JP2020189764A - Light deterioration inhibitor - Google Patents
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 37
- 230000006866 deterioration Effects 0.000 title abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001782 photodegradation Methods 0.000 claims description 42
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 14
- 150000004706 metal oxides Chemical class 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
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- 238000007254 oxidation reaction Methods 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000012901 Milli-Q water Substances 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- -1 TiO 2 and ZnO Chemical class 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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Abstract
Description
本発明は、光劣化抑制材に関する。 The present invention relates to a photodegradation inhibitor.
紫外及び可視光照射（以下「光照射」と呼称する。）は、日焼け、肌の「たるみ」及び「しわ」、印刷物の褪色、並びに、プラスチックの硬化及び「ひびわれ」等の多様な劣化現象の原因となることが広く知られている。この光照射により惹起される現象は、総称して「光劣化」と呼ばれている。 Ultraviolet and visible light irradiation (hereinafter referred to as "light irradiation") is a cause of various deterioration phenomena such as sunburn, "sagging" and "wrinkles" of the skin, fading of printed matter, and hardening and "cracking" of plastics. It is widely known to be the cause. The phenomenon caused by this light irradiation is collectively called "photodegradation".
この光劣化を防止するための技術として、特許文献１には、「平均粒径７０〜３００ｍμの微粒子状酸化亜鉛（ＺｎＯ）を１〜２５重量％配合することを特徴とする日焼け防止化粧料」が記載されている。 As a technique for preventing this photodegradation, Patent Document 1 describes "a sunburn-preventing cosmetic containing 1 to 25% by weight of fine particle zinc oxide (ZnO) having an average particle size of 70 to 300 mμ". Is described.
本発明者らは、特許文献１に記載された日焼け防止化粧料によっては、光照射下における肌の「たるみ」及び「しわ」等に代表される光劣化の発生を十分には抑制できない場合があることを知見している。 The present inventors may not be able to sufficiently suppress the occurrence of photodegradation typified by "sagging" and "wrinkles" of the skin under light irradiation depending on the sun protection cosmetics described in Patent Document 1. I know that there is.
そこで本発明は優れた光劣化抑制効果を有する光劣化抑制材を提供することを課題とする。 Therefore, an object of the present invention is to provide a photodegradation suppressing material having an excellent photodegradation suppressing effect.
本発明者らは、上記課題を達成すべく鋭意検討した結果、以下の構成により上記課題を達成することができることを見出した。 As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.
［１］ 価数の異なる２種以上のスズ（Ｓｎ）原子と酸素（Ｏ）原子とからなる結晶体を含有する光劣化抑制材。
［２］ ２００〜８００ｎｍの波長の光の少なくとも一部を吸収する［１］に記載の光劣化抑制材。
［３］ 上記結晶体が、＋２価、及び、＋４価の上記スズ原子を含有する、［１］又は［２］に記載の光劣化抑制材。
［４］
更に界面活性剤を含有する［１］〜［３］のいずれかに記載の光劣化抑制材。
［５］ 上記界面活性剤が、上記結晶体に担持されている、［４］に記載の光劣化抑制材。
［６］ 更に有機系、及び／又は、無機系のバインダを含有する［１］〜［５］のいずれかに記載の光劣化抑制材。
[1] A photodegradation inhibitor containing a crystal composed of two or more kinds of tin (Sn) atoms and oxygen (O) atoms having different valences.
[2] The photodegradation inhibitor according to [1], which absorbs at least a part of light having a wavelength of 200 to 800 nm.
[3] The photodegradation inhibitor according to [1] or [2], wherein the crystal contains +2 valent and +4 valent tin atoms.
[4]
The photodegradation inhibitor according to any one of [1] to [3], which further contains a surfactant.
[5] The photodegradation inhibitor according to [4], wherein the surfactant is supported on the crystal.
[6] The photodegradation inhibitor according to any one of [1] to [5], which further contains an organic and / or inorganic binder.
本発明によれば、優れた光劣化抑制効果を有する光劣化抑制材を提供できる。 According to the present invention, it is possible to provide a photodegradation suppressing material having an excellent photodegradation suppressing effect.
