JPH0761809A - Transparent siliceous coating - Google Patents
Transparent siliceous coatingInfo
- Publication number
- JPH0761809A JPH0761809A JP20960793A JP20960793A JPH0761809A JP H0761809 A JPH0761809 A JP H0761809A JP 20960793 A JP20960793 A JP 20960793A JP 20960793 A JP20960793 A JP 20960793A JP H0761809 A JPH0761809 A JP H0761809A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- coating liquid
- film
- aqueous solution
- layer structure
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 150
- 239000011248 coating agent Substances 0.000 title claims abstract description 148
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 8
- 150000001340 alkali metals Chemical class 0.000 abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011734 sodium Substances 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- -1 silicon alkoxide Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- 101150000971 SUS3 gene Proteins 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- GBPOWOIWSYUZMH-UHFFFAOYSA-N sodium;trihydroxy(methyl)silane Chemical compound [Na+].C[Si](O)(O)O GBPOWOIWSYUZMH-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Silicon Compounds (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
(57)【要約】
【目的】 厚膜にしてもクラックが生ぜず、高硬度の多
機能の透明シリカ質被膜を得る。
【構成】 従来から用いられているアルカリ金属の珪酸
塩を含む水溶液と、アルカリ金属の珪酸塩水溶液にアル
カリ水溶液シリコーンを混合した液と、有機トリアルコ
キシ珪酸を主成分とする有機溶媒溶液とから選ばれる２
種類の液を順次塗布して構成される２層構造の透明シリ
カ質被膜。(57) [Summary] [Purpose] Even if a thick film is formed, cracks do not occur, and a highly-hardened multifunctional transparent siliceous film is obtained. [Structure] An aqueous solution containing a silicate of an alkali metal, a liquid obtained by mixing an aqueous solution of an alkali metal silicate with an aqueous solution of silicone, and an organic solvent solution containing an organic trialkoxysilicic acid as a main component, which are conventionally used. 2
A two-layer transparent siliceous coating formed by sequentially applying different types of liquids.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属、ガラス、セラミ
ックスなどの基材表面に塗布し、耐食性、光沢、硬度な
どを付与するための透明なシリカ質被膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent siliceous coating film applied to the surface of a base material such as metal, glass or ceramics to impart corrosion resistance, gloss, hardness and the like.
【０００２】[0002]
【従来の技術】従来から透明なシリカ質被膜としては、
アルカリ金属の珪酸塩を主成分とする水溶液から形成さ
れる被膜（特開昭５８−９６７８６号に記載、以下「被
膜Ａ」という）と、アルカリ金属の珪酸塩と、アルカリ
水溶液シリコーンとを配合した水溶液から形成される被
膜（以下「被膜Ｂ」という）と、シリコンアルコキシド
を主成分とする有機溶媒から形成される被膜（以下「被
膜Ｃ」という）とがある。2. Description of the Related Art Conventionally, as a transparent siliceous film,
A coating formed from an aqueous solution containing an alkali metal silicate as a main component (described in JP-A-58-96786, hereinafter referred to as "coating A"), an alkali metal silicate, and an alkaline aqueous solution silicone were blended. There are a film formed from an aqueous solution (hereinafter referred to as "film B") and a film formed from an organic solvent containing silicon alkoxide as a main component (hereinafter referred to as "film C").
【０００３】これらの被膜は、次のような特徴があるの
で広く用いられている。すなわち被膜Ａは、親水性で高
硬度で、酸素に対するバリア性があり耐酸化性に優れて
いる。また被膜Ｂは、高硬度で１〜２０μｍの厚膜の被
膜ができ撥水性に優れている。また被膜Ｃは、被膜中に
アルカリ金属を含まず高硬度で１〜２０μｍの厚膜の被
膜ができ、第３成分の添加が容易であるため、各種の機
能の付加がし易い。These coatings are widely used because they have the following features. That is, the coating film A is hydrophilic, has high hardness, has a barrier property against oxygen, and is excellent in oxidation resistance. Further, the coating film B has a high hardness and a thick film of 1 to 20 μm, and is excellent in water repellency. In addition, the coating C can be a coating having a high hardness and a thickness of 1 to 20 μm and containing no alkali metal in the coating. Since the third component can be easily added, various functions can be easily added.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の被膜は単独で用いると、被膜Ａは薄膜しか形成でき
ず、１μｍ以上の膜厚とするとクラックが生じるという
問題がある。また被膜Ｂは、耐熱温度が４００〜４５０
℃と低いという問題がある。さらに被膜Ａおよび被膜Ｂ
は、被膜中のアルカリ金属が表面に遊離し、これが空気
中の炭酸ガスによってくもりを生じ易いという問題があ
る。また被膜Ｃは、酸素に対してのバリア性が乏しいと
いう問題がある。However, if these coatings are used alone, the coating A can form only a thin film, and if the thickness is 1 μm or more, cracks occur. The coating B has a heat resistant temperature of 400 to 450.
