JP2796211B2 - Aqueous paint composition - Google Patents
Aqueous paint compositionInfo
- Publication number
- JP2796211B2 JP2796211B2 JP2152192A JP2152192A JP2796211B2 JP 2796211 B2 JP2796211 B2 JP 2796211B2 JP 2152192 A JP2152192 A JP 2152192A JP 2152192 A JP2152192 A JP 2152192A JP 2796211 B2 JP2796211 B2 JP 2796211B2
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- JP
- Japan
- Prior art keywords
- water
- value
- soluble
- resin
- weight
- 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.)
- Expired - Lifetime
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- Paints Or Removers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗装ブース内の洗浄水
中から回収して再使用するに適した水性塗料組成物に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous coating composition suitable for being recovered from washing water in a coating booth and reused.
【０００２】[0002]
【従来の技術】塗装ブース内において塗料をスプレー塗
装するにあたって、被塗装物に塗着しない塗料のダスト
が多く発生し、この塗料ダストは塗装ブース内の洗浄水
に溶解乃至分散させて捕集される。このように洗浄水に
捕集される塗料ダストは多量であるために、これをその
まま廃棄すると塗料の損失になると共に、また環境汚染
の問題にもつながる。2. Description of the Related Art When spraying paint in a paint booth, a large amount of paint dust that is not applied to the object to be coated is generated, and this paint dust is collected by being dissolved or dispersed in washing water in the paint booth. You. Since a large amount of paint dust is collected in the washing water as described above, if the waste is discarded as it is, the paint is lost and the problem of environmental pollution is caused.
【０００３】そこで、従来から洗浄水に捕集された塗料
を回収して再使用することが検討されており、例えば特
開昭４９−５１３２４号公報に開示されるような回収方
法が提供されている。すなわちこのものは、水性塗料組
成物の噴霧されたものを水に捕集して得られる塗料希釈
水を逆浸透濾過膜や限外濾過膜などを通して水を濾過
し、濃度を元の水性塗料組成物と同程度に戻すようにし
たものであり、このように濃縮することによって塗膜形
成用の水溶性アルキド樹脂や水溶性アクリル樹脂などの
水溶性樹脂や顔料等の不揮発分濃度を元の水性塗料組成
物に近似させるようにして再生使用できるようにしたも
のである。[0003] Therefore, it has been studied to recover and reuse the paint collected in the washing water. For example, a recovery method disclosed in Japanese Patent Application Laid-Open No. 49-51324 has been provided. I have. That is, this is obtained by collecting the sprayed water-based coating composition in water and filtering the diluted water obtained through a reverse osmosis filtration membrane or an ultrafiltration membrane. The concentration of non-volatile components such as a water-soluble resin or a pigment such as a water-soluble alkyd resin or a water-soluble acrylic resin for forming a coating film can be reduced to the same level as that of the original aqueous solution. It can be recycled so as to approximate a coating composition.
【０００４】[0004]
【発明が解決しようとする課題】しかし、水性塗料組成
物には、水溶性樹脂を水に分散させるための水溶性有機
溶剤が数％程度配合されており、回収をおこなうために
水を濾過するとこの水溶性有機溶剤も水と共に濾過さ
れ、回収された水性塗料組成物中の水溶性有機溶剤の含
有率が小さくなる。この結果、濃縮する過程において水
性塗料組成物中で水溶性樹脂や顔料が分離したり凝集し
たりして、塗装塗膜にツヤヒケなどが発生するおそれが
ある。However, the water-based coating composition contains about several percent of a water-soluble organic solvent for dispersing the water-soluble resin in water, and the water is filtered to recover the water-soluble resin. This water-soluble organic solvent is also filtered together with water, and the content of the water-soluble organic solvent in the recovered water-based coating composition is reduced. As a result, the water-soluble resin or pigment may be separated or aggregated in the aqueous coating composition during the process of concentration, and there is a possibility that a shiny spot or the like may be generated on the coated coating film.
【０００５】このために、水性塗料組成物に配合する水
溶性アルキド樹脂や水溶性アクリル樹脂として酸価や水
酸基価の高いものを使用して水溶化度を高めることによ
って、濃縮過程での分離や凝集を防止して塗料安定性を
高めることが検討されている。しかしながらこのように
水溶性アルキド樹脂や水溶性アクリル樹脂として酸価や
水酸基価の高いものを使用すると、水性塗料組成物の塗
膜性能において耐湿性や耐沸水性が低下し、さらに耐衝
撃性も低下することになるという問題が生じるものであ
った。[0005] For this reason, by using a water-soluble alkyd resin or a water-soluble acrylic resin having a high acid value or a high hydroxyl value to increase the degree of water-solubility to be incorporated in the water-based coating composition, the separation in the concentration process can be improved. It has been studied to prevent agglomeration and enhance paint stability. However, when a water-soluble alkyd resin or a water-soluble acrylic resin having a high acid value or a high hydroxyl value is used as described above, the moisture resistance and boiling water resistance of the coating composition of the aqueous coating composition are reduced, and the impact resistance is also reduced. There was a problem that it would decrease.
