JP2004352994A - Polyolefin-based powder coating composition - Google Patents

Polyolefin-based powder coating composition Download PDF

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JP2004352994A
JP2004352994A JP2004190353A JP2004190353A JP2004352994A JP 2004352994 A JP2004352994 A JP 2004352994A JP 2004190353 A JP2004190353 A JP 2004190353A JP 2004190353 A JP2004190353 A JP 2004190353A JP 2004352994 A JP2004352994 A JP 2004352994A
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polyolefin
coating composition
weight
powder coating
polypropylene
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Tatsuro Okano
達郎 岡野
Masahiro Goto
正宏 後藤
Takashi Miyagawa
崇 宮川
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin-based powder coating composition giving a film excellent in adhesiveness and corrosion-control properties and having long term durability not only under normal conditions but also in the cases used for articles applied to water supplies especially for articles used under hot-water conditions such as hot-water supplying pipes. <P>SOLUTION: The polyolefin-based powder coating composition is obtained by compounding 0.1-10 pts.wt. hydrotalcites in 100 pts.wt. polyolefin resin and forms a coating film excellent in corrosion-control properties under hot-water conditions, wherein the polyolefin resin comprises 100-5 wt.% denatured polypropylene and 0-95 wt.% native polypropylene. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、ポリオレフィン系粉体塗料組成物に関する。さらに詳しくは、熱水環境下においても接着性、腐食防止性に優れた塗膜を与えるポリオレフィン系粉体塗料組成物に関する。   The present invention relates to a polyolefin-based powder coating composition. More specifically, the present invention relates to a polyolefin-based powder coating composition which gives a coating film having excellent adhesion and corrosion prevention even in a hot water environment.

オレフィン系重合体は、加工性、耐薬品性等に優れていることから、従来より粉体塗料に広く用いられている（例えば、特許文献１、特許文献２及び特許文献３参照）。しかしながら、これらの粉体塗料は、水回り製品、特に給湯管等の熱水環境下で使用される製品に用いた場合、長期にわたる使用の間に塗膜を通過した酸素、水分等により、基材と塗膜との接着面に錆が発生しやすいという欠点を有している。その結果、一旦錆が発生すると塗膜の接着性がなくなるため塗膜に膨れが生じ、ついには塗膜が破損するという問題があり、長期の耐久性の点で充分とはいえなかった。
特開昭６２−１９０２６５号公報 特開昭６２−１６７３７１号公報 特開平５−２５２２９号公報 BACKGROUND ART Olefin-based polymers have been widely used in powder coatings because of their excellent workability, chemical resistance, and the like (for example, see Patent Literature 1, Patent Literature 2, and Patent Literature 3). However, when these powder coatings are used for water-based products, particularly products used in a hot water environment such as a hot water supply pipe, the base materials are not affected by oxygen, moisture, etc. which have passed through the coating film during long-term use. There is a disadvantage that rust is easily generated on the bonding surface between the material and the coating film. As a result, once rust is generated, the adhesion of the coating film is lost, so that the coating film swells, and eventually there is a problem that the coating film is damaged, which is not sufficient in terms of long-term durability.
JP-A-62-190265 JP-A-62-167371 JP-A-5-25229

本発明は、通常の条件下ではもちろん、水回り製品、特に給湯管等の熱水環境下で使用される製品に用いた場合でも、接着性、腐食防止性に優れ、長期の耐久性を有する塗膜を与えるポリオレフィン系粉体塗料組成物を提供することを目的とする。   The present invention has excellent adhesiveness, excellent anticorrosion properties, and long-term durability, even under normal conditions, as well as water-related products, particularly when used for products used in a hot water environment such as a hot water supply pipe. An object of the present invention is to provide a polyolefin-based powder coating composition that gives a coating film.

本発明者らは、上記の課題を解決すべく鋭意研究した結果、ポリオレフィン系樹脂に腐食防止剤を配合することにより金属基材の腐食が防止されるのみならず、意外にも金属基材と塗膜との接着性が著しく改善されることを見出し、本発明を完成した。
即ち、本発明は、
（１） ポリオレフィン系樹脂１００重量部に腐食防止剤０．１〜１０重量部を配合してなるポリオレフィン系粉体塗料組成物、
（２） ポリオレフィン系樹脂が、変性ポリプロピレン１００〜５重量％と未変性ポリプロピレン０〜９５重量％とからなるポリプロピレン系樹脂である上記（１）記載のポリオレフィン系粉体塗料組成物、
（３） ポリプロピレン系樹脂が、２３０℃におけるメルトフローレート５〜８０ｇ／１０分の樹脂である上記（２）記載のポリオレフィン系粉体塗料組成物、
（４） ポリオレフィン系樹脂が、変性ポリエチレン１００〜５重量％と未変性ポリエチレン０〜９５重量％とからなるポリエチレン系樹脂である上記（１）記載のポリオレフィン系粉体塗料組成物、
（５） ポリエチレン系樹脂が、１９０℃におけるメルトフローレート１〜８０ｇ／１０分の樹脂である上記（４）記載のポリオレフィン系粉体塗料組成物、
（６） ポリオレフィン系樹脂が、エチレン−アクリル酸共重合体１００〜５重量％と未変性ポリエチレン０〜９５重量％とからなるエチレン−アクリル酸共重合体系樹脂である上記（１）記載のポリオレフィン系粉体塗料組成物、
（７） エチレン−アクリル酸共重合体系樹脂が、１９０℃におけるメルトフローレート５〜５０ｇ／１０分の樹脂である上記（６）記載のポリオレフィン系粉体塗料組成物、
（８） 腐食防止剤が、ハイドロタルサイト類化合物、リン酸塩及びモリブデン酸塩からなる群より選ばれた少なくとも１種である上記（１）〜（７）記載のポリオレフィン系粉体塗料組成物に関する。 The present inventors have conducted intensive studies to solve the above problems, and as a result, not only corrosion of the metal substrate is prevented by adding a corrosion inhibitor to the polyolefin resin, but also unexpectedly The present inventors have found that the adhesion to a coating film is remarkably improved, and have completed the present invention.
That is, the present invention
(1) a polyolefin-based powder coating composition comprising 100 parts by weight of a polyolefin-based resin and 0.1 to 10 parts by weight of a corrosion inhibitor;
(2) The polyolefin-based powder coating composition according to the above (1), wherein the polyolefin-based resin is a polypropylene-based resin composed of 100 to 5% by weight of modified polypropylene and 0 to 95% by weight of unmodified polypropylene.
(3) The polyolefin-based powder coating composition according to (2), wherein the polypropylene-based resin is a resin having a melt flow rate of 5 to 80 g / 10 minutes at 230 ° C.
(4) The polyolefin-based powder coating composition according to the above (1), wherein the polyolefin-based resin is a polyethylene-based resin composed of 100 to 5% by weight of modified polyethylene and 0 to 95% by weight of unmodified polyethylene.
(5) The polyolefin-based powder coating composition according to the above (4), wherein the polyethylene-based resin is a resin having a melt flow rate of 1 to 80 g / 10 minutes at 190 ° C.
(6) The polyolefin resin according to the above (1), wherein the polyolefin resin is an ethylene-acrylic acid copolymer resin comprising 100 to 5% by weight of an ethylene-acrylic acid copolymer and 0 to 95% by weight of an unmodified polyethylene. Powder coating composition,
(7) The polyolefin-based powder coating composition according to the above (6), wherein the ethylene-acrylic acid copolymer resin is a resin having a melt flow rate of 5 to 50 g / 10 min at 190 ° C.
(8) The polyolefin-based powder coating composition according to (1) to (7), wherein the corrosion inhibitor is at least one selected from the group consisting of hydrotalcite compounds, phosphates, and molybdates. About.

