JP6345462B2 - Water-based undercoat for road marking materials - Google Patents
Water-based undercoat for road marking materials Download PDFInfo
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- JP6345462B2 JP6345462B2 JP2014061996A JP2014061996A JP6345462B2 JP 6345462 B2 JP6345462 B2 JP 6345462B2 JP 2014061996 A JP2014061996 A JP 2014061996A JP 2014061996 A JP2014061996 A JP 2014061996A JP 6345462 B2 JP6345462 B2 JP 6345462B2
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- 239000000463 material Substances 0.000 title claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 40
- 239000000839 emulsion Substances 0.000 claims description 59
- 239000007787 solid Substances 0.000 claims description 50
- 239000003973 paint Substances 0.000 claims description 46
- 229920003051 synthetic elastomer Polymers 0.000 claims description 38
- 239000005061 synthetic rubber Substances 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 17
- 230000009477 glass transition Effects 0.000 claims description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 9
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229920000800 acrylic rubber Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002987 primer (paints) Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000010426 asphalt Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
既設の路面標示材料や路面の舗装の上に、路面標示材料の塗装に先行して塗装する、水性下塗り塗料に関する。 The present invention relates to a water-based undercoating paint that is applied on an existing road marking material or road pavement prior to the application of the road marking material.
路面標示材料の塗装の際に、路面標示材料と路面の舗装との間に十分な付着性を得るために、現状、溶剤型の下塗り塗料が塗装されている。このような下塗り塗料には、トルエンや酢酸エチル等の有機溶剤が使用されている。使用されるこれら溶剤は、アスファルト舗装表面や既設の路面標示材料の表面の樹脂成分を溶解する、あるいは、コンクリート舗装の表面から内部へ含浸して表層を強化することで路面標示材料の付着性向上に寄与している。 In order to obtain sufficient adhesion between the road marking material and the pavement of the road surface when the road marking material is applied, a solvent-type primer coating is currently applied. For such an undercoat paint, an organic solvent such as toluene or ethyl acetate is used. These solvents used improve the adhesion of road marking materials by dissolving the resin components on the surface of asphalt pavement and existing road marking materials, or by impregnating the surface of concrete pavement into the interior to strengthen the surface layer. It contributes to.
しかし、有機溶剤を使用した下塗り塗料では、近年の種々の法律、規制、環境等への影響の観点から、その揮発性有機溶剤（ＶＯＣ）の低減が求められている。さらに、トルエンや酢酸エチル等を含有している下塗り塗料では、引火の恐れがあり、取扱い時はもちろん、貯蔵時においても配慮が必要であると云った問題があった。 However, in the undercoat paint using an organic solvent, reduction of the volatile organic solvent (VOC) is required from the viewpoint of various laws, regulations, the environment and the like in recent years. Furthermore, the undercoating paint containing toluene, ethyl acetate or the like has a problem that there is a risk of ignition, and consideration must be given during storage as well as handling.
このような課題への解決法として、特許文献１にはトルエンを使用せず、代わりに高沸点芳香族系溶剤を使用するプライマーが提案されている。 As a solution to such a problem, Patent Document 1 proposes a primer that does not use toluene but instead uses a high-boiling aromatic solvent.
しかし、このような技術においても、結局、沸点１５０〜２６０℃の溶剤を２５〜３５質量％使用しているために、環境への影響の配慮や揮発性有機溶剤の低減効果は十分でない。また、一般に、交通を遮断して行うことが多く、迅速な処理が求められる路面標示設置作業で用いられるものであるにもかかわらず、高沸点溶剤を用いているために、乾燥時間が長いなどの大きな問題を有し、その改善が求められていた。 However, even in such a technique, since the solvent having a boiling point of 150 to 260 ° C. is used in an amount of 25 to 35% by mass, the effect on the environment and the effect of reducing the volatile organic solvent are not sufficient. In general, traffic is often interrupted, and although it is used for road marking installation work that requires quick processing, a high boiling point solvent is used, so the drying time is long, etc. However, there was a need for improvement.
本発明は、上記した従来の問題点を改善する、すなわち、取り扱いが容易で、揮発性有機溶剤の含有量が少なく、さらに、下塗り塗料としての効果が高いにもかかわらず、乾燥に要する時間が短い、路面標示材料用の水性下塗り塗料を提供することを目的とする。 The present invention improves the above-mentioned conventional problems, that is, handling is easy, the content of the volatile organic solvent is small, and the time required for drying is high even though the effect as an undercoat is high. The object is to provide a short, water-based primer for road marking materials.
