JP5209297B2 - Solvent-free two-component coating composition - Google Patents
Solvent-free two-component coating composition Download PDFInfo
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- JP5209297B2 JP5209297B2 JP2007337511A JP2007337511A JP5209297B2 JP 5209297 B2 JP5209297 B2 JP 5209297B2 JP 2007337511 A JP2007337511 A JP 2007337511A JP 2007337511 A JP2007337511 A JP 2007337511A JP 5209297 B2 JP5209297 B2 JP 5209297B2
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- 239000008199 coating composition Substances 0.000 title description 41
- 239000003973 paint Substances 0.000 claims description 123
- 239000003795 chemical substances by application Substances 0.000 claims description 58
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- 239000000049 pigment Substances 0.000 claims description 24
- 230000004888 barrier function Effects 0.000 claims description 21
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- 239000000203 mixture Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
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- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 239000012720 thermal barrier coating Substances 0.000 claims description 13
- 239000012024 dehydrating agents Substances 0.000 claims description 11
- 238000009500 colour coating Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000002524 organometallic group Chemical group 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
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- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- JGYUBHGXADMAQU-UHFFFAOYSA-N 2,4,6-triethylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(CC)=C1N JGYUBHGXADMAQU-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- TXDBDYPHJXUHEO-UHFFFAOYSA-N 2-methyl-4,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(SC)=C(N)C(C)=C1N TXDBDYPHJXUHEO-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 1
- JAWZFTORYMQYDT-UHFFFAOYSA-N 6-hexoxy-6-oxohexanoic acid Chemical compound CCCCCCOC(=O)CCCCC(O)=O JAWZFTORYMQYDT-UHFFFAOYSA-N 0.000 description 1
- 241001337993 Agathis <wasp> Species 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 235000015392 Sesbania grandiflora Nutrition 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、無溶媒２液型塗料組成物に関する。 The present invention relates to a solvent-free two-component coating composition.
道路面の塗装、金属性構造物、コンクリートの補修等の分野において無溶媒タイプの塗料組成物が使用されている（特許文献１〜４参照）。このような無溶媒タイプの塗料組成物は、屋外等のように塗料中の揮散の抑制が要求される用途において使用され、ラジカル重合型の塗料、エポキシ系塗料、ウレタン系塗料、ウレア系塗料等が公知である。 Solventless type coating compositions are used in the fields of road surface painting, metallic structures, concrete repair, and the like (see Patent Documents 1 to 4). Such solvent-free coating compositions are used in applications that require suppression of volatilization in paints such as outdoors, radical polymerization paints, epoxy paints, urethane paints, urea paints, etc. Is known.
しかし、ラジカル重合型の塗料は低分子モノマーを含むため、揮発性成分が含まれ臭気を生じたりする問題がある。また２液型エポキシ系塗料は、乾燥性や耐候性が不充分であることから、屋外で使用される塗料としての充分な性質を得ることが困難である。公知の無溶媒２液型ウレタン系塗料は、水分を有する被塗物上に塗装する場合、被塗物表面に存在する水分がイソシアネート化合物と反応することによって、二酸化炭素が発生し発泡を生じる、という問題を有する。よって、表面に水分が付着した被塗物表面に対しても、発泡を生じることなく塗装を行うことができるような性質が求められている。 However, since the radical polymerization type paint contains a low molecular weight monomer, there is a problem that a volatile component is contained and an odor is generated. In addition, since the two-pack type epoxy paint has insufficient drying properties and weather resistance, it is difficult to obtain sufficient properties as a paint used outdoors. When a known solvent-free two-component urethane-based paint is applied onto an object having moisture, the water present on the surface of the object reacts with an isocyanate compound, thereby generating carbon dioxide and causing foaming. Have the problem. Accordingly, there is a demand for properties that allow the surface of an object to be coated with moisture to be applied without foaming.
また、道路舗装に代表されるアスファルト舗装は、一般的に黒色であるため太陽光のエネルギーを吸収し易く、特に夏期においては路面温度が高くなりやすい。また、自然地盤のように潜熱による熱の放出が期待できないことから路面温度が高くなり易い。特に、夏期において路面温度が６０℃程度に達することもあり、都市部では舗装比率が高く、環境温度が上昇し夜になっても気温が低下せず、いわゆるヒートアイランド現象が問題となっている。 In addition, asphalt pavement typified by road pavement is generally black, so it easily absorbs solar energy, and the road surface temperature tends to be high particularly in summer. Moreover, since the heat release due to latent heat cannot be expected unlike natural ground, the road surface temperature tends to be high. In particular, the road surface temperature may reach about 60 ° C. in summer, and the pavement ratio is high in urban areas. The environmental temperature rises and the temperature does not decrease even at night, so-called heat island phenomenon is a problem.
このような道路舗装におけるヒートアイランド現象を防止する方法として、遮熱塗料を塗装する方法が開示されている（特許文献５〜７参照）。しかし、このような遮熱塗料において上述するような性能を有する塗料組成物を使用することは開示されていない。
本発明は、上記現状に鑑み、揮発性成分が含まれないために臭気を生じることがなく、道路面の塗装等のように表面に水分が付着した被塗物に対しても発泡を生じることなく塗装を行うことができる乾燥性及び耐候性に優れた無溶媒２液型塗料組成物を提供することを目的とするものである。更に、遮熱性を付与することにより、道路舗装におけるヒートアイランド現象を防止することのできる塗料組成物を提供することも目的とするものである。 In view of the above-mentioned present situation, the present invention does not generate odor because it does not contain volatile components, and also causes foaming to the object to be coated such as paint on the road surface. An object of the present invention is to provide a solvent-free two-component coating composition excellent in drying and weather resistance that can be applied without any problems. It is another object of the present invention to provide a coating composition capable of preventing a heat island phenomenon in road pavement by imparting heat shielding properties.
本発明は、ヒドロキシル基を２個以上有するポリオール、芳香族ジアミン及びすべてのα位に配位した炭素原子が分岐した構造を有する２級ジアミンからなる群より選択される少なくとも一種の化合物を含有する無溶媒主剤（１）、並びに、脂肪族多官能イソシアネートを含有する無溶媒硬化剤（２）からなることを特徴とする無溶媒２液型塗料組成物である。
上記無溶媒主剤（１）は、更に脱水剤を含有することが好ましい。
上記脱水剤は、無溶媒主剤（１）と無溶媒硬化剤（２）との合計量に対して０．３〜５質量％の割合で含まれることが好ましい。
上記無溶媒主剤（１）は、有機金属触媒を含有することが好ましい。
上記有機金属触媒は、スズエステル及び／又はビスマスエステルであることが好ましい。
上記有機金属触媒は、スズエステルであり無溶媒主剤（１）の全量に対して０．０５〜０．３質量％の割合で含まれることが好ましい。
上記化合物は、ヒドロキシル基を２個以上有するポリオールであることが好ましい。
上記脂肪族多官能イソシアネートは、ヘキサメチレンジイソシアネート又はそのアダクト体、ビュレット体若しくはイソシアヌレート体であることが好ましい。
The present invention contains at least one compound selected from the group consisting of a polyol having two or more hydroxyl groups, an aromatic diamine, and a secondary diamine having a structure in which all α-coordinated carbon atoms are branched. A solventless two-component coating composition comprising a solventless main agent (1) and a solventless curing agent (2) containing an aliphatic polyfunctional isocyanate.
The solventless main agent (1) preferably further contains a dehydrating agent.
The dehydrating agent is preferably contained in a proportion of 0.3 to 5% by mass with respect to the total amount of the solventless main agent (1) and the solventless curing agent (2).
The solventless main agent (1) preferably contains an organometallic catalyst.
The organometallic catalyst is preferably a tin ester and / or a bismuth ester.
It is preferable that the said organometallic catalyst is a tin ester, and is contained in the ratio of 0.05-0.3 mass% with respect to the whole quantity of a solventless main ingredient (1).
The compound is preferably a polyol having two or more hydroxyl groups.
The aliphatic polyfunctional isocyanate is preferably hexamethylene diisocyanate or an adduct, burette or isocyanurate thereof.
