JPH0657168A - Zinc calcium phosphite pigment, and coating material containing the same - Google Patents
Zinc calcium phosphite pigment, and coating material containing the sameInfo
- Publication number
- JPH0657168A JPH0657168A JP4248529A JP24852992A JPH0657168A JP H0657168 A JPH0657168 A JP H0657168A JP 4248529 A JP4248529 A JP 4248529A JP 24852992 A JP24852992 A JP 24852992A JP H0657168 A JPH0657168 A JP H0657168A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- phosphite
- pigment
- calcium
- coating material
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/046—Compounds of zinc containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、人体に対して毒性がな
く、防錆効果の優れた亜りん酸亜鉛カルシウム顔料の改
良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement of zinc calcium phosphite pigment which is not toxic to humans and has an excellent anticorrosive effect.
【０００２】[0002]
【従来の技術】従来、防錆塗料には、クロム酸化合物、
鉛化合物等が広く使用されてきた。しかしながら、これ
らの防錆塗料は、優れた防錆効果を発揮するものの、ク
ロム酸や鉛等の有害な化合物が含まれているため、環境
汚染や人体への影響に関する問題が新たにクローズアッ
プされてきた。そこで、これらの有害化合物を含まない
無公害塗料の開発が要請されてきた。それに即応して、
新たな無公害防錆顔料として、りん酸亜鉛、りん酸けい
素、りん酸チタン、りん酸アルミニウム等のりん酸塩、
亜りん酸亜鉛、亜りん酸バリウム、亜りん酸マンガン、
亜りん酸亜鉛カルシウム等の亜りん酸塩、及び、モリブ
デン酸亜鉛、モリブデン酸カルシウム等のモリブデン酸
塩等が検討されてきた。2. Description of the Related Art Conventionally, a chromic acid compound,
Lead compounds have been widely used. However, although these anti-corrosion paints exhibit excellent anti-corrosion effects, they contain harmful compounds such as chromic acid and lead, so problems related to environmental pollution and human body are newly highlighted. Came. Therefore, there has been a demand for the development of pollution-free paints that do not contain these harmful compounds. In response to that,
As a new pollution-free rust preventive pigment, phosphates such as zinc phosphate, silicon phosphate, titanium phosphate, aluminum phosphate,
Zinc phosphite, barium phosphite, manganese phosphite,
Phosphites such as zinc calcium phosphite and molybdates such as zinc molybdate and calcium molybdate have been studied.
【０００３】一方、特公昭５６−９９５１号公報には、
次式で表される塩基性亜りん酸亜鉛が、木材表面におけ
るタンニンによるシミの抑制剤、防カビ剤、及び、防炎
剤として有用であることが開示されている。 ＸＺｎＯ−ＺｎＨＰＯ３ （式中Ｘは１／２ないし１０
の数字を示す）On the other hand, Japanese Patent Publication No. 56-9951 discloses that
It is disclosed that the basic zinc phosphite represented by the following formula is useful as an inhibitor for tannin-induced stains on the surface of wood, a fungicide, and a flameproofing agent. XZnO—ZnHPO 3 (where X is 1/2 to 10)
Number)
【０００４】また、特開昭５８−８４１０９号公報に
は、次式で表される亜りん酸カリウム亜鉛が、無公害防
錆顔料として有用なことが開示されている。 Ｋ２Ｚｎ２（ＨＰＯ３）３−ｌＺｎＨＰＯ３−ｍＺｎＯ
−ｎＨ２Ｏ（式中ｌ＝０〜４８、ｍ＝０〜（ｌ＋３）、
