JPS60104167A - Epoxy resin powder coating and its production - Google Patents
Epoxy resin powder coating and its productionInfo
- Publication number
- JPS60104167A JPS60104167A JP21265583A JP21265583A JPS60104167A JP S60104167 A JPS60104167 A JP S60104167A JP 21265583 A JP21265583 A JP 21265583A JP 21265583 A JP21265583 A JP 21265583A JP S60104167 A JPS60104167 A JP S60104167A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin
- resin powder
- powder coating
- melting point
- 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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Links
Abstract
Description
【発明の詳細な説明】
この発明は保存性および硬化性の良好なエポキシ樹脂粉
体塗料とその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to an epoxy resin powder coating with good storage stability and curability, and a method for producing the same.
従来、エポキシ樹脂粉本塗料は、省資源、省エネルギー
の観点から、またこれより形成される塗膜がすぐれた絶
、１、石生、防食性を／バすことから、種々の用途に用
いられてきている。さらに１侍近では、塗装作業性を改
善するために、硬化促進剤を用いた速硬化タイプのエポ
キシ樹脂粉体塗料か出現してきている１゜
ところが、上記１車ｊ１史化タイプの粉体塗料は一般に
粉体状態での保存性が悪（実用性に乏しかった。Conventionally, epoxy resin powder paints have been used for a variety of purposes from the viewpoint of resource and energy conservation, and because the coating films formed from them have excellent resistance to stone formation and corrosion. ing. Furthermore, in order to improve painting workability, fast-curing type epoxy resin powder paints using curing accelerators have been appearing in recent years. generally had poor storage stability in powder form (poor practicality).
また速硬化性と１呆存性とのバランスをとる目的で硬化
促進剤のｊＪを調整する方法かあるか、元来硬化促進剤
の添加中、は少）、シーのため、上記バランスかとりに
＜＜、品質的に安定しない問題かあった。Also, is there a way to adjust the jJ of the curing accelerator in order to balance fast curing and durability? There was a problem with the quality being unstable.
さらに別の方法として硬化促進剤の室ｌｆａ付近での活
性度を低下させる目的で、硬化促進剤の活性点部分を化
学的にトラップする方法が試みられているが、この場合
高温での反応時に硬化促進剤の活性興の両生が充分でな
（なるという傾向があり、そのために期待する速硬化性
が得られないという欠点を有していた。As another method, a method of chemically trapping the active site of the curing accelerator has been attempted in order to reduce the activity of the curing accelerator near the chamber lfa, but in this case, during the reaction at high temperature, The curing accelerator tends to be insufficiently active and active, and therefore has the disadvantage that the expected rapid curing properties cannot be obtained.
この発明者らは、上記観点から鋭意検−］した結果、硬
化促進剤をエポキシ樹脂およびその硬化剤に混合するに
当たって、予め上記エポキシ樹脂より尚融点の、）δ１
脂と混合して粉末化しこれをエポキシ樹脂とその硬化剤
に溶融混合ないし粉末混合（トライブレンド）したとき
には、保ｒＹ性と硬化性とに共にすぐれた速硬化タイプ
の粉体塗料が得られることを知り、この発明を完成する
に至ったものである。As a result of intensive investigation from the above viewpoint, the inventors found that, when mixing a curing accelerator into an epoxy resin and its curing agent, the epoxy resin has a melting point of )δ1.
When mixed with fat and powdered, and melt-blended or powder-blended (tri-blend) with epoxy resin and its curing agent, a fast-curing powder coating with excellent rY retention and curing properties can be obtained. This led to the completion of this invention.
すなわち、この発明は、ａ）エポキシ４ｉｊＪ脂からな
る主剤、ｂ）その硬化剤およびＣ）硬化促進剤と上記エ
ポキシ４ｉ’ｉｉ脂主剤より闘融点の樹脂とを含む樹脂
粉末を含冶することを特徴とするエポキシ樹脂粉体塗料
に係る第１の発明と、」−記粉体塗才・１の製造方法に
１糸る？１３２の発明とから７謀る。That is, the present invention includes a resin powder containing a) a base resin made of epoxy 4ijJ resin, b) a curing agent thereof, and C) a curing accelerator and a resin having a lower melting point than the epoxy 4i'ii resin base resin. The first invention related to the characteristic epoxy resin powder coating, and the manufacturing method of ``-Powder Coating Skills/1''? 132 inventions and 7 plots.
この発明のエポキシ樹脂粉体塗料は、エポキシ樹脂主剤
およびその硬化剤に混合されてする硬化促進剤が上記主
剤より尚融点の樹脂で被覆された状態にあるため、粉体
状態での保存性に非常にすぐれているとともに、使用時
溶融硬化させる際には上記局融点樹脂による被覆が解除
されてエポキシ樹脂主剤および硬化剤との急激な接触に
より良好な硬化性を得ることができる。The epoxy resin powder coating of the present invention has good storage stability in powder form because the curing accelerator mixed with the epoxy resin base and its curing agent is coated with a resin whose melting point is lower than that of the base. In addition to being extremely excellent, when melt-curing during use, the coating with the local melting point resin is removed and good curability can be obtained by rapid contact with the epoxy resin base and curing agent.
