JP2022158089A - Thermal barrier topcoat composition and thermal barrier multi-layer coating formation method - Google Patents
Thermal barrier topcoat composition and thermal barrier multi-layer coating formation method Download PDFInfo
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- JP2022158089A JP2022158089A JP2021062752A JP2021062752A JP2022158089A JP 2022158089 A JP2022158089 A JP 2022158089A JP 2021062752 A JP2021062752 A JP 2021062752A JP 2021062752 A JP2021062752 A JP 2021062752A JP 2022158089 A JP2022158089 A JP 2022158089A
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- thermal barrier
- topcoat composition
- barrier topcoat
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、遮熱上塗塗料組成物および遮熱複層塗膜形成方法に関する。 TECHNICAL FIELD The present invention relates to a thermal barrier topcoat composition and a method for forming a thermal barrier multilayer coating film.
近年、太陽光や熱を反射・吸収して建物内部や路面の温度上昇を抑え、冷房などの設備に要するエネルギーを低減させ、そして地球温暖化を抑制する方策として遮熱塗料が注目されている。 In recent years, heat-shielding paints have been attracting attention as a means of reducing the temperature rise inside buildings and road surfaces by reflecting and absorbing sunlight and heat, reducing the energy required for air-conditioning and other equipment, and curbing global warming. .
例えば、特許文献1では、建築物外装面を構成する遮熱断熱積層体であって、外装面の屋内側から屋外側へ向かって、基材層(A)、結合材及び中空粒子を含有する下塗材により形成される断熱性下塗層(B)、非水系合成樹脂(p)、炭素数1~2のアルキル基と炭素数3以上のアルキル基が、95:5~50:50の当量比率で混在する変性シリケート化合物(q)、及び赤外線反射性粉体(r)を必須成分とし、前記非水系合成樹脂(p)の固形分100重量部に対し、前記変性シリケート化合物(q)をSiO2換算で0.1~20重量部、前記赤外線反射性粉体(r)を1~200重量部含む被覆材により形成される上塗層(C)を有することを特徴とする遮熱断熱積層体について開示されている。 For example, Patent Document 1 discloses a heat shielding and heat insulating laminate constituting an exterior surface of a building, which contains a base layer (A), a binder, and hollow particles from the indoor side to the outdoor side of the exterior surface. A heat insulating undercoat layer (B) formed from the undercoat material, a non-aqueous synthetic resin (p), and an alkyl group having 1 to 2 carbon atoms and an alkyl group having 3 or more carbon atoms in an equivalent ratio of 95:5 to 50:50. The modified silicate compound (q) and the infrared reflective powder (r) mixed at a ratio are essential components, and the modified silicate compound (q) is added to 100 parts by weight of the solid content of the non-aqueous synthetic resin (p). A heat shield and heat insulation laminate characterized by having a topcoat layer (C) formed of a coating material containing 0.1 to 20 parts by weight in terms of SiO2 and 1 to 200 parts by weight of the infrared reflective powder (r). disclosed for the body.
車両に塗装される塗料に対しても、遮熱性を有することによる省エネルギーのメリットは大きい。中でも運送用車両、鉄道車両、大型車両等は、その車体サイズの大きさに起因して冷房にかかるエネルギーが膨大となることから、より遮熱性が重要となる。 The heat-shielding properties of paints applied to vehicles also have the advantage of saving energy. In particular, transport vehicles, railroad vehicles, large vehicles, and the like require an enormous amount of energy for cooling due to their large vehicle body size, so heat shielding is more important.
また、運送用車両に遮熱性や断熱性を有する塗料を適用すると、運搬物を太陽熱による温度上昇から守ることができる。一方、生コンクリートを運搬するアジテータ車等、運搬物が高温である場合、特許文献1の積層体のように断熱性を有すると、逆に内部が過剰に発熱して品質が低下する恐れがある。 In addition, by applying a heat-shielding or heat-insulating paint to a vehicle for transportation, it is possible to protect the goods to be transported from temperature rise due to solar heat. On the other hand, when the object to be conveyed is high temperature, such as an agitator truck for conveying ready-mixed concrete, if the laminated body of Patent Document 1 has heat insulating properties, the inside may generate excessive heat and the quality may deteriorate. .
特許文献2では、高速鉄道車両の表面に近赤外線反射性能を付与する方法であって、表面に近赤外線反射性能を有する塗膜を形成することによるものであって、前記塗膜は、色調を変えずに780~2100nmの波長域における日射反射率を9%以上増大させるものであることを特徴とする近赤外線反射性能を付与する方法について開示されている。 In Patent Document 2, a method for imparting near-infrared reflective performance to the surface of a high-speed railway vehicle is provided by forming a coating film having near-infrared reflective performance on the surface, and the coating film has a color tone. A method for imparting near-infrared reflective performance is disclosed, characterized in that the solar reflectance in the 780-2100 nm wavelength region is increased by 9% or more without change.
しかし、十分な近赤外線反射性能を付与するためには膜厚が必要であり、塗装回数が増えて作業性が低下するという課題があった。また、厚膜の場合には塗膜の断熱性が上がるため、内部の熱が放熱しにくくなり、アジテータ車等の運搬車両への適用には不適であった。 However, in order to impart sufficient near-infrared reflective performance, a film thickness is required, and there is a problem that the number of times of coating increases and workability decreases. In addition, in the case of a thick film, since the heat insulating property of the coating film increases, it becomes difficult to dissipate the internal heat, making it unsuitable for application to transportation vehicles such as agitator vehicles.
一方、作業性の向上と遮熱性能を両立させるために塗装時の不揮発分濃度を上げると、塗膜の仕上がり性及び密着性が低下する不具合があった。 On the other hand, if the concentration of non-volatile matter during coating is increased in order to achieve both improved workability and heat shielding performance, there is a problem that the finish and adhesion of the coating film are reduced.
本発明が解決しようとする課題は、塗装作業性、仕上がり性、密着性に優れ、厚膜でなくても下地に影響されず良好な遮熱性を有する遮熱上塗塗料組成物を提供することである。 The problem to be solved by the present invention is to provide a heat-shielding topcoat composition that is excellent in coating workability, finish and adhesion, and has good heat-shielding properties without being affected by the base even if it is not a thick film. be.
発明者等は、上記課題を解決するために鋭意検討した結果、アクリルポリオール(a)、ポリエステルポリオール(b)及び硬化剤を含む樹脂、酸化チタンを含む顔料、並びに有機溶媒を含有する溶剤系遮熱上塗塗料組成物であって、塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であって、酸化チタンの含有量が樹脂固形分100質量部を基準にして80~145質量部である遮熱上塗塗料組成物によって、前記課題の解決が達成できることを見出し、本発明を完成するに至った。即ち、本発明は、以下の遮熱上塗塗料組成物を提供するものである。
項1.アクリルポリオール(a)、ポリエステルポリオール(b)及び硬化剤を含む樹脂、酸化チタンを含む顔料、並びに有機溶媒を含有する溶剤系遮熱上塗塗料組成物であって、
塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であって、
酸化チタンの含有量が樹脂固形分100質量部を基準にして80~145質量部である、遮熱上塗塗料組成物。
項2.アクリルポリオール(a)、ポリエステルポリオール(b)及び硬化剤を含む樹脂、酸化チタンを含む顔料、並びに有機溶媒を含有する溶剤系遮熱上塗塗料組成物であって、
被塗物上に形成した塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であって、
酸化チタンの含有量が樹脂固形分100質量部を基準にして40~145質量部であり、
さらに構造中に金属イオンを有さない有機顔料を樹脂固形分100質量部を基準にして5~20質量部含有する、遮熱上塗塗料組成物。
項3.カーボンブラックの含有量が、樹脂固形分100質量部を基準にして0.1質量部以下である、項1または2に記載の遮熱上塗塗料組成物。
項4.アクリルポリオール(a)が、スチレン、有橋脂環式炭化水素基含有重合性不飽和モノマーおよび水酸基含有重合性不飽和モノマーを構成モノマー成分として含有し、スチレンおよび有橋脂環式炭化水素基を有する重合性不飽和モノマーの合計量が構成モノマー成分100質量部を基準にして30質量部以上である、項1~3のいずれか1項に記載の遮熱上塗塗料組成物。
項5.ポリエステルポリオール(b)が、数平均分子量が500~10,000、水酸基価が0.5~200mgKOH/g、ガラス転移温度が-70~0℃の範囲内である、項1~4のいずれか1項に記載の遮熱上塗塗料組成物。
項6.ポリエステルポリオール(b)の含有量が、樹脂固形分100質量部を基準にして1~70質量部である、項1~5のいずれか1項に記載の遮熱上塗塗料組成物。
項7.アクリルポリオール(a)及びポリエステルポリオール(b)を含む樹脂、酸化チタンを含む顔料、並びに有機溶媒を含有する主剤成分(I)と、 ポリイソシアネート化合物を含む硬化剤成分(II)と、を含有する多液型塗料組成物である、項1~6のいずれか1項に記載の遮熱上塗塗料組成物。
項8.ブロックイソシアネート化合物又はメラミン化合物を含む樹脂を含有する1液型塗料組成物である、項1~6のいずれか1項に記載の遮熱上塗塗料組成物。
項9.塗装時の不揮発分が45質量%以上80質量%以下である、項1~8のいずれか1項に記載の遮熱上塗塗料組成物。
項10.被塗物上に、下塗塗料組成物を塗装して下塗塗膜を形成し、該下塗塗膜上に項1~9のいずれか1項に記載の遮熱上塗塗料組成物を塗装して上塗塗膜を形成する、遮熱複層塗膜形成方法。
項11.前記下塗塗膜の明度が50以上である、項10に記載の遮熱複層塗膜形成方法。
項12.前記被塗物が、鉄道車両、架装大型車両、特殊車両、及び貨物自動車から選ばれる少なくとも1種の車両、建設機械、もしくは構造物である、項10~11のいずれか1項に記載の遮熱複層塗膜形成方法。
項13.前記被塗物がアジテータ車のドラム部分である、項10~12のいずれか1項に記載の遮熱複層塗膜形成方法。
As a result of intensive studies to solve the above problems, the inventors have found that a resin containing acrylic polyol (a), polyester polyol (b) and a curing agent, a pigment containing titanium oxide, and a solvent-based shield containing an organic solvent. A thermal topcoat composition in which the near-infrared wavelength region solar reflectance of the coating film is 80% or more and / or the brightness is 85 or more, and the content of titanium oxide is based on 100 parts by mass of the resin solid content The inventors have found that the above problems can be solved by a thermal barrier topcoat composition containing 80 to 145 parts by mass, and have completed the present invention. That is, the present invention provides the following thermal barrier topcoat composition.
Section 1. A solvent-based thermal barrier topcoat composition containing an acrylic polyol (a), a resin containing a polyester polyol (b) and a curing agent, a pigment containing titanium oxide, and an organic solvent,
The near-infrared wavelength region solar reflectance of the coating film is 80% or more and / or the brightness is 85 or more,
A thermal barrier topcoat composition having a titanium oxide content of 80 to 145 parts by mass based on 100 parts by mass of resin solids.
Section 2. A solvent-based thermal barrier topcoat composition containing an acrylic polyol (a), a resin containing a polyester polyol (b) and a curing agent, a pigment containing titanium oxide, and an organic solvent,
The near-infrared wavelength region solar reflectance of the coating film formed on the object to be coated is 80% or more and / or the brightness is 85 or more,
The content of titanium oxide is 40 to 145 parts by mass based on 100 parts by mass of resin solids,
A thermal barrier topcoat composition further containing 5 to 20 parts by mass of an organic pigment having no metal ion in its structure based on 100 parts by mass of the solid content of the resin.
Item 3. Item 3. The thermal barrier topcoat composition according to item 1 or 2, wherein the content of carbon black is 0.1 parts by mass or less based on 100 parts by mass of resin solids.
Section 4. The acrylic polyol (a) contains styrene, a bridged alicyclic hydrocarbon group-containing polymerizable unsaturated monomer and a hydroxyl group-containing polymerizable unsaturated monomer as constituent monomer components, and comprises styrene and a bridged alicyclic hydrocarbon group. The thermal barrier topcoat composition according to any one of Items 1 to 3, wherein the total amount of the polymerizable unsaturated monomers is 30 parts by mass or more based on 100 parts by mass of the constituent monomer components.
Item 5. Any one of Items 1 to 4, wherein the polyester polyol (b) has a number average molecular weight of 500 to 10,000, a hydroxyl value of 0.5 to 200 mgKOH/g, and a glass transition temperature of -70 to 0°C. 2. The thermal barrier topcoat composition according to item 1.
Item 6. The thermal barrier topcoat composition according to any one of Items 1 to 5, wherein the content of the polyester polyol (b) is 1 to 70 parts by mass based on 100 parts by mass of the resin solid content.
Item 7. It contains a main component (I) containing a resin containing acrylic polyol (a) and polyester polyol (b), a pigment containing titanium oxide, and an organic solvent, and a curing agent component (II) containing a polyisocyanate compound. Item 7. The thermal barrier topcoat composition according to any one of Items 1 to 6, which is a multicomponent coating composition.
