TW201827493A - Hyperbaric process for applying and curing an organic polymerizable treatment - Google Patents

Abstract

Substrates are coated with a curable composition that includes at least one free radical polymerizable monomer and a heat-activated polymerization initiator. The coating is applied to the substrate and cured thereon to produce the coating. Curing is performed by purging molecular air from the vessel containing the substrate, pressuring with an oxygen-deficient gas and then curing the fabric in the oxygen-deficient gas at elevated pressure.

Description

用於施用和固化有機可聚合處理之高壓方法  High pressure method for applying and curing organic polymerizable treatment  

本發明涉及一種用於將可聚合的塗層施用和固化在基底上之方法。 The present invention relates to a method for applying and curing a polymerizable coating on a substrate.

將聚合物塗層用在多孔和無孔的基底上以向該等材料提供多種附加的屬性。 Polymer coatings are used on porous and non-porous substrates to provide a variety of additional attributes to the materials.

將親水塗層施用在基底上以增加材料或織物吸收水的傾向或者以幫助將吸收的水鋪展在更大面積上以提高吸收的水的蒸發速率。運動裝，例如，可以具有施用在其上的親水塗層以幫助吸收汗液並且在服裝的大面積上幫助芯吸該汗液從而加速蒸發和蒸發冷卻。 A hydrophilic coating is applied to the substrate to increase the tendency of the material or fabric to absorb water or to help spread the absorbed water over a larger area to increase the rate of evaporation of the absorbed water. The sportswear, for example, can have a hydrophilic coating applied thereto to help absorb sweat and help wick the sweat over a large area of the garment to accelerate evaporation and evaporative cooling.

相反，將疏水塗層施用在不同的基底上以保護它們免受水分。在紡織品應用中，例如，使用疏水塗層以向服裝如雨具和外衣像外套、帽子和鞋子提供防水面層(finish)。該等塗層被應用於其中重要的是防止水潤濕或滲透通過基底的各種各樣的工業、車輛和建築應用中。受益於疏水塗層的工業紡織品的一些實例將是房屋“包層”和屋頂材料。電子包裝係受益於疏水塗層的另一領域。 Instead, hydrophobic coatings are applied to different substrates to protect them from moisture. In textile applications, for example, hydrophobic coatings are used to provide a waterproof finish to garments such as rain gear and outerwear like jackets, hats and shoes. These coatings are used in a wide variety of industrial, automotive, and architectural applications where it is important to prevent water from wetting or penetrating through the substrate. Some examples of industrial textiles that benefit from hydrophobic coatings will be house "cladding" and roofing materials. Electronic packaging benefits from another area of hydrophobic coating.

將疏油塗層施用在紡織品或其他材料上以防止油基液體沾 污或滲透該基底。疏油塗層經常是疏油性的、疏脂性的和疏水性的。 The oleophobic coating is applied to a textile or other material to prevent oil based liquid from smearing or penetrating the substrate. The oleophobic coating is often oleophobic, lipophobic and hydrophobic.

已經開發了高度有效的塗層材料。然而，應用方法經常是不適當的，尤其是當非常低的塗層重量係希望的時，經常是這種情況。在紡織品應用中，例如，重的塗層增加了不希望的重量並且可能賦予織物沈重和堅硬感。這對於觸覺和在工業中通常稱為“透氣性”、“懸垂性”和“手感”的物理特性具有不利影響。重量還是在電子包裝和其他工業應用中的重要因素。薄的塗層還潛在地具有成本優勢，因為需要較少的塗層材料。 Highly effective coating materials have been developed. However, the application methods are often inadequate, especially when very low coating weights are desirable. In textile applications, for example, heavy coatings add undesirable weight and may impart a heavy and stiff feel to the fabric. This has a detrimental effect on the physical properties of the sense of touch and what is commonly referred to in the industry as "breathability", "drawing" and "feel". Weight is also an important factor in electronic packaging and other industrial applications. Thin coatings are also potentially cost effective because less coating material is required.

用於施用非常薄的聚合物塗層之方法受制於高成本、不適當的塗層性能，或這兩者。不適當的塗層性能總體上是由於當以低的塗層重量施用時塗層中的缺陷。 Methods for applying very thin polymer coatings are subject to high cost, inadequate coating properties, or both. Inappropriate coating properties are generally due to defects in the coating when applied at low coating weights.

紡織品，例如，通常是經常由交叉纖維製成的多孔材料。理想地，人們想要施用有效的塗層而不阻擋大部分的孔，因為這樣做減少透氣性、懸垂性和手感。常規地，將疏水塗層施用在紡織品上的最常見的方式係使用“浸軋和固化(pad and cure)”方法，該方法涉及將一段編織或針織的織物拉過水性或溶劑基化學浴、擠壓或真空處理掉過量的液體並且然後乾燥並且固化該濕織物。這種方法引起很多困難，該等困難包括紡織品收縮、活性成分的不一致施用、在浴成分的濃度上的時變改變、移除水或溶劑的大量能量的使用、以及需要再循環或者處理掉的大量化學廢物。此外，以這種方式很多潛在的最終處理化學品不能被塗覆到紡織品上，因為它們不與水相容亦或與它們自己或者該浴中的其他成分過早反應，或者因為它們將迅速地從該浴中沈澱出來。溶劑基系統具有工人暴露和環境問題、以及對於該等溶劑的回收和再使用的增加的成本的問題。美國專利公 開案2008/0107822描述了一種方法：將紡織品用奈米級層的蒸氣冷凝的單體加上附加的化學品塗覆，接著是基於電漿的固化方法以便聚合該塗覆的單體。該基於電漿的固化要求昂貴的設備、緩慢地操作，並且是視線(line-of-sight)方法，不產生均勻的固化。 Textiles, for example, are often porous materials often made from crossed fibers. Ideally, one would like to apply an effective coating without blocking most of the pores as this reduces breathability, drape and hand. Conventionally, the most common way to apply a hydrophobic coating to a textile is to use a "pad and cure" method involving pulling a length of woven or knitted fabric through an aqueous or solvent based chemical bath, Excess liquid is squeezed or vacuum treated and then the wet fabric is dried and cured. This method causes many difficulties, including textile shrinkage, inconsistent application of active ingredients, time-varying changes in the concentration of bath components, use of large amounts of energy to remove water or solvent, and the need to recycle or dispose of A large amount of chemical waste. In addition, many potential final treatment chemicals cannot be applied to textiles in this way because they are not compatible with water or react prematurely with themselves or other ingredients in the bath, or because they will rapidly Precipitated from the bath. Solvent based systems have problems with worker exposure and environmental issues, as well as increased costs for the recovery and reuse of such solvents. U.S. Patent Publication No. 2008/0107822 describes a method of coating a textile with a vapor condensed monomer of a nanoscale layer with an additional chemical, followed by a plasma based curing process to polymerize the coated monomer. . This plasma-based curing requires expensive equipment, operates slowly, and is a line-of-sight method that does not produce uniform curing.

無孔基底諸如電子裝置可以在它們的不施用重塗層難以密封的組成部分之間具有小裂縫或間隙。該等裝置通常是藉由將它們封閉在墊圈殼中，或藉由用疏水處理對它們噴霧，或藉由基於電漿的化學氣相沈積方法密封的。密封的墊圈殼包含截留的氣體。當在低於大氣壓的壓力下時，如例如在飛機上或高海拔下經常遇到的，該等截留的氣體膨脹並且可能使該殼裂開。噴霧的疏水處理在密封小裂縫和開口上有困難。電漿增強的化學氣相沈積係昂貴的、緩慢的並且是不容易覆蓋裝置的所有表面的視線方法。 Non-porous substrates such as electronic devices may have small cracks or gaps between their components that are difficult to seal without applying a heavy coating. Such devices are typically sealed by enclosing them in a gasket shell, or by spraying them with a hydrophobic treatment, or by plasma-based chemical vapor deposition. The sealed gasket shell contains trapped gas. When under subatmospheric pressure, as is often encountered, for example, on an aircraft or at high altitudes, the trapped gases expand and may crack the shell. The hydrophobic treatment of the spray has difficulty sealing small cracks and openings. Plasma enhanced chemical vapor deposition is expensive, slow, and is a line of sight method that does not easily cover all surfaces of the device.

本發明係一種用於施用有機聚合物塗覆基底之方法。該方法包括以下步驟：1)在非聚合條件下，將在22℃下為液體或一種或多種固體在液相中的懸浮液的可固化的塗料組成物施用到該基底的至少一個表面上，其中該可固化的塗料組成物含有i)至少一種可聚合單體，該可聚合單體在自由基的存在下聚合，每分子恰好具有一個可自由基聚合的基團並且具有在一個大氣壓下至少100℃的沸騰溫度，和2)至少一種熱活化的聚合引發劑，該可固化的組成物基於該塗料組成物的總重量含有按重量計不超過10%的具有在一個大氣壓下低於100℃的沸騰溫度的有機化合物和按重量計不超過5% 的水；然後2)在非聚合條件下，從含有具有施用的可固化塗層的基底的容器的內部吹掃分子氧，3)在步驟2)期間和/或之後，用貧氧氣體將該含有具有施用的可固化塗層的基底的吹掃的容器加壓至實際至少120kPa的氣體壓力，並且然後，不將該具有施用的可固化塗層的基底暴露於含有1莫耳百分數或更多氧的氣氛下，4)藉由在貧氧條件下將該具有施用的可固化的塗料組成物的基底加熱至足以活化該熱活化的聚合引發劑並且引發該至少一種可聚合單體的聚合的溫度來至少部分地固化該可固化的塗料組成物，以在該基底上形成至少部分固化的有機聚合物塗層。 The present invention is a method for applying an organic polymer coated substrate. The method comprises the steps of: 1) applying, under non-polymerization conditions, a curable coating composition of a liquid or a suspension of one or more solids in a liquid phase at 22 ° C to at least one surface of the substrate, Wherein the curable coating composition comprises i) at least one polymerizable monomer polymerized in the presence of a free radical, each molecule having exactly one free-radically polymerizable group and having at least one atmospheric pressure a boiling temperature of 100 ° C, and 2) at least one thermally activated polymerization initiator containing no more than 10% by weight based on the total weight of the coating composition and having a temperature of less than 100 ° C at one atmosphere Boiling temperature of the organic compound and no more than 5% by weight of water; then 2) purging the molecular oxygen from the interior of the vessel containing the substrate with the applied curable coating under non-polymerization conditions, 3) in the step 2) during and/or after, pressurizing the purged vessel containing the substrate with the applied curable coating to an actual gas pressure of at least 120 kPa with an oxygen-lean gas, and then, without The substrate of the applied curable coating is exposed to an atmosphere containing 1 mole percent or more of oxygen, 4) heating the substrate having the applied curable coating composition under oxygen depleted conditions sufficient to activate the substrate The thermally activated polymerization initiator and the temperature at which the polymerization of the at least one polymerizable monomer is initiated to at least partially cure the curable coating composition to form an at least partially cured organic polymer coating on the substrate.

本發明還是一種用於固化塗覆有可固化的塗料組成物的基底之反應容器，該反應容器包括：限定用於容納該塗覆的基底的該反應容器的內部空間之外壁；至少一個用於***和移除該塗覆的基底的可密封的開口；用於密封該可密封的開口之裝置；至少一個用於將氣體引入到該內部空間中和去除的氣體端口；至少一個佈置在該內部空間內的心軸，所述心軸具有縱向孔和多個開口，該等開口產生從該縱向孔進入該反應容器的該內部空間中的流體路徑，該縱向孔還與該至少一個氣體端口處於流體連通；用於將氣體輸送到所述至少一個氣體端口的至少一個中，穿過該心軸，穿過該心軸的開口並且穿過該內部空間並且與佈置在該內部空間中的 塗覆的基底接觸並且從所述至少一個氣體端口的至少一個離開的裝置，用於加壓該反應容器的該內部空間之裝置，以及用於加熱該反應容器的該內部空間之加熱裝置。 The present invention is also a reaction vessel for curing a substrate coated with a curable coating composition, the reaction vessel comprising: an outer space outer wall defining the reaction vessel for containing the coated substrate; at least one for a sealable opening for inserting and removing the coated substrate; means for sealing the sealable opening; at least one gas port for introducing gas into and removing the interior space; at least one disposed within the interior a mandrel in the space, the mandrel having a longitudinal bore and a plurality of openings, the openings creating a fluid path from the longitudinal bore into the interior space of the reaction vessel, the longitudinal bore being further in position with the at least one gas port Fluidly communicating; for delivering gas into at least one of the at least one gas port, through the mandrel, through the opening of the mandrel and through the interior space and with coating disposed in the interior space Means that contact the substrate and exit from at least one of the at least one gas port, means for pressurizing the interior space of the reaction vessel, and a heating device for heating the internal space of the reaction vessel.

圖1係用於在本發明的方法中使用的設備之正視圖。 Figure 1 is a front elevational view of an apparatus for use in the method of the present invention.

圖2係用於在本發明中使用的設備之正剖面圖。 Figure 2 is a front cross-sectional view of an apparatus for use in the present invention.

圖3係用於在本發明中使用的設備之正剖面圖，具有佈置在反應容器中並且藉由圍繞該心軸捲繞紡織品圍繞圖2的中央心軸10捲繞的纏繞的紡織品。 3 is a front cross-sectional view of an apparatus for use in the present invention having a entangled textile disposed in a reaction vessel and wound around the central mandrel 10 of FIG. 2 by winding the textile around the mandrel.

在本發明的方法之步驟1)中，將如在此描述的可固化的塗料組成物施用在該基底上。因為該可固化組成物係液體或懸浮液，可以藉由很多常規方法中的任一種將其施用到基底上，如藉由輥塗、刷塗、噴塗、將該基底浸入該組成物中，施用攪拌棒(puddle)並且使用例如氣刀或刮刀將該組成物刮至該基底上或該基底中，以及其他方法。當該可固化的塗料組成物含有大量的液體載體時，可以使用浸漬法。浸漬法之後通常接著在固化之前用於去除過量的塗料組成物的手段。 In step 1) of the process of the invention, a curable coating composition as described herein is applied to the substrate. Since the curable composition is a liquid or a suspension, it can be applied to a substrate by any of a number of conventional methods, such as by roller coating, brushing, spraying, dipping the substrate into the composition, and applying The puddle is squirted and the composition is scraped onto the substrate or into the substrate using, for example, an air knife or spatula, among other methods. When the curable coating composition contains a large amount of liquid carrier, a dipping method can be used. The means of removing excess coating composition is typically followed by a dipping process followed by curing.