以下、本発明について詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に制限されるものではない。
なお、本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
［光劣化抑制材］
本発明の実施形態に係る光劣化抑制材は、価数の異なる２種以上のスズ（Ｓｎ）原子と酸素（Ｏ）原子とからなる結晶体（以下、「特定結晶体」ともいう。）を含有する光劣化抑制材である。
[Photodegradation inhibitor]
The photodegradation inhibitor according to the embodiment of the present invention is a crystal composed of two or more kinds of tin (Sn) atoms and oxygen (O) atoms having different valences (hereinafter, also referred to as “specific crystal body”). It is a photodegradation inhibitor contained.
上記光劣化抑制材により本発明の課題が解決される機序としては必ずしも明らかではないが、本発明者らは以下のとおり推測している。なお、以下の機序は推測であり、以下の機序以外の機序により本発明の効果が得られる場合であっても本発明の範囲に含まれるものとする。 The mechanism by which the above-mentioned photodegradation inhibitor solves the problem of the present invention is not necessarily clear, but the present inventors speculate as follows. The following mechanism is speculative and is included in the scope of the present invention even when the effect of the present invention is obtained by a mechanism other than the following mechanism.
従来、光劣化の防止技術として、防護対象の表面、又は、内部に、光劣化の原因となると考えられる波長の光（典型的には２００〜８００ｎｍの波長の光）を透過しにくい、十分な光反射率、及び／又は、吸収率を有する光遮蔽材を塗布、又は、分散させるものが知られている。このような技術は、光を反射、及び／又は、吸収することで、防護対象の表面から内部への光透過を抑え、光劣化を防ごうとするものであった。 Conventionally, as a technique for preventing light deterioration, it is difficult to transmit light having a wavelength (typically light having a wavelength of 200 to 800 nm) that is considered to cause light deterioration on the surface or inside of the object to be protected. It is known that a light shielding material having a light reflectance and / or an absorption rate is applied or dispersed. Such a technique is intended to suppress light transmission from the surface of a protected object to the inside by reflecting and / or absorbing light, and to prevent photodegradation.
この場合、光遮蔽材としては、化学的に安定であって、かつ、安価であり、更に生体毒性が低いことが知られているＺｎＯ、及び、ＴｉＯ２等の金属酸化物を含有するものが多かった。 In this case, as the light shielding material, one containing ZnO, which is chemically stable, inexpensive, and has low biotoxicity, and a metal oxide such as TiO 2 is used. There were many.
しかし、上記のような金属酸化物は、酸素を含有する官能基を有する有機物、及び／又は、水分の共存下において光（特に、波長４００ｎｍ未満の紫外光）照射されると、活性酸素種（ＲＯＳ：Ｒｅａｃｔｉｖｅ Ｏｘｙｇｅｎ Ｓｐｅｃｉｅｓ）を光触媒的に発生することを、本発明者らは知見している。
つまり、上記のような金属酸化物は、光劣化の原因となる光を反射、吸収し、その影響を低減する機能を有する一方で、光によるＲＯＳ（特にヒドロキシラジカル）の発生を惹起し、光劣化を促進する機能も有するのである。
However, the above-mentioned metal oxides are active oxygen species (particularly, ultraviolet light having a wavelength of less than 400 nm) when irradiated with light (particularly, ultraviolet light having a wavelength of less than 400 nm) in the presence of an organic substance having a functional group containing oxygen and / or water. The present inventors have found that ROS (Reactive Oxygen Species) is generated photocatalytically.
That is, while the above-mentioned metal oxide has a function of reflecting and absorbing light that causes photodegradation and reducing the influence thereof, it induces the generation of ROS (particularly hydroxyl radical) by light and causes light. It also has a function of promoting deterioration.
例えば、文献１において、所望の効果が得られないのは、微粒子状亜鉛等の金属酸化物が光照射下において光触媒として機能し、環境中の水分や小型有機分子からＲＯＳを発生し、これが、ＤＮＡ鎖の切断による細胞更新の阻害、コラーゲン鎖切断による皮膚弾性の低下等をもたらし、最終的には、肌の「たるみ」や「しわ」という光劣化を生ずるためと推測される。 For example, in Document 1, the desired effect cannot be obtained because a metal oxide such as fine particle zinc functions as a photocatalyst under light irradiation and generates ROS from moisture and small organic molecules in the environment. It is presumed that this is because the cleavage of DNA strands inhibits cell renewal, the cleavage of collagen strands causes a decrease in skin elasticity, and finally, photodeterioration such as "sag" and "wrinkles" of the skin occurs.
