JPH0532431B2 - - Google Patents
Info
- Publication number
- JPH0532431B2 JPH0532431B2 JP59179915A JP17991584A JPH0532431B2 JP H0532431 B2 JPH0532431 B2 JP H0532431B2 JP 59179915 A JP59179915 A JP 59179915A JP 17991584 A JP17991584 A JP 17991584A JP H0532431 B2 JPH0532431 B2 JP H0532431B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- film
- resistance
- test
- 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.)
- Expired - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000004111 Potassium silicate Substances 0.000 claims description 5
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001723 curing Methods 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000010960 cold rolled steel Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- -1 silicon halide Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
産業上の利用分野
本発明は、金属製品の外観を損なうことなく防
錆被覆するための透明無機質被覆剤組成物及び透
明無機質皮膜形成方法に関する。
従来の技術及び問題点
従来、金属製品の防錆のために、クロメート処
理、めつき、低温焼成無機質塗料、ガラスコーテ
イング、セラミツク溶射、CVD、PVD等の研究
が行なわれている。しかしながら、設備費が安価
であり、かつ１〜２ミクロン程度の厚さで耐熱性
を備えた透明皮膜を得ることのできる金属防錆法
は見出されていないのが現状である。
問題点を解決するための手段
本発明者は、従来技術の欠点に鑑みて種々研究
を重ねた結果、特定の組成の被覆剤を200〜300℃
程度の低温で加熱硬化することにより金属製品の
外観を損なうことなく、耐熱性、耐酸性、耐アル
カリ性、耐沸騰水性、表面硬度の向上などの効果
を与える１〜２ミクロン程度の透明皮膜が得られ
ることを見出した。
即ち、本発明は、ナトリウムケイ酸塩及びカリ
ウムケイ酸塩から選ばれたアルカリケイ酸塩（固
形分換算）100重量部と超微粒子状シリカ５〜100
重量部とを50〜100℃で加熱溶解した生成物から
なる透明無機質被覆剤組成物、並びにナトリウム
ケイ酸塩及びカリウムケイ酸塩から選ばれたアル
カリケイ酸塩（固形分換算）100重量部並びに超
微粒子状シリカ５〜100重量部を50〜100℃で加熱
溶解した後、被処理物に塗付し加熱硬化させるこ
とを特徴とする透明無機質皮膜形成方法に係る。
本発明では、アルカリケイ酸塩としては、ナト
リウムケイ酸塩及びカリウムケイ酸塩から選ばれ
たものであつて、広く市販されている液状のもの
が使用でき、水ガラス１号、２号、３号、カリウ
ムシリケート溶液等が具体例として挙げられる。
これ等のアルカリケイ酸塩は単独で使用しても良
く、或いは、２種以上を併用しても良い。
本発明で使用する超微粒子状シリカとは、その
粒子表面、あるいは一部内部にシラノール基（Si
−OH）をもち、アルカリケイ酸塩により可溶で
あり、平均粒子径が40mμ程度以下のものである。
本発明では、広く市販されている超微粒子状シリ
カが使用でき、例えばホワイトカーボン（ケイ酸
ナトリウムを原料とする湿式製品）、超微粒子状
無水シリカ（ハロゲン化ケイ素を原料とする乾式
製品）などの一般名で呼ばれているものを用いる
ことができる。
本発明に於いては、アルカリケイ酸塩は、透明
皮膜の骨格となるものであり、超微粒子状シリカ
は、アルカリケイ酸塩の硬化剤として働くもので
ある。本発明では、アルカリケイ酸塩（固形分換
算）100重量部に対して超微粒子状シリカを５〜
100重量部使用することが必要である。超微粒子
状シリカが５重量部より少ないと皮膜の耐熱性、
耐薬品性、耐沸騰水性が不充分となり、100重量
部を超えると超微粒子状シリカがアルカリケイ酸
塩に溶解しなくなる。
本発明被覆剤組成物は、反応容器に所定量のア
ルカリケイ酸塩と超微粒子状シリカを入れ50〜
100℃、好ましくは80〜100℃の温度で約１〜２時
間撹拌を行ない超微粒子状シリカをアルカリケイ
酸塩に完全に溶解させることにより得られる。溶
解時に本発明透明無機質被覆剤組成物の固形分
100重量部に対して水を600重量部を上限として存
在させることができ、水の添加により、超微粒子
状シリカの混合、溶解が容易となる。得られた透