本発明はまた、上述の無溶媒２液型塗料組成物に、原色顔料を更に含有する遮熱原色塗料組成物である。
本発明はまた、上述の遮熱原色塗料組成物が、白色遮熱原色塗料、赤色遮熱原色塗料、青色遮熱原色塗料及び黄色遮熱原色塗料であって、これらからなる群より選択される少なくとも一種の遮熱原色塗料からなる遮熱塗料組成物である。
上記遮熱塗料組成物は、膜厚１００μｍのフリーフィルムの赤外線領域（波長７８０〜２１００ｎｍ）での日射吸収率が以下の範囲内のものであることが好ましい。
白色遮熱原色塗料：０％以上１５％以下
赤色遮熱原色塗料：０％以上３０％以下
青色遮熱原色塗料：０％以上６０％以下
黄色遮熱原色塗料：０％以上３０％以下
以下、本発明を詳細に説明する。
The present invention is also a heat-shielding primary color coating composition that further contains a primary color pigment in the solventless two-component coating composition.
In the present invention, the above-described heat shielding primary color paint composition is a white heat shielding primary color paint, a red heat shielding primary color paint, a blue heat shielding primary color paint, and a yellow heat shielding primary color paint, and is selected from the group consisting of these A thermal barrier coating composition comprising at least one thermal barrier primary color coating.
The thermal barrier coating composition preferably has a solar absorptivity within the following range of a 100 μm-thick free film in the infrared region (wavelength 780 to 2100 nm).
White heat shield primary color paint: 0% to 15% Red heat shield primary color paint: 0% to 30% Blue heat shield primary color paint: 0% to 60% yellow heat shield primary color paint: 0% to 30% The present invention will be described in detail.
本発明は、ヒドロキシル基を２個以上有するポリオール、芳香族ジアミン及びすべてのα位に配位した炭素原子が分岐した構造を有する２級ジアミンからなる群より選択される少なくとも一種の化合物を含有する無溶媒主剤（１）、並びに、脂肪族多官能イソシアネートを含有する無溶媒硬化剤（２）からなる無溶媒２液型塗料組成物に関する。上述の主剤と硬化剤との組み合わせにすることにより、表面に水分が付着した被塗物表面に対しても、発泡を生じることなく塗装を行うことができるものである。通常、イソシアネート化合物を硬化剤として塗料組成物に配合する場合、反応性の高い芳香族イソシアネートを使用する。しかしながら、上記芳香族イソシアネートは、その反応性の高さから、被塗物表面に付着した水分と反応し、それによって二酸化炭素が発生し発泡を生じるという問題があった。本発明は、反応性が比較的低く、更に耐候性も向上できる脂肪族多官能イソシアネートを硬化剤とし、主剤にポリオール及び／又は特定のアミンを併用した塗料組成物とすることにより、上記問題を解決したものである。 The present invention contains at least one compound selected from the group consisting of a polyol having two or more hydroxyl groups, an aromatic diamine, and a secondary diamine having a structure in which all α-coordinated carbon atoms are branched. The present invention relates to a solventless two-component coating composition comprising a solventless main agent (1) and a solventless curing agent (2) containing an aliphatic polyfunctional isocyanate. By using a combination of the above-mentioned main agent and curing agent, coating can be performed without foaming even on the surface of the object to be coated on which moisture has adhered. Usually, when an isocyanate compound is blended in a coating composition as a curing agent, a highly reactive aromatic isocyanate is used. However, the aromatic isocyanate has a problem that due to its high reactivity, it reacts with moisture adhering to the surface of the object to be coated, thereby generating carbon dioxide and causing foaming. The present invention solves the above-mentioned problems by using a coating composition in which an aliphatic polyfunctional isocyanate that has relatively low reactivity and can further improve weather resistance is used as a curing agent, and a polyol and / or a specific amine are used in combination as a main agent. It has been solved.
上記脂肪族多官能イソシアネートとしては特に限定されず、例えば、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、シクロヘキサン−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４−ジイソシアネート、メチルシクロヘキサンジイソシアネート、イソホロンジイソシアネート等を挙げることができる。 The aliphatic polyfunctional isocyanate is not particularly limited, and examples thereof include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexane diisocyanate, and isophorone diisocyanate. be able to.
なかでも、ヘキサメチレンジイソシアネート及び／又はトリメチルヘキサメチレンジイソシアネートを用いることが、塗膜の耐チッピング性能や耐候性の観点から好ましく、ヘキサメチレンジイソシアネートが特に好ましい。上記脂肪族多官能イソシアネートとしては、これらのビュレット体、イソシアヌレート体、及び、アダクト体を用いてもよい。なお、上記脂肪族多官能イソシアネート化合物は、単独でも、２種以上を混合して用いることもできる。 Among these, hexamethylene diisocyanate and / or trimethylhexamethylene diisocyanate is preferably used from the viewpoint of chipping resistance and weather resistance of the coating film, and hexamethylene diisocyanate is particularly preferable. As the aliphatic polyfunctional isocyanate, these burettes, isocyanurates, and adducts may be used. In addition, the said aliphatic polyfunctional isocyanate compound can also be used individually or in mixture of 2 or more types.
本発明の無溶媒２液型塗料組成物は、主剤として、ヒドロキシル基を２個以上有するポリオール、芳香族ジアミン及びすべてのα位に配位した炭素原子が分岐した２級ジアミンからなる群より選択される少なくとも一種の化合物を含有する無溶媒主剤を用いるものである。上記無溶剤主剤を用いることにより、反応性の比較的低い脂肪族多官能イソシアネートを硬化剤として使用しても、良好な塗膜性能を得ることができると考えられる。 The solvent-free two-component coating composition of the present invention is selected from the group consisting of a polyol having two or more hydroxyl groups, an aromatic diamine, and a secondary diamine in which all the carbon atoms coordinated to the α-position are branched. A solvent-free main ingredient containing at least one kind of compound is used. By using the solvent-free main agent, it is considered that good coating performance can be obtained even when an aliphatic polyfunctional isocyanate having a relatively low reactivity is used as a curing agent.
上記ポリオールとしては特に限定されないが、得られる無溶媒２液型塗料組成物の粘度を無溶媒型としての使用が容易となる範囲内にするため、質量平均分子量が下限１００、上限３０００の範囲であることが好ましい。上記下限は、５００がより好ましく、上記上限は、１０００がより好ましい。 Although it does not specifically limit as said polyol, In order to make the viscosity of the solvent-free two-component coating composition obtained within a range that can be easily used as a solvent-free type, the mass average molecular weight is in the range of the lower limit of 100 and the upper limit of 3000. Preferably there is. The lower limit is more preferably 500, and the upper limit is more preferably 1000.
上記ポリオールとしては、水酸基価が５０〜２０００ｍｇＫＯＨ／ｇであることが好ましい。上記水酸基価が５０ｍｇＫＯＨ／ｇ未満であると、完成膜の強度が不足するおそれがあるため好ましくない。上記水酸基価が２０００ｍｇＫＯＨ／ｇを超えると、完成膜の柔軟性が失われるおそれがある。 As said polyol, it is preferable that a hydroxyl value is 50-2000 mgKOH / g. If the hydroxyl value is less than 50 mgKOH / g, the strength of the finished film may be insufficient, such being undesirable. If the hydroxyl value exceeds 2000 mgKOH / g, the flexibility of the finished film may be lost.
上記ポリオールとしては特に限定されず、例えば、ポリエーテルジオール、ポリエステルジオール、ポリカーボネートジオール等を挙げることができ、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンプロピレングリコール、ポリテトラメチレンエーテルグリコール、ポリヘキサメチレンエーテルグリコール、ポリオクタメチレンエーテルグリコール等のポリアルキレングリコール、ポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリネオペンチルアジペート、ポリ−３−メチルペンチルアジペート、ポリエチレン／ブチレンアジペート、ポリネオペンチル／ヘキシルアジペート等のポリエステルジオール、ポリカプロラクトンジオール、ポリ−３−メチルバレロラクトンジオール等のポリラクトンジオール、ポリヘキサメチレンカーボネートジオール等のポリカーボネートジオール、ひまし油系ポリオール、これらの変性物及びこれらの混合物等を挙げることができる。なかでも、低粘度であるため、ひまし油系ポリオールが好ましい。 Examples of the polyol include, but are not limited to, polyether diol, polyester diol, and polycarbonate diol. Examples include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol. Polyalkylene glycols such as polyoctamethylene ether glycol, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, polyneopentyl / hexyl adipate, etc. Polyester diol, polycaprolactone diol, poly-3-methylvalerolactone Polylactone diols such as all, polycarbonate diols such as polyhexamethylene carbonate diol, castor oil-based polyol, and the like can be given modified products thereof, and mixtures thereof. Of these, castor oil-based polyol is preferred because of its low viscosity.
