JP2953152B2 - Heat and stain resistant paint and heat and stain resistant coating - Google Patents
Heat and stain resistant paint and heat and stain resistant coatingInfo
- Publication number
- JP2953152B2 JP2953152B2 JP31354191A JP31354191A JP2953152B2 JP 2953152 B2 JP2953152 B2 JP 2953152B2 JP 31354191 A JP31354191 A JP 31354191A JP 31354191 A JP31354191 A JP 31354191A JP 2953152 B2 JP2953152 B2 JP 2953152B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resistant
- resin
- coating film
- stain resistant
- 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 - Fee Related
Links
Landscapes
- Frying-Pans Or Fryers (AREA)
- Paints Or Removers (AREA)
- Cookers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属等の基材表面に塗
布し、焼付けることにより、撥水性等の特性が良好な
上、高硬度で耐熱性及び基材との密着性に優れた耐熱防
汚性塗膜を与え、このため加熱調理器具等の加工に有用
な耐熱防汚性塗料及びこの塗料による耐熱防汚性塗膜に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent properties such as water repellency by coating and baking on the surface of a base material such as metal, and has high hardness, excellent heat resistance and excellent adhesion to the base material. The present invention relates to a heat-resistant and soil-resistant paint which is useful for processing cooked utensils, etc.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
肉、魚等を料理する加熱調理器具（フライパン、ホット
プレート等）には油汚れを防止する目的でフッ素樹脂加
工が施されている。しかしながら、フッ素樹脂塗膜は撥
水性、撥油性が良好で防汚性にも優れる反面、耐熱性的
には２５０℃程度が限界である上、塗膜硬度に欠けるた
め、長期間の使用で塗膜がキズつき剥離してしまうとい
う欠点があった。2. Description of the Related Art
Heat cooking utensils (frying pans, hot plates, and the like) for cooking meat, fish, and the like are subjected to fluororesin processing for the purpose of preventing oil stains. However, fluororesin coatings have good water repellency and oil repellency and are excellent in antifouling properties, but have a limit of about 250 ° C in terms of heat resistance and lack the hardness of the coatings. There is a disadvantage that the film is scratched and peeled off.
【０００３】従って、良好な撥水性、撥油性、防汚性を
有し、かつ耐熱性及び塗膜硬度の面でも満足できる耐熱
防汚性塗膜を与える耐熱防汚性塗料の開発が望まれてい
た。[0003] Therefore, there is a demand for the development of a heat-resistant and stain-resistant paint which has good water repellency, oil repellency and stain resistance, and which gives a heat-resistant and stain-resistant paint film having satisfactory heat resistance and coating film hardness. I was
【０００４】[0004]
【課題を解決するための手段及び作用】本発明者は上記
事情に鑑み鋭意検討を重ねた結果、ポリカルボシラン樹
脂及びポリシラザン樹脂から選ばれる樹脂と、シラザン
化合物と、無機フィラーと、フッ素樹脂とを有機溶剤に
分散・配合したフッ素樹脂系塗料が、金属等の基材の表
面に塗布し、焼付けると撥水性、更に撥油性及び防汚性
が良好であると共に、塗膜硬度が硬く、かつ耐熱性に優
れ、高温で長時間加熱してもクラックや剥離が生じる難
く、しかも基材との密着性に優れた耐熱防汚性塗膜を与
えること、それ故、耐熱防汚性塗料として加熱器具等の
フッ素樹脂加工に有効に使用できることを知見し、本発
明をなすに至ったものである。The present inventors have made intensive studies in view of the above circumstances, and as a result, have found that a resin selected from a polycarbosilane resin and a polysilazane resin, a silazane compound, an inorganic filler, and a fluororesin. Fluororesin-based paint dispersed and blended in an organic solvent is applied to the surface of a base material such as metal, and when baked, the water repellency, oil repellency and antifouling properties are good, and the coating film hardness is hard, It is excellent in heat resistance, hardly causes cracks and peeling even when heated at high temperature for a long time, and gives a heat resistant antifouling coating film with excellent adhesion to the substrate, and therefore as a heat resistant antifouling paint The present inventors have found that they can be effectively used for processing a fluororesin such as a heating device, and have accomplished the present invention.