明無機質被覆剤組成物は、加熱によりアルカリケ
イ酸塩及び超微粒子状シリカの各々または両者間
でシラノール基の縮合反応が進行しているため、
これを常温で長時間放置してもこれ以上殆んど反
応が進行することはない。このため、一般のアル
カリケイ酸塩系無機質塗料にみられるような可使
時間の制限がなく、長時間放置しても安定であ
る。
上記方法により得られた被覆剤組成物は、スプ
レー、デイツピング等の方法により金属製品表面
に塗布される。塗布時に、被覆剤組成物の固形分
100重量部に対して水を600重量部を上限として存
在させることができ、水の添加により、皮膜厚さ
の調整が容易となる。塗布された被覆剤組成物
は、200〜300℃の温度で10〜30分間加熱すること
により、上記超微粒子状シリカの加熱溶解後の残
存するシラノール基間で脱水縮合反応が進行し、
耐食性に優れた透明皮膜が形成される。加熱硬化
した透明皮膜は、１〜2μm程度の厚さで耐熱性、
耐薬品性等の効果を発揮することがきるが、使用
目的に応じて適宜厚さを調整しても良い。水の存
在量が固形分100重量部に対し600重量部を超える
と皮膜厚さが0.5μm以下となり、耐薬品性が劣る
ので好ましくない。
本発明組成物は、金属製品のほかに、セラミツ
クス、ガラス等にも適用することができる。金属
製品の具体例としては、器物や家具の把手等の家
庭用品、日用品、、高欄、ガードレール、標識な
どの土木関係品、屋根材、天井材、雨戸、シヤツ
ター、ドア、ドア把手、水栓金具、各種建築金
物、内、外装材などの建築関係品、各種電気部
品、ステレオ、オーデイオ部品、反射板などの電
気関係品、時計部品、時計枠、ライター部品、複
写機部品、コンピユーター部品などの精密機械、
器具関係品、自動車、二輪車、自転車等の各種部
品、焼結合金、着色金属製品、真鍮、銅などの有
色金属製品、表面処理鋼板等を挙げることがで
き、本発明組成物によりこれらの金属製品の変色
防止、防錆、耐湿性改善、表面硬度付与、耐熱付
与、耐化学性の向上などを図ることができる。ま
た、建築関係の内、外装品については、金属製品
以外に、スレート、かわらなどの窯業製品などに
も好適に適用できる。
発明の効果
本発明透明無機質被覆剤組成物により、金属製
品の外観を損なうことなく、耐熱性、耐酸性、耐
アルカリ性、耐沸騰水性、表面硬度の向上などの
効果を与えることのできる数ミクロンの透明皮膜
が得られる。また、該組成物は、長期間放置して
も安定性を保ち、更に皮膜形成のために高価な設
備を必要としない。
実施例
以下実施例を挙げて本発明を詳しく説明する。
実施例 １
アルカリケイ酸塩（水ガラス１号）100重量部
（固形分換算）に対して第１表に示す量の超微粒
子状シリカを加え更に水を加えた配合物を90〜
100℃の温度で反応容器中で加熱撹拌溶解し、本
発明透明無機質被覆剤組成物を得た。これを市販
の冷間圧延鋼板（JIS Ｇ−3141 SPCC）にデイ
ツピングにより塗布し、、250℃で30分間加熱硬化
して試験板を得た。尚、No.８の試験板は、超微粒
子状シリカを常温で水ガラス中に分散させて得ら
れた組成物を用いて作成したものである。得られ
た各試験板について各種試験を行なつた結果を第
１表に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a transparent inorganic coating composition and a method for forming a transparent inorganic film for coating metal products with rust prevention without impairing their appearance. Conventional Technologies and Problems Conventionally, research has been conducted on chromate treatment, plating, low-temperature firing inorganic paint, glass coating, ceramic spraying, CVD, PVD, etc. to prevent rust on metal products. However, at present, no metal rust prevention method has been found that requires low equipment costs and can provide a heat-resistant transparent film with a thickness of about 1 to 2 microns. Means for Solving the Problems As a result of various studies in view of the shortcomings of the prior art, the present inventor has developed a coating material with a specific composition at 200 to 300°C.