上記ひまし油系ポリオールとしては特に限定されず、ひまし油及びその誘導体、例えば、ひまし油脂肪酸のジグリセライド、モノグリセライド及びこれらの混合物等を挙げることができる。 The castor oil-based polyol is not particularly limited, and examples thereof include castor oil and derivatives thereof, for example, diglyceride of castor oil fatty acid, monoglyceride, and mixtures thereof.
上記芳香族ジアミンとしては特に限定されず、例えば、ジエチルジアミノトルエン、４，４’−ジアミノ−３，３’−ジクロロジフェニルメタン、２，４−ジアミノトルエン、２，６−ジアミノトルエン、１−メチル−３，５−ジエチル−２，４−ジアミノベンゼン、１−メチル−３，５−ジエチル−２，６−ジアミノベンゼン（両者はまたジエチルトルエンジアミンまたはＤＥＴＤＡと称される）、１，３，５−トリエチル−２，６−ジアミノベンゼン、４，４’−ジアミノジフェニルメタン、３，５，３’，５’−テトラエチル−４，４’−ジアミノジフェニルメタン、３，５−ジメチルチオ−２，４−トルエンジアミン、３，５−ジメチルチオ−２，６−トルエンジアミン等を挙げることができる。これらは単独で使用してもよく、２種以上を併用してもよい。特に好ましい芳香族ジアミンは、ジエチルジアミノトルエン、４，４’−ジアミノ−３，３’−ジクロロジフェニルメタンである。 The aromatic diamine is not particularly limited. For example, diethyldiaminotoluene, 4,4′-diamino-3,3′-dichlorodiphenylmethane, 2,4-diaminotoluene, 2,6-diaminotoluene, 1-methyl- 3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene (both also referred to as diethyltoluenediamine or DETDA), 1,3,5- Triethyl-2,6-diaminobenzene, 4,4′-diaminodiphenylmethane, 3,5,3 ′, 5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,5-dimethylthio-2,4-toluenediamine, Examples include 3,5-dimethylthio-2,6-toluenediamine. These may be used alone or in combination of two or more. Particularly preferred aromatic diamines are diethyldiaminotoluene, 4,4'-diamino-3,3'-dichlorodiphenylmethane.
本発明における２級アミンは、すべてのα位に配位した炭素原子が分岐した構造を有する２級ジアミンであり、すなわち、立体障害等により反応性を抑制した２級ジアミンである。このような２級ジアミンを使用することにより、無溶媒主剤（１）と無溶媒硬化剤（２）とを混合した際のゲルタイムを好適に調整することができる。上記２級ジアミンとしては特に限定されないが、例えば、水添ジアミノジフェニルメタンにマレイン酸ジエチルを付加した下記式（Ａ）で表される化合物等を挙げることができる。 The secondary amine in the present invention is a secondary diamine having a structure in which all carbon atoms coordinated at the α-position are branched, that is, a secondary diamine having suppressed reactivity due to steric hindrance or the like. By using such a secondary diamine, it is possible to suitably adjust the gel time when the solventless main agent (1) and the solventless curing agent (2) are mixed. Although it does not specifically limit as said secondary diamine, For example, the compound etc. which are represented by the following formula (A) which added diethyl maleate to hydrogenated diaminodiphenylmethane can be mentioned.
上記無溶媒主剤（１）は、上記ポリオール、上記芳香族ジアミン及び上記２級アミンのうち、１種又は２種以上の化合物を組み合わせたものである。なかでも、ポリオールが好ましい。 The solventless main agent (1) is a combination of one or more compounds among the polyol, the aromatic diamine and the secondary amine. Of these, polyol is preferable.
本発明の無溶媒２液型塗料組成物において、上記無溶媒主剤（１）と無溶媒硬化剤（２）とは、上記無溶媒主剤（１）中のポリオール、芳香族ジアミン及び２級アミンに由来する活性水素当量１モルに対し、無溶媒硬化剤（２）中の脂肪族多官能イソシアネートに由来するイソシアネート基当量が１〜１．２モルとなる範囲で混合されることが好ましい。 In the solvent-free two-component coating composition of the present invention, the solventless main agent (1) and the solventless curing agent (2) are the polyol, aromatic diamine and secondary amine in the solventless main agent (1). It is preferable that the isocyanate group equivalent derived from the aliphatic polyfunctional isocyanate in the solvent-free curing agent (2) is mixed within a range of 1 to 1.2 mol per 1 mol of the derived active hydrogen equivalent.
上記無溶媒主剤（１）は、更に脱水剤を含有することが好ましい。上記脱水剤を含有することにより、塗装面に付着している水分と上記脂肪族多官能イソシアネートとの反応による二酸化炭素の発生をより抑制し、塗膜上に凹凸や多孔が発生することを防止することができる。上記脱水剤としては特に限定されず、従来公知のものを挙げることができるが、例えば、合成ゼオライトのモレキュラーシーブ、硫酸カルシウム、酸化カルシウム等を挙げることができる。上記脱水剤の配合量は、上記無溶媒主剤（１）及び無溶媒硬化剤（２）を混合した状態で、これらを合計した量に対して０．３〜５質量％の割合で含有されることが好ましい。上記脱水剤の配合量が０．３質量％未満であると、無溶媒２液型塗料組成物に含まれる水分を充分に脱水できない場合がある。上記配合量が５質量％を超えると、それ以上の効果を得ることができない。 The solventless main agent (1) preferably further contains a dehydrating agent. By containing the above dehydrating agent, the generation of carbon dioxide due to the reaction between the water adhering to the painted surface and the above aliphatic polyfunctional isocyanate is further suppressed, and unevenness and porosity are prevented from occurring on the coating film. can do. Although it does not specifically limit as said dehydrating agent, A conventionally well-known thing can be mentioned, For example, the molecular sieve of a synthetic zeolite, a calcium sulfate, a calcium oxide etc. can be mentioned. The amount of the dehydrating agent is 0.3 to 5% by mass with respect to the total amount of the solventless main agent (1) and the solventless curing agent (2) mixed. It is preferable. If the blending amount of the dehydrating agent is less than 0.3% by mass, the water contained in the solventless two-component coating composition may not be sufficiently dehydrated. If the blending amount exceeds 5% by mass, no further effect can be obtained.
本発明の無溶媒２液型塗料組成物は、更に、硬化触媒を含有することが好ましい。この場合、上記硬化触媒を上記無溶媒主剤（１）に添加することができる。上記硬化触媒としては特に限定されず、従来公知のものが使用でき、例えば、有機金属触媒等を挙げることができる。有機金属触媒としては、スズ、鉛、ビスマス、亜鉛等のエステルを用いることができる。具体的には、例えば、ジブチルスズジラウレート、ビスマストリス（２−エチルヘキサノエート）、オクチル酸鉛、ビスマスオクトエート等を挙げることができる。上記有機金属触媒としては、スズエステル及び／又はビスマスエステルが好ましい。 The solventless two-component coating composition of the present invention preferably further contains a curing catalyst. In this case, the curing catalyst can be added to the solventless main agent (1). The curing catalyst is not particularly limited, and a conventionally known catalyst can be used, and examples thereof include an organometallic catalyst. As the organometallic catalyst, esters such as tin, lead, bismuth, and zinc can be used. Specific examples include dibutyltin dilaurate, bismuth tris (2-ethylhexanoate), lead octylate, bismuth octoate, and the like. As said organometallic catalyst, a tin ester and / or a bismuth ester are preferable.
上記有機金属触媒としてスズエステルを使用する場合、無溶媒主剤（１）の全量に対して０．０５〜０．３質量％の割合で含まれることが好ましい。この添加量は、通常より多いものである。すなわち、本発明では、反応性が低い脂肪族多官能イソシアネートを使用するものであることから、上記硬化触媒の添加量を多くすることによって反応性を調整することが好ましい。すなわち、硬化剤として反応性が低い脂肪族多官能イソシアネートを使用して水との反応を遅延し、かつ、硬化触媒量を増やすことで硬化剤の反応を促進するものである。これによって、全体としての水との反応速度が相対的に遅くなり、発泡を抑制することができる。 When using a tin ester as said organometallic catalyst, it is preferable to be contained in the ratio of 0.05-0.3 mass% with respect to the whole quantity of a solvent-free main ingredient (1). This addition amount is larger than usual. That is, in the present invention, since an aliphatic polyfunctional isocyanate having low reactivity is used, it is preferable to adjust the reactivity by increasing the amount of the curing catalyst added. That is, the reaction of the curing agent is promoted by delaying the reaction with water using an aliphatic polyfunctional isocyanate having low reactivity as the curing agent and increasing the amount of the curing catalyst. Thereby, the reaction rate with water as a whole becomes relatively slow, and foaming can be suppressed.
