JP6060338B2 - Silicone paint and heat-shielding transparent substrate - Google Patents
Silicone paint and heat-shielding transparent substrate Download PDFInfo
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Description
本発明は、アルコキシシラン加水分解物からなるシラン溶液と、インジウム錫酸化物（ITO）粒子の分散液（以下、「ITO分散液」という。）とを、混合して使用するシリコーン系塗料に関する。特に遮熱塗料として好適なシリコーン系塗料に係る発明である。 The present invention relates to a silicone-based paint using a mixture of a silane solution composed of an alkoxysilane hydrolyzate and a dispersion of indium tin oxide (ITO) particles (hereinafter referred to as “ITO dispersion”). In particular, the invention relates to a silicone-based paint suitable as a thermal barrier paint.
省エネルギー・省コストを強く意識して開発された技術・製品の一例として、遮熱塗料が挙げられる。 One example of technology and products developed with a strong awareness of energy and cost savings is thermal barrier paint.
遮熱塗料の特長は、これを建築物等の窓ガラス（透明基材）に塗付することによって、室内に入射する近赤外線(熱線)を遮断でき、室内の温度上昇をある程度抑制できる点にある。この特長を活かして、例えば夏場の冷房の使用量を減らせれば、消費電力の削減に貢献できる。 The feature of thermal barrier paint is that it can block near-infrared rays (heat rays) incident on the room by applying it to window glass (transparent substrate) of buildings, etc., and can suppress the temperature rise in the room to some extent. is there. Taking advantage of this feature, for example, if the amount of cooling used in summer can be reduced, it can contribute to the reduction of power consumption.
このような背景を基に本願出願人の一人は、遮熱塗料として、ITO分散液を合成樹脂（アクリル樹脂とアクリル系シロキサン架橋型反応性ポリマー）に混合した製品を開発・販売してきた（特許文献１）。 Based on this background, one of the applicants of the present application has developed and sold a product that mixes ITO dispersion with synthetic resin (acrylic resin and acrylic siloxane cross-linked reactive polymer) as a thermal barrier paint (patent) Reference 1).
そして、遮熱塗料の適用範囲を広げるには、遮熱塗料で形成される遮熱塗膜は、室温乾燥（室温硬化）により、下記のような目標性能を達成する必要があることが分かってきた。 In order to broaden the application range of thermal barrier coatings, it has been found that thermal barrier coatings formed with thermal barrier coatings need to achieve the following target performance by room temperature drying (room temperature curing). It was.
1)塗膜が均一かつ緻密で、表面に割れや剥がれのような欠陥が無い、
2)粘着テープによる剥離（ピーリング）試験で全く剥がれない、
3)鉛筆硬度5H以上（実用的耐擦傷性が得られる硬度）、
4)耐熱性試験後（100℃×30min）に表面欠陥発生なし、
5)近赤外線(特に波長域約1500〜2500nm)を確実に遮断できる。
1) The coating is uniform and dense, and there are no defects such as cracks or peeling on the surface.
2) Not peeled off by peeling test with adhesive tape.
3) Pencil hardness of 5H or more (hardness that provides practical scratch resistance),
4) No surface defects after heat resistance test (100 ℃ × 30min)
5) Near infrared rays (especially in the wavelength range of about 1500 to 2500 nm) can be cut off reliably.
本発明の特許性に影響を与えるものではないが、ITO粒子を含有して熱線等を遮断する遮熱塗料に関連する先行技術文献として、特許文献２〜６等が存在する。 Although it does not affect the patentability of the present invention, Patent Documents 2 to 6 and the like exist as prior art documents related to a thermal barrier coating containing ITO particles and blocking heat rays and the like.
本発明は、上記にかんがみて、ガラス等の透明基板（透明基材）上に適用した場合、近赤外線、遠赤外線等の熱線を十分に遮断できる特性も有するとともに、表面の均一性と密着性に優れ且つ実用的な耐擦傷性を有し、さらには、実用的な耐熱性を示す遮熱塗膜が形成できるシリコーン系塗料を提供することを目的（課題）とする。 In view of the above, the present invention, when applied on a transparent substrate (transparent substrate) such as glass, has the property of sufficiently blocking heat rays such as near infrared rays and far infrared rays, and also has surface uniformity and adhesion. Another object (problem) is to provide a silicone-based paint that has excellent and practical scratch resistance and that can form a thermal barrier coating film that exhibits practical heat resistance.
本発明者らは、上記課題を解決するために鋭意開発に努力をした結果、下記構成のシリコーン系塗料に想到した。 As a result of diligent development efforts to solve the above problems, the present inventors have conceived a silicone-based paint having the following constitution.
アルコキシシラン加水分解物からなるシラン溶液と、ＩＴＯ分散液と、を混合して使用するシリコーン塗料であって、
該シラン溶液が、
一般式（Ｉ）：Ｓｉ（ＯＲ1）4（但し、Ｒ1は炭素数１〜４のアルキル基）で示されるテトラアルコキシシラン（Ａ成分）、と、
一般式（ＩＩ）：Ｒ2Ｓｉ（ＯＲ3）3（但し、Ｒ2、Ｒ3は炭素数１〜４のアルキル基）で示されるトリアルコキシシラン（Ｂ成分）、
との、前者を主体とする加水分解混合物において、
さらに、一般式（ＩＩＩ）：
該Ｃ成分に対する該Ａ成分と該Ｂ成分との合計量の混合モル比が、Ｃ成分／（Ａ成分＋Ｂ成分）＝１／１４．５〜１／８．５であり、
該加水分解混合物における該Ａ成分と該Ｂ成分の合計モル濃度が１．３〜２．５Ｍである、
ことを特徴とする。
A silane solution consisting of alkoxysilane hydrolyzate, a silicone coating material used as a mixture with ITO dispersion, and
The silane solution is
Tetraalkoxysilane (component A) represented by the general formula (I): Si (OR 1 ) 4 (where R 1 is an alkyl group having 1 to 4 carbon atoms);
Trialkoxysilane (component B) represented by the general formula (II): R 2 Si (OR 3 ) 3 (wherein R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms) ,
In the hydrolysis mixture mainly composed of the former,
Furthermore, the general formula (III):
The mixing molar ratio of the total amount of the A component and the B component to the C component is C component / (A component + B component) = 1 / 14.5 to 1 / 8.5,
The total molar concentration of the A component and the B component in the hydrolysis mixture is 1.3 to 2.5M.
