JP2017132994A - Coating film and coating material - Google Patents
Coating film and coating material Download PDFInfo
- Publication number
- JP2017132994A JP2017132994A JP2017004922A JP2017004922A JP2017132994A JP 2017132994 A JP2017132994 A JP 2017132994A JP 2017004922 A JP2017004922 A JP 2017004922A JP 2017004922 A JP2017004922 A JP 2017004922A JP 2017132994 A JP2017132994 A JP 2017132994A
- Authority
- JP
- Japan
- Prior art keywords
- binder
- carbon black
- coating film
- paint
- parts
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 114
- 239000011248 coating agent Substances 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000006229 carbon black Substances 0.000 claims abstract description 53
- 239000011230 binding agent Substances 0.000 claims abstract description 49
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000003973 paint Substances 0.000 claims description 56
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 19
- 229920000178 Acrylic resin Polymers 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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Abstract
Description
本発明は、塗膜およびそれを形成するための塗料に関する。さらに詳しくは、高い耐摩耗性（耐擦傷性、耐摩擦性ともいう）を有すると共に、低光沢性の塗膜およびそれを形成するための塗料に関する。 The present invention relates to a coating film and a coating material for forming the coating film. More specifically, the present invention relates to a coating film having high abrasion resistance (also referred to as scratch resistance or friction resistance) and having a low glossiness and a coating for forming the same.
近年、自動車等の車体の外装塗膜や建築用外装塗膜において、意匠性の観点から、光の反射が抑えられた低光沢の塗膜が注目されている。光沢が抑えられた低光沢性の塗膜としては、塗膜を形成するための塗料中に、マイクロサイズのシリカ粒子を添加した塗料が良く知られている。そのような塗料を用いて形成した塗膜は、塗膜表面にシリカ粒子に起因する微小な凹凸が形成され、入射した光が塗膜表面の凹凸によって散乱することにより低光沢性が発現する。しかし、このような塗膜表面に凹凸を有する塗膜では、摩擦等によってその表面が擦傷されると、シリカ粒子が剥落してしまい、塗膜表面の光沢が高くなるといった耐摩耗性に劣る問題があった。また、シリカ粒子自体は透明な材料であるため、黒色に代表される濃色の塗膜を得ようとすると、塗膜中のシリカ粒子の含有率が高くなるにつれて、相対的に塗膜中の着色剤（顔料や染料等）の含有率が低くなり、着色力や隠蔽性が低下してしまうといった問題点があった。 2. Description of the Related Art In recent years, low-gloss coating films in which light reflection is suppressed have attracted attention from the viewpoint of design properties in exterior coating films for automobile bodies and the like and architectural exterior coating films. As a low-gloss coating film with reduced gloss, a coating material in which micro-sized silica particles are added to a coating material for forming a coating film is well known. A coating film formed using such a paint has minute unevenness due to silica particles formed on the surface of the coating film, and low gloss is exhibited by the incident light being scattered by the unevenness of the coating film surface. However, in such a coating film having unevenness on the surface of the coating film, if the surface is scratched by friction or the like, the silica particles are peeled off, and the gloss of the coating film surface is inferior in wear resistance. was there. In addition, since the silica particles themselves are transparent materials, when trying to obtain a dark coating film typified by black, as the content of silica particles in the coating film increases, the silica particles are relatively in the coating film. There has been a problem that the content of colorants (pigments, dyes, etc.) is lowered, and coloring power and concealability are lowered.
また、光沢を抑えるためにマイクロサイズのシリカ粒子を配合した塗料は、比重の大きなシリカ粒子が塗料中で沈降してしまうため、使用直前に撹拌行う等の必要があり、ハンドリング性を損ない、プロセスコスト面からも改良が求められていた。 In addition, paints that contain micro-sized silica particles to reduce gloss will cause silica particles with a large specific gravity to settle in the paint, so it is necessary to stir immediately before use, etc. Improvements were also demanded from a cost standpoint.
上記のような耐摩耗性の問題を改良すべく、例えば、特許文献１には、アクリル樹脂被覆シリカ粒子分散体、架橋剤および被膜形成性樹脂を含有する塗料組成物が開示されている。しかし、シリカ粒子の替わりにアクリル樹脂によって被覆されたシリカ粒子を使用しても、塗膜表面に凹凸があることには変わらないため、摩擦等の物理的外力が塗膜に加わると、アクリル樹脂被覆シリカ粒子のみが剥落してしまい、満足し得る十分な耐摩耗性の塗膜を得ることはできなかった。 In order to improve the problem of abrasion resistance as described above, for example, Patent Document 1 discloses a coating composition containing an acrylic resin-coated silica particle dispersion, a crosslinking agent, and a film-forming resin. However, even if silica particles coated with acrylic resin are used instead of silica particles, there is no difference in the surface of the coating film, so if physical external force such as friction is applied to the coating film, the acrylic resin Only the coated silica particles peeled off, and it was not possible to obtain a satisfactory abrasion-resistant coating film.
着色力や隠蔽性が不足する問題を改良すべく、カーボンブラック等の顔料を内包した樹脂ビーズをシリカ粒子の代替として用いることもできるが、ビーズ内での顔料の含有量が少なく、十分な着色力や隠蔽性を得ることは困難であり、耐摩耗性の課題に関しても十分な耐摩耗性の塗膜を得ることはできなかった。 Resin beads containing carbon black and other pigments can be used as an alternative to silica particles in order to improve the problem of insufficient coloring power and hiding properties, but the pigment content in the beads is small and sufficient coloring is possible. It was difficult to obtain strength and concealment, and it was impossible to obtain a coating film having sufficient wear resistance even with respect to the problem of wear resistance.
本発明は、高い耐摩耗性ならびに隠蔽性を有する低光沢の塗膜を提供することを目的とする。また、そのような塗膜を形成するための高い分散安定性を有する塗料を提供することを目的とする。 An object of this invention is to provide the low gloss coating film which has high abrasion resistance and concealment property. Moreover, it aims at providing the coating material which has the high dispersion stability for forming such a coating film.
本発明者らは、鋭意研究の結果、カーボンブラックと結着剤とを特定の配合量により５〜２０μｍの粒子状とし、それを塗料用粒子として塗料に配合することによって、上記のようなシリカ粒子を使用せずに、高い耐摩耗性を有する低光沢の塗膜が得られることを見出し、本発明に至った。 As a result of diligent research, the inventors of the present invention made carbon black and a binder into a particle shape of 5 to 20 μm according to a specific blending amount, and blended it into a coating material as a coating particle. The inventors have found that a low-gloss coating film having high wear resistance can be obtained without using particles, and have reached the present invention.
すなわち、本発明は、カーボンブラックと結着剤とを含む塗料用粒子を含有してなる塗膜であって、カーボンブラックと結着剤との合計１００質量部に対するカーボンブラックの含有量が８０〜９０質量部であり、前記塗料用粒子の平均粒子径が５〜２０μｍであり、前記塗膜の６０°鏡面光沢度（Ｇｓ）が０．１〜１５％であることを特徴とする塗膜に関する。 That is, the present invention is a coating film containing paint particles containing carbon black and a binder, and the carbon black content is 80 to 80 parts per 100 parts by mass in total of the carbon black and the binder. It is 90 mass parts, The average particle diameter of the said particle | grains for coating materials is 5-20 micrometers, The 60 degree specular glossiness (Gs) of the said coating film is 0.1-15%, It is related with the coating film characterized by the above-mentioned. .
また、本発明は、摩擦試験前の６０°鏡面光沢度と、摩擦試験後の６０°鏡面光沢度との差（△Ｇｓ）が、０．１〜５％である上記塗膜に関する。 Moreover, this invention relates to the said coating film whose difference ((DELTA) Gs) of 60 degree specular gloss before a friction test and 60 degree specular gloss after a friction test is 0.1 to 5%.
また、本発明は、前記結着剤が、Ｆｅｄｏｒｓの溶解度パラメータ（ＳＰ値）１０以下の溶剤に対して不溶である上記塗膜に関する。 The present invention also relates to the above coating film, wherein the binder is insoluble in a solvent having a Fedors solubility parameter (SP value) of 10 or less.