Item 8. 7. The thermal barrier topcoat composition according to any one of Items 1 to 6, which is a one-part coating composition containing a resin containing a blocked isocyanate compound or a melamine compound.
Item 9. Item 9. The thermal barrier topcoat composition according to any one of Items 1 to 8, wherein the non-volatile content at the time of coating is 45% by mass or more and 80% by mass or less.
Item 10. An undercoat paint composition is applied onto an object to be coated to form an undercoat paint film, and the thermal barrier topcoat paint composition according to any one of Items 1 to 9 is applied onto the undercoat paint film to topcoat. A method for forming a heat-shielding multilayer coating film, comprising forming a coating film.
Item 11. Item 11. The method for forming a heat-shielding multilayer coating film according to Item 10, wherein the brightness of the undercoat film is 50 or more.
Item 12. Item 10. Item 11, wherein the object to be coated is at least one vehicle, construction machine, or structure selected from railway vehicles, large-sized vehicles, special vehicles, and freight vehicles. A method for forming a heat-insulating multilayer coating film.
Item 13. 13. The method for forming a heat-shielding multilayer coating film according to any one of items 10 to 12, wherein the object to be coated is a drum portion of an agitator wheel.
本発明の遮熱上塗塗料組成物によれば、塗装作業性、仕上がり性、密着性に優れ、厚膜でなくても下地に影響されず良好な遮熱性を有する遮熱塗膜を提供できる。遮熱性と放熱性を併せ持ち、光沢が高い塗膜が得られるため、アジテータ車等のドラム部への適用も可能である。 According to the thermal barrier topcoat composition of the present invention, it is possible to provide a thermal barrier coating film which is excellent in coating workability, finish, and adhesion, and which has good thermal barrier properties without being affected by the substrate even if the film is not thick. It has both heat-shielding and heat-dissipating properties, and can be applied to the drum part of an agitator wheel, etc., because a highly glossy coating film can be obtained.
本明細書において、「(メタ)アクリレート」は、アクリレート及び/又はメタクリレートを意味し、「(メタ)アクリル酸」は、アクリル酸及び/又はメタクリル酸を意味する。また、「(メタ)アクリロイル」は、アクリロイル及び/又はメタクリロイルを意味する。また、「(メタ)アクリルアミド」は、アクリルアミド及び/又はメタクリルアミドを意味する。 As used herein, "(meth)acrylate" means acrylate and/or methacrylate, and "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. "(Meth)acrylamide" means acrylamide and/or methacrylamide.
本発明の遮熱上塗塗料組成物は、塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であることが特徴である。近赤外波長域日射反射率が80%以上である塗膜は、近赤外波長域の太陽光を高効率で反射するために遮熱性が高い。また、明度が85以上である塗膜は、可視波長域の太陽光を高効率で反射するために遮熱性が高い。塗膜の近赤外波長域日射反射率が80%以上かつ明度が85以上である塗膜は、いずれか片方のみを満たす塗膜と比較して、より遮熱性能が高く好ましい。 The thermal barrier topcoat composition of the present invention is characterized in that the coating film has a near-infrared wavelength region solar reflectance of 80% or more and/or a brightness of 85 or more. A coating film having a near-infrared wavelength region solar reflectance of 80% or more reflects sunlight in the near-infrared wavelength region with high efficiency, and thus has high heat shielding properties. Moreover, a coating film having a lightness of 85 or more reflects sunlight in the visible wavelength range with high efficiency, and thus has high heat shielding properties. A coating film having a near-infrared wavelength region solar reflectance of 80% or more and a brightness of 85 or more is preferable because it has higher heat-shielding performance than a coating film satisfying only one of them.
本発明において、近赤外波長域日射反射率は、 「SolidSpec-3700」(商品名、島津製作所社製)を用いてJIS K 5602:2008に準じて測定を行った。明度は「BYK-mac i」(商品名、BYK社製)を使用して測定を行った。 In the present invention, the near-infrared wavelength region solar reflectance was measured according to JIS K 5602:2008 using "SolidSpec-3700" (trade name, manufactured by Shimadzu Corporation). The brightness was measured using "BYK-mac i" (trade name, manufactured by BYK).
なお、本発明において、塗膜の遮熱性能は、下記遮熱性能評価試験によって評価した。
<遮熱性能評価試験方法>
70×150×0.3cmのブリキ板上に塗膜を作成し、試験塗板とする。断熱材の上に試験塗板と標準黒色塗板(試験塗板と同サイズのブリキ板上に黒色塗料(レタンエコトップ黒:関西ペイント社製)を塗装して作成)を置いて、断熱材の上方50cmの距離に設置したメタルハライドランプを照射し、標準黒色塗板の温度が80℃に達した時点における試験塗板の温度を測定する。
In addition, in the present invention, the heat shielding performance of the coating film was evaluated by the following heat shielding performance evaluation test.
<Heat insulation performance evaluation test method>
A coating film is prepared on a 70 x 150 x 0.3 cm tin plate and used as a test coating plate. Place a test coated plate and a standard black coated plate (prepared by coating a tin plate of the same size as the test coated plate with black paint (Retan Eco Top Black: manufactured by Kansai Paint Co., Ltd.)) on top of the insulating material, and place it 50 cm above the insulating material. The temperature of the test coated plate is measured when the temperature of the standard black coated plate reaches 80°C.
1.樹脂
1-1.アクリルポリオール(a)
本発明の遮熱上塗塗料組成物は、樹脂成分としてアクリルポリオール(a)を含有する。アクリルポリオールとは、水酸基含有重合性不飽和モノマーを構成モノマー成分として含有するアクリル樹脂であり、ラジカル重合、アニオン重合、カチオン重合、リビング重合等の従来公知の合成方法によって合成することができる。
1. resin
1-1. acrylic polyol (a)
The thermal barrier topcoat composition of the present invention contains an acrylic polyol (a) as a resin component. Acrylic polyol is an acrylic resin containing a hydroxyl group-containing polymerizable unsaturated monomer as a constituent monomer component, and can be synthesized by conventionally known synthesis methods such as radical polymerization, anionic polymerization, cationic polymerization, and living polymerization.
水酸基含有重合性不飽和モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、2,3-ジヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート等の、多価アルコールとアクリル酸またはメタクリル酸とのモノエステル化物;上記多価アルコールとアクリル酸またはメタクリル酸とのモノエステル化物にε-カプロラクトンを開環重合した化合物、例えば、「プラクセルFA-1」、「プラクセルFA-2」、「プラクセルFA-3」、「プラクセルFA-4」、「プラクセルFA-5」、「プラクセルFM-1」、「プラクセルFM-2」、「プラクセルFM-3」、「プラクセルFM-4」、「プラクセルFM-5」(以上、いずれもダイセル化学(株)製、商品名)等の商品名で表されるもの等を挙げることができ、単独で、または2種以上を組み合わせて使用することができる。 Examples of hydroxyl group-containing polymerizable unsaturated monomers include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol. Monoesterified products of polyhydric alcohols and acrylic acid or methacrylic acid, such as mono(meth)acrylates; Compounds obtained by ring-opening polymerization of ε-caprolactone on the monoesterified products of polyhydric alcohols and acrylic acid or methacrylic acid, such as , "Praxel FA-1", "Praxel FA-2", "Praxel FA-3", "Praxel FA-4", "Praxel FA-5", "Praxel FM-1", "Praxel FM-2", Examples include those represented by trade names such as "Plaxel FM-3", "Plaxel FM-4", and "Plaxel FM-5" (all of which are trade names manufactured by Daicel Chemical Industries, Ltd.). , can be used alone or in combination of two or more.
アクリルポリオール(a)における、水酸基含有重合性不飽和モノマーの含有量としては、塗膜の硬度、仕上がり性の観点から、構成するモノマー成分100質量部を基準にして5~40質量部、好ましくは10~30質量部の範囲内であることが望ましい。 The content of the hydroxyl group-containing polymerizable unsaturated monomer in the acrylic polyol (a) is 5 to 40 parts by mass, preferably 5 to 40 parts by mass, based on 100 parts by mass of the constituent monomer components, from the viewpoint of the hardness and finish of the coating film. It is desirable to be in the range of 10 to 30 parts by mass.
本発明におけるアクリルポリオール(a)は、アクリルポリオール(a)を構成するモノマー成分として、水酸基含有重合性不飽和モノマーと共重合可能であるその他の重合性不飽和モノマーをその成分の一部として含むことができる。中でも、スチレン及び有橋脂環式炭化水素基を有する重合性不飽和モノマーを構成モノマー成分として含有するものであることが、塗膜の仕上がり性の観点から好ましい。 The acrylic polyol (a) in the present invention contains, as a monomer component constituting the acrylic polyol (a), another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer as part of its component. be able to. Among them, those containing styrene and a polymerizable unsaturated monomer having a bridged alicyclic hydrocarbon group as constituent monomer components are preferable from the viewpoint of the finish of the coating film.
有橋脂環式炭化水素基を有する重合性不飽和モノマーとしては、炭素数が10~20の有橋脂環式炭化水素基と重合性不飽和基を有する化合物を挙げることができ、炭素数が10~20の有橋脂環式炭化水素基の代表例として、イソボルニル基、トリシクロデカニル基、アダマンチル基などを挙げることができる。該モノマーの具体例としては、例えば、イソボルニル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、3,5-ジメチルアダマンチル(メタ)アクリレート、3-テトラシクロドデシル(メタ)アクリレート等を挙げることができ、単独でまたは2種以上組み合わせて使用することができる。 Examples of the polymerizable unsaturated monomer having a bridged alicyclic hydrocarbon group include compounds having a bridged alicyclic hydrocarbon group having 10 to 20 carbon atoms and a polymerizable unsaturated group. Representative examples of the bridged alicyclic hydrocarbon group having 10 to 20 include an isobornyl group, a tricyclodecanyl group and an adamantyl group. Specific examples of the monomer include isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, adamantyl (meth)acrylate, 3,5-dimethyladamantyl (meth)acrylate, and 3-tetracyclododecyl (meth)acrylate. Acrylate and the like can be mentioned, and can be used alone or in combination of two or more.
スチレン及び有橋脂環式炭化水素基を有する重合性不飽和モノマーの合計含有量としては、構成するモノマー成分100質量部を基準にして30質量部以上であることが好ましく、その量が特に45質量部以上であることが、塗膜の光沢および硬度の点からより好ましい。 The total content of styrene and polymerizable unsaturated monomers having a bridged alicyclic hydrocarbon group is preferably 30 parts by mass or more based on 100 parts by mass of the constituent monomer components, and particularly 45 parts by mass. Part by mass or more is more preferable from the viewpoint of the gloss and hardness of the coating film.
スチレンの含有量としては、構成するモノマー成分100質量部を基準にして5~60質量部、好ましくは10~50質量部の範囲内にあることが、塗膜の光沢の点から好適である。 The content of styrene is preferably in the range of 5 to 60 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the constituent monomer component, from the viewpoint of the gloss of the coating film.
有橋脂環式炭化水素基を有する重合性不飽和モノマーの含有量としては、構成するモノマー成分100質量部を基準にして5~50質量部、好ましくは10~40質量部の範囲内にあることが、塗膜の光沢の点から好適である。 The content of the polymerizable unsaturated monomer having a bridged alicyclic hydrocarbon group is in the range of 5 to 50 parts by mass, preferably 10 to 40 parts by mass, based on 100 parts by mass of the constituting monomer component. is preferable from the point of view of the gloss of the coating film.
本発明におけるアクリルポリオール(a)は、アクリルポリオール(a)を構成するモノマー成分として、上述のスチレン、有橋脂環式炭化水素基を有する重合性不飽和モノマー以外にも、水酸基含有重合性不飽和モノマーと共重合可能であるその他の重合性不飽和モノマーをその成分の一部として含むことができる。かかるその他の重合性不飽和モノマーとしては、具体的には、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、t-ブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、n-ヘプチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-ノニル(メタ)アクリレート、n-デシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、n-テトラデシル(メタ)アクリレート、n-ヘキサデシル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、「イソステアリルアクリレート」(大阪有機化学社製)等のアルキル基を有する(メタ)アクリレート;シクロヘキシル(メタ)アクリレート等のシクロアルキル基を有する(メタ)アクリレート;(メタ)アクリル酸、マレイン酸、クロトン酸、β-カルボキシエチルアクリレート等のカルボキシル基含有重合性不飽和モノマー;グリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチル(メタ)アクリレートなどのエポキシ基含有重合性不飽和モノマー;N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレート等のアミノアルキル(メタ)アクリレート;アクリルアミド、メタアクリルアミド、N,N-ジメチルアミノエチル(メタ)アクリルアミド、N,N-ジエチルアミノエチル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、N-メチロールアクリルアミド、N-メチロールアクリルアミドメチルエーテル、N-メチロールアクリルアミドブチルエーテルなどの(メタ)アクリルアミドまたはその誘導体;アクリロニトリル、メタクリロニトリル、酢酸ビニル、ベオバモノマー(シェル化学社製)、ビニルトルエン、α-メチルスチレンなどが挙げられる。これらの化合物は、1種でまたは2種以上を組合せて使用することができる。 In the acrylic polyol (a) of the present invention, as monomer components constituting the acrylic polyol (a), in addition to the above-mentioned styrene and a polymerizable unsaturated monomer having a bridged alicyclic hydrocarbon group, a hydroxyl group-containing polymerizable unsaturated monomer Other polymerizable unsaturated monomers that are copolymerizable with the saturated monomers can be included as part of the composition. Specific examples of such other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-octadecyl ( (Meth)acrylates having an alkyl group such as meth)acrylate, stearyl (meth)acrylate, and “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.); (meth)acrylates having a cycloalkyl group such as cyclohexyl (meth)acrylate; (Meth)acrylic acid, maleic acid, crotonic acid, carboxyl group-containing polymerizable unsaturated monomers such as β-carboxyethyl acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate Polymerizable unsaturated monomers; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate; acrylamide , methacrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-methylolacrylamide, N-methylolacrylamide methyl ether , N-methylolacrylamide butyl ether, and derivatives thereof; acrylonitrile, methacrylonitrile, vinyl acetate, Veova monomer (manufactured by Shell Chemical Co., Ltd.), vinyl toluene, α-methylstyrene, and the like. These compounds can be used singly or in combination of two or more.