By heating and curing at a moderately low temperature, a transparent film of approximately 1 to 2 microns can be obtained that provides effects such as improving heat resistance, acid resistance, alkali resistance, boiling water resistance, and surface hardness without damaging the appearance of metal products. I found out that it can be done. That is, the present invention comprises 100 parts by weight of an alkali silicate selected from sodium silicate and potassium silicate (in terms of solid content) and 5 to 100 parts by weight of ultrafine silica.
100 parts by weight of an alkali silicate selected from sodium silicate and potassium silicate (in terms of solid content); The present invention relates to a method for forming a transparent inorganic film, characterized in that 5 to 100 parts by weight of ultrafine particulate silica is heated and melted at 50 to 100°C, and then applied to an object to be treated and cured by heating. In the present invention, as the alkali silicate, widely available liquid ones selected from sodium silicates and potassium silicates can be used. Examples include potassium silicate solution and the like.
These alkali silicates may be used alone or in combination of two or more. The ultrafine particulate silica used in the present invention has silanol groups (Si
-OH), is soluble in alkali silicates, and has an average particle diameter of approximately 40 mμ or less.
In the present invention, widely commercially available ultrafine particulate silica can be used, such as white carbon (wet product made from sodium silicate), ultrafine anhydrous silica (dry product made from silicon halide), etc. You can use what is called by its common name. In the present invention, the alkali silicate serves as the skeleton of the transparent film, and the ultrafine silica acts as a curing agent for the alkali silicate. In the present invention, 5 to 5 parts of ultrafine silica is added to 100 parts by weight of alkali silicate (in terms of solid content).
It is necessary to use 100 parts by weight. When the ultrafine particulate silica is less than 5 parts by weight, the heat resistance of the film is
Chemical resistance and boiling water resistance become insufficient, and if the amount exceeds 100 parts by weight, ultrafine particulate silica will no longer dissolve in the alkali silicate. The coating composition of the present invention is prepared by adding a predetermined amount of alkali silicate and ultrafine silica to a reaction vessel,
It is obtained by stirring at a temperature of 100°C, preferably 80-100°C for about 1-2 hours to completely dissolve the ultrafine particulate silica in the alkali silicate. Solid content of the transparent inorganic coating composition of the present invention when dissolved
Up to 600 parts by weight of water can be present per 100 parts by weight, and the addition of water facilitates mixing and dissolving the ultrafine particulate silica. In the obtained transparent inorganic coating composition, the condensation reaction of silanol groups progresses between each or both of the alkali silicate and ultrafine particulate silica due to heating.
Even if this is left at room temperature for a long time, the reaction will hardly proceed any further. Therefore, there is no limit on pot life as seen in general alkali silicate-based inorganic paints, and it is stable even if left for a long time. The coating composition obtained by the above method is applied to the surface of a metal product by a method such as spraying or dipping. During application, the solids content of the coating composition
Up to 600 parts by weight of water can be present per 100 parts by weight, and the addition of water facilitates adjustment of the film thickness. The applied coating composition is heated at a temperature of 200 to 300°C for 10 to 30 minutes, so that a dehydration condensation reaction proceeds between the silanol groups remaining after the ultrafine particulate silica is dissolved by heating.
A transparent film with excellent corrosion resistance is formed. The heat-cured transparent film has a thickness of about 1 to 2 μm and is heat resistant.