上記硬化触媒の配合量が０．０５質量％未満であると、発泡が生じるおそれがある。上記硬化触媒の配合量が０．３質量％を超えると、硬化が早くなりすぎて取り扱い性が低下する場合がある。 There exists a possibility that foaming may arise that the compounding quantity of the said curing catalyst is less than 0.05 mass%. When the blending amount of the curing catalyst exceeds 0.3% by mass, curing may be accelerated and handling properties may be deteriorated.
本発明の無溶媒２液型塗料組成物は、上記成分以外に、顔料や、可塑剤、粘性制御剤、消泡剤、光劣化防止剤、分散剤、レベリング剤、酸化防止剤、紫外線防止剤等の通常塗料に配合される添加剤を含んでいてもよい。これらの成分を配合する場合、上記無溶媒主剤（１）及び無溶媒硬化剤（２）のいずれに配合してもよい。 In addition to the above components, the solvent-free two-component coating composition of the present invention includes pigments, plasticizers, viscosity control agents, antifoaming agents, photodegradation inhibitors, dispersants, leveling agents, antioxidants, and UV inhibitors. Additives usually blended in paints such as When mix | blending these components, you may mix | blend with any of the said solvent-free main ingredient (1) and a solvent-free hardener (2).
本発明の無溶媒２液型塗料組成物の塗布方法としては特に限定されないが、例えば、上記無溶媒主剤（１）と無溶媒硬化剤（２）の２液の成分を衝突混合させて噴霧する２液衝突混合スプレー塗布を挙げることができる。上記２液衝突混合スプレー塗布は、高圧２液衝突混合型吹付装置を使用することが好ましい。更に、塗布直前に上記無溶媒主剤（１）と無溶媒硬化剤（２）とを混合し、ドクターブレード法等の塗布方法により塗装することもできる。また、２液をエアレスで連続的に押し出す方法や、スタティックミキサーで混合し、連続的にスプレーする方法等も使用できる。上記無溶媒主剤（１）と無溶媒硬化剤（２）とを混合した際に、ゲルタイムが短すぎると均一な塗膜を得ることができないおそれがある。本発明の無溶媒２液型塗料組成物は、上述の構成よりなるため、ゲルタイムを好適な範囲とすることができる。具体的には、上記ゲルタイムは１分以上であることが好ましい。 The method for applying the solventless two-component coating composition of the present invention is not particularly limited. For example, the two-component components of the solventless main agent (1) and the solventless curing agent (2) are collided and sprayed. Two-liquid collision mixed spray application can be mentioned. The two-liquid collision mixed spray coating is preferably performed using a high-pressure two-liquid collision mixed spraying apparatus. Further, the solventless main agent (1) and the solventless curing agent (2) can be mixed immediately before coating and coated by a coating method such as a doctor blade method. Moreover, the method of extruding two liquids continuously without air, the method of mixing with a static mixer, and spraying continuously can also be used. When the solventless main agent (1) and the solventless curing agent (2) are mixed, if the gel time is too short, a uniform coating film may not be obtained. Since the solvent-free two-component coating composition of the present invention has the above-described configuration, the gel time can be in a suitable range. Specifically, the gel time is preferably 1 minute or longer.
本発明の無溶媒２液型塗料組成物は、無溶媒であるため揮発性成分を放出せず、かつ、二酸化炭素による発泡を生じないものである。このため、金属製構造物やコンクリートの補修等、屋外での使用に好適に用いられる。上述のように、特に上記無溶媒２液型塗料組成物を屋外で使用する場合、上記無溶媒２液型塗料組成物は遮熱塗料であることが好ましい。 Since the solvent-free two-component coating composition of the present invention is solvent-free, it does not release volatile components and does not cause foaming due to carbon dioxide. For this reason, it is suitably used for outdoor use such as repairing metal structures and concrete. As described above, particularly when the solventless two-component coating composition is used outdoors, the solventless two-component coating composition is preferably a thermal barrier coating.
本発明の無溶媒２液型塗料組成物に遮熱性を付与するには、上記無溶媒２液型塗料組成物に後述の原色顔料を添加して得られた遮熱原色塗料を少なくとも１種以上組み合わせることにより行うことができる。上記無溶媒２液型塗料組成物に後述の原色顔料を更に含有した遮熱原色塗料組成物も本発明の一つである。上記遮熱原色塗料は、遮熱性を有するものであれば特に限定されないが、良好な遮熱性塗膜を形成することができるため、日射吸収率を低減した遮熱原色塗料を用いることが好ましい。上記遮熱原色塗料としては、白色遮熱原色塗料、赤色遮熱原色塗料、青色遮熱原色塗料及び黄色遮熱原色塗料からなる群より選択される少なくとも一種の遮熱原色塗料が好ましい。これらの遮熱原色塗料からなる遮熱塗料組成物も本発明の一つである。 In order to impart heat-shielding properties to the solvent-free two-component coating composition of the present invention, at least one or more kinds of heat-shielding primary color coatings obtained by adding a primary color pigment described later to the solvent-free two-component coating composition. It can be done by combining. A heat-shielding primary color coating composition that further contains a primary color pigment described later in the solventless two-component coating composition is also one aspect of the present invention. The heat-insulating primary color paint is not particularly limited as long as it has a heat-shielding property. However, since a good heat-shielding coating film can be formed, it is preferable to use a heat-insulating primary color paint having a reduced solar absorptivity. As the heat-shielding primary color paint, at least one heat-shielding primary color paint selected from the group consisting of a white heat-shielding primary color paint, a red heat-shielding primary color paint, a blue heat-shielding primary color paint, and a yellow heat-shielding primary color paint is preferable. A thermal barrier coating composition comprising these thermal barrier primary color coatings is also one aspect of the present invention.
上記白色遮熱原色塗料、赤色遮熱原色塗料、青色遮熱原色塗料及び黄色遮熱原色塗料として、膜厚１００μｍのフリーフィルムの赤外線領域（波長７８０〜２１００ｎｍ）での日射吸収率が以下の範囲内のものであることが好ましい。
白色遮熱原色塗料：０％以上１５％以下
赤色遮熱原色塗料：０％以上３０％以下
青色遮熱原色塗料：０％以上６０％以下
黄色遮熱原色塗料：０％以上３０％以下
道路面の遮熱においては、塗膜自体によるエネルギー線の吸収が温度上昇の直接の原因となる。したがって、塗料組成物の日射吸収率を調整し、エネルギー線の吸収が抑制された塗料組成物とすることによって、温度上昇を抑制することができるものである。
As the white heat-insulating primary color paint, red heat-insulating primary color paint, blue heat-insulating primary color paint and yellow heat-insulating primary color paint, the solar radiation absorption rate in the infrared region (wavelength 780 to 2100 nm) of a free film having a film thickness of 100 μm is as follows. It is preferable that it is inside.
White heat shield primary color paint: 0% or more and 15% or less Red heat shield primary color paint: 0% or more and 30% or less Blue heat shield primary color paint: 0% or more and 60% or less Yellow heat shield primary color paint: 0% or more and 30% or less Road surface In the heat insulation, the absorption of energy rays by the coating film itself directly causes the temperature rise. Therefore, temperature rise can be suppressed by adjusting the solar radiation absorption rate of the coating composition to obtain a coating composition in which absorption of energy rays is suppressed.