It is characterized by that.
（但し、Ｒ4はＨ又はＣＨ3、Ｒ5は炭素数１〜４のアルキレン基、Ｒ6は炭素数１〜４のアルキル基）で示されるωグリシドキシアルキルトリアルコキシシラン（Ｃ成分）の加水分解物が添加されている、ことを特徴とする。 (Wherein R 4 is H or CH 3 , R 5 is an alkylene group having 1 to 4 carbon atoms, R 6 is an alkyl group having 1 to 4 carbon atoms) ω-glycidoxyalkyltrialkoxysilane (C component) The hydrolyzate of is added, It is characterized by the above-mentioned.
本発明のシリコーン系塗料は、近赤外線等の熱線を十分に遮断できる特性も有するとともに、表面の均一性と密着性に優れ且つ実用的な耐擦傷性を有し、さらには、実用的な耐熱性を示す遮熱塗膜が形成できる。 The silicone-based paint of the present invention has characteristics that can sufficiently block heat rays such as near infrared rays, has excellent surface uniformity and adhesion, has practical scratch resistance, and further has practical heat resistance. A thermal barrier coating film exhibiting properties can be formed.
そして、従来の如く、ITO分散液におけるITO粒子をシラン処理しなくても基材（特にガラス基材）に対する密着性が良好であり、塗料の調製工数も削減できる。 As in the prior art, even if the ITO particles in the ITO dispersion are not silane-treated, the adhesion to the substrate (particularly the glass substrate) is good, and the number of man-hours for preparing the paint can be reduced.
以下、本発明の実施形態について説明する。以下の説明で、配合単位、添加率は、特に断らない限り、質量基準とする。 Hereinafter, embodiments of the present invention will be described. In the following description, the blending unit and the addition rate are based on mass unless otherwise specified.
本発明は、アルコキシシラン加水分解物からなるシラン溶液と、ITO分散液とを混合して使用するシリコーン系塗料であることを上位概念的構成とする。 The present invention has a high-level conceptual configuration that is a silicone-based paint that is used by mixing a silane solution composed of an alkoxysilane hydrolyzate and an ITO dispersion.
（１）シラン溶液の調製：
本発明に使用するシラン溶液は、一般式（Ｉ）：Ｓｉ（ＯＲ1）4（但し、Ｒ1は炭素数１〜４のアルキル基）で示されるテトラアルコキシシラン（Ａ成分）と、
一般式（II）：Ｒ2Ｓｉ（ＯＲ3）3（但し、Ｒ2、Ｒ3は炭素数１〜４のアルキル基）で示されるトリアルコキシシラン（Ｂ成分）との、前者を主体とする加水分解混合物をベースとする。
(1) Preparation of silane solution:
The silane solution used in the present invention comprises a tetraalkoxysilane (component A) represented by the general formula (I): Si (OR 1 ) 4 (where R 1 is an alkyl group having 1 to 4 carbon atoms),
The former is mainly composed of trialkoxysilane (component B) represented by the general formula (II): R 2 Si (OR 3 ) 3 (where R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms). Based on the hydrolysis mixture.
そして、本発明のシラン溶液は、さらに、一般式(III)：
（但し、Ｒ4はＨ又はＣＨ3、Ｒ5は炭素数１〜４のアルキレン基、Ｒ6は炭素数１〜４のアルキル基）で示されるωグリシドキシアルキルトリアルコキシシラン（Ｃ成分）の加水分解物が添加されている。 (Wherein R 4 is H or CH 3 , R 5 is an alkylene group having 1 to 4 carbon atoms, R 6 is an alkyl group having 1 to 4 carbon atoms) ω-glycidoxyalkyltrialkoxysilane (C component) The hydrolyzate is added.
上記テトラアルコキシシランおよびトリアルコキシシランとしては、入手し易さの見地から、それぞれの汎用のアルコキシシランを用いる。例えば、テトラエトキシシラン（TEOS）およびメチルトリメトキシシラン（MTMOS）が望ましい。 As said tetraalkoxysilane and trialkoxysilane, each general purpose alkoxysilane is used from a viewpoint of availability. For example, tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMOS) are desirable.
上記Ａ成分と上記Ｂ成分との混合モル比は、Ａ成分／Ｂ成分＝75／25〜65／35、さらには、73／27〜67／33が望ましい。 The mixing molar ratio of the A component and the B component is preferably A component / B component = 75/25 to 65/35, more preferably 73/27 to 67/33.
すなわち、テトラアルコキシシランのみでは、塗膜の硬度が高いが脆く、熱・機械衝撃に対する耐性が低い。このため、トリアルコキシシランを適当なモル比で混合することにより、塗膜に柔軟性を付与して、熱・機械衝撃に対する耐性を高める必要がある。しかし、トリアルコキシシランが過剰になると、所要の塗膜硬度を確保し難く、耐擦傷性に問題が発生し易くなる。 That is, with tetraalkoxysilane alone, the coating film has high hardness but is brittle and has low resistance to heat and mechanical shock. For this reason, by mixing trialkoxysilane at an appropriate molar ratio, it is necessary to impart flexibility to the coating film and to increase resistance to thermal and mechanical shock. However, if the trialkoxysilane is excessive, it is difficult to ensure the required coating film hardness, and problems with the scratch resistance tend to occur.