本発明において、上記アクリルポリオール(a)は、重量平均分子量が2,000~40,000、好ましくは6,000~15,000の範囲内にあることが、遮熱上塗塗料組成物の塗装作業性の点から好適である。 In the present invention, the acrylic polyol (a) has a weight average molecular weight in the range of 2,000 to 40,000, preferably 6,000 to 15,000. It is suitable from the viewpoint of sex.
本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフ(東ソー(株)社製、「HLC8120GPC」)で測定した重量平均分子量をポリスチレンの重量平均分子量を基準にして換算した値である。カラムは、「TSKgel G-4000H×L」、「TSKgel G-3000H×L」、「TSKgel G-2500H×L」、「TSKgel G-2000H×L」(いずれも東ソー(株)社製、商品名)の4本を用い、移動相;テトラヒドロフラン、測定温度;40℃、流速;1cc/分、検出器;RIの条件で行ったものである。 As used herein, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatography (manufactured by Tosoh Corporation, "HLC8120GPC") based on the weight average molecular weight of polystyrene. The columns are “TSKgel G-4000H×L”, “TSKgel G-3000H×L”, “TSKgel G-2500H×L”, “TSKgel G-2000H×L” (all manufactured by Tosoh Corporation, trade name ), mobile phase: tetrahydrofuran, measurement temperature: 40° C., flow rate: 1 cc/min, detector: RI.
本発明において、上記アクリルポリオール(a)は、水酸基価が20~200mgKOH/g、好ましくは30~170mgKOH/gの範囲内であることが、塗膜の硬化性および仕上り性の観点から好適である。 In the present invention, the acrylic polyol (a) preferably has a hydroxyl value of 20 to 200 mgKOH/g, preferably 30 to 170 mgKOH/g, from the viewpoint of the curability and finish of the coating film. .
また、アクリルポリオール(a)のガラス転移温度としては、30~90℃、好ましくは40~80℃の範囲内にあることが、塗膜の硬度の点から好適である。 The glass transition temperature of the acrylic polyol (a) is preferably in the range of 30 to 90°C, preferably 40 to 80°C, from the viewpoint of the hardness of the coating film.
本明細書において、ガラス転移温度(絶対温度)は、下記式により算出される値である。
1/Tg=W1/T1+W2/T2+・・・Wn/Tn
式中、W1、W2・・・Wnは各モノマーの質量%〔=(各モノマーの配合量/モノマー全質量)×100〕であり、T1、T2・・・Tnは各モノマーのホモポリマーのガラス転移温度(絶対温度)である。なお、各モノマーのホモポリマーのガラス転移温度は、Polymer Hand Book (4th Edition)による値であり、該文献に記載されていないモノマーのホモポリマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が5万程度になるようにして合成したものを試料とし、そのガラス転移温度を示差走査型熱分析「DSC-50Q型」(商品名、島津製作所社製)を用いて、試料を測定カップにとり、真空吸引して溶剤を除去した後、3℃/分の昇温速度で-100℃~+100℃の範囲で熱量変化を測定し、低温側の最初のベースラインの変化点を使用する。
As used herein, the glass transition temperature (absolute temperature) is a value calculated by the following formula.
1/Tg=W1/T1+W2/T2+...Wn/Tn
In the formulas, W1, W2, ... Wn are mass% of each monomer [=(mixed amount of each monomer/total mass of monomer) x 100], and T1, T2, ... Tn are homopolymer glass of each monomer. is the transition temperature (absolute temperature). The glass transition temperature of the homopolymer of each monomer is the value according to Polymer Hand Book (4th Edition), and the glass transition temperature of the homopolymer of the monomer not described in the literature is the weight average of the homopolymer of the monomer. A sample synthesized with a molecular weight of about 50,000 is used, and the glass transition temperature is measured using a differential scanning thermal analysis "DSC-50Q type" (trade name, manufactured by Shimadzu Corporation). After removing the solvent by vacuum suction, the calorific value change is measured in the range of −100° C. to +100° C. at a heating rate of 3° C./min, and the first baseline change point on the low temperature side is used.
本発明の遮熱上塗塗料組成物におけるアクリルポリオール(a)の含有量としては、樹脂固形分100質量部を基準にして30~98質量部が好ましく、40~95質量部がより好ましく、50~90質量部が特に好ましい。 The content of the acrylic polyol (a) in the thermal barrier topcoat composition of the present invention is preferably 30 to 98 parts by mass, more preferably 40 to 95 parts by mass, based on 100 parts by mass of the resin solid content. 90 parts by weight is particularly preferred.
アクリルポリオール(a)の合成方法としては、従来公知の方法によって合成することができ、例えば、水酸基含有重合性不飽和モノマーとその他の重合性不飽和モノマーとを、有機溶媒の存在下で重合開始剤により重合させることができる。 As a method for synthesizing acrylic polyol (a), it can be synthesized by a conventionally known method. It can be polymerized by an agent.
上記重合開始剤としては、従来公知のものを制限なく使用することができ、例えば、過酸化物系重合開始剤、アゾ系重合開始剤などを挙げることができる。 As the polymerization initiator, conventionally known ones can be used without limitation, and examples thereof include peroxide-based polymerization initiators and azo-based polymerization initiators.
重合に用いられる有機溶媒としては、従来公知のものを制限なく使用することができ、例えば、アルコール系有機溶媒;エーテル系有機溶媒;炭化水素系有機溶媒;芳香族系有機溶媒;ケトン系有機溶媒;エステル系有機溶媒等が挙げられる。これらは単独で又は2種以上組み合わせて使用することができる。
As the organic solvent used for polymerization, conventionally known solvents can be used without limitation. Examples include alcohol-based organic solvents; ether-based organic solvents; hydrocarbon-based organic solvents; aromatic-based organic solvents; ; an ester-based organic solvent and the like can be mentioned. These can be used individually or in combination of 2 or more types.
1-2.ポリエステルポリオール(b)
本発明の遮熱上塗塗料組成物は、樹脂としてポリエステルポリオール(b)を含有する。ポリエステルポリオール(b)を含有することで、塗料中の顔料濃度が高い場合においても塗装作業性や塗膜の仕上がり性が良好となる。
1-2. polyester polyol (b)
The thermal barrier topcoat composition of the present invention contains a polyester polyol (b) as a resin. By containing the polyester polyol (b), even when the pigment concentration in the paint is high, the coating workability and finish of the coating film are improved.
本発明におけるポリエステルポリオール(b)は、多塩基酸と多価アルコールとを常法に従って縮合反応することにより製造することができる。 The polyester polyol (b) in the present invention can be produced by condensation reaction of a polybasic acid and a polyhydric alcohol according to a conventional method.
多塩基酸としては、例えばアジピン酸、コハク酸、イソフタル酸、テレフタル酸、無水フタル酸、無水マレイン酸、トリメリット酸、ヘキサヒドロ無水フタル酸、5-スルホイソフタル酸ナトリウムなどが挙げられ、多価アルコールとしては、例えばエチレングリコ-ル、プロピレングリコ-ル、グリセリン、トリメチロ-ルプロパン、ネオペンチルグリコ-ル、1,6-ヘキサンジオ-ル、ペンタエリスリト-ル、ソルビト-ルなどが挙げられる。さらに必要に応じて、脱水ひまし油脂肪酸、アマニ油脂肪酸、大豆油脂肪酸、トール油脂肪酸などの脂肪酸や安息香酸などの一塩基酸、油脂類を共重合成分として使用することができる。 Examples of polybasic acids include adipic acid, succinic acid, isophthalic acid, terephthalic acid, phthalic anhydride, maleic anhydride, trimellitic acid, hexahydrophthalic anhydride, sodium 5-sulfoisophthalate, and polyhydric alcohols. Examples thereof include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, pentaerythritol and sorbitol. Furthermore, if necessary, fatty acids such as dehydrated castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid and tall oil fatty acid, monobasic acids such as benzoic acid, and fats and oils can be used as copolymer components.
本発明において上記ポリエステルポリオール(b)は、数平均分子量が500~10,000の範囲内であることが好ましく、1,000~5,000の範囲内にあることがより好ましい。ポリエステルポリオール(b)の数平均分子量が500未満では、塗膜の乾燥性が著しく低下することがあり、10,000を超えると遮熱上塗塗料組成物の粘度が高くなることに伴い、塗装作業性が低下するかまたは塗装時の不揮発分が低くなるために好ましくない。 In the present invention, the polyester polyol (b) preferably has a number average molecular weight within the range of 500 to 10,000, more preferably within the range of 1,000 to 5,000. If the number average molecular weight of the polyester polyol (b) is less than 500, the drying property of the coating film may be significantly reduced, and if it exceeds 10,000, the viscosity of the thermal barrier topcoat composition will increase, resulting in difficulty in coating work. It is not preferable because it lowers the properties or lowers the non-volatile content at the time of coating.
また、上記ポリエステルポリオール(b)の水酸基価としては、0.5~200mgKOH/gの範囲内にあり、特に40~140mgKOH/gの範囲内にあることが望ましい。ポリエステルポリオール(b)の水酸基価が0.5mgKOH/g未満では、塗膜の付着性や耐水性が低下することがあり、一方200mgKOH/gを超えると遮熱上塗塗料組成物の粘度が高くなることに伴い、塗装作業性が低下するかまたは塗装時の不揮発分が低くなり、好ましくない。 Moreover, the hydroxyl value of the polyester polyol (b) is preferably in the range of 0.5 to 200 mgKOH/g, more preferably in the range of 40 to 140 mgKOH/g. If the hydroxyl value of the polyester polyol (b) is less than 0.5 mgKOH/g, the adhesion and water resistance of the coating film may decrease, while if it exceeds 200 mgKOH/g, the viscosity of the thermal barrier topcoat composition will increase. As a result, the coating workability is lowered, or the non-volatile content at the time of coating is lowered, which is not preferable.
また、ポリエステルポリオール(b)のガラス転移温度としては、-70~0℃の範囲内にあり、好ましくは-65~-10℃の範囲内にあることが好適である。ポリエステルポリオール(b)のガラス転移温度が-70℃未満では、塗膜の乾燥性が低下し、一方0℃を越えると、塗装作業性が低下し、好ましくない。 The glass transition temperature of the polyester polyol (b) is in the range of -70 to 0°C, preferably in the range of -65 to -10°C. When the glass transition temperature of the polyester polyol (b) is less than -70°C, the drying property of the coating film is lowered, and when it exceeds 0°C, the coating workability is lowered, which is not preferable.
本発明の遮熱上塗塗料組成物におけるポリエステルポリオール(b)の含有量としては、樹脂固形分100質量部を基準にして1~70質量部が好ましく、5~50質量部がより好ましく、10~30質量部が特に好ましい。
The content of the polyester polyol (b) in the thermal barrier topcoat composition of the present invention is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the resin solid content. 30 parts by weight is particularly preferred.
1-3.硬化剤
本発明の遮熱上塗塗料組成物は、硬化剤を含有する。硬化剤としては、ポリイソシアネート化合物、ブロックポリイソシアネート化合物、メラミン化合物等の、水酸基と高い反応性を持つ官能基を1分子中に2個以上有する化合物が好ましい。
1-3. Curing Agent The thermal barrier top coating composition of the present invention contains a curing agent. As the curing agent, compounds having two or more functional groups highly reactive with hydroxyl groups in one molecule, such as polyisocyanate compounds, blocked polyisocyanate compounds, and melamine compounds, are preferred.
ポリイソシアネート化合物は、常温でも水酸基と反応して架橋するため、常温乾燥、または80℃以下の比較的低温で強制乾燥させる場合にも使用できる硬化剤である。 Since the polyisocyanate compound reacts with hydroxyl groups and crosslinks even at normal temperature, it is a curing agent that can be used for normal temperature drying or forced drying at a relatively low temperature of 80° C. or less.
