JP4886227B2 - Water-based coating material - Google Patents
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Description
この発明は、養生温度が０℃以下の条件下でも硬化性に優れる水性塗材に関する。 The present invention relates to an aqueous coating material having excellent curability even under a curing temperature of 0 ° C. or less.
建築物の内外壁面に塗布される塗材として、近年では従来の有機溶剤型塗材に代えて水性塗材が多く用いられている。水性塗材とは、特許文献１にあるように、溶媒に水を用いた塗材であって、主に合成樹脂が水に溶解したバインダー成分と、体質顔料などのフィラー成分とにより構成されている。この水性塗材を塗布すると、溶媒である水が蒸発し、塗膜が形成される。 In recent years, a water-based coating material is often used in place of a conventional organic solvent-type coating material as a coating material applied to the inner and outer wall surfaces of a building. The water-based coating material is a coating material using water as a solvent as disclosed in Patent Document 1, and is mainly composed of a binder component in which a synthetic resin is dissolved in water and a filler component such as extender pigment. Yes. When this aqueous coating material is applied, water as a solvent evaporates and a coating film is formed.
また、水性塗材を構成する成分の１つである水性バインダー成分は、水性塗材中のフィラー成分を結合させたり、塗膜を被塗装物へ密着させるためのものである。この水性バインダー成分には、塗膜の耐水性や耐候性などの耐久性が優れていることから、合成樹脂エマルジョンが多く用いられている。 Moreover, the aqueous binder component which is one of the components constituting the aqueous coating material is for bonding the filler component in the aqueous coating material or for adhering the coating film to the object to be coated. Synthetic resin emulsions are often used for the aqueous binder component because the coating film has excellent durability such as water resistance and weather resistance.
ところで、この水性塗材の塗膜形成は、溶媒の水の蒸発にともなうエマルジョン粒子の凝集によるものである。そのため、乾燥時の温度が低いと、溶媒蒸発の速度が低下し、塗膜が十分に硬化しないことがある。この場合、雨水等により塗膜が流れてしまうという施工上の問題が発生する。 By the way, the formation of a coating film of this aqueous coating material is due to aggregation of emulsion particles accompanying evaporation of water as a solvent. Therefore, when the temperature at the time of drying is low, the rate of solvent evaporation decreases and the coating film may not be sufficiently cured. In this case, the construction problem that the coating film flows due to rainwater or the like occurs.
この問題解決のため、特許文献２には、低温度の条件下でも塗膜が十分に硬化する水性塗料組成物が開示されている。 In order to solve this problem, Patent Document 2 discloses an aqueous coating composition in which a coating film is sufficiently cured even under a low temperature condition.
現在のところ、気温が０℃以下となりうる寒冷地の冬期においては、有機溶剤型塗材が用いられているのが実状である。これは、養生温度が０℃以下となる条件下の使用に適した水性塗材が提供されていないためである。しかし、有機溶剤型塗材は揮発した有機溶剤が人体に悪影響を及ぼすため、好ましくない。 At present, in the cold season when the temperature can be 0 ° C. or lower, the organic solvent type coating material is actually used. This is because an aqueous coating material suitable for use under conditions where the curing temperature is 0 ° C. or lower is not provided. However, organic solvent-type coating materials are not preferred because the volatilized organic solvent adversely affects the human body.
上記特許文献２に記載の水性塗料組成物は、養生温度が５℃の条件下でしか硬化性が評価されておらず、養生温度が０℃以下の条件下でこの水性塗料組成物が使用に適するかどうかは不明である。以上のことから、気温が０℃以下となる寒冷地の冬期においても、硬化性の問題のない水性塗材が望まれていた。 The aqueous coating composition described in Patent Document 2 has been evaluated for curability only under a curing temperature of 5 ° C., and the aqueous coating composition can be used under a curing temperature of 0 ° C. or less. It is unclear whether it is suitable. In view of the above, there has been a demand for an aqueous coating material having no problem of curability even in winter in cold regions where the temperature is 0 ° C. or lower.