上記ωグリシドキシアルキルトリアルコキシシラン（Ｃ成分）としては、汎用のグリシドキシアルキルトリアルコキシシランを用いる。例えば、3-グリシドキシプロピルトリメトキシシラン（GTMOS）が望ましい。 As the ω-glycidoxyalkyltrialkoxysilane (C component), general-purpose glycidoxyalkyltrialkoxysilane is used. For example, 3-glycidoxypropyltrimethoxysilane (GTMOS) is desirable.
ωグリシドキシアルキルトリアルコキシシラン（Ｃ成分）に対する前記Ａ成分とＢ成分との合計量の混合モル比（Ｃ成分／(Ａ成分＋Ｂ成分)）＝１／14.5〜１／8.5、さらには、１／13〜１／8.5、よりさらには1／11.5〜1／12.5が望ましい。Ｃ成分の混合モル比が小さいと、塗膜に白濁が発生し易く、実用的な遮熱塗膜を形成し難い。逆に、Ｃ成分の混合モル比が大きいと、塗膜に波打ち（筋状模様）が発生し易い。 The mixing molar ratio of the total amount of the A component and the B component to the ω-glycidoxyalkyltrialkoxysilane (C component) (C component / (A component + B component)) = 1 / 14.5 to 1 / 8.5, 1/13 to 1 / 8.5, more preferably 1 / 11.5 to 1 / 12.5. If the mixing molar ratio of the component C is small, the coating film is likely to be clouded, and it is difficult to form a practical thermal barrier coating film. On the other hand, when the mixing molar ratio of the C component is large, the coating film is likely to be wavy (striated pattern).
そして、加水分解混合物の調製は、例えば、65〜75℃×3〜7ｈ、望ましくは、65〜75℃×4〜6ｈの条件で行なう。時間が長い程、加水分解が充分に進み、シリコーン塗膜の基材（特にガラス基材）に対する密着性および耐熱性が向上する。 The hydrolysis mixture is prepared, for example, under the conditions of 65 to 75 ° C. × 3 to 7 hours, preferably 65 to 75 ° C. × 4 to 6 hours. The longer the time is, the more the hydrolysis proceeds, and the adhesion and heat resistance of the silicone coating film to the substrate (particularly the glass substrate) are improved.
なお、加水分解に使用する触媒としては、慣用的に使用されている塩酸が望ましい。 As a catalyst used for hydrolysis, conventionally used hydrochloric acid is desirable.
（２）ITO分散液の用意：
ITO分散液とは、ITO粒子がIPA等の水系分散媒に分散保持されている溶液をいう。市販品を用いることができる。
(2) Preparation of ITO dispersion:
The ITO dispersion refers to a solution in which ITO particles are dispersed and held in an aqueous dispersion medium such as IPA. Commercial products can be used.
ITO粒子の平均粒径（メジアン値）は、0.2μm以下、さらには0.1μm以下、よりさらには0.04μm以下が望ましい。良好な透明性を確保するためである。（特許文献６段落0012）。 The average particle size (median value) of the ITO particles is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. This is to ensure good transparency. (Patent Document 6, paragraph 0012).
ITOとしては、Sn比［Sn／(Sn＋In)］が1〜20％のものが望ましい。Snが1％未満のときは、熱線遮蔽性能を得難いとともに、In成分が多くなるため高価となる。Sn比が20％より多くなると上記同様熱線遮蔽性能を得難い。（同段落0013）。 ITO preferably has a Sn ratio [Sn / (Sn + In)] of 1 to 20%. When Sn is less than 1%, it is difficult to obtain heat ray shielding performance, and the amount of In component increases, which is expensive. When the Sn ratio exceeds 20%, it is difficult to obtain the heat ray shielding performance as described above. (Paragraph 0013).
ITO分散液のITO粒子濃度は、通常、25〜45％、望ましくは30〜40％のものを使用する。ITO粒子濃度が低いと充分な遮熱効果を得難く、ITO粒子濃度が高すぎても、それ以上の遮熱効果を得難い又は過剰品質となる。 The ITO particle concentration of the ITO dispersion is usually 25 to 45%, preferably 30 to 40%. If the ITO particle concentration is low, it is difficult to obtain a sufficient heat shielding effect. If the ITO particle concentration is too high, it is difficult to obtain a further heat shielding effect or the quality is excessive.
（３）シリコーン系塗料の調製：
前記シラン溶液と上記ITO分散液とを混合して本発明のシリコーン系塗料とする。
(3) Preparation of silicone paint:
The silane solution and the ITO dispersion are mixed to obtain the silicone paint of the present invention.
混合比（体積基準とする。以下同じ。）は、シラン溶液／ITO分散液＝75／25〜65／35、望ましくは、72／28〜68／32とする。 The mixing ratio (based on volume; the same applies hereinafter) is silane solution / ITO dispersion = 75/25 to 65/35, preferably 72/28 to 68/32.
ITO分散液の比率が低くても高くても、ゲル化時間が短くなる傾向にあり、実用的な塗料可使時間を得難くなる。なお、ゲル化した塗料を用いた場合、塗膜が白濁状態となるとともに平滑塗膜面を得難い。 Whether the ITO dispersion ratio is low or high, the gelation time tends to be short, and it is difficult to obtain a practical paint use time. In addition, when the gelatinized coating material is used, it is difficult to obtain a smooth coating film surface while the coating film becomes cloudy.
（４）シリコーン系塗膜の形成：
こうして調製したシリコーン系塗料は、通常、ガラス基材上に塗装して室温下1日乾燥すれば、本発明のシリコーン塗膜（遮熱塗膜）を形成することができる。乾燥・硬化促進の見地から、適宜、加熱処理（例えば、90〜100℃×30〜60min）してもよい。
(4) Formation of silicone-based coating film:
The silicone-based paint thus prepared can usually form the silicone coating film (heat-shielding coating film) of the present invention if it is coated on a glass substrate and dried at room temperature for 1 day. From the viewpoint of drying / curing acceleration, heat treatment (for example, 90 to 100 ° C. × 30 to 60 min) may be appropriately performed.