上記ポリイソシアネート化合物としては、分子中に2個以上のイソシアネート基を有する化合物が包含され、その具体例としてはヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネートなどの脂肪族ジイソシアネート化合物;これらのジイソシアネート化合物のビューレットタイプ付加物、イソシアヌレート環付加物;イソホロンジイソシアネート、4,4´-メチレンビス(シクロヘキシルイソシアネート)、メチルシクロヘキサン-2,4-(または2,6-)ジイソシアネート、1,3-(または1,4-)ジ(イソシアナトメチル)シクロヘキサン、1,4-シクロヘキサンジイソシアネート、1,3-シクロペンタンジイソシアネート、1,2-シクロヘキサンジイソシアネートなどの脂環族ジイソシアネート類化合物;これらのジイソシアネート化合物のビュ-レットタイプ付加物、イソシアヌレート環付加物;キシリレンジイソシアネート、メタキシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、トリレンジイソシアネート、4,4´-ジフェニルメタンジイソシアネート、1,5-ナフタレンジイソシアネート、1,4-ナフタレンジイソシアネート、4,4´-トルイジンジイソシアネ-ト、4,4´-ジフェニルエーテルジイソシアネート、(m-もしくはp-)フェニレンジイソシアネート、4,4´-ビフェニレンジイソシアネート、3,3´-ジメチル-4,4´-ビフェニレンジイソシアネート、ビス(4-イソシアナトフェニル)スルホン、イソプロピリデンビス(4-フェニルイソシアネート)などの芳香族ジイソシアネート化合物;これらのジイソシアネ-ト化合物のビュ-レットタイプ付加物、イソシアヌレート環付加物;トリフェニルメタン-4,4´,4´´-トリイソシアネート、1,3,5-トリイソシアナトベンゼン、2,4,6-トリイソシアナトトルエン、4,4´-ジメチルジフェニルメタン-2,2´,5,5´-テトライソシアネートなどの1分子中に3個以上のイソシアネート基を有するポリイソシアネート化合物;これらのポリイソシアネート化合物のビューレットタイプ付加物、イソシアヌレート環付加物;エチレングリコール、プロピレングリコール、1,4-ブチレングリコール、ジメチロールプロピオン酸、ポリアルキレングリコール、トリメチロ-ルプロパン、ヘキサントリオ-ルなどのポリオールの水酸基にイソシアネート基が過剰量となる比率でポリイソシアネート化合物を反応させてなるウレタン化付加物;これらのウレタン化付加物のビュ-レットタイプ付加物、イソシアヌレート環付加物等のポリイソシアネート化合物を挙げることができる。 The above polyisocyanate compounds include compounds having two or more isocyanate groups in the molecule, specific examples of which include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, aliphatic diisocyanate compounds such as lysine diisocyanate; Biuret-type adducts and isocyanurate ring adducts of these diisocyanate compounds; Alicyclic diisocyanate compounds such as - (or 1,4-) di(isocyanatomethyl)cyclohexane, 1,4-cyclohexanediisocyanate, 1,3-cyclopentanediisocyanate, and 1,2-cyclohexanediisocyanate; these diisocyanate compounds biuret type adducts, isocyanurate cycloadducts of; 4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-)phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl- Aromatic diisocyanate compounds such as 4,4'-biphenylene diisocyanate, bis(4-isocyanatophenyl)sulfone, isopropylidenebis(4-phenylisocyanate); biuret type adducts of these diisocyanate compounds, isocyanurates Cycloadduct; triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane- Polyisocyanate compounds having 3 or more isocyanate groups in one molecule such as 2,2',5,5'-tetraisocyanate; Burette type adducts and isocyanurate ring adducts of these polyisocyanate compounds; Ethylene glycol , propylene glycol, 1,4-butylene glycol, dimethylolpropionic acid, polyalkylene glycol, tri urethanized adducts obtained by reacting a polyisocyanate compound with a hydroxyl group of a polyol such as methylolpropane or hexanetriol in such a ratio that the isocyanate group is excessive; Polyisocyanate compounds such as isocyanurate ring adducts can be mentioned.
一方で、ポリイソシアネート化合物は常温で水酸基と反応して架橋するため、硬化剤としてポリイソシアネート化合物を使用する場合には、水酸基を含有する樹脂とポリイソシアネート化合物とを分けておき、塗装する直前に混合することが好ましい。具体的には、アクリルポリオール(a)及びポリエステルポリオール(b)を含む樹脂、顔料、並びに有機溶媒を含有する主剤成分(I)と、ポリイソシアネート化合物を含む硬化剤成分(II)と、を含有する多液型塗料組成物とすることが好ましい。 On the other hand, polyisocyanate compounds react with hydroxyl groups at room temperature to crosslink, so when using polyisocyanate compounds as a curing agent, separate the resin containing hydroxyl groups from the polyisocyanate compound, and immediately before painting. Mixing is preferred. Specifically, it contains a main agent component (I) containing a resin containing an acrylic polyol (a) and a polyester polyol (b), a pigment, and an organic solvent, and a curing agent component (II) containing a polyisocyanate compound. It is preferable to use a multi-component coating composition that
硬化剤としてポリイソシアネート化合物を使用する際の硬化剤成分量は、上記遮熱上塗塗料組成物に含まれる樹脂中の水酸基に対してイソシアネート基が、NCO/OHの当量比で、通常、0.2~3.0、好ましくは0.5~1.5となる範囲内であることが適当である。 When a polyisocyanate compound is used as the curing agent, the amount of the curing agent component is usually 0.00, in terms of the equivalent ratio of isocyanate groups to hydroxyl groups in the resin contained in the thermal barrier topcoat composition, NCO/OH. It is suitable to be in the range of 2 to 3.0, preferably 0.5 to 1.5.
ブロックポリイソシアネート化合物、メラミン化合物は、常温において水酸基との反応性が低いため、水酸基を含有する樹脂とあらかじめ混合しておくことが可能である。したがって、硬化剤としてブロックポリイソシアネート化合物やメラミン化合物を使用する場合には、1液型塗料組成物にすることができる。一方で、常温では反応が進行しないため、塗装後に焼付乾燥を行う必要がある。 Since blocked polyisocyanate compounds and melamine compounds have low reactivity with hydroxyl groups at room temperature, they can be mixed in advance with resins containing hydroxyl groups. Therefore, when a blocked polyisocyanate compound or a melamine compound is used as a curing agent, a one-component coating composition can be obtained. On the other hand, since the reaction does not proceed at room temperature, it is necessary to bake and dry after painting.
ブロックポリイソシアネート化合物は、1分子中に2個以上のイソシアネート基を有するポリイソシアネート化合物のイソシアネート基をブロック剤でブロックしたものである。ブロック剤は、上記ポリイソシアネート化合物中の遊離のイソシアネート基を封鎖するものであり、例えば、100℃以上、好ましくは130℃以上に加熱すると、ブロック剤が解離して遊離のイソシアネート基が再生し、水酸基と容易に反応することができるようになる。かかるブロック剤としては、例えば、フェノール、クレゾール、キシレノール、ニトロフェノール、エチルフェノール、ヒドロキシジフェニル、ブチルフェノール、イソプロピルフェノール、ノニルフェノール、オクチルフェノール、ヒドロキシ安息香酸メチルなどのフェノール系;ε-カプロラクタム、δ-バレロラクタム、γ-ブチロラクタム、β-プロピオラクタムなどのラクタム系;メタノール、エタノール、プロピルアルコール、ブチルアルコール、アミルアルコール、ラウリルアルコールなどの脂肪族アルコール系;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、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、プロピレングリコールモノメチルエーテル、メトキシメタノールなどのエーテル系;ベンジルアルコール;グリコール酸;グリコール酸メチル、グリコール酸エチル、グリコール酸ブチルなどのグリコール酸エステル系;乳酸、乳酸メチル、乳酸エチル、乳酸ブチルなどの乳酸エステル系;メチロール尿素、メチロールメラミン、ジアセトンアルコール、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレートなどのアルコール系;ホルムアミドオキシム、アセトアミドオキシム、アセトオキシム、メチルエチルケトオキシム、ジアセチルモノオキシム、ベンゾフェノンオキシム、シクロヘキサンオキシムなどのオキシム系;マロン酸ジメチル、マロン酸ジエチル、マロン酸ジイソプロピル、マロン酸ジn-ブチル、メチルマロン酸ジエチル、マロン酸ベンジルメチル、マロン酸ジフェニルなどのマロン酸ジアルキルエステル、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸イソプロピル、アセト酢酸n-プロピル、アセト酢酸ベンジル、アセト酢酸フェニルなどのアセト酢酸エステル、アセチルアセトンなどの活性メチレン系;ブチルメルカプタン、t-ブチルメルカプタン、ヘキシルメルカプタン、t-ドデシルメルカプタン、2-メルカプトベンゾチアゾール、チオフェノール、メチルチオフェノール、エチルチオフェノールなどのメルカプタン系;アセトアニリド、アセトアニシジド、アセトトルイド、アクリルアミド、メタクリルアミド、酢酸アミド、ステアリン酸アミド、ベンズアミドなどの酸アミド系;コハク酸イミド、フタル酸イミド、マレイン酸イミドなどのイミド系;ジフェニルアミン、フェニルナフチルアミン、キシリジン、N-フェニルキシリジン、カルバゾール、アニリン、ナフチルアミン、ブチルアミン、ジブチルアミン、ブチルフェニルアミンなどのアミン系;イミダゾール、2-エチルイミダゾールなどのイミダゾール系;3,5-ジメチルピラゾールなどのピラゾール系;尿素、チオ尿素、エチレン尿素、エチレンチオ尿素、ジフェニル尿素などの尿素系;N-フェニルカルバミン酸フェニルなどのカルバミン酸エステル系;エチレンイミン、プロピレンイミンなどのイミン系;重亜硫酸ソーダ、重亜硫酸カリなどの亜硫酸塩系などのブロック剤を挙げることができる。 A blocked polyisocyanate compound is obtained by blocking the isocyanate groups of a polyisocyanate compound having two or more isocyanate groups in one molecule with a blocking agent. The blocking agent blocks free isocyanate groups in the polyisocyanate compound. For example, when heated to 100° C. or higher, preferably 130° C. or higher, the blocking agent dissociates to regenerate free isocyanate groups, It becomes possible to easily react with hydroxyl groups. Examples of such blocking agents include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; ε-caprolactam, δ-valerolactam, Lactams such as γ-butyrolactam and β-propiolactam; Aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol and lauryl alcohol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Ethers such as butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol; benzyl alcohol; glycolic acid; glycolic acid esters such as methyl glycolate, ethyl glycolate, butyl glycol; lactic acid, lactic acid Lactate esters such as methyl, ethyl lactate, and butyl lactate; alcohols such as methylol urea, methylol melamine, diacetone alcohol, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime , diacetyl monoxime, benzophenone oxime, cyclohexane oxime, etc.; Acid dialkyl esters, acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, benzyl acetoacetate and phenyl acetoacetate, active methylene systems such as acetylacetone; butyl mercaptan, t-butyl mercaptan, mercaptans such as hexylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol; acids such as acetanilide, acetanisidide, acetotolide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide, benzamide; Amide; succinimide, phthalimide, Imides such as maleic imide; amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine; imidazoles such as imidazole and 2-ethylimidazole ; pyrazoles such as 3,5-dimethylpyrazole; ureas such as urea, thiourea, ethyleneurea, ethylenethiourea and diphenylurea; carbamates such as phenyl N-phenylcarbamate; Blocking agents such as imine-based; sulfite-based such as sodium bisulfite and potassium bisulfite.
硬化剤としてブロックポリイソシアネート化合物を使用する際の硬化剤成分量は、上記遮熱上塗塗料組成物に含まれる樹脂中の水酸基に対してイソシアネート基が、NCO/OHの当量比で、通常、0.2~3.0、好ましくは0.5~1.5となる範囲内であることが適当である。 When a blocked polyisocyanate compound is used as a curing agent, the amount of the curing agent component is usually 0 in terms of the equivalent ratio of isocyanate groups to hydroxyl groups in the resin contained in the heat-shielding topcoat composition and NCO/OH. .2 to 3.0, preferably 0.5 to 1.5.
メラミン化合物としては、具体的には、ジ-、トリー、テトラ-、ペンタ-、ヘキサ-メチロールメラミンおよびそれらのアルキルエーテル化物(アルキルとしては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、2-エチルヘキシルアルコール等が挙げられる)並びにそれらの縮合物などを挙げることができ、市販品として、例えば、日本サイテックインダストリーズ社製のサイメル254などのサイメルシリーズ;三井化学社製のユーバン20SBなどのユーバンシリーズなどを使用することができる。また、メラミン化合物を硬化剤として使用する場合は、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンスルホン酸などのスルホン酸、およびこれらの酸とアミンとの塩を触媒として使用することができる。
Specific examples of melamine compounds include di-, tri-, tetra-, penta-, hexa-methylolmelamine and alkyl etherified products thereof (alkyl includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-ethylhexyl alcohol, etc.) and condensates thereof, and commercially available products include, for example, Cymel series such as Cymel 254 manufactured by Nippon Cytec Industries; Yuban series etc. can be used. When a melamine compound is used as a curing agent, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid and dinonylnaphthalenesulfonic acid, and salts of these acids with amines can be used as catalysts. .