在步驟1)期間的條件係非聚合條件。非聚合條件係這樣的條件使得在此步驟期間發生一種或多種單體的很少(不大於10莫耳%，較佳的是不大於5莫耳%)固化或沒有發生固化。特別地，在步驟1)期間的溫度被選擇為使得該熱活化的聚合引發劑沒有被活化。在步驟1)期間的溫度較佳的是低於該熱活化的聚合引發劑的一小時半衰期溫度。此外，較佳 的是在該塗覆步驟期間不存在其他來源的自由基。為了本發明之目的，包括低於該熱活化的聚合引發劑的一小時半衰期溫度的溫度並且不包括其他來源的自由基的條件被認為係非聚合條件。 The conditions during step 1) are non-polymerization conditions. The non-polymerization conditions are such that little or no (less than 10 mol%, preferably no more than 5 mol%) of one or more monomers are cured or not cured during this step. In particular, the temperature during step 1) is chosen such that the thermally activated polymerization initiator is not activated. The temperature during step 1) is preferably lower than the one hour half-life temperature of the heat activated polymerization initiator. Furthermore, it is preferred that no free radicals of other origin are present during the coating step. For the purposes of the present invention, conditions including a temperature below the one-hour half-life temperature of the heat-activated polymerization initiator and not including free radicals from other sources are considered to be non-polymerization conditions.

在步驟1)期間的壓力和溫度條件也被選擇為使得該一種或多種單體和熱活化的聚合引發劑不明顯地揮發。例如，步驟1)可以是在約1巴的大氣壓力，即約50至150kPa或約90至119kPa下進行。 The pressure and temperature conditions during step 1) are also selected such that the one or more monomers and the thermally activated polymerization initiator do not significantly volatilize. For example, step 1) can be carried out at an atmospheric pressure of about 1 bar, i.e., about 50 to 150 kPa or about 90 to 119 kPa.

較佳的塗層重量係1至150克/平方米被塗覆的基底的面積(g/m²)，尤其是1.5g/m²至70g/m²或1.5至20g/m²。在特定的具體實例中，該塗層重量可以是，例如，1.5至10或1.5至5g/m²或6至15g/m²，然而對於更重的基底(尤其是多孔基底)，該塗層重量可以更高。藉由浸漬填充或藉由使用兩個或更多個串聯的化學品轉移裝置或者藉由使該基底藉由化學品轉移裝置多次可以施用較高的塗覆重量。本發明的顯著優點係非常低的塗層重量容易地被施用並且存在最少的化學“廢物”或蒸發損失。 A preferred coating weight is from 1 to 150 grams per square meter of coated substrate area (g/m ² ), especially from 1.5 g/m ² to 70 g/m ² or from 1.5 to 20 g/m ² . In a particular embodiment, the coating weight can be, for example, 1.5 to 10 or 1.5 to 5 g/m ² or 6 to 15 g/m ² , whereas for heavier substrates (especially porous substrates), the coating The weight can be higher. A higher coating weight can be applied by impregnation filling or by using two or more chemical transfer devices in series or by having the substrate multiple times by a chemical transfer device. A significant advantage of the present invention is that very low coating weights are easily applied and there is minimal chemical "waste" or evaporation loss.

然後將分子氧從包含塗覆的基底的容器中吹掃。藉由“吹掃”，它簡單地是指從容器內的氣氛中將分子氧去除。較佳的是，該吹掃步驟還去除了與基底的表面接觸的分子氧，以及留在該基底中的流體連通到基底表面的任何孔或間隙空間的並且因此可以在該過程期間與施用的可固化塗料接觸的分子氧。例如，在吹掃之前，分子氧可以佔據該等孔或間隙空間的全部或一部分。在這種情況下，該分子氧典型地作為截留空氣的組分存在。紡織品，例如，通常是具有構成該材料的交叉纖維之間的孔隙空間的高度多孔的材料。一些分子氧可以化學吸附或物理吸附到基底的一個或多個表面上。在該吹掃步驟期間，化學吸附的或物理吸附的分子氧較 佳的是被去除，並且分子氧較佳的是從此類間隙空間中被去除。電子裝置在它的構成部分的連接處可以具有通孔、或者小裂縫或開口，從該等通孔、或者小裂縫或開口分子氧較佳的是在該吹掃步驟2)期間被去除。 Molecular oxygen is then purged from the vessel containing the coated substrate. By "purging" it simply means removing molecular oxygen from the atmosphere within the container. Preferably, the purging step also removes molecular oxygen in contact with the surface of the substrate, and fluid in the substrate communicates to any pores or interstitial spaces of the surface of the substrate and can therefore be applied during the process Molecular oxygen in contact with the curable coating. For example, molecular oxygen may occupy all or a portion of the pores or interstitial spaces prior to purging. In this case, the molecular oxygen is typically present as a component of trapped air. Textiles, for example, are typically highly porous materials having a void space between the intersecting fibers that make up the material. Some molecular oxygen can be chemisorbed or physically adsorbed onto one or more surfaces of the substrate. Preferably, the chemisorbed or physically adsorbed molecular oxygen is removed during the purging step, and the molecular oxygen is preferably removed from such interstitial spaces. The electronic device may have through holes, or small cracks or openings at the junction of its constituent parts, from which the molecular oxygen is preferably removed during the purge step 2).

該吹掃步驟2)係在如關於步驟1)描述的非聚合條件下進行的。此外，在該吹掃步驟2)期間的壓力和溫度條件被選擇為使得該一種或多種單體和熱活化的聚合引發劑不揮發。 This purge step 2) is carried out under the non-polymerization conditions as described in relation to step 1). Furthermore, the pressure and temperature conditions during the purge step 2) are selected such that the one or more monomers and the thermally activated polymerization initiator are not volatile.

該吹掃步驟可以以多種方式進行。 This purging step can be performed in a variety of ways.

執行該吹掃步驟的一種方式係將具有施用的可固化塗料的基底放置在容器中，並且將該容器中的氣氛替換為貧氧氣體。如果該基底係多孔的(如對於大多數紡織品的情況)，該貧氧氣體可以流動穿過該基底以從該等孔中機械地推動截留空氣或分子氧。因此，例如，可以將具有施用的可固化塗料的基底放置在容器中並且將貧氧氣體流引入到該容器中，同時去除氣體，使得該貧氧氣體的流動路徑穿過該基底和/或經過該基底的表面。穿過和/或經過該基底的這個氣體流機械地替換截留空氣或分子氧。對於電子器件的塗層，例如，使用氣體壓力說明置換在電路元件與印刷電路板之間的微小開口和小裂紋和空隙中的截留空氣。跨越容器和/或藉由該基底的約0.1至2MPa的壓力降經常足以以這種方式移去分子氧。如果希望的話，可以監測所去除的氣體的分子氧含量，並且在這種情況下貧氧氣體流可以繼續直到所抽取的氣體的分子氧含量降至小於1莫耳百分比、小於0.1莫耳百分比，或某一更低的值，如果希望的話。 One way to perform this purging step is to place the substrate with the applied curable coating in a container and replace the atmosphere in the container with an oxygen-depleted gas. If the substrate is porous (as is the case for most textiles), the oxygen-depleted gas can flow through the substrate to mechanically push trapped air or molecular oxygen from the holes. Thus, for example, a substrate having an applied curable coating can be placed in a container and an oxygen-lean gas stream can be introduced into the container while the gas is removed such that the flow path of the oxygen-depleted gas passes through the substrate and/or The surface of the substrate. This gas flow through and/or through the substrate mechanically replaces trapped air or molecular oxygen. For the coating of electronic devices, for example, the use of gas pressure is described to replace the tiny openings between the circuit components and the printed circuit board and the trapped air in the small cracks and voids. A pressure drop across the vessel and/or by the substrate of about 0.1 to 2 MPa is often sufficient to remove molecular oxygen in this manner. If desired, the molecular oxygen content of the removed gas can be monitored, and in this case the oxygen-depleted gas stream can continue until the molecular oxygen content of the extracted gas drops to less than 1 mole percent, less than 0.1 mole percent, Or a lower value, if desired.

用於本發明目的之貧氧氣體係含有最多1莫耳百分比的分子氧(O₂)、較佳的是不大於0.1莫耳百分比的分子氧的氣體。該貧氧氣體 可以含有至少98莫耳百分比、較佳的是至少99莫耳百分比並且更較佳的是至少99.9莫耳百分比的惰性氣體如氮氣、氬氣、二氧化碳、蒸汽、氦氣或其任何兩種或更多種的混合物。在一些具體實例中，該貧氧氣體可以含有一種或多種氣相、可聚合的單體，該等單體在一個大氣壓下具有40℃或更小的沸騰溫度和一個或多個可聚合的碳-碳雙鍵。此類氣相單體的實例包括乙烯、丙烯、四氟乙烯、六氟丙烯和類似物。一種較佳的貧氧氣體包括至少98莫耳百分比的氮氣和最高達0.1莫耳百分比的分子氧，其餘部分係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。另一種較佳的貧氧氣體包括至少50莫耳百分比的氮氣、最高達1莫耳百分比或最高達0.1莫耳百分比的分子氧、最高達49.9莫耳百分比的氣相單體，其餘部分(如果有的話)係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。另一種貧氧氣體包括至少98莫耳百分比的蒸汽和最高達0.1莫耳百分比的分子氧，其餘部分係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。還另一種較佳的貧氧氣體包括至少50莫耳百分比的蒸汽、最高達1莫耳百分比或最高達0.1莫耳百分比的分子氧、最高達49.9莫耳百分比的氣相單體，其餘部分(如果有的話)係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。 The oxygen-depleted system for the purposes of the present invention contains up to 1 mole percent of molecular oxygen (O ₂ ), preferably no more than 0.1 mole percent of molecular oxygen. The oxygen-depleted gas may contain at least 98 mole percent, preferably at least 99 mole percent, and more preferably at least 99.9 mole percent inert gas such as nitrogen, argon, carbon dioxide, steam, helium or any of a mixture of two or more. In some embodiments, the oxygen-depleted gas may contain one or more gas phase, polymerizable monomers having a boiling temperature of 40 ° C or less and one or more polymerizable carbons at one atmosphere pressure - Carbon double bond. Examples of such gas phase monomers include ethylene, propylene, tetrafluoroethylene, hexafluoropropylene, and the like. A preferred oxygen-depleted gas comprises at least 98 mole percent nitrogen and up to 0.1 mole percent molecular oxygen, the balance being trace gases, which are gases at room temperature and 1 atmosphere. Another preferred oxygen-depleted gas comprises at least 50 mole percent nitrogen, up to 1 mole percent or up to 0.1 mole percent molecular oxygen, up to 49.9 mole percent of gas phase monomer, and the remainder (if If any, it is a trace amount of gas which is a gas at room temperature and 1 atm. Another oxygen-depleted gas comprises at least 98 mole percent of steam and up to 0.1 mole percent of molecular oxygen, the remainder being trace gases, which are gases at room temperature and 1 atmosphere. Still another preferred oxygen-depleted gas comprises at least 50 mole percent of steam, up to 1 mole percent or up to 0.1 mole percent of molecular oxygen, up to 49.9 mole percent of gas phase monomer, and the remainder ( Trace gas, if any, is a gas at room temperature and 1 atm.

吹掃步驟可以藉由機械地壓縮該具有施用的可固化塗層的基底以從孔或其他間隙位置除去分子氧進行，如果機械壓縮可以完成而不損傷該基底的話。可以例如藉由以下方式在紡織品上進行此種壓縮：在輥之間壓縮該塗覆的紡織品，該等輥中的一個或兩個可以被加熱，靠著鼓或其他表面(其再次可以被加熱)拉緊該塗覆的紡織品，藉由物理壓縮和釋 放折疊織物絨頭，或者以其他方式。機械壓縮可以在貧氧氣體中進行使得當壓縮力被移除時分子氧不重新進入空隙空間。 The purging step can be performed by mechanically compressing the substrate with the applied curable coating to remove molecular oxygen from the pores or other interstitial locations if mechanical compression can be accomplished without damaging the substrate. This compression can be carried out on the textile, for example by compressing the coated textile between rolls, one or both of which can be heated against the drum or other surface (which can be heated again The fabric is stretched by physical compression and release of the folded fabric pile, or otherwise. Mechanical compression can be performed in an oxygen-lean gas such that molecular oxygen does not re-enter the void space when the compressive force is removed.

吹掃分子氧的另一種方式係將該基底放置在減小的大氣壓力下，只要該一種或多種單體和自由基引發劑不揮發至它們在該可固化的塗料組成物中的初始濃度的小於30%的濃度。 Another way of purging molecular oxygen is to place the substrate at a reduced atmospheric pressure as long as the one or more monomers and free radical initiator do not volatilize to their initial concentration in the curable coating composition. Less than 30% concentration.

可以使用用於移除空氣的以上方法的組合。 A combination of the above methods for removing air can be used.

在步驟2)期間和/或之後，含有該吹掃的具有該施用的可固化塗層的基底的反應容器用貧氧氣體加壓到實際至少120kPa的氣體壓力。正如步驟1)和2)，此加壓步驟3)係在非聚合條件下進行的。 During and/or after step 2), the reaction vessel containing the purged substrate having the applied curable coating is pressurized with an oxygen-depleted gas to a gas pressure of at least 120 kPa. As in steps 1) and 2), this pressurization step 3) is carried out under non-polymerization conditions.

在加壓步驟3)中，該氣體壓力可以是，例如，至少500kPa或至少750kPa。原則上不存在該氣體壓力的上限，除了對反應容器和相關設備的限制外。該氣體壓力的實際上限係約15MPa。在一些具體實例中，該氣體壓力係最高達約12MPa、最高達11MPa、最高達10MPa、最高達5MPa、3.5MPa、最高達2.5MPa或最高達1.5MPa。所有氣體壓力係實際的，除非另外指明。 In the pressurization step 3), the gas pressure may be, for example, at least 500 kPa or at least 750 kPa. In principle, there is no upper limit to the gas pressure, except for restrictions on the reaction vessel and associated equipment. The actual upper limit of the gas pressure is about 15 MPa. In some embodiments, the gas pressure system is up to about 12 MPa, up to 11 MPa, up to 10 MPa, up to 5 MPa, 3.5 MPa, up to 2.5 MPa, or up to 1.5 MPa. All gas pressures are actual unless otherwise indicated.