以下、本発明をさらに詳しく説明する。
本発明のポリオレフィン系粉体塗料組成物は、ポリオレフィン系樹脂に腐食防止剤を配合したものである。
本発明で用いられるポリオレフィン系樹脂としては、例えば、変性ポリプロピレン、未変性ポリプロピレン、変性ポリエチレン、未変性ポリエチレン、エチレン−アクリル酸共重合体等を挙げることができる。これらは単独で用いても良いし、適宜組み合わせて使用することもできるが、好ましくは、変性ポリプロピレンと未変性ポリプロピレンとからなるポリプロピレン系樹脂、変性ポリエチレンと未変性ポリエチレンとからなるポリエチレン系樹脂、エチレン−アクリル酸共重合体と未変性ポリエチレンとからなるエチレン−アクリル酸共重合体系樹脂が用いられる。 Hereinafter, the present invention will be described in more detail.
The polyolefin-based powder coating composition of the present invention is obtained by mixing a corrosion inhibitor with a polyolefin-based resin.
Examples of the polyolefin resin used in the present invention include modified polypropylene, unmodified polypropylene, modified polyethylene, unmodified polyethylene, and ethylene-acrylic acid copolymer. These may be used alone or may be used in an appropriate combination, but preferably, a polypropylene-based resin composed of modified polypropylene and unmodified polypropylene, a polyethylene-based resin composed of modified polyethylene and unmodified polyethylene, and ethylene. -An ethylene-acrylic acid copolymer resin composed of an acrylic acid copolymer and unmodified polyethylene is used.

上記未変性ポリプロピレンとしては、プロピレン９０〜９９重量％とプロピレン以外の炭素数２〜１０のα−オレフィン１０〜１重量％とのランダム共重合体が好ましい。
上記α−オレフィンとしては、例えば、エチレン、１−ブテン、２−ブテン、１−ペンテン、２−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン等が挙げられ、なかでも、エチレン、１−ブテン、２−ブテンが好ましい。
上記α−オレフィンの共重合割合が１重量％未満であると、塗料組成物の融点が高く、溶融時の粘度が大きくなるため、平滑な塗膜が得られ難く、上記α−オレフィンの共重合割合が１０重量％を超えると、塗料組成物の融点が低くなり、得られる塗膜の耐熱性及び表面硬度が低下する。 The unmodified polypropylene is preferably a random copolymer of 90 to 99% by weight of propylene and 10 to 1% by weight of an α-olefin having 2 to 10 carbon atoms other than propylene.
Examples of the α-olefin include ethylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Of these, ethylene, 1-butene and 2-butene are preferred.
If the copolymerization ratio of the α-olefin is less than 1% by weight, the coating composition has a high melting point and a high viscosity at the time of melting, so that it is difficult to obtain a smooth coating film, and the α-olefin copolymerization is difficult. If the proportion exceeds 10% by weight, the melting point of the coating composition will be low, and the heat resistance and surface hardness of the resulting coating film will be low.

上記変性ポリプロピレンとしては、上記未変性ポリプロピレンを不飽和カルボン酸又はその無水物でグラフト変性した樹脂が好ましく用いられる。
上記不飽和カルボン酸又はその無水物としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。 As the modified polypropylene, a resin obtained by graft-modifying the unmodified polypropylene with an unsaturated carboxylic acid or an anhydride thereof is preferably used.
Examples of the unsaturated carboxylic acid or anhydride thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride.