上記課題を解決する本発明の路面標示材料用の水性下塗り塗料は、
合成ゴムエマルションと、固形成分を構成する樹脂成分が軟化点を有するエマルション型粘着付与剤と、水と、を含有し、
前記合成ゴムエマルションの固形成分の含有量と、前記エマルション型粘着付与剤の固形成分の含有量と、の和が全成分の１０質量％以上５０質量％以下であり、
前記エマルション型粘着付与剤が、ロジンエステルエマルション及び石油樹脂エマルションのうちの少なくとも何れかであり、その固形成分の軟化点が６５℃以上１６５℃以下であり、かつ、
前記合成ゴムエマルションの固形成分の含有量に対する前記エマルション型粘着付与剤の固形成分の含有量が質量比で０．２倍以上１．５倍以下であることを特徴とする。
The water-based undercoat paint for road marking material of the present invention that solves the above problems is
A synthetic rubber emulsion, an emulsion-type tackifier in which the resin component constituting the solid component has a softening point, and water ,
The sum of the solid component content of the synthetic rubber emulsion and the solid component content of the emulsion-type tackifier is 10% by mass or more and 50% by mass or less of the total components,
The emulsion-type tackifier is at least one of a rosin ester emulsion and a petroleum resin emulsion, and the softening point of the solid component is 65 ° C. or higher and 165 ° C. or lower, and
And the content of solid components of the emulsion type tackifier to the content of solid components of said synthetic rubber emulsion is less than 1.5 times 0.2 times or more in mass ratio.
さらに本発明の路面標示材料用の水性下塗り塗料では、上記構成に加えて、前記合成ゴムエマルションの合成ゴム成分のガラス転移点が−６０℃以上２０℃以下であるものを用いることができる。 Furthermore, in the water-based undercoat paint for road marking materials of this invention, in addition to the said structure, the glass transition point of the synthetic rubber component of the said synthetic rubber emulsion can use -60 degreeC or more and 20 degrees C or less.
さらに、本発明の路面標示材料用の水性下塗り塗料では、前記合成ゴムエマルションが、スチレンブタジエンゴムエマルション、ニトリルゴムエマルション、及び、アクリルゴムエマルションのうちの少なくとも何れかであるものを用いることができる。 Furthermore, in the water-based undercoat paint for a road marking material of the present invention, the synthetic rubber emulsion can be at least one of a styrene butadiene rubber emulsion, a nitrile rubber emulsion, and an acrylic rubber emulsion .
さらに、本発明の路面標示材料用の水性下塗り塗料では、上記構成に加えて、全成分の５質量％以下の水溶性有機溶剤を含有することができる。 Furthermore, the aqueous primer coating for road marking material of the present invention, in addition to the above structure, containing 5 wt% or less of the water-soluble organic solvent in the entire components.
本発明の路面標示材料用の水性下塗り塗料によれば、合成ゴムエマルションと、固形成分を構成する樹脂成分が軟化点を有するエマルション型粘着付与剤と、水と、を含有し、前記合成ゴムエマルションの固形成分の含有量と、前記エマルション型粘着付与剤の固形成分の含有量と、の和が全成分の１０質量％以上５０質量％以下であり、前記エマルション型粘着付与剤が、ロジンエステルエマルション及び石油樹脂エマルションのうちの少なくとも何れかであり、その固形成分の軟化点が６５℃以上１６５℃以下であり、かつ、前記合成ゴムエマルションの固形成分の含有量に対する前記エマルション型粘着付与剤の固形成分の含有量が質量比で０．２倍以上１．５倍以下である構成により、取り扱いが容易で、揮発性有機溶剤の含有量が少なく、さらに、下塗り塗料としての効果が高いにもかかわらず、乾燥に要する時間が短い。加えて、前記エマルション型粘着付与剤の固形成分の軟化点が６５℃以上１６５℃以下であることにより、溶融型路面標示材料塗装時に熱溶融による付着性を付与することができる。 According to the water-based undercoat paint for road marking material of the present invention, the synthetic rubber emulsion contains a synthetic rubber emulsion, an emulsion-type tackifier in which the resin component constituting the solid component has a softening point, and water. The sum of the content of the solid component and the content of the solid component of the emulsion-type tackifier is 10% by mass or more and 50% by mass or less of the total component, and the emulsion-type tackifier is a rosin ester emulsion. And a petroleum resin emulsion, the softening point of the solid component is 65 ° C. or more and 165 ° C. or less, and the solid content of the emulsion-type tackifier with respect to the content of the solid component of the synthetic rubber emulsion The composition in which the content of the component is 0.2 to 1.5 times by mass ratio makes it easy to handle and the content of the volatile organic solvent is No further despite higher effect as primer coating, the time required for drying it is shorter. In addition, when the softening point of the solid component of the emulsion-type tackifier is 65 ° C. or higher and 165 ° C. or lower, adhesion by heat melting can be imparted when the melt type road marking material is applied.
さらに、合成ゴムエマルションの合成ゴム成分のガラス転移点が−６０℃以上２０℃以下であることにより、常温で舗装面や既存の路面標示材料への付着性を付与することができる。 Furthermore, when the glass transition point of the synthetic rubber component of the synthetic rubber emulsion is −60 ° C. or higher and 20 ° C. or lower, adhesion to a pavement surface or an existing road marking material can be imparted at room temperature.
さらに、全成分の５質量％以下の水溶性有機溶剤を含有することにより、取り扱い性（安全性）を損なうことなく、低温安定性を改善することができる。 Furthermore, the low temperature stability can be improved without impairing the handleability (safety) by containing 5% by mass or less of the water-soluble organic solvent of all components .
以下に、本発明の詳細について説明する。 Details of the present invention will be described below.