よって、本発明は、養生温度が０℃以下の環境下であっても、硬化性に優れる水性塗材を提供することを目的とする。 Therefore, an object of this invention is to provide the aqueous coating material which is excellent in sclerosis | hardenability, even in the environment whose curing temperature is 0 degrees C or less.
本願発明者らは，合成樹脂エマルジョンを含む水性塗材であって，この水性塗材にカルボジイミド化合物が含まれることにより，養生温度が０℃以下とのある条件下でも極めて優れた硬化性が発揮されることを見出した。すなわち，本発明の請求項１記載の発明は，固形分５０％のアクリル樹脂エマルジョン２６重量部と，細珪砂４５重量部と，炭酸カルシウム及び珪砂粉を９重量部と，二酸化チタン４重量部と，水９重量部と，増粘剤，消泡剤，分散剤，防腐剤，防カビ剤及び高沸点溶剤を含む添加剤７重量部と，カルボジイミド当量２００〜１０００のカルボジイミド化合物２乃至９重量部と，から成ることを特徴とする水性塗材である。
The inventors of the present application are water-based coating materials containing a synthetic resin emulsion, and by including a carbodiimide compound in this water-based coating material, extremely excellent curability is exhibited even under a curing temperature of 0 ° C. or less. I found out that That is, the invention according to claim 1 of the present invention includes 26 parts by weight of an acrylic resin emulsion having a solid content of 50%, 45 parts by weight of fine silica sand, 9 parts by weight of calcium carbonate and silica sand powder, and 4 parts by weight of titanium dioxide. 9 parts by weight of water, 7 parts by weight of an additive containing a thickener, an antifoaming agent, a dispersant, an antiseptic, a fungicide and a high boiling point solvent, and 2 to 9 parts by weight of a carbodiimide compound having a carbodiimide equivalent of 200 to 1000 A water-based coating material characterized by comprising:
請求項１に記載の水性塗材は、塗膜形成において、水の蒸発によるエマルジョン粒子の凝集だけではなく、エマルジョン粒子がカルボジイミド化合物と架橋反応することにより、塗膜形成が促進される。そのため、水の蒸発速度が遅い０℃以下の条件下でも塗膜が十分に硬化するものである。 In the aqueous coating material according to the first aspect, not only the aggregation of the emulsion particles by evaporation of water but also the formation of the coating film is promoted by the crosslinking reaction of the emulsion particles with the carbodiimide compound. Therefore, the coating film is sufficiently cured even under the condition of 0 ° C. or less where the water evaporation rate is slow.
また，請求項１に記載の水性塗材は，カルボジイミド化合物の含有量を２乃至９重量部とすることにより，塗膜の硬化性，及び，乾燥性が十分に発揮されるとともに，カルボジイミド化合物の含有量を１０．０重量部以下とすることにより，エマルジョン粒子とカルボジイミド化合物との過剰な反応が抑制され，塗膜強度が確保される。
In addition, the water-based coating material according to claim 1 has a carbodiimide compound content of 2 to 9 parts by weight , so that the curability and drying properties of the coating film are sufficiently exhibited, and the carbodiimide compound By setting the content to 10.0 parts by weight or less, excessive reaction between the emulsion particles and the carbodiimide compound is suppressed, and the coating strength is ensured.
以下、本発明の実施形態を説明する。本発明に用いる合成樹脂エマルジョンとしては、アクリル酸エステル共重合系樹脂、酢酸ビニル樹脂、エチレン・酢酸ビニル系樹脂、酢酸ビニル・アクリル酸エステル系樹脂、エチレン・塩化ビニル系樹脂、シリコン変性アクリル系樹脂、ウレタン系樹脂等の合成樹脂エマルジョンが使用できる。 Embodiments of the present invention will be described below. Synthetic resin emulsions used in the present invention include acrylic ester copolymer resins, vinyl acetate resins, ethylene / vinyl acetate resins, vinyl acetate / acrylic ester resins, ethylene / vinyl chloride resins, silicon-modified acrylic resins. Synthetic resin emulsions such as urethane resins can be used.