また、本発明は、前記結着剤が、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルピロリドン樹脂および酸価１００ｍｇＫＯＨ／ｇ以上のアクリル樹脂からなる群より選ばれる少なくとも１種である上記塗膜に関する。 The present invention also relates to the above coating film, wherein the binder is at least one selected from the group consisting of a polyvinyl alcohol resin, a polyvinyl acetal resin, a polyvinyl pyrrolidone resin, and an acrylic resin having an acid value of 100 mgKOH / g or more.
また、本発明は、カーボンブラックと結着剤とを含む塗料用粒子を含有してなる塗料であって、カーボンブラックと結着剤との合計１００質量部に対するカーボンブラックの含有量が８０〜９０質量部であり、前記塗料用粒子の平均粒子径が５〜２０μｍであることを特徴とする塗料に関する。 Further, the present invention is a paint comprising paint particles containing carbon black and a binder, and the carbon black content is 80 to 90 with respect to 100 parts by mass of the total of carbon black and the binder. It is a mass part, It is related with the coating material characterized by the average particle diameter of the said particle | grains for coating materials being 5-20 micrometers.
また、本発明は、塗料より形成された塗膜の６０°鏡面光沢度（Ｇｓ）が、０．１〜１５％である上記塗料に関する。 Moreover, this invention relates to the said coating material whose 60 degree specular glossiness (Gs) of the coating film formed from the coating material is 0.1 to 15%.
また、本発明は、カーボンブラックと結着剤とを含む塗料用粒子であって、カーボンブラックと結着剤との合計１００質量部に対するカーボンブラックの含有量が８０〜９０質量部であり、平均粒子径が５〜２０μｍであることを特徴とする塗料用粒子に関する。 Further, the present invention is a coating particle containing carbon black and a binder, the content of carbon black with respect to a total of 100 parts by mass of carbon black and binder is 80 to 90 parts by mass, average The present invention relates to a coating particle, wherein the particle diameter is 5 to 20 μm.
また、本発明は、カーボンブラックと結着剤とを含む塗料用粒子の製造方法であって、カーボンブラックと結着剤との合計１００質量部に対するカーボンブラックの含有量が８０〜９０質量部であるカーボンブラックと結着剤とを含む分散液を、噴霧乾燥することを特徴とする塗料用粒子の製造方法に関する。 Further, the present invention is a method for producing a coating particle containing carbon black and a binder, wherein the carbon black content is 80 to 90 parts by mass with respect to 100 parts by mass in total of the carbon black and the binder. The present invention relates to a method for producing particles for paint, characterized by spray-drying a dispersion containing a certain carbon black and a binder.
本発明により、高い耐摩耗性ならびに隠蔽性を有する光沢の抑えられた塗膜を得ることができるようになった。また、そのような塗膜を形成するための高い分散安定性を有する塗料を得ることができるようになった。 According to the present invention, it is possible to obtain a coating film having high abrasion resistance and concealment and having reduced gloss. Moreover, it has become possible to obtain a paint having high dispersion stability for forming such a coating film.
＜カーボンブラックと結着剤とを含む塗料用粒子＞
本発明におけるカーボンブラックと結着剤とを含む塗料用粒子（以下、単に「粒子」と称することがある）は、カーボンブラックと樹脂との合計１００質量部に対してカーボンブラックの含有量が８０〜９０質量部であることを特徴とする。カーボンブラックの含有量が８０〜９０質量部の場合、分散液や塗料を作製する際の物理的外力に対しても十分な強度を有することができる。該粒子を用いた塗膜も、摩擦等の物理的外力を加えても、粒子が崩壊しにくく、耐摩耗性の高い塗膜を得ることができる。さらに粒子同士の凝集が少なく、塗膜中に均一に分散することが可能となり、塗膜の光沢を抑えながら、隠蔽性が良好な塗膜を得ることができる為、上記の組成とすることが好ましい。
<Particle for paint containing carbon black and binder>
In the present invention, the particles for coating material (hereinafter sometimes simply referred to as “particles”) containing carbon black and a binder have a carbon black content of 80 with respect to 100 parts by mass in total of carbon black and resin. It is -90 mass parts, It is characterized by the above-mentioned. When the content of carbon black is 80 to 90 parts by mass, the carbon black can have sufficient strength against physical external forces when producing a dispersion or a paint. Even when a coating film using the particles is subjected to physical external force such as friction, the particles are not easily disintegrated and a coating film having high wear resistance can be obtained. Furthermore, since the particles are less agglomerated and can be uniformly dispersed in the coating film, and a coating film with good concealability can be obtained while suppressing the gloss of the coating film, the above composition can be obtained. preferable.
塗料用粒子の平均粒子径は、５〜２０μｍである。平均粒子径が、５〜２０μｍの場合、塗料の分散安定性が高く、さらに塗膜の光沢を抑えることが可能である為、好ましい。 The average particle size of the coating particles is 5 to 20 μm. When the average particle diameter is 5 to 20 μm, the dispersion stability of the paint is high, and the gloss of the coating film can be further suppressed, which is preferable.
尚、本明細書における塗料用粒子の平均粒子径は、走査型電子顕微鏡（ＳＥＭ）で観察した粒子径の算術平均値である。詳細には、塗料用粒子の粉末を倍率２００００倍で観察し、任意の１００個の粒子を選択し、各々の粒子径を平均して求めた値である。粒子形状が長軸、短軸を有する場合には、長軸と短軸の長さの平均値を、その粒子の粒子径として用いた。 In addition, the average particle diameter of the particle | grains for coating materials in this specification is an arithmetic average value of the particle diameter observed with the scanning electron microscope (SEM). Specifically, it is a value obtained by observing the powder of paint particles at a magnification of 20000, selecting arbitrary 100 particles, and averaging the particle diameters. When the particle shape has a major axis and a minor axis, the average value of the lengths of the major axis and the minor axis was used as the particle diameter of the particle.
塗料用粒子の製造方法は、特に限定されるものではないが、カーボンブラックと結着剤とを混合して均一になるよう分散して分散液を調製した後、分散液を噴霧乾燥して塗料用粒子を得ることが好ましい。 The method for producing the particles for paint is not particularly limited, but after carbon black and a binder are mixed and dispersed so as to be uniform, a dispersion is prepared, and then the dispersion is spray-dried to form a paint. It is preferable to obtain particles for use.
カーボンブラックと結着剤を均一に混合して分散液を得る際に用いられる分散機としては、ディスパー、ホモミキサー、プラネタリーミキサー、エム・テクニック社製「クレアミックス」、ＰＲＩＭＩＸ社「フィルミックス」、ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製の「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ−５」、奈良機械製作所社製「マイクロス」、ロールミル等の分散機が挙げられる。分散機は、一種類のみを使用しても良いし、複数種を併用してもよい。 Dispersers, homomixers, planetary mixers, "Clairemix" manufactured by M Technique, "PRIMIX" "Fillmix" are used as a disperser used to obtain a dispersion by uniformly mixing carbon black and a binder. , Paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, wet jet mill (manufactured by Genus) “Genus PY”, “Starburst” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, “Micros” manufactured by Nara Machinery Co., Ltd., roll mill, etc. Machine. Only one type of disperser may be used, or a plurality of types may be used in combination.
噴霧乾燥には、Ｓ Ｋ ジェット・オー・ミル、ミストドライヤー、スプレードライヤー、流動媒体槽、スラリードライヤー等の噴霧乾燥機を使用できる。粒子の粒子径は、噴霧乾燥時の分散液の濃度、噴霧時の吐出圧、吐出速度等により制御することができる。 For spray drying, spray dryers such as SK jet-o-mill, mist dryer, spray dryer, fluid medium tank, slurry dryer, and the like can be used. The particle diameter of the particles can be controlled by the concentration of the dispersion during spray drying, the discharge pressure during spraying, the discharge speed, and the like.
