JPS61190571A - Epoxy resin powder coating - Google Patents
Epoxy resin powder coatingInfo
- Publication number
- JPS61190571A JPS61190571A JP3072285A JP3072285A JPS61190571A JP S61190571 A JPS61190571 A JP S61190571A JP 3072285 A JP3072285 A JP 3072285A JP 3072285 A JP3072285 A JP 3072285A JP S61190571 A JPS61190571 A JP S61190571A
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- JP
- Japan
- Prior art keywords
- epoxy resin
- coating
- parts
- glass powder
- powder coating
- 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.)
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Abstract
Description
【発明の詳細な説明】
〔技術分野〕
この発明は常温下はもちろん低温下に於いても優れた耐
衝撃性を有する塗膜を形成しうるエポキシ樹脂粉体塗料
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an epoxy resin powder coating that can form a coating film having excellent impact resistance not only at room temperature but also at low temperature.
エポキシ樹脂粉体塗料は、通常、エポキシ樹脂に硬化剤
と粒状無機充填剤を配合してなるものであり、被塗装物
に対する良好な密着性と優れた防食性を示すことから、
従来より船舶、車両、大型構造物などの防食塗装用塗料
として汎用されている。Epoxy resin powder coatings are usually made by blending an epoxy resin with a curing agent and a granular inorganic filler, and because they exhibit good adhesion to objects to be coated and excellent corrosion resistance,
It has been widely used as an anticorrosive paint for ships, vehicles, large structures, etc.
このエポキシ樹脂粉体塗料を用いて形成された塗膜は、
一般に常温付近においては良好な耐衝撃性を有するが低
温下においての耐衝撃性が不充分であるという欠点を有
している。The coating film formed using this epoxy resin powder coating is
In general, they have good impact resistance near room temperature, but have the disadvantage of insufficient impact resistance at low temperatures.
上記の欠点を解決する方法として、上記の塗膜の厚みを
厚くする、上記の粒状無機充填剤の配合量を多くする、
あるいは上記の粒状無機充填剤のかわりにフレーク状無
機充填剤を使用するなどの方法があるが、いずれも塗膜
の可撓性を低下させるという問題がある。可撓性の不充
分な塗膜は被塗装物のハンドリングの際にクランクを生
じやすい。As a method to solve the above disadvantages, the thickness of the above coating film is increased, the blending amount of the above granular inorganic filler is increased,
Alternatively, there is a method of using a flaky inorganic filler instead of the above-mentioned particulate inorganic filler, but each method has the problem of reducing the flexibility of the coating film. A coating film with insufficient flexibility is likely to cause cranking when handling the object to be coated.
そこでこの発明者らは上記の実情に鑑みて、良好な可撓
性を持ちしかも常温下はもちろん低温下においても優れ
た耐衝撃性を存する塗膜を形成しうるエポキシ樹脂粉体
塗料を提供することを目的として鋭意検討した結果、エ
ポキシ樹脂に配合する充填剤として粒状無機充填剤と特
定の針状ガラス粉末とをそれぞれ特定量使用することに
より上記目的が達せられることを見い出し、この発明を
なすに至った。即ち、この発明はエポキシ樹脂に少なく
とも硬化剤及び充填剤を含ませてなるエポキシ樹脂粉体
塗料において、充填剤としてエポキシ樹脂100重量部
に対して、平均長さが40ffio+以上で且つアスペ
クト比が4以上の針状ガラス粉末を100〜180重量
部(但し100M量部は除く)、および平均粒子径が1
.0μm以下の粒状無機充填剤を30重量部以上含むこ
とを特徴とするエポキシ樹脂粉体塗料に係るものである
。Therefore, in view of the above-mentioned circumstances, the present inventors provide an epoxy resin powder coating that can form a coating film that has good flexibility and has excellent impact resistance not only at room temperature but also at low temperature. As a result of intensive studies aimed at this purpose, it was discovered that the above object can be achieved by using specific amounts of a granular inorganic filler and a specific acicular glass powder as fillers to be mixed into an epoxy resin, and the present invention has been made based on this finding. reached. That is, the present invention provides an epoxy resin powder coating comprising an epoxy resin containing at least a curing agent and a filler, which has an average length of 40 ffio+ or more and an aspect ratio of 4 for 100 parts by weight of the epoxy resin as the filler. 100 to 180 parts by weight of the above acicular glass powder (excluding 100 M parts) and an average particle size of 1
.. The present invention relates to an epoxy resin powder coating characterized by containing 30 parts by weight or more of a granular inorganic filler with a size of 0 μm or less.
上記の針状ガラス粉末は補強効果のおおきな充填剤とし
て知られているものであるが、この針状ガラス粉末をエ
ポキシ樹脂粉体塗料における充填剤として用いると、一
般にはこの塗料を用いて形成される塗膜の可撓性が著し
く低下する。このため、従来のエポキシ樹脂粉体塗料に
おいては上記の針状ガラス粉末を配合する例は少ない。The above-mentioned acicular glass powder is known as a filler with a large reinforcing effect, but when this acicular glass powder is used as a filler in an epoxy resin powder coating, it is generally formed using this coating. The flexibility of the coating film is significantly reduced. For this reason, there are few examples in which the above-mentioned acicular glass powder is blended in conventional epoxy resin powder coatings.