【０００５】以下、本発明につき更に詳述すると、本発
明の耐熱防汚性塗料は、ポリカルボシラン樹脂及びポリ
シラザン樹脂から選ばれる樹脂と、シラザン化合物、無
機フィラー及びフッ素樹脂を有機溶媒に分散・配合して
なるものである。Hereinafter, the present invention will be described in more detail. The heat and stain resistant coating composition of the present invention is obtained by dispersing a resin selected from polycarbosilane resin and polysilazane resin, a silazane compound, an inorganic filler and a fluororesin in an organic solvent. It is made by blending.
【０００６】ここで、ポリカルボシラン樹脂としては、
特公昭５７−２６５２７号公報に記載のもの、例えばジ
メチルジクロロシランと金属ナトリウムを反応させてポ
リシランを得た後、このポリシランを熱分解重合する等
の方法で合成することができるものが好適に使用され
る。Here, as the polycarbosilane resin,
JP-B-57-26527, for example, those which can be synthesized by a method of reacting dimethyldichlorosilane with metallic sodium to obtain a polysilane and then thermally decomposing and polymerizing the polysilane are preferably used. Is done.
【０００７】また、ポリシラザン樹脂としては本出願人
が特開昭６２−２９０７３０号公報、特開昭６３−１１
７０３７号公報、特開昭６３−１９３９００号公報、特
開昭６３−２１０１３３号公報、特開平１−１５３７３
０号公報、特開平３−５０２３８号公報、特開平３−８
１３３０号公報、特開平３−１９０９３２号公報、特開
平３−１９０９３３号公報等に提案したポリシラザン樹
脂が好ましく用いられる。As the polysilazane resin, the present applicant has disclosed in Japanese Patent Application Laid-Open Nos. 62-290730 and 63-11
7037, JP-A-63-193900, JP-A-63-210133, JP-A-1-15373
0, JP-A-3-50238, JP-A-3-8
The polysilazane resins proposed in JP-A-1330, JP-A-3-190932, JP-A-3-190933 and the like are preferably used.
【０００８】更に、上記樹脂の重合度は塗膜性能、特に
塗膜のクラック、剥離等に影響を及ぼすので、ポリカル
ボシラン樹脂はその数平均分子量が５００〜５０００、
特に６００〜２０００、より好ましくは６５０〜１２０
０となるような重合度のものが好ましい。また、ポリシ
ラザン樹脂の数平均分子量は、４００〜３０００、好ま
しくは５００〜２０００、より好ましくは５５０〜１２
００程度のものが好ましい。数平均分子量が上記値に満
たないと、塗料として使用する場合、基材との密着性が
悪くなったり、塗膜硬度が低くなったりする場合があ
り、逆に上記値を超えると塗膜にクラックが生じ、その
後の焼付け段階で塗膜が剥離するという問題が生じる場
合がある。Further, since the degree of polymerization of the above resin affects the performance of the coating film, particularly cracking and peeling of the coating film, the polycarbosilane resin has a number average molecular weight of 500 to 5,000,
Especially 600-2000, more preferably 650-120.
Those having a degree of polymerization of 0 are preferred. The number average molecular weight of the polysilazane resin is 400 to 3,000, preferably 500 to 2,000, and more preferably 550 to 2,000.
About 00 is preferable. If the number average molecular weight is less than the above value, when used as a coating, the adhesion to the substrate may be poor, or the coating film hardness may be low. There may be a problem that cracks occur and the coating film peels off in the subsequent baking stage.
