JP2001081394A - Primer composition and photocatalytic body - Google Patents
Primer composition and photocatalytic bodyInfo
- Publication number
- JP2001081394A JP2001081394A JP26081499A JP26081499A JP2001081394A JP 2001081394 A JP2001081394 A JP 2001081394A JP 26081499 A JP26081499 A JP 26081499A JP 26081499 A JP26081499 A JP 26081499A JP 2001081394 A JP2001081394 A JP 2001081394A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- primer
- photocatalyst
- substrate
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 76
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 239000008199 coating composition Substances 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 239000000080 wetting agent Substances 0.000 claims abstract description 13
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 11
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 79
- 239000011941 photocatalyst Substances 0.000 claims description 46
- 239000010410 layer Substances 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000008119 colloidal silica Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- -1 sulfate ester Chemical class 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- HDYFAPRLDWYIBU-UHFFFAOYSA-N 1-silylprop-2-en-1-one Chemical compound [SiH3]C(=O)C=C HDYFAPRLDWYIBU-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 description 77
- 238000011156 evaluation Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000003973 paint Substances 0.000 description 12
- 230000001846 repelling effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241001561902 Chaetodon citrinellus Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008268 mayonnaise Substances 0.000 description 2
- 235000010746 mayonnaise Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、基体上に密着性の
良好な光触媒層を形成するためのプライマー組成物、及
び、基体上に、プライマー組成物の塗膜層、光触媒コー
ティング組成物の塗膜層の順に形成された光触媒体に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition for forming a photocatalyst layer having good adhesion on a substrate, and a coating layer of the primer composition and a coating of the photocatalyst coating composition on the substrate. The present invention relates to a photocatalyst formed in the order of a film layer.
【０００２】[0002]
【従来の技術】二酸化チタンなどの光触媒は紫外線を照
射すると、光励起により価電子帯から伝導帯に電子が移
行して、ｎ型半導体となり、各種化合物の分解及び殺菌
効果を示すことは広く知られており、また水中有機物の
分解、有機物分解による防汚、脱臭、殺菌、ＮＯｘ、Ｓ
Ｏｘ等の環境汚染気体除去、藻類の発生防止、有機塩素
化合物の除去等に使用できることが報告されている。2. Description of the Related Art It is widely known that when a photocatalyst such as titanium dioxide is irradiated with ultraviolet rays, electrons are transferred from a valence band to a conduction band by photoexcitation to form an n-type semiconductor, which exhibits decomposition and sterilization effects of various compounds. Decomposition of organic matter in water, antifouling by organic matter decomposition, deodorization, sterilization, NOx, S
It is reported that it can be used for removing environmental pollutant gases such as Ox, preventing the generation of algae, removing organic chlorine compounds, and the like.
【０００３】しかしながら、実際にその光触媒活性を、
排気ガス中の有害ガスやタバコ、トイレ等の悪臭ガス、
農薬などの有害物質、環境汚染物質の分解除去及び殺菌
等の目的で使用する場合、その使用勝手や活性、耐光性
等の面で、主に無機バインダーを使用した光触媒コーテ
ィング組成物としたものを使用して、何らかの基体上に
担持、固定することが必要である。特に基体がガラスや
タイル以外の耐熱性の低い基体に光触媒を固定する場
合、光触媒による酸化分解から基体を保護する目的も含
め、一般には耐光性の強い有機樹脂系プライマー層を介
して光触媒コーティング組成物を塗布、成膜する方法が
とられている。However, the photocatalytic activity is actually
Toxic gas in exhaust gas, foul odor gas from cigarettes, toilets, etc.
When used for the purpose of decomposing and removing harmful substances such as pesticides and environmental pollutants, and sterilization, use a photocatalyst coating composition that mainly uses an inorganic binder in terms of its usability, activity, and light resistance. It must be used and carried and fixed on some substrate. In particular, when the photocatalyst is fixed to a substrate having low heat resistance other than glass or tile, the photocatalytic coating composition is generally provided through a light-resistant organic resin-based primer layer, including the purpose of protecting the substrate from oxidative decomposition by the photocatalyst. An object is applied and a film is formed.
【０００４】既にゾルゲル系シリカゾルをバインダーに
使用した溶剤系光触媒コーティング組成物では、そのプ
ライマー材料は数種市販されていたり文献等で報告され
ており、光触媒膜形成用材料として有用なものである。In a solvent-based photocatalytic coating composition using a sol-gel silica sol as a binder, several primer materials are commercially available or reported in literatures, and are useful as a material for forming a photocatalytic film.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、水性光
触媒コーティング組成物は、適当なプライマー材料が見
出されていないため、ガラス等親水性の強い基体以外へ
の塗工は難しく、高温焼き付けが可能な耐熱性の高い基
体以外には固定が難しく、あまり使用されていないのが
実状である。However, since no suitable primer material has been found for the aqueous photocatalyst coating composition, it is difficult to apply it to a substrate other than a substrate having strong hydrophilicity such as glass, and it is possible to perform high-temperature baking. Fixation is difficult except for a substrate having high heat resistance, and the fact is that it is rarely used.
【０００６】即ち、水性光触媒コーティング組成物は、
一般にはガラス等親水性の強い基材以外への塗工は難し
く、また基体表面への固定用の適当なプライマー材料が
ないため、表面エネルギーが低く親水性の低い材質の基
体に光触媒をコーティングするためのプライマー組成物
が必要とされている。このプライマー組成物には、基体
への密着性が良好で、上塗りの水性光触媒コーティング
組成物がはじき等の問題なく塗布が可能であり、光触媒
層とプライマー層の接着性が良好でかつプライマー層そ
のものが耐光性と耐水性の高いものであることが要求さ
れる。That is, the aqueous photocatalytic coating composition comprises:
In general, it is difficult to apply to a substrate other than a substrate having strong hydrophilicity such as glass, and there is no suitable primer material for fixing to the substrate surface, so that a photocatalyst is coated on a substrate having a low surface energy and a material having low hydrophilicity. Primer compositions are needed. The primer composition has good adhesion to a substrate, and can be coated with an overcoated aqueous photocatalyst coating composition without problems such as repelling, and has good adhesion between the photocatalyst layer and the primer layer and the primer layer itself. Is required to have high light resistance and high water resistance.
【０００７】本発明は前記課題に鑑みてなされたもので
あり、プライマー組成物として要求される特性、即ち、
あらゆる基体への密着性が良好なこと、基体上に形
成された塗膜が親水性（基体上に形成された塗膜の水と
の接触角が１０度以下）、耐光性及び耐水性を有し、後
工程で上塗りする水性光触媒コーティング組成物がはじ
き等の問題なく塗布できること、光触媒層とプライマ
ー層の接着性が良好であること、現場施工性のために
室温硬化可能であること等、を満足する特に水性光触媒
コーティング組成物に好適なプライマー組成物、及び、
基体上に前記プライマー組成物の層、光触媒体の層の順
に形成した構造の光触媒体を提供することを目的とす
る。[0007] The present invention has been made in view of the above-mentioned problems, and has the properties required for a primer composition, ie,
Good adhesion to all substrates, coating film formed on substrate is hydrophilic (contact angle with water of coating film formed on substrate is 10 degrees or less), light resistance and water resistance Then, that the aqueous photocatalyst coating composition to be overcoated in the post-process can be applied without problems such as repelling, that the adhesion between the photocatalyst layer and the primer layer is good, that it can be cured at room temperature for on-site workability, etc. A primer composition that is particularly suitable for aqueous photocatalytic coating compositions, and
An object of the present invention is to provide a photocatalyst having a structure in which a layer of the primer composition and a layer of the photocatalyst are formed in this order on a substrate.
