TWI472584B - Non-stick finish - Google Patents

Description

非黏性表面塗層Non-stick surface coating

本發明係關於展示改良耐磨性之非黏性含氟聚合物表面塗層。This invention relates to non-stick fluoropolymer surface coatings that exhibit improved wear resistance.

在諸如鋁之基板上形成一非黏性含氟聚合物表面塗層以便形成一供諸如烹飪用具之應用之釋放表面的技術通常涉及在該基板上使用至少兩個塗層，即一通常稱作底塗劑以黏附至該基板上之下塗層，及一提供該非黏性塗層(表面塗層)之外塗層。由於含氟聚合物之非黏性性質，底塗劑經調配為含有一或多種黏附促進劑。如Tannenbaum之美國專利5,562,991中所揭示，膠狀二氧化矽及熱穩定性聚合物黏合劑(通常無氟)為黏附促進劑之實例。黏附促進劑構成底塗劑之大部分，通常為以含氟聚合物加上黏附促進劑之組合重量計至少40重量%。外塗層之表面富含(即使未達全部之含量)含氟聚合物。底塗劑與外塗層中所存在之含氟聚合物可促進此等塗層之間的黏附(塗層間黏附)。The formation of a non-stick fluoropolymer surface coating on a substrate such as aluminum to form a release surface for applications such as cooking utensils generally involves the use of at least two coatings on the substrate, a commonly known The primer is applied to the underlying coating on the substrate, and a coating is provided in addition to the non-stick coating (surface coating). Due to the non-stick properties of the fluoropolymer, the primer is formulated to contain one or more adhesion promoters. Colloidal ceria and a thermally stable polymeric binder (usually fluorine free) are examples of adhesion promoters as disclosed in U.S. Patent No. 5,562,991 to Tannba. The adhesion promoter constitutes a majority of the primer, typically at least 40% by weight based on the combined weight of the fluoropolymer plus adhesion promoter. The surface of the outer coating is rich (even if not at all) of the fluoropolymer. The fluoropolymer present in the primer and overcoat promotes adhesion between the coatings (coating adhesion).

已知可將相對大顆粒之無機非金屬顆粒併入底塗層中以增加非黏性表面塗層之耐磨性。Bignami之EP 0 724 915揭示具有6.5之摩氏硬度(Moh's hardness)(相當於820之諾氏硬度(Knoop hardness))之SiO₂ 礦物cristobilite在底塗層中的用途。Thomas等人之美國專利6,291,054及Tannenbaum之美國專利6,761,964揭示較佳具有至少1200之諾氏硬度之較硬的大陶瓷顆粒在底塗層中的用途。在'054之實例1中，揭示一種單一塗層系統，其中該單一塗層極厚(19.5-59.7微米)且聚合物黏合劑之量超過含氟聚合物之量。在Shah等人之美國專利6,863,974中，底塗層中不存在含氟聚合物，僅存在耐熱性黏附促進劑(聚合物黏合劑)連同具有至少10微米之平均粒度及至少5之摩氏硬度的惰性無機顆粒(陶瓷顆粒)。與頂塗層之塗層間黏附係藉由在含有含氟聚合物之頂塗層組合物中包括黏附促進劑來獲得。It is known that relatively large particles of inorganic non-metallic particles can be incorporated into the undercoat layer to increase the abrasion resistance of the non-tacky surface coating. EP 0 724 915 to Bignami discloses the use of a SiO ₂ mineral cristobilite having a Moh's hardness of 6.5 (corresponding to a Knoop hardness of 820) in an undercoat layer. U.S. Patent No. 6, 291, 054 to Thomas et al., and U.S. Patent No. 6,761,964 to Tannenbaum discloses the use of hard, large ceramic particles having a Knott hardness of at least 1200 in an undercoat layer. In Example 1 of '054, a single coating system is disclosed in which the single coating is extremely thick (19.5-59.7 microns) and the amount of polymeric binder exceeds the amount of fluoropolymer. In U.S. Patent No. 6,863,974 to Shah et al., there is no fluoropolymer in the undercoat layer, only the heat resistant adhesion promoter (polymer binder) is present together with an average particle size of at least 10 microns and a Mohs hardness of at least 5 Inert inorganic particles (ceramic particles). The adhesion to the coating of the top coat is obtained by including an adhesion promoter in the top coat composition containing the fluoropolymer.

儘管'054及'964專利已提供耐磨性在商業基礎上之改良，但仍需要進一步改良耐磨性。Although the '054 and '964 patents have provided improvements in abrasion resistance on a commercial basis, there is still a need to further improve wear resistance.

本發明提供一種於一基板上之非黏性表面塗層，其展示進一步改良之耐磨性。因此，本發明之一實施例為一種在其上具有非黏性塗層之基板，該非黏性塗層包含一外塗層及一將該外塗層黏附至該基板上之底塗劑，該外塗層包含含氟聚合物及有效量之陶瓷顆粒，該等陶瓷顆粒具有至少約10微米之平均粒度以增加該塗層藉由乾式SBAR方法所測定之耐磨性。The present invention provides a non-stick surface coating on a substrate that exhibits further improved wear resistance. Accordingly, an embodiment of the present invention is a substrate having a non-stick coating thereon, the non-stick coating comprising an overcoat layer and a primer for adhering the overcoat layer to the substrate, The overcoat layer comprises a fluoropolymer and an effective amount of ceramic particles having an average particle size of at least about 10 microns to increase the abrasion resistance of the coating as determined by the dry SBAR process.

較佳地，具有至少約10微米之平均尺寸之陶瓷顆粒的有效量為如藉由乾式SBAR方法所測定使該基板上該塗層之耐磨性改良至少10%的量。Preferably, the effective amount of ceramic particles having an average size of at least about 10 microns is an amount that improves the wear resistance of the coating on the substrate by at least 10% as determined by the dry SBAR method.

外塗層並非底塗劑，亦即為形成非黏性表面塗層該外塗層所塗覆之表面並非容納該非黏性表面塗層之裸基板。實情為，該基板具有一用於黏附至該基板之底塗層，且該底塗層形成在其上形成含有含氟聚合物/陶瓷顆粒之外塗層的表面。外塗層不能充當底塗層，因為該外塗層之組成不含有黏附促進劑，或即使其含有黏附促進劑，但該黏附促進劑之存在量係如此之少以致於不能提供與基板之商業上有用之黏附。通常，底塗層中存在有含氟聚合物即完全為與非黏性含氟聚合物層之塗層間黏附所必需者。然而，如美國專利6,863,974中，當底塗層不含有含氟聚合物時，少量黏附促進劑可存在於外塗層中以促進底塗層與外塗層之間的塗層間黏附。The outer coating is not a primer, that is, a non-stick surface coating is formed. The surface coated by the outer coating is not a bare substrate that accommodates the non-stick surface coating. Actually, the substrate has an undercoat layer for adhering to the substrate, and the undercoat layer forms a surface on which a coating layer containing fluoropolymer/ceramic particles is formed. The overcoat layer cannot serve as an undercoat layer because the composition of the overcoat layer does not contain an adhesion promoter, or even if it contains an adhesion promoter, the adhesion promoter is present in such a small amount that it cannot provide a commercial with the substrate. Useful for sticking. Typically, the fluoropolymer is present in the undercoat layer, which is necessary for adhesion to the coating of the non-stick fluoropolymer layer. However, as in U.S. Patent No. 6,863,974, when the primer layer does not contain a fluoropolymer, a small amount of adhesion promoter may be present in the overcoat layer to promote adhesion between the primer layer and the overcoat layer.

因此，本發明為上文所述塗覆至經底塗層塗覆之基板上的外塗層之組合。外塗層可充當基板上非黏性表面塗層之暴露表面或可充當其上形成頂塗層之中間塗層。頂塗層具有濃度大於中間塗層之含氟聚合物以為整個表面塗層提供最佳非黏性特性。不管外塗層為形成非黏性塗層之暴露表面之單一層(在經底塗之基板上)亦或為含有含氟聚合物及平均尺寸為至少10微米之陶瓷顆粒的中間塗層，較佳該層含有以含氟聚合物及陶瓷顆粒之組合重量計至少3重量%之陶瓷顆粒。若黏附促進劑存在於該層中以促進該層與底塗層之間的塗層間黏附，則黏附促進劑之量應不大於外塗層中含氟聚合物重量之10重量%。本文中所用之表述外塗層係指作為形成非黏性表面塗層之暴露表面之單一層的外塗層以及在中間塗層與頂塗層之複合層中的中間塗層。Accordingly, the present invention is a combination of the overcoat applied to the undercoat coated substrate as described above. The outer coating can serve as an exposed surface of the non-stick surface coating on the substrate or can serve as an intermediate coating on which the top coating is formed. The topcoat has a fluoropolymer having a concentration greater than the intermediate coating to provide optimum non-stick properties for the entire surface coating. Whether the outer coating is a single layer (on the primed substrate) that forms the exposed surface of the non-stick coating, or an intermediate coating containing a fluoropolymer and ceramic particles having an average size of at least 10 microns, Preferably, the layer contains at least 3% by weight of ceramic particles based on the combined weight of the fluoropolymer and ceramic particles. If an adhesion promoter is present in the layer to promote adhesion between the layer and the undercoat layer, the amount of adhesion promoter should be no greater than 10% by weight of the fluoropolymer in the overcoat layer. As used herein, the expression outer coating refers to the outer coating as a single layer forming the exposed surface of the non-stick surface coating and the intermediate coating in the composite layer of the intermediate coating and the top coating.