本発明において、上記日射吸収率は、膜厚１００μｍのフリーフィルムを使用して測定した値である。上記フリーフィルムは、測定対象となる遮熱原色塗料を離型紙にドクターブレード法により塗布して得られるものである。
しかしながら、例えば、アスファルト舗装体では、骨材の隙間や窪みが生じている場合が多く、排水のために無数の穴を有する構造となっているものもある。このようなアスファルト舗装体に塗装を行う場合、全体に均一な膜厚で塗膜を形成することは困難であるため、塗膜膜厚にバラツキが生じる。よって、このような不均一な膜厚となった場合にも一定の遮熱性を維持する必要がある。本発明においては、上記範囲内の日射吸収率を示す各色遮熱原色塗料を使用することにより、膜厚が１００〜１２００μｍ程度の広範囲となった場合にも良好な遮熱性を付与することができる。
In the present invention, the solar absorptance is a value measured using a free film having a thickness of 100 μm. The free film is obtained by applying a heat shielding primary color paint to be measured to a release paper by a doctor blade method.
However, for example, asphalt pavements often have aggregate gaps or depressions, and some have a structure with numerous holes for drainage. When coating such an asphalt pavement, since it is difficult to form a coating film with a uniform film thickness on the whole, the coating film thickness varies. Therefore, it is necessary to maintain a certain heat shielding property even when such a non-uniform film thickness is obtained. In the present invention, by using each color heat-shielding primary color paint exhibiting the solar radiation absorption rate within the above range, good heat-shielding properties can be imparted even when the film thickness is in the wide range of about 100 to 1200 μm. .
「日射吸収率」の用語の意義は、ＪＩＳ Ｒ ３１０６に定義されているが、本明細書における「日射吸収率」は、特に赤外線波長域に限定したものであり、７８０〜２１００ｎｍの波長域における各波長ごとの強度によりウエイト付けした吸収率を意味するものとする。上記日射吸収率の値は、上記各遮熱原色塗料を塗布して得られた膜厚１００μｍのフリーフィルムの日射吸収率であり、島津製作所製分光光度計ＵＶ−３６００を用いてＪＩＳ Ｒ ３１０６に準拠して測定したものである。ここで、離型紙に形成したフリーフィルムでの日射吸収率を規定した理由は、下地の影響を受けないようにするためである。 The meaning of the term “solar absorptance” is defined in JIS R 3106, but “solar absorptance” in this specification is particularly limited to the infrared wavelength region, and in the wavelength range of 780 to 2100 nm. It shall mean the absorptance weighted by the intensity for each wavelength. The value of the solar absorptivity is the solar absorptivity of a 100 μm-thick free film obtained by applying each of the heat-shielding primary color paints. The spectrophotometer UV-3600 manufactured by Shimadzu Corporation is used for JIS R 3106. It was measured in compliance. Here, the reason why the solar radiation absorption rate in the free film formed on the release paper is specified is to prevent the influence of the base.
上記各色遮熱原色塗料は、赤外線領域での日射吸収率を低減したものである。通常、調色用原色塗料は、可視光波長域には各色に対応する吸収があることが特徴であり、この吸収による日射反射率の低下、すなわち、日射吸収率の増加は避けることができない。本願で使用する遮熱原色塗料は、赤外線波長域の日射吸収率に着目し、その上限を下げることによって遮熱性を有するものであり、上記遮熱原色塗料を１種又は２種以上組み合わせることによって得られる本発明の無溶媒２液型塗料組成物は、良好な遮熱性を示す塗膜を形成することができるものである。更に、白色遮熱原色塗料、赤色遮熱原色塗料、青色遮熱原色塗料及び黄色遮熱原色塗料からなる群より選択される少なくとも一種の遮熱原色塗料を使用することにより、塗料組成物を任意の塗色にも調色することができるため好ましい。 Each of the above color-shielding primary color paints has a reduced solar absorptance in the infrared region. Usually, the primary color paint for toning is characterized by absorption corresponding to each color in the visible light wavelength range, and a decrease in solar reflectance due to this absorption, that is, an increase in solar absorption rate cannot be avoided. The heat shielding primary color paint used in the present application pays attention to the solar radiation absorptivity in the infrared wavelength region, and has a heat shielding property by lowering the upper limit. By combining one or more of the above heat shielding primary color paints, The obtained solvent-free two-component coating composition of the present invention can form a coating film having good heat shielding properties. Furthermore, the coating composition can be arbitrarily selected by using at least one kind of heat-shielding primary color paint selected from the group consisting of a white heat-shielding primary color paint, a red heat-shielding primary color paint, a blue heat-shielding primary color paint, and a yellow heat-shielding primary color paint. It is preferable because the color can be adjusted to the other coating color.
本発明の無溶媒２液型塗料組成物は、上記のように日射吸収率が一定範囲内にある遮熱原色塗料を組み合わせることにより調色することが好ましい。ここで、「組み合わせる」とは、例えば、混合することによってこれらの原色とは異なる種々の色彩や色相を得る操作等を意味する。ここで「遮熱原色塗料」とは、組み合わせることによりすべての色彩の塗料を作成することができるものである。 The solvent-free two-component paint composition of the present invention is preferably toned by combining the heat-shielding primary color paints having a solar radiation absorption rate within a certain range as described above. Here, “combining” means, for example, an operation for obtaining various colors and hues different from these primary colors by mixing. Here, the “heat-shielding primary color paint” can create paints of all colors by combining them.
上記遮熱原色塗料は、原色を呈する顔料である原色顔料と、本発明で無溶媒主剤（１）に含有される上記ポリオール、芳香族ジアミン及び２級アミンからなる群より選択される少なくとも一種の化合物と、無溶媒硬化剤（２）とを構成成分として得ることができる。 The heat-shielding primary color paint is at least one selected from the group consisting of a primary color pigment that is a primary color pigment and the polyol, aromatic diamine, and secondary amine contained in the solvent-free main agent (1) in the present invention. A compound and a solventless curing agent (2) can be obtained as constituent components.
上記遮熱原色塗料に用いられる原色顔料としては特に限定されず、例えば、下記の顔料等を挙げることができる。白色遮熱原色塗料用の原色顔料としては、酸化チタンである、タイペークＣＲ−９７（石原チタン工業社製）等を挙げることができる。
赤色遮熱原色塗料用の原色顔料としては、Ｆａｓｔｏｇｅｎ Ｓｕｐｅｒ Ｍａｇｅｎｔａ ＲＨ（大日本インキ化学工業社製）、Ｆａｓｔｏｇｅｎ Ｒｅｄ ７１００Ｙ（大日本インキ化学工業社製）、ルビクロンレッド４００ＲＧ（大日本インキ化学工業社製）、パシフィックレッド２０２０（チバスペシャルティ・ケミカルズ社製）等を挙げることができる。また、これらの赤色系原色顔料を２種以上組み合わせて使用してもよい。
The primary color pigment used in the heat shielding primary color paint is not particularly limited, and examples thereof include the following pigments. Examples of the primary color pigment for the white heat-shielding primary color coating include titanium CR-97 (manufactured by Ishihara Titanium Industry Co., Ltd.), which is titanium oxide.
As primary color pigments for red heat-shielding primary color paints, Fastogen Super Magenta RH (manufactured by Dainippon Ink and Chemicals), Fastogen Red 7100Y (manufactured by Dainippon Ink and Chemicals), Rubycron Red 400RG (Dainippon Ink and Chemicals) Manufactured), Pacific Red 2020 (manufactured by Ciba Specialty Chemicals), and the like. Further, two or more of these red primary color pigments may be used in combination.
青色遮熱原色塗料用の原色顔料としては、ダイピロキサイドカラーブルー９４５３（大日精化工業社製）、Ｆａｓｔｏｇｅｎ Ｂｌｕｅ ５４８５（大日本インキ化学工業社製）、Ｆａｓｔｏｇｅｎ Ｂｌｕｅ ＲＳ（大日本インキ化学工業社製）、シアニンブルー５２４０ＫＢ（大日精化工業社製）、リオノールブルーＳＰＧ−８（大日精化工業社製）等を挙げることができる。これらの青色系原色顔料を２種以上組み合わせて使用してもよい。
黄色遮熱原色塗料用の原色顔料としては、Ｓｙｍｕｌｅｒ Ｆａｓｔ Ｙｅｌｌｏｗ ４１９２（大日本インキ化学工業社製）、シコパールイエロー Ｌ−１１１０（ＢＡＳＦ社製）、イルガカラーイエロー２ＧＬＭＡ（チバスペシャルティ・ケミカルズ社製）等を挙げることができる。これらの黄色系原色顔料を２種以上組み合わせて使用してもよい。
As primary color pigments for blue heat-shielding primary color paints, dipyroxide color blue 9453 (manufactured by Dainichi Seika Kogyo Co., Ltd.), Fastogen Blue 5485 (manufactured by Dainippon Ink & Chemicals Inc.), Fastogen Blue RS (Dainippon Ink Chemical Co., Ltd.) Product), cyanine blue 5240KB (manufactured by Dainichi Seika Kogyo Co., Ltd.), Lionol Blue SPG-8 (manufactured by Dainichi Seika Kogyo Co., Ltd.) and the like. Two or more of these blue primary color pigments may be used in combination.