なお、塗装方法は、特に限定されない。例えば、スプレー塗装、ローラ塗り、刷毛塗り等、慣用の方法が適用でき、工場塗装する場合、浸漬塗りや流し塗り等も可能である。 In addition, the coating method is not specifically limited. For example, conventional methods such as spray coating, roller coating, brush coating, and the like can be applied. When factory coating is performed, dip coating, flow coating, and the like are also possible.
このときのシリコーン系塗料の塗膜厚は、200〜2000nm、望ましくは500〜1500nmとする。塗膜厚が薄いと塗膜に必要な遮熱効果や硬度を得難くなる傾向にある。逆に、塗膜厚を厚くしても、それ以上の性能の向上が望めない又は過剰品質となる。即ち、塗料コストが嵩む。 At this time, the coating thickness of the silicone-based paint is 200 to 2000 nm, preferably 500 to 1500 nm. When the coating film thickness is thin, it tends to be difficult to obtain the heat shielding effect and hardness required for the coating film. On the contrary, even if the coating film thickness is increased, further improvement in performance cannot be expected or the quality becomes excessive. That is, the coating cost increases.
こうしてガラス基板等の透明基材上にシリコーン系塗膜（遮熱塗膜）を形成した場合、後述の実施例で示す如く、熱線波長範囲を遮断して良好な遮熱性を透明基材に付与できるとともに、該遮熱塗膜のガラス等の透明基材に対する密着性も良好である。 When a silicone-based coating film (heat-shielding coating film) is formed on a transparent substrate such as a glass substrate in this way, the heat-ray wavelength range is cut off and a good heat-shielding property is imparted to the transparent substrate as shown in the examples below. In addition, the thermal barrier coating has good adhesion to a transparent substrate such as glass.
このようにして形成した本発明の遮熱塗膜は、ITO分散液を合成樹脂に混合した遮熱塗料で形成した従来の遮熱塗膜に比して、膜厚が薄く（例えば、従来10μm前後、本発明1μm前後）、硬度も高い（例えば、従来4〜5Ｈ、本発明８Ｈ前後）という長所を有する。 The thermal barrier coating film of the present invention formed in this way has a thinner film thickness (for example, the conventional 10 μm) than the conventional thermal barrier coating film formed by the thermal barrier coating material in which the ITO dispersion liquid is mixed with the synthetic resin. Before and after, the present invention is around 1 μm) and has a high hardness (for example, 4-5H in the past, around 8H in the present invention).
以下、本発明を実施例に基づいて、さらに詳細に説明をする。
＜Ａ．試験片の調製＞
（A-1）シラン溶液（アルコキシシラン加水分解物）の調製
エタノール中、TEOSとMTMOSとを合わせたモル濃度を1Mとし、シラン:HCl:水=1:0.01:4のモル比で加えた。TEOSとMTMOSのモル比は70:30とした。この加水分解用溶液を70℃で4ｈ、加熱攪拌して均一なシラン溶液（アルコキシシラン加水分解物）を得た。
Hereinafter, the present invention will be described in more detail based on examples.
<A. Preparation of test piece>
(A-1) Preparation of Silane Solution (Alkoxysilane Hydrolyzate) The molar concentration of TEOS and MTMOS in ethanol was 1 M, and silane: HCl: water = 1: 0.01: 4 was added. The molar ratio of TEOS and MTMOS was 70:30. This solution for hydrolysis was heated and stirred at 70 ° C. for 4 hours to obtain a uniform silane solution (alkoxysilane hydrolyzate).
TEOSとMTMOSを合わせたモル濃度について、1.5M、1.75M、2Mの溶液も1Mの場合と同様に調製した。 Regarding the combined molar concentration of TEOS and MTMOS, 1.5M, 1.75M, and 2M solutions were prepared in the same manner as in the case of 1M.
また、上記TEOSとMTMOSによるシラン溶液に、GTMOSを加えた溶液も同様にして調製した。 Further, a solution in which GTMOS was added to the silane solution of TEOS and MTMOS was also prepared in the same manner.
このとき、TEOS+MTMOSとGTMOSとのモル比としては、GTMOS／(TEOS+MTMOS)=１/Xにおいて、ｘ=14〜4の範囲に亘ってシラン溶液を調製した。 At this time, as a molar ratio of TEOS + MTMOS and GTMOS, a silane solution was prepared over a range of x = 14 to 4 at GTMOS / (TEOS + MTMOS) = 1 / X.
（A-2）ITO分散液の用意：
ITO粒子（平均粒径（メジアン値）0.2μｍ）、濃度（質量比）：35％、比重1.15、分散溶媒ＩＰＡの市販品を用意した。
(A-2) Preparation of ITO dispersion:
Commercially available products of ITO particles (average particle size (median value) 0.2 μm), concentration (mass ratio): 35%, specific gravity 1.15, and dispersion solvent IPA were prepared.
（A-3）シリコーン系塗料の調製
上記(1)のシラン溶液に上記(2)のITO分散液をシラン溶液／ITO分散液＝70／30又は80／20の混合比の混合物を、室温下１ｈ攪拌して目的のシリコーン系塗料（遮熱塗料）を得た。
(A-3) Preparation of silicone-based paint The above-mentioned silane solution of (1) is mixed with the ITO dispersion liquid of (2) above at a room temperature, with a mixture ratio of silane solution / ITO dispersion liquid = 70/30 or 80/20. The mixture was stirred for 1 hour to obtain the desired silicone-based paint (thermal barrier paint).
（A-4）塗膜評価試験片の作成
試験片用基板は、塗膜面特性用は約15mm×12mm×1.2mmtの、透過率測定用は約30mm×20mm×1.2mmtの各ガラス基板を用いた。これらのガラス基板は、アセトンおよびエタノールで順次洗浄しておいた。
(A-4) Preparation of coating film evaluation test piece The test piece substrate is about 15 mm x 12 mm x 1.2 mmt for coating surface characteristics, and about 30 mm x 20 mm x 1.2 mmt for measuring transmittance. Using. These glass substrates were sequentially washed with acetone and ethanol.