＜カーボンブラック＞
本発明に用いるカーボンブラックとしては、気体若しくは液体の原料を反応炉中で連続的に熱分解し製造するファーネスブラック、エチレン重油を原料としたケッチェンブラック、原料ガスを燃焼させてその炎をチャンネル鋼底面に当てて急冷し析出させたチャンネルブラック、ガスを原料とし燃焼と熱分解を周期的に繰り返すことにより得られるサーマルブラック、アセチレンガスを原料とするアセチレンブラック等の各種カーボンブラックを単独または二種以上を併せて使用することができる。又、酸化処理されたカーボンブラックや、中空カーボン等も使用できる。上記の内、ファーネスブラックが、ハンドリング性および着色力の点から好ましい。
<Carbon black>
The carbon black used in the present invention includes furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reaction furnace, ketjen black using ethylene heavy oil as a raw material, and burning the raw material gas to channel the flame. Channel black deposited on the bottom of the steel and quenched and precipitated, thermal black obtained by periodically repeating combustion and pyrolysis using gas as raw material, and various carbon blacks such as acetylene black using acetylene gas as raw materials. More than one species can be used in combination. In addition, oxidized carbon black, hollow carbon, and the like can be used. Of the above, furnace black is preferable from the viewpoints of handling properties and coloring power.
カーボンブラックの粒子径は、着色力の点から、１０〜２００ｎｍが好ましく、１０〜３０ｎｍがより好ましい。ただし、ここでいう粒子径とは、一般にカーボンブラックの物理的特性を表す際に使用されている電子顕微鏡で測定された平均一次粒子径を表す。 The particle size of carbon black is preferably 10 to 200 nm, more preferably 10 to 30 nm, from the viewpoint of coloring power. However, the particle diameter referred to here represents an average primary particle diameter measured with an electron microscope which is generally used for expressing the physical characteristics of carbon black.
カーボンブラックのＢＥＴ比表面積は、結着剤との結着が効果的に作用する観点から、２０〜４００ｍ2／ｇが好ましく、５０〜３００ｍ2／ｇがより好ましい。ただし、ここでいうＢＥＴ比表面積は、窒素吸着によりＢＥＴ法で測定された比表面積を指し、この物性値は一般にカーボンブラックの物理特性を表すのに用いられる。 The BET specific surface area of carbon black is preferably 20 to 400 m 2 / g, more preferably 50 to 300 m 2 / g, from the viewpoint of effective binding with the binder. However, the BET specific surface area here refers to the specific surface area measured by the BET method by nitrogen adsorption, and this physical property value is generally used to represent the physical characteristics of carbon black.
＜結着剤＞
本発明に用いられる結着剤は、塗料用粒子を形成する際に、カーボンブラック同士を結着しうる材料を指す。特に、耐摩耗性の点から、塗料作成時に溶剤等によって溶解せず塗料用粒子の形状を維持できる結着剤であることが好ましく、一般的に塗料として用いられるＦｅｄｏｒｓの溶解度パラメータ（ＳＰ値）１０以下の溶剤に対して不溶であることが好ましい。中でも、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリビニルピロリドン樹脂、酸価１００ｍｇＫＯＨ／ｇ以上のアクリル樹脂が好ましい。
<Binder>
The binder used in the present invention refers to a material capable of binding carbon blacks when forming particles for paint. In particular, from the viewpoint of wear resistance, the binder is preferably a binder capable of maintaining the shape of the particles for coating without being dissolved by a solvent or the like at the time of preparing the coating. The solubility parameter (SP value) of Fedors generally used as a coating It is preferably insoluble in 10 or less solvents. Among these, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl pyrrolidone resin, and acrylic resin having an acid value of 100 mgKOH / g or more are preferable.
ここで、ＦｅｄｏｒｓのＳＰ値とは、対象とする分子の溶解度パラメータが分子を構成する原子、または、原子団の置換基の数、および種類に依存すると仮定して、下記の式に従い算出される値を指す。
ＳＰ値：δ＝（ΣＥ／ΣＶ）1/2
単位：（ｃａｌ／ｃｍ3）1/2
Ｅ：分子を構成する原子または原子団の蒸発エネルギー（単位：ｃａｌ／ｍｏｌ）
Ｖ：分子を構成する原子または原子団のモル体積（単位：ｃｍ3／ｍｏｌ）
Here, the SP value of Fedors is calculated according to the following formula, assuming that the solubility parameter of the target molecule depends on the number and type of atoms constituting the molecule or the substituent of the atomic group. Points to the value.
SP value: δ = (ΣE / ΣV) 1/2
Unit: (cal / cm 3 ) 1/2
E: Evaporation energy of atoms or atomic groups constituting the molecule (unit: cal / mol)
V: molar volume of atoms or atomic groups constituting the molecule (unit: cm 3 / mol)
結着剤の溶剤に対する溶解性は、結着剤固形物と溶剤とをよく混合後、混合液の上澄み液中に結着剤が含まれているか否かによって容易に判断できる。本明細書では、上澄み液中に結着剤が含まれていない場合を「不溶」、含まれている場合を「可溶」とした。 The solubility of the binder in the solvent can be easily judged by whether or not the binder is contained in the supernatant of the mixed solution after thoroughly mixing the binder solid and the solvent. In the present specification, the case where the binder is not contained in the supernatant is referred to as “insoluble”, and the case where it is contained is referred to as “soluble”.
＜ポリビニルアルコール樹脂＞
ポリビニルアルコール樹脂とは、ポリ酢酸ビニルのケン化物を指す。ポリビニルアルコール樹脂のケン価度は、８５ｍｏｌ％以上であることが好ましい。また、ポリビニルアルコール樹脂中の水酸基が、カルボニル化合物やアミン等によって一部変性されている変性ポリビニルアルコール樹脂であることがより好ましい。具体的には、日本酢ビ・ポバール社製ＪＰ、ＪＣ、ＪＭ、ＪＦ、Ａ、Ｄシリーズ、日本合成化学社製ゴーセノールシリーズ、ゴーセネックスシリーズ、デンカ社製デンカポバールシリーズなどが挙げられる。
<Polyvinyl alcohol resin>
The polyvinyl alcohol resin refers to a saponified product of polyvinyl acetate. The saponification degree of the polyvinyl alcohol resin is preferably 85 mol% or more. Moreover, it is more preferable that the hydroxyl group in the polyvinyl alcohol resin is a modified polyvinyl alcohol resin that is partially modified with a carbonyl compound, an amine, or the like. Specific examples include JP, JC, JM, JF, A and D series manufactured by Nippon Vinegar Poval Co., Ltd., GOHSENOL series manufactured by Nippon Gosei Chemical Co., Ltd. .
＜ポリビニルアセタール樹脂＞
ポリビニルアセタール樹脂とは、ポリビニルアルコール樹脂のアセタール化物を指し、ポリビニルホルマール、ポリビニルアセタール、ポリビニルブチラール等を挙げることができる。ポリビニルアセタール樹脂のアセタール化度は、３５ｍｏｌ％以下であることが好ましい。また、ポリビニルアセタール樹脂中の水酸基が、カルボニル化合物やアミン等によって一部変性されていることがより好ましい。具体的には、積水化学社製エスレックシリーズ、クラレ社製モビタールシリーズなどが挙げられる。
<Polyvinyl acetal resin>
The polyvinyl acetal resin refers to an acetalized product of a polyvinyl alcohol resin, and examples thereof include polyvinyl formal, polyvinyl acetal, and polyvinyl butyral. The degree of acetalization of the polyvinyl acetal resin is preferably 35 mol% or less. More preferably, the hydroxyl group in the polyvinyl acetal resin is partially modified with a carbonyl compound, an amine, or the like. Specific examples include Sekisui Chemical's ESREC series and Kuraray's Mobital series.