本発明で用いる合成ゴムエマルションとしては、スチレンブタジエンゴムエマルションやニトリルゴムエマルション、アクリルゴムエマルション等が挙げられ、これらを単独で、あるいは、２種以上併用することができる。これら合成エマルションのうち、舗装面および路面標示材料との付着性能が良好であるために、スチレンブタジエンゴムエマルションを用いることが好ましい。 Examples of the synthetic rubber emulsion used in the present invention include a styrene butadiene rubber emulsion, a nitrile rubber emulsion, and an acrylic rubber emulsion. These can be used alone or in combination of two or more. Among these synthetic emulsions, it is preferable to use a styrene butadiene rubber emulsion because of its good adhesion performance to the pavement surface and road marking material.
合成ゴムエマルションのベース成分である合成ゴムは、そのガラス転移点が−６０℃以上２０℃以下のものであることが好ましく、より好ましくは、−５５℃以上０℃以下のものである。ここで、ガラス転移点が低すぎると付着強度が低下することがあり、また、高すぎると夏季に生じやすい、アスファルトの軟化による舗装の動きに追従できずクラックが発生することがある。 The synthetic rubber, which is the base component of the synthetic rubber emulsion, preferably has a glass transition point of −60 ° C. or higher and 20 ° C. or lower, more preferably −55 ° C. or higher and 0 ° C. or lower. Here, if the glass transition point is too low, the adhesion strength may decrease, and if it is too high, cracks may occur due to the failure to follow the movement of the pavement due to softening of asphalt, which is likely to occur in summer.
本発明で用いる固形成分を構成する樹脂成分に軟化点を有するエマルション型粘着付与剤としては、一般的に粘着剤や接着剤用途に、タッキファイヤーとして用いられている市販品の、天然樹脂のロジンを誘導したエステル樹脂のロジンエステルエマルション及び石油樹脂エマルションを挙げることができ、これらの少なくとも何れかを用いる。他に参考例として、テルペンフェノール樹脂エマルションが挙げられ、これらを単独、あるいは、２種以上併用することができる。これらのうち、舗装面及び路面標示材料との付着性能が良好であるためロジンエステルエマルションを用いることが好ましい。なお、本発明において、固形成分を構成する樹脂成分に軟化点がないエマルション粘着付与剤を用いた場合には、常温で塗膜を形成しない。あるいは、塗膜強度が著しく低くなるため使用することができない。 The emulsion type tackifier having a softening point in the resin component constituting the solid component used in the present invention is a natural resin rosin, which is a commercial product generally used as a tackifier for adhesives and adhesives. Rosin ester emulsions of petroleum ester resins and petroleum resin emulsions, and at least one of them is used. Other reference examples include terpene phenol resin emulsions, which can be used alone or in combination of two or more. Among these, it is preferable to use a rosin ester emulsion because adhesion performance with a pavement surface and a road marking material is good. In addition, in this invention, when the emulsion tackifier which does not have a softening point is used for the resin component which comprises a solid component, a coating film is not formed at normal temperature. Alternatively, it cannot be used because the coating film strength is extremely low.
エマルション型粘着付与剤としては、その固形成分の軟化点が６５℃以上１６５℃以下のものが用いられ、より好ましくは８０℃以上１００℃以下のロジンエステルエマルションである。 As the emulsion-type tackifier, those having a softening point of the solid component of 65 ° C. or more and 165 ° C. or less are used , and more preferably a rosin ester emulsion having a temperature of 80 ° C. or more and 100 ° C. or less.
ここで、軟化点が低すぎると、夏季に樹脂成分が溶融することがあり、このとき、路面標示材料用の水性下塗り塗料として用いられたときに、付着強度が低下する場合がある。 Here, if the softening point is too low, the resin component may melt in the summer, and at this time, when used as a water-based undercoat paint for road marking materials, the adhesion strength may decrease.
また、軟化点が高すぎると低温時の付着性や耐衝撃性が低下しやすくなり、路面標示材料用の水性下塗り塗料として用いられたときに、クラックや塗膜の剥離が発生する場合がある。 Also, if the softening point is too high, adhesion at low temperatures and impact resistance are likely to be reduced, and cracks and peeling of the coating film may occur when used as an aqueous primer for road marking materials. .
本発明において、合成ゴムエマルションの固形成分と軟化点を有するエマルション型粘着付与剤の固形成分とにより構成される樹脂固形成分は、路面標示材料用の水性下塗り塗料の全成分全体の１０質量％以上５０質量％以下であり、必要に応じて水（、及び、後述の有機溶剤）を添加して樹脂固形成分がこの範囲となるように調整する。 In the present invention, the resin solid component composed of the solid component of the synthetic rubber emulsion and the solid component of the emulsion-type tackifier having a softening point is 10% by mass or more based on the total amount of all the components of the aqueous undercoat paint for road marking materials. It is 50 mass% or less, and it adjusts so that resin (and the below-mentioned organic solvent) may be added as needed and a resin solid component may become this range.