塗材組成物中の樹脂分は５〜２５重量％が好ましい。５重量％以上とすることにより、密着性、塗膜強度、塗布性等が良好となる。また、２５重量％以下とすることにより、以下に記載するその他の添加剤等の配合量が適切となり、さらにコストメリットを確保することができる。 The resin content in the coating material composition is preferably 5 to 25% by weight. By setting it as 5 weight% or more, adhesiveness, coating-film strength, applicability | paintability, etc. become favorable. Moreover, by setting it as 25 weight% or less, the compounding quantity of the other additive etc. which are described below becomes appropriate, and also a cost merit can be ensured.
本発明で用いるカルボジイミド化合物は、カルボジイミド当量が２００〜１０００（カルボジイミド基１モルあたりの化学式量）の範囲にあるカルボジイミド化合物を使用する。本発明においては、市販品を使用することができ、例えば、日清紡株式会社製のカルボジライトＶ−０２（商品名、登録商標）を使用することができる。 The carbodiimide compound used in the present invention is a carbodiimide compound having a carbodiimide equivalent in the range of 200 to 1000 (chemical formula amount per mole of carbodiimide group). In the present invention, commercially available products can be used. For example, Carbodilite V-02 (trade name, registered trademark) manufactured by Nisshinbo Co., Ltd. can be used.
さらに、この水性塗材は、充填材、顔料、増粘剤、分散剤、防カビ剤、及び、防藻剤を既調合とした塗材組成物であり、必要に応じて水、骨材を配合して使用することもできる。 Further, this water-based coating material is a coating composition in which a filler, a pigment, a thickener, a dispersant, an antifungal agent, and an algae-proofing agent are already prepared. It can also be used in combination.
充填剤には、固形分の調整、粘度・塗布性の調整などのため水酸化アルミニウム、重質炭酸カルシウム、クレー、カオリン、タルク、沈降性硫酸バリウム、炭酸バリウム、珪砂、細珪砂等が使用できる。このうち、重質炭酸カルシウムは安価でコスト的負担を減らすことができ、白色であるため、塗材の各種調色に好都合である。 For the filler, aluminum hydroxide, heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, silica sand, fine silica sand, etc. can be used to adjust the solid content, viscosity and coating properties. . Of these, heavy calcium carbonate is inexpensive, can reduce the cost burden, and is white, so it is convenient for various colors of coating materials.
また、顔料には、酸化チタン、酸化亜鉛、カーボンブラック、酸化第二鉄（べんがら）、クロム酸鉛（モリブデードオレンジ）黄鉛、黄色酸化鉄等の無機系顔料等が使用できる。このうち、酸化チタンは下地の隠蔽性に優れ、白色であるため、塗材の各種調色に好都合である。 As the pigment, inorganic pigments such as titanium oxide, zinc oxide, carbon black, ferric oxide (bengal), lead chromate (molybdate orange) yellow lead, yellow iron oxide, and the like can be used. Among these, titanium oxide is excellent in the concealing property of the base and is white, so it is convenient for various colors of the coating material.
充填材の配合量は、塗材組成物の固形分換算で１０〜９０重量％が好ましい。１０重量％以上とすることにより、塗材組成物の粘度が適度に高くなり、施工しやすくなる。また、９０重量％以下とすることにより、塗材組成物の塗布性、密着性、及び、塗膜強度を十分に確保することができる。 The blending amount of the filler is preferably 10 to 90% by weight in terms of solid content of the coating composition. By setting it as 10 weight% or more, the viscosity of a coating material composition becomes moderately high, and it becomes easy to construct. Moreover, by setting it as 90 weight% or less, the applicability | paintability, adhesiveness, and coating-film intensity | strength of a coating material composition are fully securable.