已經發現在加壓步驟3)中施加的壓力影響處理過的基底的特性。當該基底係織物時，在加壓步驟3)期間增加壓力傾向於產生具有比當使用較低的壓力時更高的空氣滲透性的處理過的織物。因此，對在加壓步驟3)期間所施加的壓力的選擇可以被用作指令引數以改變該處理過的織物的空氣滲透性。儘管本發明不局限於任何理論，據信較高的壓力傾向於產生較薄的塗層，這增加了紗線之間的空間，從而增加空氣滲透性。 It has been found that the pressure applied in the pressurization step 3) affects the properties of the treated substrate. When the substrate is woven, increasing the pressure during the pressurization step 3) tends to result in a treated fabric having a higher air permeability than when a lower pressure is used. Thus, the selection of the pressure applied during the pressurization step 3) can be used as an instructional index to change the air permeability of the treated fabric. Although the invention is not limited to any theory, it is believed that higher pressures tend to result in a thinner coating which increases the space between the yarns, thereby increasing air permeability.

據信該加壓步驟說明推動該塗料進入多孔基底例如紡織品 的內部並且還幫助抵靠構成該基底的單獨的纖維和/或長絲鋪展該塗層。這被認為允許塗料組成物滲透在單獨的纖維和/或長絲之間，甚至在如從紡成的纖維如紡成的短纖維織成的織物的情況下，這非常難以不使用加壓步驟實現。 It is believed that this pressurization step illustrates pushing the coating into the interior of a porous substrate, such as a textile, and also helping to spread the coating against individual fibers and/or filaments that make up the substrate. This is believed to allow the coating composition to penetrate between the individual fibers and/or filaments, even in the case of fabrics woven from stapled fibers such as spun staple fibers, which is very difficult without the use of a pressurization step. achieve.

對於電子器件基底，該加壓步驟被認為推動該塗層進入電路元件和電路元件與印刷電路板(例如)之間的微小空間並且進入微小開口，如接觸點和金屬通孔。 For electronic device substrates, this pressurization step is believed to push the coating into tiny spaces between the circuit components and circuit components and the printed circuit board (for example) and into tiny openings such as contact points and metal vias.

在一些具體實例中，該加壓步驟3)可以作為吹掃步驟2)的一部分進行。例如，該吹掃步驟2)可以藉由進行一個或多個加壓/減壓循環來執行，其中在每個循環中用貧氧氣體將含有該塗覆的基底的該容器加壓至超大氣壓(如以上關於加壓步驟3)描述的)並且然後減壓至例如實際50至150kPa的壓力。可以執行最高達20個、最高達10個或最高達3個這種加壓/減壓循環。此循環的一個或多個加壓部分對應於加壓步驟3)；在這種情況下不需要後續加壓步驟並且因此可以如期望的被消除，但是可以進行最終加壓步驟，如果希望的話。 In some embodiments, the pressurization step 3) can be performed as part of the purge step 2). For example, the purging step 2) can be performed by performing one or more pressurization/depressurization cycles in which the vessel containing the coated substrate is pressurized to superatmospheric pressure with an oxygen-depleted gas in each cycle. (as described above with respect to pressurization step 3) and then reduced to a pressure of, for example, actual 50 to 150 kPa. Up to 20, up to 10 or up to 3 such pressurization/decompression cycles can be performed. One or more pressurization portions of this cycle correspond to pressurization step 3); in this case no subsequent pressurization step is required and thus can be eliminated as desired, but a final pressurization step can be performed, if desired.

當該基底在被塗覆之前具有低空氣滲透性，如使用Textest FX 3300儀器和38cm²測試面積根據ASTM D797測量的3標準立方英呎/分鐘/平方英呎(0.01524m/秒)或更低時，進行如剛剛描述的加壓/減壓循環係特別有益的。 The substrate has low air permeability before being coated, such as using a Textest FX 3300 instrument and a 38 cm ² test area measured according to ASTM D797 of 3 standard cubic inches per minute per square inch (0.01524 m / sec) or less. At the time, it is particularly advantageous to carry out the pressurization/decompression cycle as just described.

該可固化的塗料組成物然後藉由在貧氧條件下加熱具有該施用的可固化的塗料組成物的該基底至少部分地固化。“貧氧條件”為了本發明的目的意味著聚合係在如前描述的貧氧氣氛中，或當該基底被浸入 在液體或超臨界流體中時進行的。較佳的液體具有80℃至220℃、較佳的是80℃至145℃的沸騰溫度(在1大氣壓下)。在步驟3)中用貧氧氣體加壓之後，該塗覆的基底不暴露於包含1莫耳百分比或更多氧的氣氛直至在進行步驟4)之後。 The curable coating composition is then at least partially cured by heating the substrate having the applied curable coating composition under oxygen-poor conditions. "Oxygen-poor conditions" for the purposes of the present invention means that the polymerization is carried out in an oxygen-lean atmosphere as previously described, or when the substrate is immersed in a liquid or supercritical fluid. Preferred liquids have a boiling temperature (at 1 atmosphere) of from 80 ° C to 220 ° C, preferably from 80 ° C to 145 ° C. After pressurization with the oxygen-depleted gas in step 3), the coated substrate is not exposed to an atmosphere containing 1 mole percent or more of oxygen until after step 4).

在一些具體實例中，進行聚合步驟4)而來自步驟3)的塗覆的基底係在貧氧氣體下。在此類具體實例中，聚合步驟4)可在其中進行加壓步驟3)的同一個容器中進行。在這樣的情況下，步驟4)可在如關於加壓步驟3)描述的超大氣壓下進行。 In some embodiments, the polymerization step 4) is carried out while the coated substrate from step 3) is under an oxygen-lean gas. In such specific examples, the polymerization step 4) can be carried out in the same vessel in which the pressurization step 3) is carried out. In such a case, step 4) can be carried out under superatmospheric pressure as described with respect to pressurization step 3).

在一些具體實例中，將該塗覆的基底從步驟3)開始繼續維持在這樣的超大氣壓條件下直到進行聚合步驟4)。該聚合物在超大氣壓下的固化被認為將聚合物固定在適當位置，使得當加壓條件被釋放時，該聚合物保持在適當位置以提供所希望的塗覆特性。 In some embodiments, the coated substrate is maintained from step 3) under such superatmospheric conditions until polymerization step 4) is carried out. Curing of the polymer under superatmospheric pressure is believed to hold the polymer in place such that when the pressurized conditions are released, the polymer remains in place to provide the desired coating characteristics.

在其他具體實例中，進行聚合步驟4)，其中將來自步驟3)的塗覆的基底浸入在液體或超臨界流體如超臨界二氧化碳中。 In other embodiments, polymerization step 4) is carried out wherein the coated substrate from step 3) is immersed in a liquid or supercritical fluid such as supercritical carbon dioxide.

在該固化步驟4)中，將該基底和施用的可固化的塗料組成物加熱至足以活化該熱活化的聚合引發劑並且引發聚合的溫度。 In this curing step 4), the substrate and the applied curable coating composition are heated to a temperature sufficient to activate the thermally activated polymerization initiator and initiate polymerization.

當進行固化步驟4)時，該容器可以被密封以防止氣體從該容器的內部逸出。即使被密封，該容器可以包含裝置如安全閥，其用於如果該反應器壓力超過預定值的話從該反應器的內部排出氣體，和/或用於將壓力調節到預定值。這也是在本發明的範圍內以維持在步驟4)期間氣體流通過該容器，只要維持所需壓力並且該容器中的氣氛(如果有的話)保持貧氧。 When the curing step 4) is carried out, the container can be sealed to prevent gas from escaping from the inside of the container. Even if sealed, the vessel may contain means such as a safety valve for venting gas from the interior of the reactor if the reactor pressure exceeds a predetermined value, and/or for adjusting the pressure to a predetermined value. It is also within the scope of the present invention to maintain gas flow through the vessel during step 4) as long as the desired pressure is maintained and the atmosphere in the vessel, if any, remains oxygen-lean.

在浸入在超臨界流體中的情況下，在該聚合步驟之後或期間壓力可以降低，使得超臨界流體轉化為氣相。聚合的其餘部分(如果有的話)可以在這樣的氣相下，在大氣壓力或超大氣壓力下進行。 In the case of immersion in a supercritical fluid, the pressure may be reduced after or during the polymerization step, such that the supercritical fluid is converted to the gas phase. The remainder of the polymerization, if any, can be carried out in such a gas phase at atmospheric or superatmospheric pressure.

在步驟4)中的較佳的固化溫度總體上是從80℃至210℃。該固化溫度可以是至少90℃、至少100℃或至少120℃並且可以最高達190℃、最高達175℃、最高達160℃或最高達150℃。在上述範圍內的較低的固化溫度可以有益於處理更熱敏感的織物，如聚酯、尼龍和聚丙烯織物。在較低的固化溫度，特別是150℃或更低下經常看到較少的織物收縮。例如，在那些較低的固化溫度下經常看到0.5%或更低的織物收縮。最高達140℃的溫度尤其適合用於處理丙烯酸和芳族聚醯胺織物，並且最高達150℃的溫度尤其適合用於處理棉花。 The preferred curing temperature in step 4) is generally from 80 ° C to 210 ° C. The curing temperature can be at least 90 ° C, at least 100 ° C or at least 120 ° C and can be up to 190 ° C, up to 175 ° C, up to 160 ° C or up to 150 ° C. Lower curing temperatures within the above ranges may be beneficial for handling more heat sensitive fabrics such as polyester, nylon and polypropylene fabrics. Less fabric shrinkage is often seen at lower curing temperatures, especially at 150 ° C or lower. For example, fabric shrinkage of 0.5% or less is often seen at those lower curing temperatures. Temperatures up to 140 ° C are particularly suitable for the treatment of acrylic and aromatic polyamide fabrics, and temperatures up to 150 ° C are particularly suitable for the treatment of cotton.

繼續在貧氧條件下的固化直至在該可固化的塗料組成物中至少50莫耳百分比、較佳的是至少75莫耳百分比的該一種或多種可聚合單體被轉化為聚合物。在一些具體實例中，固化係在加壓的貧氧氣體下進行直至在該可固化的塗料組成物中至少75莫耳百分比、至少85%、至少95莫耳百分比或至少98莫耳百分比的該一種或多種可聚合單體被轉化為聚合物。在此步驟期間的轉化率可以達到100%。 Curing under depleted oxygen conditions continues until at least 50 mole percent, preferably at least 75 mole percent of the one or more polymerizable monomers in the curable coating composition are converted to a polymer. In some embodiments, the curing is carried out under a pressurized oxygen-lean gas until at least 75 mole percent, at least 85%, at least 95 mole percent, or at least 98 mole percent of the curable coating composition. One or more polymerizable monomers are converted to a polymer. The conversion rate during this step can reach 100%.

在一些具體實例中，步驟4)在貧氧氣體下在如關於步驟3)描述的超大氣壓力下進行，直到在該可固化的塗料組成物中的可聚合單體的轉化率係50至99莫耳百分比，較佳的是75至95莫耳百分比並且更較佳的是85至95莫耳百分比，並且進一步的固化在實際低於120kPa，例如75至119kPa或95至105kPa的氣體壓力下進行。在其他具體實例中，步驟4) 在貧氧條件下進行直到在該可固化的塗料組成物中的可聚合單體的轉化率係50至99莫耳百分比，較佳的是75至99莫耳百分比，並且進一步的固化係在空氣下進行。在這項工作中，“固化”和“聚合”可互換地使用。 In some embodiments, step 4) is carried out under an oxygen-lean gas at a superatmospheric pressure as described in relation to step 3) until the conversion of the polymerizable monomer in the curable coating composition is from 50 to 99. The percentage of moles, preferably from 75 to 95 mole percent and more preferably from 85 to 95 mole percent, and further curing is carried out at gas pressures actually below 120 kPa, such as 75 to 119 kPa or 95 to 105 kPa. . In other embodiments, step 4) is carried out under oxygen-lean conditions until the conversion of the polymerizable monomer in the curable coating composition is from 50 to 99 mole percent, preferably from 75 to 99 moles. Percentage, and further curing is carried out under air. In this work, "cure" and "polymerization" are used interchangeably.

進行步驟4)所需的時間典型地較短，例如從0.5至60分鐘或從5至20分鐘，儘管更長或更短的時間可以在具體情況中使用。步驟4)所需的時間將當然在一定程度上取決於例如固化溫度、特定單體和特定聚合引發劑的因素。 The time required to carry out step 4) is typically short, for example from 0.5 to 60 minutes or from 5 to 20 minutes, although longer or shorter times can be used in specific situations. The time required for step 4) will of course depend to some extent on factors such as curing temperature, specific monomers and specific polymerization initiators.

它總體上對於在單個反應容器中進行至少步驟2)、3)和4)係有用的。因此，將具有施用的可固化的塗料組成物的基底佈置在該反應容器內並且吹掃分子氧與反應容器。然後將該反應容器用貧氧氣體加壓並且加熱至聚合溫度以便進行可固化的塗料組成物的固化。 It is generally useful for performing at least steps 2), 3) and 4) in a single reaction vessel. Thus, a substrate having the applied curable coating composition is disposed within the reaction vessel and the molecular oxygen is purged with the reaction vessel. The reaction vessel is then pressurized with an oxygen-depleted gas and heated to a polymerization temperature for curing of the curable coating composition.

儘管有可能在同一個反應容器中進行塗覆步驟1)，通常較佳的是在適配為用於施用薄塗層的單獨的設備中進行塗覆步驟。沒有必要在塗覆步驟1)之後立即進行步驟2)、3)和4)。 Although it is possible to carry out the coating step 1) in the same reaction vessel, it is generally preferred to carry out the coating step in a separate apparatus adapted for application of a thin coating. It is not necessary to carry out steps 2), 3) and 4) immediately after the coating step 1).

合適的反應容器係能夠處理在步驟3)和4)中遇到的壓力的高壓釜或其他容器。這樣的反應容器較佳的是包括各種氣體處理設備以進行氣體從該容器的內部空間的引入和除去，用於加壓容器並用於施加熱。這樣的裝置係熟知的並且此種裝置的特殊設計不是必要的。 Suitable reaction vessels are autoclaves or other vessels capable of treating the pressures encountered in steps 3) and 4). Such a reaction vessel preferably includes various gas treatment equipment for introducing and removing gas from the interior space of the vessel for pressurizing the vessel and for applying heat. Such devices are well known and the special design of such devices is not necessary.