Although it can exhibit effects such as chemical resistance, the thickness may be adjusted as appropriate depending on the purpose of use. If the amount of water present exceeds 600 parts by weight based on 100 parts by weight of the solid content, the film thickness will be 0.5 μm or less and chemical resistance will be poor, which is not preferable. The composition of the present invention can be applied to ceramics, glass, etc. in addition to metal products. Specific examples of metal products include household goods and daily necessities such as handles for utensils and furniture, civil engineering products such as handrails, guardrails, and signs, roofing materials, ceiling materials, shutters, shutters, doors, door handles, and faucet fittings. , construction-related items such as various building hardware, interior and exterior materials, various electrical parts, stereo, audio parts, electrical items such as reflectors, precision parts such as clock parts, clock frames, lighter parts, copier parts, computer parts, etc. machine,
Examples include appliance-related products, various parts for automobiles, motorcycles, bicycles, etc., sintered alloys, colored metal products, colored metal products such as brass and copper, surface-treated steel sheets, etc., and these metal products can be improved by the composition of the present invention. It can prevent discoloration, prevent rust, improve moisture resistance, impart surface hardness, impart heat resistance, and improve chemical resistance. Furthermore, regarding exterior products related to architecture, in addition to metal products, the present invention can also be suitably applied to ceramic products such as slate and straw. Effects of the Invention The transparent inorganic coating composition of the present invention can provide effects such as improving heat resistance, acid resistance, alkali resistance, boiling water resistance, and surface hardness without impairing the appearance of metal products. A transparent film is obtained. Further, the composition maintains stability even when left for a long period of time, and does not require expensive equipment for forming a film. EXAMPLES The present invention will be explained in detail with reference to Examples below. Example 1 A mixture of 100 parts by weight (solid content equivalent) of alkali silicate (water glass No. 1), ultrafine particulate silica in the amount shown in Table 1, and water added to 90~
The mixture was heated and stirred and dissolved in a reaction vessel at a temperature of 100°C to obtain a transparent inorganic coating composition of the present invention. This was applied to a commercially available cold rolled steel plate (JIS G-3141 SPCC) by dipping, and heated and cured at 250°C for 30 minutes to obtain a test plate. Note that test plate No. 8 was prepared using a composition obtained by dispersing ultrafine silica particles in water glass at room temperature. Table 1 shows the results of various tests performed on each of the test plates obtained.
【表】【table】
【表】
実施例 ２
第２表に示す組成となる様に調合した配合物を
実施例１と同様にして溶解し、透明無機質被覆剤
組成物を得た。これを市販の冷間圧延鋼板（JIS
Ｇ−3141 SPCC）にデイツピングで塗布し、300
℃で10分間加熱硬化した後、実施例１と同様の試
験を行なつた。結果を第２表に示す。[Table] Example 2 A composition prepared to have the composition shown in Table 2 was dissolved in the same manner as in Example 1 to obtain a transparent inorganic coating composition. This is a commercially available cold rolled steel plate (JIS
G-3141 SPCC) applied with date ping, 300
After heating and curing at °C for 10 minutes, the same test as in Example 1 was conducted. The results are shown in Table 2.
【表】
実施例 ３
実施例１で得られた透明無機質被覆剤No.４
100gを水20gで希釈し、アルミニウム黒染め製品
にデイツピングで塗布し、220℃で30分間加熱硬
化した。皮膜厚さは約1μmであつた。
この皮膜を形成した製品及び無処理製品を
10wt％水酸化ナトリウム水溶液に室温で52時間
浸漬したところ、無処理品は、完全に黒染めが脱
色し、アルミニウム素地の露出が見られたが、処
理品は、何ら異常が認められなかつた。
実施例 ４
実施例１で用いたものと同じ冷間圧延鋼板、市
販のクロムナイズド鋼板（キヤンスーバー：新日
本製鉄(株)製）及び実施例２のNo.14の組成物を冷間
圧延鋼板にデイピング塗布し、300℃で加熱硬化
して得た試験板について第３表に示す試験を行な
つた。[Table] Example 3 Transparent inorganic coating material No. 4 obtained in Example 1
100g was diluted with 20g of water, applied to black-dyed aluminum products by dipping, and cured by heating at 220°C for 30 minutes. The film thickness was approximately 1 μm. Products with this film formed and untreated products
When immersed in a 10wt% sodium hydroxide aqueous solution at room temperature for 52 hours, the black dyeing of the untreated product was completely bleached and the aluminum substrate was exposed, but no abnormality was observed in the treated product. Example 4 The same cold-rolled steel sheet as that used in Example 1, a commercially available chromized steel sheet (can-suber: manufactured by Nippon Steel Corporation), and the composition No. 14 of Example 2 were used as cold-rolled steel sheets. The tests shown in Table 3 were conducted on test plates obtained by dipping coating and heating and curing at 300°C.