【０００９】本発明では、第一必須成分としてこれらポ
リカルボシラン樹脂及びポリシラザン樹脂の１種を単独
で用いても２種を混合して使用してもよく、またその配
合量は全結合成分（有機溶剤を除いた成分）に対して１
０〜５０％（重量％、以下同様）、特に１５〜３５％が
好ましい。配合量が１０％に満たないと十分な密着性、
耐熱性、塗膜硬度が得られない場合があり、５０％を超
えると焼付け後の塗膜にクラックを生じる場合がある。In the present invention, one of these polycarbosilane resins and polysilazane resins may be used alone or as a mixture of two as the first essential components, and the amount of the polycarbosilane resin and the polysilazane resin may be mixed with all the binding components ( 1 for the components excluding the organic solvent)
0 to 50% (% by weight, hereinafter the same), particularly preferably 15 to 35%. If the blending amount is less than 10%, sufficient adhesion,
Heat resistance and coating film hardness may not be obtained in some cases. If it exceeds 50%, cracks may occur in the coating film after baking.
【００１０】次に第二必須成分のシラザン化合物として
は、例えばテトラメチルジシラザン、ヘキサメチルシク
ロトリシラザン，オクタメチルシクロテトラシラザン等
が好適に使用され、これらのうちの１種を単独で又は２
種以上を併用して用いることができる。シラザン化合物
の配合量は全結合成分に対して５〜２０％、特に８〜１
５％とすることが好ましく、５％未満では塗膜の密着性
が低下する場合があり、２０％を超えると塗膜の硬度が
低下する場合がある。Next, as the silazane compound as the second essential component, for example, tetramethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane and the like are suitably used.
More than one species can be used in combination. The compounding amount of the silazane compound is 5 to 20% with respect to all the binding components, particularly 8 to 1%.
The content is preferably 5%, and if it is less than 5%, the adhesion of the coating film may decrease, and if it exceeds 20%, the hardness of the coating film may decrease.
【００１１】更に、第三必須成分の無機フィラーとして
は、例えばＡｌ2Ｏ3，ＳｉＯ2，ＴｉＯ2，Ｆｅ2Ｏ3，Ｍ
ｇＯ，ＭｎＯ，Ｃｏ2Ｏ3，ＮｉＯ，ＺｒＯ2，ＺｎＯ，
ＣｕＯ，Ｓｉ3Ｎ4，ＳｉＣ，ＢＮ，ガラスフレーク等が
例示され、これらは１種を単独で又は２種以上を混合し
て用いることができる。これら無機フィラーの平均粒径
は特に限定されないが、０．１〜３０μ、特に１〜５μ
程度のものを用いることが好ましい。Further, as the inorganic filler as the third essential component, for example, Al 2 O 3 , SiO 2 , TiO 2 , Fe 2 O 3 , M
gO, MnO, Co 2 O 3 , NiO, ZrO 2 , ZnO,
Examples thereof include CuO, Si 3 N 4 , SiC, BN, and glass flakes, and these can be used alone or as a mixture of two or more. The average particle size of these inorganic fillers is not particularly limited, but is 0.1 to 30 μm, particularly 1 to 5 μm.
It is preferable to use a material having a size of about.
【００１２】上記無機フィラーの配合量は全結合剤成分
（有機溶剤は除く）に対して、５〜５０％、特に１０〜
３０％が好適であり、５％に満たないと塗膜硬度が十分
でなくなる場合があり、５０％を超えると塗膜の撥水
性、撥油性の性能に欠ける場合があるので上記範囲とす
るのがよい。The amount of the inorganic filler is 5 to 50%, preferably 10 to 50% based on all the binder components (excluding the organic solvent).
If it is less than 5%, the hardness of the coating film may be insufficient, and if it exceeds 50%, the water repellency and oil repellency of the coating film may be lacking. Is good.
【００１３】更に、本発明では第四必須成分としてフッ
素樹脂を用いる。この場合、フッ素樹脂としてはテトラ
フロロエチレン樹脂、パーフロロアルコキシ樹脂、フッ
化エチレンプロピレン樹脂、フッ化エチレンプロピレン
エーテル樹脂等が挙げられ、これらは単独で又は２種以
上を混合して用いることが可能である。In the present invention, a fluorine resin is used as the fourth essential component. In this case, examples of the fluororesin include tetrafluoroethylene resin, perfluoroalkoxy resin, fluorinated ethylene propylene resin, fluorinated ethylene propylene ether resin and the like, and these can be used alone or in combination of two or more. It is.