【０００６】本発明は上記の点に鑑みてなされたもので
あり、塗膜性能を低下させることなく、洗浄水から濃縮
して回収するにあたって分離や凝集を防止することがで
きる水性塗料組成物を提供することを目的とするもので
ある。[0006] The present invention has been made in view of the above points, and an aqueous coating composition capable of preventing separation and agglomeration in concentrating and recovering from washing water without deteriorating coating film performance. It is intended to provide.
【０００７】[0007]
【課題を解決するための手段】本発明に係る水性塗料組
成物は、酸価が２５〜１００、水酸基価が３５〜２０
０、ＳＰ値が１０．０〜１１．０の水溶性アルキド樹脂
あるいは水溶性アクリル樹脂を主成分とし、水溶性アル
キド樹脂あるいは水溶性アクリル樹脂のＳＰ値より０．
５〜３．０高いＳＰ値を有する硬化剤を含有して成るこ
とを特徴とするものである。The aqueous coating composition according to the present invention has an acid value of 25 to 100 and a hydroxyl value of 35 to 20.
A water-soluble alkyd resin or a water-soluble acrylic resin having an SP value of 10.0 to 11.0 is used as a main component.
It is characterized by containing a curing agent having a high SP value of 5 to 3.0.
【０００８】以下、本発明を詳細に説明する。本発明に
おいて塗膜形成用の水溶性樹脂としては、水溶性アルキ
ド樹脂や水溶性アクリル樹脂を用いるものであり、いず
れか一方を使用する他、両者を併用することもできる。
そして本発明にあって、水溶性アルキド樹脂や水溶性ア
クリル樹脂としては、酸価（ＡＶ）が２５〜１００、水
酸基価（ＯＨＶ）が３５〜２００、さらにＳＰ値が１
０．０〜１１．０のものを用いるものである。酸価が２
５未満、水酸基価が３５未満、ＳＰ価が１０．０未満で
あると、水溶性アルキド樹脂や水溶性アクリル樹脂の水
溶化度（親水化度）が低く、濃縮過程で分離等が発生す
るおそれがある。逆に酸価が１００を超え、水酸基価が
２００を超え、ＳＰ価が１１．０を超えると、水溶性ア
ルキド樹脂や水溶性アクリル樹脂の水溶化度（親水化
度）が高くなり過ぎて、塗膜の耐水性等に問題が生じる
ことになる。尚、水溶性アルキド樹脂や水溶性アクリル
樹脂の酸価は４０〜７０の範囲が、水酸基価は６０〜１
５０の範囲がより好ましいものである。また水溶性アル
キド樹脂を用いる場合は、その油長は４５以下のものが
好ましい。Hereinafter, the present invention will be described in detail. In the present invention, as the water-soluble resin for forming a coating film, a water-soluble alkyd resin or a water-soluble acrylic resin is used, and either one of them may be used, or both may be used in combination.
In the present invention, the water-soluble alkyd resin or water-soluble acrylic resin has an acid value (AV) of 25 to 100, a hydroxyl value (OHV) of 35 to 200, and an SP value of 1 to 50.
Those having a value of 0.0 to 11.0 are used. Acid value is 2
If the hydroxyl value is less than 5, the hydroxyl value is less than 35, and the SP value is less than 10.0, the water-soluble alkyd resin or the water-soluble acrylic resin has a low degree of water solubility (degree of hydrophilicity), and separation or the like may occur during the concentration process. There is. Conversely, when the acid value exceeds 100, the hydroxyl value exceeds 200, and the SP value exceeds 11.0, the degree of water solubility (degree of hydrophilicity) of a water-soluble alkyd resin or a water-soluble acrylic resin becomes too high, This causes a problem in the water resistance of the coating film. The acid value of the water-soluble alkyd resin or the water-soluble acrylic resin is in the range of 40 to 70, and the hydroxyl value is 60 to 1
A range of 50 is more preferred. When a water-soluble alkyd resin is used, the oil length is preferably 45 or less.