令人驚訝的是，外塗層中有陶瓷顆粒存在可提供耐磨性之進一步改良，此點將在實例中得以證實。因此，本發明之非黏性表面塗層(塗層)提供驚人改良之耐磨性。舉例而言，外塗層中之少量陶瓷顆粒所展示之耐磨性大於以下情況下之耐磨性：(a)底塗劑含有較大量之相同陶瓷顆粒，及(b)外塗層不含有任何陶瓷顆粒。令人驚訝的是，與僅在底塗層中使用陶瓷顆粒相比，在外塗層中置放陶瓷顆粒可改良耐磨性。Surprisingly, the presence of ceramic particles in the overcoat layer provides a further improvement in the ability to provide abrasion resistance, as will be demonstrated in the examples. Thus, the non-stick surface coating (coating) of the present invention provides surprisingly improved abrasion resistance. For example, a small amount of ceramic particles in the outer coating exhibits greater wear resistance than: (a) the primer contains a relatively large amount of the same ceramic particles, and (b) the outer coating does not contain Any ceramic particles. Surprisingly, placing ceramic particles in the outer coating improves wear resistance compared to the use of ceramic particles only in the undercoat.

在本發明之一態樣中，外塗層具有約0.5密耳至1密耳(12.7微米至25.4微米)之厚度。在另一態樣中，外塗層具有大於該等陶瓷顆粒之次要尺寸的厚度。在又一態樣中，外塗層之厚度小於該等陶瓷顆粒之主要尺寸。自前述態樣，可見陶瓷顆粒形狀通常不規則，外觀類似於砂礫或錠(在放大倍率下檢視)，具有主要尺寸(長度或長軸)及次要尺寸(高度或短軸)。在將外塗層組合物自液體介質塗覆至經底塗之基板上，隨後乾燥之後，顆粒趨於在所得外塗層之厚度內靜置，由此，僅該等顆粒之次要尺寸趨於自所塗覆之基板垂直展延。此舉趨於得到良好的非黏性暴露表面，其促成該塗層之非黏性特性。此中間塗層可經具有基本上所有含氟聚合物之頂塗層外塗以提供釋放特性之更進一步改良。In one aspect of the invention, the outer coating has a thickness of from about 0.5 mils to 1 mil (12.7 microns to 25.4 microns). In another aspect, the overcoat layer has a thickness greater than a minor dimension of the ceramic particles. In still another aspect, the thickness of the outer coating is less than the major dimension of the ceramic particles. From the foregoing, it can be seen that the shape of the ceramic particles is generally irregular, and the appearance is similar to gravel or ingot (viewed at magnification), with major dimensions (length or long axis) and minor dimensions (height or short axis). After the overcoat composition is applied from the liquid medium to the primed substrate, followed by drying, the particles tend to stand within the thickness of the resulting overcoat, whereby only the minor dimensions of the particles tend to Spread vertically from the coated substrate. This tends to result in a good non-stick exposed surface that contributes to the non-stick properties of the coating. This intermediate coating can be further coated with a topcoat having substantially all of the fluoropolymer to provide further improvements in release characteristics.

本發明之另一實施例為上述外塗層(中間塗層)組合物。此組合物可適用於在表面上，尤其在底塗層上提供非黏性耐磨性塗層，該組合物包含含氟聚合物及有效量之陶瓷顆粒，該等陶瓷顆粒具有至少約10微米之平均尺寸以如藉由乾式SBAR方法所測定，使該表面上該塗層之耐磨性改良較佳至少10%，該組合物視情況含有量至多為該含氟聚合物重量之約10重量%的黏附促進劑。較佳該含氟聚合物在外塗層中之量為在將該組合物塗覆至表面上以形成塗層之後提供該等陶瓷顆粒分散其中之連續膜的有效量，該組合物中存在之陶瓷顆粒構成該含氟聚合物及該等陶瓷顆粒之組合重量的至少約3重量%。本發明之外塗層組合物亦較佳含有作為其他組份之平均粒度小於約5微米的無機膜硬化劑顆粒。Another embodiment of the invention is the above outer coating (intermediate coating) composition. The composition may be adapted to provide a non-tacky abrasion resistant coating on a surface, particularly on an undercoat layer, the composition comprising a fluoropolymer and an effective amount of ceramic particles having at least about 10 microns The average size is preferably at least 10% improvement of the abrasion resistance of the coating on the surface as determined by the dry SBAR method, and the composition optionally contains up to about 10 parts by weight of the fluoropolymer. % adhesion promoter. Preferably, the amount of the fluoropolymer in the overcoat layer is an effective amount to provide a continuous film in which the ceramic particles are dispersed after application of the composition to a surface to form a coating, the ceramic present in the composition The particles comprise at least about 3% by weight of the combined weight of the fluoropolymer and the ceramic particles. The outer coating composition of the present invention also preferably contains, as other components, inorganic film hardener particles having an average particle size of less than about 5 microns.

本發明中所用之外塗層之主要組份為作為非黏性組份之含氟聚合物及作為耐磨性組份之平均尺寸為至少10微米的陶瓷顆粒。此等組份亦可連同足夠黏附促進劑存在於底塗層中以獲得與容納非黏性塗層之基板的黏附。The main components of the overcoat layer used in the present invention are a fluoropolymer as a non-tacky component and ceramic particles having an average size of at least 10 μm as a wear-resistant component. These components may also be present in the primer layer along with a sufficient adhesion promoter to achieve adhesion to the substrate containing the non-stick coating.

關於含氟聚合物，以下描述適用於底塗劑中及外塗層及頂塗層中所存在之含氟聚合物。含氟聚合物為氟碳化物樹脂。含氟聚合物可為具有至少1×10⁷ Pa．s之熔融蠕變黏度的不可熔融製造之含氟聚合物。一實施例為在含氟聚合物中熱穩定性最高，在380℃下具有至少1×10⁷ Pa．s之熔融蠕變黏度的聚四氟乙烯(PTFE)。該不可熔融製造之PTFE亦可含有少量在烘焙(融合)期間改良成膜能力的共聚單體改質劑，諸如尤其為六氟丙烯(HFP)之全氟烯烴，或尤其為其中烷基含有1至5個碳原子之全氟(烷基乙烯基)醚，以全氟(丙基乙烯醚)(PPVE)為較佳。該改質劑之量將不足以賦予通常不大於0.5莫耳%之PTFE以可熔融製造性。亦出於簡易之目的，PTFE可具有通常為至少1×10⁸ Pa．s之單一熔融蠕變黏度，但具有不同熔融黏度之PTFE之混合物可用以形成非黏性組份。With regard to the fluoropolymer, the following description applies to the fluoropolymer present in the primer and in the topcoat and topcoat. The fluoropolymer is a fluorocarbon resin. The fluoropolymer may have at least 1×10 ⁷ Pa. A non-meltable fluoropolymer of s melt creep viscosity. One embodiment has the highest thermal stability in the fluoropolymer and has at least 1 x 10 ⁷ Pa at 380 ° C. The s melt creep viscosity of polytetrafluoroethylene (PTFE). The non-meltable PTFE may also contain a small amount of a comonomer modifier which improves the film forming ability during baking (fusion), such as a perfluoroolefin which is especially hexafluoropropylene (HFP), or especially wherein the alkyl group contains 1 Perfluoro(alkyl vinyl) ethers having up to 5 carbon atoms are preferably perfluoro(propyl vinyl ether) (PPVE). The amount of the modifier will not be sufficient to impart meltable manufacturability to PTFE which is typically no greater than 0.5 mole percent. Also for the sake of simplicity, PTFE may have a typical of at least 1 x 10 ⁸ Pa. A single melt creep viscosity, but a mixture of PTFE having different melt viscosities can be used to form a non-stick component.

含氟聚合物亦可為與PTFE組合(摻合)或替代PTFE之可熔融製造之含氟聚合物。該等可熔融製造之含氟聚合物之實例包括TFE與該聚合物中存在之至少一種氟化可共聚合單體(共聚單體)的共聚物，該共聚單體之量足以使該共聚物之熔點大體上降低至TFE均聚物聚四氟乙烯(PTFE)之熔點以下，例如降低至不大於315℃之熔融溫度。與TFE共聚之較佳共聚單體包括全氟單體，諸如具有3－6個碳原子之全氟烯烴，及其中烷基含有1－5個碳原子，尤其1－3個碳原子之全氟(烷基乙烯醚)(PAVE)。尤其較佳之共聚單體包括六氟丙烯(HFP)、全氟(乙基乙烯醚)(PEVE)、全氟(丙基乙烯醚)(PPVE)及全氟(甲基乙烯醚)(PMVE)。較佳之TFE共聚物包括FEP(TFE/HFP共聚物)、PFA(TFE/PAVE共聚物)、TFE/HFP/PAVE，其中PAVE為PEVE及/或PPVE及MFA(TFE/PMVE/PAVE，其中PAVE之烷基具有至少兩個碳原子)。可熔融製造之四氟乙烯共聚物之分子量並不重要，只要其足以成膜且可維持模製形狀以便在下塗層塗覆中具有整體性。通常，如根據ASTM D－1238在372℃下測定，熔融黏度將為至少1×10² Pa．s，且範圍上限可高達約60－100×10³ Pa．s。The fluoropolymer may also be a melt-fabricated fluoropolymer that is combined (blended) with PTFE or substituted for PTFE. Examples of such melt-fabricable fluoropolymers include copolymers of TFE with at least one fluorinated copolymerizable monomer (comonomer) present in the polymer in an amount sufficient to render the copolymer The melting point is substantially reduced below the melting point of the TFE homopolymer polytetrafluoroethylene (PTFE), for example to a melting temperature of no more than 315 °C. Preferred comonomers copolymerized with TFE include perfluoromonomers such as perfluoroolefins having from 3 to 6 carbon atoms, and wherein the alkyl group contains from 1 to 5 carbon atoms, especially from 1 to 3 carbon atoms. (alkyl vinyl ether) (PAVE). Particularly preferred comonomers include hexafluoropropylene (HFP), perfluoro(ethyl vinyl ether) (PEVE), perfluoro(propyl vinyl ether) (PPVE), and perfluoro(methyl vinyl ether) (PMVE). Preferred TFE copolymers include FEP (TFE/HFP copolymer), PFA (TFE/PAVE copolymer), TFE/HFP/PAVE, wherein PAVE is PEVE and/or PPVE and MFA (TFE/PMVE/PAVE, of which PAVE The alkyl group has at least two carbon atoms). The molecular weight of the melt-fabricable tetrafluoroethylene copolymer is not critical as long as it is sufficiently film-forming and can maintain a molded shape for integrity in the undercoat coating. Typically, the melt viscosity will be at least 1 x 10 ² Pa as measured according to ASTM D-1238 at 372 ° C. s, and the upper limit of the range can be as high as about 60-100×10 ³ Pa. s.