ｎはｌ及びｍによって変わる０〜５１までの数）Further, JP-A-58-84109 discloses that potassium zinc phosphite represented by the following formula is useful as a pollution-free rust preventive pigment. K 2 Zn 2 (HPO 3) 3 -lZnHPO 3 -mZnO
-NH 2 O (wherein l = 0~48, m = 0~ ( l + 3),
n is a number from 0 to 51 that varies depending on l and m)
【０００５】特開昭５８−１９４７２５号公報には、次
式で表されるヒドロキシ亜りん酸亜鉛錯体が、化学安定
性や分散性において、塩基性亜りん酸亜鉛より優れてい
ることが開示されている。 〔２Ｚｎ（ＯＨ）２−ＺｎＨＰＯ３］−ＸＺｎＯ （式
中Ｘは０〜１７の数）Japanese Unexamined Patent Publication (Kokai) No. 58-194725 discloses that a zinc hydroxyphosphite complex represented by the following formula is superior to basic zinc phosphite in chemical stability and dispersibility. ing. [2Zn (OH) 2 -ZnHPO 3] -XZnO ( number of wherein X is 0 to 17)
【０００６】特開昭５９−２０４６６３号公報には、次
式で表される塩基性りん酸カリウム亜鉛化合物が、無公
害塗料として有用なことが開示されている。 ＺｎＯ−ｌＫ２Ｏ−ｍＰ２Ｏ５−ｎＨ２Ｏ（ｌ＝０．０
１〜０．５、ｍ＝０．１３〜０．５、ｎ＝０〜２）JP-A-59-204663 discloses that a basic potassium zinc phosphate compound represented by the following formula is useful as a pollution-free coating material. ZnO-lK 2 O-mP 2 O 5 -nH 2 O (l = 0.0
1-0.5, m = 0.13-0.5, n = 0-2)
【０００７】特開平１−１３１２８１号公報には、水の
存在下でりん酸イオンを放出するりん酸イオン源、及
び、水、又は水と酸素の存在鹿でバナジン酸イオンを生
成するバナジン酸イオン源となる化合物が防錆顔料とし
て有用であることが開示されている。Japanese Patent Laid-Open No. 1-131281 discloses a phosphate ion source that releases phosphate ions in the presence of water, and a vanadate ion that produces vanadate ions in water or in the presence of water and oxygen. It is disclosed that the source compound is useful as an anticorrosive pigment.
【０００８】更に、本発明者らは、特開平３−１１１４
５７号公報において、亜りん酸亜鉛カルシウムが、防錆
顔料として優れていることを開示した。Furthermore, the inventors of the present invention have disclosed in Japanese Unexamined Patent Publication No.
In JP 57, it was disclosed that zinc calcium phosphite was excellent as a rust preventive pigment.
【０００９】[0009]
【発明が解決しようとする課題】前述の特公昭５６−９
９５１号公報に開示された塩基性亜りん酸亜鉛、及び、
特開昭５８−１９４７２５号公報に開示されたヒドロキ
シ亜りん酸亜鉛錯体は、従来の亜りん酸亜鉛に比較すれ
ば高い防錆性を有しているが、クロム鉛系の防錆顔料に
比較すれば防錆性が低ので、多量に使用する必要があっ
た。また、特開昭５８−８４１０９号公報に開示された
亜りん酸カリウム亜鉛、及び、特開昭５９−２０４６６
３号公報に開示された塩基性りん酸カリウム亜鉛は、組
成中にカリウムを含有し塩基性であるため、塗料安定性
に欠けることがあった。また、特開平３−１１１４５７
号公報に開示された亜りん酸亜鉛カルシウムは、クロム
鉛系防錆顔料と同等の防錆性を有するが、まだ広い範囲
の塗料にまで高い防錆性を維持することが困難であっ
た。本発明が解決しようとする課題は、このような問題
を解決して広い範囲で高い防錆性を有する防錆塗料を提
供することにある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Basic zinc phosphite disclosed in Japanese Patent Publication No. 951 and
The zinc hydroxyphosphite complex disclosed in JP-A-58-194725 has a higher rust preventive property as compared with the conventional zinc phosphite, but it has a higher rust preventive property than the lead-chromium rust preventive pigment. If so, the rust resistance is low, so it was necessary to use a large amount. Further, potassium zinc phosphite disclosed in JP-A-58-84109 and JP-A-59-20466.