As primary color pigments for yellow heat-shielding primary color paints, Symbol Fast Yellow 4192 (manufactured by Dainippon Ink & Chemicals), Sikopearl Yellow L-1110 (manufactured by BASF), Irga Color Yellow 2GLMA (manufactured by Ciba Specialty Chemicals) Etc. Two or more of these yellow primary color pigments may be used in combination.
上記遮熱原色塗料には、必要に応じて、微粒子状の充填剤、添加剤等を含んでいてもよい。上記微粒子状の充填剤としては特に限定されず、例えば、ＳｉＯ２、ＺｒＯ２、３Ａｌ２Ｏ３・２ＳｉＯ２、ケイ酸ジルコニア、セラミックビーズ等からなる微粒子、繊維状又は粒状の微細ガラス、ガラスビーズ等を挙げることができる。上記微粒子状とは、粒子状、球状、中空球状の何れでもよい。 The above-described heat-shielding primary color paint may contain fine particle fillers, additives, and the like as necessary. The fine particle filler is not particularly limited. For example, fine particles composed of SiO 2 , ZrO 2 , 3Al 2 O 3 .2SiO 2 , zirconia silicate, ceramic beads, etc., fibrous or granular fine glass, glass beads Etc. The fine particles may be any of particles, spheres, and hollow spheres.
上記添加剤としては特に限定されず、例えば、シリカ、アルミナ等の艶消し剤、消泡剤、レベリング剤、たれ防止剤、表面調整剤、粘性調整剤、分散剤、紫外線吸収剤、ワックス等の慣用の添加剤等を挙げることができる。 The additive is not particularly limited, and examples thereof include matting agents such as silica and alumina, antifoaming agents, leveling agents, sagging inhibitors, surface conditioners, viscosity modifiers, dispersants, ultraviolet absorbers, waxes and the like. Conventional additives and the like can be mentioned.
上記遮熱原色塗料を調製する方法としては特に限定されず、例えば、ロールミル、ペイントシェーカー、ポットミル、ディスパー、サンドグラインドミル等の一般に顔料分散に使用されている機械を用いて、上記ポリオール、芳香族ジアミン及び２級アミンからなる群より選択される少なくとも一種の化合物に上記原色塗料用顔料を混合し、必要に応じて充填剤、添加剤等を加えることによりあらかじめ無溶媒主剤（１）を調製し、これに無溶媒硬化剤（２）を混合して上記遮熱原色塗料を調製することができる。 The method for preparing the heat-shielding primary color paint is not particularly limited. For example, the polyol, the aromatic, using a machine generally used for pigment dispersion, such as a roll mill, a paint shaker, a pot mill, a disper, and a sand grind mill. The solvent-free main agent (1) is prepared in advance by mixing the primary color paint pigment with at least one compound selected from the group consisting of diamines and secondary amines, and adding fillers, additives and the like as necessary. The solvent-free curing agent (2) can be mixed with this to prepare the above-described heat-shielding primary color paint.
上記遮熱原色塗料を組み合わせて遮熱塗料としての無溶媒２液型塗料組成物を調製する方法としては特に限定されず、上記遮熱原色塗料を１種又は２種以上組み合わせて混合する方法を挙げることができる。また、あらかじめ原色顔料の添加された無溶媒主剤（１）を１種又は２種以上混合し、塗装前に無溶媒硬化剤（２）を所定量混合して本発明の塗料組成物を調製することもできる。
本発明の無溶媒２液型塗料組成物を遮熱塗料として塗装する場合、膜厚が２００〜８００μｍ程度となるように塗装することが好ましい。
A method for preparing a solvent-free two-component coating composition as a heat-shielding paint by combining the heat-shielding primary color paint is not particularly limited, and a method of mixing the heat-shielding primary color paints in combination of one or more kinds. Can be mentioned. In addition, the solvent-free main agent (1) to which the primary color pigment has been added in advance is mixed, or a predetermined amount of the solvent-free curing agent (2) is mixed before coating to prepare the coating composition of the present invention. You can also.
When the solvent-free two-component coating composition of the present invention is applied as a thermal barrier coating, it is preferably applied so that the film thickness is about 200 to 800 μm.
本発明の無溶媒２液型塗料組成物は、遮熱塗料として使用することができるため、特に、道路面等の舗装体に用いた場合には、遮熱性塗膜を舗装体の表面に付与することができ、これによって、上述のようなヒートアイライド現象等の問題にも対応することができるため好ましい。上記舗装体としては特に限定されず、例えば、アスファルト舗装面、コンクリート舗装等を挙げることができる。 Since the solvent-free two-component coating composition of the present invention can be used as a heat-shielding paint, a heat-shielding coating film is applied to the surface of the pavement, particularly when used on a pavement such as a road surface. This is preferable because it can cope with problems such as the above-mentioned heat eye ride phenomenon. The pavement is not particularly limited, and examples thereof include an asphalt pavement surface and a concrete pavement.
本発明の無溶媒２液型塗料組成物により、二酸化炭素の発生を抑え、得られる塗膜表面に凹凸及び多孔が発生することを防止することができ、かつ、良好な乾燥性及び耐候性を有する塗膜を得ることができる。更に、本発明により、上述のような効果を維持しつつ、良好な遮熱性を有する塗膜を形成することができる。この良好な遮熱性を有する塗膜とは、従来の塗膜に比べて日射吸収率が低減されることによって、結果的に、日射反射率が高くなった塗膜をいう。すなわち、本発明により、従来より日射反射率の高い塗膜を得ることができ、そのことにより、遮熱性を発揮し、ヒートアイランド現象を防止することができる。ここで、上記日射反射率とは、ＪＩＳ Ｒ ３１０６に準拠して３００〜２１００ｎｍの波長域でのものである。 With the solvent-free two-component coating composition of the present invention, it is possible to suppress the generation of carbon dioxide, to prevent unevenness and porosity from occurring on the surface of the obtained coating film, and to have good drying properties and weather resistance. The coating film which has can be obtained. Furthermore, according to the present invention, it is possible to form a coating film having good heat shielding properties while maintaining the above-described effects. The coating film having a good heat shielding property refers to a coating film having a higher solar reflectance as a result of a reduction in solar radiation absorption as compared with a conventional coating film. That is, according to the present invention, it is possible to obtain a coating film having higher solar reflectance than before, thereby exhibiting heat shielding properties and preventing a heat island phenomenon. Here, the said solar reflectance is a thing in the wavelength range of 300-2100 nm based on JISR3106.
以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例１、２
樹脂としてＵＲＩＣ−Ｈ３６８（ヒマシ油系ポリオール、ＯＨ基２．５含有、伊藤製油（株）社製）、触媒としてジブチルスズラウレート（ＤＢＴＬ）及び脱水剤としてゼオラムＡ４（物質名ゼオライト、東ソー社製）、遮熱顔料（酸化チタン、タイペークＣＲ−９７、石原チタン工業社製）を表１に示した配合量（単位：質量％）で混合し、無溶媒主剤を調製した。無溶媒硬化剤として脂肪族イソシアネート（物質名ヘキサメチレンジイソシアネートの三量体、コロネートＨＸＬＶ：日本ポリウレタン社製）を官能基当量で活性水素：ＮＣＯ＝１：１．１の割合になるように使用した。得られた無溶媒主剤及び無溶媒硬化剤を塗布直前に混合した後、３０ｍｉｌドクターブレードを使用して被塗装物（木材：アガチス材）に乾燥膜厚４００μｍになるように塗装して、試験板を得た。
なお、表１中のゲルタイムは、上記無溶媒主剤と無溶媒硬化剤とを５０℃で混合した際に混合物の流動性がなくなるまでに要した時間である。
Examples 1 and 2
URIC-H368 (castor oil-based polyol, containing OH group 2.5, manufactured by Ito Oil Co., Ltd.) as a resin, dibutyltin laurate (DBTL) as a catalyst, and Zeolum A4 (substance name zeolite, manufactured by Tosoh Corporation) as a dehydrating agent In addition, a heat-shielding pigment (titanium oxide, Taipei CR-97, manufactured by Ishihara Titanium Industry Co., Ltd.) was mixed in the blending amount (unit: mass%) shown in Table 1 to prepare a solvent-free main agent. As a solvent-free curing agent, an aliphatic isocyanate (trimer of the substance hexamethylene diisocyanate, Coronate HXLV: manufactured by Nippon Polyurethane Co., Ltd.) was used so as to have a functional group equivalent of active hydrogen: NCO = 1: 1.1. . After mixing the obtained solvent-free main agent and solvent-free curing agent immediately before coating, a 30 mil doctor blade is used to coat the object to be coated (wood: agathis material) to a dry film thickness of 400 μm. Got.