2.顔料
本発明の遮熱上塗塗料組成物は、顔料として酸化チタンを含有する。中でも、塗膜の耐候性の観点から、ルチル型の酸化チタンを選択することが好ましい。
2. Pigment The thermal barrier topcoat composition of the present invention contains titanium oxide as a pigment. Among them, it is preferable to select rutile-type titanium oxide from the viewpoint of the weather resistance of the coating film.
酸化チタンの形状としては、特に限定されず、球状、棒状、針状、紡錘状、板状等、任意の形状のものを使用することができる。また、粒子径としては、塗膜の隠蔽性及び遮熱性の観点から、0.05μm以上であることが好ましく、0.1~2μmであることがより好ましく、0.2~1μmであることが特に好ましい。 The shape of titanium oxide is not particularly limited, and any shape such as spherical, rod-like, needle-like, spindle-like, and plate-like can be used. In addition, the particle diameter is preferably 0.05 μm or more, more preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm, from the viewpoint of the hiding property and heat shielding property of the coating film. Especially preferred.
本発明では、表面処理や粒子形状、粒子径の制御によって近赤外線反射能を高めた酸化チタンを用いることもできる。そのような酸化チタンとしては、具体的には、例えば、タイペーク PFR404(商品名、石原産業社製)、TITANIX JR-1000(商品名、テイカ社製)等が挙げられ、より遮熱性が高い塗膜が得られる。 In the present invention, it is also possible to use titanium oxide whose near-infrared reflectivity is enhanced by surface treatment, particle shape, and particle size control. Specific examples of such titanium oxide include Typaque PFR404 (trade name, manufactured by Ishihara Sangyo Co., Ltd.), TITANIX JR-1000 (trade name, manufactured by Tayka Co., Ltd.), and the like. A membrane is obtained.
本発明の遮熱上塗塗料組成物における酸化チタンの含有量は、遮熱上塗塗料組成物に含まれる樹脂固形分100質量部を基準にして80~145質量部の範囲である。なお、遮熱性の観点から、酸化チタンを80質量部以上含有する必要があり、特に90質量部以上含有することが好ましい。酸化チタンの含有量が80質量部未満であると、塗膜の隠ぺい性が不足して十分な遮熱性が得られない。また、145質量部を超えると塗装作業性や膜の密着性・仕上がり性が低下する。 The content of titanium oxide in the thermal barrier topcoat composition of the present invention is in the range of 80 to 145 parts by mass based on 100 parts by mass of the resin solid content contained in the thermal barrier topcoat paint composition. From the viewpoint of heat shielding properties, it is necessary to contain 80 parts by mass or more of titanium oxide, and it is particularly preferable to contain 90 parts by mass or more. If the content of titanium oxide is less than 80 parts by mass, the coating film has insufficient hiding properties and sufficient heat shielding properties cannot be obtained. On the other hand, if it exceeds 145 parts by mass, the coating workability, the adhesion of the film, and the finishing properties will be deteriorated.
一方で、樹脂固形分100質量部を基準にして、構造中に金属イオンを有さない有機顔料を5~20質量部含有する場合においては、酸化チタンを40質量部以上含有していれば、遮熱性の高い塗膜となる。これは、構造中に金属イオンを有さない有機顔料は日射反射性が高いことに起因する。構造中に金属イオンを有さない有機顔料の例としては、例えば、モノアゾイエロー、縮合アゾイエロー、ベンズイミダゾロン、イソインドリノン、イソインドリン、キノフタロン、ベンジジンイエロー、パーマネントイエロー等の黄色顔料;パーマネントオレンジ等の橙色顔料;ナフトールAS系アゾレッド、アンサンスロン、アンスラキノニルレッド、ペリレンマルーン、キナクリドン系赤顔料、ジケトピロロピロール、パーマネントレッド等の赤色顔料;キナクリドンバイオレット、ジオキサジンバイオレット等の紫色顔料、等が挙げられる。また、構造中に金属イオンを有さない有機顔料を樹脂固形分100質量部を基準にして5~20質量部含有する場合においても、酸化チタンの含有量が145質量部を超えると塗装作業性や膜の密着性、仕上がり性が低下するため、酸化チタンの含有量としては40~145質量部の範囲内である必要がある。 On the other hand, in the case of containing 5 to 20 parts by mass of an organic pigment that does not have metal ions in its structure based on 100 parts by mass of the resin solid content, if 40 parts by mass or more of titanium oxide is contained, It becomes a coating film with high heat insulation. This is because organic pigments that do not have metal ions in their structure have high solar reflectivity. Examples of organic pigments that do not have metal ions in their structure include yellow pigments such as monoazo yellow, condensed azo yellow, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; permanent orange. red pigments such as naphthol AS-based azo red, anthrone, anthraquinonyl red, perylene maroon, quinacridone-based red pigments, diketopyrrolopyrrole, and permanent red; purple pigments such as quinacridone violet and dioxazine violet, etc. is mentioned. In addition, even when 5 to 20 parts by mass of an organic pigment having no metal ions in the structure is contained based on 100 parts by mass of the resin solid content, if the content of titanium oxide exceeds 145 parts by mass, the coating workability is improved. The content of titanium oxide should be in the range of 40 to 145 parts by mass, because the adhesion and finish of the film are lowered.
本発明の遮熱上塗塗料組成物において、カーボンブラック顔料の含有量は、樹脂固形分100質量部を基準にして0.1質量部以下であることが好ましく、0.01質量部以下であることがより好ましく、実質的に含有しないことが特に好ましい。0.1質量部を超えるカーボンブラック顔料を含む場合、塗膜の遮熱性が大幅に低下する。 In the thermal barrier topcoat composition of the present invention, the content of the carbon black pigment is preferably 0.1 parts by mass or less based on 100 parts by mass of the resin solid content, and is 0.01 parts by mass or less. is more preferred, and it is particularly preferred that it does not contain substantially. When the carbon black pigment is contained in an amount exceeding 0.1 part by mass, the heat shielding properties of the coating film are greatly reduced.
酸化チタン、カーボンブラック以外の顔料としては、通常塗料分野で用いられる着色顔料、体質顔料等の顔料が使用できる。着色顔料としては、鉄黒、アニリンブラックなどの黒色顔料;黄色酸化鉄、チタンイエロー、ビスマスバナデート、銅アゾメチンイエロー、ニッケルアゾイエロー、モノアゾイエロー、縮合アゾイエロー、ベンズイミダゾロン、イソインドリノン、イソインドリン、キノフタロン、ベンジジンイエロー、パーマネントイエロー等の黄色顔料;パーマネントオレンジ等の橙色顔料;赤色酸化鉄、ウォッチングレッド、ナフトールAS系アゾレッド、アンサンスロン、アンスラキノニルレッド、ペリレンマルーン、キナクリドン系赤顔料、ジケトピロロピロール、パーマネントレッド等の赤色顔料;キナクリドンバイオレット、ジオキサジンバイオレット、コバルト紫等の紫色顔料;コバルトブルー、フタロシアニンブルー、スレンブルーなどの青色顔料;フタロシアニングリーンなどの緑色顔料;等をあげることができ、体質顔料としては、亜鉛粉、硫酸バリウム、炭酸バリウム、炭酸カルシウム、石膏、クレー、シリカ、ホワイトカーボン、珪藻土、タルク、炭酸マグネシウム、アルミナホワイト、グロスホワイト、マイカ粉などを挙げることができる。 As pigments other than titanium oxide and carbon black, pigments such as coloring pigments and extender pigments that are commonly used in the paint field can be used. Black pigments such as iron black and aniline black; yellow iron oxide, titanium yellow, bismuth vanadate, copper azomethine yellow, nickel azo yellow, monoazo yellow, condensed azo yellow, benzimidazolone, isoindolinone, yellow pigments such as indoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red pigments such as ketopyrrolopyrrole and permanent red; purple pigments such as quinacridone violet, dioxazine violet and cobalt purple; blue pigments such as cobalt blue, phthalocyanine blue and thren blue; green pigments such as phthalocyanine green; Examples of extender pigments include zinc powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, and mica powder.
その他の顔料の配合量は、塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上となるように、顔料の種類に応じて適宜調整する必要がある。 The amount of the other pigments to be blended must be appropriately adjusted according to the type of pigment so that the near-infrared wavelength region solar reflectance of the coating film is 80% or higher and/or the brightness is 85 or higher.
本発明の遮熱塗料組成物における、酸化チタンを含む顔料の含有量としては、塗装作業性や膜の密着性、仕上がり性の観点から、樹脂固形分100質量部を基準にして250質量部以下であることが好ましく、200質量部以下であることが特に好ましい。
The content of the pigment containing titanium oxide in the thermal barrier coating composition of the present invention is 250 parts by mass or less based on 100 parts by mass of the resin solid content, from the viewpoint of coating workability, film adhesion, and finish. is preferable, and it is particularly preferable that the amount is 200 parts by mass or less.
3.有機溶媒
有機溶媒は、遮熱上塗塗料組成物の製造安定性、塗装作業性、塗膜の仕上がり性の観点から配合されるものであり、従来公知の有機溶媒を制限なく使用することができる。
3. Organic solvent The organic solvent is blended from the viewpoint of production stability of the thermal barrier topcoat composition, coating workability, and finish of the coating film, and conventionally known organic solvents can be used without limitation.
本発明においては遮熱上塗塗料組成物に含まれる各樹脂同士の相溶性および形成塗膜の乾燥性を向上させることが可能であることから、有機溶媒として例えばエステル系有機溶媒およびケトン系有機溶媒から選ばれる少なくとも1種の有機溶媒を使用することが適している。 In the present invention, since it is possible to improve the compatibility of each resin contained in the thermal barrier topcoat composition and the drying property of the formed coating film, examples of organic solvents include ester-based organic solvents and ketone-based organic solvents. It is suitable to use at least one organic solvent selected from
該有機溶媒におけるエステル系有機溶媒としては、例えば酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸2エチルヘキシル、酢酸シクロヘキシル、3-メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテートなどが挙げられ、ケトン系有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、エチルイソアミルケトン、ジイソブチルケトン、メチルヘキシルケトン、イソホロンなどを挙げることができ、これらは単独でまたは2種以上組み合わせて使用することができる。 Ester-based organic solvents in the organic solvent include, for example, ethyl acetate, butyl acetate, isobutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, diethylene glycol monoethyl ether acetate, etc., and ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, ethyl isoamyl ketone, diisobutyl ketone, methylhexyl ketone, isophorone, and the like. and these can be used alone or in combination of two or more.
上記有機溶媒は、遮熱上塗塗料組成物の製造のいずれの段階においても混合することができ、あるいは塗料中に含まれる樹脂の製造において、反応溶媒または希釈溶媒として配合することもできる。 The above organic solvent can be mixed at any stage in the production of the thermal barrier topcoat composition, or can be added as a reaction solvent or diluent solvent in the production of the resin contained in the paint.
本発明の遮熱上塗塗料組成物は、有機溶媒の含有量が少なくても、十分な塗装作業性を確保できる。有機溶媒の含有量が少ないと、塗装回数が少なくても高い遮熱性能を有するため好ましい。具体的には、有機溶媒の含有量が、塗料組成物の総量を基準として20~70質量%の範囲であることが好ましく、30~55質量%であることがより好ましい。
The thermal barrier topcoat composition of the present invention can ensure sufficient coating workability even when the content of the organic solvent is small. When the content of the organic solvent is small, it is preferable because high heat-shielding performance can be obtained even if the number of times of coating is small. Specifically, the content of the organic solvent is preferably in the range of 20 to 70% by mass, more preferably 30 to 55% by mass, based on the total amount of the coating composition.
4.その他の含有物
本発明の遮熱上塗塗料組成物は、必要に応じて有機金属化合物を含有することができる。該有機金属化合物としては、例えば、オクチル酸錫、ジブチル錫ジ(2-エチルヘキサノエート)、ジオクチル錫ジ(2-エチルヘキサノエート)、ジオクチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジオクチル錫オキサイド、ジブチル錫脂肪酸塩、2-エチルヘキサン酸鉛、オクチル酸亜鉛、ナフテン酸亜鉛、脂肪酸亜鉛類、ナフテン酸コバルト、オクチル酸カルシウム、ナフテン酸銅、テトラ(2-エチルヘキシル)チタネートなどが挙げられ、これらは1種または2種以上混合して用いることができる。これらには、さらに必要に応じて第三級アミン、りん酸化合物など公知のウレタン硬化触媒を併用することもできる。
4. Other Ingredients The thermal barrier topcoat composition of the present invention may optionally contain an organometallic compound. Examples of the organometallic compounds include tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zincs, cobalt naphthenate, calcium octylate, copper naphthenate, tetra(2-ethylhexyl) titanate, etc. These can be used singly or in combination of two or more. Known urethane curing catalysts such as tertiary amines and phosphoric acid compounds can also be used in combination with these, if necessary.