【０００９】ここで、ＳＰ値（溶解度パラメーター）は
溶解性の尺度となるものであり、次のようにして測定さ
れる。参考文献ＳＵＨ，ＣＬＡＲＫＥ〔Ｊ．Ｐ．Ｓ．Ａ
−１，５，１６７１−１６８１（１９６７）〕 ・測定温度 ２０℃ ・サンプル 樹脂０．５ｇを１００ｍｌビーカーに秤量
し、良溶媒１０ｍｌをホールピペットを用いて加え、マ
グネティックスターラーにより溶解する。 ・溶媒 良溶媒：ジオキサン、アセトン 貧溶媒：ｎ−ヘキサン、イオン交換水 ・濁点測定 ５０ｍｌビュレットを用いて貧溶媒を滴下
し、濁りが生じた点を滴下量とする。 ・計算 樹脂のＳＰ値δは次式によって与えられ
る。Here, the SP value (solubility parameter) is a measure of solubility, and is measured as follows. References SUH, CLARKE [J. P. S. A
Measurement temperature: 20 ° C. Sample: 0.5 g of resin is weighed into a 100 ml beaker, 10 ml of a good solvent is added by using a whole pipette, and dissolved by a magnetic stirrer. -Solvent Good solvent: dioxane, acetone Poor solvent: n-hexane, ion-exchanged water-Measurement of turbidity The poor solvent is dropped using a 50 ml burette, and the point at which turbidity occurs is defined as the dropping amount.・ Calculation The SP value δ of the resin is given by the following equation.
【００１０】δ＝（Ｖml 1/2 δml＋Ｖmh 1/2 δmh）／
（Ｖml 1/2 ＋Ｖmh 1/2 ） Ｖm ＝Ｖ1 Ｖ2 ／（φ1 Ｖ2 ＋φ2 Ｖ1 ） δm ＝φ1 δ1 ＋φ2 δ2 Ｖi ：溶媒の分子容（ｍｌ／ｍｏｌ） φi ：濁点における各溶媒の体積分率 δi ：溶媒のＳＰ値 ｍｌ：低ＳＰ貧溶媒混合系 ｍｈ：高ＳＰ貧溶媒混合系 また本発明において硬化剤（架橋剤）としては、メラミ
ン樹脂やベンゾグアナミン樹脂などアミノ系樹脂を用い
ることができるが、ＳＰ値が上記水溶性アルキド樹脂や
水溶性アクリル樹脂のＳＰ値よりも０．５〜３．０の範
囲で高くなるように調製したものを用いるものである。
水溶性アルキド樹脂や水溶性アクリル樹脂に対して硬化
剤としてＳＰ値がこの範囲にあるものを用いることによ
って、塗装時に水溶性アルキド樹脂や水溶性アクリル樹
脂を硬化させて塗膜を形成するにあたって塗膜を疎水化
することができ、耐吸湿性や耐沸水性などの塗膜性能を
高めることができるものである。硬化剤と水溶性アルキ
ド樹脂や水溶性アクリル樹脂のＳＰ値の差が０．５未満
（逆に硬化剤のＳＰ値が水溶性アルキド樹脂や水溶性ア
クリル樹脂のＳＰ値より低い場合も含む）であると、水
性塗料組成物の安定性が悪くなって分離等が発生するお
それがあり、また逆にこのＳＰ値の差が３．０を超える
と耐吸湿性や耐沸水性などの塗膜性能を高める効果を得
ることができなくなる。Δ = (V ml 1/2 δ ml + V mh 1/2 δ mh ) /
(V ml 1/2 + V mh 1/2 ) V m = V 1 V 2 / (φ 1 V 2 + φ 2 V 1) δ m = φ 1 δ 1 + φ 2 δ 2 V i: solvent molecular volume (ml / Mol) φ i : volume fraction of each solvent at the turbid point δ i : SP value of the solvent ml: low-SP poor solvent mixed system mh: high SP poor solvent mixed system In the present invention, as a curing agent (crosslinking agent), Amino resins such as melamine resins and benzoguanamine resins can be used, but the SP value was adjusted to be higher in the range of 0.5 to 3.0 than the SP value of the water-soluble alkyd resin or water-soluble acrylic resin. It is a thing to use.
By using a water-soluble alkyd resin or water-soluble acrylic resin with a SP value within this range as a curing agent, the water-soluble alkyd resin or water-soluble acrylic resin is cured during coating to form a coating film. The film can be made hydrophobic, and the film performance such as moisture absorption resistance and boiling water resistance can be enhanced. The difference between the SP value of the curing agent and the water-soluble alkyd resin or the water-soluble acrylic resin is less than 0.5 (including the case where the SP value of the curing agent is lower than the SP value of the water-soluble alkyd resin or the water-soluble acrylic resin) If there is, the stability of the water-based coating composition may be deteriorated and separation or the like may occur. On the contrary, if the difference of the SP value exceeds 3.0, the coating properties such as moisture absorption resistance and boiling water resistance are obtained. Cannot be obtained.