In addition, the gel time in Table 1 is the time required until the fluidity of the mixture is lost when the solventless main agent and the solventless curing agent are mixed at 50 ° C.
得られた試験板について、下記の評価を行った。結果を表１に示す。
発泡性
各試験板の塗膜の表面状態を目視にて評価した後、カッターナイフで塗膜を切断し、その断面から塗膜の内部状態を同様にして評価した。評価基準は以下の通りとした。
◎：表面にも内部にも気泡及び気泡の跡は見られない。
○：表面には若干の気泡の跡は見られるが、内部には気泡は見られない。
△：表面、内部ともに若干の気泡の跡が見られる。
×：表面にも内部にも気泡及び気泡の跡が見られる。
The following evaluation was performed about the obtained test board. The results are shown in Table 1.
After visually evaluating the surface state of the coating film of each foaming test plate, the coating film was cut with a cutter knife, and the internal state of the coating film was similarly evaluated from the cross section. The evaluation criteria were as follows.
(Double-circle): The bubble and the trace of a bubble are not seen on the surface or the inside.
○: Some traces of bubbles are seen on the surface, but no bubbles are seen inside.
Δ: Some traces of bubbles are seen on the surface and inside.
X: Bubbles and traces of bubbles are observed both on the surface and inside.
指触硬化時間（分）
常温下で得られた塗膜を指で触っても指紋が付かなくなるまでの時間を測定した。
Finger touch curing time (minutes)
The time until the fingerprint was not attached even when the coating film obtained at room temperature was touched with a finger was measured.
耐候性
得られた試験板を３０日間屋外に放置した。その後、６０度グロスを測定し、外観を評価した。評価基準を以下の通りとした。
○：光沢保持率が５０％以上である。
×：光沢保持率が５０％未満である。
The weatherproof test plate was left outdoors for 30 days. Then, 60 degree gloss was measured and the external appearance was evaluated. The evaluation criteria were as follows.
○: Gloss retention is 50% or more.
X: Gloss retention is less than 50%.
比較例１〜４
無溶媒硬化剤を芳香族イソシアネート（商品名ミリオネートＭＲ−２００：日本ポリウレタン社製）に変更して表１に示した配合量で混合し、無溶剤主剤を調製したこと以外は実施例と同様にして試験板を作成し、評価した。
Comparative Examples 1-4
The solvent-free curing agent was changed to an aromatic isocyanate (trade name Millionate MR-200: manufactured by Nippon Polyurethane Co., Ltd.) and mixed in the blending amounts shown in Table 1 to prepare a solvent-free base agent in the same manner as in the examples. A test plate was prepared and evaluated.
表１より、本発明の無溶媒２液型塗料組成物により得られた塗膜は、気泡の発生が抑制され、外観に優れることが示された。また、比較例２及び３の無溶媒２液型塗料組成物は、ゲルタイムが非常に短く、取り扱い性が不良であった。脱水剤を配合しなかった比較例１、２及び４は、特に発泡性が不良であった。また、硬化触媒を配合しなかった比較例１及び４は、ゲルタイム及び指触硬化時間が非常に長く、取り扱い性が不良であった。 From Table 1, it was shown that the coating film obtained by the solvent-free two-component coating composition of the present invention has excellent appearance with suppressed generation of bubbles. Moreover, the solvent-free two-component coating compositions of Comparative Examples 2 and 3 had very short gel times and poor handleability. In Comparative Examples 1, 2 and 4 in which no dehydrating agent was blended, the foamability was particularly poor. In Comparative Examples 1 and 4 in which no curing catalyst was blended, the gel time and the touch curing time were very long, and the handleability was poor.
実施例３
表３で示す配合により、遮熱原色塗料を２種以上組み合わせて遮熱塗料を調製し、これら遮熱塗料に対する日射反射率を測定した結果を表３及び図８に示す。日射反射率は、後述の方法により測定した。
なお、白色遮熱原色塗料は、実施例１で調製した塗料を白色遮熱原色塗料とした。
また、赤色遮熱原色塗料、青色遮熱原色塗料、黄色遮熱原色塗料は、タイペークＣＲ−９７に代えて、表２に示す顔料を表２に示す含有量になるように配合したこと以外は、実施例１と同様にして調製した。得られた各遮熱原色塗料のマンセル明度は、Ｎ４であった。
なお、上記遮熱塗料は、上記の通り表３で示す配合量となるように調整されたもとしているが、実際の調整操作では、あらかじめ所定の顔料を無溶剤主剤に配合して得られたものを、所定の色になるように混合し、塗装する直前に無溶媒硬化剤を所定量加えて遮熱塗料を調製した。
Example 3
Table 3 and FIG. 8 show the results of preparing thermal barrier paints by combining two or more thermal barrier primary color paints according to the formulation shown in Table 3 and measuring the solar reflectance for these thermal barrier paints. The solar reflectance was measured by the method described later.
In addition, the white heat-shielding primary color paint used the paint prepared in Example 1 as the white heat-shielding primary color paint.
In addition, the red heat-shielding primary color paint, the blue heat-shielding primary color paint, and the yellow heat-shielding primary color paint are blended so that the pigments shown in Table 2 have the contents shown in Table 2 in place of Type CR-97. Prepared in the same manner as in Example 1. The Munsell lightness of each of the obtained heat shielding primary color paints was N4.
In addition, although the said heat-shielding coating material has been adjusted so that it may become the compounding quantity shown in Table 3 as above-mentioned, in actual adjustment operation, it was obtained by mix | blending a predetermined pigment with a solvent-free main ingredient beforehand. Those were mixed so as to have a predetermined color, and a predetermined amount of solvent-free curing agent was added immediately before coating to prepare a thermal barrier coating.
参考例１及び２
表３で示す配合により、遮熱原色塗料及び一般原色塗料を２種以上組み合わせて遮熱塗料を調製したこと以外は実施例３と同様にして遮熱塗料を調製し、これら遮熱塗料に対する日射反射率を測定した結果を表３及び図８に示す。
なお、一般赤色原色塗料、一般黒色原色塗料、一般黄色原色塗料は、タイペークＣＲ−９７に代えて、表２に示す顔料を表２に示す含有量になるように配合したこと以外は、実施例１と同様にして調製した。得られた各一般原色塗料のマンセル明度は、Ｎ４であった。
Reference examples 1 and 2
According to the formulation shown in Table 3, heat insulating paints were prepared in the same manner as in Example 3 except that two or more heat insulating primary color paints and general primary color paints were combined to prepare a heat insulating paint. The results of measuring the reflectance are shown in Table 3 and FIG.
The general red primary color paint, the general black primary color paint, and the general yellow primary color paint were used in Examples except that the pigments shown in Table 2 were blended so as to have the contents shown in Table 2 instead of Type CR-97. 1 was prepared. The Munsell lightness of each of the obtained general primary color paints was N4.