これら樹脂固形成分の含有量が少なすぎると乾燥性が低下し、施工完了までに必要な時間が長くなってしまう場合があり、また、多すぎると塗装作業性が低下することがある。好ましい樹脂固形成分の範囲は２０質量％以上４０質量％以下であり、より好ましい範囲は３０質量％以上４０質量％以下である。 If the content of these resin solid components is too small, the drying property may decrease, and the time required for completion of construction may become long. If the content is too large, the coating workability may decrease. A preferable range of the resin solid component is 20% by mass or more and 40% by mass or less, and a more preferable range is 30% by mass or more and 40% by mass or less.
本発明の路面標示材料用の水性下塗り塗料においては、さらに、合成ゴムエマルションの固形成分に対するエマルション型粘着付与剤の固形成分を質量比で０．２倍以上１．５倍以下の範囲とする必要がある。 In the water-based undercoat paint for road marking materials of the present invention, the solid component of the emulsion-type tackifier with respect to the solid component of the synthetic rubber emulsion needs to be in the range of 0.2 to 1.5 times by mass ratio. There is.
ここで、合成ゴムエマルションの固形成分に対する軟化点を有するエマルション型粘着付与剤の固形成分が少なすぎると熱溶融による付着効果が低下する場合があり、路面標示材料用の水性下塗り塗料として用いられたときに、付着強度が低下し、路面標示材料が剥離する場合がある。 Here, if there is too little solid component of the emulsion-type tackifier having a softening point with respect to the solid component of the synthetic rubber emulsion, the adhesion effect due to heat melting may be reduced, and it was used as an aqueous undercoat for road marking materials Sometimes the adhesion strength decreases and the road marking material may peel off.
また、合成ゴムエマルションの固形成分に対する軟化点を有するエマルション型粘着付与剤の固形成分が多すぎると低温時の耐衝撃性が低下し、路面標示材料用の水性下塗り塗料として用いられたときに、冬季に車両による衝撃で、路面標示材料がクラックを生じたり剥離する場合がある。前記の２つの固定成分の質量比の好ましい範囲は０．６倍以上１．５倍以下である。 Moreover, when the emulsion type tackifier having a softening point with respect to the solid component of the synthetic rubber emulsion has too many solid components, the impact resistance at low temperatures is lowered, and when used as an aqueous undercoat for road marking materials, The road marking material may crack or peel off due to the impact of the vehicle in winter. A preferable range of the mass ratio of the two fixed components is 0.6 times or more and 1.5 times or less.
本発明の路面標示材料用の水性下塗り塗料組成物には、上記必須成分の他に、水性溶剤は勿論のこと、本発明の効果を損なわない範囲で、各種の、有機溶剤、顔料、フィラー、及び、補助剤を配合することができる。 Aqueous primer coating composition for a road marking material of the present invention, the addition to the essential components, an aqueous solvent, of course, within a range not to impair the effects of the present invention, various organic solvents, pigments, fillers, and it may be formulated adjuvant.
ただし、路面標示材料用の水性下塗り塗料としての用途を考慮すると、一般に透明であることが好ましく、不透明となる顔料、フィラーは特殊な用途を除いて使用しないことが好ましい。しかし、特にこれらの配合が求められる場合はこの限りではなく、その場合、顔料及びフィラーとしては、一般的な塗料で使用される酸化チタン、黄色酸化鉄などの各種の着色顔料、シリカ、タルク、炭酸カルシウム、沈降性バリウムなどの各種の体質顔料を用いることができる。 However, considering the use as a water-based undercoat paint for road marking materials, it is generally preferable to be transparent, and opaque pigments and fillers are preferably not used except for special uses. However, this is not particularly the case when these formulations are required. In that case, as pigments and fillers, various colored pigments such as titanium oxide and yellow iron oxide used in general paints, silica, talc, Various extender pigments such as calcium carbonate and precipitated barium can be used.
本発明の路面標示材料用の水性下塗り塗料には、低温安定性の改良を目的に、水溶性有機溶剤を配合させることができる。水溶性有機溶剤としては、水に可溶であれば限定されるものではないが、アルコールであることが好ましい。アルコールとしては、水との相溶性がありかつ乾燥性が良好であるため、メタノールであることが好ましい。このような水溶性有機溶剤は路面標示材料用の水性下塗り塗料全体に対して、取り扱い性を考慮すると５質量％以下での配合が好ましく、より好ましくは２質量％以上５質量％以下である。 A water-soluble organic solvent can be blended in the water- based undercoating material for road marking materials of the present invention for the purpose of improving low-temperature stability. The water-soluble organic solvent is not limited as long as it is soluble in water, but is preferably an alcohol. The alcohol is preferably methanol since it is compatible with water and has good drying properties. Such a water-soluble organic solvent is preferably blended in an amount of 5% by mass or less, more preferably 2% by mass or more and 5% by mass or less in consideration of the handling property with respect to the entire aqueous undercoat paint for road marking materials.
本発明の路面標示材料用の水性下塗り塗料に使用可能な補助剤としては、特に限定されるものではなく、消泡剤、表面調整剤、顔料分散剤などの公知の補助剤を添加することができる。 The auxiliary agent that can be used in the water-based undercoat paint for road marking material of the present invention is not particularly limited, and it is possible to add known auxiliary agents such as an antifoaming agent, a surface conditioner, and a pigment dispersant. it can.