また、上記高融点樹脂の使用により、エポキシ樹脂主剤
および硬化／’ｒｌＩに対する硬化促進剤の相対量を保
存性の低下を音たずことなく、旧人でき、しかもエポキ
シ４’１を脂主剤および硬化剤に対してｈ’、Ｕ ＫＩ
ｓ促進剤を増量したかたちで混合できるためにこのＪ１
η量効果によって硬化促進剤の均一分散性に非常に好結
果を１１．コることかでき、これら働きによって前記」
−ぐ好ｌよ硬化性かさらに一段と助長される。In addition, by using the above-mentioned high melting point resin, the relative amount of the epoxy resin base resin and the curing accelerator can be adjusted without reducing the storage stability. h' for hardener, U KI
This J1 can be mixed with an increased amount of s accelerator.
11. Very good results in uniform dispersion of curing accelerator due to η amount effect. It is possible to do this by means of these functions.
- Good curability is further promoted.
このように、この発明によれは、粉体状態での保存性と
使用時の硬化性とに共にすくれた速１！す１化タイプの
エポキシ樹脂粉体塗料を提供て・＼るという卓越した効
果がｔ′−１られろ。As described above, the present invention has excellent storage stability in powder form and hardening properties during use. The outstanding effect of providing a monomer type epoxy resin powder coating has been achieved.
このウラ明において使用するａ、ｂ成分としてのエポキ
シ樹脂主剤および同化剤としては従来公知のものがいず
れも使用ｉ」能であるが、特に硬化剤としではフェノー
ル樹脂、クレゾール樹脂、ビスフェノールＡ１変性ビス
フエノールＡ１ハイドロキノンなどのフェノール性水酸
基を有する化合物または無水ピロメリット酸、無水ペン
ゾフエ／ンテトラカルホン酸、無水ブタンテトラカルホ
ン酸、無水トリメリット酸、無水テトラヒドロフタル酸
、無水フタル酸などの酸無水物基を有する化合物か好適
である。この硬化剤としては常ｉＬ’ｔで固形のものか
好ましい。As the epoxy resin base resin and assimilating agent as components a and b used in this process, any conventionally known epoxy resin can be used. Compounds with phenolic hydroxyl groups such as phenol A1 hydroquinone or acid anhydride groups such as pyromellitic anhydride, penzophene/tetracarphonic anhydride, butanetetracarphonic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride. Compounds having the following properties are preferred. This curing agent is usually a solid one or preferably one.
エポキシ樹脂主剤と硬化剤との使用割合は、エポキシ樹
脂１当量に対して硬化剤が通常０６〜１．３当量となる
割合、硬化剤の種類かフェノール性水酸基ないし酸無水
物基を有する化合物の場合は特に０．７〜１３当ｉ」と
なる割合とするのがよい。The ratio of the epoxy resin main agent and curing agent used is usually 0.6 to 1.3 equivalents of the curing agent per equivalent of the epoxy resin, and the type of curing agent or compound having a phenolic hydroxyl group or acid anhydride group. In particular, it is preferable to set the ratio to 0.7 to 13%.
これらエポキシ樹脂主剤と硬化剤とに／ｌ−合されるＣ
成分としての前記樹脂粉末は、硬化促進剤と上記エポキ
シ４ｉ脂主剤より高融点の樹脂を含むものであるが、こ
こで硬化促進剤としては硬化剤がフェノール性水酸基な
いし酸無水物基を有する化合物の場合イミダゾール化合
物や第三糾アミン化金物の如き塩基性化合物が好適であ
る。C combined with these epoxy resin main ingredients and curing agent
The resin powder as a component contains a curing accelerator and a resin having a higher melting point than the epoxy 4i resin base resin, but the curing accelerator is a compound having a phenolic hydroxyl group or an acid anhydride group. Basic compounds such as imidazole compounds and tertiary aminated metals are suitable.
エポキシ樹脂主剤より尚融点の樹脂としては、エポキシ
樹脂主剤の融点より１０’Ｃ以上、好適には１５′Ｃ以
上、通常１５〜４０’Ｃ市い融点を有するものであれば
よい。この高融点樹脂のｈ・１点の範囲としては６０〜
Ｊ４０”Ｃ，好ましくは７０〜１２０゛Ｃである。The resin having a melting point lower than that of the epoxy resin base resin may be one having a melting point lower than the melting point of the epoxy resin base by 10'C or more, preferably 15'C or higher, and usually 15 to 40'C lower than the melting point of the epoxy resin base resin. The h-1 point range of this high melting point resin is 60~
J40"C, preferably 70-120°C.
このような高融点樹脂として使用ｉｊＪ能な代表的なも
のとしては、エポキシ樹脂、エチレン−酢酸ビニル共重
合体およびポリエステル樹脂を挙けることかできる。Typical examples of such high melting point resins include epoxy resins, ethylene-vinyl acetate copolymers, and polyester resins.