【表】
以上の結果から本発明により得られた皮膜が優
れた耐熱性、耐酸性、耐アルカリ性、耐沸騰水
性、耐腐食性を有することが明らかである。
試験例 １
珪酸ソーダ（組成SiO229.0％、Na2O9.5％）
244.0gと試薬LiOH・H2O20.0g、水623.0gを混合
し、これにフエロシリコン副生の活性珪酸微粉末
を113.0g、活性炭を0.5g加え、油浴中で常圧下
100℃で、３時間加熱し、溶解反応させた。
この反応液を熱時ヌツチエで濾過し、濾液を減
圧下ロータリーエバポレーターで濃縮して、殆ん
ど無色透明なリチウムを含有する珪酸ソーダ溶液
を得た。この溶液を比較品Ａとする。
水ガラス１号73重量部（固形分）、リチウムシ
リケート溶液27重量部（固形分）、超微粒子状シ
リカ（商標名ニツプシールＥ−200；日本シリカ
工業社製）28重量部及び水335重量部を用いて、
実施例１と同様にして被覆剤組成物を得た。これ
を比較品Ｂとする。
上記した比較品Ａ、Ｂ及び実施例１で用いたNo.
５の組成物（本発明品Ａ）の各々を用いて、下記
の方法により、塩水噴霧試験及び硬化限界膜厚の
測定を行なつた。結果を下記第４表に示す。
〇塩水噴霧試験
冷間圧延鋼板（JIS Ｇ−3141 SPCC）を試験
片として用い、各組成物をデイツピングにより硬
化膜厚が2μmとなるように塗布し、180℃×10分
及び250℃×10分の各条件で硬化させた。
これらの試料について、JIS Ｋ−5400に従つ
て、500時間塩水噴霧試験を行ない、赤錆発生率
を求めた。
〇硬化限界膜厚
上記冷間圧延鋼板を試験片として用い、エアー
スプレーガンにより、各組成物を１〜25μmにな
るように膜厚傾斜をつけて塗布し、180℃×10分
及び250℃×10分の各条件で硬化させた。硬化し
たときに、塗膜に亀裂、白化、フクレなどが生じ
る膜厚を硬化限界膜厚として求めた。[Table] From the above results, it is clear that the film obtained by the present invention has excellent heat resistance, acid resistance, alkali resistance, boiling water resistance, and corrosion resistance. Test example 1 Sodium silicate (composition SiO 2 29.0%, Na 2 O 9.5%)
244.0g, 20.0g of reagent LiOH・H 2 O, and 623.0g of water were mixed, 113.0g of activated silicic acid fine powder as a by-product of ferrosilicon and 0.5g of activated carbon were added, and the mixture was heated in an oil bath under normal pressure.
The mixture was heated at 100°C for 3 hours to cause a dissolution reaction. The reaction solution was filtered through a hot filter, and the filtrate was concentrated using a rotary evaporator under reduced pressure to obtain an almost colorless and transparent sodium silicate solution containing lithium. This solution is referred to as Comparative Product A. Water Glass No. 1 73 parts by weight (solid content), 27 parts by weight of lithium silicate solution (solid content), 28 parts by weight of ultrafine particulate silica (trade name Nip Seal E-200; manufactured by Nippon Silica Kogyo Co., Ltd.), and 335 parts by weight of water. make use of,
A coating composition was obtained in the same manner as in Example 1. This is referred to as comparative product B. Comparative products A and B mentioned above and No. used in Example 1.