本発明者らは上記のような金属酸化物がＲＯＳ（特にヒドロキシラジカル）の発生を惹起する要因とその対策について検討を進めてきた。 The present inventors have been studying the factors that cause the above-mentioned metal oxides to generate ROS (particularly hydroxyl radicals) and their countermeasures.
上記金属酸化物は、典型的な光劣化の原因と考えられている波長領域の紫外光（ＵＶＢ（２８０ｎｍ＜波長≦３１５ｎｍ）；ＵＶＡ（３１５ｎｍ＜波長＜４００ｎｍ）の光）に対して吸収帯を有していることが知られている。
図１は、上記金属酸化物の典型的なバンド図（模式図）である。図１に示すとおり、光遮蔽材に対して、そのバンドギャップよりも高いエネルギーを有する光を照射した場合、光励起によって価電子帯頂上（ＶＢＴ）に正孔が発生し、この正孔とＯＨ基（例えば、水、及び／又は、アルコールのＯＨ基）とが反応することにより、ＲＯＳ（この場合、ヒドロキシラジカル（ＯＨ・））が生成される。なお、正孔は常に高いエネルギー準位に遷移しようとする性質があるため、ＯＨ・の生成促進に際しては、ＯＨ―／ＯＨ・酸化準位が、ＶＢＴよりもエネルギー的に高い場所に位置していることが必要条件である。
The metal oxide has an absorption band for ultraviolet light (UVB (280 nm <wavelength ≤ 315 nm); UVA (315 nm <wavelength <400 nm) light) in the wavelength region considered to be a typical cause of photodegradation. It is known to have.
FIG. 1 is a typical band diagram (schematic diagram) of the metal oxide. As shown in FIG. 1, when the light shielding material is irradiated with light having an energy higher than the band gap, holes are generated at the top of the valence band (VBT) by photoexcitation, and these holes and OH groups. (For example, water and / or the OH group of alcohol) reacts to generate ROS (in this case, hydroxyl radical (OH ·)). Since holes always tend to transition to a high energy level, the OH − / OH / oxidation level is located at a higher energy level than VBT when promoting the production of OH ·. It is a prerequisite to be there.
上記によれば、光遮蔽材としてＺｎＯ及びＴｉＯ２等の金属酸化物を用いた場合、バンドギャップよりもエネルギーの高いＵＶＢ光を効果的に反射する一方、照射された光の一部を吸収し、環境の水分や酸素から光触媒的に活性酸素種（例えばＯＨ・）を生ずるため、従来の金属酸化物を含有する光遮蔽材では、光劣化の抑制について、意図した効果が得られないことを、本発明者らは初めて知見した。 According to the above, when metal oxides such as ZnO and TiO 2 are used as the light shielding material, UVB light having a higher energy than the band gap is effectively reflected, while a part of the irradiated light is absorbed. Since active oxygen species (for example, OH) are photocatalytically generated from environmental moisture and oxygen, conventional light shielding materials containing metal oxides cannot obtain the intended effect of suppressing light deterioration. , The present inventors have discovered for the first time.
ＴｉＯ２及びＺｎＯ等の金属酸化物では、価電子帯の大部分は酸素のｐ軌道から構成されており、結果として、ＶＢＴの真空準位に対する位置は、大きく変わらないことが知られている。上記の金属酸化物の特徴を知見したからといって、ＵＶＡ及び／又はＵＶＢに吸収帯を持ち、しかもＯＨ・の生成を促進しない金属酸化物である光遮蔽材の実現は、従来困難であった。 It is known that in metal oxides such as TiO 2 and ZnO, most of the valence band is composed of p-orbitals of oxygen, and as a result, the position of VBT with respect to the vacuum level does not change significantly. Even if the above characteristics of the metal oxide are found, it has been difficult to realize a light shielding material which is a metal oxide having an absorption band in UVA and / or UVB and does not promote the formation of OH ·. It was.
本発明者らは、鋭意検討をしたところ、価数の異なる２種以上のスズ（Ｓｎ）原子と酸素（Ｏ）原子とからなる結晶体を含有する光劣化抑制材であれば、（典型的には、化学式Ｓｎ３Ｏ４で表される固体結晶（結晶体）であって、上記結晶体中に価数の異なるＳｎが２種以上存在する結晶体を含有する光劣化抑制材であれば、）上記課題を解決可能であることを知見し、本発明を完成させた。 As a result of diligent studies, the present inventors have found that any photodeterioration inhibitor containing a crystal composed of two or more kinds of tin (Sn) atoms and oxygen (O) atoms having different valences (typically). Is a light deterioration inhibitor containing a solid crystal (crystal) represented by the chemical formula Sn 3 O 4 in which two or more Sns having different valences are present in the crystal. ,) It was found that the above problems could be solved, and the present invention was completed.