圖1-3描繪了一種用於進行本發明的步驟2)、3)和4)的適合裝置。 Figures 1-3 depict a suitable apparatus for carrying out steps 2), 3) and 4) of the present invention.

在圖1-3中，反應容器1包括底部區段13B和頂部區段13A，它們一起限定內部空間5，其中基底7(圖3)被佈置用於進行本發明的步 驟2)、3)和4)。反應容器1係，例如，被適配為經受在該方法中遇到的溫度和壓力的高壓釜或其他容器。當關閉並且在操作中時，底部區段13B和頂部區段13A(圖1)沿著接合點11(圖1)使用任何合適的密封方法，例如像，螺母和螺栓12(圖1)，其他機械密封裝置如夾子、夾具或鉚釘，磁性密封裝置，黏合劑，墊圈，和類似物密封。在圖1中所示的具體實例中，該基底(未示出)被安裝在中央心軸2上，由下部支撐件2A支撐並用板2B保持在適當的位置。中央心軸2具有縱向孔並且具有外部開口10(圖2)，該等外部開口產生從縱向孔進入反應容器1的內部空間5的流體路徑。 In Figures 1-3, the reaction vessel 1 comprises a bottom section 13B and a top section 13A which together define an interior space 5, wherein the substrate 7 (Fig. 3) is arranged for carrying out steps 2), 3) of the invention and 4). The reaction vessel 1 is, for example, an autoclave or other vessel adapted to withstand the temperatures and pressures encountered in the process. When closed and in operation, the bottom section 13B and the top section 13A (Fig. 1) use any suitable sealing method along the joint 11 (Fig. 1), such as, for example, nuts and bolts 12 (Fig. 1), others Mechanical seals such as clips, clamps or rivets, magnetic seals, adhesives, gaskets, and the like are sealed. In the particular example shown in Figure 1, the substrate (not shown) is mounted on the central mandrel 2, supported by the lower support 2A and held in place by the plate 2B. The central mandrel 2 has longitudinal bores and has an outer opening 10 (Fig. 2) that creates a fluid path from the longitudinal bore into the interior space 5 of the reaction vessel 1.

反應容器1進一步包括用於將氣體引入到內部空間5中和從內部空間5中除去氣體的裝置。在所示的較佳的具體實例中，反應容器1配備有第一氣體端口4和視情況第二氣體端口9。如所示，第二氣體端口9與中央心軸2的中心孔流體連通。可替代地，單個氣體端口可以充當入口和出口端口二者。 The reaction vessel 1 further includes means for introducing a gas into and removing gas from the internal space 5. In the preferred embodiment shown, the reaction vessel 1 is equipped with a first gas port 4 and optionally a second gas port 9. As shown, the second gas port 9 is in fluid communication with the central bore of the central mandrel 2. Alternatively, a single gas port can act as both an inlet and an outlet port.

在吹掃步驟2)期間，將貧氧氣體引入內部空間5，穿過中央心軸2中的開口10，並通過氣體端口4和9之一被除去。氣體可以在氣體端口4與氣體端口9之間以任一方向流動。氣體端口4可以是入口端口，通過該入口端口貧氧氣體進入內部空間5並且從那裡流過基底7，進入開口10，通過心軸2的中心孔並且通過氣體端口9離開。可替代地，氣體流動的方向可以顛倒，在經由氣體端口4從內部空間5被提取之前通過氣體端口9流入中央心軸2的中心孔，穿過開口10進入內部空間5並且通過基底7。 During the purge step 2), an oxygen-depleted gas is introduced into the interior space 5, through the opening 10 in the central mandrel 2, and removed through one of the gas ports 4 and 9. Gas can flow in either direction between gas port 4 and gas port 9. The gas port 4 can be an inlet port through which oxygen-depleted gas enters the interior space 5 and flows therethrough from the substrate 7, into the opening 10, through the central bore of the mandrel 2 and exits through the gas port 9. Alternatively, the direction of gas flow may be reversed, flowing into the central bore of the central mandrel 2 through the gas port 9 before being withdrawn from the interior space 5 via the gas port 4, through the opening 10 into the interior space 5 and through the substrate 7.

在圖1-3中所示的具體實例係較佳的設計，特別好地被適配為用於處理成捲繞的商品如捲繞的紡織品。如圖3中所示，柔性基底7如 捲繞的紡織品被圍繞中央心軸2纏繞，或捲繞在芯上，該芯然後被安裝到中央心軸2上。當貧氧氣體從氣體端口4進入中央心軸2的開口10並且從那裡經由氣體端口9從反應容器1離開(或以從氣體端口9到氣體端口4的相反方向)時，它因此行進穿過柔性基底7。這種氣體通過基底的移動係除去在基底7的孔或其他間隙內截留的分子氧的有效方式。 The specific examples shown in Figures 1-3 are preferred designs, particularly well adapted for processing into a wounded article such as a wound textile. As shown in Fig. 3, a flexible substrate 7, such as a wound textile, is wound around a central mandrel 2 or wound onto a core which is then mounted to a central mandrel 2. When the oxygen-depleted gas enters the opening 10 of the central mandrel 2 from the gas port 4 and exits from the reaction vessel 1 via the gas port 9 (or in the opposite direction from the gas port 9 to the gas port 4), it therefore travels through Flexible substrate 7. This movement of gas through the substrate removes an effective means of trapping molecular oxygen trapped within the pores or other spaces of the substrate 7.

在圖1-3中示出的具體實例中，加壓步驟3)和固化步驟4)也在反應容器1中進行。 In the specific example shown in Figures 1-3, the pressurization step 3) and the curing step 4) are also carried out in the reaction vessel 1.

在操作期間，將具有施用的可固化塗料的基底***反應容器1的內部空間5(如果在其中沒有進行塗覆步驟1))。建立進入、穿過並且然後離開內部空間5以吹掃分子氧的貧氧氣體流。這種氣體流可以繼續，例如，直到所抽取的氣體的分子氧含量降到低於1莫耳百分比、低於0.1莫耳百分比或其他預定值。可替代地，該氣體流可以繼續直到等於內部空間5的體積的預定倍數的體積的氣體(例如從2至50反應體積或2至10反應器體積)已被傳送通過反應容器1。 During operation, the substrate with the applied curable coating is inserted into the internal space 5 of the reaction vessel 1 (if no coating step 1 is carried out therein)). An oxygen-lean gas stream that enters, passes through, and then exits the interior space 5 to purge molecular oxygen. This gas flow can continue, for example, until the molecular oxygen content of the extracted gas drops below 1 mole percent, below 0.1 mole percent, or other predetermined value. Alternatively, the gas stream may continue until a predetermined volume of gas equal to the volume of the internal space 5 (eg, from 2 to 50 reaction volumes or 2 to 10 reactor volumes) has been passed through the reaction vessel 1.

在吹掃步驟期間和/或之後，將額外的貧氧氣體引入到含有基底7的反應容器1中，以將內部空間5加壓到如之前所描述的氣體壓力。在反應容器的加壓之後，經由加熱裝置3施加加熱以增加內部空間5中的溫度從而引發聚合。該聚合係在貧氧條件下完成的，較佳的是在貧氧氣體下同時保持如之前所描述的壓力。維持加熱直到至少50莫耳百分比的可聚合單體已經轉化為聚合物。如所示，提供加熱裝置3以加熱反應容器1的內容物用於進行該方法的步驟4)。該加熱裝置可以是，例如，加熱套、電加熱器、輻射加熱器，將反應容器1放置在烘箱或使用天然氣或電加熱的 油浴、或其他適合的加熱裝置中。還有可能藉由加熱被進料到反應容器1中的貧氧氣體進行必要的加熱。 During and/or after the purge step, additional oxygen-depleted gas is introduced into the reaction vessel 1 containing the substrate 7 to pressurize the interior space 5 to the gas pressure as previously described. After the pressurization of the reaction vessel, heating is applied via the heating device 3 to increase the temperature in the internal space 5 to initiate polymerization. The polymerization is carried out under oxygen-depleted conditions, preferably under an oxygen-lean gas while maintaining the pressure as previously described. Heating is maintained until at least 50 mole percent of the polymerizable monomer has been converted to a polymer. As shown, a heating device 3 is provided to heat the contents of the reaction vessel 1 for performing step 4) of the method. The heating means may be, for example, a heating mantle, an electric heater, a radiant heater, and the reaction vessel 1 is placed in an oven or an oil bath using natural gas or electric heating, or other suitable heating means. It is also possible to carry out the necessary heating by heating the oxygen-depleted gas fed into the reaction vessel 1.

在替代具體實例中，將塗覆有該可固化的塗料組成物的紡織品基底打褶，並且在該打褶的紡織品上進行步驟2)、3)和4)。在這樣的具體實例中，該打褶的、塗覆的紡織品可以被包含在具有一個或多個氣體端口的料箱內，通過該一個或多個氣體端口氣體可以被引入或移除以進行吹掃、加壓和固化步驟。該打褶的、塗覆的紡織品可以被打褶以在該料箱中形成一系列的水平層。在這樣的情況下，氣體端口可以被安排在該料箱的底部和頂部處或附近，這樣在吹掃步驟2)期間氣體流可以被建立為向上或向下穿過打褶的、塗覆的紡織品的層。 In an alternative embodiment, the textile substrate coated with the curable coating composition is pleated and steps 2), 3) and 4) are carried out on the pleated textile. In such a specific example, the pleated, coated textile can be contained within a bin having one or more gas ports through which gas can be introduced or removed for blowing Sweep, pressurize and cure steps. The pleated, coated textile can be pleated to form a series of horizontal layers in the bin. In such a case, the gas port can be arranged at or near the bottom and top of the tank so that during the purge step 2) the gas stream can be established to pass up or down through the pleated, coated The layer of textiles.

在剛剛描述的替代具體實例中，該料箱可以是模組式的以允許在其中進行吹掃、加壓和固化步驟的較大壓力容器之外進行裝載、打褶和卸載。在裝載之後，將此類料箱中的一個或多個引入到壓力容器中，並且在該裝載的料箱停留在該壓力容器內的同時進行吹掃、加壓和聚合步驟2)、3)和4)。該壓力容器包含一個或多個入口端口和加熱裝置，該一個或多個入口端口用於將氣體引入到壓力容器和一個或多個料箱的內部並且從其中除去，該加熱裝置使該一個或多個料箱的內容物達到所需的聚合溫度。 In an alternative embodiment just described, the bin may be modular to allow for loading, pleating, and unloading outside of larger pressure vessels in which the purging, pressurizing, and curing steps are performed. After loading, one or more of such bins are introduced into the pressure vessel and the purging, pressurizing and aggregating steps 2), 3) are carried out while the loaded bin remains in the pressure vessel And 4). The pressure vessel includes one or more inlet ports for introducing gas into and out of the pressure vessel and one or more bins, the heating device causing the one or The contents of the plurality of bins reach the desired polymerization temperature.

本發明在一個特定具體實例中係一種用於固化塗覆有可固化的塗料組成物的基底之反應裝置，該反應裝置包括A.限定內部空間的外部壓力腔室，該外部壓力腔室能夠承受實際0.5至15MPa的內部壓力；B.限定內部體積的料箱，該內部體積用於容納在該料箱內的層狀基 底，使得該基底的該等層在該料箱內被水平地安排，這樣的料箱被適配為安裝在該壓力腔室的內部空間內；C.位於該料箱的內部體積的底部處之氣體空間，該氣體空間具有多個在操作期間允許氣體進入該內部體積料箱中的開口；D.至少一個位於該料箱的頂部處或頂部附近的開口用於從該料箱的該內部體積中去除氣體；以及E.用於加熱該料箱的該內部體積之加熱裝置；F.用於建立在該料箱係該外部壓力腔室的內部空間時到該氣體空間中並穿過該氣體空間，穿過該料箱中的層狀織物並且通過位於該料箱的頂部處或頂部附近的所述至少一個開口離開該料箱的氣體流之氣體循環裝置；以及G.用於在該外部壓力腔室的內部空間內建立超大氣壓之裝置。 In one particular embodiment, the invention is a reaction apparatus for curing a substrate coated with a curable coating composition, the reaction apparatus comprising A. an external pressure chamber defining an interior space, the external pressure chamber being capable of withstanding Actual internal pressure of 0.5 to 15 MPa; B. a bin defining an internal volume for receiving a layered substrate within the bin such that the layers of the substrate are horizontally arranged within the bin, Such a tank is adapted to be mounted within the interior space of the pressure chamber; C. a gas space at the bottom of the internal volume of the tank, the gas space having a plurality of gases allowed to enter the internal volume during operation An opening in the bin; D. at least one opening at or near the top of the bin for removing gas from the interior volume of the bin; and E. for heating the interior volume of the bin a heating device; F. for establishing the inner space of the outer pressure chamber of the tank into the gas space and passing through the gas space, passing through the layered fabric in the tank and passing through the material Gas circulation means of the gas flow at the top or near the top of the at least one opening exiting the tank; and G. means for establishing superatmospheric pressure within the interior space of the outer pressure chamber.

使用這樣的裝置，該層狀基底被塗覆有該可固化的塗料組成物並且以層狀方式被引入該料箱中使得多個水平排列的塗覆的基底層存在於該料箱中。然後將該料箱引入該外部壓力腔室的內部，在這裡進行吹掃步驟2)、加壓步驟3)和聚合步驟4。在至少吹掃步驟2)期間，將清洗氣體通過在該氣體空間中的開口引入到該料箱中，向上流動穿過基底的層，並且在該料箱的頂部處或附近被抽出。所抽出的氣體可以流動進入外部壓力腔室的內部空間中。加壓步驟3)藉由以下方式在該外部壓力腔室中用該料箱進行：或者藉由a)將氣體通過該氣體空間的開口引入到該料箱中(同時或者防止該氣體從該料箱逸出或藉由允許該氣體從該料箱中逸出到該外部壓力腔室)或藉由加壓該外部壓力腔室的內部空間同時允許加壓氣體通 過一個或多個連接內部空間與該料箱的內部的流體導管從該外部壓力腔室的內部空間進入該料箱。 Using such a device, the layered substrate is coated with the curable coating composition and introduced into the bin in a layered manner such that a plurality of horizontally aligned coated substrate layers are present in the bin. The tank is then introduced into the interior of the external pressure chamber where a purge step 2), a pressurization step 3) and a polymerization step 4 are carried out. During at least the purge step 2), the purge gas is introduced into the tank through an opening in the gas space, flows upward through the layer of the substrate, and is withdrawn at or near the top of the tank. The extracted gas can flow into the internal space of the external pressure chamber. Pressurization step 3) is carried out in the external pressure chamber by means of the tank: or by a) introducing a gas into the tank through an opening of the gas space (along with or preventing the gas from the material) The tank escapes or by allowing the gas to escape from the tank to the external pressure chamber or by pressurizing the internal space of the external pressure chamber while allowing pressurized gas to pass through one or more connected internal spaces A fluid conduit inside the tank enters the bin from the interior space of the external pressure chamber.