各ガラス基板の上へ、上記(A-3)で得た塗料を、塗膜面特性用は6μLずつ、透過率測定用は20μLずつ、それぞれ滴下し、室温下１日乾燥して試験片を調製した。 On each glass substrate, the coating material obtained in (A-3) above is dropped 6 μL each for coating surface properties and 20 μL each for transmittance measurement, and is dried at room temperature for 1 day. Prepared.
＜Ｂ．試験方法・結果および考察＞
（B-0）上記Ａ．でガラス基板上に形成した各シリコーン塗膜（遮熱塗膜）について、下記項目の評価試験を行った。
（I）表面状態・・・光学顕微鏡と走査電子顕微鏡(ＳＥＭ)を用いて目視観察した。
<B. Test methods, results and discussion>
(B-0) A. above. With respect to each silicone coating film (heat-shielding coating film) formed on the glass substrate, an evaluation test of the following items was performed.
(I) Surface condition: Visual observation was performed using an optical microscope and a scanning electron microscope (SEM).
（II）密着性・・・粘着テープによる剥離試験を行った。具体的には、粘着テープを塗膜面に貼り付け、これを引き剥がした後の表面状態を目視により観察した。 (II) Adhesion: A peel test with an adhesive tape was performed. Specifically, an adhesive tape was attached to the coating film surface, and the surface state after peeling it off was visually observed.
（III）硬度・・・鉛筆硬度を測定した。 (III) Hardness: Pencil hardness was measured.
（IV）耐熱性・・・試験片を乾燥器に入れ、100℃×30minの条件で耐熱試験を行い、該試験後の塗膜の表面状態を目視観察した。 (IV) Heat resistance: A test piece was placed in a drier and subjected to a heat resistance test under conditions of 100 ° C. × 30 min. The surface state of the coating film after the test was visually observed.
（V）透過率・・・分光光度計(日立製作所社製「340S」)を用いて波長範囲800〜2600nmについて測定した。 (V) Transmittance: Measured for a wavelength range of 800 to 2600 nm using a spectrophotometer (“340S” manufactured by Hitachi, Ltd.).
（B-1）塗料成分であるシラン溶液の評価：
前記（A-1）に従って調製したTEOS＋MTMOSのシラン溶液と、前記（A-3）に従って、ITO分散液とを所定の混合比で混合し、室温下1ｈ攪拌した。シラン溶液のTEOSとMTMOSを合わせた、シラン濃度は1Mと1.5Mを用いた。
(B-1) Evaluation of paint component silane solution:
The TEOS + MTMOS silane solution prepared according to (A-1) and the ITO dispersion liquid according to (A-3) were mixed at a predetermined mixing ratio, and stirred at room temperature for 1 h. The combined silane concentration of TEOS and MTMOS was 1M and 1.5M.
得られた塗料を用い、（A-4）に従ってガラス基板上に塗膜を形成した。その結果、シラン溶液とITO分散溶液の混合比が70／30の場合には、シラン濃度が1Mと1.5M共に得られた塗膜面に細かい割れ（欠陥）が観察された。また、シラン溶液とITO分散溶液の混合比が80／20の場合には、シラン濃度が1Mと1.5M共に塗膜が白濁した。 Using the obtained paint, a coating film was formed on a glass substrate according to (A-4). As a result, when the mixing ratio of the silane solution and the ITO dispersion solution was 70/30, fine cracks (defects) were observed on the surface of the coating film in which both silane concentrations were 1M and 1.5M. In addition, when the mixing ratio of the silane solution and the ITO dispersion solution was 80/20, the coating film became cloudy at both silane concentrations of 1M and 1.5M.
シリコーン塗膜の調製法を再度調べ直したが、得られる塗膜の表面状態を改善することはできなかった。 The preparation method of the silicone coating film was examined again, but the surface state of the coating film obtained could not be improved.
このため、TEOS＋MTMOSの二成分系のシラン溶液にGTMOSを添加した三成分系のシラン溶液について調べた。 Therefore, a ternary silane solution obtained by adding GTMOS to a TEOS + MTMOS binary silane solution was examined.
TEOS＋MTMOS＝1Mの場合において、「GTMOS混合比」を「１／ｘ（モル比）＝GTMOS／(TEOS+MTMOS)」としたとき、ｘ=14、12、10、8、6、4となるような混合比でGTMOSを添加して各シラン溶液を調製した。なお、塗料は、前記（A-3）に従って、シラン溶液／ITO分散液=70／30の混合比で混合して調製した。得られたシリコーン系塗料を用いてガラス基板上に塗膜を形成し、表面状態を観察した。 When TEOS + MTMOS = 1M, when "GTMOS mixing ratio" is "1 / x (molar ratio) = GTMOS / (TEOS + MTMOS)", x = 14, 12, 10, 8, 6, 4 Each silane solution was prepared by adding GTMOS in various mixing ratios. The paint was prepared by mixing at a mixing ratio of silane solution / ITO dispersion = 70/30 according to (A-3). A coating film was formed on a glass substrate using the obtained silicone-based paint, and the surface state was observed.
その結果、TEOS＋MTMOS＝1Mでは、いずれのGTMOS混合比（１／ｘ）においても、塗膜に白濁（塗膜面全体波打ちも）が観察された。TEOS＋MTMOS＝1Mでは、実用上の遮熱塗膜の形成が困難であることが分かった。 As a result, when TEOS + MTMOS = 1M, white turbidity (including the entire surface of the coating film) was observed at any GTMOS mixing ratio (1 / x). When TEOS + MTMOS = 1M, it was found that it was difficult to form a practical thermal barrier coating.