Since the basic potassium zinc phosphate disclosed in JP-A No. 3 contains potassium in the composition and is basic, the coating stability may be insufficient. In addition, Japanese Patent Laid-Open No. 3-111457
Although the zinc calcium phosphite disclosed in Japanese Patent Publication has the same rust preventive properties as the chromium lead rust preventive pigments, it is still difficult to maintain high rust preventive properties even in a wide range of paints. The problem to be solved by the present invention is to solve such problems and provide a rust preventive coating having a high rust preventive property in a wide range.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、この課題
を解決するため、亜りん酸亜鉛カルシウム１０〜９０重
量％と、モリブデン酸亜鉛、モリブデン酸カルシウム、
りん酸亜鉛、りん酸カルシウム、りん酸アルミニウム、
メタほう酸バリウム、及び、酸化亜鉛からなる群の中か
ら選ばれた１種以上の化合物１０〜９０重量％とからな
る亜りん酸亜鉛カルシウム系顔料、及び、それを含有す
る塗料を提供する。In order to solve this problem, the present inventors have found that 10 to 90% by weight of zinc calcium phosphite, zinc molybdate, calcium molybdate,
Zinc phosphate, calcium phosphate, aluminum phosphate,
Provided is a zinc calcium phosphite pigment containing 10 to 90% by weight of one or more compounds selected from the group consisting of barium metaborate and zinc oxide, and a coating containing the same.
【００１１】本発明において使用される第１の化合物
は、単に、亜りん酸亜鉛カルシウム（ＣａＺｎ（ＨＰＯ
３）２−２Ｈ２Ｏ）だけでなく、次式で表される範囲内
で、亜りん酸亜鉛、酸化亜鉛、亜りん酸カルシウム、水
酸化カルシウムを含有するものであってもよい。 ａＣａＺｎ（ＨＰＯ３）２−ｂＺｎＨＰＯ３−ｎＨ２Ｏ ａＣａＺｎ（ＨＰＯ３）２−ｂＺｎＨＰＯ３−ｃＺｎＯ
−ｎＨ２Ｏ ａＣａＺｎ（ＨＰＯ３）２−ｂＣａＨＰＯ３−ｎＨ２Ｏ ａＣａＺｎ（ＨＰＯ３）２−ｂＣａＨＰＯ３−ｃＣａ
（ＯＨ）２−ｎＨ２Ｏ なお、これらの式で、ａ，ｂ，ｃは、ａ／（ｂ＋ｃ）≧
１／６の関係を満たす１０以内の整数を表し、ｎは結晶
水分子数を表す。The first compound used in the present invention is simply zinc calcium phosphite (CaZn (HPO
3) 2 -2H 2 O) as well as within the range represented by the following formula, Allyn zinc, zinc oxide, phosphorous calcium, may be one containing calcium hydroxide. aCaZn (HPO 3) 2 -bZnHPO 3 -nH 2 O aCaZn (HPO 3) 2 -bZnHPO 3 -cZnO
-NH 2 O aCaZn (HPO 3) 2 -bCaHPO 3 -nH 2 O aCaZn (HPO 3) 2 -bCaHPO 3 -cCa
(OH) 2 −nH 2 O In these formulas, a, b, and c are a / (b + c) ≧
It represents an integer within 10 that satisfies the relationship of 1/6, and n represents the number of water molecules of crystallization.
【００１２】本発明において使用される第２の化合物
は、モリブデン酸亜鉛、モリブデン酸カルシウム、りん
酸亜鉛、りん酸カルシウム、りん酸アルミニウム、メタ
ほう酸バリウム、及び、酸化亜鉛であって、これらの中
から１種以上のものが使用される。これらの第２の化合
物の混合割合は、１０〜９０重量％の範囲であることが
必要であり、特に２０〜８０重量％の範囲であることが
好ましい。１０重量％未満であると、防錆性向上の効果
が認められず、９０重量％を超えると、増加分に対する
防錆性の向上の効果が薄くなる。The second compound used in the present invention is zinc molybdate, calcium molybdate, zinc phosphate, calcium phosphate, aluminum phosphate, barium metaborate, and zinc oxide. To one or more types are used. The mixing ratio of these second compounds needs to be in the range of 10 to 90% by weight, and particularly preferably in the range of 20 to 80% by weight. If it is less than 10% by weight, the effect of improving the rust preventive property is not recognized, and if it exceeds 90% by weight, the effect of improving the rust preventive property against the increased amount becomes small.