本発明の路面標示材料用の水性下塗り塗料は、上記の各原料を混合し、攪拌することで容易に調製することができ、また、従来の路面標示材料用の水性下塗り塗料同様に塗布し、乾燥させた後に路面標示材料の施工を行うことができる。 The water-based undercoat paint for road marking materials of the present invention can be easily prepared by mixing and stirring the above-mentioned raw materials, and is applied in the same manner as the conventional water-based undercoat paint for road marking materials, The road marking material can be applied after drying.
以上、本発明について、好ましい実施形態を挙げて説明したが、本発明の路面標示材料用の水性下塗り塗料は上記実施形態の構成に限定されるものではない。 While the present invention has been described with reference to the preferred embodiment, the water-based undercoat paint for road marking material of the present invention is not limited to the configuration of the above embodiment.
当業者は、従来公知の知見に従い、本発明の路面標示材料用の水性下塗り塗料を適宜改変することができる。このような改変によってもなお本発明の路面標示材料用の水性下塗り塗料の構成を具備する限り、もちろん、本発明の範疇に含まれるものである。 A person skilled in the art can appropriately modify the water-based undercoat paint for the road marking material of the present invention according to conventionally known knowledge. Of course, such modifications are still included in the scope of the present invention as long as they have the constitution of the water-based undercoat paint for road marking materials of the present invention.
以下に本発明の実施例及び比較例を挙げて本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples of the present invention.
＜実施例及び、比較例の水性下塗り塗料の調製＞
合成ゴムエマルションとして、ニッポールＬＸ―４２６（日本ゼオン社製スチレンブタジエンゴムエマルション、固形成分（スチレンブタジエンゴム成分）：５０質量％、合成ゴム成分のガラス転移点は−３９℃）（ただし、配合例１３（実施例１０）では同ニッポールＬＸ４３０（固形成分：４９質量％、合成ゴム成分のガラス転移点は１２℃）、配合例１４（実施例１１）では同ニッポールＬＸ４７３Ｄ（固形成分：４７．５％、合成ゴム成分のガラス転移点は−１５℃）、そして、配合例１５（実施例１２）では同ニッポールＬＸ４３２Ｍ（固形成分：４１質量％、合成ゴム成分のガラス転移点は−５５℃）、そして、配合例１８（実施例１５）では同ニッポールＬＸ８４４Ｃ（固形成分：４０質量％、合成ゴム成分のガラス転移点は３２℃）を使用し、軟化点を有するエマルション型粘着付与剤として、スーパーエステルＥ−７２０（荒川化学工業社製ロジンエステルエマルション、固形成分（樹脂成分）：５０質量％）（ただし、配合例１６（実施例１３）ではスーパーエステルＥ−６５０（荒川化学工業社製ロジンエステルエマルション、固形成分：５０質量％）、配合例１７（実施例１４）では成瀬化学社製石油樹脂エマルションＰＴ２０１、固形成分：４９質量％）、消泡剤として、ＢＹＫ社製ＢＹＫ０２５、水（イオン交換水）、及び、有機溶剤としてメタノールを用いて、以下の試験を行った。
<Preparation of water-based undercoating materials of Examples and Comparative Examples>
As a synthetic rubber emulsion, Nippon LX-426 (Nippon Zeon Co., Ltd. styrene butadiene rubber emulsion, solid component (styrene butadiene rubber component): 50% by mass, the glass transition point of the synthetic rubber component is -39 ° C.) In Example 10, the same Nippon LX430 (solid component: 49% by mass, the glass transition point of the synthetic rubber component is 12 ° C.), and in Example 14 (Example 11), the same Nippon LX473D (solid component: 47.5%, The glass transition point of the synthetic rubber component is −15 ° C.), and in Formulation Example 15 (Example 12), the same NIPPOL LX432M (solid component: 41 mass%, the glass transition point of the synthetic rubber component is −55 ° C.), and In Formulation Example 18 (Example 15), the same Nippon LX844C (solid component: 40% by mass, the glass transition point of the synthetic rubber component is As an emulsion type tackifier having a softening point, Superester E-720 (Arakawa Chemical Industries, rosin ester emulsion, solid component (resin component): 50% by mass) (however, formulation example 16 In (Example 13 ), Superester E-650 (Rosin ester emulsion manufactured by Arakawa Chemical Industry Co., Ltd., solid component: 50% by mass), in Formulation Example 17 (Example 14 ), petroleum resin emulsion PT201 manufactured by Naruse Chemical Co., Ltd., solid component: 49% by mass), BYK025 manufactured by BYK, water (ion-exchanged water) as an antifoaming agent, and methanol as an organic solvent, the following tests were performed.