There is a problem that it is as low as ℃. Further, coating A and coating B
Has a problem that the alkali metal in the coating is liberated on the surface, and this tends to cause clouding due to carbon dioxide gas in the air. Further, the coating film C has a problem that it has a poor barrier property against oxygen.
【０００５】本発明の目的は、前記欠点を補い、必要な
物性を制御することができる透明シリカ質被膜を提供す
ることである。An object of the present invention is to provide a transparent siliceous coating film which can remedy the above drawbacks and control the required physical properties.
【０００６】[0006]
【課題を解決するための手段】本発明は、基材上に、次
の塗布液Ａ、塗布液Ｂまたは塗布液Ｃから選ばれる２種
類の塗布液を順次塗布することによって構成される２層
構造の透明シリカ質被膜である。The present invention provides a two-layer structure formed by sequentially coating two kinds of coating liquids selected from the following coating liquid A, coating liquid B or coating liquid C on a substrate. It is a transparent siliceous coating having a structure.
【０００７】（ａ）塗布液Ａは、一般式Ｒ2Ｏ・ｍＬｉ2
Ｏ・ｎＳｉＯ2 で表されるアルカリ金属の珪酸塩を含む
水溶液である。（式中Ｒは、Ｎａおよび／またはＫ、
ｍ，ｎは０．１≦ｍ＜３、４≦ｎ≦１０の範囲） （ｂ）塗布液Ｂは、一般式Ｒ2Ｏ・ｍＬｉ2Ｏ・ｎＳｉＯ
2 で表されるアルカリ金属の珪酸塩水溶液の固形分１０
０重量部に対し、アルカリ水溶性シリコーンをその固形
分が３〜１００重量部配合した水溶液である。（式中Ｒ
は、Ｎａおよび／またはＫ、ｍ，ｎは０．１≦ｍ＜３、
４≦ｎ≦１０の範囲） （ｃ）塗布液Ｃは、一般式Ｒ1Ｓｉ（ＯＲ2）3 で表され
る有機トリアルコキシ珪酸を主成分とし、これに必要に
応じ、Ｓｉ（ＯＲ3）4、Ｔｉ（ＯＲ4）4、Ｚｒ（ＯＲ
5 ）4 の１種類以上を混ぜた有機溶媒溶液。（式中Ｒ1
は炭素数１〜６のアルキル基、Ｒ2 〜Ｒ5 は炭素数１〜
４のアルキル基） また本発明は、前記２層構造の被膜が、基材上に塗布液
Ａを塗布して室温〜３００℃で乾燥した後、塗布液Ｃを
塗布することによって構成されることを特徴とする。(A) The coating liquid A has the general formula R 2 O.mLi 2
It is an aqueous solution containing an alkali metal silicate represented by O · nSiO 2 . (In the formula, R is Na and / or K,
m and n are in the range of 0.1 ≦ m <3, 4 ≦ n ≦ 10) (b) The coating liquid B has the general formula R 2 O.mLi 2 O.nSiO.
Solid content of aqueous solution of alkali metal silicate represented by 2 10
It is an aqueous solution in which the solid content of the alkali water-soluble silicone is 3 to 100 parts by weight with respect to 0 parts by weight. (R in the formula
Is Na and / or K, m, n is 0.1 ≦ m <3,
4 ≦ n ≦ 10) (c) The coating liquid C contains an organic trialkoxysilicic acid represented by the general formula R 1 Si (OR 2 ) 3 as a main component, and if necessary, Si (OR 3 ) 4 , Ti (OR 4 ) 4 , Zr (OR
5 ) An organic solvent solution in which one or more of 4 is mixed. (Where R 1
Is an alkyl group having 1 to 6 carbon atoms, R 2 to R 5 are 1 to 6 carbon atoms
Alkyl group of 4) Further, the present invention is configured such that the coating film having the two-layer structure is formed by applying the coating liquid A on a substrate, drying the coating liquid at room temperature to 300 ° C., and then applying the coating liquid C. Is characterized by.