【００１４】また、フッ素樹脂の配合量は全結合剤成分
（有機溶剤は除く）に対して５〜７０％、特に３０〜５
５％が好ましく、５％未満では十分な撥水性、撥油性が
得られない場合があり、７０％を超えると塗膜の硬度が
低下する場合がある。The content of the fluororesin is 5 to 70% with respect to all the binder components (excluding the organic solvent), especially 30 to 5%.
If it is less than 5%, sufficient water repellency and oil repellency may not be obtained, and if it exceeds 70%, the hardness of the coating film may be reduced.
【００１５】本発明は上記した４つの必須結合成分を含
有してなるが、これら結合成分以外の添加物として一般
の塗料に使用される無機顔料等の任意成分を本発明の効
果を妨げない範囲で配合することもできる。The present invention contains the above-mentioned four essential binding components. However, as an additive other than these binding components, an optional component such as an inorganic pigment used in general paints is used as long as the effect of the present invention is not impaired. Can also be blended.
【００１６】次いで、前記結合剤を分散させる有機溶剤
としては、例えばトルエン、キシレン、Ｎ−メチル−２
−ピロリドン等が挙げられる。有機溶剤の使用量は別に
限定されないが、全結合剤成分に対して１０〜４００％
が通常である。Next, as the organic solvent in which the binder is dispersed, for example, toluene, xylene, N-methyl-2
-Pyrrolidone and the like. The amount of the organic solvent used is not particularly limited, but is 10 to 400% with respect to all the binder components.
Is normal.
【００１７】上述したような本発明の耐熱防汚性塗料
は、公知の方法例えば塩化メチレン、トリクロルエチレ
ン等の溶剤で脱脂処理した金属基材等の基材表面にスプ
レーコート，フローコート，ロールコート，刷毛等の方
法で塗布した後、焼付けを行うことにより、耐熱防汚性
塗膜を形成することが可能である。The above-mentioned heat-resistant and antifouling paint of the present invention can be spray-coated, flow-coated, roll-coated on the surface of a metal substrate or the like which has been degreased with a solvent such as methylene chloride or trichloroethylene. It is possible to form a heat-resistant and stain-resistant coating film by performing baking after coating by a method such as brushing.
【００１８】この場合金属基材に特に制限はなく、例え
ばアルミニウム、スチール等が使用できる。In this case, the metal substrate is not particularly limited, and for example, aluminum, steel and the like can be used.
【００１９】また、耐熱防汚性塗料を金属基材表面に塗
布する際は、塗膜の厚さが１０〜１００μｍ、特に２０
〜５０μｍの範囲となるように塗布量を調整することが
好ましい。When the heat-resistant and antifouling paint is applied to the surface of the metal substrate, the thickness of the paint film is 10 to 100 μm, especially 20 to 100 μm.
It is preferable to adjust the amount of application so as to be in the range of 50 μm to 50 μm.
【００２０】次に、焼付けは空気中で２００℃以上の温
度で１５〜６０分程度行うのが望ましく、温度が２００
℃より低いと塗膜の強度が低く、硬度が十分でなくなる
場合かある。なお、焼付けの条件としては、特に３５０
〜４００℃程度の温度で１５分〜６０分の条件で実施す
るのが好ましい。４００℃以上では塗料中のフッ素樹脂
の分解が起こるため撥水性、撥油性能が低下するので避
けることが好ましい。また、必要により不活性ガス雰囲
気や他の雰囲気で焼付けを行うこともできる。Next, baking is preferably performed in air at a temperature of 200 ° C. or more for about 15 to 60 minutes.
If the temperature is lower than ° C, the strength of the coating film may be low and the hardness may not be sufficient. In addition, the conditions for baking are, in particular, 350
It is preferable to carry out at a temperature of about 400 ° C. for about 15 minutes to 60 minutes. If the temperature is 400 ° C. or higher, the fluororesin in the coating material is decomposed, so that the water repellency and oil repellency are reduced. Further, if necessary, baking can be performed in an inert gas atmosphere or another atmosphere.