上記硬化促進剤と尚融点樹脂とを含む樹脂粉末は、両成
分を溶融混合し冷却後粉砕してつくられるか、粒子径と
しては６ｏメツシユパス、好適には８０メツシユパスで
あるのがよい。粒子径が大きすきてはエポキシ樹脂主剤
および１便化剤に対する均一分散性や硬化性に問題を生
じるおそれかあるため、好ましくない。The resin powder containing the hardening accelerator and the melting point resin is preferably prepared by melt-mixing the two components, cooling and pulverizing them, or has a particle size of 60 mesh pass, preferably 80 mesh pass. If the particle size is too large, it is not preferable because it may cause problems in uniform dispersibility and curing properties for the epoxy resin main ingredient and the facilitator.
この樹脂粉末のエポキシ樹脂主剤および硬化剤に対する
配合割合は、エポキシ樹脂主剤と硬化剤との合計’；：
＋ｋ ５０〜９２重量％、好適には７０〜９０重量％に
対して、樹脂粉末中の硬化促進剤と高融点樹脂との合計
量が５０〜８山量％、好適には３０〜１０重量％である
のがよい。The blending ratio of this resin powder to the epoxy resin base resin and curing agent is the sum of the epoxy resin base resin and curing agent.
+k 50 to 92% by weight, preferably 70 to 90% by weight, and the total amount of the curing accelerator and high melting point resin in the resin powder is 50 to 8% by weight, preferably 30 to 10% by weight. It is good to be.
またこのときの硬化促進剤量としては、これと高融点樹
脂との合計社中０５〜２０市Ｍｋ％、好適には０７〜１
５重伍％を占める割合、つまりはエポキシ樹脂主剤、硬
化剤、高融点樹脂および硬化促進剤からなる四成分中に
占める硬化促進剤の割合が０．０５〜１０重量％、好適
には０１〜５重量％となる割合とされているのがよい。In addition, the amount of curing accelerator at this time is the total amount of this and the high melting point resin, preferably 0.5 to 20 Mk%, preferably 0.7 to 1.
The proportion accounting for 5% by weight, that is, the proportion of the curing accelerator in the four components consisting of the epoxy resin base, curing agent, high melting point resin, and curing accelerator is 0.05 to 10% by weight, preferably 01 to 10% by weight. It is preferable that the proportion is 5% by weight.
樹脂粉末および硬化促進剤の使用門が過少ないし過多と
なると、いずれも保存性と速硬化性とのｔ１ｊ立力糟Ｉ
Ｌシ＜なり、また樹脂粉末か過多となる七エポキシ樹脂
本来の特性が損なわれる結果となり、好ましくない。If too little or too much resin powder and curing accelerator are used, both will affect the stability and fast curing properties.
This is not preferable because the original properties of the 7-epoxy resin are impaired due to excessive amount of resin powder.
つきに、上記この発明のエポキシ樹脂粉体塗料の製造法
につき説明する。この製造θＳには、一般の粉体塗ネ」
の場合と同様のふたつの方法がある。Finally, the method for producing the epoxy resin powder coating of the present invention will be explained. This manufacturing θS requires general powder coating.
There are two methods similar to the case of .
ひとつは、エポキシ樹脂主剤と硬化剤とを含む樹脂粉末
を常法にしたがって調製しこれに硬化促進剤とエポキシ
樹脂主剤より制融点の樹脂とを含む前記樹脂粉末を粉末
混合つまりドライフレンドする方法である。この方法自
体は、トライブレンドするべき硬化促進剤が尚融点樹脂
で被覆されていること以外は、従来と特に異ｌｊらない
。One method is to prepare a resin powder containing an epoxy resin base resin and a curing agent according to a conventional method, and mix the resin powder with a curing accelerator and a resin having a lower melting point than the epoxy resin base resin, that is, dry friend the resin powder. be. This method itself is not particularly different from conventional methods, except that the curing accelerator to be triblended is still coated with a melting point resin.
上記トライブレンドにより得られるこの発明のエポキシ
樹脂粉体塗料は、エポキシ樹脂主１ｙＩｌ系粉末と有史
化促進剤系粉末とが均一に分散混合されてなるものであ
り、エポキシ樹脂主剤系粉末の粒子径としては、硬化促
進剤系粉末の場合と同様に６０メツシユパス、好適には
８０メツシユパスであるのがよい。The epoxy resin powder coating of the present invention obtained by the above-mentioned triblend is made by uniformly dispersing and mixing the epoxy resin-based 1yIl-based powder and the historicization accelerator-based powder, and the particle size of the epoxy resin-based powder is As in the case of hardening accelerator powder, 60 mesh passes, preferably 80 mesh passes are preferred.
この発明のエポキシ樹脂粉体塗料を胃る他のひとつは、
エボキシイ：ｒｊ脂主剤および硬化剤に硬化促進剤とエ
ポキシ樹脂主剤より高融点の樹脂とを含む樹脂粉末を配
合したのち溶融混合し、冷却後粉砕して粉末化する方法
である。溶融混合法自体は公知であるが、上記溶融混合
に際しては、上記高融点樹脂の融点より低い温度下で行
って溶融混合後も上記粉末の状態を維持させる必要があ
り、この点において公知の溶融混合法とは全く異なる方
法といえる。Another advantage of the epoxy resin powder coating of this invention is:
Epoxy resin: This is a method in which a resin powder containing an RJ resin base resin and a curing agent, a curing accelerator, and a resin with a higher melting point than the epoxy resin base resin is blended, melt-mixed, cooled, and then pulverized to form a powder. Although the melt mixing method itself is known, it is necessary to carry out the melt mixing at a temperature lower than the melting point of the high melting point resin to maintain the powder state even after melt mixing. This method can be said to be completely different from the mixed method.