較佳組合物為具有例如在1×10⁷ Pa．s至1×10¹¹ Pa．s範圍內之熔融蠕變黏度之不可熔融製造之含氟聚合物與具有例如在1×10³ Pa．s至1×10⁵ Pa．s範圍內之黏度之可熔融製造之含氟聚合物的摻合物。A preferred composition is, for example, at 1 x 10 ⁷ Pa. s to 1×10 ¹¹ Pa. A non-meltable fluoropolymer having a melt creep viscosity in the range of s and having, for example, at 1 × 10 ³ Pa. s to 1×10 ⁵ Pa. A blend of melt-fabricated fluoropolymers having a viscosity in the range of s.

當含氟聚合物存在於相鄰層中時，該含氟聚合物經選擇於底塗層與外塗層中及中間塗層與頂塗層中以便彼此足夠相容以在烘焙後達成塗層間黏附。When the fluoropolymer is present in an adjacent layer, the fluoropolymer is selected in the undercoat and overcoat and in the intermediate and topcoat layers to be sufficiently compatible with each other to achieve a coating after baking. Adhesion.

含氟聚合物組份一般可以聚合物於水中之分散液形式購得，出於易於應用及環境可接受之目的，其為本發明中所用之底塗劑、外塗層、中間塗層及頂塗層組合物之較佳形式。“分散液”意謂含氟聚合物樹脂顆粒尺寸為膠狀且穩定分散於水性介質中，以便在使用分散液之時間內該等顆粒不發生沉降。此目的係藉由通常約小於0.5微米之小尺寸含氟聚合物顆粒且分散液製造商在水性分散液中使用界面活性劑來達成。該等分散液可直接藉由如水性分散液聚合，視情況隨後濃縮及/或進一步添加界面活性劑之已知方法獲得。The fluoropolymer component is generally commercially available as a dispersion of the polymer in water, which is the primer, overcoat, intermediate coating and top used in the present invention for ease of application and environmentally acceptable purposes. A preferred form of the coating composition. By "dispersion" is meant that the fluoropolymer resin particles are colloidal in size and are stably dispersed in an aqueous medium so that the particles do not settle during the time the dispersion is used. This object is achieved by using small sized fluoropolymer particles typically less than about 0.5 microns and the dispersion manufacturer using a surfactant in the aqueous dispersion. These dispersions can be obtained directly by known methods such as polymerization of an aqueous dispersion, followed by concentration and/or further addition of a surfactant.

待用以形成上述層之任一者的含氟聚合物之另一液體形式為含氟聚合物於有機液體中之分散液。當含氟聚合物為具有熔融流動性之低分子量PTFE之PTFE微粉時，此形式尤其適用。PTFE微粉亦可以水性分散液形式使用。上述含氟聚合物之水性分散液可包括可混溶之有機液體。Another liquid form of the fluoropolymer to be used to form any of the above layers is a dispersion of the fluoropolymer in an organic liquid. This form is especially useful when the fluoropolymer is a PTFE micropowder of low molecular weight PTFE having melt flowability. The PTFE micropowder can also be used in the form of an aqueous dispersion. The aqueous dispersion of the above fluoropolymer may include a miscible organic liquid.

關於陶瓷顆粒組份，由其製得顆粒之陶瓷為一或多種無機非金屬填料型材料，其相對於該組合物之其他組份為惰性的且在其最終烘焙溫度(融合該含氟聚合物)下熱穩定。陶瓷顆粒不可溶於水及/或溶劑中，以便其通常均一分散但不溶解於含氟聚合物所分散之水性或有機介質中。陶瓷顆粒較佳具有不大於約50微米之平均粒度。陶瓷顆粒之較佳平均粒度為約14微米至36微米且最佳為約20微米至30微米。如本文中所揭示具有至少約10微米之平均粒度之陶瓷顆粒可描述為大陶瓷顆粒。With regard to the ceramic particle component, the ceramic from which the particles are made is one or more inorganic non-metallic filler materials which are inert with respect to the other components of the composition and at their final baking temperature (fusion of the fluoropolymer) ) The heat is stable. The ceramic particles are insoluble in water and/or solvent so that they are generally uniformly dispersed but are not soluble in the aqueous or organic medium in which the fluoropolymer is dispersed. The ceramic particles preferably have an average particle size of no greater than about 50 microns. The ceramic particles preferably have an average particle size of from about 14 microns to about 36 microns and most preferably from about 20 microns to about 30 microns. Ceramic particles having an average particle size of at least about 10 microns as disclosed herein can be described as large ceramic particles.

陶瓷顆粒較佳具有至少1200且更佳至少1500之諾氏硬度。諾氏硬度為描述材料耐壓痕性或耐刮擦性之量度。大陶瓷顆粒藉由使施加於塗層表面之磨損力偏向來賦予本發明中所用之非黏性塗層以耐磨性，耐久性。The ceramic particles preferably have a Knott hardness of at least 1200 and more preferably at least 1500. Knoop hardness is a measure of the indentation or scratch resistance of a material. The large ceramic particles impart abrasion resistance and durability to the non-stick coating used in the present invention by biasing the abrasion force applied to the surface of the coating.

大陶瓷顆粒通常具有大於1.5之縱橫比，指示形狀略不規則，但較佳不大於約5：1以便不為盤狀。如美國專利6,291,054之圖1中所示，縱橫比意謂顆粒之最長直徑或尺寸(長軸或長度)與垂直於顆粒之最長直徑所量測之次要尺寸(高度)的最大距離之比。縱橫比為量化較佳顆粒形狀及方位之手段。The large ceramic particles typically have an aspect ratio greater than 1.5, indicating a slightly irregular shape, but preferably no greater than about 5:1 so as not to be disc shaped. As shown in Figure 1 of U.S. Patent No. 6,291,054, the aspect ratio means the ratio of the longest diameter or dimension (long axis or length) of the particle to the maximum distance of the minor dimension (height) measured perpendicular to the longest diameter of the particle. The aspect ratio is a means of quantifying the shape and orientation of the preferred particles.

無機填料膜硬化劑之實例包括具有至少1200之諾氏硬度的無機氧化物、碳化物、硼化物及氮化物。較佳為鋯、鉭、鈦、鎢、硼、鋁及鈹之無機氧化物、氮化物、硼化物及碳化物。尤其較佳為碳化矽及氧化鋁。較佳無機組合物之典型諾氏硬度值為：鋯(1200)；氮化鋁(1225)；鈹(1300)；氮化鋯(1510)；硼化鋯(1560)；氮化鈦(1770)；碳化鉭(1800)；碳化鎢(1880)；氧化鋁(2025)；碳化鋯(2150)；碳化鈦(2470)；碳化矽(2500)；溴化鋁(2500)；硼化鈦(2850)。因此，經由由其製備本發明中所用之大陶瓷顆粒之陶瓷的前述實例可見，陶瓷為無機化合物而非單一元素。亦可將陶瓷視為金屬元素之氧化物、氮化物、硼化物或碳化物。本發明中所用之組合物之大陶瓷顆粒組份可為單一陶瓷或不同陶瓷顆粒之混合物。較佳之大陶瓷顆粒為SiC。另一較佳之大陶瓷顆粒為Al₂ O₃ 。Examples of the inorganic filler film hardener include inorganic oxides, carbides, borides, and nitrides having a Knott hardness of at least 1200. Preferred are inorganic oxides, nitrides, borides and carbides of zirconium, hafnium, titanium, tungsten, boron, aluminum and cerium. Particularly preferred are niobium carbide and aluminum oxide. Typical Kelvin hardness values of preferred inorganic compositions are: zirconium (1200); aluminum nitride (1225); lanthanum (1300); zirconium nitride (1510); zirconium boride (1560); titanium nitride (1770) Tantalum carbide (1800); tungsten carbide (1880); alumina (2025); zirconium carbide (2150); titanium carbide (2470); niobium carbide (2500); aluminum bromide (2500); titanium boride (2850) . Therefore, it can be seen from the foregoing examples of the ceramic from which the large ceramic particles used in the present invention are prepared that the ceramic is an inorganic compound rather than a single element. Ceramics can also be considered as oxides, nitrides, borides or carbides of metal elements. The large ceramic particle component of the composition used in the present invention may be a single ceramic or a mixture of different ceramic particles. The preferred large ceramic particles are SiC. Another preferred large ceramic particle is Al ₂ O ₃ .

根據本發明，大陶瓷顆粒存在於外塗層中且亦較佳存在於底塗層中。According to the invention, large ceramic particles are present in the outer coating and are also preferably present in the undercoat layer.