【００１１】上記水溶性アルキド樹脂あるいは水溶性ア
クリル樹脂、硬化剤、さらに顔料や水溶性有機溶剤等を
配合することによって、本発明に係る水性塗料組成物を
得ることができる。この顔料としては、二酸化チタン、
カーボン、キナクリドン系等の着色顔料や、炭酸カルシ
ウム等の体質顔料などを用いることができるものであ
り、配合量はＰＶＣ＝０〜３５％程度が好ましい。また
水溶性有機溶剤としてはブチルセロソルブ等を用いるこ
とができる。ここで、水溶性アルキド樹脂あるいは水溶
性アクリル樹脂に対する硬化剤の配合比率は、固形分に
換算して５０：５０〜９５：５の範囲に設置するのが好
ましい。The aqueous coating composition according to the present invention can be obtained by blending the above-mentioned water-soluble alkyd resin or water-soluble acrylic resin, a curing agent, a pigment and a water-soluble organic solvent. This pigment includes titanium dioxide,
Color pigments such as carbon and quinacridone and extender pigments such as calcium carbonate can be used, and the blending amount is preferably about PVC = 0 to 35%. As the water-soluble organic solvent, butyl cellosolve or the like can be used. Here, the compounding ratio of the curing agent to the water-soluble alkyd resin or the water-soluble acrylic resin is preferably set in the range of 50:50 to 95: 5 in terms of solid content.
【００１２】そしてこのように調製される水性塗料組成
物を水で希釈することによって塗装に使用することがで
きるものである。そしてこの塗料を塗装ブース内におい
てスプレー塗装するにあたって発生する塗料ダストを塗
装ブース内の洗浄水に溶解乃至分散させて捕集した後、
既述の特開昭４９−５１３２４号公報等で提供される方
法に従って、回収した洗浄水を限外濾過等して水を濾過
し、水性塗料組成物の固形分濃度を元の状態に戻すよう
に濃縮することによって、再生使用することができるも
のである。ここで、上記のように硬化剤として水溶性ア
ルキド樹脂や水溶性アクリル樹脂のＳＰ値より０．５〜
３．０高いものを用いることによって、塗膜を疎水化し
て耐吸湿性や耐沸水性などの塗膜性能を高めるようにし
ているために、水溶性アルキド樹脂や水溶性アクリル樹
脂としては上記のように水溶化度の比較的高いものを用
いることができる。従って、濃縮する過程で水溶性有機
溶媒が濾過されてその含有率が小さくなっても水溶性ア
ルキド樹脂や水溶性アクリル樹脂の分離を防ぐと共に顔
料の凝集を防止することができ、塗装塗膜にツヤヒケ等
が発生することを防ぐことができるものである。The aqueous coating composition thus prepared can be used for coating by diluting it with water. And after this paint is collected by dissolving or dispersing paint dust generated at the time of spray painting in the painting booth in the washing water in the painting booth,
According to the method provided in the above-mentioned Japanese Patent Application Laid-Open No. 49-51324, the collected washing water is subjected to ultrafiltration or the like to filter the water and return the solid content concentration of the aqueous coating composition to the original state. It can be recycled and used by concentration. Here, the SP value of the water-soluble alkyd resin or the water-soluble acrylic resin as the curing agent as described above is 0.5 to 0.5.
The use of a 3.0-higher one makes the coating hydrophobic and enhances the coating properties such as moisture absorption resistance and boiling water resistance. Therefore, as the water-soluble alkyd resin or water-soluble acrylic resin, As described above, those having a relatively high degree of water solubility can be used. Therefore, even when the water-soluble organic solvent is filtered in the course of concentration and its content is reduced, separation of the water-soluble alkyd resin and water-soluble acrylic resin can be prevented and aggregation of the pigment can be prevented. It is possible to prevent the occurrence of gloss marks and the like.
【００１３】[0013]
【実施例】次に、本発明を実施例によって例証する。 （実施例１）攪拌機、温度制御装置、デカンターを備え
た容器に次の組成の原料を仕込み、攪拌しながら加熱し
た。The present invention will now be illustrated by examples. (Example 1) A raw material having the following composition was charged into a container equipped with a stirrer, a temperature controller, and a decanter, and heated while stirring.
【００１４】 大豆油脂肪酸 ３４重量部 イソフタル酸 ２５重量部 無水トリメリット酸 ９重量部 トリメチロールプロパン ３１重量部 キシレン １重量部 ジブチルスズオキサイド ０．０２重量部 反応進行に伴って生成する水をキシレンと共沸させて除
去し、酸価５０、水酸基価１２５になるまで加熱を継続
し、反応を終了させた。得られた樹脂を不揮発分７３重
量％となるようにブチルセロソルブで希釈してアルキド
樹脂ワニスを得た。この樹脂ワニスはガードナー粘度Ｚ
2 であり、ＳＰ値＝１０．３７であった。この樹脂ワニ
スをジメチルエタノールアミンで理論上１００％中和
し、脱イオン水にて不揮発分４０重量％になるように調
整して水溶性アルキド樹脂ワニスＡを得た。Soybean oil fatty acid 34 parts by weight Isophthalic acid 25 parts by weight Trimellitic anhydride 9 parts by weight Trimethylolpropane 31 parts by weight Xylene 1 part by weight Dibutyltin oxide 0.02 parts by weight Water generated as the reaction proceeds with xylene Heating was continued until the acid value reached 50 and the hydroxyl value reached 125, and the reaction was terminated. The obtained resin was diluted with butyl cellosolve so as to have a nonvolatile content of 73% by weight to obtain an alkyd resin varnish. This resin varnish has a Gardner viscosity Z
2 , and the SP value was 10.37. This resin varnish was theoretically neutralized to 100% with dimethylethanolamine and adjusted to a non-volatile content of 40% by weight with deionized water to obtain a water-soluble alkyd resin varnish A.