すなわち、上記溶融混合を、エポキシ樹脂主剤の融点以
−］二の温度でかつ制融点樹脂粉末の融点より１０”Ｃ
，好適には１５゛Ｃ低い／ｆｉｉｉ度下で行うことによ
り、溶融混合時の硬化促進剤とエポキシ樹脂主剤および
（＋！Ｊ１化剤とのＨｉ′−を接の接Ｊｉｉ’ｉｔをさ
Ｉｔｊ１以って保存性−１（よひ１１史化性の良好なエ
ポキシ樹脂粉体塗料の製造をＩＩＪ能ならしめるもので
ある。That is, the above-mentioned melt-mixing was carried out at a temperature of two degrees above the melting point of the epoxy resin main ingredient and 10"C below the melting point of the melting point resin powder.
, preferably at a temperature of 15 degrees Celsius (15 degrees Celsius). Therefore, it is possible to manufacture an epoxy resin powder coating with good preservability.
上記溶融混合法で得られるこの発明のエポキシ樹脂粉体
塗料は、エポキシ樹脂主剤および硬化剤の内部にｊｊＪ
４ （Ｉｓ促進剤と上記主剤より高融点の樹脂とを含む
樹脂粉末が均一に分散混合された如き構造をイ〕する一
般に４０メツシユパス、好適には６０メツシユパスの粒
子径を有するものである。ここで硬化促進剤はエポキシ
樹脂主剤系に取り込まれたかたちとなっているが、この
場合でも硬化促進剤とエポキシ樹脂主剤および硬化剤と
の直接の接触は高融点樹脂によって防がれているため、
前記トライブレンドの場合と同様に、やはり保存性およ
び硬化性とに共にすぐれたものとなる。The epoxy resin powder coating of the present invention obtained by the above-mentioned melt mixing method has jjj inside the epoxy resin main ingredient and curing agent.
4 (having a structure in which a resin powder containing an Is accelerator and a resin having a higher melting point than the above-mentioned main resin is uniformly dispersed and mixed) and generally has a particle size of 40 mesh passes, preferably 60 mesh passes. The curing accelerator is incorporated into the epoxy resin base system, but even in this case, the high melting point resin prevents direct contact between the curing accelerator and the epoxy resin base and curing agent.
As with the triblend, it also has excellent storage stability and curing properties.
なお、この発明のエポキシ樹脂粉体塗料には、前述した
各成分つまりエポキシ樹脂主剤、硬化剤、硬化促進剤お
よびエポキシ樹脂主剤より高融点の樹脂のほか、必要に
応じて顔料、充てん剤などの公知の各種添加剤を配合し
ても差し支えない。The epoxy resin powder coating of the present invention contains the above-mentioned components, ie, the epoxy resin base, a curing agent, a curing accelerator, and a resin with a higher melting point than the epoxy resin base, as well as pigments, fillers, etc. as necessary. Various known additives may be blended.
これら添加剤はエポキシ樹脂主剤および硬化剤からなる
系に配合してもよいし、また硬化促進剤とエポキシ樹脂
主剤により尚融点の樹脂とを含む樹脂粉末中に配合して
もよい。These additives may be blended into a system consisting of an epoxy resin base and a curing agent, or may be blended into a resin powder containing a curing accelerator and a resin whose melting point is maintained by an epoxy resin base.
この発明のエポキシ樹脂粉体塗料を用いて塗１）・ツ形
成するには、被塗物上に公知の手段で粉末塗工したのち
、エポキシ樹脂主剤およびこの主剤より尚融点の樹脂成
分が共に溶融軟化する温度、一般には１５０〜２４０℃
の温度で、０〜１５分間加熱して硬化させればよい。形
成される通常０．１〜３ ｍＩｎ程１１のｊＪみを荷す
る硬化髄膜は良好な硬化性によって絶縁性、１防食性、
血Ｊ熱性なとのエポキシ樹脂本来のすくれた性能を発揮
する。In order to form a coating 1) using the epoxy resin powder coating of this invention, the powder is coated on the object to be coated by a known method, and then the epoxy resin base and the resin component at the melting point of this base are combined. Melting and softening temperature, generally 150-240℃
It may be cured by heating at a temperature of 0 to 15 minutes. The hardened meninges that are formed usually carry a jJ of 11 to 0.1 to 3 mIn, and have good hardening properties that give them insulation, anti-corrosion properties,
Demonstrates the original performance of epoxy resin, which is blood-resistant.
以下に、この発明の実施例を記載してより具体的に説明
する。EXAMPLES Below, examples of the present invention will be described in more detail.