上記有機金属化合物を含ませることによって、前述のポリイソシアネート硬化剤を配合した場合などにおいて塗膜の乾燥性を向上させる効果がある。その使用量は、通常、遮熱上塗塗料組成物中に含まれる樹脂の合計100質量部に対して0.01~10質量部、好ましくは0.02~5質量部の範囲内が適当である。 Incorporation of the organometallic compound has the effect of improving the drying property of the coating film when the above-described polyisocyanate curing agent is blended. The amount to be used is generally 0.01 to 10 parts by mass, preferably 0.02 to 5 parts by mass, based on the total 100 parts by mass of the resin contained in the thermal barrier topcoat composition. .
上記本発明の遮熱上塗塗料組成物は、さらに必要に応じて、上記(a)、(b)及び硬化剤以外の樹脂、増粘剤、紫外線吸収剤、光安定剤、酸化防止剤、表面調整剤、顔料分散剤、硬化触媒などの塗料用添加剤を配合することができる。
The heat-shielding topcoat composition of the present invention further contains, if necessary, a resin other than the above (a), (b) and a curing agent, a thickener, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface Coating additives such as modifiers, pigment dispersants, and curing catalysts can be incorporated.
5.遮熱上塗塗料組成物の塗装
本発明の遮熱上塗塗料組成物はハイソリッド型であることができ、塗装時における揮発性物質の放散量を少なくせしめることができる。具体的には塗装時の塗料不揮発分が、45質量%以上80質量%以下、さらには60質量%以上80質量%以下とすることができる。これにより、少ない塗装回数で目的の膜厚の塗膜が得られる。
5. Application of Thermal Insulation Topcoat Composition The thermal insulation topcoat composition of the present invention can be of a high solid type, and can reduce the amount of volatile substances emitted during coating. Specifically, the non-volatile content of the paint at the time of coating can be 45% by mass or more and 80% by mass or less, further 60% by mass or more and 80% by mass or less. As a result, a coating film having a desired film thickness can be obtained with a small number of times of coating.
本明細書において塗装時の不揮発分は、温度が20℃、湿度が60%の条件において塗装に適した粘度に調整した塗装直前の試料をブリキ皿に1.0g秤量し、加熱温度105℃、3時間で蒸発成分を除き、残量を質量百分率として算出することによって求めることができる。 In this specification, the non-volatile content at the time of coating is 1.0 g of a sample immediately before coating adjusted to a viscosity suitable for coating under the conditions of a temperature of 20 ° C. and a humidity of 60%, and a heating temperature of 105 ° C. It can be obtained by removing the evaporated components in 3 hours and calculating the remaining amount as a mass percentage.
本発明の遮熱上塗塗料組成物は、希釈シンナーにより塗装に適した粘度に調整した後塗装することができる。多液型塗料組成物の場合は、使用直前に混合され、必要に応じて希釈シンナーにより塗装に適した粘度に調整され塗装に供されることが望ましい。 The thermal barrier topcoat composition of the present invention can be coated after adjusting the viscosity to be suitable for coating with a diluted thinner. In the case of a multicomponent paint composition, it is desirable to mix just before use, adjust the viscosity to a suitable level for painting with a diluted thinner, if necessary, and then apply the composition.
本発明の遮熱上塗塗料組成物は、鉄、アルミニウム、真鍮、銅板、ステンレス鋼板、ブリキ板、亜鉛めっき鋼板、合金化亜鉛(Zn-Al、Zn-Ni、Zn-Feなどの)めっき鋼板などの金属;これらの金属表面に燐酸塩処理、クロメート処理などの化成処理を施した表面処理金属;プラスチック、木材、コンクリート、モルタル等の素材に、直接にまたは該被塗物素材に下塗および/または中塗および/または上塗着色ベースを塗装した被塗物の硬化塗膜面または未硬化塗膜面に塗布でき、乾燥させることによって塗膜物性が良好で、仕上り性に優れた塗膜を形成することができる。中でも、下塗塗膜を塗装した被塗物の上に本発明の遮熱上塗塗料組成物を塗装することが適している。 The thermal barrier topcoat composition of the present invention can be used for iron, aluminum, brass, copper plate, stainless steel plate, tin plate, galvanized steel plate, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel plate, etc. metals; surface-treated metals that have undergone chemical conversion treatments such as phosphate treatment and chromate treatment on the surface of these metals; plastics, wood, concrete, mortar, etc., directly or on the material to be coated and / or To be able to be applied to the cured or uncured film surface of a substrate coated with an intermediate coating and/or topcoat colored base, and to form a coating film having good physical properties and an excellent finish by drying. can be done. Above all, it is suitable to apply the thermal barrier topcoat composition of the present invention onto an object to be coated with an undercoat film.
被塗物の具体例としては、乗用車、大型車両、オートバイ、運送用車両、鉄道車両;航空機;建造物;家電製品などを挙げることができるが、これらに限定されるものではない。一方、鉄道車両、架装大型車両、特殊車両、及び貨物自動車から選ばれる車両、建設機械、もしくは構造物への適用が好ましく、アジテータ車のドラム部分への適用が特に好ましい。本発明の遮熱複層塗膜形成方法で得られる塗膜をアジテータ車のドラム部分に適用すると、内部の生コンクリートが太陽熱により過剰に発熱することを防ぐことができる。 Specific examples of objects to be coated include, but are not limited to, passenger cars, large vehicles, motorcycles, transportation vehicles, railroad vehicles, aircraft, buildings, and household electrical appliances. On the other hand, application to vehicles selected from railway vehicles, large-sized vehicles, special vehicles, and freight vehicles, construction machinery, or structures is preferable, and application to the drum portion of an agitator vehicle is particularly preferable. When the coating film obtained by the method for forming a heat-shielding multilayer coating film of the present invention is applied to the drum portion of the agitator wheel, it is possible to prevent the ready-mixed concrete inside from generating excessive heat due to solar heat.
下塗塗膜を塗装した被塗物の上に本発明の遮熱上塗塗料組成物を塗装する場合、下塗塗膜の明度が高いほどより高い遮熱効果が期待される。具体的には、下塗塗膜の明度が50以上であることが好ましく、70以上であることがより好ましく、85以上であることが特に好ましい。 When the heat-insulating topcoat composition of the present invention is applied onto an object coated with an undercoat film, the higher the brightness of the undercoat film, the higher the heat-insulating effect is expected. Specifically, the brightness of the undercoat film is preferably 50 or more, more preferably 70 or more, and particularly preferably 85 or more.
塗装手段としては、従来公知の方法を特に制限なく使用することができ、例えば、スプレー塗装、静電塗装、ハケ塗装、ローラー塗装等が挙げられる。
乾燥方法としては、加熱乾燥、強制乾燥、常温乾燥のいずれであってもよい。ただし、硬化剤としてブロックポリイソシアネート化合物又はメラミン化合物を使用した1液型塗料組成物の場合には、乾燥方法は加熱乾燥となる。
As the coating means, conventionally known methods can be used without particular limitation, and examples thereof include spray coating, electrostatic coating, brush coating, roller coating and the like.
As a drying method, any of heat drying, forced drying, and normal temperature drying may be used. However, in the case of a one-component coating composition using a blocked polyisocyanate compound or a melamine compound as a curing agent, the drying method is heat drying.
乾燥方法としては、主剤成分(I)とポリイソシアネート化合物を含む硬化剤成分(II)とを含有する多液型塗料組成物の場合、加熱乾燥、強制乾燥、常温乾燥のいずれであってもよく、通常120℃未満、好ましくは10~100℃、さらに好ましくは20~80℃の温度で乾燥することが好適である。一方、ブロックイソシアネート化合物又はメラミン化合物を含む樹脂を含有する1液型塗料組成物の場合、乾燥方法は加熱乾燥であり、通常100~200℃、好ましくは120~180℃で乾燥することが好適である。 As a drying method, in the case of a multicomponent coating composition containing a main component (I) and a curing agent component (II) containing a polyisocyanate compound, any of heat drying, forced drying, and normal temperature drying may be used. , usually less than 120°C, preferably 10 to 100°C, more preferably 20 to 80°C. On the other hand, in the case of a one-component coating composition containing a resin containing a blocked isocyanate compound or a melamine compound, the drying method is heat drying, and it is usually 100 to 200°C, preferably 120 to 180°C. be.
乾燥後の塗膜の膜厚としては、塗装作業性と遮熱性の観点から、30~120μmが好ましく、40~100μmがより好ましく、50~80μmが特に好ましい。 The thickness of the coating film after drying is preferably 30 to 120 μm, more preferably 40 to 100 μm, particularly preferably 50 to 80 μm, from the viewpoint of coating workability and heat shielding properties.
また、本発明の塗装方法においては、本発明の遮熱上塗塗料組成物を塗装するだけのモノコート塗装仕上げ用として使用することによって、光沢、仕上がり性、硬度等に優れた塗膜を形成することができるが、必要に応じて形成塗膜上に従来公知のクリヤー塗料を塗装し2コート塗装仕上げとすることも可能である。
In addition, in the coating method of the present invention, a coating film excellent in gloss, finish, hardness, etc. is formed by using the thermal barrier top coating composition of the present invention as a mono-coat finish by simply applying it. However, if necessary, it is also possible to apply a conventionally known clear paint on the formed coating film to finish with two coats.
以下、実施例を挙げて本発明をさらに詳細に説明する。ここで「部」および「%」はそれぞれ「質量部」および「質量%」を意味する。 The present invention will be described in more detail below with reference to examples. Here, "parts" and "%" mean "mass parts" and "mass%" respectively.
<アクリルポリオールの合成>
製造例1 アクリルポリオール(a-1)の合成
撹拌装置、温度計、還流冷却器、サーモスタットおよび滴下用ポンプを備えた反応容器に、酢酸ブチル60部を仕込み、撹拌しながら125℃まで昇温し、下記単量体と重合開始剤との混合物を、滴下用ポンプを利用して3時間かけて一定速度で滴下した。滴下終了後、同温度で2時間熟成し反応を終了した。次いで酢酸ブチルで希釈して樹脂溶液の不揮発分を60%に調整した。
スチレン 38部
イソボルニルアクリレート 20部
イソブチルメタクリレート 5部
2-エチルヘキシルアクリレート 10部
2-ヒドロキシエチルメタクリレート 20部
2-ヒドロキシエチルアクリレート 7部
t-ブチルパーオキシヘキサノエート 6.1部
得られたアクリルポリオール(a-1)の重量平均分子量は10000、水酸基価は120mgKOH/g、ガラス転移温度は48℃であった。
<Synthesis of acrylic polyol>
Production Example 1 Synthesis of acrylic polyol (a-1) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, thermostat and dropping pump was charged with 60 parts of butyl acetate, and the temperature was raised to 125°C while stirring. A mixture of the following monomer and polymerization initiator was dropped at a constant rate over 3 hours using a dropping pump. After the dropwise addition was completed, the mixture was aged at the same temperature for 2 hours to terminate the reaction. Then, the resin solution was diluted with butyl acetate to adjust the non-volatile content of the resin solution to 60%.
Styrene 38 parts Isobornyl acrylate 20 parts Isobutyl methacrylate 5 parts 2-Ethylhexyl acrylate 10 parts 2-Hydroxyethyl methacrylate 20 parts 2-Hydroxyethyl acrylate 7 parts t-butyl peroxyhexanoate 6.1 parts Obtained acrylic polyol (a-1) had a weight average molecular weight of 10,000, a hydroxyl value of 120 mgKOH/g, and a glass transition temperature of 48°C.
製造例2 アクリルポリオール(a-2)の合成
上記製造例1において滴下物を下記組成とする以外は上記製造例1と同様にして、不揮発分60%のアクリルポリオール(a-2)を得た。
スチレン 20部
イソボルニルアクリレート 10部
イソブチルメタクリレート 22部
2-エチルヘキシルメタクリレート 20部
2-ヒドロキシエチルメタクリレート 28部
t-ブチルパーオキシ-2-エチルヘキサノエート 6.1部
得られたアクリルポリオール(a-2)の重量平均分子量は10000、水酸基価は120mgKOH/g、ガラス転移温度は50℃であった。
Production Example 2 Synthesis of acrylic polyol (a-2) An acrylic polyol (a-2) having a non-volatile content of 60% was obtained in the same manner as in Production Example 1 above, except that the composition of the drops was changed to the following. .
Styrene 20 parts isobornyl acrylate 10 parts isobutyl methacrylate 22 parts 2-ethylhexyl methacrylate 20 parts 2-hydroxyethyl methacrylate 28 parts t-butyl peroxy-2-ethylhexanoate 6.1 parts obtained acrylic polyol (a- 2) had a weight average molecular weight of 10,000, a hydroxyl value of 120 mgKOH/g, and a glass transition temperature of 50°C.
製造例3 アクリルポリオール(a-3)の合成
上記製造例1において滴下物を下記組成とする以外は上記製造例1と同様にして、不揮発分60%のアクリルポリオール(a-3)を得た。
スチレン 10部
イソボルニルアクリレート 15部
イソブチルメタクリレート 42部
2-エチルヘキシルアクリレート 5部
2-ヒドロキシエチルメタクリレート 28部
t-ブチルパーオキシ-2-エチルヘキサノエート 6.1部
得られたアクリルポリオール(a-3)の重量平均分子量は10000、水酸基価は120mgKOH/g、ガラス転移温度は55℃であった。
Production Example 3 Synthesis of acrylic polyol (a-3) An acrylic polyol (a-3) having a non-volatile content of 60% was obtained in the same manner as in Production Example 1 except that the composition of the drops was changed to the following. .