しかしながら、本発明に於いては、エポキシ樹脂粉体塗
料の充填剤として上記の針状ガラス粉末と粒状無機充填
剤とを併用し、かつ両者の使用量を特定量とすることに
より、エポキシ樹脂粉体塗料を良好な可撓性を持ちしか
も常温下はもちろん低温下においても優れた耐衝撃性を
有する塗膜を形成しうるちのとしている。However, in the present invention, the acicular glass powder and the granular inorganic filler are used together as fillers in the epoxy resin powder coating, and by using specific amounts of both, the epoxy resin powder The body paint has good flexibility and forms a coating film that has excellent impact resistance not only at room temperature but also at low temperature.
本発明と関連のある発明として特願昭59−13349
4 (以下先願発明という)があり、この先願発明と本
発明とは、使用する成分は同一であるが、その夫々の使
用割合が若干具なっている。Patent application No. 59-13349 as an invention related to the present invention
4 (hereinafter referred to as the "prior invention"), and although the components used in the prior invention and the present invention are the same, the proportions of each component used are slightly different.
即ちガラス粉末の使用量が本発明では100〜180重
量部(但し100ii量部を除く)と先願発明よりも多
く使用しており、これにより得られる塗膜の平滑性なら
びに可撓性を毫も損なうことなく耐衝撃性の著しい向上
を図っている。そしてこのように多量のガラス粉末を使
用することにより、ガラス粉末としての使用範囲が先願
発明よりも広がり、より広い範囲からガラス粉末を選択
使用出来るに至る効果がある。即ち本発明は先願発明に
比し、耐衝撃性が著しく向上し、しかもこのPEA塗膜
の可撓性と平滑性については、毫もこれ等を損なわず、
加えて使用するガラス粉末としての範囲が平均長さ並び
にアスペクト比に於いて若干拡大され、産業上極めて有
利となるという効果を有する。In other words, the amount of glass powder used in the present invention is 100 to 180 parts by weight (excluding 100 parts by weight), which is larger than in the prior invention, and this improves the smoothness and flexibility of the resulting coating film. The impact resistance has been significantly improved without compromising the performance of the material. By using such a large amount of glass powder, the scope of use of the glass powder is wider than in the prior invention, and glass powder can be selected and used from a wider range. That is, the present invention has significantly improved impact resistance compared to the prior invention, and the flexibility and smoothness of the PEA coating film are not impaired by the coating.
In addition, the range of glass powder that can be used is slightly expanded in terms of average length and aspect ratio, which has the effect of being extremely advantageous industrially.
本発明に於いて使用するエポキシ樹脂としては、ビスフ
ェノールA型エポキシ樹脂、ノボラック型エポキシ樹脂
などのグリシジルエーテル型のエポキシ樹脂が使用可能
であり、とくにビスフェノールA型エポキシ樹脂が好適
である。また、ビスフェノールA型エポキシ樹脂を使用
する場合ビスフェノール、F型エポキシ樹脂などの他の
エポキシ樹脂を適当量混合して耐熱性などを向上させる
ことも出来る。この場合ビスフェノールA型エポキシ樹
脂の使用量は、全エポキシ樹脂使用量の70重置%以上
とするのが好ましい。As the epoxy resin used in the present invention, glycidyl ether type epoxy resins such as bisphenol A type epoxy resin and novolac type epoxy resin can be used, and bisphenol A type epoxy resin is particularly suitable. Furthermore, when using bisphenol A type epoxy resin, heat resistance etc. can be improved by mixing an appropriate amount of other epoxy resins such as bisphenol and F type epoxy resin. In this case, the amount of bisphenol A type epoxy resin used is preferably 70% or more of the total amount of epoxy resin used.
なお、本発明で用いるエポキシ樹脂としては、通常、分
子量が900〜3600であり、またエポキシ当量とし
ては450〜1800程度のものが好適に使用される。The epoxy resin used in the present invention usually has a molecular weight of 900 to 3,600 and an epoxy equivalent of about 450 to 1,800.
このエポキシ当量が小さすぎるとエポキシ樹脂粉体塗料
にブロッキングを生じやすく塗装作業性が悪くなるため
好ましくない。If the epoxy equivalent is too small, blocking tends to occur in the epoxy resin powder coating, which impairs coating workability, which is not preferable.
またこのエポキシ当量が大きすぎるとエポキシ樹脂粉体
塗料の熔融粘度が高すぎて均一な塗膜が得られないため
好ましくない。Moreover, if the epoxy equivalent is too large, the melt viscosity of the epoxy resin powder coating will be too high, making it impossible to obtain a uniform coating film, which is not preferable.