また、顔料の配合量は、塗材組成物の固形分換算で２０重量％以下が好ましい。２０重量％以下とすることにより、塗材組成物の粘度が適度に低くすることができ、施工に適するものとなる。 Further, the blending amount of the pigment is preferably 20% by weight or less in terms of solid content of the coating material composition. By setting it as 20 weight% or less, the viscosity of a coating material composition can be made low moderately, and will become suitable for construction.
添加剤として、増粘剤、成膜助剤、分散剤、防カビ剤、及び、防藻剤が使用される。添加剤の配合量は、塗材組成物中の固形分換算で２０重量％以下が好ましい。２０重量％以下とすることにより、塗膜の環境性や安全性を確保することができる。 As additives, thickeners, film-forming aids, dispersants, antifungal agents, and antialgal agents are used. The amount of the additive is preferably 20% by weight or less in terms of solid content in the coating composition. By setting it as 20 weight% or less, the environmental property and safety | security of a coating film are securable.
骨材には、一般に塗料に配合されるものであれば何ら問題無く使用でき、寒水石、珪砂、大理石、山砂、ガラス粉砕物、セラミック粉砕物等が使用できる。骨材の配合量は塗材組成物の固形分換算で９０重量％以下が好ましい。９０重量％以下とすることにより、塗材組成物の粘度が適度に低くなり、施工に適したものとなる。さらに、骨材の粒径としては、０．０５〜１０ｍｍのものが好ましい。０．０５ｍｍ以上とすることにより、作業性が確保されるとともに、１０ｍｍ以下とすることにより、美しい外観を確保することができる、 The aggregate can be used without any problem as long as it is generally blended with a paint, and cryogenic stone, quartz sand, marble, mountain sand, glass pulverized material, ceramic pulverized material and the like can be used. The blending amount of the aggregate is preferably 90% by weight or less in terms of solid content of the coating composition. By setting it as 90 weight% or less, the viscosity of a coating material composition becomes moderately low, and it becomes a thing suitable for construction. Further, the aggregate particle size is preferably 0.05 to 10 mm. Workability is ensured by being 0.05 mm or more, and a beautiful appearance can be secured by being 10 mm or less.
本発明の水性塗材の塗布方法としてコテ、ローラー、吹き付けガン等を使用して、塗布量０．５〜１．５ｋｇ/ｍ2を塗布し、上塗り層の吸い込みむら防止、下地の隠蔽のため、下塗り層を形成する。適正粘度としては塗布作業の面から、３００〜７００Ｐａ・Ｓ/０℃が好ましい。このような適正粘度にするため、下塗り層用の塗材組成物中に水を加えて調整することができる。該下塗り層の乾燥後、上塗り層として仕上がり外観によっては、下塗り層と同一の水系塗材組成物に骨材を配合して使用することも可能である。 As a coating method of the aqueous coating material of the present invention, using a trowel, roller, spray gun, etc., a coating amount of 0.5 to 1.5 kg / m 2 is applied to prevent uneven coating of the topcoat layer and conceal the underlying layer. Forming an undercoat layer. The appropriate viscosity is preferably 300 to 700 Pa · S / 0 ° C. from the viewpoint of coating work. In order to obtain such an appropriate viscosity, it can be adjusted by adding water to the coating composition for the undercoat layer. Depending on the finished appearance of the undercoat layer after drying the undercoat layer, it is also possible to mix and use the aggregate in the same aqueous coating material composition as the undercoat layer.
以下、実施例により本発明をさらに具体的に説明する。言うまでもなく、本発明はこれらの実施例に限定されるものではない。以下、重量部を単に部と記載する。 Hereinafter, the present invention will be described more specifically with reference to examples. Needless to say, the present invention is not limited to these examples. Hereinafter, parts by weight are simply referred to as parts.