日射反射率の測定
得られた各遮熱塗料を離型紙にドクターブレードを用いて塗布して得られたフリーフィルム（膜厚４００μｍ）をサンプルとして、島津社製分光光度計ＵＶ−３６００に島津社製ＵＶ３６００／３１００シリーズ用積分球付属装置を設置した測定装置を用いて測定した。
Measurement of solar reflectivity Each thermal barrier paint obtained was applied to a release paper using a doctor blade, and a free film (
ＪＩＳ Ｒ ３１０６に準拠して波長３００〜２１００ｎｍまでの分光反射率をもとに日射反射率を計算すると、実施例３、参考例１及び２で得られる遮熱塗料の日射反射率は、それぞれ４５．２％、１８．８％及び４１．９％であることが分かった。一般原色塗料を含まない実施例３の遮熱塗料は、良好な日射反射率を示し、遮熱塗料として有用であることが示された。一方、一般原色塗料を含む参考例１及び２の遮熱塗料は、実施例３よりも日射反射率が低下した。特に、カーボンブラックを含有する参考例１では顕著であった。また、一般原色塗料を用いて、所定の明度、ここではカーボンブラックを用いずにＮ４に調整した塗料に比べて本発明での遮熱塗料の日射反射率は高くなっていることが確認された。 When the solar reflectance is calculated based on the spectral reflectance up to a wavelength of 300-2100 nm in accordance with JIS R 3106, the solar reflectance of the thermal barrier paint obtained in Example 3 and Reference Examples 1 and 2 is 45, respectively. It was found to be 2%, 18.8% and 41.9%. The thermal barrier paint of Example 3 that does not contain a general primary color paint showed good solar reflectance and was shown to be useful as a thermal barrier paint. On the other hand, the solar radiation reflectance of the thermal barrier paints of Reference Examples 1 and 2 including the general primary color paint was lower than that of Example 3. This was particularly remarkable in Reference Example 1 containing carbon black. In addition, it was confirmed that the solar reflectance of the heat-shielding paint in the present invention is higher than that of a paint adjusted to N4 without using carbon black and using a general primary color paint. .
さらに、各遮熱原色塗料及び一般原色塗料の日射特性を評価した。上述の日射反射率の測定方法と同様にして得られたフリーフィルムをサンプルとして、同様の測定装置を用いて測定した。結果を図１〜７に示す。なお、フリーフィルム中に含まれる各顔料の含有量を表２に示した。図より、赤外線波長域における各遮熱原色塗料の膜厚１００μｍにおける日射吸収率は、白色遮熱原色塗料が５％であり、赤色遮熱原色塗料が２２％であり、青色遮熱原色塗料が３８．５％であり、黄色遮熱原色塗料が２０％であった。一方、一般赤色塗料及び一般黄色塗料の日射吸収率は高く（３０％超過）、一般黒色塗料の日射吸収率は９０％であることから、遮熱原色塗料には適さないことが示された。 Furthermore, the solar radiation characteristics of each heat shielding primary color paint and general primary color paint were evaluated. It measured using the same measuring apparatus by using the free film obtained by carrying out similarly to the measuring method of the above-mentioned solar reflectance as a sample. The results are shown in FIGS. The content of each pigment contained in the free film is shown in Table 2. From the figure, the solar radiation absorptivity of each heat-shielding primary color paint in the infrared wavelength region at a film thickness of 100 μm is 5% for the white heat-shielding primary color paint, 22% for the red heat-shielding primary color paint, and the blue heat-shielding primary color paint. It was 38.5%, and the yellow heat-shielding primary color paint was 20%. On the other hand, the general red paint and the general yellow paint have high solar absorptivity (exceeding 30%), and the general black paint has a solar absorptivity of 90%, indicating that it is not suitable for a heat-shielding primary color paint.
実施例４
実施例３で調製した遮熱塗料（マンセル明度Ｎ４）を一般アスファルト舗装面に膜厚が４００μｍとなるように塗装し、次いで、白色セラミック骨材（商品名「セラサンドＷＢ」美州興産社製）を０．６ｋｇ／ｍ２で散布した後、上記塗料が硬化した後に、更に上記の遮熱塗料を膜厚４００μｍになるように塗布して、すぐに０．２ｋｇ／ｍ２となるようにガラスカレット（商品名「クリスタルサンド」、環境保全サービス（株）社製）を散布して、再び硬化させた。そして、各時刻における路面温度を測定した。その結果を図に示す。なお、比較として、上記遮熱塗料を塗装していない一般アスファルト舗装面における路面温度も同日に測定した。
なお、日射透過率及び日射吸収率は、ＪＩＳ Ｒ ３１０６に準拠して、波長８００〜２１００ｎｍの範囲で計算した。フリーフィルムの調整は、上述したのと同様に、得られた遮熱塗料を離型紙にドクターブレードを用いて塗布して行った。
全天日射量は、長短波放射計（ＭＲ−５０、英弘精機社製）を用いて測定した。路面温度は、温度データーロガー（「温度とりＪｒ」、Ｔ＆Ｄ社製）で測定した。
その結果、上記の遮熱塗料を舗装面に塗装することにより１０℃程度の温度低下が確認された。
Example 4
The thermal barrier paint (Munsell lightness N4) prepared in Example 3 was applied to a general asphalt pavement surface to a film thickness of 400 μm, and then white ceramic aggregate (trade name “Cerasand WB” manufactured by Mishu Kosan Co., Ltd.) Is sprayed at 0.6 kg / m 2 , and after the coating is cured, the thermal barrier coating is further applied to a film thickness of 400 μm, and glass is immediately applied to 0.2 kg / m 2. The cullet (trade name “Crystal Sand”, manufactured by Environmental Conservation Service Co., Ltd.) was sprayed and cured again. And the road surface temperature in each time was measured. The results are shown in the figure. For comparison, the road surface temperature on a general asphalt pavement surface not coated with the thermal barrier paint was also measured on the same day.
In addition, the solar radiation transmittance and the solar radiation absorptivity were calculated in a wavelength range of 800 to 2100 nm in accordance with JIS R 3106. In the same manner as described above, the free film was adjusted by applying the obtained thermal barrier paint to a release paper using a doctor blade.
The total solar radiation amount was measured using a long / short wave radiometer (MR-50, manufactured by Eihiro Seiki Co., Ltd.). The road surface temperature was measured with a temperature data logger (“Temperature Jr”, manufactured by T & D).
As a result, a temperature drop of about 10 ° C. was confirmed by applying the above-described thermal barrier paint on the pavement surface.
本発明により、発泡性が抑制され、かつ、乾燥性及び耐光性に優れた無溶媒２液型塗料組成物を得ることができた。上記無溶媒２液型塗料組成物は、特に舗装体の塗装等、屋外での使用に好適に用いることができる。 According to the present invention, it was possible to obtain a solvent-free two-component coating composition with suppressed foamability and excellent drying and light resistance. The solvent-free two-component coating composition can be suitably used for outdoor use, particularly for paving.
Claims (4)
白色遮熱原色塗料：０％以上１５％以下
赤色遮熱原色塗料：０％以上３０％以下
青色遮熱原色塗料：０％以上６０％以下
黄色遮熱原色塗料：０％以上３０％以下 The solvent-free two-component thermal barrier coating composition according to claim 3, wherein the thermal barrier primary color coating has a solar absorptivity in the infrared range (wavelength of 780 to 2100 nm) of a free film having a thickness of 100 µm within the following range. object.
White heat shield primary color paint: 0% to 15% Red heat shield primary color paint: 0% to 30% Blue heat shield primary color paint: 0% to 60% Yellow heat shield primary color paint: 0% to 30%
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| CN112521849A (en) * | 2020-12-04 | 2021-03-19 | 榕珍新材料科技发展(上海)有限公司 | Weather-resistant solvent-free two-component polyurethane coating and preparation method and use method thereof |
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| JPH07166127A (en) * | 1993-12-13 | 1995-06-27 | Hamamatsu Puratetsuku:Kk | Abrasion-resistant thick coating material |
| JPH10292150A (en) * | 1997-04-16 | 1998-11-04 | Toagosei Co Ltd | Two pack type polyurethane coating |
| JP3933281B2 (en) * | 1997-12-03 | 2007-06-20 | 伊藤製油株式会社 | Urethane coating composition |
| JP3794837B2 (en) * | 1998-10-27 | 2006-07-12 | 長島特殊塗料株式会社 | Thermal barrier paint and coating method thereof |
| JP2007327328A (en) * | 2001-12-20 | 2007-12-20 | Nippo Corporation:Kk | Solar-heat interrupting paving body |
| JP2007009101A (en) * | 2005-07-01 | 2007-01-18 | Raito Black:Kk | Two-pack type aliphatic polyurea resin-forming composition |
| JP4404850B2 (en) * | 2005-12-28 | 2010-01-27 | 奥アンツーカ株式会社 | Thermal barrier paint |
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| KR101389961B1 (en) | 2014-03-14 | 2014-04-30 | 안효상 | Paint composition having improved oxidation resistance and thermal insulation effects, and method for producing and painting thereof |
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