【０００８】[0008]
【課題を解決するための手段】本発明のプライマー組成
物は、アクリル樹脂、アクリル変成シリコン樹脂、及び
アクリルシラン樹脂の少なくとも１種の樹脂成分を含有
するエマルションに、湿潤剤を０．１〜２０ｗｔ％添加
したプライマー組成物であって、塗膜として５％以下の
ヘーズ値を有し、前記塗膜と水との接触角が１０度以下
であることを特徴とする。According to the present invention, there is provided a primer composition comprising: an emulsion containing at least one resin component of an acrylic resin, an acrylic modified silicone resin, and an acrylic silane resin; % Of the primer composition, wherein the coating has a haze value of 5% or less, and a contact angle between the coating and water is 10 ° or less.
【０００９】前記湿潤剤を、リン酸エステル系、スルホ
ン酸系、硫酸エステル系及びカルボン酸系の少なくとも
１種のイオン系界面活性剤とすることができる。The wetting agent may be at least one of a phosphate ester type, a sulfonic acid type, a sulfate type and a carboxylic acid type.
【００１０】本発明のプライマー組成物は、更にコロイ
ダルシリカ及び／又はアルミナゾルを含有することがで
きる。[0010] The primer composition of the present invention may further contain colloidal silica and / or alumina sol.
【００１１】また、本発明の光触媒体は、基体と、該基
体表面に形成された前記のプライマー組成物の塗膜層
と、該プライマー組成物の塗膜上に形成された水性光触
媒コーティング組成物の塗膜層と、からなることを特徴
とする。The photocatalyst of the present invention comprises a substrate, a coating layer of the primer composition formed on the surface of the substrate, and an aqueous photocatalyst coating composition formed on the coating of the primer composition. And a coating layer.
【００１２】前記水性光触媒コーティング組成物は、光
触媒酸化チタンを含有することができる。[0012] The aqueous photocatalytic coating composition may contain a photocatalytic titanium oxide.
【００１３】前記水性光触媒コーティング組成物は、更
にコロイダルシリカ及び／又はアルミナゾルを含有する
ことができる。[0013] The aqueous photocatalytic coating composition may further contain colloidal silica and / or alumina sol.
【００１４】前記光触媒体の前記基体を、アルミニウ
ム、鉄、チタン、ニッケル、クロム及び銅の金属並びに
前記金属の１種以上を含む合金、ガラス、セラミック
ス、セメント、木材、合成樹脂、樹脂フィルム、布、繊
維及び紙の少なくとも１種から形成することができる。The substrate of the photocatalyst is made of aluminum, iron, titanium, nickel, chromium and copper and alloys containing at least one of the above metals, glass, ceramics, cement, wood, synthetic resin, resin film, cloth , Fibers and paper.
【００１５】[0015]
【発明の実施の形態】本発明に用いられる樹脂として
は、親水性のみの付与であれば、例えばアクリル樹脂溶
液のみの使用で目標が達せられるが、耐光性と耐水性が
不充分であるため、エマルションタイプの樹脂の使用が
必要である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As a resin used in the present invention, if only hydrophilicity is imparted, the target can be achieved by using only an acrylic resin solution, for example, but the light resistance and water resistance are insufficient. It is necessary to use an emulsion type resin.
【００１６】エマルションタイプの樹脂の種類は、耐光
性の高いものを選択する必要があり、シリコーン樹脂、
アクリル樹脂、アクリル変成シリコン樹脂、高耐光性ウ
レタン樹脂、アクリルシラン樹脂、オキシシラン樹脂等
のエマルションを用いることが出来るが、水性光触媒塗
料に使用する無機バインダーとの反応接着性を考慮する
と、アクリル樹脂のエマルション、またはアクリル変成
シリコン樹脂、アクリルシラン樹脂等のアクリル変成樹
脂のエマルションが好ましい。It is necessary to select an emulsion type resin having a high light resistance.
Emulsions such as acrylic resins, acrylic modified silicone resins, high light-resistant urethane resins, acrylic silane resins, and oxysilane resins can be used, but in consideration of the reactive adhesiveness with the inorganic binder used in the aqueous photocatalytic paint, An emulsion or an emulsion of an acrylic modified resin such as an acrylic modified silicone resin or an acrylic silane resin is preferred.
【００１７】このようなエマルションは、例えば、樹脂
成分３０〜５０ｗｔ％、成膜助剤１〜５％、乳化剤０．
１〜１％、残部水を配合することによって形成すること
ができる。また、これらに、適宜、消泡剤、防腐剤を加
えて形成することもできる。Such an emulsion contains, for example, 30 to 50% by weight of a resin component, 1 to 5% of a film-forming aid, and 0.1% of an emulsifier.
It can be formed by mixing 1 to 1% with the balance being water. In addition, an antifoaming agent and a preservative can be appropriately added to these to form them.
【００１８】但し、エマルションは一般には親油性であ
り、基体によってははじいて塗工できない場合と、更に
上塗り水性光触媒コーティング組成物がプライマー塗膜
上ではじいて塗布できない場合があるため、エマルショ
ンに適合する湿潤剤を適量添加することで、基体への塗
工性と密着性が改良され、かつ上塗りの水性光触媒塗料
の塗工性も良好にすることができる。However, since the emulsion is generally lipophilic and may not be applied by repelling depending on the substrate, or it may not be able to be applied by repelling the overcoated aqueous photocatalyst coating composition on the primer coating film. By adding an appropriate amount of the wetting agent, the coatability and adhesion to the substrate can be improved, and the coatability of the overcoated aqueous photocatalytic paint can be improved.
【００１９】含有させる湿潤剤は、陰イオン系界面活性
剤でリン酸エステル系、スルホン酸系、硫酸エステル
系、カルボン酸系のものが使用できる。湿潤剤の添加量
は０．１〜２０ｗｔ％の範囲である。０．１ｗｔ％より
少ないと前記の効果が十分でなく、２０ｗｔ％より多い
とエマルションの粘度が高くなって塗布が困難となるの
で好ましくない。湿潤剤の添加量が前記範囲内であれ
ば、エマルションの粘度が１０〜１０００ｃｐとなり、
基体上への塗布を容易に行うことができる。As the wetting agent to be contained, phosphate-based, sulfonic-acid-based, sulfate-based, and carboxylic-acid-based surfactants can be used. The amount of the wetting agent added is in the range of 0.1 to 20 wt%. If the amount is less than 0.1% by weight, the above effect is not sufficient, and if it is more than 20% by weight, the viscosity of the emulsion becomes high and the application becomes difficult. If the amount of the wetting agent is within the above range, the viscosity of the emulsion will be 10 to 1000 cp,
The coating on the substrate can be easily performed.
【００２０】また、本発明のプライマー組成物の形成塗
膜、即ちプライマー層の膜厚は１〜３０μｍの範囲とす
ることが好ましい。この範囲の膜厚では、プライマー層
表面の水との接触角が１０度以下となり、良好な親水性
を呈する。膜厚が１μｍより小さいと塗膜の耐水性が低
くなり、好ましくない。膜厚が３０μｍより大きいとプ
ライマー層表面の水との接触角が１０度を超え、親水性
が低下するので好ましくない。It is preferable that the thickness of the formed coating film of the primer composition of the present invention, that is, the thickness of the primer layer is in the range of 1 to 30 μm. With the film thickness in this range, the contact angle with water on the surface of the primer layer becomes 10 degrees or less, and good hydrophilicity is exhibited. When the film thickness is smaller than 1 μm, the water resistance of the coating film is lowered, which is not preferable. If the film thickness is larger than 30 μm, the contact angle with water on the surface of the primer layer exceeds 10 degrees, and the hydrophilicity is undesirably reduced.