（実施例１）
アクリル樹脂エマルジョンとして、アクロナール２９５ＤＮ（固形分５０％、ＢＡＳＦ社製、商品名）を２６部、骨材として細珪砂を４５部、充填材として、炭酸カルシウム及び珪砂粉を９部、顔料として二酸化チタンを４部、水を９部、添加剤として、増粘剤、消泡剤、分散剤、防腐剤、防カビ剤、高沸点溶剤等を７部配合し、さらに、カルボジイミド化合物として、カルボジライトＶ−０２（以下、カルボジイミドと記載）を２部添加し、実施例１の水性塗材を調製した。
Example 1
As acrylic resin emulsion, 26 parts of Acronal 295DN (solid content 50%, manufactured by BASF, trade name), 45 parts of fine silica sand as aggregate, 9 parts of calcium carbonate and silica sand powder as filler, titanium dioxide as pigment 4 parts, 9 parts of water, 7 parts of thickener, antifoaming agent, dispersant, preservative, antifungal agent, high boiling point solvent, etc. as a additive, and carbodiimide V- 02 parts (hereinafter referred to as carbodiimide) was added to prepare an aqueous coating material of Example 1.
（実施例２）
実施例１の水性塗材において、カルボジイミド２部の添加に代えて、カルボジイミドを９部添加したものを実施例２の水性塗材とした。
(Example 2)
In the aqueous coating material of Example 1, instead of adding 2 parts of carbodiimide, 9 parts of carbodiimide was added as the aqueous coating material of Example 2.
（比較例１）
実施例１の水性塗材において、カルボジイミドを添加しないものを比較例１の水性塗材とした。
(Comparative Example 1)
In the aqueous coating material of Example 1, the water-based coating material of Comparative Example 1 was used without adding carbodiimide.
（比較例２）
実施例１の水性塗材において、カルボジイミド２部の添加に代えて、カルボジイミドを１２部添加したものを比較例２の水性塗材とした。
(Comparative Example 2)
In the aqueous coating material of Example 1, 12 parts of carbodiimide was added in place of the addition of 2 parts of carbodiimide, and the aqueous coating material of Comparative Example 2 was used.
上記で調製した基準塗材、実施例の水性塗材、及び、比較例の水性塗材について、以下の通り、乾燥性、耐候性、作業性、及び、仕上がり性を評価した。 About the reference | standard coating material prepared above, the water-based coating material of an Example, and the water-based coating material of a comparative example, dryability, a weather resistance, workability | operativity, and finish were evaluated as follows.
（硬化性）
フレキシブルボード（縦×横×厚み＝１５０ｍｍ×１５０ｍｍ×８ｍｍ）に、シーラーとして水性アクリル系下塗材（ＪＳ−５６０、アイカ工業株式会社製、商品名）を塗布して乾燥したのち、実施例、及び、比較例の水性塗材をそれぞれ２．０ｋｇ／ｍ2づつコテ塗り仕上げし、その後、養生温度０℃で４８時間養生させた。さらに、４８時間、養生後の塗膜を水中浸漬（水温２０℃）させた後、塗膜のふくれ、及び、はがれの有無を目視確認した。
評価基準
○：塗膜のふくれ、及び、はがれが認められない。
×：塗膜のふくれ、または、はがれが認められる。
(Curable)
A flexible board (length x width x thickness = 150 mm x 150 mm x 8 mm) was coated with a water-based acrylic primer (JS-560, manufactured by Aika Kogyo Co., Ltd., trade name) as a sealer, dried, examples, and The water-based coating materials of the comparative examples were each coated with a trowel by 2.0 kg / m 2 , and then cured at a curing temperature of 0 ° C. for 48 hours. Furthermore, after the cured coating film was immersed in water (water temperature 20 ° C.) for 48 hours, the presence or absence of blistering and peeling of the coating film was visually confirmed.
Evaluation criteria ○: No swelling or peeling of the coating film is observed.
X: Swelling or peeling of the coating film is observed.