本発明においては、上記変性ポリプロピレン単独で用いてもよいが、上記変性ポリプロピレンと上記未変性ポリプロピレンとからなるポリプロピレン系樹脂が好ましく用いられる。その配合割合は、上記変性ポリプロピレン１００〜５重量％に対して、上記未変性ポリプロピレン０〜９５重量％の割合が好ましい。更に好ましくは、上記変性ポリプロピレン１００〜１５重量％に対して、上記未変性ポリプロピレン０〜８５重量％の割合である。上記変性ポリプロピレンの割合が５重量％未満であると、金属への接着力が不充分になり、上記未変性ポリプロピレンの割合が９５重量％を越えると塗膜の経時的な収縮により、被塗物のエッジの被覆が不充分となるいわゆるエッジ切れが発生し好ましくない。   In the present invention, the above-mentioned modified polypropylene may be used alone, but a polypropylene-based resin composed of the above-mentioned modified polypropylene and the above-mentioned unmodified polypropylene is preferably used. The mixing ratio is preferably from 0 to 95% by weight of the unmodified polypropylene to 100 to 5% by weight of the modified polypropylene. More preferably, the ratio is from 0 to 85% by weight of the unmodified polypropylene with respect to 100 to 15% by weight of the modified polypropylene. If the ratio of the modified polypropylene is less than 5% by weight, the adhesion to metal becomes insufficient. If the ratio of the unmodified polypropylene exceeds 95% by weight, the coating film shrinks over time, and This is not preferable because so-called edge breakage occurs in which the coating of the edge becomes insufficient.

本発明のポリプロピレン系樹脂としては、樹脂の溶融時の流動性の指標であるメルトフローレート（ＭＦＲ）が、２３０℃において５〜８０ｇ／１０分の樹脂が用いられる。更に好ましくは、ＭＦＲが１０〜６０ｇ／１０分の樹脂が用いられる。ＭＦＲが５ｇ／１０分未満であると、溶融性が不充分なため塗膜表面の平滑性が悪化するおそれがあり、ＭＦＲが８０ｇ／１０分を超えると、表面の平滑性は良くなるが、加工し難くなるばかりか、融点が低下して目的とする塗膜が得られない場合がある。   As the polypropylene resin of the present invention, a resin having a melt flow rate (MFR) of 5 to 80 g / 10 minutes at 230 ° C., which is an index of the fluidity of the resin at the time of melting, is used. More preferably, a resin having an MFR of 10 to 60 g / 10 min is used. When the MFR is less than 5 g / 10 minutes, the meltability is insufficient, so that the smoothness of the coating film surface may be deteriorated. When the MFR exceeds 80 g / 10 minutes, the surface smoothness is improved, Not only does processing become difficult, but the melting point is lowered, and the desired coating film may not be obtained.

本発明で用いられる未変性ポリエチレンとしては、例えば、低密度ポリエチレン、高密度ポリエチレン等のエチレンホモポリマー；エチレンとプロピレン等のα−オレフィンとの共重合体である線状低密度ポリエチレン等を挙げることができる。
本発明で用いられる変性ポリエチレンとしては、上記の未変性ポリエチレンを不飽和カルボン酸又はその無水物でグラフト変性した樹脂が好ましく用いられる。上記不飽和カルボン酸又はその無水物としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。 Examples of the unmodified polyethylene used in the present invention include, for example, ethylene homopolymers such as low-density polyethylene and high-density polyethylene; and linear low-density polyethylene which is a copolymer of ethylene and an α-olefin such as propylene. Can be.
As the modified polyethylene used in the present invention, a resin obtained by graft-modifying the above unmodified polyethylene with an unsaturated carboxylic acid or an anhydride thereof is preferably used. Examples of the unsaturated carboxylic acid or anhydride thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride.

本発明においては、上記変性ポリエチレン単独で用いてもよいが、上記変性ポリエチレンと上記未変性ポリエチレンとからなるポリエチレン系樹脂が好ましく用いられる。その配合割合としては、上記変性ポリエチレン１００〜５重量％に対して、上記未変性ポリエチレン０〜９５重量％の割合が好ましい。更に好ましくは、上記変性ポリエチレン１００〜１５重量％に対して、上記未変性ポリエチレン０〜８５重量％の割合である。上記変性ポリエチレンの割合が５重量％未満であると、金属への接着力が不充分になり、上記未変性ポリエチレンの割合が９５重量％を超えると、塗膜の耐久性が低下する。   In the present invention, the above-mentioned modified polyethylene may be used alone, but a polyethylene resin composed of the above-mentioned modified polyethylene and the above-mentioned unmodified polyethylene is preferably used. The blending ratio is preferably from 0 to 95% by weight of the unmodified polyethylene to 100 to 5% by weight of the modified polyethylene. More preferably, the ratio is 0 to 85% by weight of the unmodified polyethylene with respect to 100 to 15% by weight of the modified polyethylene. If the ratio of the modified polyethylene is less than 5% by weight, the adhesion to metal becomes insufficient, and if the ratio of the unmodified polyethylene exceeds 95% by weight, the durability of the coating film is reduced.

本発明のポリエチレン系樹脂としては、１９０℃におけるＭＦＲが１〜８０ｇ／１０分の範囲であることが好ましい。ＭＦＲが１ｇ／１０分未満であると、溶融性が不充分なため塗膜表面の平滑性が悪化し、ＭＦＲが８０ｇ／１０分を超えると、極端に物性が低下し、塗膜として使用できない。   The polyethylene resin of the present invention preferably has an MFR at 190 ° C. of 1 to 80 g / 10 minutes. When the MFR is less than 1 g / 10 min, the meltability is insufficient, so that the smoothness of the coating film surface is deteriorated. When the MFR exceeds 80 g / 10 min, the physical properties are extremely reduced and the film cannot be used as a coating film. .

本発明で用いられるエチレン−アクリル酸共重合体としては、アクリル酸含量が１〜２０重量％のものが好ましく、この範囲内のものであれば特に限定されない。上記アクリル酸含量が１重量％未満であると、金属への接着力が不充分となり、上記アクリル酸含量が２０重量％を超えると、樹脂物性が極端に低下し塗膜として使用できない。   The ethylene-acrylic acid copolymer used in the present invention preferably has an acrylic acid content of 1 to 20% by weight, and is not particularly limited as long as it is within this range. If the acrylic acid content is less than 1% by weight, the adhesive strength to metal becomes insufficient, and if the acrylic acid content exceeds 20% by weight, the physical properties of the resin are extremely reduced and the resin cannot be used as a coating film.

