosion resistance test are shown in Table 2-? 6. 2 Example row 2 ■ Trisodium phosphate (12 hydrate) 77y- to water 17
3y-nin understand.

■　硼砂（２０水塩）３５５’を水ｘ６ｓｙＶｃ溶４す
る。■ Dissolve 355' of borax (20 hydrate salt) in 4 x 6 syVc of water.

■　１号ケイ酸ソーダ（Ｓｉｎ、　３２慢）金１４Ｐ用
意する。■ Prepare 14P of No. 1 Sodium Silicate (Sin, 32C) gold.

■　硫化ストロンチウム溶液（ＳｒＳ　８．５チ）金７
５０ｙ−調製する。■ Strontium sulfide solution (SrS 8.5T) gold 7
50y- Prepare.

上記■■■■のそれぞれの溶銭金５０　’ＣＶＣ加温し
反応させる。ついで１３０℃まで昇温し、引き続＠６時
間１：燻拌した。反応ｔＬ（ｉニブフナ−ロートで１遇
し、このケーキを純水３４ｉ用いて水洗する。Heat 50' CVC of each of the above molten metals and react. Then, the temperature was raised to 130°C, and the mixture was continuously smoked for 6 hours. Reaction tL(i) was mixed once in a nibuchner funnel, and the cake was washed with 34ml of pure water.

ついで水洗ケーキｉｔ、１３０℃で１６時間乾燥しｆＣ
後、サンプルミルで粉砕して顔料ｔ−得几。この顔料の
組成を表１に示し、更に防虞性試験の結果を表２〜６に
示す。Then, the water-washed cake was dried at 130℃ for 16 hours and fC
After that, it was ground in a sample mill to obtain pigment. The composition of this pigment is shown in Table 1, and the results of the risk-proofing test are shown in Tables 2-6.

実施例３ 反応物Ａの調製 ■　リン酸三ナトリウム（１２水塩）７７ｆｉ’ｔ−水
１７３ｙ−に溶解する。Example 3 Preparation of Reactant A (1) Trisodium phosphate (12 hydrate) is dissolved in 77 fi't of water.

■　１号ケイ酸ソーダ（８ｉ０２３２チ）′（１１−７
ｆＦ用意する。■ No. 1 Sodium Silicate (8i0232chi)' (11-7
Prepare fF.

■　硫化バリウム溶液（ＢａＳ　ｌ　２４　）　ｔ−３
７５ＰＪ４製する。■ Barium sulfide solution (BaS l 24 ) t-3
Manufactured by 75PJ4.

上記■■■のそれぞれのめ′ｅ、を５０℃に加温する。Heat each of the above-mentioned holes to 50°C.

これらを別に用意した圧力４器に同時に添加しながら攪
拌し反応させる。These are simultaneously added to four pressure vessels prepared separately while stirring and reacting.

反応物Ｂの、Ｊ解裂 ■　硼砂（１０水塩）４４？ｉ’／に２０６１ｉＦ−に
溶解′ｒ心。J cleavage of reactant B ■ Borax (decahydrate salt) 44? i'/dissolved in 2061iF-'r heart.

（９１号ケイ酸ソーダ（８１０，３２％）全７を用１区
すゐ。(No. 91 Sodium Silicate (810,32%) All 7 are used in 1 section.

■　硫化バリウム、＠液（ＢａＳ　１２チ）　ｆ　３７
５　Ｐ１衷Ｔ　’ｂ　。■ Barium sulfide, @liquid (BaS 12cm) f 37
5 P1 衷T'b.

上記■■（ののそれぞれの浴液を５００に加４し、これ
ら音別に用意した圧力容器に同時に添カロしながら攪拌
し反応させる。反応物ＡとＢとｔ別の圧力＃ａに人ルで
混合し几後、１３０　ＩＣまで上昇し引き続き６時間攪
拌した。反応液金ブフナーｏ　−トでＰＩＭし、このケ
ーキを純水３　Ｊ３　ｆｃ用いて水洗する。ついで水洗
ケーキｉ　、ｌｉ（３０”Ｃで１６時間乾燥した後、サ
ンプルミルで粉砕して顔料金得た。Add 500% of each of the above bath solutions and react by stirring and reacting at the same time into pressure vessels prepared separately. After mixing and cooling, the mixture was raised to 130 IC and stirred for 6 hours.The reaction solution was PIMed with gold Buchnert, and the cake was washed with pure water 3J3 fc.Then, the washed cakes i and li (30" After drying at C for 16 hours, it was ground in a sample mill to obtain a pigment.