Using each of the compositions No. 5 (product A of the present invention), a salt spray test and measurement of the curing critical film thickness were conducted by the following method. The results are shown in Table 4 below. 〇Salt spray test Using a cold rolled steel plate (JIS G-3141 SPCC) as a test piece, each composition was applied by dipping to a cured film thickness of 2 μm, and the test was conducted at 180°C for 10 minutes and at 250°C for 10 minutes. It was cured under the following conditions. These samples were subjected to a salt spray test for 500 hours in accordance with JIS K-5400, and the incidence of red rust was determined. 〇 Curing limit film thickness Using the above cold rolled steel plate as a test piece, apply each composition with an air spray gun with a film thickness gradient of 1 to 25 μm, 180°C x 10 minutes and 250°C x It was cured under each condition for 10 minutes. The film thickness at which cracks, whitening, blisters, etc. occur in the coating film when cured was determined as the curing limit film thickness.
【表】
以上の結果から判るように、水酸化リチウムを
用いて得られる比較品Ａにより形成される塗膜
は、耐食性が劣り、硬化限界膜厚も非常に薄くな
つた。また、リチウムシリケート溶液を用いて得
られる比較品Ｂについても、本発明品Ａと比べる
と、耐食性及び硬化限界膜厚のいずれも劣るもの
であつた。
試験例 ２
試験例１で用いた比較品A100重量部に、顔料
としてTiO210重量部及びα−Al2O315重量部（比
較品Ａの固形分100重量部を基準とした場合には、
TiO239.2重量部及びα−Al2O358.8重量部）を加
えて、ペブルミルで12時間分散させて無機質塗料
組成物を得た。この組成物を比較塗料１とする。
また、上記比較塗料１に、硬化剤として、
ZnO15重量部及びAlPO42重量部を加えて１時間
分散させた。これを比較塗料２とする。
実施例１で用いたNo.５の組成物100重量部（固
形分）に顔料としてTiO239.2重量部及びα−
Al2O358.8重量部を加えて、ペブルミルで12時間
分散させた。これを塗料組成物Ａとする。
上記各塗料に水を添加してスプレー可能な粘度
とし、試験例１と同じ鋼板に硬化膜厚が約20μm
となるようにスプレー塗装し、250℃で10分間硬
化させた。得られた各塗板を沸騰水中に５時間浸
漬して、耐沸騰水性を求めた。結果を下記第５表
に示す。評価方法は次の通りである。
〇外観目視 耐沸騰水試験後の塗膜表面を目視観
察する。
〇塗膜表面状態 耐沸騰水試験後、塗膜表面を指
で擦り、塗料の指への付着を調べた。
〇セロテープ引張りテスト 耐沸騰水試験後、塗
膜表面にセロテープを付着させ、引つ張つてセロ
テープを剥がし、鋼板からの塗膜剥離を調べた。[Table] As can be seen from the above results, the coating film formed by Comparative Product A obtained using lithium hydroxide had poor corrosion resistance and the curing limit film thickness was extremely thin. Comparative product B obtained using a lithium silicate solution was also inferior to product A of the present invention in both corrosion resistance and curing limit film thickness. Test Example 2 100 parts by weight of Comparative Product A used in Test Example 1, 10 parts by weight of TiO 2 and 15 parts by weight of α-Al 2 O 3 as pigments (based on 100 parts by weight of solid content of Comparative Product A) ,
39.2 parts by weight of TiO 2 and 58.8 parts by weight of α-Al 2 O 3 ) were added and dispersed in a pebble mill for 12 hours to obtain an inorganic coating composition. This composition is referred to as Comparative Paint 1. In addition, as a curing agent, in the comparative paint 1,
15 parts by weight of ZnO and 2 parts by weight of AlPO 4 were added and dispersed for 1 hour. This is designated as comparative paint 2. To 100 parts by weight (solid content) of composition No. 5 used in Example 1, 39.2 parts by weight of TiO 2 and α-
58.8 parts by weight of Al 2 O 3 was added and dispersed in a pebble mill for 12 hours. This is referred to as coating composition A. Water was added to each of the above paints to achieve a sprayable viscosity, and a cured film thickness of approximately 20 μm was applied to the same steel plate as in Test Example 1.