【０００８】また本発明は、前記２層構造の被膜が、基
材上に塗布液Ｂを塗布して室温〜３００℃で乾燥した
後、塗布液Ｃを塗布することによって構成されることを
特徴とする。Further, the present invention is characterized in that the coating film of the two-layer structure is constituted by applying the coating liquid B on a substrate, drying the coating liquid at room temperature to 300 ° C., and then coating the coating liquid C. And
【０００９】また本発明は、前記２層構造の被膜が、基
材上に塗布液Ｂを塗布して室温〜３００℃で乾燥し、ア
ルカリ処理した後、塗布液Ａを塗布することによって構
成されることを特徴とする。Further, the present invention is constituted by applying the coating solution B on a substrate, drying the coating solution B at room temperature to 300 ° C., performing an alkali treatment, and then applying the coating solution A. It is characterized by
【００１０】[0010]
【作用】本発明に従えば、従来用いられていた被膜Ａ、
被膜Ｂおよび被膜Ｃのうちの２種を２層構造の被膜とし
て用いるものである。According to the present invention, the coating A, which has been used conventionally,
Two kinds of the coating B and the coating C are used as a coating having a two-layer structure.
【００１１】被膜Ａを形成する塗布液Ａは、アルカリ金
属の珪酸塩であるが、珪酸ナトリウムおよび／または珪
酸カリウムのみの場合は耐水性が劣り、珪酸リチウムの
みの場合は密着性がよくない。ナトリウムとカリウムの
合計量に対するリチウムのモル比は０．１〜３、好まし
くは０．１〜２である。The coating liquid A for forming the coating film A is a silicate of an alkali metal. However, when only sodium silicate and / or potassium silicate is used, the water resistance is poor, and when only lithium silicate is used, the adhesion is poor. The molar ratio of lithium to the total amount of sodium and potassium is 0.1-3, preferably 0.1-2.
【００１２】アルカリ金属と珪素のモル比は４〜１０、
好ましくは５〜８である。この値が４未満では形成され
る被膜の耐水性が低下し、１０を越えると密着性が低下
する。The molar ratio of alkali metal to silicon is 4 to 10,
It is preferably 5 to 8. If this value is less than 4, the water resistance of the coating film formed will decrease, and if it exceeds 10, the adhesion will decrease.
【００１３】被膜Ｂを形成する塗布液Ｂについてもアル
カリ金属の珪酸塩水溶液については上に述べた関係がい
える。アルカリ金属の珪酸塩とアルカリ水溶性シリコー
ンの配合割合は、前者の固形分１００重量部に対し、後
者の固形分３〜１００重量部、好ましくは５〜７０重量
部である。アルカリ水溶性シリコーンの量が３重量部よ
り少ないと、５μｍ以上の膜厚としたときクラックが入
り易く、また１００重量部より多いと被膜の耐湿性が悪
くなる。With respect to the coating solution B for forming the coating film B, the above-mentioned relation can be said for the aqueous solution of alkali metal silicate. The mixing ratio of the alkali metal silicate and the alkali water-soluble silicone is 3 to 100 parts by weight, preferably 5 to 70 parts by weight, with respect to the former solid content of 100 parts by weight. If the amount of the alkali-water-soluble silicone is less than 3 parts by weight, cracks are likely to occur when the film thickness is 5 μm or more, and if it is more than 100 parts by weight, the moisture resistance of the coating film is deteriorated.
【００１４】被膜Ｃを形成する塗布液Ｃの有機トリアル
コキシ珪酸としては、メチルトリエトキシシランＣＨ3
Ｓｉ（ＯＣ2Ｈ5）3，エチルトリエトキシシランＣ2Ｈ5
Ｓｉ（ＯＣ2Ｈ5）3 などが例示され、有機溶媒として
は、プロパノール、ブタノールなどのアルコール類また
はメチルセルソルブ、エチルセルソルブ、ブチルセルソ
ルブなどのセルソルブ類が例示される。As the organic trialkoxysilicic acid of the coating liquid C for forming the coating C, methyltriethoxysilane CH 3
Si (OC 2 H 5 ) 3 , ethyltriethoxysilane C 2 H 5
Si (OC 2 H 5 ) 3 and the like are exemplified, and examples of the organic solvent include alcohols such as propanol and butanol, and cellsolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve.