１リットル（Ｌ）ビーカーに、表１〜４に配合例１〜１８として示した配合量（質量）で各原料を取り、十分に攪拌して、それぞれ路面標示材料用の水性下塗り塗料（以下「水性下塗り塗料」とも云う。）を調製した。これら表には、合成ゴムエマルションの固形成分の質量を１としたときの前記軟化点を有するエマルション型粘着付与剤の固形成分の質量比を「質量比」として、併せて記載した。なお、アルコール有機溶剤に関しては表において括弧内に含有率（質量％）を記載した。なお、表１〜４では、用いた合成ゴムエマルションの合成ゴムのガラス転移点を括弧内に記載し、また、路面標示材料用の水性下塗り塗料全体量中の、合成ゴムエマルションの固形成分と前記軟化点を有するエマルション型粘着付与剤の固形成分とにより構成される樹脂固形成分の含有量（質量％）も「樹脂含有量（％）」として併せて記載した。 In a 1 liter (L) beaker, each raw material is taken in the blending amounts (mass) shown as blending examples 1 to 18 in Tables 1 to 4, and sufficiently stirred, respectively. Also referred to as “water-based undercoat”. In these tables, the mass ratio of the solid component of the emulsion-type tackifier having the softening point when the mass of the solid component of the synthetic rubber emulsion is 1 is also described as “mass ratio”. In addition, regarding the alcohol organic solvent, the content (mass%) was described in parentheses in the table. In Tables 1 to 4, the glass transition point of the synthetic rubber of the used synthetic rubber emulsion is described in parentheses, and the solid component of the synthetic rubber emulsion in the total amount of the aqueous undercoat paint for road marking material and the above-mentioned The content (% by mass) of the resin solid component composed of the solid component of the emulsion-type tackifier having a softening point is also described as “resin content (%)”.
また、これらとは別に従来技術の、溶剤を用いる下塗り塗料として、トルエンを７２質量％を含有するアトミクス社製プライマーＮｏ.１を比較例４の溶剤型下塗り塗料とした。 Apart from these, as a conventional undercoating material using a solvent, Primer No. 1 manufactured by Atomics Co., which contains 72% by mass of toluene, was used as the solvent-based undercoating material of Comparative Example 4.
＜溶融型路面標示用塗料＞
溶融型路面標示用塗料としてＪＩＳ Ｋ５６６５ ３種相当材料であるアトミクス社製アトムライン＃１５を用いた。
<Melting type road marking paint>
As a melt type road marking paint, Atom Line # 15 manufactured by Atomics Co., Ltd., which is a material corresponding to JIS K5665, is used.
＜評価＞
以下に、評価方法、及び、評価結果について説明する。なお、各評価で、不十分な結果となったサンプルについては、以降、他項目の評価は省略した。
<Evaluation>
Below, an evaluation method and an evaluation result are explained. In addition, about the sample which became inadequate result in each evaluation, evaluation of other items was abbreviate | omitted hereafter.
＜＜乾燥性＞＞
上記実施例及び比較例の水性下塗り塗料をアスファルト面（３００ｍｍ×３００ｍｍ（アスファルトブロックを使用））に塗布し、室温にて１０分、及び、６０分（完全乾燥）静置した後に、これら水性下塗り塗料の塗装面に、上塗り塗料として２００℃に加熱した、上記で調製した溶融型路面標示用塗料を塗布した。その後、溶融型路面標示用塗料の塗膜の外観変化の評価を行った。このとき、下塗り材組成物の乾燥が十分でないと溶融型路面標示用塗料にピンホールや膨れなどの外観変化が生じる。
<< Dryability >>
After applying the water-based undercoating paints of the above Examples and Comparative Examples to the asphalt surface (300 mm × 300 mm (using asphalt block)) and leaving them to stand at room temperature for 10 minutes and 60 minutes (completely dry), these water-based undercoats The melt-type road marking paint prepared above and heated to 200 ° C. as the top coat was applied to the paint surface. Then, the external appearance change of the coating film of the melt type road marking paint was evaluated. At this time, if the undercoat material composition is not sufficiently dried, appearance changes such as pinholes and swelling occur in the melt-type road marking paint.
溶融型路面標示用塗料の外観変化が、従来技術の、比較例４の溶剤型下塗り材を用いた場合に比べて大きい場合を水性下塗り塗料の「乾燥性」として不十分であるとして「×」、溶融型路面標示用塗料の機能が損なわれない程度に小さい場合は、水性下塗り塗料の「乾燥性」として概ね十分であるとして「△」、同等の場合に水性下塗り塗料の「乾燥性」として十分であるとして「○」として、それぞれ評価を行った。 The case where the change in the appearance of the melt-type road marking paint is larger than that in the case of using the solvent-type primer of Comparative Example 4 in the prior art is regarded as insufficient as “drying” of the water-based primer. If the function of the melt-type road marking paint is small enough not to be impaired, “△” indicates that the “dryability” of the water-based undercoat is generally sufficient, and “dryability” of the water-based undercoat in the equivalent case. Each was evaluated as “◯” as being sufficient.
＜＜固形成分の軟化点＞＞
固形成分の軟化点（なお、表１〜４では「軟化点」と、略して記載する）は次のようにして調べた。
<< Softening point of solid component >>
The softening point of the solid component (abbreviated as “softening point” in Tables 1 to 4) was examined as follows.