該加熱裝置F.可以是如在以上描述的任何加熱裝置。 The heating device F. may be any of the heating devices as described above.

該氣體循環裝置G.包括用於將氣體從氣體源供應到該氣體空間的導管，和用於建立壓力差的裝置，該壓力差提供用於通過該氣體空間的開口移動氣體，穿過該料箱中的基底層並且在該料箱的頂部處或附近離開開口的動力。該用於建立壓力差的裝置可以包括，例如，加壓氣體來源；風扇或鼓風機或泵；真空泵和類似物。 The gas circulation device G. includes a conduit for supplying a gas from the gas source to the gas space, and means for establishing a pressure difference, the pressure differential providing for moving the gas through the opening of the gas space, through the material The base layer in the tank and the power to leave the opening at or near the top of the tank. The means for establishing a pressure differential may include, for example, a source of pressurized gas; a fan or blower or pump; a vacuum pump and the like.

已經發現在固化之前塗覆、吹掃和加壓的順序步驟導致固化的塗層的有效性的顯著和出乎意外的改進，特別是當施用於紡織品和電子裝置時。特別地，以這種方式施用和固化的塗層通常表現出比當省略加壓步驟3)時顯著更好的拒水性。儘管本發明不局限於任何理論，據信在步驟3)中施加的增加的壓力機械地迫使該可固化的塗料組成物進入基底的表面中的孔、間隙、裂縫或其他小的開口中，由此有助於該塗料組成物滲透進入此類小開口中並使它們密封。該可固化組成物然後在適當位置固化以便當氣體壓力被釋放時產生永久性密封。 It has been found that the sequential steps of coating, purging and pressurizing prior to curing result in significant and unexpected improvements in the effectiveness of the cured coating, particularly when applied to textiles and electronic devices. In particular, coatings applied and cured in this manner generally exhibit significantly better water repellency than when the pressurization step 3) is omitted. Although the invention is not limited to any theory, it is believed that the increased pressure applied in step 3) mechanically forces the curable coating composition into holes, gaps, cracks or other small openings in the surface of the substrate, This helps the coating composition to penetrate into such small openings and seal them. The curable composition is then cured in place to create a permanent seal when the gas pressure is released.

在其中該可固化的塗料組成物含有小顆粒的情況下，小顆粒的一些或所有可以被迫進入此類開口中以形成機械密封或用於錨定所述顆粒，由此提供針對使用相關的顆粒損失的衣物耐久性和耐磨性二者。 Where the curable coating composition contains small particles, some or all of the small particles may be forced into such openings to form a mechanical seal or for anchoring the particles, thereby providing for use-related Both grain durability and abrasion resistance of the fabric are lost.

在步驟4)中的增加的壓力傾向於限制在固化步驟4)期間該可固化的塗料組成物的各種組分的揮發，特別是如下所述的某些載體化合物和/或揮發性單體。特別地，已經發現當該可固化的塗料組成物含有 一種或多種在聚合步驟4)的溫度下具有1至67kPa(約10至500托)、尤其是6.7至53kPa(約50至400托)的蒸氣壓力的化合物時該方法係相當有益的。這樣的化合物可以是，例如，如以下所述的一種或多種單體和/或一種或多種載體材料。在110℃至125℃的聚合溫度下具有在上述範圍內的蒸氣壓力的可固化的塗料組成物的組分的實例包括，例如，三甲氧基(1H,1H,2H,2H-十七氟癸基)矽烷、全氟己基乙基丙烯酸酯、全氟己基乙烯和全氟辛基乙烯。該可固化的塗料組成物可以包含，例如，至少1重量百分比、至少5重量百分比、至少10重量百分比、至少25重量百分比或至少45重量百分比的具有如在本段中所描述的蒸氣壓力的化合物。 The increased pressure in step 4) tends to limit the volatilization of the various components of the curable coating composition during the curing step 4), particularly certain carrier compounds and/or volatile monomers as described below. In particular, it has been found that when the curable coating composition contains one or more of from 1 to 67 kPa (about 10 to 500 Torr), especially from 6.7 to 53 kPa (about 50 to 400 Torr) at the temperature of the polymerization step 4) This method is quite beneficial when it comes to vapor pressure compounds. Such compounds may be, for example, one or more monomers and/or one or more carrier materials as described below. Examples of the component of the curable coating composition having a vapor pressure within the above range at a polymerization temperature of 110 ° C to 125 ° C include, for example, trimethoxy (1H, 1H, 2H, 2H-heptadecafluoroquinone). Base) decane, perfluorohexylethyl acrylate, perfluorohexylethylene and perfluorooctylethylene. The curable coating composition can comprise, for example, at least 1 weight percent, at least 5 weight percent, at least 10 weight percent, at least 25 weight percent, or at least 45 weight percent of a compound having a vapor pressure as described in this paragraph. .

以這種方法塗覆的基底不受特別限制，並且可以在該基底中使用在其上可以根據本發明產生塗層的任何固體材料。在其中該基底係多孔的和/或具有有待藉由施用的塗層密封的小的裂紋或間隙空間的情況下看到特別益處。 The substrate coated in this way is not particularly limited, and any solid material on which a coating layer can be produced according to the present invention can be used in the substrate. A particular benefit is seen in the case where the substrate is porous and/or has a small crack or interstitial space to be sealed by the applied coating.

有用的多孔基底包括纖維紡織品。藉由“纖維的”係指紡織品的表面由至少一種類型的纖維組成或者包括至少一種類型的纖維。該等纖維限定間隙空位空間，其中在施用時和在加壓步驟3)期間空氣和/或分子氧被截留並且該施用的可固化的塗料組成物可以滲透進入該等空間內。所表徵的這樣的多孔織物可以具有，在根據本發明的塗覆之前，如使用Textest FX 3300儀器和38cm²測試面積根據ASTM D737測量的至少0.2立方英呎/分鐘/平方英呎(0.001016m/s)的空氣滲透率。更較佳的是，該多孔織物具有至少10(0.0508)、至少50(0.204)、至少75(0.3060)或至少130(0.6604)英呎/分鐘/平方英呎(m/s)的空氣滲透率。該多孔織物的空氣滲透率可以是 任何更高的值，如最高達200立方英呎/分鐘/平方英呎(1.016m/s)。一些織物，如基於PTFE或聚胺甲酸酯的膜織物，可以是對濕蒸汽更可滲透的，超過它們對空氣。這樣的織物可具有如根據JISL 1099B1測量的至少1000g/平方米/24小時、較佳的是5000至20,000g/平方米/24小時的水分透過率。 Useful porous substrates include fibrous textiles. By "fiber" it is meant that the surface of the textile consists of or comprises at least one type of fiber. The fibers define a gap vacancy space wherein air and/or molecular oxygen is trapped during application and during the pressurization step 3) and the applied curable coating composition can penetrate into the spaces. Such a porous fabric characterized may have at least 0.2 cubic inches per minute per square inch (0.001016 m/) measured according to ASTM D737 prior to coating according to the present invention, such as using a Textest FX 3300 instrument and a 38 cm ² test area. s) air permeability. More preferably, the porous fabric has an air permeability of at least 10 (0.0508), at least 50 (0.204), at least 75 (0.3060), or at least 130 (0.6604) mile per minute per square inch (m/s). . The air permeability of the porous fabric can be any higher value, such as up to 200 cubic feet per minute per square inch (1.016 m/s). Some fabrics, such as PTFE or polyurethane based film fabrics, may be more permeable to wet steam than they are to air. Such a fabric may have a moisture permeability of at least 1000 g/m 2 /24 hours, preferably 5,000 to 20,000 g/m 2 /24 hours as measured according to JIS L 1099B1.

可以將多孔基底的纖維，例如，編織、針織、纏繞(entangle)、打結(knot)、氈製(felt)、膠合或以其他方式形成為具有被傳送通過本發明方法的足夠的機械完整性的織物、無紡布或紡織品。此類織物包括纖維，該等纖維可以是，例如，天然纖維，如棉、***、羊毛、亞麻、蠶絲、天絲(tencel)、人造絲、皮革、竹子、纖維素以及類似物，或合成纖維，如尼龍、對-或間-芳族聚醯胺、聚丙烯、聚酯(包括PET)、聚乙酸酯、聚丙烯酸、聚乳酸、纖維素酯，或其他纖維以及以上中的任何兩種或更多種的共混物。它可以是光滑或起絨的織物並且它可以含有少量(按重量計最高達50%、較佳的是最高達10%或最高達3%)的可伸展的纖維，如彈性纖維(Elastane)、萊卡彈力纖維(Lycra)、或斯潘德克斯彈力纖維(Spandex)。 The fibers of the porous substrate can be, for example, woven, knitted, entangled, knotted, felted, glued or otherwise formed to have sufficient mechanical integrity to be transported by the method of the invention. Fabric, non-woven or textile. Such fabrics include fibers, which may be, for example, natural fibers such as cotton, hemp, wool, linen, silk, tencel, rayon, leather, bamboo, cellulose, and the like, or synthetic fibers. , such as nylon, p- or m-aromatic polyamide, polypropylene, polyester (including PET), polyacetate, polyacrylic acid, polylactic acid, cellulose ester, or other fibers and any two of the above A blend of more or more. It may be a smooth or piled fabric and it may contain a small amount (up to 50% by weight, preferably up to 10% or up to 3%) of stretchable fibers, such as Elastane, Lycra, or Spandex.

如之前描述的，本發明特別適合用於處理紡織品卷狀材料。當該基底呈薄片的形式時，它應具有不大於約12mm的厚度、並且較佳的是具有不大於10mm或不大於8mm的厚度。該基底可以具有任何更小的厚度，只要它具有藉由該方法進行實施的足夠的機械完整性。在一些具體實例中，將該可固化的組成物施用到紡織品輥物品上，該等物品可具有100mm或更大，如1600mm至7米或更大的寬度。 As previously described, the invention is particularly suitable for treating textile roll materials. When the substrate is in the form of a sheet, it should have a thickness of not more than about 12 mm, and preferably has a thickness of not more than 10 mm or not more than 8 mm. The substrate can have any smaller thickness as long as it has sufficient mechanical integrity to be implemented by the method. In some embodiments, the curable composition is applied to a textile roll article, which may have a width of 100 mm or greater, such as 1600 mm to 7 meters or greater.

該方法不限於卷狀材料織物。折疊的或展開的紡織品片可以被用作基底，如可以被用作具有紡織品組分的成品。本發明對於將塗層施 用到衣物如襯衫、褲子、毛衣、外套、長袖運動衫、手套、帽子、圍巾、腿-和手臂-暖套(warmer)和長襪、以及鞋子和其他鞋類、窗簾、被褥和其他紡織品材料的物品上是有用的。本發明的方法可以用於再處理已經使先前施用的塗層穿掉或洗滌掉或以其他方式除去的衣服物品，並且其要求再施用塗層以恢復所需要的功能屬性。 The method is not limited to a roll of web material. A folded or unfolded piece of textile can be used as the substrate, as can be used as a finished product having a textile component. The present invention is useful for applying a coating to clothing such as shirts, pants, sweaters, outerwear, long sleeve sweatshirts, gloves, hats, scarves, leg- and arms-warmers and stockings, as well as shoes and other footwear, curtains. It is useful on items such as bedding and other textile materials. The method of the present invention can be used to reprocess garment items that have been worn or washed away or otherwise removed from previously applied coatings, and which require reapplication of the coating to restore the desired functional attributes.

在其他具體實例中，包括，但不限於鞋，通常情況係該基底在一側上可以塗覆有例如皮革、或者合成皮革製品，如乙烯樹脂，或者對於運動鞋，塗覆有聚酯、聚丙烯或尼龍，包括合成纖維和天然纖維的混合物，該等纖維在該塗覆的側上具有暴露的纖維或網狀表面。該塗層，和因此該固化的聚合物，可以施用在所施加的特徵如縫製接縫、標識、標籤、裝飾特徵、尼龍搭扣緊固件、按鈕、卡扣、鉚釘以及拉鍊的頂部。該基底可以是無紡布或者纖維素材料，如紙、棉紙或紙板以及類似物。 In other specific examples, including but not limited to shoes, the substrate is typically coated on one side with, for example, leather, or a synthetic leather article, such as vinyl, or for sports shoes, coated with polyester, poly. Propylene or nylon, including a mixture of synthetic fibers and natural fibers having exposed fibers or web surfaces on the coated side. The coating, and thus the cured polymer, can be applied to the top of the applied features such as seams, logos, labels, decorative features, Velcro fasteners, buttons, snaps, rivets, and zippers. The substrate can be a nonwoven or cellulosic material such as paper, tissue or paperboard and the like.

在其他具體實例中，該基底係電子元件。該等類型的電子元件不是關鍵的。該電子元件可以是，例如，離散地包裝的基礎電子元件，或電子元件的陣列或網路如半導體積體電路，混合積體電路或厚膜裝置。它可以是全套單元，例如像，行動電話、MP3播放機、健身電子產品、“智慧”紡織品(即，可佩戴的電子設備)和軍事電子設備。每個單獨的基礎電子部件可以是，例如，半導體裝置，如電晶體、真空管或二極體，無源部件如電阻器、電感器、變壓器或電容器，光電設備，和光學檢測器或發射器，電源，磁感應設備，記憶體，和RC或LC網路，天線，壓電設備，晶體，諧振器，終端機或連接器，天線，電纜，開關，保護裝置，如保險絲、斷路器、變阻器或湧流限制器，或機電部件，除了其他之外。 In other embodiments, the substrate is an electronic component. These types of electronic components are not critical. The electronic component can be, for example, a discretely packaged basic electronic component, or an array of electronic components or a network such as a semiconductor integrated circuit, a hybrid integrated circuit or a thick film device. It can be a full set of units such as, for example, mobile phones, MP3 players, fitness electronics, "smart" textiles (ie, wearable electronics) and military electronics. Each individual basic electronic component can be, for example, a semiconductor device such as a transistor, a vacuum tube or a diode, a passive component such as a resistor, an inductor, a transformer or capacitor, an optoelectronic device, and an optical detector or emitter, Power, magnetic induction devices, memory, and RC or LC networks, antennas, piezoelectric devices, crystals, resonators, terminals or connectors, antennas, cables, switches, protective devices such as fuses, circuit breakers, varistors or surges Limiters, or electromechanical components, among others.