【００２１】[0021]
【発明の効果】本発明の耐熱防汚性塗料は、金属等の基
材の表面に塗布し、焼付けることにより、撥水性、更に
は撥油性及び防汚性が良好な上、高硬度で４００℃程度
の温度にも耐えて耐熱性に優れ、かつ基材との密着性の
良い耐熱防汚性塗膜を与える。従って、本発明は塗料は
加熱調理器具等のフッ素樹脂加工に有効である。The heat and stain resistant paint of the present invention has good water repellency, oil repellency and antifouling properties, and has high hardness by being applied to the surface of a substrate such as a metal and baked. A heat-resistant and stain-resistant coating film that withstands a temperature of about 400 ° C., has excellent heat resistance, and has good adhesion to a substrate. Therefore, in the present invention, the paint is effective for processing a fluororesin such as a heating cooker.
【００２２】[0022]
【実施例】以下、参考例、実施例及び比較例を示し本発
明を具体的に説明するが、本発明は下記の実施例に制限
されるものではない。EXAMPLES Hereinafter, the present invention will be described in detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２３】〔参考例１〕５リットルの三口フラスコに
無水キシレン２．５リットルと金属ナトリウム４００ｇ
を入れ、窒素気流下でキシレンの沸点まで加熱して金属
ナトリウムを溶解、分散させた後、ジメチルジクロロシ
ラン１リットルを１時間かけて滴下した。滴下終了後、
加熱還流して反応を完結させた。次に、生成した沈殿物
を濾過した後、メタノールにて洗浄し、更に水洗、乾燥
して白色粉末のポリシラン４００ｇを得た。次いで、得
られたポリシラン４００ｇをガス導入管、撹拌器、冷却
器及び留出管を装備したオートクレーブに仕込み、５ｋ
ｇ／ｃｍ2Ｇの加圧下、４５０℃にて加熱重合してポリ
カルボシランＡを得た。このものは、数平均分子量（ベ
ンゼンモル凝固点降下法）１２５０であった。Reference Example 1 2.5 liters of anhydrous xylene and 400 g of metallic sodium were placed in a 5 liter three-necked flask.
And heated to the boiling point of xylene under a nitrogen stream to dissolve and disperse the metallic sodium, and then 1 liter of dimethyldichlorosilane was added dropwise over 1 hour. After dropping,
The reaction was completed by heating to reflux. Next, the produced precipitate was filtered, washed with methanol, further washed with water and dried to obtain 400 g of polysilane as white powder. Next, 400 g of the obtained polysilane was charged into an autoclave equipped with a gas inlet tube, a stirrer, a cooler, and a distilling tube, and 5 k
Polycarbosilane A was obtained by heat polymerization at 450 ° C. under a pressure of g / cm 2 G. This had a number average molecular weight (benzene molar freezing point depression method) of 1250.
【００２４】〔参考例２〕参考例１と同様な方法でポリ
シランをオートクレーブに仕込み、５ｋｇ／ｃｍ2Ｇの
加圧下で４３０℃にて加熱重合して数平均分子量９００
のポリカルボシランＢを得た。REFERENCE EXAMPLE 2 Polysilane was charged into an autoclave in the same manner as in Reference Example 1, and was heated and polymerized at 430 ° C. under a pressure of 5 kg / cm 2 G to give a number average molecular weight of 900.
Of polycarbosilane B was obtained.
【００２５】〔参考例３〕撹拌機、温度計、ＮＨ3導入
管、水冷コンデンサーを装備し乾燥した１リットルの４
つ口フラスコにヘキサン８５０ｍｌを仕込んだ後、メチ
ルジクロロシラン４０．３ｇ、メチルトリクロロシラン
７．５ｇ、ジメチルジクロロシラン１２．９ｇを加え
た。更に、過剰の気体状アンモニアを１２リットル／Ｈ
ｒの速度で４時間この溶液に加えた。次いで、反応混合
物を５０℃まで温めた後、室温に戻した。副生した塩化
アンモニウムを濾過により除去し、ヘキサンを減圧下で
留去して液体状のシラザンオリゴマー２７．３ｇを得
た。REFERENCE EXAMPLE 3 A 1 liter dried 4 equipped with a stirrer, a thermometer, an NH 3 introduction pipe, and a water-cooled condenser.