【００２１】膜厚が前記範囲の場合には塗膜の乾燥が速
く、エマルション同士の合体が不充分なままで乾燥する
ため膜に細孔や微細な隙間が多数存在し、膜の細孔や微
細な隙間が毛細管現象により、良好な親水性を現出して
いることが推定される。一方、膜厚が３０μｍを超える
と、乾燥に時間がかかり過ぎ、エマルションの合体が充
分に行われるため、細孔が減少した結果、親水性が低下
するものと推定される。When the film thickness is in the above range, drying of the coating film is fast, and drying is performed while the coalescence of the emulsions is insufficient, so that a large number of pores and fine gaps are present in the film. It is presumed that the fine gaps exhibit good hydrophilicity due to the capillary phenomenon. On the other hand, when the film thickness exceeds 30 μm, it takes a long time for drying, and the emulsion is sufficiently coalesced, so that it is estimated that the pores are reduced and the hydrophilicity is reduced.
【００２２】本発明のプライマー組成物は、透明性の高
い材料であり、プライマー層の膜厚が前記範囲であれ
ば、透明性が高くヘーズ値が５％以下となる。光触媒体
に透明性が要求される場合、プライマー層の膜厚を薄く
することで、ヘーズ値を０．２％程度まで下げることも
可能である。水性透明性光触媒コーティング組成物を使
用した場合、塗膜のヘーズ値は光触媒層の膜厚が０．２
μｍ以下であればプライマー層も含めた光触媒体のヘー
ズ値を１％以下にすることができる。The primer composition of the present invention is a material having high transparency. If the thickness of the primer layer is within the above range, the transparency is high and the haze value is 5% or less. When the photocatalyst requires transparency, the haze value can be reduced to about 0.2% by reducing the thickness of the primer layer. When the aqueous transparent photocatalytic coating composition was used, the haze value of the coating film was 0.2 μm for the photocatalytic layer.
If it is not more than μm, the haze value of the photocatalyst including the primer layer can be made 1% or less.
【００２３】本発明のプライマー組成物は、代表的に
は、前記アクリル樹脂エマルションまたはアクリル変性
樹脂エマルションに前記湿潤剤を添加混合することによ
って得られ、必要であればこの組成物に前記コロイダル
シリカ及び／またはアルミナゾルを添加混合することに
よって得られる。The primer composition of the present invention is typically obtained by adding the wetting agent to the acrylic resin emulsion or the acrylic-modified resin emulsion, and if necessary, adding the colloidal silica and the colloidal silica to the composition. And / or by adding and mixing alumina sol.
【００２４】プライマー組成物にコロイダルシリカ及び
／またはアルミナゾルを含有させると、基体との固定強
度や、塗膜の耐水性及び硬度を更に高めることができ
る。コロイダルシリカ及び／またはアルミナゾルの含有
量は、樹脂エマルションに対して０．１〜５００ｗｔ
％、好ましくは１〜３００ｗｔ％である。コロイダルシ
リカ及びまたはアルミナゾルの含有量が前記範囲であれ
ば、樹脂との間に有機無機複合体を形成し、塗膜の耐水
性や硬度が大幅に改善される。When the primer composition contains colloidal silica and / or alumina sol, the fixing strength to the substrate and the water resistance and hardness of the coating film can be further increased. The content of the colloidal silica and / or alumina sol is 0.1 to 500 wt with respect to the resin emulsion.
%, Preferably 1 to 300 wt%. When the content of colloidal silica and / or alumina sol is in the above range, an organic-inorganic composite is formed between the resin and the resin, and the water resistance and hardness of the coating film are significantly improved.
【００２５】更に、本発明においては、基体と、該基体
表面に形成された前記プライマー組成物の塗膜層と、該
プライマー組成物の塗膜上に形成された水性光触媒コー
ティング組成物の塗膜層とから光触媒体を形成すること
ができる。Further, in the present invention, a substrate, a coating layer of the primer composition formed on the surface of the substrate, and a coating film of the aqueous photocatalyst coating composition formed on the coating film of the primer composition A photocatalyst can be formed from the layer.
【００２６】ここで言う水性光触媒コーティング組成物
は、代表的には、一次粒径が２０ｎｍ程度の微粒子メタ
チタン酸と、粒径が１〜１０ｎｍの微粒子コロイダルシ
リカ及び／またはアルミナゾルの無機バインダーを含有
した、水性でほぼ中性（弱塩基性）の酸化チタンの水分
散組成物とすることができる。The aqueous photocatalyst coating composition referred to herein typically contains a particulate metatitanic acid having a primary particle size of about 20 nm and an inorganic binder of fine particle colloidal silica and / or alumina sol having a particle size of 1 to 10 nm. And an aqueous, substantially neutral (weakly basic) titanium oxide aqueous dispersion composition.
【００２７】微粒子メタチタン酸は光触媒活性向上を目
的にＮｂ2Ｏ3を二酸化チタン基準で０．０５〜５ｗｔ％
固溶させたものであり、好ましくは０．１〜２ｗｔ％で
ある。０．０５ｗｔ％より少ない場合は、活性向上の効
果が少なく、５ｗｔ％より多い場合は、これ以上の活性
向上は望めずコスト的にも好ましくない。The particulate metatitanic acid is 0.05 to 5% by weight of Nb 2 O 3 based on titanium dioxide for the purpose of improving photocatalytic activity.
It is a solid solution, preferably 0.1 to 2 wt%. When the content is less than 0.05 wt%, the effect of activity improvement is small, and when the content is more than 5 wt%, further activity improvement cannot be expected, which is not preferable in terms of cost.
【００２８】前記水性光触媒コーティング組成物は、ゾ
ルゲルタイプ酸性シリカゾルを使用した組成物が長期保
管でゲル化しやすく且つ強酸性で溶剤を含むのに対し、
安定性が良好で長期保管が可能であり、更に水性でほぼ
中性であるため、現在環境問題となっているＶＯＣの放
出や酸の漏洩もなく、環境に優しいという長所を有す
る。この長所は本発明のプライマー組成物についても同
様である。In the aqueous photocatalytic coating composition, the composition using a sol-gel type acidic silica sol is easily gelled in a long-term storage and is strongly acidic and contains a solvent.
It has good stability, can be stored for a long period of time, and has an advantage that it is environmentally friendly because there is no release of VOC and no leakage of acid, which are currently environmental problems, because it is aqueous and almost neutral. This advantage is the same for the primer composition of the present invention.