また、上記のエポキシ樹脂としては、全末端基数におけ
る非反応性末端基数つまりエポキシ基以外の末端基数(
エポキシ基が開環したグリコール、クロルヒドリンなど
を有するもの)の割合が5%未満であるものが好ましい
、この非反応性末端基数の割合が大きすぎると塗膜の可
撓性および耐衝撃性に悪影響を及ぼすため好ましくない
。In addition, for the above epoxy resin, the number of non-reactive terminal groups in the total number of terminal groups, that is, the number of terminal groups other than epoxy groups (
It is preferable that the proportion of non-reactive end groups (containing glycol, chlorohydrin, etc. in which the epoxy group is ring-opened) is less than 5%. If the proportion of this non-reactive end group is too large, the flexibility and impact resistance of the coating film will be adversely affected. This is undesirable because it causes
本発明において使用する硬化剤としては、エポキシ樹脂
粉体塗料に一般的に使用されるものから目的に応じて選
択される。この硬化剤の具体例としては、たとえばジア
ミノジフェニルアミンの如き芳香族ジアミン、脂肪族ア
ミンと脂肪族ジカルボン酸の縮合物、ジシアンジアミド
、イミダゾール類などのアミン系硬化剤、無水テトラヒ
ドロフタル酸、無水ペンゾフエノルテトラカルボン酸、
無水トリメリット酸などの有機酸無水物系硬化剤、フェ
ノール樹脂、ビスフェノールAなどのフェノール系硬化
剤などが挙げられる。また硬化剤の配合量は、用いるエ
ポキシ樹脂の1エポキシ当量当たり、一般的に0.5〜
1,5当量使用される。The curing agent used in the present invention is selected depending on the purpose from those commonly used for epoxy resin powder coatings. Specific examples of this curing agent include aromatic diamines such as diaminodiphenylamine, condensates of aliphatic amines and aliphatic dicarboxylic acids, amine curing agents such as dicyandiamide, imidazoles, tetrahydrophthalic anhydride, penzophthalic anhydride, etc. nortetracarboxylic acid,
Examples include organic acid anhydride curing agents such as trimellitic anhydride, phenolic resins, and phenol curing agents such as bisphenol A. The amount of the curing agent is generally 0.5 to 1 per 1 epoxy equivalent of the epoxy resin used.
1.5 equivalents are used.
本発明の粉体塗料中に含まれる充填剤は特定の針状ガラ
ス粉末と粒状無機充填剤とからなるものである。The filler contained in the powder coating of the present invention consists of a specific acicular glass powder and a granular inorganic filler.
上記の針状ガラス粉末とは平均長さが40μm以上で且
つアスペクト比(平均長さ/平均太さ)が4以上のもの
、好ましくは平均長さが40〜350μmでアスペクト
比が4〜100で且つ平均太さが1〜30μm程度のも
のである。The above-mentioned acicular glass powder has an average length of 40 μm or more and an aspect ratio (average length/average thickness) of 4 or more, preferably an average length of 40 to 350 μm and an aspect ratio of 4 to 100. Moreover, the average thickness is about 1 to 30 μm.
この針状ガラス粉末の平均長さが40μm未満であった
リアスペクト比が4未満では、エポキシ樹脂粉体塗料を
用いて形成される塗膜の耐衝撃性がとくに低温下(0℃
以下)において不充分となる。また、この針状ガラス粉
末の平均長さが長すぎると粉体塗料化が困難となる場合
が生じるとともに上記の塗膜の平滑性が低下するため好
ましくない。When the average length of the acicular glass powder is less than 40 μm and the rear aspect ratio is less than 4, the impact resistance of the coating film formed using the epoxy resin powder coating is particularly poor at low temperatures (0°C
(below) will be insufficient. Furthermore, if the average length of the acicular glass powder is too long, it may become difficult to form into a powder coating, and the smoothness of the coating film will decrease, which is not preferable.
また、この針状・ガラス粉末としては、その表面がシラ
ン系カンプリング剤で表面処理されたものを使用するの
が好ましい、この表面処理によって塗膜における針状ガ
ラス粉末とエポキシ樹脂とのぬれ性が向上して両者の接
着性が良好となり、これによって上記針状ガラス粉末と
エポキシ樹脂との界面への水分の浸入が防止される。こ
のため上記塗膜の防食性が向上して水分の浸入による塗
膜のふくれや塗膜の絶縁性の低下に起因する被塗装物の
腐食が良好に防止される。In addition, it is preferable to use the needle-shaped glass powder whose surface has been treated with a silane-based camping agent.This surface treatment improves the wettability of the needle-shaped glass powder and the epoxy resin in the coating film. This improves the adhesion between the two, thereby preventing moisture from entering the interface between the acicular glass powder and the epoxy resin. Therefore, the anticorrosion properties of the coating film are improved, and corrosion of the object to be coated due to blistering of the coating film due to moisture infiltration and deterioration of the insulation properties of the coating film is effectively prevented.
上記シラン系カップリング剤としては、N−フェニル−
T−アミノプロピルトリメトキシシラン、n−β−(ア
ミノエ゛チル)T−アミノプロピルトリメトキシシラン
、γ−アミノプロピルトリエトキシシランなどのアミノ
シラン、γ−グリシドキシプロビルメチルジェトキシシ
ラン、β−(3゜4−エポキシシクロヘキシル)エチル
トリメトキシシランなどのエポキシシラン、あるいはT
−メルカプトプロピルトリメトキシシランなどのメルカ
プトシランがと(に好ましいものとして挙げられる。As the silane coupling agent, N-phenyl-
Aminosilanes such as T-aminopropyltrimethoxysilane, n-β-(aminoethyl)T-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropylmethyljethoxysilane, β- Epoxysilane such as (3゜4-epoxycyclohexyl)ethyltrimethoxysilane, or T
-Mercaptosilanes such as mercaptopropyltrimethoxysilane are preferred.
針状ガラス粉末の配合量としては、上記のエポキシ樹脂
100重量部に対して100〜180重量部(但し10
0f!量部は除く)好ましくは100〜150重量部(
但し100重量部は除く)である、この範囲内では針状
ガラス粉末の配合量が多くなればなる程得られる目的物
塗膜の耐衝撃性が大き(なり、またこの際の配合量が1
80重量部をこえると塗膜の平滑性ならびに可撓性が低
下する傾向がある。The blending amount of the acicular glass powder is 100 to 180 parts by weight (however, 100 parts by weight) per 100 parts by weight of the above epoxy resin.