実施例１
エポキシ当量９３０のビスフェノールＡ型エポキシ樹脂
（融点９７°Ｃ）９８．５ｙと２−ウンデシルイミダゾ
ール１．５ｙとを２軸押１１３機により溶融混練し、冷
却後粉砕して８０メツシユ／ｓｏスの樹脂粉末へを得た
。Example 1 98.5y of bisphenol A epoxy resin (melting point 97°C) with an epoxy equivalent of 930 and 1.5y of 2-undecylimidazole were melt-kneaded in a twin-screw press 113 machine, cooled, and then crushed to give 80 mesh/mesh. Obtained SOS resin powder.
この樹脂粉末Ａ２０！Ｖ、エポキシ当量６３０のビスフ
ェノールＡ型エポキシ樹脂（融点８１°Ｃ）６９６ｙお
よび水酸基当ｍ１２０Ｐ／当量のノボラックフェノール
樹脂１０４ｙを、２軸押用機で８２゛Ｃ下で溶融混合し
、冷却後粉砕して８０メ・ンシュパスのエポキシ樹脂粉
体を料とした。This resin powder A20! V, bisphenol A type epoxy resin (melting point 81 °C) 696y with epoxy equivalent of 630 and novolak phenol resin 104y with 120 P/equivalent of hydroxyl group were melt-mixed at 82 °C in a twin-screw extruder, cooled and crushed. The material was 80 mesh epoxy resin powder.
比較例１
実施例１て用いたエポキシ当量６３０のビスフェノール
Ａ型エポキシ樹脂８６．７Ｐ、実施例１で用いた水酸基
当ｍ１２０ｙ／当量のノボラックフェノール樹脂１３ｙ
および２−ウンデシルイミダゾール０７３ｙを、２軸押
用機で溶融混合し、冷却後粉砕して８０メツシユパスの
エポキシ樹脂粉体塗料とした。Comparative Example 1 Bisphenol A epoxy resin 86.7P with epoxy equivalent of 630 used in Example 1, novolac phenol resin 13y with m120y/equivalent of hydroxyl group used in Example 1
and 2-undecylimidazole 073y were melt-mixed using a twin-screw extruder, cooled, and pulverized to obtain an 80 mesh pass epoxy resin powder coating.
実施例２
実施例１で用いたエポキシ当量６３０のビスフェノール
Ａ型エポキシ樹脂６９．６ （／と水酸基当量１２０、
！／／当量の７ホラツクフエノール］る刊旨１０．４グ
とを浴融混合し、冷却後粉砕して８０メツシユパスの樹
脂粉末Ｂを得た。この樹脂粉末Ｂ８０ｙに実施例１で得
た２−ウンデシルイミダゾールを含む樹脂粉末Ａ２０ｙ
をトライブレンドしてエポキシ樹脂粉体塗料とした。Example 2 Bisphenol A type epoxy resin used in Example 1 with an epoxy equivalent of 630, 69.6 (/ and a hydroxyl equivalent of 120,
! //Equivalent amount of 7-holic phenol] was mixed in a bath melt, and after cooling, it was pulverized to obtain a resin powder B of 80 mesh. Resin powder A20y containing 2-undecylimidazole obtained in Example 1 in this resin powder B80y.
was triblended to make an epoxy resin powder coating.
比較例２
実施例１で用いたエポキシ当量６３０のヒスフェノール
Ａ型エポキシ樹脂８６７ｙと実施例］て用いた水酸基当
−１７ｌ２０ｙ／当量の７ホラツクフエノール１舅脂１
３Ｆとを溶融混合し、冷却後粉砕して８０メツシユパス
の樹脂粉末Ｃを得た。この樹脂粉末Ｃ９９，７ｙに２−
ウンデシルイミダゾール０．３ｙをトライブレンドして
エポキシ樹脂粉体塗料とした。Comparative Example 2 Hisphenol A type epoxy resin 867y with an epoxy equivalent weight of 630 used in Example 1 and 1 hydroxyl group equivalent of -17l20y/equivalent of 7-horacic phenol 1 fat used in Example]
3F was melt-mixed, cooled and pulverized to obtain 80 mesh passes of resin powder C. This resin powder C99,7y has 2-
An epoxy resin powder coating was prepared by triblending 0.3y of undecyl imidazole.
実施例３
無水トリメリット酸０１モルおよびイ・ノフタル酸０．
５モルと過剰量のエチレングリコールとから得られる酸
１１ＩＩｉ０．３ミリ当ｉ１Ｑ ／ ｙ＋氷水酸価０ミ
１ノ当社＃＋融点１００℃のポリエステル樹脂９０ｙと
、トリエチレンジアミンＩＱとを、２！ｌ！１ｌＩ４甲
出機により溶融混練し、冷却後：：分砕して６０メ゛ン
シユパスの樹脂粉末りを得た。Example 3 0.1 mole of trimellitic anhydride and 0.0 mole of i-nophthalic acid.