本発明においては、上記エチレン−アクリル酸共重合体単独で用いてもよいが、上記エチレン−アクリル酸共重合体と上記未変性ポリエチレンとからなるエチレン−アクリル酸共重合体系樹脂が好ましく用いられる。その配合割合としては、上記エチレン−アクリル酸共重合体１００〜５重量％に対して、上記未変性ポリエチレン０〜９５重量％の割合が好ましい。更に好ましくは、上記エチレン−アクリル酸共重合体１００〜１５重量％に対して上記未変性ポリエチレン０〜８５重量％の割合である。上記エチレン−アクリル酸共重合体の割合が５重量％未満であると、金属への接着力が不充分になり、上記未変性ポリエチレンの割合が９５重量％を超えると、発生した錆が進行しやすく、塗膜の耐久性が低下する。   In the present invention, the ethylene-acrylic acid copolymer may be used alone, but an ethylene-acrylic acid copolymer resin composed of the ethylene-acrylic acid copolymer and the unmodified polyethylene is preferably used. The mixing ratio is preferably from 0 to 95% by weight of the unmodified polyethylene to 100 to 5% by weight of the ethylene-acrylic acid copolymer. More preferably, the ratio of the unmodified polyethylene is 0 to 85% by weight based on 100 to 15% by weight of the ethylene-acrylic acid copolymer. When the proportion of the ethylene-acrylic acid copolymer is less than 5% by weight, the adhesive strength to metal becomes insufficient, and when the proportion of the unmodified polyethylene exceeds 95% by weight, rust generated proceeds. Easily, and the durability of the coating film decreases.

本発明のエチレン−アクリル酸系共重合体樹脂としては、１９０℃におけるＭＦＲが５〜５０ｇ／１０分の範囲であることが好ましい。ＭＦＲが５ｇ／１０分未満であると、溶融性が不充分で塗膜表面の平滑性が悪くなり、ＭＦＲが５０ｇ／１０分を超えると、融点が低下し粉末化が困難となり、塗膜として使用できない。   The ethylene-acrylic acid-based copolymer resin of the present invention preferably has an MFR at 190 ° C. of 5 to 50 g / 10 minutes. If the MFR is less than 5 g / 10 minutes, the meltability is insufficient and the smoothness of the surface of the coating film deteriorates. If the MFR exceeds 50 g / 10 minutes, the melting point decreases and powdering becomes difficult, and I can not use it.

本発明で用いられる腐食防止剤としては、例えば、ハイドロタルサイト類化合物、リン酸塩、モリブデン酸塩、アミン類、チオ尿素類、亜硝酸塩、クロム酸塩、ケイ酸塩等が挙げられる。中でもハイドロタルサイト類化合物、リン酸塩、モリブデン酸塩が好適に用いられる。   Examples of the corrosion inhibitor used in the present invention include hydrotalcite compounds, phosphates, molybdates, amines, thioureas, nitrites, chromates, silicates, and the like. Among them, hydrotalcite compounds, phosphates and molybdates are preferably used.

上記ハイドロタルサイト類化合物とは、下記の一般式（Ｉ）
［Ｍ２＋ １−ｘＭ３＋ ｘ（ＯＨ）２］ｘ＋［Ａｎ− ｘ／ｎ・ｍＨ２Ｏ］ｘ− （Ｉ）
（式中、Ｍ２＋は、Ｍｇ２＋、Ｍｎ２＋、Ｆｅ２＋、Ｃｏ２＋、Ｎｉ２＋、Ｃｕ２＋又はＺｎ２＋を表し、Ｍ３＋は、Ａｌ３＋、Ｆｅ３＋、Ｃｒ３＋、Ｃｏ３＋又はＩｎ３＋を表し、Ａｎ−は、ＯＨ− 、Ｆ− 、Ｃｌ− 、Ｂｒ− 、ＮＯ３ − 、ＣＯ３ ２−、ＳＯ４ ２−、Ｆｅ（ＣＮ）６ ３−、ＣＨ３ＣＯＯ− 、シュウ酸イオン又はサリチル酸イオンを表し、ｎはこれらに対応して１〜３の整数を表す。ｍは、正の整数を表し、ｘは、０＜ｘ≦０．３３の範囲を示す。）
で表される不定比化合物であり、例えば、Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ、Ｍｇ４・３Ａｌ２（ＯＨ）１２・６ＣＯ３・ｍＨ２Ｏ等を挙げることができる。 The hydrotalcite compound is represented by the following general formula (I)
[M 2+ 1-x M 3+ x (OH) 2] x + [A n- x / n · mH 2 O] x- (I)
( Wherein , M 2+ represents Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ or Zn 2+ , and M 3+ represents Al 3+ , Fe 3+ , Cr 3+ , Co 3+ or In 3+ . represents, A n-is, OH -, F -, Cl -, Br -, NO 3 -, CO 3 2-, SO 4 2-, Fe (CN) 6 3-, CH 3 COO -, oxalic acid ion or Represents a salicylate ion, n represents an integer of 1 to 3 corresponding thereto, m represents a positive integer, and x represents a range of 0 <x ≦ 0.33.)
In a non-stoichiometric compound represented, for example, be mentioned Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O, Mg 4 · 3 Al 2 (OH) 12 · 6 CO 3 · mH 2 O , etc. it can.

上記リン酸塩としては、例えば、リン酸亜鉛、リン酸カルシウム、リンモリブデン酸アルミニウム等を挙げることができる。
上記モリブデン酸塩としては、例えば、モリブデン酸カルシウム、モリブデン酸亜鉛等を挙げることができる。 Examples of the phosphate include zinc phosphate, calcium phosphate, and aluminum phosphomolybdate.
Examples of the molybdate include calcium molybdate and zinc molybdate.