【００１３】第１の化合物と第２の化合物の混合方法
は、乾式法でも、湿式法でもよい。また、予め塗料化前
に混合してもよいし、塗料化の際に別々に塗料に分散さ
せてもよい。The mixing method of the first compound and the second compound may be a dry method or a wet method. Further, they may be mixed in advance before being made into a paint, or may be separately dispersed in the paint when being made into a paint.
【００１４】本発明に係わる亜りん酸亜鉛カルシウム系
顔料を含有する塗料は、前述の亜りん酸亜鉛カルシウム
系顔料を使用して塗料化したものであれば、どのような
ものでもよく、着色顔料等の他の顔料を含んでいてもよ
い。The paint containing the zinc calcium phosphite-based pigment according to the present invention may be any paint as long as it is made into a paint using the aforementioned zinc calcium phosphite-based pigment. Other pigments such as
【００１５】[0015]
【作用】本発明に係わる亜りん酸亜鉛カルシウム系顔料
及びそれを含有する塗料が、どのような作用で優れた防
錆性を発揮するのか、詳細は不明であるが、一応、次の
ような作用が関与するものと考えられる。すなわち、穏
やかではあるが持続的に還元力を有する亜りん酸亜鉛カ
ルシウムが、塗膜を通過してきた溶存酸素を補足して、
錆の発生を防止すると同時に、第２の化合物から遊離し
た亜りん酸イオンやモリブデン酸イオンが、鉄の表面に
難溶性の強固な皮膜を形成するためと考えられる。The details of the action of the zinc calcium phosphite-based pigment and the coating material containing the same according to the present invention, which exhibit excellent rust-preventive properties, are unknown. It is considered that the action is involved. That is, zinc calcium phosphite, which is mild but has a continuous reducing power, captures dissolved oxygen that has passed through the coating film,
It is considered that the phosphite ion and the molybdate ion liberated from the second compound simultaneously form a hardly soluble strong film on the surface of iron while preventing the generation of rust.
【００１６】[0016]
１．亜りん酸亜鉛カルシウム系顔料等の調製 〔実施例１〕亜りん酸亜鉛カルシウム１００ｇとモリブ
デン酸亜鉛１００ｇとを水５００ｇに投入し１時間攪拌
して湿式混合した後、濾過、脱水、乾燥、粉砕して顔料
（以下「顔料１」という）を得た。1. Preparation of zinc calcium phosphite pigment etc. [Example 1] 100 g of zinc calcium phosphite and 100 g of zinc molybdate were added to 500 g of water, stirred for 1 hour and wet mixed, and then filtered, dehydrated, dried and pulverized. To obtain a pigment (hereinafter referred to as "Pigment 1").
【００１７】〔実施例２〕亜りん酸亜鉛カルシウム１３
０ｇとモリブデン酸カルシウム８０ｇとを粉末のまま乾
式混合し顔料（以下「顔料２」というを得た。[Example 2] Zinc calcium phosphite 13
0 g and 80 g of calcium molybdate were dry mixed as a powder to obtain a pigment (hereinafter referred to as "pigment 2").
【００１８】〔実施例３〕亜りん酸亜鉛カルシウム１５
０ｇとりん酸亜鉛３０ｇを粉末のまま乾式混合し顔料
（以下「顔料３」というを得た。[Example 3] Zinc calcium phosphite 15
A powder (hereinafter referred to as "Pigment 3") was obtained by dry-mixing 0 g and 30 g of zinc phosphate as powder.
【００１９】〔実施例４〕亜りん酸亜鉛カルシウム１０
０ｇとりん酸アルミニウム１００ｇとを５０℃に加温し
た温水５００ｇに投入し１時間攪拌して湿式混合した
後、濾過、脱水、乾燥、粉砕して顔料（以下「顔料４」
という）を得た。[Example 4] Zinc calcium phosphite 10
0 g and 100 g of aluminum phosphate were put into 500 g of warm water heated to 50 ° C., stirred for 1 hour and wet-mixed, and then filtered, dehydrated, dried and pulverized to obtain a pigment (hereinafter referred to as “Pigment 4”).
I got).