視情況氧化預處理步驟可以在塗覆步驟1)之前進行。這樣的氧化預處理步驟可以包括在含氧氣氛下在超大氣壓下將該基底加熱到例如100℃至220℃、較佳的是150℃至190℃的升高的溫度。溫度應低於該基底降解或永久地變形的溫度。該含氧氣氛可以包含至少20莫耳百分比、至少50莫耳百分比或至少75莫耳百分比的分子氧，並且可以包含最高達100莫耳百分比、最高達99莫耳百分比或最高達95莫耳百分比的分子氧。該超大氣壓力可以是，例如125kPa至15MPa，較佳的是300kPa至5MPa。該基底可以被保持在氧化預處理步驟的條件下持續，例如，1分鐘至1小時的一段時間。 Optionally, the oxidation pretreatment step can be carried out prior to the coating step 1). Such an oxidative pretreatment step can include heating the substrate under superatmospheric pressure to an elevated temperature of, for example, 100 ° C to 220 ° C, preferably 150 ° C to 190 ° C under an oxygen-containing atmosphere. The temperature should be below the temperature at which the substrate degrades or permanently deforms. The oxygen-containing atmosphere may comprise at least 20 mole percent, at least 50 mole percent, or at least 75 mole percent of molecular oxygen, and may comprise up to 100 mole percent, up to 99 mole percent, or up to 95 mole percent Molecular oxygen. The superatmospheric pressure may be, for example, 125 kPa to 15 MPa, preferably 300 kPa to 5 MPa. The substrate can be maintained under the conditions of the oxidative pretreatment step, for example, for a period of from 1 minute to 1 hour.

已經發現該氧化預處理步驟改善了隨後施用的塗層的性能。具體地，當進行該氧化預處理步驟時，獲得了更好的拒水特性和/或更好的疏油特性。儘管本發明不局限於任何理論，據信經常在織物製造期間被施用的表面塗層如施膠劑和/或潤滑劑在該氧化預處理步驟期間被氧化去除，從而允許基底表面與可固化的塗料組成物之間的更好的接觸。 This oxidative pretreatment step has been found to improve the performance of the subsequently applied coating. Specifically, when the oxidation pretreatment step is performed, better water repellency characteristics and/or better oleophobic characteristics are obtained. Although the invention is not limited to any theory, it is believed that surface coatings such as sizing agents and/or lubricants that are often applied during fabric manufacture are oxidatively removed during the oxidative pretreatment step, thereby allowing the substrate surface to be curable. Better contact between the coating compositions.

該氧化預處理提供超過替代方法的顯著優點。潤滑劑從織物的去除(退漿)可以使用水基清潔步驟完成。然而，已知一些織物例如芳族聚醯胺暴露於水係削弱纖維強度，並且此外水清潔步驟要求乾燥步驟並且經常促進織物收縮。含氧大氣壓電漿，含有例如90%氬氣+10%氧氣的氣體混合物，也可以用於此退漿步驟，然而，應注意的是，基於電漿的清潔係比上述高壓氧氣清潔方法更昂貴的方法，並且織物暴露於原子氧可以減弱纖維。該高壓氧化預處理步驟避免了該等可能隨基於電漿的清潔發生的問題。可以使用這兩種方法以提供紡織品和非織造物的無水清潔或退漿 和/或用於黏合促進和/或用於該處理的改善的衣物耐久性。 This oxidative pretreatment provides significant advantages over alternative methods. The removal of the lubricant from the fabric (de-slurry) can be accomplished using a water-based cleaning step. However, some fabrics such as aromatic polyamines are known to be exposed to water-based weakened fiber strength, and in addition the water cleaning step requires a drying step and often promotes fabric shrinkage. An oxygen-containing atmospheric piezoelectric slurry containing a gas mixture such as 90% argon + 10% oxygen may also be used in this desizing step, however, it should be noted that the plasma-based cleaning system is more expensive than the above-described high pressure oxygen cleaning method. The method and exposure of the fabric to atomic oxygen can weaken the fiber. This high pressure oxidation pretreatment step avoids such problems that may occur with plasma based cleaning. Both methods can be used to provide anhydrous cleaning or desizing of the textile and nonwoven and/or improved adhesion durability for adhesion promotion and/or for the treatment.

該可固化的塗料組成物包含a)一種或多種自由基可固化的單體，該等自由基可固化的單體具有每分子恰好一個自由基可聚合的基團。該自由基可固化的單體組分a)具有至少100℃的沸騰溫度。該沸騰溫度較佳的是至少120℃並且更較佳的是至少150℃。在此提及的所有沸騰溫度係在一個大氣壓下給出，除非另外指明。 The curable coating composition comprises a) one or more free-radically curable monomers having exactly one free-radically polymerizable group per molecule. The free-radically curable monomer component a) has a boiling temperature of at least 100 °C. The boiling temperature is preferably at least 120 ° C and more preferably at least 150 ° C. All boiling temperatures mentioned herein are given at one atmosphere unless otherwise indicated.

該自由基可固化的單體較佳的是具有至少一個烴基，該烴基具有至少六個直接或間接鍵合到該可聚合的基團上的碳原子。該等烴基可以是部分氟化的、全氟化的或非氟化的。 The radical curable monomer preferably has at least one hydrocarbyl group having at least six carbon atoms bonded directly or indirectly to the polymerizable group. The hydrocarbyl groups can be partially fluorinated, perfluorinated or non-fluorinated.

較佳的是，至少一種組分a)單體在該方法的步驟4)中的聚合溫度下具有不大於6.7kPa、更較佳的是不大於1kPa的蒸氣壓力。 Preferably, at least one component a) monomer has a vapor pressure of no greater than 6.7 kPa, more preferably no greater than 1 kPa at the polymerization temperature in step 4) of the process.

該一種或多種組分a)單體可以在22℃下是液體或固體。如果使用單體的混合物，它們可以全部是液體、可以全部係固體、或者它們可包括固體和液體單體的混合物。在較佳的具體實例中，組分a)係至少兩種單體的混合物，其中的至少一種在22℃下是固體並且其中的至少一種在22℃下是液體。 The one or more components of component a) may be liquid or solid at 22 °C. If a mixture of monomers is used, they may all be liquid, may be all solid, or they may comprise a mixture of solid and liquid monomers. In a preferred embodiment, component a) is a mixture of at least two monomers, at least one of which is solid at 22 ° C and at least one of which is liquid at 22 ° C.

該自由基可聚合的基團可以是在自由基聚合中聚合的任何一種，但是較佳的是烯基、丙烯酸酯基團、甲基丙烯酸酯基團或氯矽烷基團。丙烯酸酯基團和/或甲基丙烯酸酯基團係最較佳的。 The radical polymerizable group may be any one polymerized in a radical polymerization, but is preferably an alkenyl group, an acrylate group, a methacrylate group or a chloroalkyl group. Acrylate groups and/or methacrylate groups are most preferred.

該烴基可以是直鏈或支鏈的脂肪族基團、脂環族基團、芳香族基團或含有其兩種或更多種的基團。該烴基可含有至少10個或至少12個碳原子。該烴基可含有，例如，6至24個碳原子、8至24個碳原子、10 至20個碳原子、或12至18個碳原子。在一些具體實例中，該烴基係具有8至24、10至20或12至18個碳原子的直鏈烷基或烯基。在一些具體實例中，該烴基係部分或全氟化的，並且含有6至24、或者較佳的是8至20個碳原子。 The hydrocarbon group may be a linear or branched aliphatic group, an alicyclic group, an aromatic group or a group containing two or more kinds thereof. The hydrocarbyl group may contain at least 10 or at least 12 carbon atoms. The hydrocarbyl group may contain, for example, 6 to 24 carbon atoms, 8 to 24 carbon atoms, 10 to 20 carbon atoms, or 12 to 18 carbon atoms. In some embodiments, the hydrocarbyl group is a linear alkyl or alkenyl group having from 8 to 24, from 10 to 20, or from 12 to 18 carbon atoms. In some embodiments, the hydrocarbyl moiety is partially or perfluorinated and contains from 6 to 24, or preferably from 8 to 20 carbon atoms.

可以將該烴基直接鍵合(即，藉由共價鍵)到該自由基可聚合的基團上、或間接地藉由連接基鍵合到其上。 The hydrocarbyl group can be bonded directly (i.e., by a covalent bond) to the free radical polymerizable group, or indirectly via a linker.

較佳的是水可溶於該一種或多種組分a)單體中至30℃下每100重量份該一種或多種單體不大於2重量份、更較佳的是不大於1重量份並且更較佳的是不大於0.25重量份的程度。 It is preferred that water is soluble in the one or more components a) of the monomer to not more than 2 parts by weight, more preferably not more than 1 part by weight per 100 parts by weight of the one or more monomers at 30 ° C and More preferably, it is not more than 0.25 parts by weight.

組分a)單體的實例包括，但不限於，以下項中的一種或多種：丙烯酸、甲基丙烯酸甲酯、丙烯酸2-乙基己酯、丙烯酸正辛酯、丙烯酸2-乙基己酯、甲基丙烯酸正辛酯、丙烯酸癸酯、甲基丙烯酸癸酯、丙烯酸月桂酯、丙烯酸十八烷基酯、甲基丙烯酸月桂酯、丙烯酸十八烷基酯、甲基丙烯酸十八烷基酯、丙烯酸2-(全氟己基)乙酯、丙烯酸2-(全氟辛基)乙酯、丙烯酸2-(全氟癸基)乙酯、甲基丙烯酸2-(全氟己基)乙酯、甲基丙烯酸2-(全氟辛基)乙酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酯、甲基丙烯酸2-(全氟癸基)乙酯、2-(全氟辛基)乙基三氯甲矽烷以及乙烯基萘。在該等之中，以上描述的丙烯酸酯和甲基丙烯酸酯單體係最較佳的。 Examples of component a) monomers include, but are not limited to, one or more of the following: acrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate , n-octyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, octadecyl acrylate, lauryl methacrylate, octadecyl acrylate, octadecyl methacrylate , 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorohexyl)ethyl methacrylate, A 2-(perfluorooctyl)ethyl acrylate, lauryl methacrylate, stearyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorooctyl)ethyl Trichloromethane and vinyl naphthalene. Among these, the acrylate and methacrylate monosystems described above are most preferred.

該可固化的塗料組成物還包括b)一種或多種熱活化的或UV活化的自由基引發劑。適合的聚合引發劑包括自由基引發劑，例如像，1)醯基過氧化物，如乙醯基或苯甲醯基過氧化物，2)烷基過氧化物，如異丙苯基、二異丙苯基、月桂醯基、或三級丁基過氧化物，3)氫過氧化物， 如三級丁基或異丙苯基氫過氧化物，4)過酸酯，如三級丁基過苯甲酸酯，5)其他有機過氧化物，包括1,1-雙(三級丁基過氧基)-3,3,5-三甲基環己烷、醯基烷基磺醯基過氧化物、二烷基過氧二碳酸酯、二過氧縮酮、酮過氧化物、或1,1-雙(三級丁基過氧基)-3,3,5-三甲基環己烷，6)偶氮化合物，如2,2'-偶氮二異丁腈(AIBN)或2,2'-偶氮雙(2,4-二甲基戊腈)、4,4'-偶氮雙(4-氰基戊酸)、或1,1'-偶氮雙(環己甲腈)，7)各種四以及8)各種過硫酸鹽化合物，如過硫酸鉀。在22℃下是固體的聚合引發劑係較佳的，如具有在60℃或更高的溫度下10小時半衰期的那些。具有至少100℃的1分鐘半衰期溫度的那些係尤其較佳的。在一些具體實例中，該聚合引發劑還可具有在100℃下至少一分鐘的半衰期或者在100℃下至少5分鐘的半衰期。 The curable coating composition also includes b) one or more thermally activated or UV activated free radical initiators. Suitable polymerization initiators include free radical initiators such as, for example, 1) mercapto peroxides such as ethenyl or benzhydryl peroxide, 2) alkyl peroxides such as cumene, Phenylphenyl, lauryl, or tertiary butyl peroxide, 3) hydroperoxides, such as tertiary butyl or cumyl hydroperoxide, 4) peresters, such as tertiary butyl Base benzoate, 5) other organic peroxides, including 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, mercaptoalkylsulfonate Peroxide, dialkyl peroxydicarbonate, diperoxy ketal, ketone peroxide, or 1,1-bis(tertiary butylperoxy)-3,3,5-trimethyl Cyclohexane, 6) azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4' - azobis(4-cyanovaleric acid), or 1,1'-azobis(cyclohexanecarbonitrile), 7) various four And 8) various persulfate compounds such as potassium persulfate. Polymerization initiators which are solid at 22 ° C are preferred, such as those having a half-life of 10 hours at a temperature of 60 ° C or higher. Those having a one minute half-life temperature of at least 100 ° C are especially preferred. In some embodiments, the polymerization initiator may also have a half life of at least one minute at 100 ° C or a half life of at least 5 minutes at 100 ° C.