Acid 11IIi obtained from 5 moles and an excess amount of ethylene glycol per 0.3 milliliter of i1Q/y + ice water acid value 0 milliliter of our #+ polyester resin 90y with a melting point of 100°C and triethylenediamine IQ, 2! l! The mixture was melt-kneaded using a 1lI4 machine, cooled, and then crushed to obtain a 60-millimeter resin powder.
この樹脂粉末Ｄ３０Ｐ、実施例１で川０た工４ゼキシ当
ｉｔ ６３０のヒスフェノールＡ型エポキシ樹脂６４４
ｙおよび無水ペンゾフエノンテトラフＪルポン酸５６ｙ
を、２軸押用機で８５′”Ｃ下で浴融混合し、冷却後′
Ｊｌω砕して６０メツシユノマスの工、１ミキシ樹脂扮
体塗料とした。This resin powder D30P, in Example 1, had 630 hisphenol A type epoxy resin 644
y and anhydrous penzophenone tetraph J luponic acid 56y
were bath-melt mixed at 85'C using a twin-screw extruder, and after cooling,
Jlω was crushed to make 60 mesh units and 1 mixi resin disguise paint.
比較例３
実施例１で用いたエポキシ当ｈＬ６３０のビスフェノー
ルＡ型エポキシ（＜１４脂８９．２＋ｌｉ’、無水ベン
゛）゛フエノンアトラカルボン酸１．８’；／ｂよひト
リエチレンジアミン３ｙを、２軸押出槻で溶融混合し、
冷却後粉砕して６０メツシユ／ ｓｏスのエポキシ樹脂
粉体塗料とした。Comparative Example 3 The epoxy used in Example 1 was L630 bisphenol A type epoxy (<14 fat 89.2+li', anhydrous benzene), phenone atracarboxylic acid 1.8';/b, triethylenediamine 3y, Melt and mix using a twin-screw extruder,
After cooling, it was crushed to obtain an epoxy resin powder coating of 60 mesh/sos.
実施例４
実施例１で用いたエポキシ当量６３０のビスフェノール
Ａ型エポキシ樹脂６４．４ｙと（７１６水ベンゾフェノ
ンテトラカルボン酸５６ｙとを溶融混合し、冷却後粉砕
して８０メツシユパスの樹脂粉末Ｅを得た。この樹脂粉
末Ｅ７０Ｐに実施例３で得たトリエチレンジアミンを含
む樹脂粉末Ｄ３０ｆ／をトライブレンドしてエポキシ樹
脂粉体を料とした。Example 4 64.4y of the bisphenol A type epoxy resin used in Example 1 with an epoxy equivalent of 630 and 56y of (716 water benzophenone tetracarboxylic acid) were melt-mixed, cooled and pulverized to obtain a resin powder E of 80 mesh pass. This resin powder E70P was triblended with the triethylenediamine-containing resin powder D30f obtained in Example 3 to prepare an epoxy resin powder.
比較例４
実施例１で用いたエポキシ当量６３０のビスフェノール
Ａ型エポキシ樹脂８９．２ ｙと無水ベンゾフェノンテ
トラカルボン酸７８ｙとを溶融混合し、冷却後粉砕して
８０メツシユパスの樹脂粉末Ｆを得た。この樹脂粉末Ｆ
、９７ｙにトリエチレンジアミン３ｙを′帛温下で混合
してエポキシ樹脂粉体塗料とした。Comparative Example 4 89.2 y of the bisphenol A type epoxy resin used in Example 1 with an epoxy equivalent of 630 and 78 y of anhydrous benzophenone tetracarboxylic acid were melt-mixed, cooled and pulverized to obtain a resin powder F of 80 mesh pass. This resin powder F
, 97y and triethylenediamine 3y were mixed at a temperature of 100°C to obtain an epoxy resin powder coating.
上記実施例１〜４および比較例１〜４の各塗料のゲル化
時間、保存性および硬化性を調べた結果は、後記の第１
表に示されるとおりであった。なお、各特性は以下の如
（測定した。The results of examining the gelation time, preservability and curing properties of each of the paints of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Section 1 below.
It was as shown in the table. In addition, each characteristic was measured as follows.
〈ゲル化時間〉
熱板法により１５０℃および２００ °Ｃでのゲル化時
間を測定した。<Gelification time> Gelation time at 150°C and 200°C was measured by the hot plate method.
く保 存 性〉
塗料を３０’Ｃで３ケ月間保存したのち、１５０’ｃに
加熱した被塗物上に約０．３１１ｕ厚の塗膜を形成し、
この塗膜の平滑性が良好である場合を（○）、外観が不
良である場合を（×）と判断した。Storage property> After storing the paint at 30'C for 3 months, a coating film with a thickness of about 0.311U is formed on the object heated to 150'C.
The case where the smoothness of this coating film was good was judged as (○), and the case where the appearance was poor was judged as (x).
〈硬 化性〉
塗料を被塗物上に加熱塗工して１５０’Ｃで３０分間硬
化させて約０．３ ｍｍ厚の塗膜を形成し、この壁膜表
面をアセトンを含浸させた布でこすったときに、表向光
沢に変化か認められない場合を（○入光沢が著しく減少
する場合を（×）とした。<Curing properties> The paint is heated onto the object to be coated and cured at 150'C for 30 minutes to form a coating film approximately 0.3 mm thick, and the surface of this wall film is coated with a cloth impregnated with acetone. A case where no change was observed in the surface gloss when rubbed with a ○ mark was given as (x) a case where the gloss decreased significantly.