Styrene 10 parts isobornyl acrylate 15 parts isobutyl methacrylate 42 parts 2-ethylhexyl acrylate 5 parts 2-hydroxyethyl methacrylate 28 parts t-butyl peroxy-2-ethylhexanoate 6.1 parts obtained acrylic polyol (a- 3) had a weight average molecular weight of 10,000, a hydroxyl value of 120 mgKOH/g, and a glass transition temperature of 55°C.
<アクリルポリオールの合成>
製造例4 ポリエステルポリオール(b-1)の合成
加熱装置、温度計、攪拌機、精留塔および水分離器の付属した還流冷却器を備えた反応器に下記成分を仕込み加熱し、3時間かけて160℃から230℃まで昇温させた。
1,4-シクロヘキサンジカルボン酸 23.5部
アジピン酸 34.2部
ネオペンチルグリコ-ル 37部
トリメチロールプロパン 5.3部
これを230℃で1時間保ち、精留塔を用いて生成した縮合水を留去させた。次いで酢酸ブチルを5部加え、酢酸ブチルと縮合水を還流させ水分離器を用いて水を取り除いた。酢酸ブチル添加の2時間後から、酸価を測定し始め、酸価が2以下になったところで120℃まで冷却した後、酢酸ブチルで不揮発分70%となるよう希釈し、ポリエステルポリオール(b-1)溶液を得た。得られたポリエステルポリオール(b-1)の数平均分子量は3,800、水酸基価は52mgKOH/g、ガラス転移温度は-50℃であった。
<Synthesis of acrylic polyol>
Production Example 4 Synthesis of polyester polyol (b-1) The following components were charged into a reactor equipped with a heating device, a thermometer, a stirrer, a rectifying column and a reflux condenser equipped with a water separator, and heated for 3 hours. The temperature was raised from 160°C to 230°C.
1,4-Cyclohexanedicarboxylic acid 23.5 parts Adipic acid 34.2 parts Neopentyl glycol 37 parts Trimethylolpropane 5.3 parts This was kept at 230°C for 1 hour, and condensed water was produced using a rectification column. was distilled off. Then, 5 parts of butyl acetate was added, and the butyl acetate and condensed water were refluxed to remove water using a water separator. 2 hours after the addition of butyl acetate, start measuring the acid value. When the acid value becomes 2 or less, cool to 120° C., then dilute with butyl acetate so that the non-volatile content is 70%, polyester polyol (b- 1) A solution was obtained. The resulting polyester polyol (b-1) had a number average molecular weight of 3,800, a hydroxyl value of 52 mgKOH/g and a glass transition temperature of -50°C.
製造例5 ポリエステルポリオール(b-2)の合成
上記製造例4において、配合組成を下記組成とする以外は上記製造例4と同様にして、不揮発分70%のポリエステルポリオール(b-2)溶液を得た。
1,4-シクロヘキサンジカルボン酸 3.5部
アジピン酸 53部
ネオペンチルグリコ-ル 38部
トリメチロールプロパン 5.5部
得られたポリエステルポリオール(b-2)の数平均分子量は3,700、水酸基価は54mgKOH/g、ガラス転移温度は-66℃であった。
Production Example 5 Synthesis of Polyester Polyol (b-2) A solution of polyester polyol (b-2) having a non-volatile content of 70% was prepared in the same manner as in Production Example 4 except that the formulation composition was changed to the following composition. Obtained.
1,4-cyclohexanedicarboxylic acid 3.5 parts adipic acid 53 parts neopentyl glycol 38 parts trimethylolpropane 5.5 parts The resulting polyester polyol (b-2) had a number average molecular weight of 3,700 and a hydroxyl value. was 54 mgKOH/g, and the glass transition temperature was -66°C.
製造例6 ポリエステルポリオール(b-3)の合成
上記製造例4において、配合組成を下記組成とする以外は上記製造例4と同様にして、不揮発分70%のポリエステルポリオール(b-3)溶液を得た。
1,4-シクロヘキサンジカルボン酸 5部
アジピン酸 34.8部
ネオペンチルグリコ-ル 59.6部
トリメチロールプロパン 5.1部
得られたポリエステルポリオール(b-3)の数平均分子量は4,100、水酸基価は49mgKOH/g、ガラス転移温度は-10℃であった。
Production Example 6 Synthesis of Polyester Polyol (b-3) A solution of polyester polyol (b-3) having a non-volatile content of 70% was prepared in the same manner as in Production Example 4 except that the formulation was changed to the following composition. Obtained.
1,4-cyclohexanedicarboxylic acid 5 parts adipic acid 34.8 parts neopentyl glycol 59.6 parts trimethylolpropane 5.1 parts The resulting polyester polyol (b-3) had a number average molecular weight of 4,100, The hydroxyl value was 49 mgKOH/g and the glass transition temperature was -10°C.
製造例7 ポリエステルポリオール(b-4)の合成
上記製造例4において、配合組成を下記組成とする以外は上記製造例4と同様にして、不揮発分70%のポリエステルポリオール(b-4)溶液を得た。
1,4-シクロヘキサンジカルボン酸 20.5部
アジピン酸 33.8部
ネオペンチルグリコ-ル 39.9部
トリメチロールプロパン 5.8部
得られたポリエステルポリオール(b-4)の数平均分子量は1,200、水酸基価は120mgKOH/g、ガラス転移温度は-54℃であった。
Production Example 7 Synthesis of Polyester Polyol (b-4) A solution of polyester polyol (b-4) having a non-volatile content of 70% was prepared in the same manner as in Production Example 4 except that the formulation composition was changed to the following composition. Obtained.
1,4-cyclohexanedicarboxylic acid 20.5 parts adipic acid 33.8 parts neopentyl glycol 39.9 parts trimethylolpropane 5.8 parts 200, the hydroxyl value was 120 mgKOH/g, and the glass transition temperature was -54°C.
製造例8 ポリエステルポリオール(b-5)の合成
上記製造例4において、配合組成を下記組成とする以外は上記製造例4と同様にして、不揮発分70%のポリエステルポリオール(b-5)溶液を得た。
1,4-シクロヘキサンジカルボン酸 22.5部
アジピン酸 36.1部
ネオペンチルグリコ-ル 36.2部
トリメチロールプロパン 5.2部。
得られたポリエステルポリオール(b-5)の数平均分子量は9,800、水酸基価は34mgKOH/g、ガラス転移温度は-51℃であった。
Production Example 8 Synthesis of Polyester Polyol (b-5) A solution of polyester polyol (b-5) having a non-volatile content of 70% was prepared in the same manner as in Production Example 4 except that the formulation was changed to the following composition. Obtained.
1,4-cyclohexanedicarboxylic acid 22.5 parts adipic acid 36.1 parts neopentyl glycol 36.2 parts trimethylolpropane 5.2 parts.
The resulting polyester polyol (b-5) had a number average molecular weight of 9,800, a hydroxyl value of 34 mgKOH/g and a glass transition temperature of -51°C.
<ベース塗料組成物の製造>
製造例9 白色ベース塗料組成物X-1の製造
上記製造例1で得られたアクリルポリオール(a-1)溶液29.0部、平均粒子径0.25~0.3μmの酸化チタン顔料42.0部、顔料分散剤(「BYK-161」、商品名、BYK-chemie社製)1.5部、酢酸ブチル2.5部をディスパーで20分攪拌した後、サンドミルで分散し、顔料分散ペーストを得た。得られた顔料分散ペーストにアクリルポリオール(a-1)溶液14.0部、上記製造例4で得られたポリエステルポリオール(b-1)溶液7.0部、酢酸ブチル4.0部を加えてディスパーで撹拌し、白色ベース塗料組成物X-1を得た。
<Production of base paint composition>
Production Example 9 Production of White Base Coating Composition X-1 29.0 parts of acrylic polyol (a-1) solution obtained in Production Example 1 above, titanium oxide pigment having an average particle size of 0.25 to 0.3 μm 42. 0 part, 1.5 parts of a pigment dispersant ("BYK-161", trade name, manufactured by BYK-chemie), and 2.5 parts of butyl acetate are stirred for 20 minutes with a disper, and then dispersed with a sand mill to obtain a pigment dispersion paste. got 14.0 parts of the acrylic polyol (a-1) solution, 7.0 parts of the polyester polyol (b-1) solution obtained in Production Example 4, and 4.0 parts of butyl acetate were added to the obtained pigment dispersion paste. The mixture was stirred with a disper to obtain a white base paint composition X-1.
製造例10~24 白色ベース塗料組成物X-2~X-16
各成分の配合を下記表1に示す配合とする以外は製造例9と同様にして、白色ベース塗料組成物X-2~X-16を得た。
Production Examples 10 to 24 White Base Paint Compositions X-2 to X-16
White base paint compositions X-2 to X-16 were obtained in the same manner as in Production Example 9 except that the formulations of the respective components were as shown in Table 1 below.
<表1>
<Table 1>
製造例25~31 着色ベース塗料組成物Y-1~Y-7の製造
各成分の配合を下記表2に示す配合とする以外は上記製造例9と同様にして、着色ベース塗料組成物Y-1~Y-7を得た。
Production Examples 25 to 31 Production of Colored Base Paint Compositions Y-1 to Y-7 In the same manner as in Production Example 9 above, except that the formulations of the respective components are shown in Table 2 below, colored base paint compositions Y- 1 to Y-7 were obtained.
<表2>
<Table 2>
<遮熱上塗塗料組成物の製造>
実施例1,2
下記表3に示す配合にて、上記製造例で得られたベース塗料組成物及び硬化剤を混合し、希釈シンナー(関西ペイント社製、商品名:レタンPGエコシンナー20)により不揮発分が65質量%となるように希釈して、1液型遮熱上塗塗料組成物Z-1及びZ-2を作成した。
<Production of thermal barrier topcoat composition>
Examples 1 and 2
The base coating composition obtained in the above production example and the curing agent were mixed according to the formulation shown in Table 3 below, and diluted thinner (manufactured by Kansai Paint Co., Ltd., trade name: Retan PG Eco Thinner 20) was used to reduce the non-volatile content to 65 mass. % to prepare one-liquid thermal barrier topcoat compositions Z-1 and Z-2.
実施例3
上記製造例9で得られた白色ベース塗料組成物(X-1)100部に、硬化触媒としてネオスタンU-100(日東化成社製、ジブチル錫ジラウレート)0.01部を加えて混合し、主剤成分(I)とした。また、スミジュールN3300(住化コベストロウレタン社製、ポリイソシアネート、固形分100%)10部に酢酸ブチル10部を加えて混合し、硬化剤成分(II)とした。主剤成分(I)と硬化剤成分(II)とを混合し、希釈シンナー(関西ペイント社製、商品名:レタンPGエコシンナー20)により不揮発分が65質量%となるように希釈して、多液型遮熱上塗塗料組成物Z-1を作成した。なお、主剤成分(I)と硬化剤成分(II)とを混合して希釈する作業は、塗装直前(1時間以内)に行った。また、Z-17及びZ-18については、不揮発分が65質量%以下であったため、希釈シンナーを使用しなかった。
Example 3
To 100 parts of the white base coating composition (X-1) obtained in Production Example 9 above, 0.01 part of Neostan U-100 (manufactured by Nitto Kasei Co., Ltd., dibutyltin dilaurate) as a curing catalyst was added and mixed to form a main component. This was used as component (I). Further, 10 parts of butyl acetate was added to 10 parts of Sumidule N3300 (manufactured by Sumika Covestro Urethane Co., Ltd., polyisocyanate, solid content 100%) and mixed to obtain a curing agent component (II). The main component (I) and the curing agent component (II) are mixed, diluted with a diluent thinner (trade name: Retan PG Eco Thinner 20, manufactured by Kansai Paint Co., Ltd.) so that the non-volatile content is 65% by mass, and A liquid-type thermal barrier topcoat composition Z-1 was prepared. The operation of mixing and diluting the main agent component (I) and the curing agent component (II) was performed immediately before coating (within 1 hour). Further, for Z-17 and Z-18, since the non-volatile content was 65% by mass or less, no diluent thinner was used.
実施例4~24、比較例1~9
各成分の配合を下記表3~6に示す配合とする以外は実施例3と同様にして、多液型遮熱上塗塗料組成物Z-4~33を作成した。
Examples 4-24, Comparative Examples 1-9
Multicomponent thermal barrier topcoat paint compositions Z-4 to Z-33 were prepared in the same manner as in Example 3, except that the formulations of the respective components were as shown in Tables 3 to 6 below.
<表3>
<Table 3>
<表4>
<Table 4>
<表5>
<Table 5>
<表6>
<Table 6>
(注1)「NACURE5076」:KING INDUSTRIES社製、ドデシルベンゼンスルホン酸。 (Note 1) “NACURE5076”: Dodecylbenzenesulfonic acid manufactured by KING INDUSTRIES.