図２は、上記結晶体のバンド図を模式的に示したものである。図２に示したように、上記結晶体は、２００〜８００ｎｍの波長の光に対して（特に、ＵＶＡ及びＵＶＢ）に吸収帯を持ち、しかも、その特殊な価電子帯電子構造により、ＶＢＴがＯＨ−酸化準位よりも高いエネルギー位置をとることを本発明者らは見出した。 FIG. 2 schematically shows a band diagram of the crystal body. As shown in FIG. 2, the above-mentioned crystal has an absorption band for light having a wavelength of 200 to 800 nm (particularly UVA and UVB), and its special valence band electronic structure makes VBT. We have found that it takes an energy position higher than the OH − oxidation level.
図３は、ＺｎＯ、ＴｉＯ２、及び、上記結晶体（図中、「Ｓｎ３Ｏ４」と示した）のバンド図である（３．３７、３．０、２．５はそれぞれ単位がｅＶである）。エネルギーギャップから、いずれもＵＶＡ及びＵＶＢに吸収帯を有する（すなわち、光の遮蔽効果を有する）ことがわかる。Ｓｎ３Ｏ４は、価電子帯上部に、Ｓｎ２＋の５ｄ軌道に由来する状態密度を有することがわかる。この結果、ＵＶ光照射下にあっても、ＶＢＴに生成された正孔は、ＯＨ−酸化準位よりもエネルギー的に高い準位に位置するため、ＯＨ基と結合してＯＨ・を生成することが禁制される。従って、光を吸収してもＲＯＳを発生しにくい。
一方でＺｎＯ及びＴｉＯ２は、価電子帯が酸素のｐ軌道から構成されているため、価電子帯の上端がＯＨ−酸化準位よりも低く、光照射によりＯＨ・が生成することがわかる。
FIG. 3 is a band diagram of ZnO, TiO 2 , and the above-mentioned crystal (indicated as “Sn 3 O 4 ” in the figure) (3.37, 3.0, and 2.5 have units of eV, respectively). Is). From the energy gap, it can be seen that both UVA and UVB have absorption bands (that is, they have a light shielding effect). It can be seen that Sn 3 O 4 has a density of states derived from the 5d orbital of Sn 2+ in the upper part of the valence band. As a result, even under UV irradiation, the holes generated in the VBT are located at a level higher in energy than the OH − oxidation level, and therefore combine with the OH group to generate OH ·. Is forbidden. Therefore, even if light is absorbed, ROS is unlikely to be generated.
On the other hand, in ZnO and TiO 2 , since the valence band is composed of p-orbitals of oxygen, the upper end of the valence band is lower than the OH − oxidation level, and it can be seen that OH · is generated by light irradiation.
このように、上記Ｓｎ３Ｏ４は、その特徴的な価電子帯構造のために、光劣化の原因となる光が入射した際、一部を反射し、一部を吸収し、更に、光を吸収してもＯＨ・生成を促進しない光劣化抑制材として、従来の金属酸化物系光遮蔽材にない機能を発揮する。以下、本光劣化抑制材に含有される成分ついて詳述する。 As described above, due to its characteristic valence band structure, the Sn 3 O 4 reflects a part of the light, absorbs a part of the light, and further absorbs the light when the light that causes photodegradation is incident. As a photodegradation inhibitor that does not promote OH / generation even if it absorbs light, it exhibits a function not found in conventional metal oxide-based light shielding materials. Hereinafter, the components contained in this photodegradation inhibitor will be described in detail.
〔特定結晶体〕
本光劣化抑制材は特定結晶体を含有する。光劣化抑制材における特定結晶体の含有量としては特に制限されないが、より優れた本発明の効果を有する光劣化抑制材が得られる点で、一般に、光劣化抑制材の全質量に対して、１〜９９質量％が好ましい。なお、光劣化抑制材は、特定結晶体の１種を単独で含有してもよく、２種以上を含有していてもよい。光劣化抑制材が、２種以上の特定結晶体を含有する場合には、その合計含有量が上記数値範囲内であることが好ましい。
[Specific crystal]
This photodegradation inhibitor contains a specific crystal body. The content of the specific crystal body in the photodegradation inhibitor is not particularly limited, but generally, the total mass of the photodegradation inhibitor is relative to the total mass of the photodegradation inhibitor in that a photodegradation inhibitor having a better effect of the present invention can be obtained. 1 to 99% by mass is preferable. The light deterioration inhibitor may contain one type of the specific crystal body alone, or may contain two or more types. When the photodegradation inhibitor contains two or more kinds of specific crystals, the total content thereof is preferably within the above numerical range.