本發明的可固化的塗料組成物還可以包含以下任選組分中的一種或多種： The curable coating composition of the present invention may further comprise one or more of the following optional components:

c)至少一種交聯單體，該至少一種交聯單體具有至少兩個自由基可固化的基團以及至少100℃的沸騰溫度。該沸騰溫度較佳的是至少125℃並且更較佳的是至少150℃。除非另外指明，本說明書中的所有沸騰溫度係在一個大氣壓下。該交聯單體較佳的是22℃下的液體。該等自由基可固化的可聚合的基團可以是如以上關於組分a)描述的，其中丙烯酸酯或甲基丙烯酸酯基團係較佳的。該等交聯單體可以具有每分子例如2至20、較佳的是2至8並且更較佳的是2至6個自由基可固化的基團。交聯單體的實例包括具有每分子2至20、較佳的是2至8或2至6個丙烯酸酯和/或甲基丙烯酸酯基團的聚丙烯酸酯或聚甲基丙烯酸酯化合物。特定實例包括具有2至50、2至20或4至12個碳原子的多元醇的丙烯酸酯和/或甲基丙烯酸酯，如1,4- 丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,8-辛二醇二丙烯酸酯、環己烷二甲醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、甘油三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、相應的甲基丙烯酸酯、以及類似物。所謂的乾性油像亞麻籽油、紅花油和桐油也是有用的交聯劑。 c) at least one crosslinking monomer having at least two free radical curable groups and a boiling temperature of at least 100 °C. The boiling temperature is preferably at least 125 ° C and more preferably at least 150 ° C. All boiling temperatures in this specification are at one atmosphere unless otherwise indicated. The crosslinking monomer is preferably a liquid at 22 °C. The radically curable polymerizable groups may be as described above for component a), with acrylate or methacrylate groups being preferred. The crosslinking monomers may have, for example, from 2 to 20, preferably from 2 to 8, and more preferably from 2 to 6 free radical curable groups per molecule. Examples of the crosslinking monomer include a polyacrylate or polymethacrylate compound having 2 to 20, preferably 2 to 8, or 2 to 6 acrylate and/or methacrylate groups per molecule. Specific examples include acrylates and/or methacrylates of polyols having 2 to 50, 2 to 20 or 4 to 12 carbon atoms, such as 1,4-butanediol diacrylate, 1,6-hexane Alcohol diacrylate, 1,8-octanediol diacrylate, cyclohexane dimethanol diacrylate, trimethylolpropane triacrylate, triglyceride, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol hexaacrylate, the corresponding methacrylate, and the like. So-called dry oils like linseed oil, safflower oil and tung oil are also useful crosslinkers.

d)一種或多種不用於組分a)和c)的自由基可固化的單體。這樣的單體可以具有低於100℃的沸騰溫度。此類單體可恰好具有一個自由基可聚合的基團、或者可具有多於一個此種基團，在這種情況下它將起交聯劑的作用。此類單體可以是22℃下的液體或固體。該組分d)單體(如果存在的話)較佳的是與該等組分a)和c)單體可共聚的。在該一種或多種組分d)單體上的較佳的自由基可聚合的基團係丙烯酸酯和甲基丙烯酸酯。組分d)單體的實例包括：丙烯酸己酯、丙烯酸丁酯、丙烯酸羥乙酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸己酯、甲基丙烯酸丁酯、甲基丙烯酸羥乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸2-(全氟丁基)乙酯、甲基丙烯酸2-(全氟丁基)乙酯、苯乙烯、乙烯苯、氯苯乙烯、以及類似物。 d) one or more free-radically curable monomers which are not used for components a) and c). Such monomers may have a boiling temperature below 100 °C. Such a monomer may have exactly one free radical polymerizable group, or may have more than one such group, in which case it will function as a crosslinking agent. Such monomers may be liquid or solid at 22 °C. The component d) monomer, if present, is preferably copolymerizable with the components a) and c). Preferred free radical polymerizable groups on the one or more component d) monomers are acrylates and methacrylates. Examples of component d) monomers include: hexyl acrylate, butyl acrylate, hydroxyethyl acrylate, methyl acrylate, ethyl acrylate, hexyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, Methyl methacrylate, ethyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, styrene, vinylbenzene, chlorostyrene, and the like Things.

e)一種或多種載體。有用的載體或者載體混合物在22℃下是液體亦或係22℃下是固體、但是具有100℃或更低、較佳的是50℃或更低的熔化溫度的材料。該載體較佳的是還具有至少100℃、更較佳的是至少125℃並且還更較佳的是至少150℃的沸騰溫度。該載體不含有自由基可聚合的基團。較佳的載體具有如相對於該等組分a)單體描述的水溶性特徵。然而，該載體較佳的是可溶於或變得部分夾帶於當固化該塗料組成物時形成的該聚合物內。 e) One or more carriers. Useful carriers or carrier mixtures are liquid at 22 ° C or materials which are solid at 22 ° C but have a melting temperature of 100 ° C or lower, preferably 50 ° C or lower. The carrier preferably also has a boiling temperature of at least 100 ° C, more preferably at least 125 ° C and still more preferably at least 150 ° C. The carrier does not contain a radical polymerizable group. Preferred carriers have water soluble characteristics as described with respect to the monomers of component a). However, the carrier is preferably soluble or partially entrained within the polymer formed when the coating composition is cured.

有用的載體的實例係(i)具有14至30個碳原子的脂肪族單醇或脂肪族單羧酸；(ii)脂肪酸與脂肪醇的酯，該酯具有18至48個碳原子、較佳的是20至36個碳原子；(iii)具有一個或多個羥基的聚醚；(iv)聚矽氧烷，該聚矽氧烷可以是直鏈的、支鏈的或環狀的；(v)聚矽氧烷-聚(伸烷基二醇)共聚物；(vi)蠟，如聚乙烯蠟、蜂蠟、羊毛脂、巴西棕櫚蠟、小燭樹蠟、小冠椰子蠟、甘蔗蠟、霍霍巴蠟(jojoba wax)、角質層蠟(epicuticular wax)、椰子蠟、石油蠟、石蠟以及類似物，尤其具有大於22℃、較佳的是大於35℃但是不大於100℃、尤其不大於50℃的熔化溫度的蠟；(vii)氟聚合物，(viii)固體植物和/或動物油或脂肪；(viii)另一種具有最高達100℃的純相熔化或軟化溫度的有機低聚物或聚合物，或(ix)各種增塑劑。 Examples of useful carriers are (i) an aliphatic monool or an aliphatic monocarboxylic acid having 14 to 30 carbon atoms; (ii) an ester of a fatty acid with a fatty alcohol having from 18 to 48 carbon atoms, preferably 20 to 36 carbon atoms; (iii) polyether having one or more hydroxyl groups; (iv) polyoxyalkylene, which may be linear, branched or cyclic; v) polyoxyalkylene-poly(alkylene glycol) copolymer; (vi) waxes such as polyethylene wax, beeswax, lanolin, carnauba wax, candelilla wax, small crown coconut wax, sugar cane wax, Jojoba wax, epicuticular wax, coconut wax, petroleum wax, paraffin wax and the like, especially having a temperature greater than 22 ° C, preferably greater than 35 ° C but not greater than 100 ° C, especially not greater than 50 a melting temperature wax of °C; (vii) a fluoropolymer, (viii) a solid vegetable and/or animal oil or fat; (viii) another organic oligomer or polymerization having a pure phase melting or softening temperature of up to 100 °C , or (ix) various plasticizers.

在該等脂肪族單醇之中的是脂肪醇，包括飽和的脂肪醇如1-十二烷醇、1-十四烷醇、1-十六烷醇、1-十八烷醇、以及類似物，以及在該脂肪醇鏈中具有一個或多個碳-碳不飽和的位點的脂肪醇。在該等有用的脂肪酸與脂肪醇的酯之中的是，例如己基十八烷酸酯、辛基十八烷酸酯、十二烷基十八烷酸酯、十八烷基十八烷酸酯(hexadodecyl octadecanoate)、以及類似物。該酯的脂肪酸和/或脂肪醇部分可以含有一個或多個碳-碳不飽和的位點。 Among the aliphatic monoalcohols are fatty alcohols, including saturated fatty alcohols such as 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecyl alcohol, and the like. And a fatty alcohol having one or more sites of carbon-carbon unsaturation in the fatty alcohol chain. Among the esters of such useful fatty acids and fatty alcohols are, for example, hexyl octadecanoate, octyl octadecanoate, dodecyl octadecanoate, octadecyl octadecanoic acid. Ethyl (hexadodecyl octadecanoate), and the like. The fatty acid and/or fatty alcohol portion of the ester may contain one or more sites of carbon-carbon unsaturation.

適合的聚醚係一種或多種環醚(如環氧丙烷、四亞甲基二醇以及類似物)之聚合物。分子量係足夠高的以產生具有最高達100℃的熔化溫度的聚合物。該聚醚可含有一個或多個羥基。它可以是直鏈或支鏈的。該聚醚可含有末端烷基酯基團。適合聚醚的特定實例包括聚(環氧乙烷)、聚(環氧乙烷)的單烷基酯、聚(環氧丙烷)、聚(環氧丙烷)的單烷基酯、環氧乙烷 -環氧丙烷共聚物和其單烷基酯、聚(四氫呋喃)以及類似物。 Suitable polyethers are polymers of one or more cyclic ethers such as propylene oxide, tetramethylene glycol and the like. The molecular weight is sufficiently high to produce a polymer having a melting temperature of up to 100 °C. The polyether may contain one or more hydroxyl groups. It can be straight or branched. The polyether can contain terminal alkyl ester groups. Specific examples of suitable polyethers include poly(ethylene oxide), poly(ethylene oxide) monoalkyl esters, poly(propylene oxide), poly(propylene oxide) monoalkyl esters, epoxy B. Alkylene-propylene oxide copolymers and monoalkyl esters thereof, poly(tetrahydrofuran) and the like.

有用的聚矽氧烷包括，例如，聚(二甲基矽氧烷)(PDMS)以及其共聚物。該聚矽氧烷可以是直鏈的、支鏈的或環狀的。有用的矽氧烷-聚(伸烷基二醇)共聚物包括，例如，聚(二甲基矽氧烷-聚(乙二醇)共聚物，該等共聚物可以具有嵌段或接枝結構。 Useful polyoxyalkylene oxides include, for example, poly(dimethyloxane) (PDMS) and copolymers thereof. The polyoxyalkylene can be linear, branched or cyclic. Useful oxane-poly(alkylene glycol) copolymers include, for example, poly(dimethyloxane-poly(ethylene glycol) copolymers, which may have a block or graft structure .

作為該載體或載體的混合物的組分有用的具有低於100℃的熔化溫度的有機聚合物包括低分子量聚醯胺、低分子量聚醚、低分子量聚苯乙烯、低分子量丙烯酸酯聚合物和共聚物(如聚(乙二醇)甲醚甲基丙烯酸酯(PEGMEA))、聚丙烯醯胺、聚(N-異丙基丙烯醯胺)、聚(丙烯酸)、低分子量熱塑性纖維素醚和酯、聚(2-乙基丙烯酸)、聚(乙烯基膦酸)、聚(4-苯乙烯磺酸鈉)、聚(2-乙基-2-唑啉)以及類似物。 Organic polymers having a melting temperature below 100 ° C useful as a component of the carrier or carrier include low molecular weight polyamines, low molecular weight polyethers, low molecular weight polystyrenes, low molecular weight acrylate polymers, and copolymerizations. (eg poly(ethylene glycol) methyl ether methacrylate (PEGMEA)), polypropylene decylamine, poly( N -isopropyl acrylamide), poly(acrylic acid), low molecular weight thermoplastic cellulose ethers and esters , poly(2-ethylacrylic acid), poly(vinylphosphonic acid), poly(4-styrenesulfonate), poly(2-ethyl-2- Oxazolines) and analogs.

在該等增塑劑之中的是鄰苯二甲酸酯、偏苯三酸酯、己二酸酯、馬來酸酯、苯甲酸酯、對苯二甲酸酯、各種脂肪酸酯、環氧化的植物油、磺醯胺、有機磷酸酯、檸檬酸烷基酯、乙醯化的單甘酯以及類似物。 Among the plasticizers are phthalates, trimellitates, adipates, maleates, benzoates, terephthalates, various fatty acid esters, Epoxidized vegetable oil, sulfonamide, organophosphate, alkyl citrate, acetylated monoglyceride, and the like.

該載體可以將某些功能屬性提供給該固化的組成物。在一些具體實例中，該載體將增加的疏水性和/或疏油性特性提供給該固化的組成物。它還可以行使增塑功能。 The carrier can provide certain functional attributes to the cured composition. In some embodiments, the carrier provides increased hydrophobicity and/or oleophobic properties to the cured composition. It can also perform plasticization functions.

尤其較佳的載體包括聚矽氧烷油、蠟和醇載體。尤其較佳的聚矽氧烷油包括八甲基環四矽氧烷、十甲基環戊矽氧烷、和直鏈或支鏈的聚二甲基矽氧烷(PDMS)油(如六甲基二矽氧烷、八甲基三矽氧烷、十甲基四矽氧烷、十二甲基五矽氧烷)、聚甲基氫矽氧烷(PMHS)油、以及其他液體環聚二甲基矽氧烷。石蠟或蜂蠟蠟係尤其較佳的蠟載體。硬脂醇和 鯨蠟醇係尤其較佳的醇載體並且在22℃下是固體。 Particularly preferred carriers include polyoxyalkylene oils, waxes and alcohol carriers. Particularly preferred polyoxyalkylene oils include octamethylcyclotetraoxane, decamethylcyclopentanoxane, and linear or branched polydimethyloxane (PDMS) oils (such as Rouge Dioxazane, octamethyltrioxane, decamethyltetraoxane, dodecamethylpentaoxane, polymethylhydroquinone (PMHS) oil, and other liquid cyclopolymers Methyl decane. Paraffin wax or beeswax wax is a particularly preferred wax carrier. Stearyl alcohol and cetyl alcohol are particularly preferred alcohol carriers and are solid at 22 °C.