＜酸価１００ｍｇＫＯＨ／ｇ以上のアクリル樹脂＞
酸価１００ｍｇＫＯＨ／ｇ以上のアクリル樹脂とは、該アクリル樹脂１ｇを中和するのに必要な水酸化カリウムを１００ｍｇ以上要するアクリル樹脂を指す。アクリル樹脂の中でも、特にスチレンと、アクリル酸またはメタクリル酸との共重合体を含有する樹脂が好ましい。具体的には、ＢＡＳＦ社製ジョンクリルシリーズ、星光ＰＭＣ社製ＲＳ、ＶＳ、ＹＳシリーズ、日本触媒社製アクアリックシリーズなどが挙げられる。
<Acrylic resin with an acid value of 100 mgKOH / g or more>
An acrylic resin having an acid value of 100 mgKOH / g or more refers to an acrylic resin that requires 100 mg or more of potassium hydroxide necessary to neutralize 1 g of the acrylic resin. Among the acrylic resins, a resin containing a copolymer of styrene and acrylic acid or methacrylic acid is particularly preferable. Specifically, BASF Co., Ltd. John Krill series, Seiko PMC Co., Ltd. RS, VS, YS series, Nippon Shokubai Co., Ltd. Aquaric series, etc. are mentioned.
＜ポリビニルピロリドン樹脂＞
ポリビニルピロリドン樹脂とは、Ｎ−ビニル−２−ピロリドンの重合物を含有する高分子化合物である。他結着剤と比較して、ポリビニルピロリドン樹脂を用いると、塗膜の隠蔽性がより向上することから好ましい。ポリビニルピロリドン樹脂は、共重合することによって、塩基性官能基、ならびに、酸性官能基を含有させることが可能であり、隠蔽性の観点から塩基性可能基を含有させた樹脂がより好ましい。具体的には、ＢＡＳＦ社製ソカランＫシリーズ、ソカランＶＡシリーズ、ＩＳＰ社製ＰＶＰＫシリーズ、日本触媒社製ポリビニルピロリドンＫシリーズ、スタイリーゼＷ−２０、大阪有機化学工業社製Ｈ．Ｃ．ポリマーシリーズ、コスカットＧＡ４６７、ＧＡ４６８などが挙げられる。
<Polyvinylpyrrolidone resin>
The polyvinylpyrrolidone resin is a polymer compound containing a polymer of N-vinyl-2-pyrrolidone. Compared with other binders, it is preferable to use a polyvinylpyrrolidone resin because the concealability of the coating film is further improved. The polyvinyl pyrrolidone resin can contain a basic functional group and an acidic functional group by copolymerization, and a resin containing a basic group is more preferable from the viewpoint of concealability. Specifically, BASF Sokaran K series, Sokaran VA series, ISP PVPK series, Nippon Shokubai polyvinyl pyrrolidone K series, Stylee W-20, Osaka Organic Chemical Industry H. C. Polymer series, Koscut GA467, GA468, etc. are mentioned.
＜塗料＞
本発明の塗料は、塗料用粒子を含む塗料であり、更に、適宜用途に応じて、一般的な塗料に用いられる塗膜形成用樹脂、硬化剤、溶剤等を含むことが好ましい。
<Paint>
The paint of the present invention is a paint containing particles for paint, and further preferably contains a resin for forming a coating film, a curing agent, a solvent, and the like used for a general paint according to the intended use.
＜塗膜形成用樹脂＞
本発明における塗膜形成用樹脂（以下、単に「樹脂」と称することがある）は、天然高分子樹脂と合成高分子樹脂に分類され、特に限定されるものではない。具体的には、天然高分子樹脂としては、にかわ、ゼラチン、ガゼイン、アルブミンなどのたんぱく質類、アラビアゴム、トラガントゴム、キサンタンガムなどの天然ゴム類、サポニンなどのグルコシド類、アルギン酸およびアルギン酸プロピレングルコールエステル、アルギン酸トリエタノールアミン、アルギン酸アンモニウムなどのアルギン酸誘導体、メチルセルロース、ニトロセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、エチルヒドロキシセルロースなどのセルロース誘導体やシェラック樹脂などが挙げられる。
<Resin for coating film formation>
The resin for forming a coating film in the present invention (hereinafter sometimes simply referred to as “resin”) is classified into a natural polymer resin and a synthetic polymer resin, and is not particularly limited. Specifically, natural polymer resins include proteins such as glue, gelatin, casein, albumin, natural gums such as gum arabic, tragacanth, and xanthan gum, glucosides such as saponin, alginic acid and propylene glycol alginate, Examples include alginic acid derivatives such as triethanolamine alginate and ammonium alginate, cellulose derivatives such as methylcellulose, nitrocellulose, carboxymethylcellulose, hydroxymethylcellulose, and ethylhydroxycellulose, and shellac resin.
合成高分子樹脂の例としては、アクリル系共重合体、スチレン・アクリル酸系共重合体、アルキド樹脂、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂、セルロース樹脂、ポリビニルピロリドン樹脂、アクリル酸−アクリロニトリル共重合体、アクリルカリウム−アクリロニトリル共重合体、酢酸ビニル−アクリル酸エステル共重合体、スチレン−メタクリル酸共重合体、スチレン−メタクリル酸−アクリル酸エステル共重合体、スチレン−α−メチルスチレンアクリル酸共重合体、スチレン−α−メチルスチレン−アクリル酸−アクリル酸エステル共重合体、スチレン−無水マレイン酸共重合体、ビニルナフタレン−アクリル酸共重合体、ビニルナフタレン−マレイン酸共重合体、酢酸ビニル−エチレン共重合体、酢酸ビニル−脂肪酸ビニルエチレン共重合体、酢酸ビニル−マレイン酸エステル共重合体、酢酸ビニル−クロトン酸共重合体、酢酸ビニル−アクリル酸共重合体およびこれらの塩などが挙げられる。 Examples of synthetic polymer resins include acrylic copolymers, styrene / acrylic acid copolymers, alkyd resins, epoxy resins, polyester resins, urethane resins, cellulose resins, polyvinylpyrrolidone resins, acrylic acid-acrylonitrile copolymers. , Acrylic potassium-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene acrylic acid copolymer Styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-ethylene copolymer Polymer, vinyl acetate-fatty acid vinyl Examples thereof include a ruethylene copolymer, a vinyl acetate-maleic acid ester copolymer, a vinyl acetate-crotonic acid copolymer, a vinyl acetate-acrylic acid copolymer, and salts thereof.
樹脂は、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、繊維強化樹脂、フッ素樹脂、セルロース樹脂、アクリルエマルジョン等が好ましい。これらの中でもアクリル樹脂がより好ましい。アクリル樹脂の例としては、メラミン硬化性アクリル樹脂、自己架橋アクリル樹脂、ポリイソシアネート硬化性アクリル樹脂、湿気硬化型シリコン・アクリル樹脂などが挙げられ、具体的には、三菱レイヨン社製ダイヤナールシリーズ、ＤＩＣ社製アクリディックシリーズ、日立化成社製ヒタロイドシリーズなどが挙げられる。前述の樹脂は１種または２種以上併用しても良く、分散組成物中での配合量は特に限定されるものではないが、塗料用粒子の総和に対して２〜５０００質量％が好ましく、より好ましくは５〜９００質量％である。 The resin is preferably an acrylic resin, a urethane resin, an epoxy resin, a fiber reinforced resin, a fluororesin, a cellulose resin, an acrylic emulsion, or the like. Among these, an acrylic resin is more preferable. Examples of acrylic resins include melamine curable acrylic resin, self-crosslinking acrylic resin, polyisocyanate curable acrylic resin, moisture curable silicone / acrylic resin, and more specifically, Mitsubishi Rayon Co., Ltd. Examples include the DIC ACRICID series and the Hitachi Chemical Hitaroid series. The above-mentioned resins may be used alone or in combination of two or more, and the blending amount in the dispersion composition is not particularly limited, but is preferably 2 to 5000% by mass with respect to the total of the particles for paint, More preferably, it is 5-900 mass%.