すなわち、エマルション型粘着付与剤をメタノール中に投入し、析出した沈殿物を加熱・減圧により水分を除去後、ＪＩＳ Ｋ２２０７に準じた測定方法にて測定した。なお、この試験時に、水分を除去したにも関わらず沈殿物が析出しない場合、及び、水分を除去したにも関わらず、残留物が液状である場合には、軟化点がないと判断した。 That is, an emulsion type tackifier was added to methanol, and the deposited precipitate was heated and subjected to reduced pressure to remove moisture, and then measured by a measuring method according to JIS K2207. In this test, it was determined that there was no softening point when no precipitate was deposited despite the removal of moisture, and when the residue was liquid despite the removal of moisture.
＜＜付着強度＞＞
付着強度については次のようにして調べた。
<< Adhesion strength >>
The adhesion strength was examined as follows.
上記実施例及び比較例の水性下塗り塗料を、それぞれアスファルト面（３００ｍｍ×３００ｍｍ（アスファルトブロックを使用））に塗布し、十分に乾燥させた後、上塗り塗料として２００℃に加熱した、上記で調製した溶融型路面標示用塗料を塗布した。次いで、塗布表面を研磨し、建研式接着試験器の治具を接着剤にて貼り付け、それぞれ付着強度を測定した。 The aqueous undercoat paints of the above Examples and Comparative Examples were each prepared on the asphalt surface (300 mm × 300 mm (using an asphalt block)), sufficiently dried and then heated to 200 ° C. as a top coat paint. A melt type road marking paint was applied. Next, the coated surface was polished, the jig of the Kenken type adhesion tester was attached with an adhesive, and the adhesion strength was measured for each.
＜＜耐衝撃性＞＞
耐衝撃性は次のようにして調べた。
<< Shock resistance >>
The impact resistance was examined as follows.
上記実施例、及び、比較例の水性下塗り塗料をそれぞれ亜鉛メッキ鋼板（１５０ｍｍ×７０ｍｍ、厚さ：３ｍｍ）の一方の表面に塗布し、十分に乾燥させた後、上塗り塗料として２００℃に加熱した、上記の溶融型路面標示用塗料を塗布した。これら試験板について、室温（２３℃、使用錘は５００ｇ、高さは５００ｍｍ）、及び、５℃環境下（使用錘は５００ｇ、高さは５００ｍｍ）で、ＪＩＳ Ｋ５６００−５−３に準拠し、デュポン式耐衝撃試験を行った。このとき、衝撃により基板から塗装の剥離がない場合を十分な耐衝撃性が得られたとして「○」、衝撃により変形した部位にのみに剥離が生じた場合を「△」及び、衝撃を与えた部位に加えて周辺にも剥離が生じた場合は十分な耐衝撃性が得られなかったとして「×」と、それぞれ評価した。 The water-based undercoating paints of the above Examples and Comparative Examples were each applied to one surface of a galvanized steel sheet (150 mm × 70 mm, thickness: 3 mm), sufficiently dried, and then heated to 200 ° C. as a topcoating paint. The melt type road marking paint was applied. About these test plates, in accordance with JIS K5600-5-3 at room temperature (23 ° C., weight used is 500 g, height is 500 mm) and in a 5 ° C. environment (use weight is 500 g, height is 500 mm), A DuPont impact resistance test was conducted. At this time, if there was no peeling of the paint from the substrate due to the impact, “○” was given as sufficient shock resistance, and “△” was given when the peeling occurred only at the part deformed by the impact, and an impact was given. In the case where peeling occurred also in the periphery in addition to the above-mentioned part, it was evaluated as “x” because sufficient impact resistance could not be obtained.
＜＜引火点＞＞
取り扱い性の目安として、引火点を測定した上記実施例及び比較例の水性下塗り塗料の、２１℃及び７０℃での引火点を、それぞれＪＩＳ Ｋ２２６５に準拠して、セタ密閉式の測定方法で測定した。
<< Flash point >>
As a measure of handleability, the flash points at 21 ° C. and 70 ° C. of the water-based undercoats of the above examples and comparative examples, whose flash points were measured, were measured by a seta-sealed measurement method in accordance with JIS K2265, respectively. did.
ここで、水性下塗り塗料に引火点がないと、貯蔵や取り扱いが容易になるとともに、実際の施工を安全に行うことができる。 Here, if there is no flash point in the water-based undercoating material, storage and handling become easy and actual construction can be performed safely.
試験温度において引火が認められた場合は「引火」として評価し、引火が認められなかった場合は「○」として評価した。 When ignition was observed at the test temperature, it was evaluated as “flammable”, and when ignition was not observed, it was evaluated as “◯”.
＜＜低温安定性＞＞
低温安定性は、路面標示材料用の水性下塗り塗料において、冬季の寒冷地での保管による塗料性状の変化であり、重要なパラメータである。ここで、上記の実施例及び比較例の水性下塗り塗料について、それらの低温安定性験を行った。
<< Low temperature stability >>
Low-temperature stability is an important parameter for water-based undercoat paints for road marking materials, which is a change in paint properties due to storage in cold regions in winter. Here, the low temperature stability test was done about the water-based undercoat of the said Example and comparative example.