この顔料の組成２表１に示し、更に防食性試験の結果を
表２〜６に示す。The composition of this pigment is shown in Table 2, and the results of the corrosion resistance test are shown in Tables 2 to 6.

実Ｍ例４ ■　リン酸三ナトリウム（１２水塩）７７？（＋−水１
７３５１’に溶解する。Actual M Example 4 ■ Trisodium phosphate (decahydrate) 77? (+-water 1
Dissolves in 7351'.

■　硼砂（１０水塩ン４４　ｐ’ｉ水２０６１ＣＭ＋１
丁ゐ。■ Borax (10 water salt 44 p'i water 2061CM+1
Ding.

■　硫化バリウム溶液（ＢａＳ　１２φ）金７５０を調
製する。(2) Prepare barium sulfide solution (BaS 12φ) gold 750.

上記［Ｆ］■■のそれぞれの溶銭金５０　’Ｃに／ＪＬ
Ｉ温し、これＩ−１勿別に用意した圧力容器に同時に添
／Ｊｌｌ　Ｌ　ｔ’ｘ。For each of the above [F]■■ melted coins 50'C/JL
Warm the mixture and add it simultaneously to the pressure vessel prepared separately.

がら撹拌し反応させゐ。ついで１３０　Ｇまで昇温し、
引き続＠６時間攪拌した。反ＬＩＪ　７にτブ７ナーロ
ートでＣ遇し、このケーー？全純水３．６に用いて水洗
する。ついで水洗ケーキ１１３０ｃで１６時間乾燥し７
２．後、サンプルミルで粉砕して顔料金得た。この顔料
の組成を表１に示し、更に防食性試験の結果を表２〜６
に示した。Stir thoroughly to react. Then, the temperature was raised to 130 G,
Stirring was continued for 6 hours. Anti-LIJ 7 was treated with C by τb7naroth, and this case? Wash with pure water (3.6). Then, dry the washed cake for 16 hours at 1130c.
2. After that, it was ground in a sample mill to obtain a pigment. The composition of this pigment is shown in Table 1, and the results of the corrosion resistance test are shown in Tables 2 to 6.
It was shown to.

表１　顔料の組成 ※　６００℃で２４間力ｎ熱後の減破全ｄ分率で示した
。Table 1 Pigment composition* Shown as total d fraction after heating at 600°C for 24 hours.

防食（性試験 ＋ＡＪ　＊　Ｊ　１生メラミン・アルキド＋封）Ｍ　ａ
　４”ｆｉｌｌ　塗４＋岨成 顔料重竣鎮度（ＰＷＣ）　５　Ｕチ ＊１　日本ライヒホールド（株ン製、水溶１生アルキド
１１１脂、Ｉ稲１）［ら分６５９６ ※２　日本ライヒ小−ルド（休）製、水ｍ１生メラミン
園ｊ旨。Corrosion prevention (sex test + AJ * J 1 raw melamine alkyd + seal) M a
4” fill Coating 4 + Pigment heavy finish (PWC) 5 Uchi*1 Nippon Reichhold (manufactured by Co., Ltd., water-soluble 1 raw alkyd 111 fat, I-rice 1) [Ramin 6596 *2 Nihon Reich small-hold (closed), water m1 raw melamine garden j.