上記腐食防止剤の配合量は、通常、ポリオレフィン系樹脂１００重量部に対して０．１〜１０重量部、好ましくは０．５〜８重量部である。上記腐食防止剤が０．１重量部未満であると、充分な防錆効果を示さないばかりでなく、熱水環境下での充分な接着性が得られず、１０重量部を超えると、防錆効果は充分であるが、粉体塗料にした際の加工性、塗膜の表面平滑性が損なわれ、良好な塗膜が形成し難くなるため、上記範囲に限定される。   The amount of the corrosion inhibitor is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the polyolefin resin. When the amount of the corrosion inhibitor is less than 0.1 part by weight, not only does not show a sufficient rust preventive effect, but also sufficient adhesiveness in a hot water environment cannot be obtained. Although the rust effect is sufficient, the workability and the surface smoothness of the coating film in powder coating are impaired, and it becomes difficult to form a good coating film.

本発明のポリオレフィン系粉体塗料組成物は、上記ポリオレフィン系樹脂と上記腐食防止剤とを混練押出機、加熱ロール、バンバリーミキサー、ニーダー等の各種混練機を用いて混合・溶融混練した後、例えばペレットに成形し、これをさらに、機械粉砕法、液体チッソを用いる冷凍粉砕法等の手段により粉砕して得られる。   The polyolefin-based powder coating composition of the present invention is obtained by mixing and melting and kneading the polyolefin-based resin and the corrosion inhibitor with a kneading extruder, a heating roll, a Banbury mixer, various kneading machines such as a kneader, It is obtained by molding into pellets, which are further pulverized by means such as a mechanical pulverization method and a freeze pulverization method using liquid nitrogen.

このようにして得られた粉体塗料組成物に、さらに通常の着色剤、耐熱安定剤、酸化防止剤、紫外線吸収剤、滑剤、顔料等の添加剤を適宣配合しても良い。   Additives such as ordinary colorants, heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, pigments and the like may be appropriately added to the powder coating composition thus obtained.

本発明のポリオレフィン系粉体塗料組成物は、従来の粉体塗装方法、例えば、流動浸漬法、静電塗装法、溶射法、散布法等の手段によって基材に塗装する。上記基材としては特に限定されず、例えば、金属、主として鉄、鉄合金、亜鉛又はそれらのメッキ品等が好適に用いられる。   The polyolefin-based powder coating composition of the present invention is applied to a substrate by a conventional powder coating method, for example, a fluid immersion method, an electrostatic coating method, a thermal spraying method, a spraying method, or the like. The substrate is not particularly limited, and for example, metals, mainly iron, iron alloys, zinc, or plated products thereof are preferably used.

本発明のポリオレフィン系粉体塗料組成物は、ポリオレフィン系樹脂に腐食防止剤を配合することにより、接着性、腐食防止性に優れるとともに、熱水環境下でも、長期の耐久性を有する塗膜を形成することができる。   The polyolefin-based powder coating composition of the present invention, by blending a corrosion inhibitor with a polyolefin-based resin, has excellent adhesion and corrosion prevention properties, and can provide a coating film having long-term durability even in a hot water environment. Can be formed.

以下、実施例及び比較例により本発明をさらに詳しく説明するが、本発明はこれらの実施例等によりなんら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

実施例１
未変性ポリプロピレンを無水マレイン酸でグラフト変性した変性ポリプロピレン（三井石油化学工業社製：接着性ポリプロピレン）２０重量部、ポリプロピレン９５重量％とポリエチレン５重量％とのランダム共重合体（住友化学工業社製：ノーブレンＺ１３１）８０重量部、ハイドロタルサイト（協和化学工業社製：ＤＨＴ−４Ａ、Ｍｇ４・３Ａｌ２（ＯＨ）１２・６ＣＯ３・ｍＨ２Ｏ）３重量部をヘンシェルミキサーで予備混合し、次いで押出機を使用して１９０℃で溶融混練してペレットを得た。ＭＦＲは３０ｇ／１０分であった。ＭＦＲは、ＪＩＳ Ｋ ６７５８（２３０℃、２．１６ｋｇ荷重）に準拠して測定した。
得られたペレットを液体チッソを使用し冷凍粉砕し、４０メッシュパスに分級して粉体塗料組成物を得た。 Example 1
20 parts by weight of a modified polypropylene obtained by graft-modifying unmodified polypropylene with maleic anhydride (adhesive polypropylene manufactured by Mitsui Petrochemical Industries, Ltd.), and a random copolymer of 95% by weight of polypropylene and 5% by weight of polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) : Noblen Z131) 80 parts by weight of hydrotalcite (Kyowa chemical industry Co., Ltd.: DHT-4A, Mg 4 · 3 Al 2 (OH) 12 · 6 CO 3 · mH 2 O) premixed 3 parts by weight in a Henschel mixer Then, the mixture was melt-kneaded at 190 ° C. using an extruder to obtain pellets. MFR was 30 g / 10 minutes. The MFR was measured in accordance with JIS K 6758 (230 ° C., 2.16 kg load).
The obtained pellets were frozen and pulverized using liquid nitrogen, and classified into 40 mesh passes to obtain a powder coating composition.

得られた粉体塗料組成物を用いて、流動浸漬法による粉体塗装を行った。すなわち、粉体塗料組成物の粉末を流動浸漬槽に入れ、多孔質の槽底部より空気を送り込み、安定した流動状態に保持する。その中に、３６０℃のオーブンで４分間前加熱した長さ１５０ｍｍ、幅７０ｍｍ、厚さ２ｍｍの鋼板試験片を８秒間浸漬した。試験片を取り出した後２００℃のオーブンで２分間後加熱を行い、室温下で放冷して塗装品を得た。
得られた塗装品を８０℃の熱水中に１月間浸漬し、耐久性試験を行った。試験後の塗膜の評価結果を表１に示した。 Using the obtained powder coating composition, powder coating was performed by a fluid immersion method. That is, the powder of the powder coating composition is put into a fluidized immersion tank, and air is sent from the bottom of the porous tank to maintain a stable fluidized state. A steel plate test piece having a length of 150 mm, a width of 70 mm, and a thickness of 2 mm pre-heated in a 360 ° C. oven for 4 minutes was immersed therein for 8 seconds. After taking out the test piece, it was post-heated in a 200 ° C. oven for 2 minutes and allowed to cool at room temperature to obtain a coated product.
The obtained coated product was immersed in hot water at 80 ° C. for one month to perform a durability test. Table 1 shows the evaluation results of the coating films after the test.