【００２９】この水性光触媒コーティング組成物は、塗
布されるプライマー層表面が親水性であるため、はじか
ずに塗布できる。コロイダルシリカをバインダーとした
微粒子酸化チタンのコーティング組成物は、プライマー
層表面に強固に固定される。それはコロイダルシリカと
プライマー層の表層部分のアクリル樹脂とが縮合反応し
て結合し、有機無機複合体として光触媒層が接着される
ためと考えられる。この固定は室温硬化でも強固であ
り、ＪＩＳ−Ｋ５４００の塗膜付着試験の結果、碁盤目
付着性が評価点１０で全く問題がないものである。The aqueous photocatalyst coating composition can be applied without repelling because the surface of the primer layer to be applied is hydrophilic. The coating composition of fine particle titanium oxide using colloidal silica as a binder is firmly fixed on the surface of the primer layer. This is probably because colloidal silica and the acrylic resin on the surface of the primer layer are condensed and bonded to each other, and the photocatalyst layer is bonded as an organic-inorganic composite. This fixation is strong even when cured at room temperature, and as a result of a coating film adhesion test according to JIS-K5400, the grid adhesion is evaluated to be 10 and there is no problem at all.
【００３０】この水性光触媒コーティング組成物は代表
的には、前記無機バインダーに前記微粒子メタチタン酸
を添加し、サンタドグラインダーミル、ホモジナイザ
ー、ホモミキサー等を使用して酸化チタンの水分散組成
物とすることによって得られる。The aqueous photocatalyst coating composition is typically obtained by adding the above-mentioned fine particle metatitanic acid to the above-mentioned inorganic binder and using a Santado grinder mill, a homogenizer, a homomixer or the like to form an aqueous dispersion of titanium oxide. Obtained by:
【００３１】前記基体は、アルミニウム、鉄、チタン、
ニッケル、クロム、銅等の金属並びに前記金属の１種以
上を含む合金、ガラス、セラミックス、セメント、木
材、合成樹脂、樹脂フィルム、布、繊維、紙等の少なく
とも１種以上から形成することができる。The substrate is made of aluminum, iron, titanium,
Metals such as nickel, chromium, copper and the like, and alloys containing at least one of the above metals, glass, ceramics, cement, wood, synthetic resin, resin film, cloth, fiber, paper, etc. .
【００３２】前記水性光触媒コーティング組成物用プラ
イマー組成物及び水性光触媒コーティング組成物を基板
に塗布する方法としては、公知の方法が使用できるが、
基体の種類やプライマー層の性質に応じて、ロールコー
ティング法、フローコート法、吹き付け法、浸漬法、ス
ピンコーティング法等の適当な塗装方法を選択すること
ができる。As a method for applying the primer composition for an aqueous photocatalyst coating composition and the aqueous photocatalyst coating composition to a substrate, known methods can be used.
An appropriate coating method such as a roll coating method, a flow coating method, a spraying method, a dipping method, and a spin coating method can be selected according to the type of the substrate and the properties of the primer layer.
【００３３】[0033]
【実施例】［実施例１］アクリル樹脂エマルションに陰
イオン系スルホン酸系湿潤剤を１ｗｔ％添加した粘度７
５ｃｐのプライマー組成物を作製し、ガラス板、アクリ
ル板、アルミニウム板、脱脂処理したステンレス板、Ｐ
ＥＴフィルム、に２ミルのドクターブレードで塗布し、
室温にて１２時間乾燥してプライマー塗膜とした。この
時基体へ塗布するときにはじき等の塗工上の不具合はい
ずれの基体においても認められなかった。このプライマ
ー塗膜は膜厚が５μｍであり、親水性を呈し、水との接
触角が１０度で呼気による防曇性も有していた。なお、
塗膜の水との接触角の測定は、協和界面科学株式会社製
の接触角計ＣＡ−Ｘ１５０型を用いて測定した。またヘ
ーズ値は０．２％であった。塗膜付着性はＪＩＳ法によ
る碁盤目剥離試験で評価点が１０で付着性は良好であっ
た。[Example 1] Viscosity of 1% by weight of anionic sulfonic acid type wetting agent added to acrylic resin emulsion
A primer composition of 5 cp was prepared, and a glass plate, an acrylic plate, an aluminum plate, a degreased stainless steel plate, P
ET film, applied with a 2 mil doctor blade,
After drying at room temperature for 12 hours, a primer coating film was obtained. At this time, no coating defects such as repelling were observed on any of the substrates when applied to the substrates. This primer coating film had a thickness of 5 μm, exhibited hydrophilicity, had a contact angle with water of 10 °, and also had anti-fogging property by exhalation. In addition,
The contact angle of the coating film with water was measured using a contact angle meter CA-X150 manufactured by Kyowa Interface Science Co., Ltd. The haze value was 0.2%. The adhesion of the coating film was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 10, and the adhesion was good.
【００３４】光触媒用二酸化チタン（チタン工業製ＰＣ
−１０２，Ｎｂ含有量０．４５ｗｔ％）６ｇと水性シリ
カゾル（粒径１０ｎｍ）２３．５ｇを３ｍｍのガラスビ
ーズ６０ｇとともに１２０ｍｌのマヨネーズ瓶に仕込
み、レッドデビル社製のペイントコンディショナーで３
０分間分散して塗料とした。この触媒塗料の酸化チタン
含有率は２０ｗｔ％である。これを、プライマー層の上
に２ミルのドクターブレードを用いて塗布した。その結
果、プライマー上ではじき等の塗工上の問題も無く塗布
が可能であった。室温で乾燥後１２０℃で３０分焼き付
け処理して光触媒塗膜とした。尚アクリル板とＰＥＴフ
ィルムは７０℃での焼き付けとした。この塗膜は塗布面
を手でこすっても粉の付着は無く、またＪＩＳ法での碁
盤目剥離試験で光触媒塗膜の付着性は基材の種類に関係
なくいずれも評価点１０で全く問題が無かった。Titanium dioxide for photocatalyst (PC manufactured by Titanium Industry Co., Ltd.)
-102, Nb content 0.45 wt%) and aqueous silica sol (particle diameter 10 nm) (23.5 g) were charged into a 120 ml mayonnaise bottle together with 3 mm glass beads (60 g) and mixed with a red Devil paint conditioner.
It was dispersed for 0 minutes to obtain a paint. The titanium oxide content of this catalyst paint is 20% by weight. This was applied onto the primer layer using a 2 mil doctor blade. As a result, it was possible to apply on the primer without any coating problems such as repelling. After drying at room temperature, it was baked at 120 ° C. for 30 minutes to obtain a photocatalytic coating film. The acrylic plate and the PET film were baked at 70 ° C. This coating film did not adhere to the powder even if it was rubbed by hand, and the adhesion of the photocatalytic coating film was not a problem at the evaluation point 10 regardless of the type of the substrate in the cross-cut peeling test by the JIS method. There was no.
【００３５】上記の光触媒を塗布したアルミニウム基板
を５ｃｍ×１ｃｍに切り出して１２０ｍｌのガラス製瓶
に入れ、アセトアルデヒドを瓶内のガス濃度が１００ｐ
ｐｍになる量を注入し、瓶の外から波長３５２ｎｍの紫
外線を０．４ｍＷ／ｃｍ2で３０分間照射した後、瓶内
の空気を柳本製作所製ガスクロマトグラフＧ３８００
（検出器ＦＩＤ）で測定したところ、アセトアルデヒド
濃度は０ｐｐｍであった。同様にして、エチルメルカプ
タンの浄化能を測定した結果、３０分間照射後のエチル
メルカプタン濃度は３０ｐｐｍであり、光触媒によるガ
ス分解性能を有することが確認できた。An aluminum substrate coated with the above photocatalyst was cut into 5 cm × 1 cm and placed in a 120 ml glass bottle, and acetaldehyde was added to the bottle at a gas concentration of 100 p.
pm, and ultraviolet light having a wavelength of 352 nm was irradiated from the outside of the bottle at 0.4 mW / cm 2 for 30 minutes, and the air in the bottle was gas chromatographed by Yanagimoto Seisakusho G3800.