0f! (excluding parts by weight), preferably 100 to 150 parts by weight (
However, 100 parts by weight is excluded. Within this range, the larger the amount of acicular glass powder blended, the greater the impact resistance of the target coating film.
If it exceeds 80 parts by weight, the smoothness and flexibility of the coating film tend to decrease.
次に、上記針状ガラス粉末と併用される粒状無機充填剤
とは、平均粒子径が1.0μm以下、好ましくは0.1
〜0.7μm程度のものである。Next, the granular inorganic filler used in combination with the acicular glass powder has an average particle diameter of 1.0 μm or less, preferably 0.1 μm or less.
It is about 0.7 μm.
この平均粒子径が1.0μmを越えるとエポキシを
樹脂粉体塗料により形成された塗膜の可撓性が不充分と
なる。また、この粒状無機充填剤のアスペクト比(長径
/短径)は粒状無機充填剤2以下が好ましい。If the average particle diameter exceeds 1.0 μm, the flexibility of the coating film formed from the epoxy resin powder coating will be insufficient. Further, the aspect ratio (major axis/breadth axis) of this granular inorganic filler is preferably 2 or less.
この粒状無機充填剤の具体例としては、たとえばそれぞ
れ平均粒子径が1.0μm以下で且つアスペクト比が2
以下の粒土の二酸化チタン、硫酸バリウム、溶融シリカ
、アルミナ、炭酸カルシウムなどが挙げられる。Specific examples of this granular inorganic filler include those having an average particle diameter of 1.0 μm or less and an aspect ratio of 2.
The following granular soils include titanium dioxide, barium sulfate, fused silica, alumina, and calcium carbonate.
尚、この粒状無機充填剤としては、エポキシ樹脂とのぬ
れ性向上のための表面処理が施されているものが好まし
い、この表面処理としてはZn−Al−5i処理がとく
に好ましく、その他Al単独処理、樹脂酸、脂肪酸、シ
ランカップリング剤、チタンカップリング剤が充填剤の
種類に応じて使用出来る。The granular inorganic filler is preferably one that has been subjected to a surface treatment to improve wettability with the epoxy resin. As this surface treatment, Zn-Al-5i treatment is particularly preferred, and other Al alone treatment is also preferred. , resin acids, fatty acids, silane coupling agents, and titanium coupling agents can be used depending on the type of filler.
上記Zn−Aj!−3i処理とはケイ酸、酸化アルミお
よび酸化亜鉛の水和物を充填剤表面にコーティングする
ことによって、充填剤と樹脂の親和性、親水性を改良す
るものである。The above Zn-Aj! The -3i treatment improves the affinity and hydrophilicity between the filler and the resin by coating the surface of the filler with hydrates of silicic acid, aluminum oxide, and zinc oxide.
上記表面処理によって塗膜における粒状無機充填剤とエ
ポキシ樹脂との接着性が良好になるため上記針状ガラス
粉末における表面処理の場合と同様に塗膜の防食性およ
び絶縁性を向上させることが出来る。The above surface treatment improves the adhesion between the granular inorganic filler and the epoxy resin in the coating film, so it is possible to improve the anticorrosion and insulation properties of the coating film, similar to the surface treatment of the acicular glass powder described above. .
上記の粒状無機充填剤の配合量としては、上記のエポキ
シ樹脂100重量部に対して30重量部以上、好ましく
は30〜150重量部、特に好ましくは40−140重
量部である。この配合量が30未満ではエポキシ樹脂粉
体塗料により形成される塗膜の可撓性が不充分となる。The amount of the granular inorganic filler blended is 30 parts by weight or more, preferably 30 to 150 parts by weight, particularly preferably 40 to 140 parts by weight, based on 100 parts by weight of the epoxy resin. If this amount is less than 30, the flexibility of the coating film formed by the epoxy resin powder coating will be insufficient.
また、この配合量が多すぎると上記塗膜の平滑性が低下
するため好ましくない。In addition, if the amount is too large, the smoothness of the coating film will decrease, which is not preferable.
本発明のエポキシ樹脂粉体塗料は上記のエポキシ樹脂、
硬化剤、針状ガラス粉末および粒状無機充填剤を必須成
分とするが、これら成分以外に必要に応じて含量、レベ
リング剤、流れ調整剤などの添加剤を含んでいてもよい
、これら添加剤の配合量としては、通常上記エポキシ樹
脂100重量部に対して5重量部以下とするのがよい。The epoxy resin powder coating of the present invention includes the above-mentioned epoxy resin,
The hardening agent, acicular glass powder, and granular inorganic filler are essential ingredients, but in addition to these ingredients, additives such as content, leveling agents, flow control agents, etc. may be included as necessary. The amount to be blended is usually 5 parts by weight or less per 100 parts by weight of the epoxy resin.
本発明のエポキシ樹脂粉体塗料は、溶融混合法あるいは
乾式混合法によって得られるが、好ましくは熔融混合法
を採用して得るのがよく、上記のエポキシ樹脂、針状ガ
ラス粉末、粒状無機充填剤を充分に混合することにより
良好な塗膜の平滑性、可撓性が得られる。この熔融混合
法では、各成分を溶融混合したのち所定の粒度に粉砕す
る工程を含む、したがって、この粉砕工程で、前記充填
剤の大きさ、つまり針状ガラス粉末の平均長さやアスペ
クト比あるいは粒状無機充填剤の平均粒子径が粉砕時に
変化することが考えられる。The epoxy resin powder coating of the present invention can be obtained by a melt mixing method or a dry mixing method, but preferably by a melt mixing method. By sufficiently mixing these, good coating film smoothness and flexibility can be obtained. This melt mixing method includes the step of melt-mixing each component and then pulverizing it to a predetermined particle size. Therefore, in this pulverizing step, the size of the filler, that is, the average length and aspect ratio of the acicular glass powder, or the granularity It is conceivable that the average particle size of the inorganic filler changes during pulverization.