【００１５】さらに塗布液Ａ、塗布液Ｂおよび塗布液Ｃ
には、ホウ酸を含むことが好ましい。ホウ酸は、ホウ砂
またはホウ酸のアルカリ金属塩として添加してもよい。
ホウ酸は、珪素の量が少ないときに耐水性を向上する作
用がある。ホウ酸の添加量は、各塗布液の固形分に対し
０．３〜５重量％が好ましい。０．３％未満では添加の
効果がなく、５％を越えると溶解しない。この他にアル
ミニウム塩、亜鉛塩を耐水性向上剤として添加し、使用
することが可能である。Further, coating liquid A, coating liquid B and coating liquid C
Preferably contains boric acid. Boric acid may be added as borax or an alkali metal salt of boric acid.
Boric acid has the effect of improving water resistance when the amount of silicon is small. The addition amount of boric acid is preferably 0.3 to 5% by weight based on the solid content of each coating solution. If it is less than 0.3%, there is no effect of addition, and if it exceeds 5%, it does not dissolve. In addition to these, aluminum salts and zinc salts can be added and used as water resistance improvers.
【００１６】２層被膜構造の構成は、用途によって各塗
布液のいずれかを用いるかまたその塗布の順序をいかに
するかを決めるべきであるが、次の（１）〜（３）に述
べる組合わせが好ましい。In the constitution of the two-layer coating structure, it is necessary to decide which of the coating solutions is to be used and the order of the coating depending on the application. The groups described in the following (1) to (3) Matching is preferred.
【００１７】（１）下層が塗布液Ａで構成される被膜で
あり、上層が塗布液Ｃで構成される被膜である２層構造
の被膜。(1) A two-layer structure film in which the lower layer is a film composed of the coating liquid A and the upper layer is a film composed of the coating liquid C.
【００１８】基材上に塗布液Ａを塗布し、室温〜３００
℃で乾燥処理する。その上に、塗布液Ｃを塗布した後、
２００〜５００℃で焼成する。The coating solution A is applied onto the substrate, and the temperature is from room temperature to 300.
Dry at ℃. After applying the coating liquid C on it,
Baking at 200 to 500 ° C.
【００１９】被膜Ｃは、単独で耐アルカリ性に劣るが、
被膜Ａを下塗りした上に被膜Ｃを形成するので耐アルカ
リ性が増し、酸素バリア性がある。また上層には、アル
カリ金属が含まれず、アルカリ金属が表面に遊離しない
ため表面がくもりにくい。また上層のシリコンアルコキ
シドは、チタン、ジルコニウムなどの他の金属のアルコ
キシドと相溶性があるため、容易に紫外線吸収能、赤外
線反射能、抗菌性などの機能を付加した機能性複合膜を
得ることができる。The coating C alone is inferior in alkali resistance,
Since the coating C is formed as the undercoat, the coating C is formed, so that the alkali resistance is increased and the oxygen barrier property is provided. Further, since the upper layer contains no alkali metal and the alkali metal is not released to the surface, the surface is hard to become cloudy. Moreover, since the upper silicon alkoxide is compatible with alkoxides of other metals such as titanium and zirconium, it is possible to easily obtain a functional composite film with added functions such as ultraviolet absorbing ability, infrared reflecting ability and antibacterial ability. it can.
【００２０】（２）下層が塗布液Ｂで構成される被膜で
あり、上層が塗布液Ｃで構成される被膜である２層構造
の被膜。(2) A coating having a two-layer structure in which the lower layer is a coating composed of the coating liquid B and the upper layer is a coating composed of the coating liquid C.
【００２１】基材上に塗布液Ｂを塗布し、室温〜３００
℃で乾燥処理する。その上に、塗布液Ｃを塗布した後、
２００〜４００℃で焼成する。The coating solution B is applied onto the substrate, and the temperature is from room temperature to 300.
Dry at ℃. After applying the coating liquid C on it,
Baking at 200 to 400 ° C.
【００２２】被膜Ｂと塗布液Ｃの両方の長所を有するこ
とは（１）で説明したのと同じである。さらに被膜Ｂが
厚膜にできる利点を利用して被膜の厚さを（１）よりも
厚くできる。The advantages of both the coating B and the coating liquid C are the same as described in (1). Furthermore, the thickness of the coating can be made thicker than (1) by utilizing the advantage that the coating B can be made thick.