＜硬化剤＞
結着剤や樹脂が、水酸基やカルボキシル基、アミノ基等の反応性官能基を有する場合、塗膜の堅牢性を高めるために硬化剤を使用する事ができる。硬化剤としては、上記反応性官能基と反応することができる化合物が挙げられる。具体的には、使用する樹脂の種類によって異なるが、アミノ樹脂、ポリイソシアネート化合物、エポキシ基含有化合物、カルボキシル基含有化合物などが挙げられる。
<Curing agent>
When the binder or resin has a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group, a curing agent can be used to enhance the fastness of the coating film. As a hardening | curing agent, the compound which can react with the said reactive functional group is mentioned. Specific examples include amino resins, polyisocyanate compounds, epoxy group-containing compounds, carboxyl group-containing compounds, and the like, depending on the type of resin used.
＜溶剤＞
溶剤としては、主に有機溶剤を用いることができるが、塗料として用いられる溶剤であれば制限されない。有機溶剤としては、ケトン類、エステル類、炭化水素系溶剤、アルコール類、エーテル類などが挙げられる。結着剤の溶解性の観点からＦｅｄｏｒｓの溶解度パラメータ（ＳＰ値）１０以下のケトン類、エステル類、炭化水素系溶剤、エーテル類からなる群より選ばれる１種以上の有機溶剤が好ましい。
<Solvent>
As the solvent, an organic solvent can be mainly used, but it is not limited as long as it is a solvent used as a paint. Examples of the organic solvent include ketones, esters, hydrocarbon solvents, alcohols, ethers and the like. From the viewpoint of solubility of the binder, one or more organic solvents selected from the group consisting of ketones, esters, hydrocarbon solvents, and ethers having a Fedors solubility parameter (SP value) of 10 or less are preferred.
ケトン類としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン、メチルプロピルケトン、メチルアミルケトン、メチルイソアミルケトン、ジイソブチルケトン、シクロヘキサノン、イソホロン等が挙げられる。 Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclohexanone, and isophorone.
エステル類としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸メトキシプロピル、酢酸メトキシブチル、酢酸セロソルブ、酢酸アミル、酢酸３−エトキシエタノール、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸イソプロピル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸メトキシプロピル、プロピオン酸メトキシブチル、プロピオン酸セロソルブ、プロピオン酸アミル、プロピオン酸３−エトキシエタノール、酪酸メチル、酪酸エチル、酪酸プロピル、酪酸イソプロピル、酪酸ブチル、酪酸イソブチル、酪酸メトキシプロピル、酪酸メトキシブチル、酪酸セロソルブ、酪酸アミル、酪酸３−エトキシエタノール、イソ酪酸メチル、イソ酪酸エチル、イソ酪酸プロピル、イソ酪酸イソプロピル、イソ酪酸ブチル、イソ酪酸イソブチル、イソ酪酸メトキシプロピル、イソ酪酸メトキシブチル、イソ酪酸セロソルブ、イソ酪酸アミル、イソ酪酸３−エトキシエタノール、乳酸メチル、乳酸エチル、乳酸ブチル、１−メトキシプロピル−２−アセテート等が挙げられる。 Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, 3-ethoxyethanol acetate, methyl propionate, and ethyl propionate. , Propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methoxypropyl propionate, methoxybutyl propionate, cellosolve propionate, amyl propionate, 3-ethoxyethanol propionate, methyl butyrate, ethyl butyrate, propyl butyrate , Isopropyl butyrate, butyl butyrate, isobutyl butyrate, methoxypropyl butyrate, methoxybutyl butyrate, cellosolve butyrate, amyl butyrate, 3-ethoxyethanol butyrate, methyl isobutyrate , Ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, methoxypropyl isobutyrate, methoxybutyl isobutyrate, cellosolve isobutyrate, amyl isobutyrate, 3-ethoxyethanol isobutyrate, methyl lactate, lactic acid Examples include ethyl, butyl lactate, and 1-methoxypropyl-2-acetate.
炭化水素系溶剤としては、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、エチルベンゼン、スチレン等が挙げられる。
アルコール類としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、ｎ−ブチルアルコール、ｓ−ブチルアルコール、ｔ−ブチルアルコール、ｎ−アミルアルコール、イソアミルアルコール、ｔ−アミルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等が挙げられる。
Examples of the hydrocarbon solvent include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, styrene and the like.
Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, ethylene glycol, propylene glycol, Examples include diethylene glycol and dipropylene glycol.
エーテル類としては、イソプロピルエーテル、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノフェニルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノフェニルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールモノフェニルエーテル、ジオキサン等が挙げられる。 Examples of ethers include isopropyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether Le, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, and dioxane.
更には、必要に応じて、上記以外の有機溶剤を併用することもできる。上記以外の有機溶剤としては、石油ベンジン、ミネラルスピリット、ソルベントナフサ等が挙げられる。上記の溶剤は、所望する塗料を得る目的で、１種のみ使用しても、２種以上を混合して使用しても差し支えない。 Furthermore, organic solvents other than those described above can be used in combination as required. Examples of organic solvents other than the above include petroleum benzine, mineral spirit, and solvent naphtha. The above solvents may be used alone or in combination of two or more for the purpose of obtaining a desired paint.
本発明における塗料としての適性を向上させるために、塗料に種々の添加剤を配合してもよい。添加剤としては、分散剤、増粘剤、ｐＨ調整剤、乾燥防止剤、防腐剤、防かび剤、キレート剤、紫外線吸収材、酸化防止剤、消泡剤、レオロジーコントロール剤等が挙げられる。 In order to improve suitability as a paint in the present invention, various additives may be blended in the paint. Examples of the additive include a dispersant, a thickener, a pH adjuster, a drying inhibitor, an antiseptic, a fungicide, a chelating agent, an ultraviolet absorber, an antioxidant, an antifoaming agent, and a rheology control agent.
＜塗膜＞
本発明における塗膜は、塗料用粒子を含む塗料を基材上に塗工し、乾燥、場合によっては、硬化することにより形成される。意匠性の観点から、塗膜の光沢は、ＪＩＳ Ｋ ５６００−４−７：１９９９で規定された６０°鏡面光沢度が、０．１〜１５％であり、０．１〜５％であることが好ましい。また、意匠性の耐久性が高いことが好ましく、摩擦によって鏡面光沢度の変化が小さいことが好ましい。例えば、本発明にて得られた塗膜に対して、ＪＩＳ Ｌ０８４９：２０１３に規定された摩擦試験機（学振形）法に従い塗膜表面を摩擦し、摩擦試験を行い、摩擦試験前後それぞれの塗膜について６０°鏡面光沢度を測定し。摩擦試験前の６０°鏡面光沢度と摩擦試験後の６０°鏡面光沢度との差の絶対値（ΔＧｓ）が、０．１〜５％であることが好ましく、０．１〜１％であることがより好ましい。
<Coating film>
The coating film in the present invention is formed by coating a coating material containing coating particles on a substrate, drying, and optionally curing. From the viewpoint of design properties, the gloss of the coating film is such that the 60 ° specular gloss specified in JIS K 5600-4-7: 1999 is 0.1 to 15% and 0.1 to 5%. Is preferred. Moreover, it is preferable that the durability of design property is high, and it is preferable that the change in specular glossiness is small due to friction. For example, with respect to the coating film obtained in the present invention, the surface of the coating film is rubbed in accordance with a friction tester (Gakushin shape) method specified in JIS L0849: 2013, and a friction test is performed. Measure the 60 ° specular gloss of the coating. The absolute value (ΔGs) of the difference between the 60 ° specular gloss before the friction test and the 60 ° specular gloss after the friction test is preferably 0.1 to 5%, preferably 0.1 to 1%. It is more preferable.
＜基材＞
基材としては、塗料が塗工可能なものであれば、特に制限されず、ポリエチレン、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、トリアセテート、ポリフェニレンサルファイド、アラミド、アクリル、ポリフッ化ビニリデン等の樹脂や、アルミニウム、ステンレス、鉄等の金属製のフィルム、板、成形物等が挙げられる。
<Base material>
The base material is not particularly limited as long as it can be applied with a coating material, such as polyethylene, polyethylene terephthalate, polycarbonate, polyimide, triacetate, polyphenylene sulfide, aramid, acrylic, polyvinylidene fluoride, aluminum, stainless steel, and the like. And metal films such as iron, plates, molded products, and the like.