【００２０】〔実施例５〕亜りん酸亜鉛カルシウム１６
０ｇとりん酸カルシウム４０ｇを水５００ｇに投入し１
時間攪拌して湿式混合した後、濾過、脱水、乾燥、粉砕
して顔料（以下「顔料５」という）を得た。[Example 5] Zinc calcium phosphite 16
Add 0 g and 40 g of calcium phosphate to 500 g of water and add 1
After stirring for a period of time and wet mixing, a pigment (hereinafter referred to as "Pigment 5") was obtained by filtration, dehydration, drying and pulverization.
【００２１】〔実施例６〕亜りん酸亜鉛カルシウム５０
ｇ、メタほう酸バリウム１００ｇ、及び、酸化亜鉛１０
０ｇを粉末のまま乾式混合し顔料（以下「顔料６」とい
うを得た。Example 6 Zinc calcium phosphite 50
g, barium metaborate 100 g, and zinc oxide 10
The powder (0 g) was dry-mixed to obtain a pigment (hereinafter referred to as "Pigment 6").
【００２２】〔比較例〕比較例として、市販のジンクク
ロメート（ＺＰＣ型）を「顔料７」とし、モリブデン酸
亜鉛を「顔料８」とし、モリブデン酸カルシウムを「顔
料９」とし、りん酸亜鉛を「顔料１０」とし、りん酸ア
ルミニウムを「顔料１１」とし、りん酸カルシウムを
「顔料１２」とし、メタほう酸バリウムを「顔料１３」
とし、亜りん酸亜鉛カルシウムを「顔料１４」とした。Comparative Example As a comparative example, commercially available zinc chromate (ZPC type) was used as “pigment 7”, zinc molybdate was used as “pigment 8”, calcium molybdate was used as “pigment 9”, and zinc phosphate was used. "Pigment 10", aluminum phosphate "Pigment 11", calcium phosphate "Pigment 12", barium metaborate "Pigment 13"
And zinc calcium phosphite was designated as "Pigment 14".
【００２３】２． 水溶性エポキシエテスル樹脂系塗料
の製造 前述の実施例１〜６及び比較例で得られた顔料１〜１４
を、それぞれ、表１の配合比で調製し、ガラスビーズ
（Φ１．５ｍｍ）１００ｇと共にサンドミルで３０分間
分散して塗料化し、それぞれ、塗料（以下「塗料Ａ１」
〜「塗料Ａ１４」という）を得た。なお、ここで使用し
た水溶性エポキシエステル樹脂は大日本インキ化学工業
（株）製のウォーターゾールＣＤ−５４０で不揮発分３
９．２％のものである。これらの顔料１〜１４の塗料化
に際して特に問題はなく、また、得られた塗料の安定性
も特に問題はなかった。2. Production of Water-Soluble Epoxy Ethesul Resin-Based Paint Pigments 1-14 Obtained in Examples 1-6 and Comparative Examples
Were prepared at the compounding ratios shown in Table 1 and dispersed with 100 g of glass beads (Φ1.5 mm) in a sand mill for 30 minutes to form a paint.
-"Paint A14") was obtained. The water-soluble epoxy ester resin used here is Watersol CD-540 manufactured by Dainippon Ink and Chemicals, Inc.
It is 9.2%. There was no particular problem in making these pigments 1 to 14 into a coating material, and the stability of the obtained coating material also had no particular problem.
【表１】 [Table 1]
【００２４】３．中油性アルキッド樹脂系塗料の製造 前述の実施例１〜６及び比較例で得られた顔料１〜１４
を、それぞれ、表２の配合比で調製し、ガラスビーズ
（Φ１．５ｍｍ）１００ｇと共にサンドミルで３０分間
分散して塗料化し、それぞれ、塗料（以下「塗料Ｂ１」
〜「塗料Ｂ１４」という）を得た。なお、ここで使用し
た中油性アルキッド樹脂は大日本インキ化学工業（株）
製のベッコゾール１３３４ＥＬで不揮発分５０％のもの
であり、皮張り防止剤は楠本化成（株）製のデイスパロ
ン５１０、流れ止め剤は楠本化成（株）製のデイスパロ
ン４２００−２０である。これらの顔料１〜１４の塗料
化に際して特に問題はなく、また、得られた塗料の安定
性も特に問題はなかった。3. Production of mid-oil alkyd resin paints Pigments 1 to 14 obtained in the above Examples 1 to 6 and Comparative Example
Were prepared at the compounding ratios shown in Table 2, and dispersed with 100 g of glass beads (Φ1.5 mm) in a sand mill for 30 minutes to form a paint.