外塗層中存在之大陶瓷顆粒之量為使此層之耐磨性與該層在不存在大陶瓷顆粒下之耐磨性相比增加至少20%的有效量。更佳地，大陶瓷顆粒係以使耐磨性與無大陶瓷顆粒下之該層相比增加至少50%，且甚至更佳增加至少100%之有效量存在。外塗層中所存在之含氟聚合物之量至少為在烘焙該層之後提供連續膜之足夠(有效)量，其中該含氟聚合物形成大陶瓷顆粒分散於其中之基質。當大陶瓷顆粒之含量為以含有該等大陶瓷顆粒與含氟聚合物之外塗層中兩種組份之組合重量計至少約3重量%，較佳以該層中之大陶瓷顆粒及含氟聚合物之組合重量計約3重量%至40重量%，由此含氟聚合物含量為96重量%至60重量%時，耐磨性獲得顯著改良。此含氟聚合物之量足以在烘焙由該組合物獲得之塗層之後提供所要膜。更佳地，大陶瓷顆粒構成約5－40重量%，最佳約5重量%至20重量%，兩者均以含有此等顆粒及含氟聚合物之層中兩種組份之組合重量計，由此含氟聚合物含量為95重量%至60重量%。大陶瓷顆粒與含氟聚合物之此等比例適用於上文所揭示之大陶瓷顆粒之每一粒度。The amount of large ceramic particles present in the outer coating is an effective amount that increases the wear resistance of the layer by at least 20% compared to the wear resistance of the layer in the absence of large ceramic particles. More preferably, the large ceramic particles are present in an amount effective to increase the abrasion resistance by at least 50%, and even more preferably by at least 100%, compared to the layer without the large ceramic particles. The amount of fluoropolymer present in the outer coating is at least a sufficient (effective) amount to provide a continuous film after baking the layer, wherein the fluoropolymer forms a matrix in which the large ceramic particles are dispersed. When the content of the large ceramic particles is at least about 3% by weight based on the combined weight of the two components in the coating layer containing the large ceramic particles and the fluoropolymer, preferably the large ceramic particles in the layer and The combined weight of the fluoropolymer is from about 3% by weight to 40% by weight, whereby the fluoropolymer content is from 96% by weight to 60% by weight, and the abrasion resistance is remarkably improved. The amount of fluoropolymer is sufficient to provide the desired film after baking the coating obtained from the composition. More preferably, the large ceramic particles constitute from about 5 to 40% by weight, most preferably from about 5% to 20% by weight, both based on the combined weight of the two components of the layer comprising the particles and the fluoropolymer. Thus, the fluoropolymer content is from 95% by weight to 60% by weight. Such ratios of large ceramic particles to fluoropolymers are suitable for each particle size of the large ceramic particles disclosed above.

其他組份可存在於本發明中所用之非黏性塗層之外塗層中。舉例而言，外塗層可含有小粒度之無機膜硬化劑，亦即具有小於5微米，較佳小於約3微米，且更佳小於約1微米之平均粒度的無機膜硬化劑。除大顆粒與小顆粒不必具有相同顆粒一致性以外，小粒度無機膜硬化劑之一致性可與大陶瓷顆粒之一致性相同。小無機膜硬化劑顆粒之存在並不趨於增加由本發明中所用之組合物獲得之非黏性塗層的耐磨性，但增加該塗層之硬度且由此增加其抗刮擦之耐久性。因此，本發明中所用之外塗層可含有0至約30重量%之小無機膜硬化劑顆粒。較佳存在以單一層中大陶瓷顆粒、含氟聚合物及小無機膜硬化劑顆粒之組合重量計約5重量%至30重量%，更佳約8重量%至20重量%之此等小顆粒。Other components may be present in the outer coating of the non-stick coating used in the present invention. For example, the overcoat layer may comprise a small particle size inorganic film hardener, i.e., an inorganic film hardener having an average particle size of less than 5 microns, preferably less than about 3 microns, and more preferably less than about 1 micron. The consistency of the small particle size inorganic film hardener may be the same as that of the large ceramic particles, except that the large particles and the small particles do not have to have the same particle consistency. The presence of the small inorganic film hardener particles does not tend to increase the abrasion resistance of the non-stick coating obtained from the composition used in the present invention, but increases the hardness of the coating and thereby increases its scratch-resistant durability. . Therefore, the outer coating layer used in the present invention may contain from 0 to about 30% by weight of the small inorganic film hardener particles. Preferably, there are about 5% by weight to 30% by weight, more preferably about 8% by weight to 20% by weight, of such small particles, based on the combined weight of the large ceramic particles, the fluoropolymer and the small inorganic film hardener particles in a single layer. .

本發明中所用之外塗層較佳不含有(亦即無)黏附促進劑。黏附促進劑為通常存在於底塗層中以將該底塗層黏附至未經塗覆之基板上的材料，諸如金屬材料、玻璃材料或陶瓷材料。含氟聚合物因其非黏性特性而並不黏附至未經塗覆之基板上且因此並不執行黏附促進劑功能。外塗層中所存在之含氟聚合物亦不為黏附促進劑，儘管此含氟聚合物會在烘焙過程中將此層黏附至含有含氟聚合物之相鄰層上，亦即為了提供塗層間黏附。然而，少量黏附促進劑可存在於本發明中所用之外塗層組合物中以當其上塗覆外塗層組合物之層中不含有含氟聚合物時獲得塗層間黏附。由於由該組合物形成之層中存在黏附促進劑趨於(a)減損該層之暴露表面之非黏性特性，及(b)增加噴塗呈水性分散液形式之組合物的難度，因此黏附促進劑之量應盡可能少。組合物中存在之黏附促進劑之量(若存在)以外塗層中含氟聚合物之重量計較佳不大於約8重量%，更佳不大於約5重量%。該組合物亦可大體上不含黏附促進劑，亦即含有小於2重量%，較佳小於1.5重量%，且更佳小於1重量%之黏附促進劑，此等重量係以組合物中含氟聚合物之重量計。The outer coating used in the present invention preferably does not contain (i.e., does not have) an adhesion promoter. The adhesion promoter is a material that is typically present in the undercoat layer to adhere the undercoat layer to an uncoated substrate, such as a metallic material, a glass material, or a ceramic material. The fluoropolymer does not adhere to the uncoated substrate due to its non-stick properties and thus does not perform the adhesion promoter function. The fluoropolymer present in the overcoat layer is also not an adhesion promoter, although the fluoropolymer will adhere to the adjacent layer containing the fluoropolymer during the baking process, i.e., to provide a coating Adhesion between layers. However, a small amount of the adhesion promoter may be present in the outer coating composition used in the present invention to obtain adhesion between the coating layers when the layer on which the overcoat composition is applied does not contain the fluoropolymer. Since adhesion promoters present in the layer formed from the composition tend to (a) detract from the non-stick properties of the exposed surface of the layer, and (b) increase the difficulty of spraying the composition in the form of an aqueous dispersion, adhesion promotion The amount of the agent should be as small as possible. The amount of adhesion promoter present in the composition, if present, is preferably no greater than about 8% by weight, more preferably no greater than about 5% by weight, based on the weight of the fluoropolymer in the coating. The composition may also be substantially free of adhesion promoters, i.e., containing less than 2% by weight, preferably less than 1.5% by weight, and more preferably less than 1% by weight of the adhesion promoter, such weight being in the composition. The weight of the polymer.

黏附促進劑一般不含氟。典型的黏附促進劑為用於底塗層中者，諸如膠狀二氧化矽及/或熱穩定聚合物，通常稱為聚合物黏合劑。儘管聚合物黏合劑一般不含氟，但其黏附至含氟聚合物以及底塗劑所塗覆之基板上。在該種狀況下，尤其當底塗劑儘管含有聚合物黏合劑但不含有含氟聚合物時，黏附促進劑促進塗層間黏附。較佳之聚合物黏合劑為可溶於水或水與用於黏合劑之有機溶劑之混合物中的聚合物黏合劑，該溶劑可與水混溶。此溶解性有助於黏合劑與呈水性分散液形式之含氟聚合物組份摻合。Adhesion promoters generally do not contain fluorine. Typical adhesion promoters are those used in the undercoat layer, such as colloidal cerium oxide and/or thermally stable polymers, commonly referred to as polymeric binders. Although the polymeric binder is generally free of fluorine, it adheres to the substrate to which the fluoropolymer and the primer are applied. In this case, especially when the primer contains a polymer binder but does not contain a fluoropolymer, the adhesion promoter promotes adhesion between the coating layers. Preferred polymeric binders are polymeric binders which are soluble in water or a mixture of water and an organic solvent used in the binder which is miscible with water. This solubility facilitates blending of the binder with the fluoropolymer component in the form of an aqueous dispersion.

黏合劑組份之一實例為在烘焙組合物後轉化成聚醯胺醯亞胺(PAI)之聚醯胺酸鹽。此黏合劑較佳，因為其係呈藉由烘焙聚醯胺酸鹽獲得之完全醯亞胺化形式，此黏合劑具有超過250℃之連續使用溫度。聚醯胺酸鹽一般可以聚醯胺酸形式獲得，如呈於N,N－二甲基乙醯胺中之0.5重量%溶液形式在30℃下所量測，該聚醯胺酸具有至少0.1之固有黏度。將其溶解於諸如N－甲基吡咯啶酮之聚結劑中，及諸如糠醇之降黏劑中，且使其與較佳為三乙胺之第三胺反應以形成可溶於水中之鹽，如更詳細地描述於美國專利4,014,834(Concannon)中。隨後可將所得含有聚醯胺酸鹽之反應介質與含氟聚合物水性分散液摻合，且由於聚結劑及降黏劑可混溶於水中，因此摻合程序產生均一塗層組合物。摻合可藉由將液體簡單混合在一起來達成，而不使用過度攪動以避免含氟聚合物水性分散液凝結。適合與本發明一起使用之其他黏合劑之實例包括聚醯胺醯亞胺(PAI)、聚醯亞胺(PI)、聚苯硫醚(PPS)、聚醚碸(PES)、聚伸芳基－醚酮、聚醚醯亞胺及聚(1,4(2,6－二甲基苯基)氧化物)(通常稱為聚苯醚(PPO))。所有此等樹脂在至少140℃之溫度下熱穩定。聚醚碸為具有高達190℃之持續使用溫度(熱穩定性)及220℃之玻璃轉移溫度的非晶形聚合物。聚醯胺醯亞胺在至少250℃之溫度下熱穩定且在至少290℃之溫度下熔融。聚苯硫醚在285℃下熔融。聚伸芳基醚酮在至少250℃之溫度下熱穩定且在至少300℃之溫度下熔融。An example of a binder component is a polyamidomate that is converted to polyamidoximine (PAI) after baking the composition. This binder is preferred because it is in the form of a fully yttrium imidized form obtained by baking a polyamidate having a continuous use temperature in excess of 250 °C. The polyamidate can generally be obtained in the form of poly-proline, as measured in a 0.5% by weight solution in N,N-dimethylacetamide at 30 ° C, the polyamine having at least 0.1 Intrinsic viscosity. Dissolving it in a coalescent such as N-methylpyrrolidone, and a viscosity reducing agent such as decyl alcohol, and reacting it with a third amine, preferably triethylamine, to form a salt soluble in water. , as described in more detail in U.S. Patent 4,014,834 (Concannon). The resulting polyammonium containing reaction medium can then be blended with the aqueous fluoropolymer dispersion, and since the coalescent and viscosity reducing agent are miscible in water, the blending procedure produces a uniform coating composition. Blending can be achieved by simply mixing the liquids together without excessive agitation to avoid coagulation of the aqueous fluoropolymer dispersion. Examples of other binders suitable for use with the present invention include polyamidimide (PAI), polyimine (PI), polyphenylene sulfide (PPS), polyether oxime (PES), polyarylene - ether ketone, polyether oximine and poly(1,4(2,6-dimethylphenyl) oxide) (commonly known as polyphenylene ether (PPO)). All such resins are thermally stable at temperatures of at least 140 °C. The polyether oxime is an amorphous polymer having a continuous use temperature (thermal stability) of up to 190 ° C and a glass transition temperature of 220 ° C. The polyamidoximine is thermally stable at a temperature of at least 250 ° C and melts at a temperature of at least 290 ° C. The polyphenylene sulfide was melted at 285 °C. The poly(aryl ether ketone) is thermally stable at a temperature of at least 250 ° C and melts at a temperature of at least 300 ° C.