本発明においては粉砕後の上記充填剤の大きさが前記範
囲内に設定されていることが重要であり、このため前記
設定値以外の針状ガラス粉末や粒状無機充填剤を用いた
場合でも粉砕後に前記設定値の範囲内に入るものであれ
ばこの発明の粉体塗料として前記効果を得ることが出来
る。たとえば、後述する実施例に示す粉体塗料の製造条
件では、粉砕後の針状ガラス粉末の平均長さは配合前の
それの70〜90%に変化し、一方針状ガラス粉末の平
均太さや粒状無機充填剤の平均粒子径には変化が見られ
なかった。In the present invention, it is important that the size of the filler after pulverization is set within the above range, so even if acicular glass powder or granular inorganic filler other than the set value is used, the pulverization If the powder coating falls within the range of the above-mentioned set values, the above-mentioned effects can be obtained as the powder coating of the present invention. For example, under the powder coating manufacturing conditions shown in the Examples below, the average length of the acicular glass powder after pulverization changes to 70 to 90% of that before blending, and the average thickness of the acicular glass powder changes to 70% to 90% of that before blending. No change was observed in the average particle diameter of the granular inorganic filler.
上記熔融混合法により得られるあるいは乾式混合法にて
得られるこの発明のエポキシ樹脂粉体塗料の粒度は、こ
の粉体塗料の用途によっても異なるが粒状無機充填剤は
その最大粒度が200〜40メンシ工程度とされる。The particle size of the epoxy resin powder coating of the present invention obtained by the above-mentioned melt mixing method or dry mixing method varies depending on the use of the powder coating, but the maximum particle size of the granular inorganic filler is 200 to 40 mm. It is considered as a process level.
このエポキシ樹脂粉体塗料を用いて塗膜を形成するため
の塗装方法としては、一般に粉体塗装方法として知られ
ている方法がいずれも通用され、たとえば静電スプレー
法、静電浸漬法、流動浸漬法などが挙げられる。As a coating method for forming a coating film using this epoxy resin powder coating, all methods generally known as powder coating methods are commonly used, such as electrostatic spray method, electrostatic dipping method, and flow coating method. Examples include the immersion method.
上記エポキシ樹脂粉体塗料により塗装された被塗装物に
は上記粉体塗料が融着してなる塗膜が形成される。この
塗膜の厚みは目的に応じて設定されるが、薄すぎると塗
膜に欠陥を生じやすく、また厚すぎると可撓性が低下す
るため通常は0. 1〜1.0μm程度とするのがよい
。A coating film is formed on the object coated with the epoxy resin powder coating by fusing the powder coating. The thickness of this coating film is set depending on the purpose, but if it is too thin, defects will easily occur in the coating film, and if it is too thick, the flexibility will decrease, so it is usually 0. The thickness is preferably about 1 to 1.0 μm.
このようにして形成された塗膜は常温下はもちろん粒状
無機充填剤−50℃程度までの低温下においても優れた
耐衝撃性を有するとともに可撓性も良好である。The coating film thus formed has excellent impact resistance and flexibility not only at room temperature but also at low temperatures of about -50° C. using the granular inorganic filler.
本発明のエポキシ樹脂粉体塗料は上記のように優れた特
性を有する塗膜を形成しうるため、船舶、車両、大型構
造物などの防食塗装用をはじめとして、電気製品などの
美装および防食用、電気絶縁用、固着用などの粉体塗料
として極めて有用である。The epoxy resin powder coating of the present invention can form a coating film with excellent properties as described above, so it can be used for anti-corrosion coating of ships, vehicles, large structures, etc., as well as for aesthetic and anti-corrosion coating of electrical products, etc. It is extremely useful as a powder coating for food, electrical insulation, adhesion, etc.
以下にこの発明の実施例を記載する。なお、以下におい
て部とあるのは重量部を意味する。Examples of this invention will be described below. In addition, in the following, parts mean parts by weight.
実施例1
ビスフェノールA型エポキシ樹脂(エポキシ当量750
、全末端基数における非反応性末端基数の割合3.5%
)100部、N−フェニル−T−アミノプロピルトリメ
トキシシランにより表面処理された針状ガラス粉末(平
均長さ100μm、平均太さ9μm、アスペクト比10
)1)0部、Zn−Aj−5t処理された粒状の二酸化
チタン(平均粒子ao、35μm)50部を、プラネタ
リ−ミキサーにより130℃で2時間溶融混合した後、
取り出し、冷却後ハンマーミルにより粉砕し、この粉砕
物270部に対してエピクロルヒドリン1分子にビスフ
ェノール2分子を付加して得られる水酸基当量25Gで
ある樹脂(硬化剤)24部、2−メチルイミダゾール1
.0部、顔料0.5部およびレベリング剤0.5部から
なる組成物を二軸押出機で溶融混練した。Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 750
, the ratio of the number of non-reactive end groups to the total number of end groups is 3.5%
) 100 parts, acicular glass powder surface-treated with N-phenyl-T-aminopropyltrimethoxysilane (average length 100 μm, average thickness 9 μm, aspect ratio 10
) 1) After melt-mixing 50 parts of granular titanium dioxide (average particle ao, 35 μm) treated with 0 parts and Zn-Aj-5t at 130°C for 2 hours using a planetary mixer,
It was taken out, cooled, and pulverized in a hammer mill. To 270 parts of this pulverized product, 24 parts of a resin (curing agent) with a hydroxyl equivalent of 25 G obtained by adding 2 molecules of bisphenol to 1 molecule of epichlorohydrin, and 1 part of 2-methylimidazole were added.