(注2)ブロックポリイソシアネートH-1
温度計、サーモスタット、攪拌機、還流冷却器、滴下ポンプ等を備え付けた反応装置に「デュラネートTPA-100」(旭化成社製、イソシアヌレート構造含有ポリイソシアヌレート、数平均分子量約600、イソシアヌレート含量23.1%)605部、酢酸エチル120部を入れ、100℃に昇温し、窒素気流下で「オキソコールC13」(協和油化社製、トリデカノールの構造異性体)80部を加え100℃で2時間保持した。その後マロン酸ジエチル345部、酢酸エチル60部を加えて60℃に保持したのち、窒素気流下でナトリウムメトキシドの28%メタノール溶液を7.0部加え、60℃で12時間保持し、ブロックポリイソシアネート化合物溶液を得た。NCO価を測定したところ、イソシアネート含有量は0.1%であった。このブロックポリイソシアネート化合物溶液605gを別の同様の反応装置に取り出し、2-エチルヘキサノール488部を入れ、90℃に昇温した。これを減圧条件下で、系の温度を90~110℃に保ちながら1.5時間かけて溶剤を留出・除去し、ブロックポリイソシアネート化合物溶液872部を得た。除去溶媒簡易トラップには、エタノールが43部含まれていた。得られたブロックポリイソシアネート化合物溶液に2-エチルヘキサノールを添加し固形分含有率80%のブロックポリイソシアネート化合物溶液H-1を得た。該ブロックポリイソシアネート化合物の数平均分子量は約3,500であった。
(Note 2) Block polyisocyanate H-1
A reactor equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, a dropping pump, etc., was charged with "Duranate TPA-100" (manufactured by Asahi Kasei Co., Ltd., polyisocyanurate containing an isocyanurate structure, number average molecular weight of about 600, isocyanurate content of 23.0%). 1%) and 120 parts of ethyl acetate are added, the temperature is raised to 100°C, and 80 parts of "Oxocol C13" (manufactured by Kyowa Yuka Co., Ltd., a structural isomer of tridecanol) is added under a nitrogen stream, and the mixture is maintained at 100°C for 2 hours. held. After that, 345 parts of diethyl malonate and 60 parts of ethyl acetate were added and the temperature was kept at 60°C. Then, 7.0 parts of a 28% methanol solution of sodium methoxide was added under a nitrogen stream, and the temperature was kept at 60°C for 12 hours. An isocyanate compound solution was obtained. The NCO value was measured and found to have an isocyanate content of 0.1%. 605 g of this blocked polyisocyanate compound solution was taken out into another similar reactor, 488 parts of 2-ethylhexanol was added, and the temperature was raised to 90°C. Under reduced pressure, the solvent was distilled off and removed over 1.5 hours while maintaining the temperature of the system at 90 to 110° C. to obtain 872 parts of a blocked polyisocyanate compound solution. The stripped solvent simple trap contained 43 parts ethanol. 2-Ethylhexanol was added to the resulting blocked polyisocyanate compound solution to obtain a blocked polyisocyanate compound solution H-1 having a solid content of 80%. The blocked polyisocyanate compound had a number average molecular weight of about 3,500.
(注3)「ユーバン28-60」:三井化学社製、ブチルエーテル化メラミン樹脂、固形分60%。 (Note 3) “Uban 28-60”: manufactured by Mitsui Chemicals, butyl etherified melamine resin, solid content 60%.
(注4)PHR:遮熱上塗塗料組成物中の樹脂固形分100質量部を基準にした顔料の含有量の単位(Per Hundred Resin)。
(Note 4) PHR: A unit of pigment content based on 100 parts by mass of resin solid content in the thermal barrier topcoat composition (Per Hundred Resin).
<評価>
70×150×0.3cmのブリキ板上にCOODEフィラーホワイト(L90)(関西ペイント社製、プライマーサーフェイサー)を膜厚60μmとなるよう塗装したものを被塗物とし、実施例及び比較例で作成した遮熱上塗塗料組成物を気温20℃にて乾燥膜厚60μmとなるようにスプレー塗装を行った。実施例1、4~24及び比較例1~9については気温温度20℃、湿度75%の恒温恒湿室中にて1日静置、実施例2及び3については塗装後に120℃で30分間焼付乾燥を行うことで、各試験塗板を得た。得られた試験板について、後述する方法で、仕上がり性、耐水性、付着性の試験を行った。また、後述する方法で、隠蔽性、遮熱性能、乾燥性の試験を行った。
これらについて下記基準にてS、A、B、Cの4段階で評価を行った。評価結果を上記表3~6にあわせて示す。なお、本発明においては、評価試験における全項目の性能に優れていることが重要であり、いずれか1つに「C」の評価がある場合、不合格となる。
<Evaluation>
A 70 × 150 × 0.3 cm tin plate coated with COODE Filler White (L90) (manufactured by Kansai Paint Co., Ltd., Primer Surfacer) to a film thickness of 60 μm was used as an object to be coated, and was prepared in Examples and Comparative Examples. The resulting thermal barrier topcoat composition was spray-coated at an air temperature of 20°C so as to give a dry film thickness of 60 µm. Examples 1, 4 to 24, and Comparative Examples 1 to 9 were left to stand for one day in a constant temperature and humidity room with an air temperature of 20°C and a humidity of 75%. Each test coated plate was obtained by baking and drying. Finishability, water resistance, and adhesion were tested on the obtained test plates by the methods described later. In addition, the test of hiding property, heat shielding performance and drying property was conducted by the method described later.
These were evaluated in four grades of S, A, B, and C according to the following criteria. The evaluation results are also shown in Tables 3 to 6 above. In the present invention, it is important that all the items in the evaluation test are excellent in performance, and if any one of them is evaluated as "C", it is rejected.
隠蔽性評価
実施例及び比較例で作成した遮熱上塗塗料組成物を白黒隠蔽紙上に塗装し、隠蔽膜厚を測定した。評価基準は下記のとおりである。
S:隠蔽膜厚が50μm未満である。
A:隠蔽膜厚が50μm以上60μm未満である。
B:隠蔽膜厚が60μm以上70μm未満である。
C:隠蔽膜厚が70μm以上である。
Evaluation of Hiding Property Each of the heat-shielding topcoat compositions prepared in Examples and Comparative Examples was applied on a black-and-white hiding paper, and the hiding film thickness was measured. Evaluation criteria are as follows.
S: The hiding film thickness is less than 50 µm.
A: The concealing film thickness is 50 μm or more and less than 60 μm.
B: The concealing film thickness is 60 μm or more and less than 70 μm.
C: The concealing film thickness is 70 μm or more.
遮熱性能評価
70×150×0.3cmのブリキ板上に黒色塗料(レタンエコトップ黒:関西ペイント社製)を塗装して標準黒色塗板を作成した。断熱材の上に試験塗板と標準黒色塗板を置いて、断熱材の上方50cmの距離に設置したメタルハライドランプを照射し、標準黒色塗板の温度が80℃に達した時点における試験塗板の温度を測定した。評価基準は下記のとおりである。
S:試験塗板の温度が45℃未満である
A:試験塗板の温度が45℃以上50℃未満である。
B:試験塗板の温度が50℃以上55℃未満である。
C:試験塗板の温度が55℃以上である。
Evaluation of Thermal Insulation Performance A standard black coated plate was prepared by coating a tin plate of 70×150×0.3 cm with a black paint (Retan Eco Top Black: manufactured by Kansai Paint Co., Ltd.). Place the test coated plate and the standard black coated plate on the insulating material, irradiate the metal halide lamp installed at a distance of 50 cm above the insulating material, and measure the temperature of the test coated plate when the temperature of the standard black coated plate reaches 80 ° C. did. Evaluation criteria are as follows.
S: The temperature of the test coated plate is less than 45°C. A: The temperature of the test coated plate is 45°C or more and less than 50°C.
B: The temperature of the test coated plate is 50°C or more and less than 55°C.
C: The temperature of the test coated plate is 55°C or higher.
仕上がり性評価
各試験塗板の光沢を目視判定した。評価基準は下記のとおりである。
S:光沢が非常にあり良好である
A:光沢が良好である。
B:やや光沢が劣る。
C:光沢が非常に低く不良である。
Evaluation of finish The gloss of each test coated plate was visually evaluated. Evaluation criteria are as follows.
S: Very good gloss A: Good gloss.
B: Slightly inferior gloss.
C: Very low gloss and unsatisfactory.
乾燥性評価
実施例及び比較例で作成した遮熱上塗塗料組成物を、温度20℃、湿度75%の恒温恒湿室中で、塗装膜厚100μmとなるようにドクターブレードにてガラス板に塗装し、指で触って塗料が指に付かなくなるまでの指触乾燥時間を測定した。評価基準は下記のとおりである。
S:指触乾燥時間が5分未満である。
A:指触乾燥時間が5分以上、10分未満である。
B:指触乾燥時間が10分以上、15分未満である
C:指触乾燥時間が15分以上である。
Evaluation of dryness The thermal barrier topcoat paint compositions prepared in Examples and Comparative Examples were dried in a constant temperature and humidity room at a temperature of 20°C and a humidity of 75% with a doctor blade so that the coating thickness was 100 µm. The paint was applied to a glass plate and touched with a finger, and the dry-to-the-touch time until the paint stopped sticking to the finger was measured. Evaluation criteria are as follows.
S: The dry-to-the-touch time is less than 5 minutes.
A: Dry-to-touch time is 5 minutes or more and less than 10 minutes.
B: The dry-to-the-touch time is 10 minutes or longer and less than 15 minutes. C: The dry-to-the-touch time is 15 minutes or longer.
耐水性評価
各試験塗板を、温度20℃、湿度75%の恒温恒湿室中で7日間放置後、20℃の水道水に7日間浸漬させ、塗面状態を調べた。評価基準は下記のとおりである。
S:水浸漬後の試験塗板に異常がみられない。
A:水浸漬後の試験塗板にわずかにツヤ引けがみられる。
B:水浸漬後の試験塗板にツヤ引けがみられる。
C:水浸漬後の試験塗板にフクレが生じている。
Water resistance evaluation Each test coated plate was allowed to stand in a constant temperature and humidity room at 20°C and 75% humidity for 7 days, and then immersed in tap water at 20°C for 7 days to examine the state of the coated surface. Evaluation criteria are as follows.
S: No abnormality is observed on the test coated plate after being immersed in water.
A: Slight loss of luster is observed on the test coated plate after immersion in water.
B: Gloss loss is observed on the test coated plate after immersion in water.
C: Blistering occurs on the test coated plate after being immersed in water.
付着性評価
上記耐水性評価を行った後の各試験塗板について、布で水分を拭き取り、2mm四方の碁盤目を100個ナイフで素地に達するようにカットし、粘着テ-プによる剥離試験を行なった。評価基準は下記のとおりである。
S:剥離試験後の碁盤目の残数が95以上である。
A:剥離試験後の碁盤目の残数が80以上95未満である。
B:剥離試験後の碁盤目の残数が50以上80未満である。
C:剥離試験後の碁盤目の残数が50未満である。
Adhesion evaluation For each test coated plate after the above water resistance evaluation, water was wiped off with a cloth, 100 grids of 2 mm square were cut with a knife so as to reach the substrate, and adhesive tape was applied. A peel test was performed. Evaluation criteria are as follows.
S: The number of grids left after the peeling test is 95 or more.
A: 80 or more and less than 95 cross-cuts remaining after the peeling test.
B: 50 or more and less than 80 cross-cuts remaining after the peeling test.
C: Less than 50 cross-cuts remaining after peeling test.
Claims (13)
塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であって、
酸化チタンの含有量が樹脂固形分100質量部を基準にして80~145質量部である、遮熱上塗塗料組成物。 A solvent-based thermal barrier topcoat composition containing an acrylic polyol (a), a resin containing a polyester polyol (b) and a curing agent, a pigment containing titanium oxide, and an organic solvent,
The near-infrared wavelength region solar reflectance of the coating film is 80% or more and / or the brightness is 85 or more,
A thermal barrier topcoat composition having a titanium oxide content of 80 to 145 parts by mass based on 100 parts by mass of resin solids.
被塗物上に形成した塗膜の近赤外波長域日射反射率が80%以上及び/又は明度が85以上であって、
酸化チタンの含有量が樹脂固形分100質量部を基準にして40~145質量部であり、
さらに構造中に金属イオンを有さない有機顔料を樹脂固形分100質量部を基準にして5~20質量部含有する、遮熱上塗塗料組成物。 A solvent-based thermal barrier topcoat composition containing an acrylic polyol (a), a resin containing a polyester polyol (b) and a curing agent, a pigment containing titanium oxide, and an organic solvent,
The near-infrared wavelength region solar reflectance of the coating film formed on the object to be coated is 80% or more and / or the brightness is 85 or more,
The content of titanium oxide is 40 to 145 parts by mass based on 100 parts by mass of resin solids,
A thermal barrier topcoat composition further containing 5 to 20 parts by mass of an organic pigment having no metal ion in its structure based on 100 parts by mass of the solid content of the resin.
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