出於簡易之目的，可僅使用一種聚合物黏合劑來形成外塗層之黏附促進劑組份(若存在)。然而，亦預期將多種聚合物黏合劑用於本發明中。此對於在底塗層中使用聚合物黏合劑尤其適用。較佳之聚合物黏合劑為至少一種選自由PAI、PES及PPS組成之群的聚合物。此優先選擇適用於底塗劑及外塗層(若黏附促進劑存在於外塗層中)中所用之聚合物黏合劑。For the sake of simplicity, only one polymeric binder may be used to form the adhesion promoter component of the topcoat, if present. However, a variety of polymeric binders are also contemplated for use in the present invention. This is especially true for the use of polymeric binders in the basecoat. Preferred polymeric binders are at least one polymer selected from the group consisting of PAI, PES and PPS. This preference applies to the polymeric binder used in the primer and overcoat (if the adhesion promoter is present in the overcoat).

本發明之非黏性塗層可在構成該非黏性塗層之一或多層中含有具有小於1200之諾氏硬度值之其他填補材料。合適之其他填料包括玻璃薄片、玻璃珠、玻璃纖維、矽酸鋁或矽酸鋯、雲母、金屬薄片、金屬纖維、陶瓷細粉、二氧化矽、硫酸鋇、滑石粉等等，其可用於底塗劑、外塗層及/或頂塗層中。非黏性塗層亦可含有顏料，其量應視所要顏色及所用特定顏料而定。顏料可存在於本發明中所用之底塗劑、外塗層及頂塗層(組合物)之任一者中。The non-stick coating of the present invention may comprise other filler materials having a Knoop hardness value of less than 1200 in one or more of the non-stick coatings. Suitable other fillers include glass flakes, glass beads, glass fibers, aluminum niobate or zirconium silicate, mica, metal flakes, metal fibers, ceramic fine powder, ceria, barium sulfate, talc, etc., which can be used for the bottom. In the paint, top coat and / or top coat. Non-stick coatings may also contain pigments, depending on the desired color and the particular pigment used. The pigment may be present in any of the primer, top coat and top coat (composition) used in the present invention.

本發明之非黏性塗層之每一層可經由習知方式依次塗覆至基板上，較佳呈液體介質形式，且更佳其中該介質之液體包含水且塗覆至基板上之組合物為水性分散液。底塗劑可為先前技術中所揭示之底塗劑中之任一者，其通常含有諸如上文所述之黏附促進劑及含氟聚合物作為必需成份。尤其當需要諸如可撓性、硬度或腐蝕防護之某些最終用途特性時，底塗劑中可使用多種聚合物黏合劑。常用組合包括PAI/PES、PAI/PPS及PES/PPS。底塗劑中之黏附促進劑亦可包括不同黏附促進劑(例如膠狀二氧化矽及聚合物黏合劑)之組合。Each layer of the non-stick coating of the present invention can be applied to the substrate in a conventional manner, preferably in the form of a liquid medium, and more preferably wherein the liquid of the medium contains water and the composition applied to the substrate is Aqueous dispersion. The primer may be any of the primers disclosed in the prior art, and usually contains an adhesion promoter such as those described above and a fluoropolymer as an essential component. A variety of polymeric binders can be used in the primer, especially when certain end use properties such as flexibility, hardness or corrosion protection are desired. Common combinations include PAI/PES, PAI/PPS, and PES/PPS. The adhesion promoter in the primer may also include a combination of different adhesion promoters such as colloidal cerium oxide and polymeric binders.

底塗劑含有黏附促進劑且如上所述可能用於外塗層中之黏附促進劑可用於底塗劑中。底塗劑中所用之較佳黏附促進劑包括PAI、PES及PPS中之至少一者。然而，底塗劑可能含有或可能不含有大陶瓷顆粒且可能不包括含氟聚合物。當將大陶瓷顆粒(至少10微米之平均尺寸)用於底塗層中時，其以增加其中外塗層亦含有大陶瓷顆粒之非黏性塗層之耐磨性(乾式SBAR)的有效量存在。通常，此將需要在底塗層中存在以底塗層之總重量計(以乾燥固體計)至少3重量%之大陶瓷顆粒。底塗層亦可含有以底塗層重量計(以乾燥固體計)高達60重量%之大陶瓷顆粒。底塗層亦可含有如上所述具有小於5微米之平均粒度之無機膜硬化劑。在底塗層中使用含氟聚合物係較佳的，但並非為實施本發明所必需。因此，底塗劑可大體上無含氟聚合物，亦即將含有以底塗層組合物中之固體重量計小於10重量%之含氟聚合物，較佳小於5重量%之含氟聚合物。本文中提及的固體重量係指烘焙後之重量。The primer contains an adhesion promoter and the adhesion promoter which may be used in the overcoat layer as described above can be used in the primer. Preferred adhesion promoters for use in the primer include at least one of PAI, PES, and PPS. However, the primer may or may not contain large ceramic particles and may not include fluoropolymers. When large ceramic particles (average size of at least 10 microns) are used in the undercoat layer, they increase the effective amount of wear resistance (dry SBAR) of the non-stick coating in which the outer coating also contains large ceramic particles. presence. Typically, this would require the presence of at least 3% by weight of large ceramic particles in the basecoat based on the total weight of the primer layer (as dry solids). The undercoat layer may also contain up to 60% by weight of large ceramic particles based on the weight of the primer layer (as dry solids). The undercoat layer may also contain an inorganic film hardener having an average particle size of less than 5 μm as described above. The use of a fluoropolymer in the undercoat layer is preferred, but is not required to practice the invention. Thus, the primer may be substantially free of fluoropolymer, i.e., will contain less than 10% by weight, based on the weight of the solids in the basecoat composition, of a fluoropolymer, preferably less than 5% by weight of the fluoropolymer. The solid weight referred to herein refers to the weight after baking.

一般而言，當含氟聚合物存在於底塗層中時，其將構成底塗層之10－45重量%，中間塗層之至少70重量%及外塗層之至少90重量%。所有此等重量百分比均係以固體計。In general, when the fluoropolymer is present in the primer layer, it will constitute from 10 to 45% by weight of the primer layer, at least 70% by weight of the intermediate coating layer and at least 90% by weight of the overcoat layer. All such weight percentages are based on solids.

視經底塗劑塗覆之基板而定，形成每一層之噴塗及滾塗為最方便之塗覆方法。包括浸漬塗覆及線圈塗覆(coil coating)之其他熟知塗覆方法為合適的。外塗層可在其乾燥之前經由習知方法塗覆至底塗層上。然而，當底塗劑及外塗層組合物為水性分散液時，外塗層組合物可較佳在觸感乾燥之後塗覆至底塗層上。此同樣適用於將頂塗層塗覆至外塗層上，外塗層隨後變成非黏性表面塗層之中間塗層。頂塗層組合物可為任何已公開之頂塗層含氟聚合物組合物。當底塗層係藉由自有機溶劑塗覆底塗劑組合物來製備，且該外塗層係由水性介質塗覆時，在塗覆外塗層之前，應使底塗層乾燥以便將所有與水不相容之溶劑移除。底塗劑與基板及塗層間黏附之黏附特性將在乾燥及烘焙外塗層以及乾燥及烘焙底塗劑(強制性存在)及頂塗層(視情況存在)以在該基板上形成非黏性表面塗層之後自身顯現。Depending on the substrate to which the primer is applied, the coating and roll coating of each layer is the most convenient coating method. Other well known coating methods including dip coating and coil coating are suitable. The overcoat layer can be applied to the undercoat layer by a conventional method before it is dried. However, when the primer and topcoat composition are aqueous dispersions, the overcoat composition may preferably be applied to the primer after drying. The same applies to the application of the top coat to the top coat, which then becomes the intermediate coat of the non-stick surface coating. The topcoat composition can be any of the disclosed topcoat fluoropolymer compositions. When the undercoat layer is prepared by coating the primer composition from an organic solvent, and the overcoat layer is coated with an aqueous medium, the undercoat layer should be dried to coat all of the coat prior to application of the overcoat layer. Solvent incompatible with water. Adhesion properties between the primer and the substrate and coating will be in the dry and baked overcoat as well as the dry and baked primer (mandatory) and topcoat (as appropriate) to form a non-sticky layer on the substrate. After the surface coating, it appears on its own.