(Detector FID), the acetaldehyde concentration was 0 ppm. Similarly, the purification ability of ethyl mercaptan was measured. As a result, the concentration of ethyl mercaptan after irradiation for 30 minutes was 30 ppm, and it was confirmed that the composition had gas decomposition performance by a photocatalyst.
【００３６】更にこの塗膜をスガ試験機（株）製デュー
パネル光コントロールウェザーメーターを使用して、紫
外線照度３ｍＷ／ｃｍ2で１０００時間の紫外線照射を
行ったが、塗膜の変色、塗膜の剥落は生じなかった。ま
た、鉛筆硬度による塗膜剥離試験(ＪＩＳ−Ｋ５４００)
を行ったところ、鉛筆硬度は３Ｈ以上であった。付着性
は評価点１０で問題がなかった。Further, this coating film was irradiated with ultraviolet light for 3 hours at an ultraviolet illuminance of 3 mW / cm 2 using a Dew panel light control weather meter manufactured by Suga Test Instruments Co., Ltd. Did not occur. In addition, paint film peeling test by pencil hardness (JIS-K5400)
Was performed, the pencil hardness was 3H or more. There was no problem with the adhesion at an evaluation point of 10.
【００３７】［実施例２］実施例１において、プライマ
ー用樹脂材料にアクリル変性シリコン樹脂エマルション
を使用した(粘度１１０ｃｐ)以外は、同様にしてプライ
マー塗膜を作製した。基体へ塗布するときにはじき等の
塗工上の不具合はいずれの基体においても認められなか
った。このプライマー塗膜は膜厚が１０μｍであり、親
水性を呈し、水との接触角が１０度で呼気による防曇性
も有した。また塗膜付着性はＪＩＳ法による碁盤目剥離
試験で評価点が１０で付着性は良好であった。Example 2 A primer coating film was prepared in the same manner as in Example 1, except that an acrylic-modified silicone resin emulsion was used as the resin material for the primer (viscosity: 110 cp). When applying to the substrates, no coating defects such as cissing were observed in any of the substrates. This primer coating film had a thickness of 10 μm, exhibited hydrophilicity, had a contact angle with water of 10 °, and also had anti-fogging property by exhalation. The adhesion of the coating film was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 10, and the adhesion was good.
【００３８】実施例１と同じ水性光触媒コーティング組
成物を、プライマー層の上に２ミルのドクターブレード
を用いて塗布した。その結果、プライマー上ではじき等
の塗工上の問題も無く塗布が可能であった。室温で乾燥
後１２０℃で３０分焼き付け処理して光触媒塗膜とし
た。尚アクリル板とＰＥＴフィルムは７０℃での焼き付
けとした。この塗膜は塗布面を手でこすっても粉の付着
は無く、またＪＩＳ法での碁盤目剥離試験で光触媒塗膜
の付着性は基材の種類に関係なくいずれも評価点１０で
全く問題が無かった。The same aqueous photocatalytic coating composition as in Example 1 was applied over the primer layer using a 2 mil doctor blade. As a result, it was possible to apply on the primer without any coating problems such as repelling. After drying at room temperature, it was baked at 120 ° C. for 30 minutes to obtain a photocatalytic coating film. The acrylic plate and the PET film were baked at 70 ° C. This coating film did not adhere to the powder even if it was rubbed by hand, and the adhesion of the photocatalytic coating film was not a problem at the evaluation point 10 regardless of the type of the substrate in the cross-cut peeling test by the JIS method. There was no.
【００３９】更にこの塗膜をスガ試験機（株）製デュー
パネル光コントロールウェザーメーターを使用して、１
０００時間の紫外線照射を行ったが、塗膜の変色、塗膜
の剥落は生じなかった。Further, this coating film was coated with a Suga Test Machine Co., Ltd.
Irradiation with ultraviolet light for 000 hours did not cause discoloration of the coating film or peeling of the coating film.
【００４０】［実施例３］実施例１において、プライマ
ー組成物に粒径１０ｎｍのコロイダルシリカを２０ｗｔ
％添加した(粘度４０ｃｐ)以外は同様の方法でプライマ
ー塗膜を作製した。基体へ塗布するときにはじき等の塗
工上の不具合はいずれの基体においても認められなかっ
た。このプライマー塗膜は膜厚が８μｍであり、親水性
を呈し、水との接触角が１０度で呼気による防曇性も有
した。また塗膜付着性はＪＩＳ法による碁盤目剥離試験
で評価点が１０で付着性は良好であった。Example 3 In Example 1, 20 wt% of colloidal silica having a particle diameter of 10 nm was added to the primer composition.
A primer coating film was prepared in the same manner except for adding% (viscosity 40 cp). When applying to the substrates, no coating defects such as cissing were observed in any of the substrates. This primer coating film had a thickness of 8 μm, exhibited hydrophilicity, had a contact angle with water of 10 °, and also had anti-fogging property by exhalation. The adhesion of the coating film was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 10, and the adhesion was good.
【００４１】実施例１と同じ水性光触媒コーティング組
成物を、プライマー層の上に２ミルのドクターブレード
を用いて塗布した。その結果、プライマー上ではじき等
の塗工上の問題も無く塗布が可能であった。室温で乾燥
後１２０℃で３０分焼き付け処理して光触媒塗膜とし
た。尚アクリル板とＰＥＴフィルムは７０℃での焼き付
けとした。この塗膜は塗布面を手でこすっても粉の付着
は無く、またＪＩＳ法での碁盤目剥離試験で光触媒塗膜
の付着性は基材の種類に関係なくいずれも評価点１０で
全く問題が無かった。鉛筆硬度による塗膜剥離試験(Ｊ
ＩＳ−Ｋ５４００)を行ったところ、鉛筆硬度は４Ｈ以
上であった。The same aqueous photocatalytic coating composition as in Example 1 was applied over the primer layer using a 2 mil doctor blade. As a result, it was possible to apply on the primer without any coating problems such as repelling. After drying at room temperature, it was baked at 120 ° C. for 30 minutes to obtain a photocatalytic coating film. The acrylic plate and the PET film were baked at 70 ° C. This coating film did not adhere to the powder even if it was rubbed by hand, and the adhesion of the photocatalytic coating film was not a problem at the evaluation point 10 regardless of the type of the substrate in the cross-cut peeling test by the JIS method. There was no. Paint film peeling test by pencil hardness (J
IS-K5400), the pencil hardness was 4H or more.
【００４２】更にこの塗膜をスガ試験機（株）製デュー
パネル光コントロールウェザーメーターを使用して、１
０００時間の紫外線照射を行ったが、塗膜の変色、塗膜
の剥落は生じなかった。Further, this coating film was coated with a Suga Test Machine Co., Ltd.
Irradiation with ultraviolet light for 000 hours did not cause discoloration of the coating film or peeling of the coating film.