【００１５】この水溶性アルキド樹脂ワニスＡに二酸化
チタンをラボミキサーを用いて分散し、さらに硬化剤と
してメタノール・エタノール変性ベンゾグアナミン樹脂
（ＳＰ値＝１１．４７）を用いて表１に示す組成比率に
なるようにステンレス容器に秤量して配合し、水性塗料
組成物を調製した。 （実施例２）硬化剤としてメタノール・ブタノール変性
メラミン樹脂（ＳＰ値＝１１．９０）を用いるようにし
た他は、実施例１と同様にして水性塗料組成物を調製し
た。Titanium dioxide is dispersed in this water-soluble alkyd resin varnish A using a laboratory mixer, and a methanol / ethanol-modified benzoguanamine resin (SP value = 11.47) is used as a curing agent to obtain the composition ratio shown in Table 1. The resulting mixture was weighed and blended in a stainless steel container to prepare an aqueous coating composition. (Example 2) An aqueous coating composition was prepared in the same manner as in Example 1 except that a methanol / butanol-modified melamine resin (SP value = 11.90) was used as a curing agent.
【００１６】（実施例３）攪拌機、温度調節器、冷却管
を備えた反応容器にエチレングリコールモノブチルエー
テル７６重量部を仕込み、さらにスチレン１２２重量
部、ラウリルメタクリレート６６重量部、２−ヒドロキ
シエチルメタクリレート６６重量部、メタクリル酸２３
重量部、アゾビスイソブチルニトリル３重量部からなる
モノマー溶液を６１重量部添加して、攪拌下温度を１２
０℃に調整した。さらにこのモノマー溶液２４５重量部
を３時間で滴下した後、攪拌を１時間継続した。そして
これにジメチルエタノールアミン２４重量部と脱イオン
水２００重量部を添加することによって、揮発分５０重
量％、樹脂の数平均分子量が６０００の水溶性アクリル
樹脂ワニスＢを得た。この樹脂は酸価５０、水酸基価９
５、ＳＰ値１０．５であった。Example 3 76 parts by weight of ethylene glycol monobutyl ether was charged into a reaction vessel equipped with a stirrer, a temperature controller, and a condenser, and 122 parts by weight of styrene, 66 parts by weight of lauryl methacrylate, and 66 parts by weight of 2-hydroxyethyl methacrylate 66 were added. Parts by weight, methacrylic acid 23
61 parts by weight of a monomer solution consisting of 3 parts by weight of azobisisobutylnitrile and 3 parts by weight of azobisisobutylnitrile were added.
The temperature was adjusted to 0 ° C. After 245 parts by weight of this monomer solution was added dropwise over 3 hours, stirring was continued for 1 hour. Then, 24 parts by weight of dimethylethanolamine and 200 parts by weight of deionized water were added thereto to obtain a water-soluble acrylic resin varnish B having a volatile content of 50% by weight and a resin number average molecular weight of 6000. This resin has an acid value of 50 and a hydroxyl value of 9
5, SP value was 10.5.
【００１７】この水溶性アクリル樹脂ワニスＡに二酸化
チタンをラボミキサーを用いて分散し、さらに硬化剤と
してメタノール・エタノール変性ベンゾグアナミン樹脂
（ＳＰ値＝１１．４７）を用いて表１に示す組成比率に
なるようにステンレス容器に秤量して配合し、水性塗料
組成物を調製した。 （比較例１〜３）実施例１で得た水溶性アルキド樹脂ワ
ニスＡを用い、二酸化チタンをラボミキサーを用いて分
散し、さらに硬化剤として表２に示すものを用いて表２
に示す組成比率になるようにステンレス容器に秤量して
配合し、水性塗料組成物を調製した。Titanium dioxide is dispersed in the water-soluble acrylic resin varnish A using a lab mixer, and a methanol / ethanol-modified benzoguanamine resin (SP value = 11.47) is used as a curing agent to obtain the composition ratio shown in Table 1. The resulting mixture was weighed and blended in a stainless steel container to prepare an aqueous coating composition. (Comparative Examples 1 to 3) Using the water-soluble alkyd resin varnish A obtained in Example 1, titanium dioxide was dispersed using a lab mixer, and further, using those shown in Table 2 as curing agents, Table 2
Was weighed and mixed in a stainless steel container so as to have the composition ratio shown in Table 1 to prepare an aqueous coating composition.