塗膜の評価方法は以下の通りである。
（１）外観
塗膜表面を目視により観察した。
（２）錆の発生
塗膜をカッターナイフで剥離し、塗膜に接した金属面の錆の発生状況を目視により観察した。
（３）接着強度
塗膜に、カッターナイフで２５ｍｍ幅の平行ノッチを金属素材まで達するように入れ、引張試験機を用いて５０ｍｍ／分の引っ張り速度で、１８０度剥離させた時の接着強度を測定した（単位：ｋｇ／２５ｍｍ幅）。 The evaluation method of the coating film is as follows.
(1) Appearance The coating film surface was visually observed.
(2) Rust generation The coating film was peeled off with a cutter knife, and the state of rust generation on the metal surface in contact with the coating film was visually observed.
(3) Adhesive strength A 25 mm-wide parallel notch was inserted into the coating using a cutter knife so as to reach the metal material, and the adhesive strength when peeled 180 ° at a pulling speed of 50 mm / min using a tensile tester was measured. It was measured (unit: kg / 25 mm width).

実施例２〜４
変性ポリプロピレンと未変性ポリプロピレンとの配合割合を表１に示した割合に変更した以外は実施例１と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Examples 2 to 4
A powder coating composition was obtained in the same manner as in Example 1 except that the mixing ratio of the modified polypropylene and the unmodified polypropylene was changed to the ratio shown in Table 1. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

実施例５
ハイドロタルサイトの配合量を３重量部から７重量部に変更した以外は実施例２と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Example 5
A powder coating composition was obtained in the same manner as in Example 2, except that the blending amount of hydrotalcite was changed from 3 parts by weight to 7 parts by weight. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

実施例６、７
腐食防止剤としてハイドロタルサイトの代わりにリン酸カルシウム（キクチカラー社製：ＬＦボウセイ ＣＰ−Ｚ）を表１に示した配合割合で用いた以外は実施例２と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Examples 6 and 7
A powder coating composition was obtained in the same manner as in Example 2 except that calcium phosphate (manufactured by Kikuchi Color Co., Ltd .: LF-Bosei CP-Z) was used in place of hydrotalcite as a corrosion inhibitor in the mixing ratio shown in Table 1. Was. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

実施例８、９
腐食防止剤としてハイドロタルサイトの代わりにリン酸亜鉛（キクチカラー社製：ＬＦボウセイ Ｐ−ＷＦ）を表１に示した配合割合で用いた以外は実施例２と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Examples 8 and 9
Powder coating composition in the same manner as in Example 2 except that zinc phosphate (manufactured by Kikuchi Color Co., Ltd .: LF Bousei P-WF) was used in place of hydrotalcite as a corrosion inhibitor in the mixing ratio shown in Table 1. Got. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

比較例１
腐食防止剤を配合しないこと以外は、実施例４と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Comparative Example 1
A powder coating composition was obtained in the same manner as in Example 4, except that no corrosion inhibitor was added. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

比較例２、３
腐食防止剤としてハイドロタルサイトを表１に示した配合割合で用いた以外は実施例４と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１と同様にして塗装品の評価を行った。結果を表１に示した。 Comparative Examples 2 and 3
A powder coating composition was obtained in the same manner as in Example 4 except that hydrotalcite was used as a corrosion inhibitor in the mixing ratio shown in Table 1. A coated article was evaluated in the same manner as in Example 1 using the obtained powder coating composition. The results are shown in Table 1.

Figure 2004352994
Figure 2004352994

実施例１０
未変性ポリエチレンを無水マレイン酸でグラフト変性した変性ポリエチレン（三井石油化学工業社製：アドマーＮＥ１００）２０重量部、線状低密度ポリエチレン（三井石油化学工業社製：ウルトゼックス２５１００）８０重量部、ハイドロタルサイト（協和化学工業社製：ＤＨＴ−４Ａ、Ｍｇ４・３Ａｌ２（ＯＨ）１２・６ＣＯ３・ｍＨ２Ｏ）３重量部をヘンシェルミキサーで予備混合し、次いで押出機を使用して１５０℃で溶融混練してペレットを得た。ＭＦＲは１０ｇ／１０分であった。ＭＦＲは、ＪＩＳ Ｋ ６７６０（１９０℃、２．１６ｋｇ荷重）に準拠して測定した。得られたペレットを常温で粉砕し、４０メッシュパスに分級して粉体塗料組成物を得た。 Example 10
20 parts by weight of a modified polyethylene obtained by graft-modifying unmodified polyethylene with maleic anhydride (Admer NE100, manufactured by Mitsui Petrochemical Industries, Ltd.), 80 parts by weight of linear low-density polyethylene (Ultzex 25100, manufactured by Mitsui Petrochemicals, Inc.) hydrotalcite: use (manufactured by Kyowa chemical industry Co., Ltd. DHT-4A, Mg 4 · 3 Al 2 (OH) 12 · 6 CO 3 · mH 2 O) 3 parts by weight were premixed with a Henschel mixer, followed by an extruder Pellets were obtained by melt-kneading at 150 ° C. The MFR was 10 g / 10 minutes. MFR was measured according to JIS K 6760 (190 ° C., 2.16 kg load). The obtained pellets were pulverized at room temperature and classified into 40 mesh passes to obtain a powder coating composition.