続いて、TEOSとMTMOSを合わせたシラン濃度を1.5Mと濃くして、上記1Mの場合と同様な条件で塗膜を形成した。 Subsequently, the silane concentration of TEOS and MTMOS was increased to 1.5M, and a coating film was formed under the same conditions as in the case of 1M.
これらの塗膜の表面状態を観察した結果、ｘ＝14,12,10のいずれの場合にも、白濁が発生しないが、ｘ＝14の場合、塗膜面に波打ちが、ｘ＝12,10の場合、塗膜縁部に波打ちが発生することがわかった。ｘ＝14,12,10に、波打ちが発生しても、塗膜に白濁が発生せず、実用上の遮熱塗膜の形成が可能であることが分かった。 As a result of observing the surface state of these coating films, no white turbidity occurs in any case of x = 14,12,10, but in the case of x = 14, the surface of the coating film is wavy, x = 12,10 In the case of, it was found that undulations occurred at the edges of the coating film. It was found that even when undulations occurred at x = 14, 12, 10, no white turbidity occurred in the coating film, and it was possible to form a practical thermal barrier coating film.
ｘ＝8、6、4においては、塗膜に白濁（塗膜面波打ちも）が観察され、実用上の遮熱塗膜の形成が困難であることが分かった。 When x = 8, 6, and 4, white turbidity (also surface waviness of the coating film) was observed, indicating that it was difficult to form a practical thermal barrier coating film.
TEOS＋MTMOS＝1.75M，2Mの場合においても同様な条件で塗膜を形成したところ、得られた塗膜の表面状態は1.5Mの場合と同様な傾向を示し、1.75Mと2M共にｘ=10,12の場合が良好な結果を示した。 When TEOS + MTMOS = 1.75M and 2M, a coating film was formed under the same conditions. The surface condition of the obtained coating film showed the same tendency as 1.5M, and both 1.75M and 2M had x = 10, The case of 12 showed a good result.
ただし、TEOSとMTMOSを合わせたシラン濃度が2.5Mを超えると、塗膜面の平滑性（均一性）が低下して塗膜面に波打ちが発生し易い傾向があった。 However, when the combined silane concentration of TEOS and MTMOS exceeded 2.5M, the smoothness (uniformity) of the coating film surface was lowered and the coating film surface tended to be wavy.
それらの結果をまとめたものを表１に示す。 The results are summarized in Table 1.
続いて、上記で得られた塗膜の耐熱性を前記(B-0)(IV)に基づいて調べた。 Subsequently, the heat resistance of the coating film obtained above was examined based on (B-0) (IV).
その結果、TEOS＋MTMOS＝1.5Mの場合には全く問題ないが、それ以上になると、基板の縁部分において、一部割れや剥がれが見られる場合があった。加えて、TEOS＋MTMOS＝2Mを用いた際、室温下で長期間(１週間以上)乾燥した塗膜において、表面に大きな割れや剥がれが生成した場合があった。 As a result, when TEOS + MTMOS = 1.5M, there is no problem at all. However, when the thickness is higher than that, some cracks or peeling may be observed at the edge of the substrate. In addition, when TEOS + MTMOS = 2M was used, there were cases where large cracks or peelings were generated on the surface of the coating film dried at room temperature for a long time (one week or more).
これらの結果から、TEOS＋MTMOSのシラン濃度が低すぎると（例えば１M)、塗膜が白濁し、高すぎると塗膜面の平滑性が低下し、さらに、乾燥・硬化後の塗膜が割れたり剥がれたりすることが判明した。 From these results, when the silane concentration of TEOS + MTMOS is too low (eg 1M), the coating film becomes cloudy, and when it is too high, the smoothness of the coating film surface decreases, and the coating film after drying / curing breaks or peels off. It turned out to be.
上記結果を基に、さらに詳細なGTMOS混合比（1／ｘ）の最適範囲を調べることにした。 Based on the above results, we decided to investigate the optimal range of more detailed GTMOS mixing ratio (1 / x).
そこで、TEOS＋MTMOS＝1.5M、1.75M、2Mについて、ｘ=10に加えてｘ=11と9のシラン溶液を調製した。その結果、いずれの場合においても、塗膜面の平滑性と透明性から判断すると、ｘ=11が最も優れていることが判明した。 Therefore, for TEOS + MTMOS = 1.5M, 1.75M, and 2M, in addition to x = 10, x = 11 and 9 silane solutions were prepared. As a result, in any case, it was found that x = 11 was the best when judged from the smoothness and transparency of the coating surface.
さらに、TEOS＋MTMOSおよびGTMOSを用いた、加水分解物調製であるシラン溶液の調製において、加熱時間を4ｈから6ｈへと長くしたシラン溶液を調べることにした。 Furthermore, in the preparation of a silane solution that is a hydrolyzate preparation using TEOS + MTMOS and GTMOS, it was decided to investigate a silane solution with a heating time increased from 4 h to 6 h.
得られた塗料を用いて塗膜の検討を繰り返した結果、再現性良く、白濁無しで塗膜面平滑な塗膜を形成できることがわかった。 As a result of repeating the examination of the coating film using the obtained coating material, it was found that a coating film with good reproducibility and a smooth coating surface can be formed without white turbidity.
また、TEOS＋MTMOS＝1.5Mにおいて、ｘ＝11とした塗料で形成した塗膜は、密着性が良好で、鉛筆硬度は8Hと高い値を示した。 In addition, the coating film formed from the paint with x = 11 at TEOS + MTMOS = 1.5M had good adhesion and a high pencil hardness of 8H.
加えて、耐熱性試験を行った結果、割れや剥がれは全く観察されなかった。 In addition, as a result of the heat resistance test, no cracks or peeling were observed.
1.75Mの場合においても、加熱時間を長くすることにより同様の改善が見られた。しかし、1.75Mの場合には、6時間加熱後に溶液中に若干のシラン溶液にゲルの生成が見られた。 In the case of 1.75M, the same improvement was seen by increasing the heating time. However, in the case of 1.75M, gel formation was observed in some silane solutions in the solution after heating for 6 hours.