特定結晶は価数の異なるスズ（Ｓｎ）原子を２種以上（好ましくは２種）有するため、価数の異なるＳｎ原子が結晶格子中で隣接配置されるため、ＶＢＴが、ＯＨ−／ＯＨ・酸化準位の上に位置する。 Since the specific crystal has two or more types (preferably two types) of tin (Sn) atoms having different valences, Sn atoms having different valences are arranged adjacent to each other in the crystal lattice, so that VBT is OH − / OH ·. Located above the oxidation level.
特定結晶体における価数の異なるＳｎ原子としては、＋２価（Ｓｎ２＋）、及び、＋４価（Ｓｎ４＋）であることが好ましく、２つのＳｎ２＋とＳｎ４＋Ｏ６八面体とからなる構造が規則的に配列されてなる結晶であることが好ましい。
図４は、特定結晶体の一例を示す構造モデル平面図（ａ）及び構造モデル側面図（ｂ）である。
The different Sn atom valences in the specific crystal, +2 (Sn 2+), and is preferably a +4 (Sn 4+), structure composed of two Sn 2+ and Sn 4+ O 6 octahedra It is preferably a crystal that is regularly arranged.
FIG. 4 is a structural model plan view (a) and a structural model side view (b) showing an example of the specific crystal body.
図４に示すように、特定結晶体は、２つのＳｎ２＋とＳｎ４＋Ｏ６八面体（Ｏｃｔａｈｅｄｒａ）とからなる構造が規則的に配列されてなり、（Ｓｎ２＋）２（Ｓｎ４＋）Ｏ４で表される混合原子価Ｓｎ酸化物の結晶である。
なお、図４は、Ｓｎ３Ｏ４の化学式で表される理想的な結晶体の結晶構造の模式図を表しており、本発明の光劣化抑制材が含有する特定結晶体としては上記に制限されず、Ｓｎ２＋とＳｎ４＋Ｏ６八面体との配列により、ＳｎＯｘ（１＜ｘ＜２）で表される常温常圧で安定な構造であってもよい。
As shown in FIG. 4, the specific crystal has a regularly arranged structure consisting of two Sn 2+ and Sn 4+ O 6 octahedron (Oxtahedra), and (Sn 2+ ) 2 (Sn 4+ ) O 4 It is a crystal of a mixed valence Sn oxide represented by.
Note that FIG. 4 shows a schematic diagram of the crystal structure of an ideal crystal represented by the chemical formula of Sn 3 O 4 , and the specific crystal contained in the photodeterioration inhibitor of the present invention is limited to the above. However, due to the arrangement of Sn 2+ and Sn 4 + O 6 octahedron, the structure may be stable at normal temperature and pressure represented by SnO x (1 <x <2).
特定結晶の製造方法としては特に制限されないが、例えば、原料と界面活性剤とを水中に分散して、分散液を調製する工程Ｓ１と、上記分散液中にＮａＯＨ水溶液を加えて、アルカリ性分散液を調製する工程Ｓ２と、上記アルカリ性分散液を加熱して、光触媒を水熱合成する工程Ｓ３と、を有する構成が好ましい。 The method for producing the specific crystal is not particularly limited, but for example, the step S1 of preparing a dispersion liquid by dispersing the raw material and the surfactant in water, and the alkaline dispersion liquid by adding an aqueous NaOH solution to the dispersion liquid. A configuration having a step S2 for preparing the above and a step S3 for hydrothermally synthesizing the photocatalyst by heating the alkaline dispersion is preferable.