-"Paint B14") was obtained. The oily alkyd resin used here is Dainippon Ink and Chemicals, Inc.
Beccosol 1334EL manufactured by Kusumoto Chemicals Co., Ltd. with a non-volatile content of 50%, the anti-skin agent is Desparon 510 manufactured by Kusumoto Kasei Co., Ltd., and the anti-flow agent is Desparon 4200-20 manufactured by Kusumoto Kasei Co., Ltd. There was no particular problem in making these pigments 1 to 14 into a coating material, and the stability of the obtained coating material also had no particular problem.
【表２】 [Table 2]
【００２５】４． 防錆試験 前述の方法によって得られた塗料Ａ１〜１４及び塗料Ｂ
１〜１４を、それぞれ、日本テストパネル工業（株）製
の冷間圧延鋼板ＪＩＳ Ｇ３１４１ ＳＰＣＣ−ＳＢ
１．０×７０×１５０ｍｍにバーコータを用いて１回塗
りし、乾燥後の膜厚が３０μｍになるようにした。その
後、室温で１週間乾燥し、上塗りすることなく、スガ試
験機（株）製の塩水噴霧試験機ＳＴ−ＩＳＯ−３を用い
て５％食塩水による塩水噴霧試験を行った。その結果を
表３に示した。この表３において、評価の欄の数字は、
１は錆の発生が１００％のもの、２は錆の発生が７５％
以下のもの、３は錆の発生が５０％以下のもの、４は錆
の発生が２５％以下のもの、５はふくれや錆の発生がま
ったくないものを表す。この表３から、本発明に係わる
亜りん酸亜鉛カルシウム系顔料（顔料１〜６）を含有す
る塗料（塗料Ａ１〜６及びＢ１〜６）が、従来から使用
されてきた防錆顔料であるジンククロメートを使用した
塗料や亜りん酸亜鉛カルシウムを単独に使用した塗料よ
りも優れた防錆性を有することがわかる。4. Anticorrosion test Paints A1 to 14 and paint B obtained by the above method
1 to 14 are cold rolled steel sheets JIS G3141 SPCC-SB manufactured by Nippon Test Panel Industry Co., Ltd., respectively.
It was applied once to 1.0 × 70 × 150 mm using a bar coater so that the film thickness after drying was 30 μm. Then, it was dried at room temperature for 1 week, and a salt spray test with 5% saline was performed using a salt spray tester ST-ISO-3 manufactured by Suga Test Instruments Co., Ltd. without overcoating. The results are shown in Table 3. In Table 3, the numbers in the evaluation column are
1 is 100% rust generation, 2 is 75% rust generation
The following items, 3 represents rust generation of 50% or less, 4 represents rust generation of 25% or less, and 5 represents no swelling or rust formation. From Table 3, coating materials (paints A1 to 6 and B1 to 6) containing the zinc calcium phosphite pigments (pigments 1 to 6) according to the present invention are zinc rust pigments that have been used conventionally. It can be seen that it has superior rust prevention properties to the paint using chromate and the paint using zinc calcium phosphite alone.
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】本発明に係わる亜りん酸亜鉛カルシウム
系顔料及びそれを含有する塗料は、前述のような構成と
作用を有し、無公害で優れた防錆性を有するので、従来
の有害物質を含む防錆顔料や防錆塗料に替わって、環境
を汚染することなく各種の設備や機械等を防錆保全する
のに役立ち、日常の生活や産業活動に大きく寄与するも
のと考えられる。Industrial Applicability The zinc calcium phosphite pigment and the coating material containing the same according to the present invention have the above-mentioned constitution and function, are pollution-free and have excellent rust preventive properties, and therefore are not harmful to the conventional harmful substances. It is considered that, instead of rust-preventive pigments and rust-preventive paints containing substances, it helps prevent rust-preservation of various facilities and machines without polluting the environment and greatly contributes to daily life and industrial activities.