It was spray painted and cured at 250℃ for 10 minutes. Each obtained coated plate was immersed in boiling water for 5 hours to determine its boiling water resistance. The results are shown in Table 5 below. The evaluation method is as follows. 〇Visual appearance Visually observe the coating surface after the boiling water resistance test. 〇 Paint film surface condition After the boiling water resistance test, the paint film surface was rubbed with a finger to examine whether the paint adhered to the finger. 〇 Sellotape tensile test After the boiling water resistance test, Sellotape was attached to the surface of the coating film, and the Sellotape was peeled off by pulling to examine the peeling of the coating film from the steel plate.
【表】
以上の試験結果から判る様に、硬化剤を配合し
ていない比較塗料１は、耐水性が非常に劣るもの
である。これに対して、本発明の組成物に、比較
塗料１と同様に顔料を配合して得た塗料組成物Ａ
は、硬化剤を配合することなく、充分な耐水性を
有する硬化塗膜を形成することができる。
試験例 ３
SiO230〜31％、Na2O0.55〜0.65％、PH９〜10
（25℃において）、粒子径７〜９（mμ）、粘度10以
下（cp、25℃において）、比重1.20〜1.22（25℃に
おいて）のコロイドシリカ50重量部と水ガラス１
号50重量部を25℃で撹拌混合して、比較品Ｃを得
た。
一方、上記コロイドシリカ50重量部と水ガラス
１号50重量部を混合し、90〜100℃で１時間加熱
し、溶解反応させて、本発明品Ｂを得た。
比較品Ｃ及び本発明品Ｂの各々をよく脱脂した
冷間圧延鋼板にデイツピングにより塗布し、250
℃で10分間硬化させた後、皮膜特性を調べた。試
験方法は次の通りである。
試験方法
耐熱性：電気炉中に500℃×１時間放置したのち
の皮膜表面を目視観察する。
耐酸性：10wt％硫酸水溶液に常温５時間浸漬後
の皮膜表面を目視観察する。
耐アルカリ性：10wt％水酸化ナトリウムに80℃
×５時間浸漬後の皮膜表面を目視観察する。
耐沸騰水試験：沸騰水中に10時間浸漬後の皮膜表
面を目視観察する。
結果を下記第６表に示す。[Table] As can be seen from the above test results, Comparative Paint 1, which does not contain a curing agent, has very poor water resistance. On the other hand, paint composition A obtained by blending a pigment into the composition of the present invention in the same manner as comparative paint 1
can form a cured coating film with sufficient water resistance without adding a curing agent. Test example 3 SiO 2 30-31%, Na 2 O 0.55-0.65%, PH 9-10
50 parts by weight of colloidal silica with a particle size of 7 to 9 (mμ), a viscosity of 10 or less (cp, at 25 °C), and a specific gravity of 1.20 to 1.22 (at 25 °C) and 1 part of water glass
Comparative product C was obtained by stirring and mixing 50 parts by weight of No. 1 at 25°C. On the other hand, 50 parts by weight of the above colloidal silica and 50 parts by weight of water glass No. 1 were mixed and heated at 90 to 100°C for 1 hour to cause a dissolution reaction, thereby obtaining product B of the present invention. Each of Comparative Product C and Inventive Product B was coated on a well-degreased cold-rolled steel plate by dipping, and
After curing for 10 minutes at °C, the film properties were examined. The test method is as follows. Test method Heat resistance: Visually observe the surface of the film after leaving it in an electric furnace at 500°C for 1 hour. Acid resistance: Visually observe the surface of the film after immersing it in a 10wt% sulfuric acid aqueous solution for 5 hours at room temperature. Alkali resistance: 80℃ to 10wt% sodium hydroxide
* Visually observe the surface of the film after immersion for 5 hours. Boiling water resistance test: Visually observe the surface of the film after immersing it in boiling water for 10 hours. The results are shown in Table 6 below.