ただし、このゲルを除いた溶液を用いれば、問題なく平滑な塗膜が得られた。 However, if a solution excluding this gel was used, a smooth coating film was obtained without problems.
一方、2Mの場合には、ゲル化がかなり進行してしまうため、塗膜調製には細心の注意が必要である。これらの結果から、TEOS＋MTMOS＝1.5M又は1.75M、GTMOS混合比＝１／ｘにおいて、ｘ=11を最適なシラン溶液と結論付けることができる。 On the other hand, in the case of 2M, since gelation proceeds considerably, careful attention is required for coating film preparation. From these results, it can be concluded that x = 11 is an optimum silane solution when TEOS + MTMOS = 1.5M or 1.75M and GTMOS mixing ratio = 1 / x.
即ち、TEOS＋MTMOSのシラン濃度を1.3〜１.8M（さらには、1.4〜1.6M)において、GTMOS混合比（１／ｘ）としたとき、ｘ＝１4.5〜8.5、さらには13〜8.5、よりさらには11.5〜10.5とすることが望ましい。 That is, when the silane concentration of TEOS + MTMOS is 1.3 to 1.8M (and further 1.4 to 1.6M) and the GTMOS mixing ratio (1 / x), x = 14.5 to 8.5, and further 13 to 8.5. Furthermore, it is desirable to set it as 11.5-10.5.
また、今回検討した、TEOS＋MTMOSのモル濃度が1M，1.5M,1.75Mおよび2Mにおいて、TEOS＋MTMOSのモル濃度が1MおよびGTMOS混合比（１／ｘ）がｘ＝8,6,4のいずれかに該当する場合は、本発明の塗料として不適であることが分かった。 In addition, the TEOS + MTMOS molar concentration examined here is 1M, 1.5M, 1.75M and 2M, and the TEOS + MTMOS molar concentration is 1M and the GTMOS mixing ratio (1 / x) is either x = 8, 6, 4 When it does, it turned out that it is unsuitable as a coating material of this invention.
本発明における、シラン溶液とITO分散液の体積混合比は、シラン溶液／ITO分散液＝75／25〜65／35、望ましくは72／28〜68／32の範囲とする。 In the present invention, the volume mixing ratio of the silane solution and the ITO dispersion is silane solution / ITO dispersion = 75/25 to 65/35, preferably 72/28 to 68/32.
ITO分散液の割合が減った場合、例えば混合比を80／20とすると、塗料が若干不均一かつ青白色となり、この溶液により得られる塗膜は、白濁する。 When the proportion of the ITO dispersion is reduced, for example, when the mixing ratio is 80/20, the paint becomes slightly non-uniform and bluish white, and the coating film obtained by this solution becomes cloudy.
なお、ITO分散液に関して、これをシラン溶液へ加える際に、冷却状態（冷蔵庫保管）のITO分散液を用いて混合溶液を調製すると、これにより得られる塗膜は強く白濁した。よって、室温下で保存したITO分散液を利用することが、白濁の無い塗膜作製には重要であることがわかった。 When the ITO dispersion liquid was added to the silane solution and a mixed solution was prepared using the ITO dispersion liquid in a cooled state (stored in a refrigerator), the resulting coating film became strongly cloudy. Therefore, it was found that the use of an ITO dispersion stored at room temperature is important for producing a coating film free of white turbidity.
また、TEOSとMTMOSおよびGTMOSによるシラン溶液に関して、調製後、直ちにITO分散液と混合するのではなく、調製後、室温下において１日程度置いた方が、白濁の少ない塗膜が得られる傾向が見られた。 Also, regarding the silane solution by TEOS, MTMOS, and GTMOS, rather than immediately mixing with the ITO dispersion after preparation, it is more likely that a film with less cloudiness will be obtained if it is left at room temperature for about one day after preparation. It was seen.
続いて、上記最適組成の塗料から形成した塗膜の透過率を測定（測定波長領域：800〜2600nm）した。 Then, the transmittance | permeability of the coating film formed from the coating material of the said optimal composition was measured (measurement wavelength range: 800-2600 nm).
測定結果である図１は、塗膜を施したガラス基板では、波長800nm付近で透過率約85%を示したが、これ以降波長が長くなるに連れて低下し続け、波長1500〜2600nmの範囲において、ほぼ0%を示した。なお、未処理のガラス基板では、通常、測定波長範囲全般において約90%と高い透過率を示すとされている。 Fig. 1 shows the measurement results. The glass substrate with the coating film showed a transmittance of about 85% near the wavelength of 800 nm, but after that, it continued to decrease as the wavelength increased, and the wavelength ranged from 1500 to 2600 nm. It showed almost 0%. Note that an untreated glass substrate usually has a high transmittance of about 90% over the entire measurement wavelength range.
この結果から、本塗膜をガラス基板上へ導入することにより、大幅に近赤外線が遮断できることが確認できた。また、本塗膜は、透過率の測定終了後においても、塗膜面の劣化は全く観察されなかった。 From this result, it was confirmed that the near-infrared rays can be largely blocked by introducing this coating film onto the glass substrate. In addition, no deterioration of the coating film surface was observed even after the measurement of the transmittance of the coating film was completed.
さらに、本塗膜の(a)表面状態と(b)断面のSEM像を図２に示す。 Furthermore, the SEM image of the (a) surface state and (b) cross section of this coating film is shown in FIG.
図２(a)から、塗膜面には割れや剥がれのような欠陥は無く、塗膜面平滑であることが確認できた。また、図２(b)から、ITO粒子が均一かつ緻密に分散している状態が観察され、また、塗膜の膜厚は約1.5μmであることが判明した。 From FIG. 2 (a), it was confirmed that the coating film surface was smooth and free from defects such as cracking and peeling. Further, from FIG. 2 (b), it was observed that the ITO particles were uniformly and densely dispersed, and the film thickness of the coating film was about 1.5 μm.