【００１８】（比較例４）攪拌機、温度制御装置、デカ
ンターを備えた容器に次の組成の原料を仕込み、攪拌し
ながら加熱した。 イソフタル酸 ３０重量部 無水トリメリット酸 ５重量部 ハートールＦＡ−１ ＊１ ２７重量部 トリメチロールプロパン １５重量部 ネオペンチルグリコール １１重量部 ＢＡＰ８Ｇｌｙｃｏｌ ＊２ ５重量部 ＰＰＧ１０００ ＊３ ５重量部 キシレン ２重量部 ジブチルスズオキサイド ０．０２重量部 ＊１…播磨化成社製トール油脂肪酸 ＊２…日本乳化剤社製ビスフェノールＡのプロピレンオ
キサイド付加物 ＊３…三洋化成社製ポリプロピレングリコール（分子量
約１０００） 反応進行に伴って生成する水をキシレンを水と共沸させ
て除去し、酸価３０、水酸基価４０になるまで加熱を継
続し、反応を終了させた。得られた樹脂を不揮発分７３
重量％となるようにブチルセロソルブで希釈してアルキ
ド樹脂ワニスを得た。この樹脂ワニスはガードナー粘度
Ｚ2 〜Ｚ3 であり、ＳＰ値＝１０．５０であった。この
樹脂ワニスをトリエチルアミンで理論上１００％中和
し、脱イオン水にて不揮発分４０重量％になるように調
整して水溶性アルキド樹脂ワニスＣを得た。Comparative Example 4 Raw materials having the following composition were charged into a vessel equipped with a stirrer, a temperature controller and a decanter, and heated while stirring. Isophthalic acid 30 parts by weight Trimellitic anhydride 5 parts by weight Hartol FA-1 * 1 27 parts by weight Trimethylolpropane 15 parts by weight Neopentyl glycol 11 parts by weight BAP8Glycol * 2 5 parts by weight PPG1000 * 3 5 parts by weight Xylene 2 parts by weight Dibutyltin Oxide 0.02 parts by weight * 1: Tall oil fatty acid manufactured by Harima Kasei Co., Ltd. * 2: Propylene oxide adduct of bisphenol A manufactured by Nippon Emulsifier Co., Ltd. * 3: Polypropylene glycol manufactured by Sanyo Chemical Co., Ltd. (molecular weight: about 1,000) Generated as the reaction proceeds The formed water was removed by azeotropically removing xylene with water, and heating was continued until the acid value reached 30 and the hydroxyl value reached 40, thereby terminating the reaction. The obtained resin is subjected to a non-volatile content 73.
The alkyd resin varnish was obtained by diluting with butyl cellosolve so as to obtain a weight percent. This resin varnish had a Gardner viscosity of Z 2 to Z 3 and an SP value of 10.50. This resin varnish was theoretically neutralized to 100% with triethylamine and adjusted to a non-volatile content of 40% by weight with deionized water to obtain a water-soluble alkyd resin varnish C.
【００１９】この水溶性アルキド樹脂ワニスＣを用い、
あとは上記比較例１〜３と同様にして水性塗料組成物を
調製した。Using this water-soluble alkyd resin varnish C,
Thereafter, an aqueous coating composition was prepared in the same manner as in Comparative Examples 1 to 3.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】上記のようにして得られた実施例１〜３及
び比較例１〜４の水性塗料組成物をＮＫ＃２カップで５
０秒になるまで水で希釈し、これをリン酸亜鉛処理板
（日本テストパネル社製、厚さ０．８ｍｍ）上に乾燥塗
膜膜厚が２５〜３０μｍになるようにスプレーして、１
６０℃で２０分間焼き付けた。この塗膜について耐沸水
性（０．５時間）、耐衝撃性（デュポン式衝撃性試験
機、１／２φインチ５００ｇ×３０ｃｍ以上合格）を測
定し、また各水性塗料組成物の安定性（４０℃×３０
日）を試験した。結果を表３及び表４に示す。The aqueous coating compositions of Examples 1 to 3 and Comparative Examples 1 to 4 obtained as described above were mixed with 5 cups of NK # 2.
The solution was diluted with water until it reached 0 seconds, and sprayed on a zinc phosphate treated plate (manufactured by Nippon Test Panel Co., Ltd., 0.8 mm in thickness) so that the dry film thickness became 25 to 30 μm.
Bake at 60 ° C. for 20 minutes. The coating film was measured for boiling water resistance (0.5 hours) and impact resistance (DuPont type impact tester, 1 / 2φ inch 500 g × 30 cm or more), and the stability of each aqueous coating composition (40 ° C x 30
Days). The results are shown in Tables 3 and 4.