得られた粉体塗料組成物を用いて、流動浸漬法による粉体塗装を行った。すなわち、粉体塗料組成物の粉末を流動浸漬槽に入れ、多孔質の槽底部より空気を送り込み、安定した流動状態に保持する。その中に、３６０℃のオーブンで４分間前加熱した長さ１５０ｍｍ、幅７０ｍｍ、厚さ２ｍｍの鋼板試験片を６秒間浸漬した。試験片を取り出した後１８０℃のオーブンで２分間後加熱を行い、室温下で放冷して塗装品を得た。得られた塗装品を８０℃の熱水中に１月間浸漬し、耐久性試験を行った。試験後の塗膜の評価結果を表２に示した。   Using the obtained powder coating composition, powder coating was performed by a fluid immersion method. That is, the powder of the powder coating composition is put into a fluidized immersion tank, and air is sent from the bottom of the porous tank to maintain a stable fluidized state. A steel plate test piece having a length of 150 mm, a width of 70 mm and a thickness of 2 mm pre-heated in an oven at 360 ° C. for 4 minutes was immersed therein for 6 seconds. After the test piece was taken out, it was post-heated in an oven at 180 ° C. for 2 minutes and allowed to cool at room temperature to obtain a coated product. The obtained coated product was immersed in hot water at 80 ° C. for one month to perform a durability test. Table 2 shows the evaluation results of the coating films after the test.

実施例１１〜１３
変性ポリエチレンと未変性ポリエチレンとの配合割合を表２に示した割合に変更した以外は実施例１０と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１０と同様にして塗装品の評価を行った。結果を表２に示した。 Examples 11 to 13
A powder coating composition was obtained in the same manner as in Example 10, except that the mixing ratio of the modified polyethylene and the unmodified polyethylene was changed to the ratio shown in Table 2. The coated product was evaluated in the same manner as in Example 10 using the obtained powder coating composition. The results are shown in Table 2.

比較例４
腐食防止剤を配合しないこと以外は、実施例１３と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１０と同様にして塗装品の評価を行った。結果を表２に示した。 Comparative Example 4
A powder coating composition was obtained in the same manner as in Example 13 except that no corrosion inhibitor was added. The coated product was evaluated in the same manner as in Example 10 using the obtained powder coating composition. The results are shown in Table 2.

実施例１４
アクリル酸含量が７重量％のエチレン−アクリル酸共重合体（三菱化学社製：ＥＡＡ−Ａ２１０Ｍ）２０重量部、線状低密度ポリエチレン（三井石油化学工業社製：ウルトゼックス２５１００）８０重量部、ハイドロタルサイト（協和化学工業社製：ＤＨＴ−４Ａ、Ｍｇ４・３Ａｌ２（ＯＨ）１２・６ＣＯ３・ｍＨ２Ｏ）３重量部をヘンシェルミキサーで予備混合し、次いで押出機を使用して１５０℃で溶融混練してペレットを得た。ＭＦＲは１０ｇ／１０分であった。ＭＦＲは、ＪＩＳ Ｋ ６７６０（１９０℃、２．１６ｋｇ荷重）に準拠して測定した。得られたペレットを常温で粉砕し、４０メッシュパスに分級して粉体塗料組成物を得た。 Example 14
20 parts by weight of an ethylene-acrylic acid copolymer having an acrylic acid content of 7% by weight (manufactured by Mitsubishi Chemical Corporation: EAA-A210M), 80 parts by weight of linear low-density polyethylene (Ultzex 25100, manufactured by Mitsui Petrochemical Industries, Ltd.) hydrotalcite: a (Kyowa chemical industry Co., Ltd. DHT-4A, Mg 4 · 3 Al 2 (OH) 12 · 6 CO 3 · mH 2 O) 3 parts by weight were premixed in a Henschel mixer, then using an extruder At 150 ° C. to obtain pellets. The MFR was 10 g / 10 minutes. MFR was measured according to JIS K 6760 (190 ° C., 2.16 kg load). The obtained pellets were pulverized at room temperature and classified into 40 mesh passes to obtain a powder coating composition.

得られた粉体塗料組成物を用いて、流動浸漬法による粉体塗装を行った。すなわち、粉体塗料組成物の粉末を流動浸漬槽に入れ、多孔質の槽底部より空気を送り込み、安定した流動状態に保持する。その中に、３２０℃のオーブンで６分間前加熱した長さ１５０ｍｍ、幅７０ｍｍ、厚さ２ｍｍの鋼板試験片を６秒間浸漬した。試験片を取り出した後１８０℃のオーブンで６分間後加熱を行い、室温下で放冷して塗装品を得た。
得られた塗装品を８０℃の熱水中に１月間浸漬し、耐久性試験を行った。試験後の塗膜の評価結果を表２に示した。 Using the obtained powder coating composition, powder coating was performed by a fluid immersion method. That is, the powder of the powder coating composition is put into a fluidized immersion tank, and air is sent from the bottom of the porous tank to maintain a stable fluidized state. A steel plate test piece having a length of 150 mm, a width of 70 mm, and a thickness of 2 mm pre-heated in a 320 ° C. oven for 6 minutes was immersed therein for 6 seconds. After the test piece was taken out, it was heated in an oven at 180 ° C. for 6 minutes and allowed to cool at room temperature to obtain a coated product.
The obtained coated product was immersed in hot water at 80 ° C. for one month to perform a durability test. Table 2 shows the evaluation results of the coating films after the test.

実施例１５〜１７
エチレン−アクリル酸共重合体と線状低密度ポリエチレンとの配合割合を表２に示した割合に変更した以外は実施例１４と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１４と同様にして塗装品の評価を行った。結果を表２に示した。 Examples 15 to 17
A powder coating composition was obtained in the same manner as in Example 14, except that the mixing ratio of the ethylene-acrylic acid copolymer and the linear low-density polyethylene was changed to the ratio shown in Table 2. The coated product was evaluated in the same manner as in Example 14 using the obtained powder coating composition. The results are shown in Table 2.