所得複合層狀結構可經烘焙以同時融合所有塗層以在基板上形成非黏性表面塗層。當含氟聚合物為PTFE時，快速高烘焙溫度為較佳，例如在800℉(427℃)之溫度下開始且上升至815℉(435℃)歷時5分鐘。當底塗劑或外塗層中之含氟聚合物為PTFE與FEP(例如，50－70重量% PTFE與50－30重量% FEP)之摻合物時，烘焙溫度可在3分鐘(總烘焙時間)內降低至780℉(415℃)，上升至800℉(427℃)。The resulting composite layer structure can be baked to simultaneously fuse all of the coating to form a non-stick surface coating on the substrate. When the fluoropolymer is PTFE, a fast high baking temperature is preferred, for example starting at a temperature of 800 °F (427 °C) and rising to 815 °F (435 °C) for 5 minutes. When the fluoropolymer in the primer or overcoat is a blend of PTFE and FEP (for example, 50-70% by weight PTFE and 50-30% by weight FEP), the baking temperature can be 3 minutes (total baking) Within time), it is reduced to 780 °F (415 °C) and rises to 800 °F (427 °C).

所得經塗覆之基板較佳具有厚度不大於0.6密耳(16微米)，更佳厚度為0.3密耳至0.5密耳(8－13微米)之底塗層。較佳中間塗層較底塗層厚，且更佳較之厚至少50%。烘焙後中間塗層厚度可為0.5密耳至1.0密耳(12.5微米至15微米)。烘焙後，中間塗層(層)較佳具有大於該中間塗層中所存在之陶瓷顆粒之次要尺寸且小於此等顆粒之主要尺寸的厚度。較佳該中間塗層為0.6密耳至0.9密耳(15－23微米)厚且頂塗層為0.2密耳至0.5密耳(5－12微米)厚。烘焙後含有大陶瓷顆粒之層的厚度係藉由渦電流原理(ASTM B244)來量測。渦電流值反映該基板上之值的平均值，該等值包括大顆粒之高度及顆粒之間凹部的深度。此方法在測試方法下進一步描述為應用於在形成非黏性塗層中基板上塗層各層之構建。底塗層厚度亦可在經烘焙之非黏性塗層上藉由拆分該經塗覆之基板(例如煎鍋)，及由得自掃描電子顯微鏡(SEM)之顯微照片量測厚度來量測。藉由使用SEM，可對大顆粒之高度與顆粒之間凹部之深度加以區別。報導顆粒之間凹部內底塗劑厚度之SEM值為所報導之渦電流值的約50%。The resulting coated substrate preferably has an undercoat layer having a thickness of no greater than 0.6 mils (16 microns), more preferably from 0.3 mils to 0.5 mils (8-13 microns). Preferably, the intermediate coating is thicker than the base coat and more preferably at least 50% thicker. The intermediate coating thickness after baking can range from 0.5 mils to 1.0 mils (12.5 microns to 15 microns). After baking, the intermediate coating (layer) preferably has a thickness greater than the minor dimension of the ceramic particles present in the intermediate coating and less than the major dimension of the particles. Preferably, the intermediate coating is from 0.6 mils to 0.9 mils (15-23 microns) thick and the topcoat layer is from 0.2 mils to 0.5 mils (5-12 microns) thick. The thickness of the layer containing large ceramic particles after baking is measured by the eddy current principle (ASTM B244). The eddy current value reflects the average of the values on the substrate, including the height of the large particles and the depth of the recess between the particles. This method is further described under test methods as being applied to the construction of layers of the coating on the substrate in the formation of a non-stick coating. The thickness of the undercoat layer can also be measured on the baked non-stick coating by splitting the coated substrate (eg, a frying pan) and measuring the thickness from a photomicrograph obtained by scanning electron microscopy (SEM). Measure. By using SEM, the height of the large particles can be distinguished from the depth of the recess between the particles. The SEM value of the thickness of the inner coating of the recess between the particles is reported to be about 50% of the reported eddy current value.

本發明中所用之基板可為金屬或陶瓷，其實例包括鋁、陽極化鋁、冷軋鋼、不銹鋼、搪瓷、玻璃及高溫陶質。此等材料可形成整個基板，或在複合材料之狀況下，僅形成該基板之表面。該基板可為平滑的，亦即如由Alpa Co.(Milan,Italy)製造的型號RT 60表面測試儀所量測具有小於50微吋(1.25微米)之表面概況且需要潔淨。對於高溫陶質及一些玻璃而言，改良結果係藉由諸如經由輕微化學蝕刻來活化基板表面而獲得，該等化學蝕刻不可為裸眼所見，亦即該表面仍平滑。基板亦可用諸如聚醯胺酸鹽之薄霧狀塗層之黏附劑進行化學處理，諸如Tannenbaum之美國專利5,079,073中所揭示。The substrate used in the present invention may be metal or ceramic, and examples thereof include aluminum, anodized aluminum, cold rolled steel, stainless steel, enamel, glass, and high temperature ceramic. These materials may form the entire substrate or, in the case of a composite, only the surface of the substrate. The substrate can be smooth, i.e., has a surface profile of less than 50 micro 吋 (1.25 microns) as measured by a model RT 60 surface tester manufactured by Alpa Co. (Milan, Italy) and needs to be clean. For high temperature ceramics and some glasses, the improved results are obtained by activating the surface of the substrate, such as by slight chemical etching, which is not visible to the naked eye, ie the surface is still smooth. The substrate can also be chemically treated with an adhesive such as a mist-like coating of a polyamidamine, such as disclosed in U.S. Patent No. 5,079,073 to Tannba.

具有本發明之非黏性表面塗層之產物包括烹飪用具、烘焙器皿、煮飯器及其插件、水壺、鐵腳盤、輸送機、斜槽、捲筒表面、切割刀片等等。Products having the non-stick surface coating of the present invention include cooking utensils, baking utensils, rice cookers and their inserts, kettles, iron legs, conveyors, chutes, reel surfaces, cutting blades, and the like.

測試方法testing method

乾式SBAR測試： 使用SBAR測試就非黏性塗層之耐磨性對非黏性塗覆基板進行評估。此測試係基於烹飪用具之英國標準規格BS 7069：1988，其中使塗覆系統經受附著於進行相對水平移動之垂直臂上的研磨墊。該設備係以±10 m/min之平均速度自圓筒中心進行100 mm±5 mm(4 in.＋/－ 0.25 in.)之臂相對水平移動。研磨墊(3M Scotch－Brite 7447)為用酚系樹脂浸漬之無規耐綸織物，且將氧化鋁緊固於圓筒上且裝載以對塗層施加±15 N之總力(臂質量＋靜重＝4.5 kg或10 lbs)。測試樣品係藉由如實例中所說明塗覆基板，同時按規定乾燥及烘焙來製備。 Dry SBAR test: The non-stick coated substrate was evaluated for the abrasion resistance of the non-stick coating using the SBAR test. This test is based on British Standard Specification BS 7069:1988 for Cooking Appliances, in which the coating system is subjected to a polishing pad attached to a vertical arm that is relatively horizontally moved. The device moves relative to the arm at 100 mm ± 5 mm (4 in. +/- 0.25 in.) from the center of the cylinder at an average speed of ±10 m/min. The polishing pad (3M Scotch-Brite 7447) is a random nylon fabric impregnated with a phenolic resin, and the alumina is fastened to the cylinder and loaded to apply a total force of ±15 N to the coating (arm mass + static) Weight = 4.5 kg or 10 lbs). Test samples were prepared by coating the substrate as illustrated in the examples while drying and baking as specified.

測試所製備的未經洗滌之塗覆基板。將塗覆基板固定於固定支撐物上且將所加載之研磨墊施加於非黏性表面上。使樣本保持不動且使研磨墊臂在圓筒中心點之兩側上以50 mm±2.5 mm(2 in ＋/－ 0.1 in)之距離向前及向後移動。The prepared unwashed coated substrate was tested. The coated substrate is affixed to a fixed support and the loaded polishing pad is applied to a non-stick surface. The sample was held stationary and the pad arm was moved forward and backward at a distance of 50 mm ± 2.5 mm (2 in +/- 0.1 in) on both sides of the center point of the cylinder.

250次循環之後，翻轉研磨墊且在又250次循環之後重新開始。繼續此程序直至可見金屬且隨後記錄塗層穿透之循環數。塗層穿透為測試之結束點。After 250 cycles, the polishing pad was turned over and restarted after another 250 cycles. This procedure is continued until the metal is visible and the number of cycles through which the coating penetrates is then recorded. The coating penetration was the end of the test.

釋放測試 將非黏性塗覆之平底鍋加熱至374℉(190℃)至392℉(200℃)之範圍且在整個測試中保持在此溫度範圍內，如藉由基板表面上之接觸式高溫計所量測。在未加調料之平底鍋上煎蛋。為進行該測試，將蛋在平底鍋上打破且烹飪3分鐘。用鍋鏟將蛋提起且將平底鍋傾斜以使得蛋滑動。評定蛋滑動之容易度。將平底鍋重新置放於燃燒器上且將蛋翻轉。用鍋鏟將蛋黃搗破且將蛋再烹飪2分鐘。用鍋鏟再次將蛋提起且鍋鏟將蛋自非黏性塗層移除之容易度為該塗層之釋放速率。在每次對非黏性塗層進行7500次SBAR測試循環之後重複此釋放測試。對於以下實例之所有非黏性塗層(包括比較塗層)而言，在塗層於SBAR測試中之使用壽命達至基板之金屬首次變得可見之時間中蛋易於藉由鍋鏟自非黏性表面移除。對於此觀測結果例外者為表8中實例12之非黏性塗層，其中釋放在45000次循環處開始削弱。 The release test heats the non-stick coated pan to a range of 374 °F (190 °C) to 392 °F (200 °C) and remains within this temperature range throughout the test, such as by contact high temperature on the surface of the substrate. Measured by the meter. Omelette on a pan without seasoning. For this test, the eggs were broken on a pan and cooked for 3 minutes. Lift the egg with a spatula and tilt the pan to allow the egg to slide. Evaluate the ease of egg slip. Reposition the pan on the burner and turn the egg over. Use a spatula to break the egg yolk and cook the egg for another 2 minutes. The ease with which the egg is lifted by the spatula and the spatula removes the egg from the non-stick coating is the release rate of the coating. This release test was repeated after each of the 7500 SBAR test cycles for the non-stick coating. For all non-stick coatings (including comparative coatings) of the following examples, the egg is easily self-adhesive by the spatula during the time when the coating is used in the SBAR test until the metal of the substrate becomes visible for the first time. Sexual surface removal. The exception to this observation was the non-stick coating of Example 12 in Table 8, where the release began to weaken at 45,000 cycles.