After 850 ml of hexane was charged into a one-necked flask, 40.3 g of methyldichlorosilane, 7.5 g of methyltrichlorosilane, and 12.9 g of dimethyldichlorosilane were added. In addition, excess gaseous ammonia is removed at 12 liters / H
The solution was added at a rate of r for 4 hours. The reaction mixture was then warmed to 50 ° C. and then returned to room temperature. By-product ammonium chloride was removed by filtration, and hexane was distilled off under reduced pressure to obtain 27.3 g of a liquid silazane oligomer.
【００２６】次に、３００ｍｌのフラスコに撹拌機、温
度計、滴下ロート、冷却器を装備した。これに水素化カ
リウム０．２ｇ及びテトラヒドロフラン１２５ｍｌを注
入し、室温下にて滴下ロートよりテトラヒドロフラン７
５ｍｌに溶解した液状のシラザンオリゴマー２７．３ｇ
を加えた。この滴下の間に多量のガスの発生が認められ
た。更に温度を上げ６０℃にて２時間反応させて反応を
完結させた。次いで、反応液を冷却した後、ヨウ化メチ
ルを２．５ｇ加えるとＫＩの白色沈殿が生成した。大部
分のテトラヒドロフランを除去し、残留する白色スラリ
ーにヘキサン８０ｍｌを加えた。この混合物を濾過し、
濾液から減圧下（１ｍｍＨｇ）、７０℃にてヘキサンを
除去すると、固体状のポリシラザンＣ２５．３ｇが得ら
れた。このものは、数平均分子量１２００であった。Next, a 300 ml flask was equipped with a stirrer, thermometer, dropping funnel and cooler. 0.2 g of potassium hydride and 125 ml of tetrahydrofuran were poured into the mixture, and tetrahydrofuran 7 was added through a dropping funnel at room temperature.
27.3 g of liquid silazane oligomer dissolved in 5 ml
Was added. A large amount of gas was generated during this dropping. The temperature was further raised and reacted at 60 ° C. for 2 hours to complete the reaction. Next, after cooling the reaction solution, 2.5 g of methyl iodide was added, and a white precipitate of KI was formed. Most of the tetrahydrofuran was removed and 80 ml of hexane was added to the remaining white slurry. The mixture is filtered,
The hexane was removed from the filtrate at 70 ° C. under reduced pressure (1 mmHg) to obtain 25.3 g of solid polysilazane C. This had a number average molecular weight of 1200.
【００２７】〔参考例４〕撹拌機、温度計、ガス導入
管、コンデンサーを装備し、乾燥した２リットルの４つ
口フラスコにトルエン１．５リットルを仕込み、更にメ
チルトリクロロシラン１４７９．５ｇ（１ｍｏｌ）及び
トリメチルクロロシラン２６１ｇ（２．４ｍｏｌ）を仕
込んだ。次いで、室温下でアンモニアガスを９０リット
ル／分の速度で３時間この溶液に加えた（アンモニア全
添加量１２モル）。更に、撹拌しながら１時間室温下で
熟成して反応を完結させた。副生した塩化アンモニウム
を濾過により除去し、塩化アンモニウムを更に２リット
ルのトルエンで洗浄し、得られた濾液から１２０℃，３
０ｔｏｒｒ下でトルエンを除去してシラザンオリゴマー
８９ｇを得た。このものは数平均分子量４３６であっ
た。REFERENCE EXAMPLE 4 A dry 2-liter four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, and a condenser was charged with 1.5 liters of toluene, and 1479.5 g (1 mol) of methyltrichlorosilane was further added. ) And 261 g (2.4 mol) of trimethylchlorosilane. Then, at room temperature, ammonia gas was added to the solution at a rate of 90 l / min for 3 hours (total amount of ammonia added: 12 mol). The mixture was further aged at room temperature for 1 hour with stirring to complete the reaction. The by-product ammonium chloride was removed by filtration, and the ammonium chloride was further washed with 2 liters of toluene.