比較例５
腐食防止剤を配合しないこと以外は、実施例１７と同様にして粉体塗料組成物を得た。得られた粉体塗料組成物を用いて実施例１４と同様にして塗装品の評価を行った。結果を表２に示した。 Comparative Example 5
A powder coating composition was obtained in the same manner as in Example 17 except that no corrosion inhibitor was added. The coated product was evaluated in the same manner as in Example 14 using the obtained powder coating composition. The results are shown in Table 2.

Figure 2004352994
Figure 2004352994

本発明のポリオレフィン系粉体塗料組成物は、ポリオレフィン系樹脂に腐食防止剤を配合することにより、接着性、腐食防止性に優れるとともに、熱水環境下でも、長期の耐久性を有する塗膜を形成することができる。   The polyolefin-based powder coating composition of the present invention, by blending a corrosion inhibitor with a polyolefin-based resin, has excellent adhesion and corrosion prevention properties, and can provide a coating film having long-term durability even in a hot water environment. Can be formed.

Claims (3)

ポリオレフィン系樹脂１００重量部にハイドロタルサイト類化合物０．１〜１０重量部を配合してなり、熱水環境下においても腐食防止性に優れた塗膜を与えるポリオレフィン系粉体塗料組成物であって、
前記ポリオレフィン系樹脂が、変性ポリプロピレン１００〜５重量％と未変性ポリプロピレン０〜９５重量％とからなるポリプロピレン系樹脂であるポリオレフィン系粉体塗料組成物。 A polyolefin-based powder coating composition comprising 100 parts by weight of a polyolefin-based resin and 0.1 to 10 parts by weight of a hydrotalcite compound to give a coating film having excellent corrosion resistance even in a hot water environment. hand,
A polyolefin-based powder coating composition, wherein the polyolefin-based resin is a polypropylene-based resin comprising 100 to 5% by weight of modified polypropylene and 0 to 95% by weight of unmodified polypropylene. ポリプロピレン系樹脂が、２３０℃におけるメルトフローレート５〜８０ｇ／１０分の樹脂である請求項１記載のポリオレフィン系粉体塗料組成物。 The polyolefin-based powder coating composition according to claim 1, wherein the polypropylene-based resin is a resin having a melt flow rate at 230 ° C of 5 to 80 g / 10 minutes. 基材と、前記基材上にポリオレフィン系粉体塗料組成物を塗装することにより形成した塗膜とを含む給湯管であって、
前記ポリオレフィン系粉体塗料組成物が、ポリオレフィン系樹脂１００重量部にハイドロタルサイト類化合物０．１〜１０重量部を配合してなるものであり、
前記ポリオレフィン系樹脂が、変性ポリプロピレン１００〜５重量％と未変性ポリプロピレン０〜９５重量％とからなるポリプロピレン系樹脂である給湯管。 A hot water supply pipe comprising a substrate and a coating film formed by applying a polyolefin-based powder coating composition on the substrate,
The polyolefin-based powder coating composition is obtained by blending 0.1 to 10 parts by weight of a hydrotalcite compound in 100 parts by weight of a polyolefin-based resin,
A hot water supply pipe wherein the polyolefin-based resin is a polypropylene-based resin comprising 100 to 5% by weight of modified polypropylene and 0 to 95% by weight of unmodified polypropylene.
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JP2005336002A (en) * 2004-05-26 2005-12-08 Nippon Chem Ind Co Ltd Nitrite ion-type hydrotalcite powder, its manufacturing method, rust-preventive composition, and rust-preventive coating composition
JP2010037491A (en) * 2008-08-07 2010-02-18 Sumitomo Seika Chem Co Ltd Powder-coating composition and article coated with the same
JP2010242067A (en) * 2009-04-03 2010-10-28 Rohm & Haas Co Corrosion-resistant and chip-resistant powder coating
US8574708B2 (en) 2007-10-31 2013-11-05 Akzo Nobel Coatings International B.V. Thin chip resistant powder topcoats for steel
US10011736B2 (en) 2009-07-29 2018-07-03 Akzo Nobel Coatings International B.V. Powder coating compositions capable of having a substantially non-zinc containing primer

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005336002A (en) * 2004-05-26 2005-12-08 Nippon Chem Ind Co Ltd Nitrite ion-type hydrotalcite powder, its manufacturing method, rust-preventive composition, and rust-preventive coating composition
JP4636587B2 (en) * 2004-05-26 2011-02-23 日本化学工業株式会社 Nitrite ion type hydrotalcite powder, production method thereof, rust preventive composition and rust preventive coating composition
US8574708B2 (en) 2007-10-31 2013-11-05 Akzo Nobel Coatings International B.V. Thin chip resistant powder topcoats for steel
JP2010037491A (en) * 2008-08-07 2010-02-18 Sumitomo Seika Chem Co Ltd Powder-coating composition and article coated with the same
JP2010242067A (en) * 2009-04-03 2010-10-28 Rohm & Haas Co Corrosion-resistant and chip-resistant powder coating
EP2565240A2 (en) * 2009-04-03 2013-03-06 Akzo Nobel Coatings International B.V. Powder corrosion and chip-resistant coating
EP2565240A3 (en) * 2009-04-03 2013-05-29 Akzo Nobel Coatings International B.V. Powder corrosion and chip-resistant coating
US10344178B2 (en) 2009-04-03 2019-07-09 Akzo Nobel Coatings International B.V. Powder corrosion and chip-resistant coating
US10011736B2 (en) 2009-07-29 2018-07-03 Akzo Nobel Coatings International B.V. Powder coating compositions capable of having a substantially non-zinc containing primer
US10550283B2 (en) 2009-07-29 2020-02-04 Akzo Nobel Coating International B.V. Powder coating compositions capable of having a substantially non-zinc containing primer

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