.. A composition consisting of 0 part of pigment, 0.5 part of pigment, and 0.5 part of leveling agent was melt-kneaded using a twin-screw extruder.
次いで上記混練物をハンマーミルにより粒度が120メ
ツシユ以下となるように粉砕し、この発明のエポキシ樹
脂粉体塗料を得た。この塗料中に含まれる針状ガラス粉
末の平均長さは80μm、平均太さは10μm、アスペ
クト比は8.0であり、粒状二酸化チタンの平均粒子径
は0.35μmであった。Next, the above-mentioned kneaded material was pulverized with a hammer mill to a particle size of 120 mesh or less to obtain an epoxy resin powder coating of the present invention. The average length of the acicular glass powder contained in this paint was 80 μm, the average thickness was 10 μm, and the aspect ratio was 8.0, and the average particle diameter of the granular titanium dioxide was 0.35 μm.
ここで、針状ガラス粉末の平均長さ、平均太さおよび粒
状無機充填剤の平均粒子径は顕微鏡法によって求めたも
のであり、塗料中の上記充填剤については塗料を有機溶
剤に溶解、希釈、乾燥して、顕微鏡法により求めた。Here, the average length and average thickness of the acicular glass powder and the average particle diameter of the granular inorganic filler were determined by microscopy, and the above fillers in the paint were determined by dissolving and diluting the paint in an organic solvent. , dried and determined by microscopy.
実施例2〜4
針状ガラス粉末および二酸化チタンの配合量をそれぞれ
下記の第1表に示す量とした以外は実施例1と同様にし
てこの発明のエポキシ樹脂粉体塗料を得た。なお、粉砕
後の針状ガラス粉末および粒状二酸化チタンの大きさは
、いずれも前記実施例1の場合とほぼ同じこの発明の範
囲内にあった。Examples 2 to 4 Epoxy resin powder coatings of the present invention were obtained in the same manner as in Example 1, except that the amounts of acicular glass powder and titanium dioxide were as shown in Table 1 below. Incidentally, the sizes of the acicular glass powder and the granular titanium dioxide after pulverization were both within the range of the present invention, which is almost the same as in Example 1 above.
比較例1〜7
針状ガラス粉末および二酸化チタンの配合量をそれぞれ
下記の第1表に示す量とした以外は実施例1と同様にし
てエポキシ樹脂粉体塗料を得た。Comparative Examples 1 to 7 Epoxy resin powder coatings were obtained in the same manner as in Example 1, except that the amounts of acicular glass powder and titanium dioxide were as shown in Table 1 below.
上記の実施例1〜5および比較例1〜9で得られたエポ
キシ樹脂粉体塗料を用いて形成される塗膜の特性評価を
次のようにして行い、これらの結果を下記の第1表に示
した。Characteristics of coating films formed using the epoxy resin powder coatings obtained in Examples 1 to 5 and Comparative Examples 1 to 9 above were evaluated as follows, and the results are shown in Table 1 below. It was shown to.
〈耐衝撃性〉
税脂処理され且つショツトブラストにより最大粗さ50
μmに表面研掃された100+mX1001)1)X
121)1)1の熱間圧延鋼板を240℃に予熱し、こ
の鋼板に上記のエポキシ樹脂粉体塗料を静電スプレーで
塗布し、しかるのち200℃で10分間加熱して上記粉
体塗料を硬化させ厚さ0.3〜0.4msの塗膜を形成
し、これを試験片とした。<Impact resistance> Maximum roughness 50 by grain treatment and shot blasting
100+mX1001)1)X surface polished to μm
121) Preheat the hot rolled steel plate of 1) 1 to 240°C, apply the above epoxy resin powder coating to this steel plate by electrostatic spray, and then heat it at 200°C for 10 minutes to apply the above powder coating. It was cured to form a coating film with a thickness of 0.3 to 0.4 ms, which was used as a test piece.
ガードナ一式衝撃試験機を用い、棒状鉄の先端に5部8
インチの直径の鋼球を固着してなる重量IKgの重錘を
上記試験片の塗膜表面に落下させ、塗膜が破談しない最
大高さを求めた。この測定は20℃および一30℃で行
った。Using a Gardner set impact tester, 5 parts and 8
A weight having a weight of I kg, which was made by fixing a steel ball with a diameter of inch, was dropped onto the surface of the coating film of the above test piece, and the maximum height at which the coating film would not fail was determined. This measurement was carried out at 20°C and -30°C.