【００２３】また、図１に示す塗装ブース１において上
記各水性塗料組成物を用いてスプレー機２でスプレー塗
装をおこなった。そして洗浄水６に塗料ダストが分散乃
至溶解して、洗浄水６中の不揮発分の濃度が１５重量％
に達すると、塗料濃縮タンク３に塗装ブース１から塗料
が希釈されたこの洗浄水６を移し、これを限外濾過膜と
してデサリネーションシステムズ（ＤＥＳＡＲＬＩＮＡ
ＴＩＯＮ ＳＹＳＴＥＭＳ）社製「ＥＷ４０２６」を用
いた限外濾過装置４に通して洗浄水６を濾過して濃縮
し、濾液８は濾液タンク５に回収して塗装ブース１に返
送した。このように限外濾過装置４で濃縮して得られる
不揮発分が５５重量％の再生水性塗料組成物７を、塗料
濃縮タンク３からスプレー機２に供給して再使用した。
このように洗浄水６に分散乃至溶解して希釈された塗料
を限外濾過で濃縮する過程での塗料の状態を観察し、ま
た再生した水性塗料組成物７を再使用して得られた塗膜
の外観を観察した。結果を表３及び表４に示す。Further, in the coating booth 1 shown in FIG. 1, spray coating was performed by the spraying machine 2 using each of the above aqueous coating compositions. Then, the paint dust is dispersed or dissolved in the washing water 6, and the concentration of the nonvolatile components in the washing water 6 is 15% by weight.
Is reached, the wash water 6 containing the diluted paint is transferred from the paint booth 1 to the paint concentration tank 3, and this is used as an ultrafiltration membrane as a desalination system (DESARLINA).
The washing water 6 was filtered and concentrated through an ultrafiltration device 4 using “EW4026” manufactured by Tion Systems, Inc., and the filtrate 8 was collected in a filtrate tank 5 and returned to the coating booth 1. The reclaimed aqueous coating composition 7 having a non-volatile content of 55% by weight obtained by concentrating in the ultrafiltration apparatus 4 was supplied from the paint concentration tank 3 to the sprayer 2 and reused.
The state of the paint in the process of concentrating by ultrafiltration the paint dispersed or dissolved in the wash water 6 and diluted as described above was observed, and the paint obtained by reuse of the regenerated aqueous paint composition 7 was observed. The appearance of the film was observed. The results are shown in Tables 3 and 4.
【００２４】[0024]
【表３】 [Table 3]
【００２５】[0025]
【表４】 [Table 4]
【００２６】表３及び表４にみられるように、各実施例
の水性塗料組成物は、その塗膜の性能が優れると共に塗
料安定性にも優れることが確認され、さらに塗装ブース
から濃縮して再生使用するにあたって塗料に分離等が発
生することがないと共に塗膜の状態も良好であることが
確認される。一方、硬化剤として水溶性アルキド樹脂の
ＳＰ価より小さいＳＰ価のものを用いた比較例１のもの
では塗料安定性が悪く、濃縮して再生使用するにあたっ
ても濃縮の際に塗料に分離が発生すると共に塗膜にツヤ
ヒケが発生し、また硬化剤として水溶性アルキド樹脂の
ＳＰ価より３．０以上高いＳＰ価のものを用いた比較例
２のものでは塗膜性能が低下するものであった。さらに
水に可溶の硬化剤を用いた比較例３のものでは塗膜性能
が低下し、また比較例４のものでは濃縮して再生使用す
るにあたって濃縮の際に塗料に分離が発生すると共に塗
膜にツヤヒケが発生するものであった。As shown in Tables 3 and 4, it was confirmed that the water-based coating compositions of the examples had excellent coating performance and coating stability, and were further concentrated from a coating booth. It is confirmed that there is no separation or the like in the paint when recycled, and that the state of the coating film is good. On the other hand, in the case of Comparative Example 1 in which a water-soluble alkyd resin having an SP value smaller than that of the water-soluble alkyd resin was used, the paint stability was poor, and even when concentrated and recycled, the paint was separated during concentration. In addition, gloss was generated in the coating film, and in the case of Comparative Example 2 using a water-soluble alkyd resin having an SP value higher than that of the water-soluble alkyd resin by at least 3.0, the coating film performance was deteriorated. . Further, in the case of Comparative Example 3 in which a water-soluble curing agent was used, the coating film performance was deteriorated. In the case of Comparative Example 4, when concentrated and recycled, the paint was separated during concentration and the coating was performed. Luster was generated on the film.