【表】
以上の結果から判るように、コロイドシリカ及
び水ガラスを常温で混合して得られる組成物から
形成される皮膜は、各成分を加温溶解させて得ら
れる組成物から形成される皮膜と比べて、皮膜外
観、耐熱性、耐酸性、耐アルカリ性、耐沸騰水性
のいずれにも劣るものであつた。
試験例 ４
上記した本発明品Ｂ及び比較品Ｃを、密封容器
中で14日間常温放置したのち、経時変化を調査し
た。結果を下記第７表に示す。[Table] As can be seen from the above results, a film formed from a composition obtained by mixing colloidal silica and water glass at room temperature is different from a film formed from a composition obtained by heating and dissolving each component. The film was inferior in appearance, heat resistance, acid resistance, alkali resistance, and boiling water resistance. Test Example 4 The above-mentioned product B of the present invention and comparative product C were left at room temperature in a sealed container for 14 days, and then their changes over time were investigated. The results are shown in Table 7 below.
【表】【table】
Claims (1)
ら選ばれたアルカリケイ酸塩（固形分換算）100
重量部と超微粒子状シリカ５〜100重量部とを50
〜100℃で加熱溶解した生成物からなる透明無機
質被覆剤組成物。 ２ ナトリウムケイ酸塩及びカリウムケイ酸塩か
ら選ばれたアルカリケイ酸塩（固形分換算）100
重量部並びに超微粒子状シリカ５〜100重量部を
50〜100℃で加熱溶解した後、被処理物に塗布し
加熱硬化させることを特徴とする透明無機質皮膜
形成方法。[Claims] 1. Alkali silicate selected from sodium silicate and potassium silicate (solid content equivalent) 100
50 parts by weight and 5 to 100 parts by weight of ultrafine particulate silica
A transparent inorganic coating composition consisting of a product heated and dissolved at ~100°C. 2 Alkali silicate selected from sodium silicate and potassium silicate (solid content equivalent) 100
parts by weight and 5 to 100 parts by weight of ultrafine particulate silica.
A method for forming a transparent inorganic film, which comprises heating and melting at 50 to 100°C, applying the material to the object to be treated, and heating and curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17991584A JPS6157654A (en) | 1984-08-29 | 1984-08-29 | Transparent inorganic coating composition and method for forming transparent inorganic coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17991584A JPS6157654A (en) | 1984-08-29 | 1984-08-29 | Transparent inorganic coating composition and method for forming transparent inorganic coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6157654A JPS6157654A (en) | 1986-03-24 |
| JPH0532431B2 true JPH0532431B2 (en) | 1993-05-17 |
Family
ID=16074138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17991584A Granted JPS6157654A (en) | 1984-08-29 | 1984-08-29 | Transparent inorganic coating composition and method for forming transparent inorganic coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6157654A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143979A (en) * | 1995-11-29 | 1997-06-03 | Furootechno Kk | Ground hardening material injecting device |
| US8937689B2 (en) | 2009-03-02 | 2015-01-20 | Apple Inc. | Techniques for strengthening glass covers for portable electronic devices |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0794619B2 (en) * | 1986-05-26 | 1995-10-11 | 奥野製薬工業株式会社 | Inorganic coating composition |
| JPH06228722A (en) * | 1992-12-18 | 1994-08-16 | Praxair St Technol Inc | Melting resistant metal eroding sealing material and production thereof |
| US6322687B1 (en) | 1997-01-31 | 2001-11-27 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
| US20100218855A1 (en) * | 2007-10-05 | 2010-09-02 | Duncan Roy Coupland | Metal protection |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136297A (en) * | 1980-03-27 | 1981-10-24 | Nippon Oil & Fats Co Ltd | Coated arc electrode |
| JPS5742527A (en) * | 1980-08-25 | 1982-03-10 | Central Glass Co Ltd | Preparation of lithium-containing high molar ratio sodium silicate |
-
1984
- 1984-08-29 JP JP17991584A patent/JPS6157654A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136297A (en) * | 1980-03-27 | 1981-10-24 | Nippon Oil & Fats Co Ltd | Coated arc electrode |
| JPS5742527A (en) * | 1980-08-25 | 1982-03-10 | Central Glass Co Ltd | Preparation of lithium-containing high molar ratio sodium silicate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143979A (en) * | 1995-11-29 | 1997-06-03 | Furootechno Kk | Ground hardening material injecting device |
| US8937689B2 (en) | 2009-03-02 | 2015-01-20 | Apple Inc. | Techniques for strengthening glass covers for portable electronic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6157654A (en) | 1986-03-24 |
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