（耐候性）
ＪＩＳ Ａ ６９０９の耐候性試験Ａ法に準じてキセノン光源照射（３００ｈ）を行い、ＪＩＳ Ｌ ０８０４に規定するグレースケールを用い、ＪＩＳ Ｚ ８７２３によって変色の程度を基準の未照射試験体と比較するとともに、表面のひび割れ、及び、はがれの有無を目視で確認した。
評価基準
○：ひび割れ及びはがれが認められず、かつ、グレースケール３号以上である。
×：ひび割れ、または、はがれが認められるか、もしくは、グレースケールが３号より大きい。
(Weatherability)
Xenon light source irradiation (300h) is performed according to JIS A 6909 weather resistance test A method, and the gray scale specified in JIS L 0804 is used, and the degree of discoloration is compared with the standard unirradiated specimen according to JIS Z 8723. The presence or absence of surface cracks and peeling was confirmed visually.
Evaluation standard (circle): A crack and peeling are not recognized and it is more than gray scale No. 3.
X: Cracking or peeling is recognized or the gray scale is larger than No. 3.
（作業性）
コテ塗りにおいて、作業性を下記の基準により評価した。
○：０℃条件下において、巻き込み泡、及び、塗布ムラが認められず、さらに、塗布から１０分後にパターン付けが可能である。
×：同条件下において、巻き込み泡、または、塗布ムラが認められるか、もしくは、塗布から１０分後にパターン付けが不可能である。
(Workability)
In the trowel coating, workability was evaluated according to the following criteria.
◯: No entrainment bubbles and coating unevenness are observed under 0 ° C., and patterning is possible 10 minutes after coating.
X: Under the same conditions, entrained bubbles or coating unevenness is observed, or patterning is impossible 10 minutes after coating.
（仕上り性）
コテ塗り後の仕上がり性を下記の基準により評価した。
○：乾燥後の塗膜にパターンのタレ、てかり、及び、ひび割れが認められない。
×：乾燥後の塗膜にパターンのタレ、または、てかり、もしくは、ひび割れが認められる。
(Finishing)
The finish after ironing was evaluated according to the following criteria.
○: Pattern sagging, shining, and cracks are not observed in the dried coating film.
X: Pattern sagging, lighting, or cracks are observed in the dried coating film.
上記の評価結果を表１に示す。
上記評価結果に示される通り、比較例１の水性塗材は、耐候性、作業性、及び、仕上り性においては良好であるものの、硬化性が劣っている。 As shown in the above evaluation results, the aqueous coating material of Comparative Example 1 is good in weather resistance, workability, and finish, but is inferior in curability.
一方、実施例１及び２の水性塗材は、それぞれ比較例１の水性塗材にカルボジイミド化合物を適量添加したものであり、これらは、耐候性、作業性、及び、仕上り性に加え、硬化性についても良好な結果を示し、養生温度が０℃の条件下でも使用に適することが確認された。 On the other hand, each of the aqueous coating materials of Examples 1 and 2 is obtained by adding an appropriate amount of a carbodiimide compound to the aqueous coating material of Comparative Example 1, and these are curable in addition to weather resistance, workability, and finish. As a result, it was confirmed that it was suitable for use even under a curing temperature of 0 ° C.
また、比較例２の水性塗材は、耐候性を除く評価項目において劣る結果となった。これは、比較例２の水性塗材は、塗布後の塗膜硬化が実施例の水性塗材よりも急速に進行するため、これらと比較して作業性及び仕上り性が劣化するとともに、溶媒の水が乾燥時に十分に蒸発せず、塗膜中に大量に残ってしまうからと考えられる。 Moreover, the water-based coating material of Comparative Example 2 was inferior in evaluation items excluding weather resistance. This is because, in the aqueous coating material of Comparative Example 2, since the coating film curing after coating proceeds more rapidly than the aqueous coating material of the Examples, workability and finish performance are deteriorated compared to these, and the solvent This is probably because water does not evaporate sufficiently during drying and remains in the coating film in large quantities.
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