（分散液調製工程Ｓ１）
この工程では、原料と界面活性剤を水中に分散して、分散液を調製する。原料としては、ＳｎＣｌ２・２Ｈ２Ｏが挙げられる。また、界面活性剤として、クエン酸ナトリウム（Ｎａ３Ｃ６Ｈ５Ｏ７・Ｈ２Ｏ）が挙げられる。界面活性剤を添加することにより、原料をより均一に分散できる。水は超純水であることが好ましい。不純物を少なくすることにより、得られる結晶の純度を向上させることができる。
(Dispersion liquid preparation step S1)
In this step, the raw material and the surfactant are dispersed in water to prepare a dispersion. As a raw material, it includes SnCl 2 · 2H 2 O. Moreover, as a surfactant, sodium citrate (Na 3 C 6 H 5 O 7 · H 2 O) can be mentioned. By adding a surfactant, the raw materials can be dispersed more uniformly. The water is preferably ultrapure water. By reducing the impurities, the purity of the obtained crystal can be improved.
（アルカリ性分散液調製工程Ｓ２）
この工程では、分散液中にＮａＯＨ水溶液を加えて、アルカリ性分散液を調製する。この時、ＮａＯＨ濃度を０．２Ｍ以下とすることが好ましい。
(Alkaline dispersion preparation step S2)
In this step, an aqueous NaOH solution is added to the dispersion to prepare an alkaline dispersion. At this time, the NaOH concentration is preferably 0.2 M or less.
（水熱合成工程Ｓ３）
この工程では、アルカリ性分散液を加熱して、光触媒を水熱合成する。
アルカリ性分散液の加熱温度は、１５０℃以上２００℃以下であることが好ましく、１７０℃以上１９０℃以下とすることがより好ましい。また、加熱温度に５時間以上１９時間以下保持することが好ましく、１０時間以上１４時間以下保持することがより好ましい。これにより、水熱合成による結晶の生成効率を向上させることができる。
(Hydrothermal synthesis step S3)
In this step, the alkaline dispersion is heated to hydrothermally synthesize the photocatalyst.
The heating temperature of the alkaline dispersion is preferably 150 ° C. or higher and 200 ° C. or lower, and more preferably 170 ° C. or higher and 190 ° C. or lower. Further, it is preferable to keep the heating temperature for 5 hours or more and 19 hours or less, and more preferably for 10 hours or more and 14 hours or less. As a result, the efficiency of crystal formation by hydrothermal synthesis can be improved.
特定結晶としては、例えば、特開２０１５−１５７２８２号公報に記載の光触媒を用いることができ、上記明細書の記載は本明細書に組み込まれる。 As the specific crystal, for example, the photocatalyst described in JP-A-2015-157282 can be used, and the description of the above specification is incorporated in the present specification.
〔他の成分〕
本光劣化抑制材は特定結晶体を含有していれば、本発明の効果を奏する範囲内において他の成分を含有していてもよく、他の成分としては特に制限されないが、溶媒、界面活性剤、及び、有機系、及び／又は、無機系バインダ（以下、単に「バインダ」ともいう。）等が挙げられる。
[Other ingredients]
As long as the present photodegradation inhibitor contains a specific crystal, it may contain other components within the range in which the effects of the present invention are exhibited, and the other components are not particularly limited, but the solvent and surface activity are not particularly limited. Examples thereof include agents, organic and / or inorganic binders (hereinafter, also simply referred to as “binders”) and the like.
本光劣化抑制材が界面活性剤を含有すると、親水／油性を調製でき、より優れた分散性が得られる。界面活性剤としては特に制限されず、アニオン系、カチオン系、及び、ノニオン系の界面活性剤が使用できる。
本光劣化抑制材が界面活性剤を含有する場合、その形態としては特に制限されないが、特定結晶体に担持されている形態が好ましい。
When this photodegradation inhibitor contains a surfactant, hydrophilicity / oiliness can be adjusted and more excellent dispersibility can be obtained. The surfactant is not particularly limited, and anionic, cationic, and nonionic surfactants can be used.
When the photodegradation inhibitor contains a surfactant, its form is not particularly limited, but a form supported on a specific crystal is preferable.
本光劣化抑制材がバインダを含有すると、保護対象物上に本光劣化抑制材による被膜をより簡便に形成可能であり、より優れた本発明の効果が得られる。バインダとしては特に制限されないが、樹脂、及び、セラミックス等が挙げられる。 When the present photodegradation inhibitor contains a binder, a film formed by the present photodegradation inhibitor can be more easily formed on the object to be protected, and a more excellent effect of the present invention can be obtained. The binder is not particularly limited, and examples thereof include resins and ceramics.