試験方法はＪＩＳ Ｋ５６６５に準拠し、ただし、試験温度は−１０℃とした。塗料性状に変状（ゲル化、大幅な増粘）が見られた場合は不十分であるとして「×」と、変状がない場合は低温安定性が十分であるとして「○」と、それぞれ評価した。 The test method conformed to JIS K5665, except that the test temperature was −10 ° C. If the paint properties are deformed (gelation, significant thickening), “x” indicates that the coating is insufficient, and “○” indicates that the low-temperature stability is sufficient if there is no deformation. evaluated.
＜＜低温付着性試験＞＞
低温付着性は、路面標示材料用の水性下塗り塗料において、冬季の路面標示材料との付着性を評価する指標であり、重要なパラメータである。
<< Low-temperature adhesion test >>
The low temperature adhesion is an important parameter for evaluating the adhesion with the road marking material in winter in the water-based undercoating material for the road marking material.
実施例及び比較例の下塗り材組成物をそれぞれアスファルト面（３００ｍｍ×３００ｍｍ）に塗布し、十分に乾燥を行った後、上塗り塗料として２００℃に加熱した、上述の溶融型路面標示用塗料を塗布した。その後、溶融型路面標示用塗料の表面を研磨し、建研式接着試験器の治具を、接着剤を用いて貼り付け、５℃の環境下にて付着強度を測定した。 After applying the undercoat material compositions of Examples and Comparative Examples to the asphalt surface (300 mm × 300 mm) and drying sufficiently, the above-mentioned melt type road marking paint heated to 200 ° C. was applied as the top coat paint. did. Thereafter, the surface of the melt-type road marking coating material was polished, a jig of a Kenken type adhesion tester was attached using an adhesive, and the adhesion strength was measured in an environment of 5 ° C.
これら評価結果について、表１〜４に併せて示した。 These evaluation results are also shown in Tables 1 to 4.
＜評価結果について＞
上記表１〜５より、次のことが理解される。
<About evaluation results>
From Tables 1 to 5, the following is understood.
上記実施例の下塗り材組成物によれば、合成ゴムエマルションとエマルション型粘着付与剤とを適切な比で配合した実施例の水性下塗り塗料では、高い乾燥性、非常に優れた付着強度、さらに、室温及び５℃において良好な耐衝撃性が得られることが理解される。 According to the undercoat material composition of the above example, the water-based undercoat of the example in which the synthetic rubber emulsion and the emulsion-type tackifier are blended at an appropriate ratio, has high drying properties, very excellent adhesion strength, It is understood that good impact resistance is obtained at room temperature and 5 ° C.
また、合成ゴムエマルション配合比率が高い方がより優れた耐衝撃性を得られること、有機溶剤含有量が５質量％以下であれば７０℃の環境であっても引火しないこと、アルコール有機溶剤含有量が２．３％以上であれば−１０℃（冬季の寒冷地での保管を想定。）での低温安定性が得られることが理解される。 Also, higher impact resistance can be obtained when the blending ratio of the synthetic rubber emulsion is higher. If the organic solvent content is 5% by mass or less, it will not ignite even in an environment of 70 ° C. It is understood that if the amount is 2.3% or more, low temperature stability at −10 ° C. (assuming storage in a cold region in winter) is obtained.
さらに、低温環境下（５℃）での付着性においては、合成ゴムエマルション中の合成ゴムのガラス転移点が低いほど、かつ、前記エマルション型粘着付与剤樹脂固形成分の軟化点が６５℃以上１６５℃以下の範囲では低い方である方が、より高い低温付着性が得られることが理解される。 Furthermore, in terms of adhesion in a low temperature environment (5 ° C.), the lower the glass transition point of the synthetic rubber in the synthetic rubber emulsion, and the softening point of the emulsion-type tackifier resin solid component is 65 ° C. or higher and 165 ° C. It is understood that higher low-temperature adhesion is obtained when the temperature is lower in the range of ° C or lower.
Claims (4)
前記合成ゴムエマルションの固形成分の含有量と、前記エマルション型粘着付与剤の固形成分の含有量と、の和が全成分の１０質量％以上５０質量％以下であり、
前記エマルション型粘着付与剤が、ロジンエステルエマルション及び石油樹脂エマルションのうちの少なくとも何れかであり、その固形成分の軟化点が６５℃以上１６５℃以下であり、かつ、
前記合成ゴムエマルションの固形成分の含有量に対する前記エマルション型粘着付与剤の固形成分の含有量が質量比で０．２倍以上１．５倍以下であることを特徴とする路面標示材料用の水性下塗り塗料。 A synthetic rubber emulsion, an emulsion-type tackifier in which the resin component constituting the solid component has a softening point, and water ,
The sum of the solid component content of the synthetic rubber emulsion and the solid component content of the emulsion-type tackifier is 10% by mass or more and 50% by mass or less of the total components,
The emulsion-type tackifier is at least one of a rosin ester emulsion and a petroleum resin emulsion, and the softening point of the solid component is 65 ° C. or higher and 165 ° C. or lower, and
Water content for road marking materials characterized in that the content of the solid component of the emulsion-type tackifier relative to the content of the solid component of the synthetic rubber emulsion is 0.2 to 1.5 times by mass ratio Undercoat paint.
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