【手続補正書】[Procedure amendment]
【提出日】平成４年１０月６日[Submission date] October 6, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】[0015]
【作用】本発明に係わる亜りん酸亜鉛カルシウム系顔料
及びそれを含有する塗料が、どのような作用で優れた防
錆性を発揮するのか、詳細は不明であるが、一応、次の
ような作用が関与するものと考えられる。すなわち、穏
やかではあるが持続的に還元力を有する亜りん酸亜鉛カ
ルシウムが、塗膜を通過してきた溶存酸素を補足して、
錆の発生を防止すると同時に、第２の化合物から遊離し
たりん酸イオンやモリブデン酸イオンが、鉄の表面に難
溶性の強固な皮膜を形成するためと考えられる。The details of the action of the zinc calcium phosphite-based pigment and the coating material containing the same according to the present invention, which exhibit excellent rust-preventive properties, are unknown. It is considered that the action is involved. That is, zinc calcium phosphite, which is mild but has a continuous reducing power, captures dissolved oxygen that has passed through the coating film,
Prevents the formation of rust and at the same time liberates from the second compound
Have enough does acid ions and molybdate ions is considered to form a strong film slightly soluble in the surface of the iron.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Name of item to be corrected] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２３】２． 水溶性エポキシエステル樹脂系塗料
の製造 前述の実施例１〜６及び比較例で得られた顔料１〜１４
を、それぞれ、表１の配合比で調整し、ガラスビーズ
（φ１．５ｍｍ）１００ｇと共にサンドミルで３０分間
分散して塗料化し、それぞれ、塗料（以下「塗料Ａ１」
〜「塗料Ａ１４」という）を得た。なお、ここで使用し
た水溶性エポキシエステル樹脂は大日本インキ化学工業
（株）製のウォーターゾールＣＤ−５４０で不揮発分３
９．２％のものである。これらの顔料１〜１４の塗料化
に際して特に問題はなく、また、得られた塗料の安定性
も特に問題はなかった。2. Production of Water-Soluble Epoxy Ester Resin-Based Paint Pigments 1-14 Obtained in Examples 1-6 and Comparative Examples
Were adjusted with the compounding ratios shown in Table 1 and dispersed with 100 g of glass beads (φ1.5 mm) in a sand mill for 30 minutes to form a paint.
-"Paint A14") was obtained. The water-soluble epoxy ester resin used here is Watersol CD-540 manufactured by Dainippon Ink and Chemicals, Inc.
It is 9.2%. There was no particular problem in making these pigments 1 to 14 into a coating material, and the stability of the obtained coating material also had no particular problem.
【表１】 [Table 1]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Name of item to be corrected] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】３． 中油性アルキッド樹脂系塗料の製造 前述の実施例１〜６及び比較例で得られた顔料１〜１４
を、それぞれ、表２の配合比で調整し、ガラスビーズ
（φ１．５ｍｍ）１００ｇと共にサンドミルで３０分間
分散して塗料化し、それぞれ、塗料（以下「塗料Ｂ１」
〜「塗料Ｂ１４」という）を得た。なお、ここで使用し
た中油性アルキッド樹脂は大日本インキ化学工業（株）
製のベッコゾール１３３４ＥＬで不揮発分５０％のもの
であり、皮張り防止剤は楠本化成（株）製のデイスパロ
ン５１０、流れ止め剤は楠本化成（株）製のデイスパロ
ン４２００−２０である。これらの顔料１〜１４の塗料
化に際して特に問題はなく、また、得られた塗料の安定
性も特に問題はなかった。3. Production of mid-oil alkyd resin paints Pigments 1 to 14 obtained in the above Examples 1 to 6 and Comparative Example
Were adjusted with the compounding ratios shown in Table 2 and dispersed with 100 g of glass beads (φ1.5 mm) in a sand mill for 30 minutes to form a paint.
-"Paint B14") was obtained. The oily alkyd resin used here is Dainippon Ink and Chemicals, Inc.