く可撓性〉
熱間圧延鋼板として離型処理を施したものを使用した以
外は上記の耐衝撃性測定のための試験片の場合と同様に
して塗膜を形成し、しかるのちこの塗膜を剥離してフィ
ルムを得た。このフィルムをJIS−に−71)3に規
定される2号ダンベルで打ち抜き、このダンベル状フィ
ルムを東洋ボールドウィン社製テンシロンUTM−1)
I型により引張速度50+wm/分で引張り試験を行い
、このフィルムの破壊時の伸び率を求めた。この測定は
20℃および一30℃で行った。Flexibility> A coating film was formed in the same manner as in the case of the test piece for impact resistance measurement above, except that a hot-rolled steel plate that had been subjected to mold release treatment was used, and then this coating film was was peeled off to obtain a film. This film was punched out with a No. 2 dumbbell specified in JIS-71)3, and this dumbbell-shaped film was cut into Tensilon UTM-1) manufactured by Toyo Baldwin Co., Ltd.
A tensile test was conducted using Type I at a tensile speed of 50+wm/min, and the elongation rate of this film at break was determined. This measurement was carried out at 20°C and -30°C.
く平滑性〉
耐衝撃性測定のための試験片における塗膜の外観を目視
により観察した。Smoothness> The appearance of the coating film on the test piece for measuring impact resistance was visually observed.
〈防食性〉
耐衝撃性試験の場合と同様にして作製した試験片を用い
てこれを沸騰水中に10日間浸漬したのち、塗膜のプリ
スフ−発生の有無を観察し、同時に塗膜の体積抵抗率を
測定した。<Corrosion resistance> Using a test piece prepared in the same manner as in the impact resistance test, it was immersed in boiling water for 10 days, and then the presence or absence of prism formation in the paint film was observed, and at the same time, the volume resistance of the paint film was measured. The rate was measured.
実施例5
ビスフェノールA型エポキシ樹脂(エポキシ当量850
、全末端基数における非反応性末端基数の割合3.0%
)100部、γ−グリシドキシプロビルメチルジェトキ
シシランにより表面処理された針状ガラス粉末(平均長
さ80μm、平均太さ9μm、アスペクト比8.9)1
20部、Zn−Al−3t処理された粒状の硫酸バリウ
ム(平均粒子径0.25μm)80部をプラネタリ−ミ
キサーにより130℃で2時間溶融部合した後、取り出
し、冷却後ハンマーミルにより粉砕し、この粉砕物30
0部に対してジアミノジフェニルメタ710部、2−メ
チルイミダゾール0.2部、顔料0.5部およびレベリ
ング剤0.5部からなる組成物を実施例1と同様に二軸
押出機で熔融混練し、しかるのち粒度が120メツシユ
以下となるように粉体化し、この発明のエポキシ樹脂粉
体塗料を得た。この塗料中に含まれる針状ガラス粉末の
平均長さは70μm1平均太さは9μm、アスペクト比
は7.8であり、粒状硫酸バリウムの平均粒子径は0.
25μmであった。Example 5 Bisphenol A type epoxy resin (epoxy equivalent: 850
, the ratio of the number of non-reactive end groups to the total number of end groups is 3.0%
) 100 parts, acicular glass powder surface-treated with γ-glycidoxypropylmethyljethoxysilane (average length 80 μm, average thickness 9 μm, aspect ratio 8.9) 1
After melting and combining 20 parts of Zn-Al-3t-treated granular barium sulfate (average particle size 0.25 μm) at 130°C for 2 hours using a planetary mixer, the mixture was taken out, cooled, and pulverized using a hammer mill. , this crushed material 30
A composition consisting of 710 parts of diaminodiphenylmeth, 0.2 parts of 2-methylimidazole, 0.5 parts of pigment, and 0.5 parts of leveling agent was melt-kneaded using a twin-screw extruder in the same manner as in Example 1. Then, it was pulverized to a particle size of 120 mesh or less to obtain an epoxy resin powder coating of the present invention. The average length of the acicular glass powder contained in this paint is 70 μm, the average thickness is 9 μm, and the aspect ratio is 7.8, and the average particle size of the granular barium sulfate is 0.8 μm.
It was 25 μm.
実施例6
針状ガラス粉末および硫酸バリウムの配合量を下記の第
2表に示す量とした以外は実施例6と同様にしてこの発
明のエポキシ樹脂粉体塗料を得た。Example 6 An epoxy resin powder coating of the present invention was obtained in the same manner as in Example 6, except that the amounts of acicular glass powder and barium sulfate were as shown in Table 2 below.
なお、粉砕後の針状ガラス粉末および粒状硫酸バリウム
の大きさは、いずれも前記実施例6の場合とほぼ同じこ
の発明の範囲内にあった。The sizes of the acicular glass powder and the granular barium sulfate after pulverization were both within the same range of the present invention as in Example 6.
比較例8
針状ガラス粉末としてγ−グリシドキシプロビルメチル
ジェトキシシランにより表面処理された平均長さ30μ
m、平均太さ13μm、アスペクト比2.3のものを使
用した以外は実施例6と同様にしてエポキシ樹脂粉体塗
料を得た。Comparative Example 8 Needle-like glass powder surface-treated with γ-glycidoxypropyl methyljethoxysilane, average length 30μ
An epoxy resin powder coating material was obtained in the same manner as in Example 6 except that a coating material having an average diameter of 13 μm and an aspect ratio of 2.3 was used.
比較例9
硫酸バリウムとしてZn−Al−5+処理された平均粒
子径3.0μmのものを使用した以外は実施例6と同様
にしてエポキシ樹脂粉体塗料を得た。Comparative Example 9 An epoxy resin powder coating was obtained in the same manner as in Example 6, except that barium sulfate treated with Zn-Al-5+ and having an average particle diameter of 3.0 μm was used.