【００２３】（３）下層が塗布液Ｂで構成される被膜で
あり、上層が塗布液Ａで構成される被膜である２層構造
の被膜。(3) A two-layer structure film in which the lower layer is a coating film composed of the coating liquid B and the upper layer is a coating film composed of the coating liquid A.
【００２４】基材上に塗布液Ｂを塗布し、室温〜３００
℃で乾燥処理する。これによって構成された被膜Ｂは、
撥水性であるため、塗布液Ａとの密着性が悪いので、水
酸化ナトリウム溶液を被膜Ｂに浸漬させ、塗布液Ａを塗
布した後、２００〜４００℃で焼成する。The coating solution B is applied onto the base material at room temperature to 300
Dry at ℃. The coating B formed by this is
Since it is water-repellent and has poor adhesion to the coating liquid A, a sodium hydroxide solution is dipped in the coating film B to apply the coating liquid A, and then baking is performed at 200 to 400 ° C.
【００２５】このようにして構成された被膜は、上層の
被膜Ａが親水性であるので、親水性であって厚膜の被膜
となり、耐食性に優れた熱交換器のチューブなどに使用
できる。Since the upper coating A is hydrophilic, the coating thus constructed is hydrophilic and becomes a thick coating, and can be used in tubes of heat exchangers having excellent corrosion resistance.
【００２６】２層被膜構造を構成する際に、下層の塗布
液Ａまたは塗布液Ｂは、上層の塗布液を塗布するに際
し、室温〜３００℃、好ましくは５０〜２５０℃で乾燥
する。これは下層被膜の耐水性を保持するためと、上層
被膜との密着性を増すためである。すなわち、下層の塗
布液は、水溶液の形で塗布されるので５０℃以下では、
耐水性が不充分となる場合があり、また２５０℃以上で
は、上層との密着性が悪くなる場合があるためである。
特に被膜Ｂの上に被膜Ａを構成する場合には、アルカリ
処理をしても２５０℃以上で下層を処理すると上層が剥
離することがある。When forming the two-layer coating structure, the lower layer coating liquid A or coating liquid B is dried at room temperature to 300 ° C., preferably 50 to 250 ° C. when the upper layer coating liquid is applied. This is to maintain the water resistance of the lower layer coating and to increase the adhesion with the upper layer coating. That is, since the lower layer coating solution is applied in the form of an aqueous solution, at 50 ° C or lower,
This is because the water resistance may be insufficient, and at 250 ° C. or higher, the adhesion with the upper layer may be poor.
In particular, when the coating A is formed on the coating B, the upper layer may be peeled off when the lower layer is treated at 250 ° C. or higher even if the alkali treatment is performed.
【００２７】[0027]
【実施例】以下、実施例を用いて本発明をより具体的に
説明するが、本発明はこれによって限定されるものでは
ない。EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
【００２８】なお、実施例で用いた塗布液Ａ、塗布液Ｂ
および塗布液Ｃは次のようにして調合した。The coating liquids A and B used in the examples
The coating liquid C was prepared as follows.
【００２９】（１）塗布液Ａ Ｎａ2Ｏ ８．７％とＳｉＯ2 ２７．８％とを含む珪酸
ナトリウム水溶液１００重量部と、Ｌｉ2Ｏ ２．２％
とＳｉＯ2 ２０．０％とを含む珪酸リチウム水溶液５
０重量部と、ホウ酸１．２重量部と、水３．６重量部と
を混合した。(1) Coating Solution A 100 parts by weight of an aqueous sodium silicate solution containing 8.7% Na 2 O and 27.8% SiO 2 and 2.2% Li 2 O.
Lithium silicate aqueous solution containing 5 and SiO 2 20.0% 5
0 parts by weight, 1.2 parts by weight boric acid, and 3.6 parts by weight of water were mixed.
【００３０】（２）塗布液Ｂ Ｎａ2Ｏ ８．７％とＳｉＯ2 ２７．８％とを含む珪酸
ナトリウム水溶液１００重量部と、Ｌｉ2Ｏ ２．２％
とＳｉＯ2 ２０．０％とを含む珪酸リチウム水溶液５
０重量部と、Ｎａ2Ｏ １０．７％と（ＣＨ3Ｓｉ）2Ｏ3
２０％とを含むナトリウムメチルシリコネート水溶液
４０重量部とを混合した。(2) Coating solution B 100 parts by weight of an aqueous sodium silicate solution containing 8.7% Na 2 O and 27.8% SiO 2 and 2.2% Li 2 O.