固形分６６％ （２）　試験板の作成 基板：ボ／・プライト＄１４４処理軟鋼取焼付二６０℃
×２０′後　１４０ＣＸ３ｏ’膜厚：２０−１３μ（１
−Ｃｏａｔ） （３）　試俟績果 表　２ ※ＪＩＳ　Ｋ　５４００　Ｌ’）　７８　に準嘘し、４
００時間試験ケ行った。塗ｊ漠の平面部とクロス部の７
タレの密度を目視評価し、クロス部金セロテープにテパ
ン製２４辱籾Ｃ剥離して剥離ｒｌＪ金測定し、片ｌｌｌ
１易で表示した。Solid content 66% (2) Test plate creation Substrate: Bo/Prite $144 treated mild steel 260℃
× 20' after 140CX3o' film thickness: 20-13μ (1
-Coat) (3) Test result table 2 *JIS K 5400 L') 78, 4
00 hour test was conducted. 7 of the flat part and cross part of the desert
Visually evaluate the density of the sauce, peel off Tepan's 24 paddy C on the cross section gold cellophane tape, measure the peeling rl J gold, and measure the peeling.
Displayed in 1 easy.

水分散差エポキシ変性耐ｔ＋Ｖｔ塗料 （υ　塗＋１）組成 顔料Ｉｔ量Ａ度＜ｐｅａ）５６チ 壷　日本触媒化学工業（抹）装、水分散型エボキ７変性
１対Ｉｊ旨、　−ノ杉分４０　％ ＋２７　、、Ｉ、試験板の作成 基板：未処理磨軟鋼板 乾燥：室温５日間 膜厚：５１−５５μ（２−Ｃｏａｔ） （３）　試１倹結釆 表　３ （ＯＪ　アクリルエマルジョン塗料 （Ｉ）塗料組成 顔料重重濃度（ＰＷＯ）　５８チ 毫　ローム・アンド・八−ス社裏、アクリルエマルジョ
ン、固形分　４６％ （２）　試験板のｒｌ：成 基板：未処理磨軟鋼板 乾燥二ｙ温５日間 膜厚：５８〜６２μ（２−ｃｏａｔ） り３）試験結果 表　４ （句　中油性アルキド１封ｊ指ｍ科 （１１塗４＋組成 顔料重置ａ度（ｐｗｏ）　４９９６ 毫　日本ライヒホールド（銅製、アマニ油変性アルキド
樹脂、油長５２％、固形分５０チ゛（２）　試験板の作
成 基板：ポルデライト＄１４４処理軟鋼板乾燥：室温５日
間 膜厚：３１〜３３μ（１−Ｃｏａｔ） （３）　試験結果 表　５ （均　フェノール変性アルキド樹脂塗料１１）　ａ、科
組成 （イ」　ド　塗　Ｖ　塗孝斗 ｔｓｔｔａ度（ｐｒｏ）　６０　％ ※　日本ライヒホールド（甲裏、フェノール変性アルキ
ド樹脂、油長５２・メ、１１！ＬＩ形汁５０チ（弓　上
塗り塗料 顔料点景濃度（ＰＷＯ）　４９％ （２）　試１倹板の作成 基板：未処理磨軟鋼板 乾燥：下塗り塗料塗布後２日間室温乾燥し、と塗り塗料
塗布後５日間室温乾燥 Ｊ漢ノ４：下塗０塗膜３２〜３５μ 上塗り塗ｊ莫２９〜３３μ （３）試験結果 表　６Water dispersion differential epoxy modification resistant t + Vt paint (υ coating + 1) composition Pigment It amount A degree < pea) 56 bottles Nippon Shokubai Chemical Co., Ltd., water dispersion type epoxy 7 modification 1 to Ij effect, -Nosugi portion 40 % +27,, I, Preparation of test plate Substrate: Untreated polished mild steel plate Drying: Room temperature for 5 days Film thickness: 51-55μ (2-Coat) (3) Trial 1 Savings Table 3 (OJ Acrylic emulsion paint (I) ) Paint composition Pigment concentration (PWO) 58 cm Rohm & Eighth Co., Ltd., acrylic emulsion, solid content 46% (2) Test plate RL: Substrate: Untreated polished mild steel plate Dry at 5 yen temperature Daily film thickness: 58-62μ (2-coat) 3) Test results table 4 , linseed oil-modified alkyd resin, oil length 52%, solid content 50% (2) Test plate creation Substrate: Polderite $144 treated mild steel plate Drying: 5 days at room temperature Film thickness: 31-33μ (1-Coat) (3) Test result table 5 (Uniform phenol-modified alkyd resin paint 11) a. Family composition (I) Coating V Coating degree (pro) 60% * Nippon Reichhold (back of upper, phenol-modified alkyd resin, oil length 52. Me, 11! LI type juice 50chi (bow) Topcoat paint pigment odor concentration (PWO) 49% (2) Trial 1 Creation of board Substrate: Untreated polished mild steel board Drying: After applying the undercoat paint, dry at room temperature for 2 days, Dry at room temperature for 5 days after application.Undercoat 0 coating 32-35μ Topcoat 29-33μ (3) Test results table 6