＜塗工方法＞
通常、塗工に用いられる方法であれば、特に制限されず、例えば、基材がフィルムや板のような平面状物体の場合には、バーコーター、ドクターブレード、スピンコーター等を用いて塗工する方法が挙げられる。また、基材が立体状物体の場合には、ディップコート、スプレーコート等を用いて塗工する方法が挙げられる。
<Coating method>
Usually, the method is not particularly limited as long as it is a method used for coating. For example, when the substrate is a planar object such as a film or a plate, coating is performed using a bar coater, a doctor blade, a spin coater, or the like. The method of doing is mentioned. Moreover, when a base material is a three-dimensional object, the method of coating using a dip coat, a spray coat, etc. is mentioned.
＜膜厚＞
本発明における塗膜の膜厚は、特に制限されるものではないが、一般的な塗膜である５〜１００μｍ程度であることが好ましい。
<Film thickness>
Although the film thickness of the coating film in this invention is not specifically limited, It is preferable that it is about 5-100 micrometers which is a common coating film.
本発明の塗料より形成される塗膜は、近年の市場要求に合致した光沢の抑えられた意匠性と高い耐摩耗性を有することから、自動車の外装および内装塗料、建築用塗料、遮光用塗料、その他様々な用途に利用可能である。 The coating film formed from the paint of the present invention has a design with reduced gloss and high wear resistance that meet recent market demands, so it can be applied to automobile exterior and interior paints, architectural paints, and light-shielding paints. It can be used for various other purposes.
以下に、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。なお、例中、特に断りのない限り、「部」は質量部、「％」は質量％をそれぞれ意味する。まず、実施例および比較例で用いた材料等を以下に示す。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, unless otherwise specified, “part” means part by mass, and “%” means mass%. First, materials used in Examples and Comparative Examples are shown below.
＜カーボンブラック＞
ＣＢ―Ａ：ミツビシカーボン＃３３（三菱化学社製、ファーネスカーボン、粒子径３０ｎｍ）
ＣＢ−Ｂ：ミツビシカーボン＃８５０（三菱化学社製、ファーネスカーボン、粒子径１７ｎｍ）
<Carbon black>
CB-A: Mitsubishi Carbon # 33 (Mitsubishi Chemical Corporation, furnace carbon, particle size 30 nm)
CB-B: Mitsubishi Carbon # 850 (Mitsubishi Chemical Corporation, furnace carbon, particle size 17 nm)
＜結着剤＞
＜アクリル樹脂＞
結着剤Ａ：ジョンクリルＨＰＤ−９６Ｊ（ＢＡＳＦ社製、不揮発分３４％、酸価２４０ｍｇＫＯＨ／ｇ）１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
結着剤Ｂ：ジョンクリル５７Ｊ（ＢＡＳＦ社製、不揮発分３７％、酸価２１５ｍｇＫＯＨ／ｇ）１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
結着剤Ｃ：ジョンクリル５８６（ＢＡＳＦ社製、不揮発分１００％、酸価１０８ｍｇＫＯＨ／ｇ）を水酸化ナトリウムにて中和、溶解することで不揮発分２０％の水溶液とし、この水溶液１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
結着剤Ｄ：ジョンクリル８１９（ＢＡＳＦ社製、不揮発分１００％、酸価７５ｍｇＫＯＨ／ｇ）を水酸化ナトリウムにて中和、溶解することで不揮発分２０％の水溶液としとし、この水溶液１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
結着剤Ｅ：ＢＹＫ−１９０（ＢＹＫ Ｃｈｅｍｉｅ社製、不揮発分４０％、酸価１０ｍｇＫＯＨ／ｇ）１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
<Binder>
<Acrylic resin>
Binder A: 100 parts of Joncrill HPD-96J (manufactured by BASF, nonvolatile content 34%, acid value 240 mgKOH / g) was dried at 140 ° C. for 1 hour to obtain a resin powder.
Binder B: 100 parts of Joncrill 57J (manufactured by BASF, nonvolatile content: 37%, acid value: 215 mgKOH / g) was dried at 140 ° C. for 1 hour to obtain a resin powder.
Binder C: Joncrill 586 (BASF, non-volatile content: 100%, acid value: 108 mg KOH / g) is neutralized with sodium hydroxide and dissolved to obtain an aqueous solution having a non-volatile content of 20%. It was dried at 140 ° C. for 1 hour to obtain a resin powder.
Binder D: Joncryl 819 (manufactured by BASF, nonvolatile content: 100%, acid value: 75 mgKOH / g) is neutralized with sodium hydroxide and dissolved to obtain an aqueous solution having a nonvolatile content of 20%. Was dried at 140 ° C. for 1 hour to obtain a resin powder.
Binder E: 100 parts of BYK-190 (BYK Chemie, nonvolatile content 40%, acid value 10 mgKOH / g) was dried at 140 ° C. for 1 hour to obtain a resin powder.
＜ポリビニルブチラール樹脂＞
結着剤Ｆ：エスレックＫＷ−１（積水化学工業社製、不揮発分２０％、アセタール化度９ｍｏｌ％）１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
結着剤Ｇ：エスレックＫＷ−３（積水化学工業社製、不揮発分２０％、アセタール化度３０ｍｏｌ％）１００部を１４０℃ １時間乾燥させ、樹脂粉末として得た。
<Polyvinyl butyral resin>
Binder F: 100 parts of ESREC KW-1 (manufactured by Sekisui Chemical Co., Ltd., nonvolatile content 20%, acetalization degree 9 mol%) was dried at 140 ° C. for 1 hour to obtain a resin powder.
Binder G: 100 parts of ESREC KW-3 (manufactured by Sekisui Chemical Co., Ltd., nonvolatile content 20%, acetalization degree 30 mol%) was dried at 140 ° C. for 1 hour to obtain a resin powder.
＜ポリビニルアルコール樹脂＞
結着剤Ｈ：ゴーセノールＮＬ−０５（日本合成化学工業社製、不揮発分１００％、ケン化度９８．５ｍｏｌ％）
結着剤Ｉ：ゴーセノールＡＬ−０６Ｒ（日本合成化学工業社製、不揮発分１００％、ケン化度９１．０ｍｏｌ％）
結着剤Ｊ：ゴーセノールＧＬ−０３（日本合成化学工業社製、不揮発分１００％、ケン化度８６．５ｍｏｌ％）
結着剤Ｋ：ゴーセノールＮＫ−０５Ｒ（日本合成化学工業社製、不揮発分１００％、ケン化度９５．０ｍｏｌ％、カルボン酸変性）
<Polyvinyl alcohol resin>
Binder H: Gohsenol NL-05 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., nonvolatile content: 100%, saponification degree: 98.5 mol%)
Binder I: Gohsenol AL-06R (manufactured by Nippon Synthetic Chemical Industry, nonvolatile content 100%, saponification degree 91.0 mol%)
Binder J: Gohsenol GL-03 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., nonvolatile content 100%, saponification degree 86.5 mol%)
Binder K: Gohsenol NK-05R (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., nonvolatile content 100%, saponification degree 95.0 mol%, carboxylic acid modification)
＜ポリビニルピロリドン樹脂＞
結着剤Ｌ：ソカランＫ−１７（ＢＡＳＦ社製、不揮発分１００％）
結着剤Ｍ：コスカットＧＡ６４８（大阪有機化学工業社製、不揮発分１００％、アミン変性）
<Polyvinylpyrrolidone resin>
Binder L: Socaran K-17 (BASF, non-volatile content 100%)
Binder M: Koscut GA648 (manufactured by Osaka Organic Chemical Industry Co., Ltd., nonvolatile content 100%, amine-modified)
＜シリカ＞
ＡＣＥＭＡＴＴ ＨＫ１２５（エボニック社製、二次凝集体の平均粒子径 ７μｍ）
<Silica>
ACEMATT HK125 (manufactured by Evonik, average particle size of secondary aggregate 7 μm)
＜黒色着色アクリルビーズ＞
ア−トパールＧＲ−４００ＢＫ（根上工業社製、平均粒子径 １５μｍ）
<Black colored acrylic beads>
Art Pearl GR-400BK (Negami Kogyo Co., Ltd., average particle size 15 μm)
＜塗膜形成用樹脂＞
ダイヤナールＢＲ−７７（三菱レイヨン社製、不揮発分１００％）
ダイヤナールＢＲ−７７の３０部を、メチルエチルケトン３５部およびトルエン３５部に添加し、十分に溶解させることで固形分３０％の塗膜形成用樹脂溶液を得た。
<Resin for coating film formation>
Dialnal BR-77 (Mitsubishi Rayon, non-volatile content 100%)
30 parts of Dialnal BR-77 was added to 35 parts of methyl ethyl ketone and 35 parts of toluene, and dissolved sufficiently to obtain a resin solution for forming a coating film having a solid content of 30%.