【００２７】[0027]
【発明の効果】上記のように本発明は、酸価が２５〜１
００、水酸基価が３５〜２００、ＳＰ値が１０．０〜１
１．０の水溶性アルキド樹脂あるいは水溶性アクリル樹
脂を主成分とし、水溶性アルキド樹脂あるいは水溶性ア
クリル樹脂のＳＰ値より０．５〜３．０高いＳＰ値を有
する硬化剤を配合して水性塗料組成物を調製するように
したものであり、塗膜性能を低下させることなく、塗装
ブースの洗浄水から濃縮して回収するにあたって分離や
凝集を防止することができるものである。As described above, the present invention has an acid value of 25 to 1
00, hydroxyl value 35-200, SP value 10.0-1
A water-soluble alkyd resin or a water-soluble acrylic resin having a SP value of 1.0 as a main component and a curing agent having an SP value 0.5 to 3.0 higher than the SP value of the water-soluble alkyd resin or the water-soluble acrylic resin are compounded. A coating composition is prepared, which can prevent separation and agglomeration in collecting and recovering from washing water in a coating booth without lowering coating film performance.
【図１】塗料再生使用のシステムを示す概略図である。FIG. 1 is a schematic diagram showing a paint recycling system.
１ 塗装ブース ２ スプレー機 ３ 塗料濃縮タンク ４ 限外濾過装置 ５ 濾液タンク ６ 洗浄水 ７ 再生水性塗料組成物 ８ 濾液 DESCRIPTION OF SYMBOLS 1 Painting booth 2 Sprayer 3 Paint concentration tank 4 Ultrafiltration device 5 Filtrate tank 6 Washing water 7 Reclaimed aqueous paint composition 8 Filtrate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 長崎 正博 大阪府寝屋川市池田中町19番17号 日本 ペイント株式会社内 (72)発明者 楫野 哲郎 大阪府寝屋川市池田中町19番17号 日本 ペイント株式会社内 (58)調査した分野(Int.Cl.6，ＤＢ名) C09D 167/00 - 167/08 C09D 5/00 C09D 133/06 - 133/12 C09D 161/20 - 161/24──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiro Nagasaki 19-17 Ikedananakacho, Neyagawa City, Osaka Japan Paint Co., Ltd. (72) Inventor Tetsuro Kashino 19-17 Ikedananakacho, Neyagawa City, Osaka Japan Paint Stock In-company (58) Investigated fields (Int.Cl. 6 , DB name) C09D 167/00-167/08 C09D 5/00 C09D 133/06-133/12 C09D 161/20-161/24
Claims (2)
２００、ＳＰ値が１０．０〜１１．０の水溶性アルキド
樹脂あるいは水溶性アクリル樹脂を主成分とし、水溶性
アルキド樹脂あるいは水溶性アクリル樹脂のＳＰ値より
０．５〜３．０高いＳＰ値を有する硬化剤を含有して成
ることを特徴とする水性塗料組成物。An acid value of 25 to 100 and a hydroxyl value of 35 to
200, SP value is mainly composed of water-soluble alkyd resin or water-soluble acrylic resin having a SP value of 10.0 to 11.0, and SP value is 0.5 to 3.0 higher than SP value of water-soluble alkyd resin or water-soluble acrylic resin. An aqueous coating composition comprising a curing agent having the following formula:
を特徴とする請求項１に記載の水性塗料組成物。2. The aqueous coating composition according to claim 1, wherein an amino resin is used as a curing agent.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152192A JP2796211B2 (en) | 1992-02-07 | 1992-02-07 | Aqueous paint composition |
| DE69313314T DE69313314T3 (en) | 1992-02-07 | 1993-02-04 | Use of aqueous paint compositions |
| AT93101730T ATE157387T1 (en) | 1992-02-07 | 1993-02-04 | USE OF AQUEOUS PAINT COMPOSITIONS |
| EP93101730A EP0554865B2 (en) | 1992-02-07 | 1993-02-04 | Use of water-based paint composition |
| CA002088854A CA2088854A1 (en) | 1992-02-07 | 1993-02-05 | Water-based paint composition |
| US08/015,406 US5319017A (en) | 1992-02-07 | 1993-02-05 | Water-based paint composition |
| KR1019930001683A KR100247519B1 (en) | 1992-02-07 | 1993-02-08 | Water-based paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2152192A JP2796211B2 (en) | 1992-02-07 | 1992-02-07 | Aqueous paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05214292A JPH05214292A (en) | 1993-08-24 |
| JP2796211B2 true JP2796211B2 (en) | 1998-09-10 |
Family
ID=12057266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2152192A Expired - Lifetime JP2796211B2 (en) | 1992-02-07 | 1992-02-07 | Aqueous paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796211B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19504947C2 (en) * | 1994-06-20 | 2003-07-03 | Bollig & Kemper Gmbh & Co Kg | Multi-layer coating |
-
1992
- 1992-02-07 JP JP2152192A patent/JP2796211B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05214292A (en) | 1993-08-24 |
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