以下に実施例に基づいて本発明をさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
（実施例１）
（特定結晶の水熱合成）
まず、原料としてＳｎＣｌ２・２Ｈ２Ｏ（０．９０ｇ、４．０ｍｍｏｌ）、界面活性剤としてクエン酸ナトリウム（Ｎａ３Ｃ６Ｈ５Ｏ７・Ｈ２Ｏ）（０．２９４ｇ、１０ｍｍｏｌ）を用意し、これらを超純水（Ｍｉｌｌｉ−Ｑ ｗａｔｅｒ）１０ｍｌ中に分散してから、撹拌して、均一分散させて、分散液を調製した。
(Example 1)
(Hydrothermal synthesis of specific crystals)
First, the raw material as SnCl 2 · 2H 2 O (0.90g , 4.0mmol), sodium citrate as a surfactant (Na 3 C 6 H 5 O 7 · H 2 O) (0.294g, 10mmol) prepared Then, these were dispersed in 10 ml of ultrapure water (Milli-Q water), and then stirred and uniformly dispersed to prepare a dispersion liquid.
次に、上記分散液中に０．２ＭのＮａＯＨ水溶液１０ｍｌを加えて攪拌して、アルカリ性分散液を調製した。 Next, 10 ml of a 0.2 M NaOH aqueous solution was added to the dispersion and stirred to prepare an alkaline dispersion.
次に、アルカリ性分散液を４０ｍｌのポリテトラフルオロエチレン製裏地付きステンレス鋼製の加圧滅菌器（オートクレーブ）に移した。
次に、オートクレーブを電気炉内で、１８０℃で１２時間、加熱してから、室温に戻した。
次に、遠心分離により沈殿物を得た後、この沈殿物を、０．２ＭＮａＯＨ水溶液にて数回洗浄後、超純水（Ｍｉｌｌｉ−Ｑ ｗａｔｅｒ）とアセトンで逐次的に数回、洗浄した。
以上の工程により、Ｓｎ３Ｏ４の結晶を得た。
The alkaline dispersion was then transferred to a 40 ml polytetrafluoroethylene lined stainless steel pressure sterilizer (autoclave).
Next, the autoclave was heated in an electric furnace at 180 ° C. for 12 hours and then returned to room temperature.
Next, after obtaining a precipitate by centrifugation, the precipitate was washed several times with a 0.2 M NaOH aqueous solution, and then washed with ultrapure water (Milli-Q water) and acetone several times in sequence.
By the above steps, crystals of Sn 3 O 4 were obtained.
ＳＥＭ（Ｓｃａｎｉｎｇ ｅｌｅｃｔｒｏｎ ｍｉｃｒｏｓｃｏｐｅ、Ｈｉｔａｃｈｉ製）により、上記で得られたＳｎ３Ｏ４を顕微鏡観察した。
ＳＥＭにはＦＩＢ（Ｆｏｃｕｓｅｄ ｉｏｎ ｂｅａｍ、ＳＩＩ Ｎａｎｏ ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃ．製）を備えたものを用いた。
図５は、上記結晶の顕微鏡観察結果を示す写真である。
The Sn 3 O 4 obtained above was observed under a microscope by SEM (Scanning electron microscope, manufactured by Hitachi).
As the SEM, one provided with FIB (Focused ion beam, manufactured by SII Nano technology Inc.) was used.
FIG. 5 is a photograph showing the results of microscopic observation of the crystals.
（Ｘ線光電子分光）
図６は、Ｘ線光電子分光の結果を示すグラフである。価電子帯頂上部に、Ｓｎ２＋の５ｄ軌道に由来する状態密度を持つ。このＳｎ２＋の５ｄ軌道の存在によりＵＶ光照射下にあっても、ＶＢＴに生成された正孔は、ＯＨ−酸化準位よりもエネルギー的に高い準位に位置することができるため、ＯＨ基と結合してＯＨ・を生成することが禁制される結果となる。
(X-ray photoelectron spectroscopy)
FIG. 6 is a graph showing the results of X-ray photoelectron spectroscopy. At the top of the valence band, it has a density of states derived from the Sn 2+ 5d orbit. Due to the presence of the 5d orbital of Sn 2+ , the holes generated in the VBT can be located at an energy level higher than the OH − oxidation level even under UV irradiation, and thus the OH group. As a result, it is forbidden to combine with and generate OH ·.
Claims (6)
The photodegradation inhibitor according to any one of claims 1 to 5, further containing an organic and / or inorganic binder.
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