第 １ 表
なお、上記実施例１，２および比較例１，２の各塗料は
いずれも硬化促進剤としての２−ランチシルイミダゾー
ルを同−市川いたものであり、また上記実施例３，４お
よび比較例３，４の各塗料はいずれも睨化促進剤として
のトリエチレンジアミンを同−市川いたものである。Table 1 Note that the coatings of Examples 1 and 2 and Comparative Examples 1 and 2 all contained 2-lanticylimidazole as a curing accelerator, and the coatings of Examples 3, 4 and Each of the paints of Comparative Examples 3 and 4 contained triethylenediamine as a glare accelerator.
上記結果からも明らかなように、従来の粉体塗料では硬
化性か保存性かのいずれかに劣っており、特に硬化促進
剤としてトリエチレンジアミンを用いた比較例３，４中
溶融混合法を採用した比較例３では製造直後からほとん
どフロー性がなく、またトライブレンド法を採用した比
較例４にあっても１週間以上保存することは困難であっ
た。As is clear from the above results, conventional powder coatings are inferior in either curing properties or storage stability, and in particular, the melt mixing method was used in Comparative Examples 3 and 4 using triethylenediamine as a curing accelerator. In Comparative Example 3, there was almost no flowability immediately after production, and even in Comparative Example 4, which adopted the triblend method, it was difficult to store for more than one week.
これに苅してこの発明の粉体塗料はいずれの場合も良好
な保存性を有してかつ硬化性にもすぐれて」６す、保存
性と硬化性との両立を容易になしうるものであった。な
お、実施例３，４において（イ（脂粉末Ｉ〕の使用量を
５７にｄｌ；’ｇらし、そのぶんエポキシ樹脂主剤およ
び硬化剤最を増加させたときには、硬化性がやや低下す
る仰向がみられた。これより、樹脂粉末りの使用量をあ
まりに少なく］−ることは、（１史化促進剤であるトリ
エチレンジアミンの絶対ｈ↓不足をきたして好ましくな
いものであることか判った。In addition, the powder coating of the present invention has good storage stability and excellent curability in all cases, and can easily achieve both storage stability and curability. there were. In addition, in Examples 3 and 4, when the amount of (i) (fat powder I) used was increased to 57 dl;'g and the epoxy resin main ingredient and curing agent were increased accordingly, the curability was slightly decreased. From this, it was found that using too little amount of resin powder is undesirable because it leads to an absolute shortage of triethylenediamine, which is an accelerator. .
特許出願人 日東電気工業株式会社Patent applicant: Nitto Electric Industry Co., Ltd.
Claims (1)
およびＣ）硬化促進剤と上記エポキシ樹脂主剤より薗融
点の樹脂とを含む樹脂粉末を含有することをＱ４徴とす
るエポキシ樹脂粉体塗料。 （２）硬化剤がフェノール性水酸基ないし酸無水物基を
有する化合物からなり、かつ硬化促進剤が塩基性化合物
からなる特許請求の範囲第（１）項記載のエポキシ樹脂
粉体塗料。 （３）塩基性化合物がイミタゾール化合物ないし第三級
アミン化合物からなる特許請求の範囲第（２）項記載の
エポキシ樹脂粉体塗料。 （４）エポキシ樹脂主剤より高融点の樹脂かエポキシ樹
脂、エチレン−酢酸ビニル共也合体ないしその斐性物お
よびポリエステル樹脂の中から選ばれた少なくとも１桶
である特許請求の範囲項のいずれかに記載のエポキシ樹
脂粉体塗料。 （５）硬化促進剤とエポキシ樹脂上７ｆＵより高融点の
樹脂とを含む樹脂粉末が６０メツシユノ々スである特許
請求の範囲第（１）〜（４）項のいずれかに記載のエポ
キシ樹脂粉体塗料。 （６）エポキシ樹脂主剤と硬化剤との合計ｍｌ．５０〜
９２重潰５随〜９２ 剤より商１−’ｌ’ｌ！点の樹脂との合計量が５０〜８
市緻％である特許請求の範囲第（１）〜（５）項のいず
れかに記載のエポキシ樹脂粉体塗料。 （７）ＩＩＩＩＩ化促進剤がこれとエポキシ樹脂主剤よ
り高融点の樹脂との合計量中０５〜２０市鴫％を占める
特許請求の範囲第（６）項記載のエポキシ樹脂粉体塗料
。 （８）エポキシ樹脂からなる主剤およひその硬化剤に硬
化促進剤と上記エポキシ樹脂主剤より高１１；”ｌ”’
点の樹脂とを含む樹脂粉末を配合したのち、エポキシ樹
脂主剤の融点以上でかつ上記樹脂粉末の素点より低いｌ
素度下で溶融混合し、冷却後粉砕することを特徴とする
エポキシ樹脂粉体塗料の製造法。[Scope of Claims] tl) The Q4 characteristic includes a resin powder containing a) a base resin made of an epoxy resin, b) a curing agent thereof, and C) a curing accelerator and a resin having a melting point lower than that of the epoxy resin base resin. Epoxy resin powder coating. (2) The epoxy resin powder coating according to claim (1), wherein the curing agent comprises a compound having a phenolic hydroxyl group or an acid anhydride group, and the curing accelerator comprises a basic compound. (3) The epoxy resin powder coating according to claim (2), wherein the basic compound is an imitazole compound or a tertiary amine compound. (4) Any one of the claims that is at least one resin selected from a resin having a higher melting point than the epoxy resin base resin, an epoxy resin, an ethylene-vinyl acetate combination or its constituents, and a polyester resin. Epoxy resin powder coating as described. (5) The epoxy resin powder according to any one of claims (1) to (4), wherein the resin powder contains a curing accelerator and a resin having a melting point higher than 7 fU on the epoxy resin. body paint. (6) Total ml of epoxy resin base and curing agent. 50～