【００４３】［実施例４］一次粒径が２０ｎｍのメタチ
タン酸（Ｎｂ含有量が酸化チタン基準で０．２ｗｔ％）
を硝酸解膠処理し中和洗浄したケーキを酸化チタンとし
て２．５ｇと水性シリカゾル（粒径５ｎｍ）１５．０ｇ
を３ｍｍのガラスビーズ６０ｇとともに１２０ｍｌのマ
ヨネーズ瓶に仕込み、レッドデビル社製のペイントコン
ディショナーで３０分間分散して塗料とした。この触媒
塗料の酸化チタン含有率は１０ｗｔ％である。これを純
水で７倍に希釈し、実施例１のプライマー層を形成させ
たガラス基板の上に１ミルのドクターブレードで塗布
し、室温乾燥して塗膜とした。この塗膜を９０℃×３０
分の条件で洗浄したが、塗膜の付着性は評価点１０で問
題がなかった。Example 4 Metatitanic acid having a primary particle size of 20 nm (Nb content: 0.2 wt% based on titanium oxide)
2.5 g as a titanium oxide and 15.0 g of an aqueous silica sol (particle size: 5 nm) obtained by peptizing nitric acid and neutralizing and washing.
Was placed in a 120 ml mayonnaise bottle together with 60 g of 3 mm glass beads, and dispersed with a paint conditioner manufactured by Red Devil for 30 minutes to obtain a paint. The titanium oxide content of this catalyst paint is 10% by weight. This was diluted 7-fold with pure water, applied to the glass substrate on which the primer layer of Example 1 was formed with a 1-mil doctor blade, and dried at room temperature to obtain a coating film. 90 ° C x 30
Although the substrate was washed under the conditions of minutes, the adhesion of the coating film was evaluated at evaluation point 10 without any problem.
【００４４】上記の光触媒を塗布したガラス基板のヘー
ズ値は０．９％で、実施例１で使用した酸化チタンを用
い、同一処方で塗布したもののヘーズ値８５％よりかな
り低く、塗膜の透明性が大幅に改良されたものであっ
た。また光触媒層の塗膜厚はTEMの断面写真より０．１
５μｍであった。The haze value of the glass substrate coated with the above photocatalyst was 0.9%, which was considerably lower than the haze value of 85% of the titanium oxide used in Example 1, which was coated with the same formulation, and the coating film was transparent. The properties were greatly improved. The thickness of the photocatalyst layer was 0.1
It was 5 μm.
【００４５】上記の光触媒を塗布したガラス基板を５ｃ
ｍ×１ｃｍに切り出して１２０ｍｌのガラス製瓶に入
れ、アセトアルデヒドを瓶内のガス濃度が１００ｐｐｍ
になる量注入し、瓶の外から波長３５２ｎｍの紫外線を
０．４ｍＷ／ｃｍ２で３０分間照射した後、瓶内の空気
を柳本製作所製ガスクロマトグラフＧ３８００（検出器
ＦＩＤ）で測定したところ、アセトアルデヒド濃度は７
５ｐｐｍであった。同様にして、エチルメルカプタンの
浄化能を測定した結果、３０分間照射後のエチルメルカ
プタン濃度は８５ｐｐｍであった。The glass substrate coated with the above photocatalyst is
Cut into mx 1 cm, put into a 120 ml glass bottle, and acetaldehyde was added to a bottle with a gas concentration of 100 ppm.
After irradiating with ultraviolet light having a wavelength of 352 nm from the outside of the bottle at 0.4 mW / cm2 for 30 minutes, the air in the bottle was measured with a gas chromatograph G3800 (detector FID) manufactured by Yanagimoto Seisakusho. Is 7
It was 5 ppm. Similarly, the purification ability of ethyl mercaptan was measured, and as a result, the ethyl mercaptan concentration after irradiation for 30 minutes was 85 ppm.
【００４６】更にこの塗膜をスガ試験機（株）製デュー
パネル光コントロールウェザーメーターを使用して、１
０００時間の紫外線照射を行ったが、塗膜の変色、塗膜
の剥落は生じなかった。また、鉛筆硬度による塗膜剥離
試験(ＪＩＳ−Ｋ５４００)を行ったところ、付着性は評
価点１０で、鉛筆硬度は３Ｈ以上であった。Further, this coating film was coated with a Suga Test Machine Co., Ltd.
Irradiation with ultraviolet light for 000 hours did not cause discoloration of the coating film or peeling of the coating film. In addition, when a paint film peeling test (JIS-K5400) was performed using a pencil hardness, the adhesion was evaluated at a score of 10, and the pencil hardness was 3H or more.
【００４７】［比較例１］実施例１において、プライマ
ー用樹脂材料にアクリル樹脂水溶液を使用した以外は、
同様にしてプライマー塗膜を作製した。基体へ塗布する
ときにはじき等の塗工上の不具合はいずれの基体におい
ても認められなかった。このプライマー塗膜は親水性を
呈し、水との接触角が１５度で呼気による防曇性も有し
た。塗膜付着性はＪＩＳ法による碁盤目剥離試験で評価
点が２で付着性は低いものであった。Comparative Example 1 In Example 1, except that an aqueous acrylic resin solution was used as the resin material for the primer,
Similarly, a primer coating film was prepared. When applying to the substrates, no coating defects such as cissing were observed in any of the substrates. This primer coating film exhibited hydrophilicity, had a contact angle with water of 15 degrees, and also had anti-fogging property by exhalation. The adhesion of the coating film was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 2, and the adhesion was low.
【００４８】実施例１と同じ水性光触媒コーティング組
成物を、プライマー層の上に２ミルのドクターブレード
を用いて塗布した。その結果、プライマー上ではじき等
の塗工上の問題も無く塗布が可能であった。室温で乾燥
後１２０℃で３０分焼き付け処理して光触媒塗膜とし
た。尚アクリル板とＰＥＴフィルムは７０℃での焼き付
けとした。この塗膜はプライマー層単独の場合と同様、
付着性は基材の種類に関係なくいずれも評価点２で固定
強度が低く、また９０℃×３０分の条件で塗膜を洗浄し
たところ、塗膜が完全に溶出した。The same aqueous photocatalytic coating composition as in Example 1 was applied over the primer layer using a 2 mil doctor blade. As a result, it was possible to apply on the primer without any coating problems such as repelling. After drying at room temperature, it was baked at 120 ° C. for 30 minutes to obtain a photocatalytic coating film. The acrylic plate and the PET film were baked at 70 ° C. This coating is similar to the case of the primer layer alone,
Regardless of the adhesiveness, the fixing strength was low at evaluation point 2 regardless of the type of the base material. When the coating film was washed at 90 ° C. for 30 minutes, the coating film was completely eluted.
【００４９】［比較例２］実施例１において、プライマ
ー用樹脂材料にウレタン樹脂エマルションを使用した以
外は、同様にしてプライマー塗膜を作製した。基体へ塗
布するときにはじき等の塗工上の不具合はいずれの基体
においても認められなかった。このプライマー塗膜は親
水性を呈し、水との接触角が１５度で呼気による防曇性
も有した。塗膜付着性はＪＩＳ法による碁盤目剥離試験
で評価点が１０で付着性は問題ないものであった。Comparative Example 2 A primer coating film was prepared in the same manner as in Example 1, except that a urethane resin emulsion was used as the resin material for the primer. When applying to the substrates, no coating defects such as cissing were observed in any of the substrates. This primer coating film exhibited hydrophilicity, had a contact angle with water of 15 degrees, and also had anti-fogging property by exhalation. The coating film adhesion was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 10, and the adhesion was not a problem.