上記の実施例5.6および比較例8.9で得られたエポ
キシ樹脂粉体塗料を用いて形成される塗膜の特性評価を
上記の方法で行い、これらの結果を下記の第2表に示し
た。Characteristics of coating films formed using the epoxy resin powder coatings obtained in Example 5.6 and Comparative Example 8.9 above were evaluated by the above method, and the results are shown in Table 2 below. Indicated.
以上の結果から明らかなように、この発明のエポキシ樹
脂粉体塗料によると、常温下はもちろん低温下において
も耐衝撃性に優れるとともに可撓性も良好な塗膜が形成
されることがわかる。As is clear from the above results, it can be seen that according to the epoxy resin powder coating of the present invention, a coating film having excellent impact resistance and flexibility is formed not only at room temperature but also at low temperature.
(以上)(that's all)
Claims (4)
ませてなるエポキシ樹脂粉体塗料において、充填剤とし
てエポキシ樹脂100重量部に対して、平均長さが40
mm以上でかつアスペクト比が4以上の針状ガラス粉末
を100〜 180重量部(但し100重量部は除く)、および平均
粒子径が1.0μm以下の粒状無機充填剤を30重量部
以上含むことを特徴とするエポキシ樹脂粉体塗料。(1) In an epoxy resin powder coating made of an epoxy resin containing at least a curing agent and a filler, the average length is 40 parts by weight based on 100 parts by weight of the epoxy resin as the filler.
Contains 100 to 180 parts by weight (excluding 100 parts by weight) of acicular glass powder with a diameter of 1.5 mm or more and an aspect ratio of 4 or more, and 30 parts by weight or more of a granular inorganic filler with an average particle size of 1.0 μm or less. An epoxy resin powder coating featuring:
基数の割合が5%未満である特許請求の範囲第(1)項
記載のエポキシ樹脂粉体塗料。(2) The epoxy resin powder coating according to claim (1), wherein the proportion of the number of non-reactive terminal groups in the total number of terminal groups of the epoxy resin is less than 5%.
である特許請求の範囲第(1)項または第(2)項記載
のエポキシ樹脂粉体塗料。(3) The epoxy resin powder coating according to claim (1) or (2), wherein the epoxy resin is a bisphenol A epoxy resin.
またはメルカプトシランにより表面処理されており、か
つ粒状無機充填剤がエポキシ樹脂とのぬれ性向上のため
の表面処理が施されている特許請求の範囲第(1)〜(
3)項のいずれかに記載のエポキシ樹脂粉体塗料。(4) The acicular glass powder is surface-treated with aminosilane, epoxysilane, or mercaptosilane, and the granular inorganic filler is surface-treated to improve wettability with the epoxy resin. (1)~(
The epoxy resin powder coating according to any of item 3).
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3072285A JPS61190571A (en) | 1985-02-19 | 1985-02-19 | Epoxy resin powder coating |
EP85304530A EP0172624B1 (en) | 1984-06-27 | 1985-06-25 | Powdered coating composition of epoxy resin and filler |
DE8585304530T DE3565850D1 (en) | 1984-06-27 | 1985-06-25 | Powdered coating composition of epoxy resin and filler |
US06/749,251 US4639476A (en) | 1984-06-27 | 1985-06-27 | Epoxy resin powder coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3072285A JPS61190571A (en) | 1985-02-19 | 1985-02-19 | Epoxy resin powder coating |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61190571A true JPS61190571A (en) | 1986-08-25 |
JPS6332829B2 JPS6332829B2 (en) | 1988-07-01 |
Family
ID=12311539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3072285A Granted JPS61190571A (en) | 1984-06-27 | 1985-02-19 | Epoxy resin powder coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61190571A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5239061A (en) * | 1975-09-18 | 1977-03-26 | Siemens Ag | Transmission coupling device |
JPS5456631A (en) * | 1977-10-14 | 1979-05-07 | Nitto Electric Ind Co Ltd | Plastic powder for spray coating |
JPS5513797A (en) * | 1978-07-13 | 1980-01-30 | Westinghouse Electric Corp | Uniform*finely crushed*solid*insulating powder coating composition |
JPS58168619A (en) * | 1982-03-30 | 1983-10-05 | Nitto Electric Ind Co Ltd | Epoxy resin composition |
JPS5978267A (en) * | 1982-10-27 | 1984-05-07 | Toa Paint Kk | Coating composition |
JPS60206821A (en) * | 1984-03-30 | 1985-10-18 | Toshiba Corp | Casting epoxy resin composition |
-
1985
- 1985-02-19 JP JP3072285A patent/JPS61190571A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5239061A (en) * | 1975-09-18 | 1977-03-26 | Siemens Ag | Transmission coupling device |
JPS5456631A (en) * | 1977-10-14 | 1979-05-07 | Nitto Electric Ind Co Ltd | Plastic powder for spray coating |
JPS5513797A (en) * | 1978-07-13 | 1980-01-30 | Westinghouse Electric Corp | Uniform*finely crushed*solid*insulating powder coating composition |
JPS58168619A (en) * | 1982-03-30 | 1983-10-05 | Nitto Electric Ind Co Ltd | Epoxy resin composition |
JPS5978267A (en) * | 1982-10-27 | 1984-05-07 | Toa Paint Kk | Coating composition |
JPS60206821A (en) * | 1984-03-30 | 1985-10-18 | Toshiba Corp | Casting epoxy resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPS6332829B2 (en) | 1988-07-01 |
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