92 double crushing 5 pieces~92 From the agent, the quotient 1-'l'l! The total amount of point resin is 50 to 8
The epoxy resin powder coating according to any one of claims (1) to (5), which is a solid %. (7) The epoxy resin powder coating according to claim (6), in which the III conversion accelerator accounts for 05 to 20% of the total amount of the III conversion accelerator and the resin having a higher melting point than the epoxy resin base resin. (8) A base resin consisting of an epoxy resin, a curing accelerator, and a curing accelerator, which is higher than the epoxy resin base resin by 11;
After blending resin powder containing point resin, l
A method for producing an epoxy resin powder coating, which is characterized by melt-mixing at a bare temperature, cooling, and then pulverizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21265583A JPS60104167A (en) | 1983-11-09 | 1983-11-09 | Epoxy resin powder coating and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21265583A JPS60104167A (en) | 1983-11-09 | 1983-11-09 | Epoxy resin powder coating and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60104167A true JPS60104167A (en) | 1985-06-08 |
| JPS6332827B2 JPS6332827B2 (en) | 1988-07-01 |
Family
ID=16626216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21265583A Granted JPS60104167A (en) | 1983-11-09 | 1983-11-09 | Epoxy resin powder coating and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60104167A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232176A (en) * | 1988-07-21 | 1990-02-01 | Nippon Yupika Kk | Resin composition for powdery coating |
| US9065093B2 (en) | 2011-04-07 | 2015-06-23 | Massachusetts Institute Of Technology | Controlled porosity in electrodes |
| US10569480B2 (en) | 2014-10-03 | 2020-02-25 | Massachusetts Institute Of Technology | Pore orientation using magnetic fields |
| US10675819B2 (en) | 2014-10-03 | 2020-06-09 | Massachusetts Institute Of Technology | Magnetic field alignment of emulsions to produce porous articles |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308312A (en) * | 1988-06-03 | 1989-12-13 | Shinko Electric Co Ltd | Part straightening feeder in vibration part supplier |
| JPH024489A (en) * | 1988-06-21 | 1990-01-09 | Shinko Electric Co Ltd | Vibration type parts feeder |
| JPH037124U (en) * | 1989-06-09 | 1991-01-23 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49108136A (en) * | 1973-02-16 | 1974-10-15 | ||
| JPS5046739A (en) * | 1973-08-07 | 1975-04-25 | ||
| JPS5163834A (en) * | 1974-11-29 | 1976-06-02 | Nitto Electric Ind Co | HYOMENMOYOOKEISEISHIURUFUNMATSUTOSOYOJUSHISOSEIBUTSU |
| JPS56129267A (en) * | 1980-03-14 | 1981-10-09 | Kubota Ltd | Powdered paint |
-
1983
- 1983-11-09 JP JP21265583A patent/JPS60104167A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49108136A (en) * | 1973-02-16 | 1974-10-15 | ||
| JPS5046739A (en) * | 1973-08-07 | 1975-04-25 | ||
| JPS5163834A (en) * | 1974-11-29 | 1976-06-02 | Nitto Electric Ind Co | HYOMENMOYOOKEISEISHIURUFUNMATSUTOSOYOJUSHISOSEIBUTSU |
| JPS56129267A (en) * | 1980-03-14 | 1981-10-09 | Kubota Ltd | Powdered paint |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0232176A (en) * | 1988-07-21 | 1990-02-01 | Nippon Yupika Kk | Resin composition for powdery coating |
| US9065093B2 (en) | 2011-04-07 | 2015-06-23 | Massachusetts Institute Of Technology | Controlled porosity in electrodes |
| US10164242B2 (en) | 2011-04-07 | 2018-12-25 | Massachusetts Institute Of Technology | Controlled porosity in electrodes |
| US10569480B2 (en) | 2014-10-03 | 2020-02-25 | Massachusetts Institute Of Technology | Pore orientation using magnetic fields |
| US10675819B2 (en) | 2014-10-03 | 2020-06-09 | Massachusetts Institute Of Technology | Magnetic field alignment of emulsions to produce porous articles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6332827B2 (en) | 1988-07-01 |
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