【００５０】実施例１と同じ水性光触媒コーティング組
成物を、プライマー層の上に２ミルのドクターブレード
を用いて塗布した。その結果、プライマー上ではじき等
の塗工上の問題も無く塗布が可能であった。室温で乾燥
後１２０℃で３０分焼き付け処理して光触媒塗膜とし
た。尚アクリル板とＰＥＴフィルムは７０℃での焼き付
けとした。この塗膜の付着性は基材の種類に関係なくい
ずれも評価点０で固定強度がほとんど認められなかっ
た。The same aqueous photocatalytic coating composition as in Example 1 was applied over the primer layer using a 2 mil doctor blade. As a result, it was possible to apply on the primer without any coating problems such as repelling. After drying at room temperature, it was baked at 120 ° C. for 30 minutes to obtain a photocatalytic coating film. The acrylic plate and the PET film were baked at 70 ° C. Regarding the adhesion of the coating film, regardless of the type of the substrate, the fixing strength was hardly recognized at the evaluation point 0 in any case.
【００５１】［比較例３］実施例１において、アクリル
樹脂エマルションに陰イオン系スルホン酸系湿潤剤を
０．０５ｗｔ％添加したプライマー組成物を作製した以
外は、同様にしてプライマー塗膜を作製したが、塗布す
る時にいずれの基材においてもはじきが少し認められ、
塗工上の不具合が認められた。このプライマー塗膜は親
水性が低く、水との接触角が４０度で呼気による防曇性
も認められなかった。塗膜付着性はＪＩＳ法による碁盤
目剥離試験で評価点が１０で付着性は良好であった。実
施例１と同じ水性光触媒コーティング組成物を、プライ
マー層の上に２ミルのドクターブレードを用いて塗布し
た。その結果、プライマー上でコーティング組成物がは
じいてしまい、塗膜として固定できなかった。Comparative Example 3 A primer coating film was prepared in the same manner as in Example 1 except that a primer composition was prepared by adding 0.05% by weight of an anionic sulfonic acid type wetting agent to an acrylic resin emulsion. However, when applied, repelling is slightly recognized in any of the substrates,
Coating defects were observed. This primer coating film had low hydrophilicity, a contact angle with water of 40 degrees, and no antifogging property by exhalation was observed. The adhesion of the coating film was evaluated by a cross-cut peeling test according to the JIS method at an evaluation point of 10, and the adhesion was good. The same aqueous photocatalytic coating composition as in Example 1 was applied over the primer layer using a 2 mil doctor blade. As a result, the coating composition repelled on the primer and could not be fixed as a coating film.
【００５２】[0052]
【発明の効果】本発明のプライマー組成物は、アクリル
樹脂、アクリル変成シリコン樹脂、及びアクリルシラン
樹脂の少なくとも１種の樹脂成分を含有するエマルショ
ンに、湿潤剤を０．１〜２０ｗｔ％添加したプライマー
組成物であって、塗膜として５％以下のヘーズ値を有
し、前記塗膜と水との接触角が１０度以下であることを
特徴とするので、基体への塗工性と密着性が良好で耐光
性、耐水性、透明性、親水性に優れ、かつ上塗りの水性
光触媒塗料の塗工性も良好なプライマー組成物の塗膜層
を提供することができる。The primer composition of the present invention is a primer obtained by adding 0.1 to 20% by weight of a wetting agent to an emulsion containing at least one resin component of an acrylic resin, an acrylic modified silicone resin and an acrylic silane resin. The composition is characterized by having a haze value of 5% or less as a coating film and a contact angle between the coating film and water of 10 ° or less, so that coating properties and adhesion to a substrate can be obtained. And a coating layer of a primer composition which is excellent in light resistance, water resistance, transparency, and hydrophilicity, and has good coatability of an overcoated aqueous photocatalytic paint.
【００５３】また、湿潤剤を、リン酸エステル系、スル
ホン酸系、硫酸エステル系及びカルボン酸系の少なくと
も１種のイオン系界面活性剤とすることにより、上記効
果を確実に達成することができる。Further, the above effect can be surely achieved by using at least one kind of ionic surfactants of phosphoric acid ester type, sulfonic acid type, sulfate ester type and carboxylic acid type as the wetting agent. .
【００５４】更に、プライマー組成物に、コロイダルシ
リカ及び／又はアルミナゾルを含有させることにより、
基体との固定強度や、塗膜の耐水性及び硬度を高めるこ
とができる。Further, by adding colloidal silica and / or alumina sol to the primer composition,
The fixing strength to the substrate and the water resistance and hardness of the coating film can be increased.
【００５５】また、本発明の光触媒体は、基体と、該基
体表面に形成された前記のプライマー組成物の塗膜層
と、該プライマー組成物の塗膜上に形成された水性光触
媒コーティング組成物の塗膜層と、からなることを特徴
とするので、基体上に強固に固定された光触媒によっ
て、排気ガス中の有害ガスやタバコ、トイレ等の悪臭ガ
ス、農薬などの有害物質、環境汚染物質の分解除去及び
殺菌等を効率よく行うことができる。The photocatalyst of the present invention comprises a substrate, a coating layer of the primer composition formed on the surface of the substrate, and an aqueous photocatalyst coating composition formed on the coating of the primer composition. The film is characterized by a photocatalyst firmly fixed on the substrate, harmful gases in exhaust gas, odorous gases such as tobacco and toilets, harmful substances such as agricultural chemicals, and environmental pollutants. Can be efficiently decomposed, removed and sterilized.
【００５６】更に、水性光触媒コーティング組成物に、
更にコロイダルシリカ及び／又はアルミナゾルを含有さ
せることにより、水性光触媒層をプライマー層に更に強
固に固定することができる。Further, the aqueous photocatalytic coating composition
Further, by containing colloidal silica and / or alumina sol, the aqueous photocatalyst layer can be more firmly fixed to the primer layer.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０５Ｄ 7/24 ３０２ Ｂ０５Ｄ 7/24 ３０２Ｐ ３０２Ｙ Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｌ Ｄ // Ｂ０１Ｆ 17/00 Ｂ０１Ｆ 17/00 (72)発明者 長岡 茂 山口県宇部市大字小串1978番地の25 チタ ン工業株式会社内 (72)発明者 落合 正則 山口県宇部市大字小串1978番地の25 チタ ン工業株式会社内 Ｆターム(参考） 4D075 CA34 CA36 DB11 DB20 DB21 DB31 EA06 EA13 EB22 EB43 EC01 EC03 EC35 4D077 AB06 AB20 AC06 BA07 BA13 DC02Y DC26Y DC54Y DC59Y DC67Y 4G069 AA03 AA08 BA00 BA01A BA02A BA02B BA04A BA04B BA13A BA14A BA14B BA18 BA22A BA22B BA29A BA48A BE08A BE08B BE09A BE09B BE32A BE32B BE37A BE37B CA10 CA17 EA07 EA09 ED05 FA03 FB23 4J038 CG141 CL001 DL101 HA216 HA446 JC09 JC13 JC24 KA09 MA08 PA07 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B05D 7/24 302 B05D 7/24 302P 302Y C09D 5/00 C09D 5/00 L D // B01F 17/00 B01F 17/00 (72) Inventor: Shigeru Nagaoka, 1978 Kogushi, Ogushi, Ube City, Yamaguchi Prefecture Inside 25 Titan Kogyo Co., Ltd. (72) Inventor Masanori Ochiai, 1978 Kogushi, Uji City, Ube City, Yamaguchi Prefecture, 25 Titan Kogyo Co., Ltd. F-term (reference) 4D075 CA34 CA36 DB11 DB20 DB21 DB31 EA06 EA13 EB22 EB43 EC01 EC03 EC35 4D077 AB06 AB20 AC06 BA07 BA13 DC02Y DC26Y DC54Y DC59Y DC67Y 4G069 AA03 AA08 BA00 BA01A BA02A BA02A BA08A BA18A BAA BAA BAA BAA BE09B BE32A BE32B BE37A BE37B CA10 CA17 EA07 EA09 ED05 FA03 FB23 4J038 CG141 CL001 DL101 HA216 HA446 JC09 J C13 JC24 KA09 MA08 PA07
Claims (7)
脂、及びアクリルシラン樹脂の少なくとも１種の樹脂成
分を含有するエマルションに、湿潤剤を０．１〜２０ｗ
ｔ％添加したプライマー組成物であって、塗膜として５
％以下のヘーズ値を有し、前記塗膜と水との接触角が１
０度以下であることを特徴とするプライマー組成物。1. An emulsion containing at least one resin component of an acrylic resin, an acrylic modified silicone resin, and an acrylic silane resin, a wetting agent of 0.1 to 20 watts.
a primer composition to which at least 5% of t
% And a contact angle between the coating film and water of 1% or less.