Toluene was removed at 0 torr to obtain 89 g of a silazane oligomer. This had a number average molecular weight of 436.
【００２８】次に、得られたシラザンオリゴマー８９ｇ
を温度計、撹拌機、コンデンサーを装備した３００ｍｌ
フラスコに仕込んだ後、Ｎ2ガス雰囲気下にて反応器内
を置換し、温度をゆっくりと上げた。２７０℃になった
ところで低分子量物が留出した。更に、温度を３００℃
まで上げ、この温度で２時間保持した後、フラスコを冷
却すると薄黄色の固体５５ｇ（ポリシラザンＤ）が得ら
れた。このものの数平均分子量は１０７０であった。Next, 89 g of the obtained silazane oligomer
300ml equipped with thermometer, stirrer and condenser
After charging the flask, the inside of the reactor was replaced under an N 2 gas atmosphere, and the temperature was slowly increased. When the temperature reached 270 ° C., a low molecular weight substance was distilled off. Further, the temperature is set to 300 ° C.
The temperature was maintained at this temperature for 2 hours, and then the flask was cooled to obtain 55 g of a pale yellow solid (polysilazane D). Its number average molecular weight was 1,070.
【００２９】〔実施例，比較例〕参考例１〜４で得たポ
リカルボシラン、ポリシラザンを使用し、表１に示した
ような配合で塗料を調製した。これらの塗料を予め脱脂
処理したアルミニウム基材（５０ｍｍ×５０ｍｍ×１ｍ
ｍ）にバーコータにて厚さが５０μになるように塗布
し、室温にて乾燥させた後、表１に示した温度で焼き付
けた。このようにして得られた被膜に対して下記の性能
試験を実施した。結果を表１に併記する。 塗膜硬度：ＪＩＳ−Ｋ−５４００に準じ、鉛筆ひっかき
試験法により塗膜に傷がつく鉛筆硬度で評価した。 密着性： ＪＩＳ−Ｋ−５４００に準じ、試験片の表面
に１ｍｍ間隔のゴバン目（ます目）を刻み、その上に粘
着テープを接着した後、引き剥し、塗膜の残っているゴ
バン目の数で評価した。 耐熱性： 焼き付けた塗膜の空気中４００℃の温度で２
週間加熱して、塗膜のクラック，剥離の有無を観察し
た。 撥水性 ：接触角を測定して評価した。（協和界面科学
社製接触角計）[Examples and Comparative Examples] Using the polycarbosilane and polysilazane obtained in Reference Examples 1 to 4, coating materials were prepared according to the formulations shown in Table 1. Aluminum base (50 mm x 50 mm x 1 m
m) was applied using a bar coater to a thickness of 50 μm, dried at room temperature, and baked at the temperature shown in Table 1. The following performance test was performed on the coating thus obtained. The results are also shown in Table 1. Coating film hardness: According to JIS-K-5400, the coating film was evaluated by a pencil hardness at which a coating film was damaged by a pencil scratch test. Adhesion: In accordance with JIS-K-5400, cut the surface of the test piece with squares (squares) at intervals of 1 mm, adhere an adhesive tape on it, peel off, and peel off the squares with the coating film remaining. Evaluated by number. Heat resistance: 2 at 400 ° C in air
After heating for a week, the coating film was observed for cracks and peeling. Water repellency: The contact angle was measured and evaluated. (Contact angle meter manufactured by Kyowa Interface Science Co., Ltd.)