【図面の簡単な説明】[Brief explanation of drawings]

添付図面に、水浴性メラミン・アルキド樹Ｊ１旨塗料に
、本発明の顔料及び従来顔料の混汁物ケ配合し′／ｃ場
会の防食性並びに耐水性と、Ｂ２０．／Ｐ２０゜（ｙ／
ｘ）　の関係全説明するグラフであって、Δムは防食性
、○・は耐水性金示す。 ■ 手続補正書 昭和５９年１月２７日 ’ｌ１ＩＦ順昭５８−１９８９１１万 ２、発明の名称 新規顔料 ３、補正ｋｆｂ者 代表者　松　本　１４ ４、代理人 東京都千代田、Ｘ丸の内二「ｄ４ｉ１号５、補正酷舎の
日付　自　活 ６、補正の対象 明細薯の爵＋ｉ’Ｆ　請求の範囲、発明の詳細な説明の
薦ｉｌｌ　明ａ沓の特許請求の範囲を横を別紙のとおり
訂正する。 （２）　明Ｉ咄誓中、下記のとおり訂正する。 頁　行　誤　正 ３２〜３　鉄鋼　金属 ５　８　ｘｓ　Ｙｓ　ｚｘｓ　７−　ｚｓ　ｎｏ　５１
１　新顔料　新規顔料 ５１７　メラミン−アル中ト水溶ｉ生メラミンＱア千ド ロ　４　Ｂ、Ｏ，’　Ｂ２０゜ ６　５　Ｆ、０３Ｆ、０゜ ６８　防水性　防食性 ７１３　併用　１ｊＦ有 −１０１３６，１３６１，３ １４１０１脣化　塩素化 １６１９　ピストリプトル錫　ビストリブチル錫１７１
１〜１２　酸化　素　酸化酵素 ２２８　圧力容器　容器 ２２１８　圧力容器　（各４ 〔別紙〕 特許請求のｌｉ！ｄ ＋１）　ＩＪン酸化合物及びホウ酸化合物と、Ｏａ％ｓ
ｒ。 Ｂａ、Ｚｎ、　Ａｔ　Ｏ化合物のｈ　４ｆｆｌ又ぼ２種
以上とを反応させて優られ、その組成が ＭｅＯ＠　ＸＰ、Ｏ，、＠　ｙＢ２０．　ａ　ｎＨｌＩ
Ｏここに、Ｍｅ　（１０ａ、　Ｓｒ、　Ｂａ、　Ｚｎ、
　Ａｔｆ示し、ｂｙ、ニーμそれぞれＭθＯ１モルに対
して、Ｘ　＆：ｃＯ，１〜０．９．７　ＰＩ　１）、　
１〜０．９、ｎｒｚｏ〜２である で表わされる新規顔料。 （２）　りン設化会物、ホウ酸化会゛吻及びケイ酸化合
物と、Ｏａ、　Ｓｒ、　Ｂａ、　Ｚｎ、　Ａｔ　の化付
物の１４４又ｒＣ２檎以上とを反応させて得られ、その
組成が ＭｅＯ＠ｘＰｔＣ１，＊　ｙＢ２０．１１　ＺＳ　ｉｏ
、　＊　ｎＬ輸０ここに、Ｍｅ　ｉ　Ｏａ％５ｒ１Ｂａ
、　Ｚｎ、　Ａｔｆ示し、！、　７．　ｚ、ｎＦｌそれ
ぞれＭｅｏ　１モルに対して、Ｘ　ｆＸ　Ｏ，１〜０．
９．７　ｆＸ　Ｏ，ｌ　−１１，９、ｚ１’！　０．８
以Ｆ、ｎ１ｘｏ−２でｈｂで表わされる新規顔料。The attached drawings show that a mixture of the pigment of the present invention and a conventional pigment is blended into a water-bathable melamine alkyd resin J1 paint to provide corrosion resistance and water resistance of B20. /P20゜(y/
x) is a graph that fully explains the relationship, Δm indicates corrosion resistance, and ○ indicates water resistance. ■ Procedural amendment January 27, 1989 'l1IF order 1989-1989112, name of invention New pigment 3, amendment kfb representative Matsumoto 14 4, agent Tokyo Chiyoda, X Marunouchi 2 "d4i1" 5. Date of amendment 6. Recommendation of the scope of the amendment and detailed description of the invention The scope of the claims of the patent is corrected as shown in the attached sheet. (2) During the Mei I swearing, the following corrections are made. Page Line Wrong Correct 32-3 Steel Metal 5 8 xs Ys zxs 7- zs no 51
1 New Pigment New Pigment 517 Melamine-aluminum water soluble raw melamine Q 1,000 4 B, O,' B20゜6 5 F, 03F, 0゜68 Waterproofing Corrosion resistance 713 Combined use 1jF-10136, 1361, 3 14101 Chlorination 1619 Pistryptoltin Bistributyltin 171
1 to 12 Oxidizing element Oxidizing enzyme 228 Pressure vessel Container 2218 Pressure vessel (4 each [Attachment] Patent claim li!d +1) IJ phosphoric acid compound and boric acid compound, and Oa%s
r. Ba, Zn, At2O compounds are reacted with h4ffl or two or more types, and the composition is MeO@XP,O,,@yB20. a nHlI
O here, Me (10a, Sr, Ba, Zn,
Atf, by, nee μ, respectively, for 1 mol of MθO, X &: cO, 1 ~ 0.9.7 PI 1),
1-0.9, nrzo-2. (2) A compound obtained by reacting a phosphorous compound, a boric acid compound, and a silicic acid compound with 144 or rC2 or more of a compound of Oa, Sr, Ba, Zn, At, and having the following composition: is MeO@xPtC1, *yB20.11 ZS io
, * nL import 0 here, Me i Oa%5r1Ba
, Zn, Atf,! , 7. z, nFl, respectively, X fX O, 1 to 0.
9.7 fX O,l -11,9,z1'! 0.8
F, a new pigment represented by hb in n1xo-2.