Lithium silicate aqueous solution containing 5 and SiO 2 20.0% 5
0 parts by weight, Na 2 O 10.7% and (CH 3 Si) 2 O 3
40% by weight of an aqueous solution of sodium methylsiliconate containing 20% was mixed.
【００３１】（３）塗布液Ｃ メチルトリエトキシシランＣＨ3Ｓｉ（ＯＣ2Ｈ5）3３２
重量部とテトラエトキシシランＳｉ（ＯＣ2Ｈ5）4 １
６．７重量部とｉ−プロパノール３．９重量部とに塩酸
水溶液１２．４重量部を混合し、塩酸を全体の３０ｐｐ
ｍになるようにした。この液を還流冷却器を付して８０
℃に２時間保持し、その後室温まで冷却してｎ−ブタノ
ール３５重量部を混合した。(3) Coating liquid C Methyltriethoxysilane CH 3 Si (OC 2 H 5 ) 3 32
Parts by weight and tetraethoxysilane Si (OC 2 H 5 ) 4 1
6.7 parts by weight and 3.9 parts by weight of i-propanol were mixed with 12.4 parts by weight of an aqueous solution of hydrochloric acid, and hydrochloric acid was added to the whole amount of 30 pp.
It was set to m. This liquid is attached with a reflux condenser to 80
The temperature was maintained at 0 ° C for 2 hours, then cooled to room temperature, and 35 parts by weight of n-butanol was mixed.
【００３２】実施例１ 大きさ１０ｃｍ×１０ｃｍ、厚さ０．５ｍｍのＳＵＳ３
０４のステンレス基板の表面をよく脱脂、洗浄した。次
いで塗布液Ａを水で３倍に希釈したものを本基板に塗布
し、１５０℃で１５分乾燥した。このものの膜厚は約
０．５μｍであった。この下層被膜Ａの上に塗布液Ｃを
乾燥後の厚さが約２μｍになるよう塗布し、１５０〜５
００℃で焼成した。得られた２層構造被膜の性状を表１
に示す。Example 1 SUS3 having a size of 10 cm × 10 cm and a thickness of 0.5 mm
The surface of the 04 stainless steel substrate was thoroughly degreased and washed. Then, the coating solution A diluted three times with water was applied to the substrate and dried at 150 ° C. for 15 minutes. The film thickness of this product was about 0.5 μm. The coating solution C is applied on the lower layer coating A so that the thickness after drying is about 2 μm,
It was baked at 00 ° C. The properties of the obtained two-layer structure coating film are shown in Table 1.
Shown in.
【００３３】比較例１ 実施例１と同じステンレス基板に塗布液Ｃを乾燥後の厚
さが２μｍになるように塗布し、１５０〜５００℃で焼
成した。得られた被膜の性状を表１に示す。Comparative Example 1 The same stainless steel substrate as in Example 1 was coated with the coating liquid C so that the thickness after drying was 2 μm, and baked at 150 to 500 ° C. The properties of the obtained coating film are shown in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】試験方法は、次のとおりである。The test method is as follows.
【００３６】・鉛筆硬度 東洋精機製鉛筆塗膜硬さ試験機にて測定した。Pencil hardness Measured with a pencil coating film hardness tester manufactured by Toyo Seiki.
【００３７】・耐アルカリ性 ２０％ＮａＯＨ水溶液に室温で１日浸漬したのち、表面
観察を行った。Alkali resistance After immersing in an aqueous 20% NaOH solution at room temperature for 1 day, the surface was observed.
【００３８】・耐酸性 ２０％Ｈ2ＳＯ4水溶液に室温で１日浸漬したのち、表面
観察を行った。After immersing in an acid resistant 20% H 2 SO 4 aqueous solution at room temperature for 1 day, the surface was observed.
【００３９】・耐水性 室温の水に１日浸漬したのち、表面観察を行った。Water resistance After immersing in water at room temperature for 1 day, the surface was observed.
【００４０】なお耐アルカリ性、耐酸性、耐水性の評価
の結果は、○印良好、△印一部損傷、×印不良をそれぞ
れ示す。The results of evaluation of alkali resistance, acid resistance, and water resistance show good marks, good marks, partial damage, and bad marks.