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１の結果より、ポリカルボシラン樹脂又
はポリシラザン樹脂、シラザン化合物、無機フィラー、
フッ素樹脂を有機溶剤に分散した塗料（実施例１〜６）
は、これら成分のうちシラザン化合物やフッ素樹脂を欠
く塗料（比較例１，２）に比べ、高硬度で撥水性、金属
との密着性、耐熱性に優れた被膜を与えることが確認さ
れた。From the results shown in Table 1, the polycarbosilane resin or polysilazane resin, silazane compound, inorganic filler,
Paint in which fluororesin is dispersed in organic solvent (Examples 1 to 6)
It was confirmed that, compared to the paints (Comparative Examples 1 and 2) lacking the silazane compound and the fluororesin among these components, a film having high hardness, excellent water repellency, excellent adhesion to metals, and excellent heat resistance was obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｄ 183/16 Ｃ０９Ｄ 183/16 (72)発明者 曽我 眞守 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 小川 一文 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭63−234069（ＪＰ，Ａ) 特開 平２−92969（ＪＰ，Ａ) 特開 平２−240152（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09D 5/16 C09D 5/00 C09D 127/12 - 127/20 C09D 183/16 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C09D 183/16 C09D 183/16 (72) Inventor Mamoru Soga 1006 Ojidoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Kazufumi Ogawa 1006 Kazuma Kadoma, Kazuma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-63-234069 (JP, A) JP-A-2-92969 (JP, A) JP-A Hei 2-240152 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C09D 5/16 C09D 5/00 C09D 127/12-127/20 C09D 183/16
Claims (2)
樹脂から選ばれる樹脂と、シラザン化合物と、無機フィ
ラーと、フッ素樹脂とを有機溶剤に分散・配合してなる
ことを特徴とする耐熱防汚性塗料。1. A heat-resistant and antifouling paint comprising a resin selected from a polycarbosilane resin and a polysilazane resin, a silazane compound, an inorganic filler, and a fluororesin dispersed and compounded in an organic solvent.
面に塗布し、焼付けることにより得られる耐熱防汚性塗
膜。2. A heat-resistant and stain-resistant paint film obtained by applying the heat-resistant stain-proof paint according to claim 1 to the surface of a substrate and baking it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31354191A JP2953152B2 (en) | 1991-11-01 | 1991-11-01 | Heat and stain resistant paint and heat and stain resistant coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31354191A JP2953152B2 (en) | 1991-11-01 | 1991-11-01 | Heat and stain resistant paint and heat and stain resistant coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05156176A JPH05156176A (en) | 1993-06-22 |
| JP2953152B2 true JP2953152B2 (en) | 1999-09-27 |
Family
ID=18042565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31354191A Expired - Fee Related JP2953152B2 (en) | 1991-11-01 | 1991-11-01 | Heat and stain resistant paint and heat and stain resistant coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2953152B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101149899B1 (en) | 2010-10-18 | 2012-05-31 | 에스제이아이 주식회사 | Tile Coating Composition and Tile Using Thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3414504B2 (en) * | 1994-07-20 | 2003-06-09 | 東燃ゼネラル石油株式会社 | Manufacturing method of water-repellent ceramic coating |
| JP4767317B2 (en) * | 2006-06-08 | 2011-09-07 | アートブリード株式会社 | Coating liquid and coating method |
| JP5267460B2 (en) * | 2007-07-06 | 2013-08-21 | 富士通株式会社 | Insulating film material, multilayer wiring board and manufacturing method thereof, and semiconductor device and manufacturing method thereof |
| WO2009008041A1 (en) * | 2007-07-06 | 2009-01-15 | Fujitsu Limited | Material for insulating film, multilayered wiring board, method for manufacturing the multilayered wiring board, semiconductor device, and method for manufacturing the semiconductor device thereof |
| JP5947178B2 (en) * | 2012-09-24 | 2016-07-06 | シャープ株式会社 | Insulation, heating container and cooking device |
-
1991
- 1991-11-01 JP JP31354191A patent/JP2953152B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101149899B1 (en) | 2010-10-18 | 2012-05-31 | 에스제이아이 주식회사 | Tile Coating Composition and Tile Using Thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05156176A (en) | 1993-06-22 |
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