＜硬化剤＞
ユーバン２０ＳＥ−６０（三井化学社製、不揮発分６０％、アミノ樹脂）
<Curing agent>
Uban 20SE-60 (Mitsui Chemicals, nonvolatile content 60%, amino resin)
＜結着剤の溶剤溶解性＞
結着剤の溶剤に対する溶解性は、以下に示す方法により判断した。まず、各結着剤を、結着剤固形分５部に対して、以下に示す各溶剤９５部をそれぞれ添加し、十分混合した後に２５℃にて１時間静置した。この混合液を１５０００ｒｐｍにて遠心分離し、上澄み液を基材上に滴下した後、５０℃にて２時間乾燥させた。結着剤固形分が溶剤に溶解して上澄み液中に含まれているか否かによって、下記の基準にて判定した。結果を表１に示す。
（溶剤）
酢酸ブチル（ＳＰ値 ８．７）
メチルエチルケトン（ＳＰ値 ９．０）
シクロヘキサノン（ＳＰ値 ９．８）
（判定基準）
○：結着剤の固形分が認められない。（不溶）
×：結着剤の固形分が認められる。（可溶）
<Solvent solubility of binder>
The solubility of the binder in the solvent was determined by the following method. First, each binder was added to 95 parts of each of the following solvents with respect to 5 parts of the binder solid content, sufficiently mixed, and then allowed to stand at 25 ° C. for 1 hour. This mixed solution was centrifuged at 15000 rpm, and the supernatant was dropped onto the substrate, followed by drying at 50 ° C. for 2 hours. The determination was made according to the following criteria depending on whether the binder solid content was dissolved in the solvent and contained in the supernatant. The results are shown in Table 1.
(solvent)
Butyl acetate (SP value 8.7)
Methyl ethyl ketone (SP value 9.0)
Cyclohexanone (SP value 9.8)
(Criteria)
○: Solid content of the binder is not recognized. (Insoluble)
X: The solid content of a binder is recognized. (soluble)
＜カーボンブラック分散液の製造＞
表２に示す配合組成にて、カーボンブラック、結着剤および水を、それぞれ均一になるように撹拌混合した後に、１ｍｍのガラスビーズを用いてサンドミルにて５時間分散し、各カーボンブラック分散液を得た。尚、表２中の数値は部を表し、空欄は配合していないことを表す。
<Production of carbon black dispersion>
In the blending composition shown in Table 2, carbon black, binder and water were stirred and mixed so as to be uniform, and then dispersed in a sand mill for 5 hours using 1 mm glass beads. Got. In addition, the numerical value of Table 2 represents a part, and the blank represents that it is not mix | blended.
＜塗料用粒子の製造＞
表２に挙げた各カーボンブラック分散液を、それぞれ噴霧乾燥器（日本ビュッヒ社製、Ｂ−２９０）を用いて、噴霧温度１５０℃の条件にて噴霧時の吐出圧、吐出速度を調整し、噴霧乾燥することで、表３に示す塗料用粒子を得た。得られた塗料用粒子の平均粒子径を併せて表３に示す。
<Manufacture of particles for paint>
Each of the carbon black dispersions listed in Table 2 is adjusted using a spray drier (manufactured by Nippon Büch Co., Ltd., B-290) to adjust the discharge pressure and discharge speed during spraying at a spray temperature of 150 ° C. The particles for paint shown in Table 3 were obtained by spray drying. The average particle diameter of the obtained particles for paint is also shown in Table 3.
実施例１〜１８、比較例１〜４
＜塗料の調整＞
上記の方法で得られた塗料用粒子４部、塗膜形成用樹脂溶液４７部、硬化剤３部、メチルエチルケトン２３部、トルエン２３部を均一になるように撹拌混合し、塗料を得た。
Examples 1-18, Comparative Examples 1-4
<Adjustment of paint>
4 parts of paint particles obtained by the above method, 47 parts of a resin solution for forming a coating film, 3 parts of a curing agent, 23 parts of methyl ethyl ketone, and 23 parts of toluene were stirred and mixed uniformly to obtain a paint.
＜塗膜の製造＞
得られた塗料を、基材として１００μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム表面に、乾燥後の膜厚が２０μｍとなるように塗工し、２５℃で５分間静置した後、さらに１４０℃で３０分間加熱乾燥させ、塗膜を得た。
<Manufacture of coating film>
The obtained paint was applied to a 100 μm thick polyethylene terephthalate (PET) film surface as a base material so that the film thickness after drying was 20 μm, and allowed to stand at 25 ° C. for 5 minutes, and further at 140 ° C. The coating film was obtained by heating and drying for 30 minutes.
比較例５
ＣＢ−Ａ ２部、塗料用樹脂 ４７部、メチルエチルケトン ２３部、トルエン２３部を均一になるように撹拌混合した後に、１ｍｍのガラスビーズを用いてサンドミルにて５時間分散し、カーボンブラック分散液を得た。得られたカーボンブラック分散液 ９５．３３部対してシリカ ２部、硬化剤３部を添加し、均一になるように撹拌混合し、塗料を得た。得られた塗料を実施例１と同様な方法により塗膜を得た。
Comparative Example 5
2 parts of CB-A, 47 parts of coating resin, 23 parts of methyl ethyl ketone and 23 parts of toluene were stirred and mixed uniformly, and then dispersed in a sand mill for 5 hours using 1 mm glass beads to obtain a carbon black dispersion. Obtained. 2 parts of silica and 3 parts of a curing agent were added to 95.33 parts of the obtained carbon black dispersion, and the mixture was stirred and mixed uniformly to obtain a paint. A coating film was obtained from the obtained paint in the same manner as in Example 1.
比較例６
黒色着色アクリルビーズ４部、塗膜形成用樹脂溶液４７部、硬化剤３部、メチルエチルケトン２３部、トルエン２３部を均一になるように撹拌混合し、塗料を得た。得られた塗料を実施例１と同様な方法により塗膜を得た。
Comparative Example 6
4 parts of black colored acrylic beads, 47 parts of a resin solution for forming a coating film, 3 parts of a curing agent, 23 parts of methyl ethyl ketone, and 23 parts of toluene were stirred and mixed uniformly to obtain a paint. A coating film was obtained from the obtained paint in the same manner as in Example 1.
＜評価方法＞
得られた塗料および塗膜に対して、以下に示す分散安定性、光沢、耐摩耗性、隠蔽性について評価を行い、結果を表４に示した。
＜分散安定性＞
上記実施例および比較例に示した塗料を、それぞれガラス瓶にとり、密栓し、２５℃で静置した後の凝集物の有無を下記の基準に基づいて評価した。
◎：４日静置しても凝集物が認められなかった。極めて良好。
○：２〜３日静置後に凝集物の発生が認められた。良好。
×：１日静置後に凝集物の発生が認められた。不良。
<Evaluation method>
The obtained paint and coating film were evaluated for the following dispersion stability, gloss, abrasion resistance, and concealment properties, and the results are shown in Table 4.
<Dispersion stability>
The paints shown in the above Examples and Comparative Examples were each taken in a glass bottle, sealed, and the presence or absence of aggregates after standing at 25 ° C. was evaluated based on the following criteria.
(Double-circle): The aggregate was not recognized even if it left still for 4 days. Very good.
A: Generation of aggregates was observed after standing for 2 to 3 days. Good.