【００４１】実施例１と比較例１の結果から、焼成温度
３００℃以上のこの２層構造の被膜が焼成温度５００℃
の単独の被膜Ｃよりも優れていることが判る。From the results of Example 1 and Comparative Example 1, the coating film of this two-layer structure having a baking temperature of 300 ° C. or higher was baked at a temperature of 500 ° C.
It is found that the coating C is superior to the coating C alone.
【００４２】実施例２ 大きさ１０ｃｍ×１０ｃｍ、厚さ０．５ｍｍのＳＵＳ３
０４のステンレス基板の表面をよく脱脂、洗浄した。次
いで塗布液Ｂを本基板に塗布し、１５０℃で１５分乾燥
した。このものの膜厚は約５μｍであった。この下層被
膜Ｂ上に、塗布液Ｃを乾燥後の厚さが約１μｍになるよ
うに塗布し、３００℃で１５分焼成した。得られた２層
構造の被膜は、密着性良好で、鉛筆硬度は９Ｈ以上であ
った。被膜Ｂを上層にした被膜は、表面にＮａが存在す
るため、長時間空気中に滞留すると二酸化炭素によって
くもりが生ずることがあるが、この２層構造の被膜の場
合には、そのような現象は認められなかった。Example 2 SUS3 having a size of 10 cm × 10 cm and a thickness of 0.5 mm
The surface of the 04 stainless steel substrate was thoroughly degreased and washed. Next, the coating liquid B was applied to the main substrate and dried at 150 ° C. for 15 minutes. The film thickness of this product was about 5 μm. The coating liquid C was applied onto the lower layer coating B so that the thickness after drying was about 1 μm, and baked at 300 ° C. for 15 minutes. The obtained coating having a two-layer structure had good adhesion and a pencil hardness of 9H or higher. Since the surface of the film having the film B as the upper layer contains Na, if it stays in the air for a long time, clouding may occur due to carbon dioxide. However, in the case of the film having the two-layer structure, such a phenomenon occurs. Was not recognized.
【００４３】実施例３ 大きさ１０ｃｍ×１０ｃｍ、厚さ０．５ｍｍのＳＵＳ３
０４のステンレス基板をよく脱脂、洗浄した。次いで塗
布液Ｂを本基板に塗布し、１５０℃で１５分乾燥した。
このものの膜厚は約５μｍであった。Example 3 SUS3 having a size of 10 cm × 10 cm and a thickness of 0.5 mm
The 04 stainless steel substrate was thoroughly degreased and washed. Next, the coating liquid B was applied to the main substrate and dried at 150 ° C. for 15 minutes.
The film thickness of this product was about 5 μm.
【００４４】この下層被膜Ｂを２０％ＮａＯＨ水溶液に
約１時間浸漬し、表面を水に対して濡れ易くした後、引
き続き塗布液Ａを乾燥後の厚さが約０．５μｍになるよ
う塗布し、２００℃で１５分焼成した。This lower layer coating B was dipped in a 20% NaOH aqueous solution for about 1 hour to make the surface easily wettable with water, and then the coating solution A was applied so that the thickness after drying was about 0.5 μm. It was baked at 200 ° C. for 15 minutes.
【００４５】得られたものは密着性良好で、鉛筆硬度は
９Ｈ以上であった。被膜Ｂは撥水性があったが、この２
層構造被膜は親水性であった。The obtained product had good adhesion and a pencil hardness of 9H or more. Coating B had water repellency, but this 2
The layer structure coating was hydrophilic.
【００４６】[0046]
【発明の効果】以上述べたように本発明によれば、２層
構造被膜はそれを構成する単独の被膜の長所を有し、各
層の密着性も良好である。また膜厚もクラックを生じさ
せずに厚くすることができる。As described above, according to the present invention, the two-layer structure coating film has the advantages of the single coating film constituting the two-layer structure coating film, and the adhesion of each layer is also good. Further, the film thickness can be increased without causing cracks.