乾燥膜厚度(DFT) 烘焙塗層厚度係用膜厚度儀器(例如Fisherscope)基於渦電流原理(ASTM B244)來量測。由於塗層中存在大顆粒，因此厚度測定係對置放於平底鍋中之試片進行。為製備試片，將一試片附著於金屬平底鍋上且在進行任何塗層塗覆之前用膠帶黏住兩個相鄰點。如實例中所規定塗覆底塗劑且移除一處膠帶以暴露裸金屬，在其上置放第二試片。隨後塗覆中間塗層且為了暴露而移除第二處膠帶，在其上施加第三試片。第一試片之量測提供總共三個塗層－底塗劑、中間塗層及頂塗層之總厚度。第二試片之量測提供中間塗層及頂塗層之厚度。第三試片之量測提供頂塗層之厚度。底塗劑厚度及中間塗層厚度之個別值係藉由減法來計算。底塗劑厚度係藉由第一試片之厚度值減去第二試片之厚度值來確定。中間塗層厚度係藉由第二試片之厚度減去第三試片之厚度來確定。 Dry film thickness (DFT) baked coating thickness is measured using a film thickness instrument (eg, Fisherscope) based on the eddy current principle (ASTM B244). Thickness measurements were made on test pieces placed in a pan due to the presence of large particles in the coating. To prepare the test piece, a test piece was attached to a metal pan and taped to two adjacent points before any coating was applied. The primer was applied as specified in the examples and a tape was removed to expose the bare metal, and a second test piece was placed thereon. The intermediate coating is then applied and the second tape is removed for exposure, and a third test piece is applied thereon. The measurement of the first test piece provides a total thickness of a total of three coats - primer, intermediate coat and top coat. The measurement of the second test piece provides the thickness of the intermediate coating and the top coating. The measurement of the third test piece provides the thickness of the top coat. The individual values of the primer thickness and the thickness of the intermediate coating are calculated by subtraction. The thickness of the primer is determined by subtracting the thickness value of the second test piece from the thickness value of the first test piece. The thickness of the intermediate coating is determined by subtracting the thickness of the third test piece from the thickness of the second test piece.

含氟聚合物 PTFE分散液：固體含量為59－61重量%且RDPS為170－210奈米之DuPont TFE含氟分散液。PTFE含氟聚合物分散液等級30可得自DuPont Company,Wilmington,DE。 Fluoropolymer PTFE dispersion: DuPont TFE fluorine dispersion having a solids content of 59-61% by weight and an RDPS of 170-210 nm. The PTFE fluoropolymer dispersion grade 30 is available from DuPont Company, Wilmington, DE.

FEP分散液：固體含量為54.5－56.5重量%且RDPS為150－210奈米之TFE/HFP含氟聚合物分散液，HFP含量為9.3－12.4重量%且熔融流率如經由如美國專利4,380,618中所述修改之ASTM D－1238方法在372℃下所量測為11.8－21.3 g/10 min的樹脂。FEP dispersion: a TFE/HFP fluoropolymer dispersion having a solids content of 54.5 to 56.5 wt% and an RDPS of 150 to 210 nm, having a HFP content of 9.3-12.4% by weight and a melt flow rate as in, for example, U.S. Patent 4,380,618 The modified ASTM D-1238 method measures 11.8-21.3 g/10 min of resin at 372 °C.

PFA分散液：固體含量為58－62重量%且RDPS為185－245奈米之DuPont PFA含氟聚合物分散液，PPVE含量為2.9－3.6重量%且熔融流率如經由如美國專利4,380,618中所述修改之ASTM D－1238方法在372℃下所量測為1.3－2.7 g/10 min的樹脂。PFA含氟聚合物分散液等級335可得自DuPont Company,Wilmington,DE。PFA dispersion: DuPont PFA fluoropolymer dispersion having a solids content of 58-62% by weight and an RDPS of 185-245 nm, a PPVE content of 2.9-3.6 wt% and a melt flow rate as taught in, for example, U.S. Patent 4,380,618. The modified ASTM D-1238 method measures 1.3 to 2.7 g/10 min of resin at 372 °C. PFA fluoropolymer dispersion grade 335 is available from DuPont Company, Wilmington, DE.

聚合物黏合劑 PAI為TorlonAI－10聚(醯胺－醯亞胺)(Solvay Advanced polymers)，含有6－8%之殘餘NMP之固體樹脂(其可還原成聚醯胺酸鹽)。 Polymer binder PAI is Torlon AI-10 poly(Solvay Advanced polymers), a solid resin containing 6-8% of residual NMP (which can be reduced to polyamidomate).

聚醯胺酸鹽一般可以如呈於N,N－二甲基乙醯胺中之0.5重量%溶液形式在30℃下所量測具有至少0.1之固有黏度的聚醯胺酸形式獲得。將其溶解於諸如N－甲基吡咯啶酮之聚結劑中，及諸如糠醇之降黏劑中，且使其與較佳為三乙胺之第三胺反應以形成可溶於水中之鹽，如美國專利4,014,834(Concannon)中更詳細地描述。The polyamidate can generally be obtained as a polyglycine having a viscosity of at least 0.1 as measured in a 0.5% by weight solution in N,N-dimethylacetamide at 30 °C. Dissolving it in a coalescent such as N-methylpyrrolidone, and a viscosity reducing agent such as decyl alcohol, and reacting it with a third amine, preferably triethylamine, to form a salt soluble in water. It is described in more detail in U.S. Patent 4,014,834 (Concannon).

碳化矽 使用由Elektroschmelzwerk Kempten GmbH(ESK),Munich Germany供應之碳化矽。 Tantalum carbide The tantalum carbide supplied by Elektroschmelzwerk Kempten GmbH (ESK), Munich Germany.

P 1200＝15.3±1微米平均粒度P 600＝25.8±1微米平均粒度P 400＝35.0±1.5微米平均粒度P 320＝46.2±1.5微米平均粒度F 1000－D＝5－7微米平均粒度平均粒度係藉由沈積法使用FEPA－標準－43－GB 1984R 1993 resp.ISO 8486根據由供應商提供之資訊來量測。P 1200 = 15.3 ± 1 micron average particle size P 600 = 25.8 ± 1 micron average particle size P 400 = 35.0 ± 1.5 micron average particle size P 320 = 46.2 ± 1.5 micron average particle size F 1000-D = 5-7 micron average particle size average particle size system The FEPA-Standard-43-GB 1984R 1993 resp. ISO 8486 is used by the deposition method to measure according to the information provided by the supplier.

氧化鋁 氧化鋁(小顆粒)係由Aluminum Corporation(America)供應－等級SG A－16，0.35－0.50微米平均粒度。 Alumina Alumina (small particles) was supplied by Aluminum Corporation (America) - grade SG A-16, 0.35-0.50 micron average particle size.

實例Instance

將本發明之代表性3－塗層非黏性系統噴霧至測試平滑鋁平底鍋上，其已僅藉由洗滌處理以移除油脂但未經機械粗糙化。底塗劑、中間塗層及頂塗層之水性分散液組合物分別列於表1、2、3及4中。A representative 3-coat non-stick system of the present invention was sprayed onto a test smooth aluminum pan which had been treated by a wash only to remove grease but not mechanically roughened. The aqueous dispersion compositions of the primer, intermediate coating and topcoat are listed in Tables 1, 2, 3 and 4, respectively.

底塗劑A具有含氟聚合物與SiC。底塗劑B具有含氟聚合物但不具有SiC。底塗劑C具有SiC但不具有含氟聚合物。Primer A has a fluoropolymer and SiC. Primer B has a fluoropolymer but does not have SiC. Primer C has SiC but no fluoropolymer.

中間塗層A不含有SiC，且中間塗層B含有SiC。The intermediate coating A does not contain SiC, and the intermediate coating B contains SiC.

中間塗層C、D、E、F及J含有約相等量之SiC，但具有不同平均粒度。中間塗層G、H及I含有相同平均粒度SiC但量不同。The intermediate coatings C, D, E, F, and J contain about equal amounts of SiC, but have different average particle sizes. The intermediate coatings G, H and I contain the same average particle size SiC but differ in amount.

將底塗劑噴霧至鋁基板上且在150℉(66℃)下乾燥10分鐘。隨後將中間塗層噴霧於乾燥底塗劑上。將頂塗層濕至濕地塗覆(噴霧)於中間塗層上。將塗層在300℉(149℃)下強制乾燥10分鐘，且隨後在800℉(427℃)下固化5分鐘。藉由試片，使用如上所述之渦電流分析來測定底塗劑/中間塗層/頂塗層之乾燥塗層膜厚度(DFT)。一般而言，厚度為：底塗劑0.31－0.55密耳(7.8－13.8微米)/中間塗層0.62－0.82密耳(15.5－20.5微米)/頂塗層0.2－0.48密耳(5－12微米)。The primer was sprayed onto an aluminum substrate and dried at 150 °F (66 °C) for 10 minutes. The intermediate coating is then sprayed onto the dry primer. The top coat is wet-to-wet coated (sprayed) onto the intermediate coat. The coating was forced to dry at 300 °F (149 °C) for 10 minutes and then cured at 800 °F (427 °C) for 5 minutes. The dry coating film thickness (DFT) of the primer/intermediate coating/topcoat layer was determined by eddy current analysis as described above by means of a test piece. In general, the thickness is: primer 0.11-0.55 mil (7.8-13.8 micron) / intermediate coating 0.62-0.82 mil (15.5-20.5 micron) / top coat 0.2-0.48 mil (5-12 micron) ).