X: Generation of aggregates was observed after standing for 1 day. Bad.
＜光沢＞
上記の方法によって得られた塗膜について、光沢計（ＶＧ−７０００、日本電色工業社製）を用いてＪＩＳ Ｋ ５６００−４−７：１９９９に基づいて６０°鏡面光沢度の値（Ｇｓ）を測定し、下記の基準に基づいて評価した。
◎：６０°鏡面光沢度が０．１％以上５％未満。極めて良好。
○：６０°鏡面光沢度が５％以上１５％以下。良好。
×：６０°鏡面光沢度が１５％を超える。不良。
<Glossy>
About the coating film obtained by said method, 60 degree specular glossiness value (Gs) based on JISK5600-4-7: 1999 using a gloss meter (VG-7000, Nippon Denshoku Industries Co., Ltd.). Was measured and evaluated based on the following criteria.
A: 60 ° specular gloss is 0.1% or more and less than 5%. Very good.
○: 60 ° specular gloss is 5% or more and 15% or less. Good.
X: 60 degree specular glossiness exceeds 15%. Bad.
＜耐摩耗性＞
上記の方法によって得られた塗膜を２２ｃｍ×３ｃｍの大きさに切削して試験片を得た。この試験片を、染色堅ろう度摩擦試験機（ＦＲ−２、スガ試験機社製）を用いてＪＩＳ Ｌ０８４９：２０１３に規定された摩擦試験機 ＩＩ 形（学振形）法に従い塗膜表面を摩擦し、摩擦試験を行った。摩擦試験前後それぞれの塗膜について６０°鏡面光沢度を測定した。摩擦試験前の６０°鏡面光沢度と摩擦試験後の６０°鏡面光沢度との差の絶対値（ΔＧｓ）を、下記の基準に基づいて判定した。
◎：ΔＧｓが０．１以上１未満。極めて良好。
○：ΔＧｓが１以上５以下。良好。
×：ΔＧｓが５を超える。不良。
<Abrasion resistance>
The coating film obtained by the above method was cut into a size of 22 cm × 3 cm to obtain a test piece. The test piece was rubbed against the surface of the paint film using a dyeing fastness friction tester (FR-2, manufactured by Suga Test Instruments Co., Ltd.) according to the friction tester II type (Gakuken type) defined in JIS L0849: 2013. Then, a friction test was performed. The 60 ° specular glossiness of each coating film before and after the friction test was measured. The absolute value (ΔGs) of the difference between the 60 ° specular gloss before the friction test and the 60 ° specular gloss after the friction test was determined based on the following criteria.
A: ΔGs is 0.1 or more and less than 1. Very good.
○: ΔGs is 1 or more and 5 or less. Good.
X: ΔGs exceeds 5. Bad.
＜隠蔽性＞
上記の方法によって得られた塗膜について、マクベス濃度計（Ｘ−Ｒｉｔｅ ３６１Ｔ、サカタインクスエンジニアリング株式会社）を用いて光学濃度（ＯＤ）を測定した。なお、ＯＤとは、隠蔽性を示す数値であり、数値が大きい程、隠蔽性が高く良好である。隠蔽性に関しては、下記の基準に従って評価した。
◎：５．０以上（隠蔽性が著しく高い）
○：３．０以上５．０未満（隠蔽性が高い）
×：３．０未満（隠蔽性が低い）
<Concealment>
About the coating film obtained by said method, the optical density (OD) was measured using the Macbeth densitometer (X-Rite 361T, Sakata Inx Engineering Co., Ltd.). The OD is a numerical value indicating the concealing property. The larger the numerical value, the higher the concealing property and the better. Concealability was evaluated according to the following criteria.
A: 5.0 or more (concealment is remarkably high)
○: 3.0 or more and less than 5.0 (high concealment)
X: Less than 3.0 (low concealment)
表４に示すように、実施例１〜１８では、塗料としての分散安定性、塗膜としての光沢、耐摩耗性共に良好だった。特に実施例１〜８、１１〜１８では、塗料としての分散安定性、塗膜の耐摩耗性からより好ましい。さらに実施例１７、１８は、隠蔽性からより好ましい。 As shown in Table 4, in Examples 1 to 18, the dispersion stability as the paint, the gloss as the coating film, and the wear resistance were good. Especially in Examples 1-8, 11-18, it is more preferable from the dispersion stability as a coating material, and the abrasion resistance of a coating film. Furthermore, Examples 17 and 18 are more preferable from the concealment property.
Claims (8)
It is a coating film containing paint particles containing carbon black and a binder, and the content of carbon black with respect to 100 parts by mass in total of carbon black and binder is 80 to 90 parts by mass, An average particle diameter of the particles for paint is 5 to 20 μm, and a 60 ° specular gloss (Gs) of the coating film is 0.1 to 15%.
The coating film according to claim 1, wherein the difference (ΔGs) between the 60 ° specular gloss before the friction test and the 60 ° specular gloss after the friction test is 0.1 to 5%.
The coating film according to claim 1, wherein the binder is insoluble in a solvent having a Fedors solubility parameter (SP value) of 10 or less.
The coating film according to any one of claims 1 to 3, wherein the binder is at least one selected from the group consisting of a polyvinyl alcohol resin, a polyvinyl acetal resin, a polyvinyl pyrrolidone resin, and an acrylic resin having an acid value of 100 mgKOH / g or more.
A paint comprising particles for paint containing carbon black and a binder, wherein the carbon black content is 80 to 90 parts by mass with respect to a total of 100 parts by mass of the carbon black and the binder, A paint having an average particle diameter of 5 to 20 μm.
The paint according to claim 5, wherein the 60 ° specular gloss (Gs) of the coating film formed from the paint is 0.1 to 15%.
Particles for paint containing carbon black and a binder, wherein the carbon black content is 80 to 90 parts by mass with respect to a total of 100 parts by mass of the carbon black and the binder, and the average particle size is 5 to 20 μm. Particles for paint characterized by
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04370160A (en) * | 1991-06-15 | 1992-12-22 | Nippon Shokubai Co Ltd | Colored spherical fine particle, production and use thereof |
| JP3064083U (en) * | 1999-04-02 | 1999-12-14 | 株式会社呉竹精昇堂 | Calligraphy ink |
| JP2000281955A (en) * | 1999-04-01 | 2000-10-10 | Kuretake Seishiyoudou:Kk | Material, such as sumi, used for calligraphy or painting and production thereof |
| JP2005517074A (en) * | 2002-02-04 | 2005-06-09 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment preparation |
| JP2005526867A (en) * | 2002-02-01 | 2005-09-08 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment granules |
| JP2012509969A (en) * | 2008-11-27 | 2012-04-26 | エボニック カーボンブラック ゲゼルシャフト ミット ベシュレンクテル ハフツング | Pigment granules, their production method and use |
| JP2015085561A (en) * | 2013-10-29 | 2015-05-07 | 株式会社神戸製鋼所 | Black coated metal plate |
-
2017
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04370160A (en) * | 1991-06-15 | 1992-12-22 | Nippon Shokubai Co Ltd | Colored spherical fine particle, production and use thereof |
| JP2000281955A (en) * | 1999-04-01 | 2000-10-10 | Kuretake Seishiyoudou:Kk | Material, such as sumi, used for calligraphy or painting and production thereof |
| JP3064083U (en) * | 1999-04-02 | 1999-12-14 | 株式会社呉竹精昇堂 | Calligraphy ink |
| JP2005526867A (en) * | 2002-02-01 | 2005-09-08 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment granules |
| JP2005517074A (en) * | 2002-02-04 | 2005-06-09 | ビーエーエスエフ アクチェンゲゼルシャフト | Pigment preparation |
| JP2012509969A (en) * | 2008-11-27 | 2012-04-26 | エボニック カーボンブラック ゲゼルシャフト ミット ベシュレンクテル ハフツング | Pigment granules, their production method and use |
| JP2015085561A (en) * | 2013-10-29 | 2015-05-07 | 株式会社神戸製鋼所 | Black coated metal plate |
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