Claims (4)
は塗布液Ｃから選ばれる２種類の塗布液を順次塗布する
ことによって構成される２層構造の透明シリカ質被膜。 （ａ）塗布液Ａは、一般式Ｒ2Ｏ・ｍＬｉ2Ｏ・ｎＳｉＯ
2 で表されるアルカリ金属の珪酸塩を含む水溶液であ
る。（式中Ｒは、Ｎａおよび／またはＫ、ｍ，ｎは０．
１≦ｍ＜３、４≦ｎ≦１０の範囲） （ｂ）塗布液Ｂは、一般式Ｒ2Ｏ・ｍＬｉ2Ｏ・ｎＳｉＯ
2 で表されるアルカリ金属の珪酸塩水溶液の固形分１０
０重量部に対し、アルカリ水溶性シリコーンをその固形
分が３〜１００重量部配合した水溶液である。（式中Ｒ
は、Ｎａおよび／またはＫ、ｍ，ｎは０．１≦ｍ＜３、
４≦ｎ≦１０の範囲） （ｃ）塗布液Ｃは、一般式Ｒ1Ｓｉ（ＯＲ2）3 で表され
る有機トリアルコキシ珪酸を主成分とし、これに必要に
応じ、Ｓｉ（ＯＲ3）4、Ｔｉ（ＯＲ4）4、Ｚｒ（Ｏ
Ｒ5）4 の１種類以上を混ぜた有機溶媒溶液。（式中Ｒ1
は炭素数１〜６のアルキル基、Ｒ2 〜Ｒ5 は炭素数１〜
４のアルキル基）1. A transparent siliceous coating having a two-layer structure formed by sequentially coating two kinds of coating liquids selected from the following coating liquid A, coating liquid B or coating liquid C on a substrate. (A) The coating liquid A is of the general formula R 2 O.mLi 2 O.nSiO.
An aqueous solution containing an alkali metal silicate represented by 2 . (In the formula, R is Na and / or K, and m and n are 0.
1 ≦ m <3, 4 ≦ n ≦ 10) (b) The coating liquid B has a general formula of R 2 O.mLi 2 O.nSiO.
Solid content of aqueous solution of alkali metal silicate represented by 2 10
It is an aqueous solution in which the solid content of the alkali water-soluble silicone is 3 to 100 parts by weight with respect to 0 parts by weight. (R in the formula
Is Na and / or K, m, n is 0.1 ≦ m <3,
4 ≦ n ≦ 10) (c) The coating liquid C contains an organic trialkoxysilicic acid represented by the general formula R 1 Si (OR 2 ) 3 as a main component, and if necessary, Si (OR 3 ) 4 , Ti (OR 4 ) 4 , Zr (O
An organic solvent solution in which one or more of R 5 ) 4 is mixed. (Where R 1
Is an alkyl group having 1 to 6 carbon atoms, R 2 to R 5 are 1 to 6 carbon atoms
4 alkyl group)
Ａを塗布して室温〜３００℃で乾燥した後、塗布液Ｃを
塗布することによって構成されることを特徴とする請求
項１記載の透明シリカ質被膜。2. The coating having a two-layer structure is constituted by applying the coating liquid A on a substrate, drying the coating liquid at room temperature to 300 ° C., and then coating the coating liquid C. Item 1. The transparent siliceous film according to Item 1.
Ｂを塗布して室温〜３００℃で乾燥した後、塗布液Ｃを
塗布することによって構成されることを特徴とする請求
項１記載の透明シリカ質被膜。3. The coating film having the two-layer structure is constituted by applying the coating liquid B on a substrate, drying the coating liquid at room temperature to 300 ° C., and then coating the coating liquid C. Item 1. The transparent siliceous film according to Item 1.
Ｂを塗布して室温〜３００℃で乾燥し、アルカリ処理し
た後、塗布液Ａを塗布することによって構成されること
を特徴とする請求項１記載の透明シリカ質被膜。4. The coating film having a two-layer structure is formed by applying the coating liquid B on a substrate, drying the coating liquid at room temperature to 300 ° C., performing an alkali treatment, and then coating the coating liquid A. The transparent siliceous coating according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20960793A JPH0761809A (en) | 1993-08-24 | 1993-08-24 | Transparent siliceous coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20960793A JPH0761809A (en) | 1993-08-24 | 1993-08-24 | Transparent siliceous coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0761809A true JPH0761809A (en) | 1995-03-07 |
Family
ID=16575612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20960793A Pending JPH0761809A (en) | 1993-08-24 | 1993-08-24 | Transparent siliceous coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015214131A (en) * | 2014-05-09 | 2015-12-03 | ホンタンサワット ワラポン | Inorganic micro-film substrate and production method thereof |
-
1993
- 1993-08-24 JP JP20960793A patent/JPH0761809A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015214131A (en) * | 2014-05-09 | 2015-12-03 | ホンタンサワット ワラポン | Inorganic micro-film substrate and production method thereof |
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