Beccosol 1334EL manufactured by Kusumoto Chemicals Co., Ltd. with a non-volatile content of 50%, the anti-skin agent is Desparon 510 manufactured by Kusumoto Kasei Co., Ltd., and the anti-flow agent is Desparon 4200-20 manufactured by Kusumoto Kasei Co., Ltd. There was no particular problem in making these pigments 1 to 14 into a coating material, and the stability of the obtained coating material also had no particular problem.
【表２】 [Table 2]
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 7/12 ＰＳＫ 7211−4Ｊ Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display area C09D 7/12 PSK 7211-4J
Claims (2)
％と、モリブデン酸亜鉛、モリブデン酸カルシウム、り
ん酸亜鉛、りん酸カルシウム、りん酸アルミニウム、メ
タほう酸バリウム、及び、酸化亜鉛からなる群の中から
選ばれた１種以上の化合物１０〜９０重量％とからなる
亜りん酸亜鉛カルシウム系顔料1. A group consisting of 10 to 90% by weight of zinc calcium phosphite, zinc molybdate, calcium molybdate, zinc phosphate, calcium phosphate, aluminum phosphate, barium metaborate, and zinc oxide. Zinc calcium phosphite-based pigment consisting of 10 to 90% by weight of one or more compounds selected from
系顔料を含有する塗料2. A coating material containing the zinc calcium phosphite pigment according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04248529A JP3089347B2 (en) | 1992-08-04 | 1992-08-04 | Rust prevention pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04248529A JP3089347B2 (en) | 1992-08-04 | 1992-08-04 | Rust prevention pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0657168A true JPH0657168A (en) | 1994-03-01 |
| JP3089347B2 JP3089347B2 (en) | 2000-09-18 |
Family
ID=17179547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04248529A Expired - Fee Related JP3089347B2 (en) | 1992-08-04 | 1992-08-04 | Rust prevention pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3089347B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5722609A (en) * | 1996-03-12 | 1998-03-03 | Daiwa Seiko, Inc. | Traverse mechanism for a spinning reel |
| US7462233B2 (en) * | 2006-04-13 | 2008-12-09 | The Sherwin-Williams Company | Pigment and coating composition capable of inhibiting corrosion of substrates |
| JP2010540747A (en) * | 2007-10-02 | 2010-12-24 | ビー・エイ・エス・エフ、コーポレーション | Coating composition and reflective coating system comprising the composition |
| JP2012518696A (en) * | 2009-02-20 | 2012-08-16 | ソシエテ ヌヴェル デ クルール ジンシク | Detoxification method to obtain zinc-containing pigment compounds without ecotoxicity |
| CN106009843A (en) * | 2016-07-20 | 2016-10-12 | 沈旭源 | Zinc chrome yellow antirust paint for metals |
| CN106590034B (en) * | 2016-12-13 | 2019-01-01 | 广西壮族自治区化工研究院 | A kind of phosphite powder of nano-oxide inorganic coating and water paint containing the powder |
-
1992
- 1992-08-04 JP JP04248529A patent/JP3089347B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5722609A (en) * | 1996-03-12 | 1998-03-03 | Daiwa Seiko, Inc. | Traverse mechanism for a spinning reel |
| US7462233B2 (en) * | 2006-04-13 | 2008-12-09 | The Sherwin-Williams Company | Pigment and coating composition capable of inhibiting corrosion of substrates |
| US7601213B2 (en) * | 2006-04-13 | 2009-10-13 | The Sherwin-Williams Company | Pigment and coating composition capable of inhibiting corrosion of substrates |
| JP2010540747A (en) * | 2007-10-02 | 2010-12-24 | ビー・エイ・エス・エフ、コーポレーション | Coating composition and reflective coating system comprising the composition |
| JP2012518696A (en) * | 2009-02-20 | 2012-08-16 | ソシエテ ヌヴェル デ クルール ジンシク | Detoxification method to obtain zinc-containing pigment compounds without ecotoxicity |
| CN106009843A (en) * | 2016-07-20 | 2016-10-12 | 沈旭源 | Zinc chrome yellow antirust paint for metals |
| CN106590034B (en) * | 2016-12-13 | 2019-01-01 | 广西壮族自治区化工研究院 | A kind of phosphite powder of nano-oxide inorganic coating and water paint containing the powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3089347B2 (en) | 2000-09-18 |
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