下表中所提出之實例展示在該塗層系統之中間塗層中具有不同量及尺寸之SiC顆粒的3－塗層系統之耐磨性。使非黏性塗覆測試平底鍋經受乾式SBAR測試以評估耐磨性。The examples presented in the table below show the wear resistance of 3-coat systems with different amounts and sizes of SiC particles in the intermediate coating of the coating system. The non-stick coated test pan was subjected to a dry SBAR test to evaluate wear resistance.

中間塗層中之SiC顆粒－%裝載 表5中展示在中間塗層中具有SiC顆粒之3－塗層系統之磨損測試結果。SiC粒度係保持在25.8微米而重量%變化。即使對於少量SiC仍可見乾式SBAR結果大大改良且其隨SiC顆粒裝載愈高而增加。所用底塗劑(底塗劑B)中不存在SiC顆粒。 SiC Particles in the Intermediate Coating - % Loading Table 5 shows the wear test results for the 3-coating system with SiC particles in the intermediate coating. The SiC particle size system was maintained at 25.8 microns and varied in weight percent. Even for a small amount of SiC, the dry SBAR results are greatly improved and it increases as the SiC particles are loaded higher. There is no SiC particles present in the primer (primer B) used.

中間塗層中之SiC顆粒－粒度效應 表6及表7中展示在中間塗層中具有SiC顆粒之3－塗層系統之磨損測試結果。中間塗層中之SiC粒度係在5－7微米至46微米之範圍內，在乾燥膜中之裝載率為約12重量%。在表6中，樣品在底塗劑中亦具有SiC顆粒，彼等顆粒具有25.8微米之粒度。表7中，樣品在底塗劑中不具有SiC顆粒。結果展示在中間塗層中具有14微米以上之顆粒之所有樣品的乾式SBAR結果增加，在中間塗層中含有20－30微米範圍內之SiC顆粒的樣品具有極良好的結果。將其中底塗劑含有19.30重量% SiC之比較實例2與表5之其中底塗劑中不存在SiC顆粒且僅在中間塗層中存在3.98重量% SiC的實例1相比較揭示中間塗層中存在大SiC顆粒遠比底塗劑中存在大SiC顆粒有效。實例1之塗層展示SBAR耐磨性優於比較實例2大於40%之改良，其中底塗劑中所用SiC之量較之比較實例2少25%。 SiC Particles in the Intermediate Coating - Particle Size Effect The wear test results for the 3-coating system with SiC particles in the intermediate coating are shown in Tables 6 and 7. The SiC particle size in the intermediate coating was in the range of 5-7 microns to 46 microns and the loading in the dried film was about 12% by weight. In Table 6, the sample also had SiC particles in the primer, and the particles had a particle size of 25.8 microns. In Table 7, the sample did not have SiC particles in the primer. The results show that the dry SBAR results for all samples having particles larger than 14 microns in the intermediate coating are increased, and samples containing SiC particles in the range of 20-30 microns in the intermediate coating have very good results. Comparative Example 2 in which the primer contained 19.30% by weight of SiC and Example 1 in Table 5 in which the SiC particles were absent and only 3.98% by weight of SiC was present in the intermediate coating were compared to reveal the presence of the intermediate coating. Large SiC particles are much more effective than the presence of large SiC particles in the primer. The coating of Example 1 exhibited an improvement in SBAR abrasion resistance over Comparative Example 2 greater than 40%, wherein the amount of SiC used in the primer was 25% less than Comparative Example 2.

改良之計算%：((29.0－18.4)÷18.4)×100 Improved calculation %: ((29.0-18.4)÷18.4)×100

底塗劑中具有含氟聚合物之系統與底塗劑中無含氟聚合物之系統的比較 表8中展示具有底塗劑A(含氟聚合物)及C(無含氟聚合物)，均塗覆有中間塗層B(以SiC與含氟聚合物之組合重量計13.2重量%之SiC)的3－塗層系統之磨損測試結果。中間塗層中之SiC平均粒度為25.8微米。 Comparison of a system with a fluoropolymer in a primer and a system without a fluoropolymer in a primer. Table 8 shows primer A (fluoropolymer) and C (no fluoropolymer). Abrasion test results were applied to a 3-coat system with an intermediate coating B (13.2% by weight of SiC based on the combined weight of SiC and fluoropolymer). The average SiC particle size in the intermediate coating was 25.8 microns.

在本發明之另一實例中，不具有含氟聚合物之底塗劑與不具有黏附促進劑之中間塗層組合使用。除SiC全部為P600，亦即構成底塗劑組合物乾重之25.2重量%以外，底塗劑與底塗劑C類似。除SiC之量為以組合物之乾重計11.7重量%以外，中間塗層與中間塗層D類似。如在中間塗層D之狀況下，此實例中所用之中間塗層組合物不具有PAI黏附促進劑。該頂塗層為與表4中相同之組合物。底塗劑、中間塗層及頂塗層組合物係以與上文所述相同之方式相繼塗覆至基板(鋁煎鍋)上以在該基板上形成非黏性塗層。塗層厚度(乾燥)為：底塗層0.45密耳(11.3微米)，中間塗層0.76密耳(19微米)，且頂塗層0.37密耳(9.3微米)。對此塗層之SBAR測試結果為39,000次循環。In another embodiment of the present invention, a primer having no fluoropolymer is used in combination with an intermediate coating having no adhesion promoter. The primer was similar to the primer C except that the SiC was all P600, that is, 25.2% by weight of the dry weight of the primer composition. The intermediate coating was similar to the intermediate coating D except that the amount of SiC was 11.7% by weight based on the dry weight of the composition. The intermediate coating composition used in this example did not have a PAI adhesion promoter as in the case of the intermediate coating D. The top coat was the same composition as in Table 4. The primer, intermediate coating and topcoat composition were applied sequentially to a substrate (aluminum frying pan) in the same manner as described above to form a non-stick coating on the substrate. The coating thickness (dry) was 0.45 mil (11.3 microns) for the base coat, 0.76 mils (19 microns) for the intermediate coat, and 0.37 mils (9.3 microns) for the top coat. The SBAR test results for this coating were 39,000 cycles.

Claims (9)

一種基板，在其上具有非黏性塗層，該非黏性塗層包含一外塗層及一將該外塗層黏附至該基板上之底塗劑，該外塗層包含含氟聚合物及至少3重量%之陶瓷顆粒，該等陶瓷顆粒具有至少10微米之平均粒度，該重量%係以該外塗層中該等陶瓷顆粒及該含氟聚合物之組合重量計，其中該非黏性塗層包括一包含含氟聚合物之頂塗層，且其中該底塗劑不含具有平均粒度至少10微米之該等陶瓷顆粒。 a substrate having a non-stick coating thereon, the non-stick coating comprising an outer coating layer and a primer for adhering the outer coating layer to the substrate, the outer coating layer comprising a fluoropolymer and At least 3% by weight of ceramic particles having an average particle size of at least 10 microns, based on the combined weight of the ceramic particles and the fluoropolymer in the overcoat layer, wherein the non-stick coating The layer comprises a top coat comprising a fluoropolymer, and wherein the primer is free of such ceramic particles having an average particle size of at least 10 microns. 如請求項1之基板，其中該底塗劑包含黏附促進劑及視情況使用之含氟聚合物。 The substrate of claim 1, wherein the primer comprises an adhesion promoter and, optionally, a fluoropolymer. 如請求項1之基板，其中另外的無機膜硬化劑係存在於該底塗劑及該外塗層之至少一者中，該無機膜硬化劑具有小於5微米之平均粒度。 The substrate of claim 1, wherein an additional inorganic film hardener is present in at least one of the primer and the overcoat, the inorganic film hardener having an average particle size of less than 5 microns. 如請求項1之基板，其中該外塗層之厚度比該底塗劑之厚度大至少50%。 The substrate of claim 1, wherein the thickness of the overcoat layer is at least 50% greater than the thickness of the primer. 如請求項1之基板，其中該外塗層含有以該含氟聚合物之重量計至多10重量%之量的黏附促進劑。 The substrate of claim 1, wherein the overcoat layer contains an adhesion promoter in an amount of up to 10% by weight based on the weight of the fluoropolymer. 如請求項5之基板，其中該黏附促進劑係選自由下列各物組成之群：聚醯胺醯亞胺、聚醚碸及聚苯硫醚。 The substrate of claim 5, wherein the adhesion promoter is selected from the group consisting of polyamidoximine, polyether oxime, and polyphenylene sulfide. 如請求項1之基板，其中該外塗層大體上不含黏附促進劑。 The substrate of claim 1, wherein the overcoat layer is substantially free of an adhesion promoter. 如請求項1之基板，其中該等陶瓷顆粒具有至少1200之諾氏硬度(Knoop hardness)。 The substrate of claim 1, wherein the ceramic particles have a Knoop hardness of at least 1200. 如請求項1之基板，其中該基板為烹飪用具、烘焙器皿、煮飯器及其插件、水壺、鐵腳盤、輸送機、斜槽、捲筒表面、切割刀片。The substrate of claim 1, wherein the substrate is a cooking utensil, a baking vessel, a rice cooker and an insert thereof, a kettle, an iron foot plate, a conveyor, a chute, a roll surface, and a cutting blade.