＜Ｃ．考察まとめ＞
以下に、本研究によって得られた成果をまとめる。
1)ITO分散液へのシラン処理剤（シランカップリング剤）の添加を行わず、ITO分散液をそのまま使用し、これとシラン溶液との混合を試みた。TEOSとMTMOSのみによるシラン溶液を用いて塗膜を作製したが、塗膜面に細かい割れが発生する場合や、白濁する場合もあった。これを改善するために、様々な溶液の調製条件を調べたが、良好な表面状態を有する塗膜を得ることができなかった。
<C. Summary of Discussion>
The results obtained from this study are summarized below.
1) Without adding a silane treatment agent (silane coupling agent) to the ITO dispersion, the ITO dispersion was used as it was, and an attempt was made to mix this with the silane solution. A coating film was prepared using a silane solution consisting only of TEOS and MTMOS. However, there were cases in which fine cracks occurred on the coating surface or white turbidity occurred. In order to improve this, the preparation conditions of various solutions were investigated, but a coating film having a good surface state could not be obtained.
2)上記1)の結果を受け、シラン溶液の改良として、TEOSとMTMOSの溶液に対して、さらにGTMOSを加えたシラン溶液について調べた。この際、TEOSとMTMOSを合わせたシラン濃度、加えるGTMOSの濃度、シラン溶液とITO分散液との混合比等、様々な条件で最適範囲を模索した。 2) Based on the result of 1) above, as an improvement of the silane solution, a silane solution in which GTMOS was further added to the TEOS and MTMOS solution was examined. At this time, the optimum range was sought under various conditions such as the combined silane concentration of TEOS and MTMOS, the concentration of GTMOS to be added, and the mixing ratio of the silane solution and the ITO dispersion.
その結果、表面状態と密着性および硬度に優れ、耐熱性も問題が無く、さらに近赤外線(特に約1500〜2600nm)を確実に遮断できる塗膜を作製できるシリコーン系塗料が開発できた。 As a result, it was possible to develop a silicone-based paint that can produce a coating film that is excellent in surface condition, adhesion and hardness, has no problem with heat resistance, and can reliably block near infrared rays (particularly about 1500 to 2600 nm).
また、溶液の塗付性も良好で、平滑な塗膜を形成できることを確認した。 Moreover, the applicability | paintability of the solution was also favorable and it confirmed that a smooth coating film could be formed.
なお、実際にITO分散液と混合する際には、室温下で1日程度静置したシラン溶液を使用した方が良い(塗膜平滑性が向上し、白濁化を防ぐ)。本シラン溶液は封をした状態で室温下保存すれば、約1ヶ月以上、場合によっては5〜6ケ月使用できることを確認している。 When actually mixing with the ITO dispersion, it is better to use a silane solution that is allowed to stand at room temperature for about 1 day (the coating film smoothness is improved and clouding is prevented). It has been confirmed that the silane solution can be used for about 1 month or more, and in some cases, 5 to 6 months if stored at room temperature in a sealed state.
本シラン溶液をITO分散液と混合して、塗料を調製する際、所定時間（例えば、１ｈ以上）できる限り攪拌を強くし均一に混合することが望ましい。 When preparing the paint by mixing this silane solution with the ITO dispersion liquid, it is desirable to stir as strongly as possible for a predetermined time (for example, 1 h or longer) to mix uniformly.
Claims (5)
該シラン溶液が、
一般式（Ｉ）：Ｓｉ（ＯＲ1）4（但し、Ｒ1は炭素数１〜４のアルキル基）で示されるテトラアルコキシシラン（Ａ成分）、と、
一般式（ＩＩ）：Ｒ2Ｓｉ（ＯＲ3）3（但し、Ｒ2、Ｒ3は炭素数１〜４のアルキル基）で示されるトリアルコキシシラン（Ｂ成分）、
との、前者を主体とする加水分解混合物において、
さらに、一般式（ＩＩＩ）：
該Ｃ成分に対する該Ａ成分と該Ｂ成分との合計量の混合モル比が、Ｃ成分／（Ａ成分＋Ｂ成分）＝１／１４．５〜１／８．５であり、
該加水分解混合物における該Ａ成分と該Ｂ成分の合計モル濃度が１．３〜２．５Ｍである、
ことを特徴とするシリコーン系塗料。 Alkoxysilane silane consisting hydrolyzate solution, an indium tin oxide (ITO) dispersion of particles (hereinafter, referred to as. "ITO dispersion") a silicone-based paint used in admixture with, a,
The silane solution is
Tetraalkoxysilane (component A) represented by the general formula (I): Si (OR 1 ) 4 (where R 1 is an alkyl group having 1 to 4 carbon atoms);
Trialkoxysilane (component B) represented by the general formula (II): R 2 Si (OR 3 ) 3 (wherein R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms) ,
In the hydrolysis mixture mainly composed of the former,
Furthermore, the general formula (III):
The mixing molar ratio of the total amount of the A component and the B component to the C component is C component / (A component + B component) = 1 / 14.5 to 1 / 8.5,
The total molar concentration of the A component and the B component in the hydrolysis mixture is 1.3 to 2.5M.
A silicone-based paint characterized by that.
ていることを特徴とする遮熱構造透明基材。 A heat-shielding transparent substrate having a heat-shielding coating film formed of the silicone-based paint according to any one of claims 1 to 4 on a transparent substrate.
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| WO2017043486A1 (en) * | 2015-09-07 | 2017-03-16 | 株式会社エフコンサルタント | Water-based coating material and method for forming coating film |
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| JP2000144051A (en) * | 1998-11-18 | 2000-05-26 | Teijin Chem Ltd | Composition for coating |
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| JP2005200546A (en) * | 2004-01-15 | 2005-07-28 | Shin Etsu Chem Co Ltd | Silicone resin composition and coated article using the same |
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