Claims (1)

【特許請求の範囲】 ｉｌｌ　Ｕノ酸化会物及びホウ酸化合物と、Ｑａ、Ｓｒ
。 Ｂａ、　Ｚｎ、　Ａｔの化＠−物の１橋又は２橋以上と
を反応させて得られ、その組成が ＭｅＯａ　ｘＰ２０．　＊　７Ｂ２０３＊　ｎＨ２Ｏで
表わされる新＠順料。 （２）リン酸化合物、ホウ酸化合物及びケイ酸イヒ曾物
と、Ｇａ、　Ｓｒ、　Ｂａ、　Ｚｎ、　Ａｔ　の化縫物
の１ｍ父に２橋以上とを反応させて得られ、その組成が ＭｅＯ＠　ＸＰｔ０．　＠　ｙＢ、Ｏ，＊　２ＳｉＯ，
ａ　ｎＨ，０で表わされる新規顔料。[Claims] ill U oxide compound and boric acid compound, Qa, Sr
. It is obtained by reacting one or more bridges of compounds of Ba, Zn, and At with a composition of MeOaxP20. *7B203* New@junryo expressed as nH2O. (2) It is obtained by reacting a phosphoric acid compound, a boric acid compound, and a silicate compound with two or more bridges in 1 m of a compound of Ga, Sr, Ba, Zn, At, and its composition is MeO. @XPt0. @yB,O,*2SiO,
A new pigment represented by a nH,0.