A primer composition having a temperature of 0 degrees or less.
ホン酸系、硫酸エステル系及びカルボン酸系の少なくと
も１種のイオン系界面活性剤であることを特徴とする請
求項１に記載のプライマー組成物。2. The primer according to claim 1, wherein the wetting agent is at least one ionic surfactant of a phosphoric acid ester type, a sulfonic acid type, a sulfate ester type and a carboxylic acid type. Composition.
ナゾルを含有することを特徴とする請求項１又は請求項
２に記載のプライマー組成物。3. The primer composition according to claim 1, further comprising colloidal silica and / or alumina sol.
１乃至請求項３のいずれか１項に記載のプライマー組成
物の塗膜層と、該プライマー組成物の塗膜上に形成され
た水性光触媒コーティング組成物の塗膜層と、からなる
ことを特徴とする光触媒体。4. A substrate, a coating layer of the primer composition according to claim 1 formed on the surface of the substrate, and a coating layer formed on the coating film of the primer composition. And a coated layer of the aqueous photocatalyst coating composition.
触媒酸化チタンを含有することを特徴とする請求項４に
記載の光触媒体。5. The photocatalyst according to claim 4, wherein the aqueous photocatalyst coating composition contains a photocatalytic titanium oxide.
更にコロイダルシリカ及び／又はアルミナゾルを含有す
ることを特徴とする請求項４又は請求項５に記載の光触
媒体。6. The aqueous photocatalyst coating composition according to claim 1, wherein
The photocatalyst according to claim 4 or 5, further comprising colloidal silica and / or alumina sol.
ン、ニッケル、クロム及び銅の金属並びに前記金属の１
種以上を含む合金、ガラス、セラミックス、セメント、
木材、合成樹脂、樹脂フィルム、布、繊維及び紙の少な
くとも１種から形成されていることを特徴とする請求項
４乃至請求項６のいずれか１項に記載の光触媒体。7. The substrate according to claim 1, wherein the substrate is made of a metal of aluminum, iron, titanium, nickel, chromium and copper, and one of the metals.
Alloys, glass, ceramics, cement,
The photocatalyst according to any one of claims 4 to 6, wherein the photocatalyst is formed of at least one of wood, synthetic resin, resin film, cloth, fiber, and paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26081499A JP2001081394A (en) | 1999-09-14 | 1999-09-14 | Primer composition and photocatalytic body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26081499A JP2001081394A (en) | 1999-09-14 | 1999-09-14 | Primer composition and photocatalytic body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001081394A true JP2001081394A (en) | 2001-03-27 |
Family
ID=17353139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26081499A Pending JP2001081394A (en) | 1999-09-14 | 1999-09-14 | Primer composition and photocatalytic body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001081394A (en) |
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| US20050269550A1 (en) * | 2003-09-24 | 2005-12-08 | Petrov Viacheslav A | Method for the application of active materials onto active surfaces and devices made with such methods |
| KR101025957B1 (en) | 2010-12-21 | 2011-03-30 | 주식회사 세명크리텍 | Rubber asphalt emulsion flood protecting agent using acryl-silane primer and fast dried rubber asphalt emulsion and improving wetting adhesion and method for flood protection using the same |
| KR101353918B1 (en) | 2013-11-13 | 2014-01-22 | (주)우암건설 | A flexible, eco-friendly waterborne acrylic coating system for concrete surface protection and waterproofing, stopping salt intrusion and carbonation protection of reinforced concrete structures |
| JP2017160116A (en) * | 2016-03-04 | 2017-09-14 | 富士ゼロックス株式会社 | Metatitanic acid particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| US10471417B2 (en) | 2016-03-04 | 2019-11-12 | Fuji Xerox Co., Ltd. | Titanium oxide particle and method for producing the same |
| US10500579B2 (en) | 2017-04-26 | 2019-12-10 | Fuji Xerox Co., Ltd. | Metatitanic acid particle, composition for forming photocatalyst, and photocatalyst |
| US10512895B2 (en) | 2017-04-26 | 2019-12-24 | Fuji Xerox Co., Ltd. | Titanium oxide particle, composition for forming photocatalyst, and photocatalyst |
| US10668457B2 (en) | 2016-12-12 | 2020-06-02 | Fuji Xerox Co., Ltd. | Metatitanic acid particle, composition for forming photocatalyst, and photocatalyst |
| US10668456B2 (en) | 2016-12-12 | 2020-06-02 | Fuji Xerox Co., Ltd. | Titanium oxide particle, composition for forming photocatalyst, and photocatalyst |
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| US20050269550A1 (en) * | 2003-09-24 | 2005-12-08 | Petrov Viacheslav A | Method for the application of active materials onto active surfaces and devices made with such methods |
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| KR101025957B1 (en) | 2010-12-21 | 2011-03-30 | 주식회사 세명크리텍 | Rubber asphalt emulsion flood protecting agent using acryl-silane primer and fast dried rubber asphalt emulsion and improving wetting adhesion and method for flood protection using the same |
| KR101353918B1 (en) | 2013-11-13 | 2014-01-22 | (주)우암건설 | A flexible, eco-friendly waterborne acrylic coating system for concrete surface protection and waterproofing, stopping salt intrusion and carbonation protection of reinforced concrete structures |
| JP2017160116A (en) * | 2016-03-04 | 2017-09-14 | 富士ゼロックス株式会社 | Metatitanic acid particle and method for producing the same, photocatalyst forming composition, photocatalyst, and structure |
| US10471417B2 (en) | 2016-03-04 | 2019-11-12 | Fuji Xerox Co., Ltd. | Titanium oxide particle and method for producing the same |
| US10668457B2 (en) | 2016-12-12 | 2020-06-02 | Fuji Xerox Co., Ltd. | Metatitanic acid particle, composition for forming photocatalyst, and photocatalyst |
| US10668456B2 (en) | 2016-12-12 | 2020-06-02 | Fuji Xerox Co., Ltd. | Titanium oxide particle, composition for forming photocatalyst, and photocatalyst |
| US10500579B2 (en) | 2017-04-26 | 2019-12-10 | Fuji Xerox Co., Ltd. | Metatitanic acid particle, composition for forming photocatalyst, and photocatalyst |
| US10512895B2 (en) | 2017-04-26 | 2019-12-24 | Fuji Xerox Co., Ltd. | Titanium oxide particle, composition for forming photocatalyst, and photocatalyst |
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