該載體還可包括具有低於100℃的沸騰溫度的低分子量有機化合物，但是如果此類材料存在，它們較佳的是合計構成該可固化的組成物的不大於2重量百分比、並且較佳的是不大於其1重量百分比或0.25重量百分比。該等低分子量有機化合物包括，例如，液體聚醚和聚醚單烷基酯如PPG-14單丁酯；液體烷烴，如正己烷、正戊烷、正庚烷、二十一烷、二十二烷、二十三烷、二十四烷、二十五烷、二十六烷、二十七烷、二十八烷、二十九烷、三十烷以及類似物；液體醇，如正丙醇、異丙醇、正丁醇、三級丁醇、甲醇和乙醇；氟化烷烴，如全氟己烷、全氟庚烷、全氟癸烷-蒎烷、全氟癸烷-辛烷、全氟十二烷和類似物；氯化烷烴和氯化的芳族化合物，如異戊基氯、異丁基氯和苄基氯；烷烴二醇和聚伸烷基二醇，如乙二醇、丙二醇、二乙二醇、三乙二醇、二丙二醇、三丙二醇和1,4-丁二醇；液體酯，如癸二酸二異丙酯和甘油三棕櫚酸酯；酮，如丙酮和甲基乙基酮；液體脂肪酸，如硬脂酸、油酸、棕櫚酸、月桂酸和類似物；1-萘亞甲基胺；聯苯；二苯甲酮；二苯基胺；1,2-二苯乙烷；馬來酸酐；吡；百里酚；甘油；山梨醇或其他糖；和二伸苄基山梨醇。 The carrier may further include a low molecular weight organic compound having a boiling temperature of less than 100 ° C, but if such materials are present, they are preferably not more than 2% by weight, and preferably, of the curable composition. It is not more than 1% by weight or 0.25% by weight. Such low molecular weight organic compounds include, for example, liquid polyethers and polyether monoalkyl esters such as PPG-14 monobutyl ester; liquid alkanes such as n-hexane, n-pentane, n-heptane, behenic, twenty Dioxane, tricosane, tetracosane, dipentadecane, hexadecane, heptacosane, octacosane, octadecane, triacontane and the like; liquid alcohol, such as positive Propyl alcohol, isopropanol, n-butanol, tertiary butanol, methanol and ethanol; fluorinated alkanes such as perfluorohexane, perfluoroheptane, perfluorodecane-decane, perfluorodecane-octane , perfluorododecane and analogs; chlorinated alkanes and chlorinated aromatic compounds such as isoamyl chloride, isobutyl chloride and benzyl chloride; alkane diols and polyalkylene glycols such as ethylene glycol , propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and 1,4-butanediol; liquid esters such as diisopropyl sebacate and glyceryl tripalmitate; ketones such as acetone and Methyl ethyl ketone; liquid fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid and the like; 1-naphthylmethylamine; biphenyl; benzophenone; diphenylamine; -diphenyl Alkoxy; maleic anhydride; pyrazol ; thymol; glycerin; sorbitol or other sugars; and di-benzyl sorbitol.

f)一種或多種最終處理屬性化學品。“最終處理屬性化學品”係不同於該載體和一種或多種單體的化合物，在本發明的處理方法之後該化合物與該基底保持在一起並且將一些希望的特徵賦予給該基底。最終處理屬性化學品的實例包括，例如： f) One or more final processing attribute chemicals. A "final processing attribute chemical" is a compound that differs from the carrier and one or more monomers that remain with the substrate after the processing method of the present invention and imparts some desirable characteristics to the substrate. Examples of final processing of attribute chemicals include, for example:

f-1)疏水性處理劑(treatment)，即，將防水性和/或疏水性特徵賦予給該處理過的基底的化學品； F-1) a hydrophobic treatment, that is, a chemical that imparts water repellency and/or hydrophobic characteristics to the treated substrate;

f-2)疏油性和疏脂性處理劑，即，致使該處理過的基底不容易地吸收脂肪和油、或者排斥脂肪和油的物質； F-2) an oleophobic and lipophobic treatment agent, that is, a substance which causes the treated substrate to not easily absorb fat and oil, or to repel fat and oil;

f-3)超疏水性試劑；即，賦予非常高(>130°)的水滴與該處理過的基底的表面的接觸角的物質。該超疏水性試劑可包括從50nm至100微米尺寸的固體顆粒，如粉狀的氟碳聚合物粉末。其他超疏水性試劑包括氯化或氟化的矽酮化合物，如十七氟癸基三甲氧基矽烷、三甲氧基(1H,1H,2H,2H-十七氟癸基)矽烷、十八烷基二甲基氯矽烷、三(三甲基甲矽烷氧基)矽基乙基二甲基氯矽烷、辛基二甲基氯矽烷、二甲基二氯矽烷、丁基二甲基氯矽烷以及三甲基氯矽烷。 F-3) a superhydrophobic agent; that is, a substance that imparts a very high (>130°) water droplet to the contact angle of the surface of the treated substrate. The superhydrophobic agent may comprise solid particles ranging in size from 50 nm to 100 microns, such as powdered fluorocarbon polymer powder. Other superhydrophobic agents include chlorinated or fluorinated anthrone compounds such as heptadecafluorodecyltrimethoxydecane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluoroindenyl) decane, octadecane Dimethylchlorodecane, tris(trimethylformamoxy)decylethyldimethylchlorodecane, octyldimethylchlorodecane, dimethyldichlorodecane, butyldimethylchlorodecane, and Trimethylchlorodecane.

f-4)行使功能的微粒固體，如芯吸劑、填充劑、水清除劑、著色劑、阻燃劑、磨料、流變改性劑、和類似物。此類微粒固體包括，例如，矽膠顆粒、氣相二氧化矽、疏水性氣相二氧化矽、玻璃或其他陶瓷顆粒、聚苯乙烯顆粒、聚四氟乙烯顆粒、聚(氟乙烯)顆粒、聚(偏二氟乙烯)顆粒、聚(六氟丙烯)顆粒、聚(全氟丙基乙烯基醚)顆粒、聚-(全氟甲基乙烯基醚)顆粒、聚(氯三氟乙烯)顆粒、聚丙烯微球、礦物粉末(如滑石)、碳酸鐵和碳酸鈣、和阻燃劑礦物(如碳酸鈣)、氫氧化鋁、氫氧化鎂、各種硼酸鹽、硼和/或磷化合物和無機水合物、碳化鈦、碳化鎢、浮石、碳化矽、氧化鋯氧化鋁。 F-4) Functional solid particulate solids such as wicking agents, fillers, water scavengers, colorants, flame retardants, abrasives, rheology modifiers, and the like. Such particulate solids include, for example, silicone particles, gas phase cerium oxide, hydrophobic gas phase cerium oxide, glass or other ceramic particles, polystyrene particles, polytetrafluoroethylene particles, poly(vinyl fluoride) particles, poly (vinylidene fluoride) particles, poly(hexafluoropropylene) particles, poly(perfluoropropyl vinyl ether) particles, poly-(perfluoromethyl vinyl ether) particles, poly(chlorotrifluoroethylene) particles, Polypropylene microspheres, mineral powders (such as talc), iron carbonate and calcium carbonate, and flame retardant minerals (such as calcium carbonate), aluminum hydroxide, magnesium hydroxide, various borate, boron and / or phosphorus compounds and inorganic hydration Matter, titanium carbide, tungsten carbide, pumice, tantalum carbide, zirconia alumina.

f-5)抗微生物處理劑，即，抑制微生物生長和/或殺死微生物的物質，包括Cu、Zn、Ag化合物，以及殼聚糖顆粒。 F-5) An antimicrobial treatment agent, that is, a substance that inhibits growth of microorganisms and/or kills microorganisms, including Cu, Zn, Ag compounds, and chitosan particles.

f-6)UV吸收劑和/或UV反射劑，如阿伏苯宗(avobenzone)、金紅石二氧化鈦、二氧化矽、胡莫柳酯(homosalate)、羥苯甲酮、4-胺基苯 甲酸(PABA)、水楊酸辛酯、辛烯(octocylene)、2-乙基己基4-二甲基胺基苯甲酸酯以及類似物； F-6) UV absorbers and/or UV reflectors, such as avobenzone, rutile titanium dioxide, cerium oxide, homosalate, oxybenzone, 4-aminobenzoic acid (PABA), octyl salicylate, octocylene, 2-ethylhexyl 4-dimethylaminobenzoate, and the like;

f-7)著色劑如染料和顏料。該等包括酸性染料、反應性染料、和分散染料。 F-7) Colorants such as dyes and pigments. These include acid dyes, reactive dyes, and disperse dyes.

f-8)抗皺劑，如三聚氰胺-甲醛樹脂和脲-甲醛樹脂； F-8) anti-wrinkle agents such as melamine-formaldehyde resins and urea-formaldehyde resins;

f-9)織物軟化劑和抗擦傷劑(anti-chafing agent)，如聚二甲基矽氧烷和聚甲基氫矽烷； F-9) fabric softeners and anti-chafing agents such as polydimethylsiloxane and polymethylhydrogenane;

f-10)光和/或熱反射材料，如反光的金屬顆粒、二氧化鈦或ZnO顆粒以及類似物。 F-10) Light and/or heat reflective materials such as reflective metal particles, titanium dioxide or ZnO particles and the like.

f-11)產生例如柔軟性、穿著舒適性和/或保濕特性的柔軟劑。 F-11) A softener which produces, for example, softness, wearing comfort and/or moisturizing properties.

f-12)殺蟲劑和/或驅蟲劑，如甲氧苄氟菊酯(metofluthrin)、四氟菊酯(transfluthrin)、敵敵畏(dichlovos)、氯菊酯(permethrin)、百里香油、迷迭香油、香茅油、桂皮油、檸檬桉樹油、檸檬草油、以及香柏油。 F-12) insecticides and/or insect repellents, such as metofluthrin, transfluthrin, dichhlovos, permethrin, thyme oil, rosemary Balsamic oil, citronella oil, cinnamon oil, lemon eucalyptus oil, lemongrass oil, and cedar oil.

f-13)固體或液體阻燃劑，包括各種有機磷、含磷、含溴和含硼的化合物，包括四硼酸鈉和硼酸。 F-13) Solid or liquid flame retardants, including various organophosphorus, phosphorus-containing, bromine- and boron-containing compounds, including sodium tetraborate and boric acid.

f-14)被添加至該配製物中以幫助檢測假冒商品或假冒最終處理處理劑的痕量司法鑒定化學標記物(trace forensic chemical marker)。此類標記物可以含有稀土元素(如釔、鈧、鈰、銪或鉺)、或其他通常不在紡織品中發現的元素、或者當暴露於紫外光時提供可檢測的螢光的化合物。 F-14) A trace forensic chemical marker that is added to the formulation to aid in the detection of counterfeit goods or counterfeit final treatment agents. Such labels may contain rare earth elements (such as ruthenium, osmium, iridium, osmium or iridium), or other elements not normally found in textiles, or compounds that provide detectable fluorescence when exposed to ultraviolet light.

該化學處理混合物還可以包括g)一種或多種促進劑或活化劑用於聚合引發劑。金屬鹽(如鐵鹽、鈦鹽或釩鹽)和錳離子或錳係此類促進劑的實例。 The chemical treatment mixture may also include g) one or more promoters or activators for the polymerization initiator. Examples of metal salts (such as iron salts, titanium salts or vanadium salts) and manganese ions or manganese-based accelerators.

該化學處理混合物可以進一步含有h)一種或多種發泡劑。適合的發泡劑包括在22℃下是液體但在該固化步驟的條件下揮發的物理(吸熱)類型，以及在該固化反應的條件下分解或者以其他方式反應以形成氣體的物理類型。如果存在有機物理發泡劑，則它應當以少量使用，這樣使得該可固化的組成物含有按重量計不大於10%、較佳的是不大於5%、更較佳的是不大於2%並且還更較佳的是不大於1%、甚至更較佳的是不大於0.25%的具有小於100℃的沸騰溫度的有機化合物。化學發泡劑較佳的是產生二氧化碳或氮氣；該等包括所謂的偶氮類型、過氧基發泡劑(如過氧化酯、過氧碳酸酯以及類似物)、以及某些胺基甲酸酯和檸檬酸酯化合物。 The chemical treatment mixture may further comprise h) one or more blowing agents. Suitable blowing agents include the physical (endothermic) type which is liquid at 22 ° C but volatilizes under the conditions of the curing step, and the physical type which decomposes or otherwise reacts to form a gas under the conditions of the curing reaction. If an organic physical blowing agent is present, it should be used in a small amount such that the curable composition contains no more than 10% by weight, preferably no more than 5%, more preferably no more than 2% by weight and Still more preferably, no more than 1%, even more preferably no more than 0.25%, of an organic compound having a boiling temperature of less than 100 °C. Chemical blowing agents preferably produce carbon dioxide or nitrogen; these include so-called azo types, peroxy blowing agents (such as peroxyesters, peroxycarbonates, and the like), and certain urethanes. Ester and citrate compounds.

該可固化的塗料組成物的各種成分的選擇、它們的比例以及製備該組成物的方式全部進行為使得該塗料組成物係在22℃下的液體或者在22℃下和在標準壓力下一種或多種固體在液相中的懸浮液，並且該塗料組成物含有，基於該塗料組成物的總重量，按重量計不大於10%的具有低於100℃的沸騰溫度的有機化合物以及按重量計不大於5%的水。該可固化塗料組成物較佳的是含有按重量計不大於5%、更較佳的是不大於2%、還更較佳的是不大於1%、並且甚至更較佳的是不大於0.25%的具有低於100℃的沸騰溫度的有機化合物，以及按重量計不大於2%、更較佳的是不大於1%並且還更較佳的是不大於0.25%的水。 The selection of the various components of the curable coating composition, their proportions, and the manner in which the composition is prepared are all carried out such that the coating composition is at a liquid at 22 ° C or at 22 ° C and at standard pressure or a suspension of a plurality of solids in a liquid phase, and the coating composition contains, based on the total weight of the coating composition, no more than 10% by weight of an organic compound having a boiling temperature of less than 100 ° C and not by weight More than 5% water. The curable coating composition preferably contains no more than 5% by weight, more preferably no more than 2%, still more preferably no more than 1%, and even more preferably no more than 0.25. % of the organic compound having a boiling temperature of less than 100 ° C, and not more than 2% by weight, more preferably not more than 1% and still more preferably not more than 0.25% by weight of water.

該可固化的塗料組成物可以包含例如至少1、至少5、至少10或至少25重量百分比的化合物，該等化合物在聚合步驟4)的溫度下具有1至67kPa、較佳的是6.7至53kPa的蒸氣壓力(在一個大氣壓下)。 The curable coating composition may comprise, for example, at least 1, at least 5, at least 10 or at least 25 weight percent of a compound having a temperature of from 1 to 67 kPa, preferably from 6.7 to 53 kPa, at the temperature of the polymerization step 4). Vapor pressure (at one atmosphere).

組分a)單體(和組分c)單體，如果存在的話)可以一起 構成，例如，該可固化的組成物的重量的0.5%至100%。在一些具體實例中，該等組分a)和c)單體一起構成該可固化的塗料組成物的重量的至少1%、至少1.5%、至少2%、至少5%、至少10%、至少25%或至少40%。組分a)和c)一起可構成該可固化的塗料組成物的重量的最高達90%、最高達80%、最高達70%、最高達60%、最高達50%、最高達40%、最高達25%、最高達10%或最高達5%。在一些具體實例中，組分c)構成組分a)和b)的組合重量的5%至50%、10%至40%、10%至30%或15%至25%。 The components a) monomer (and component c) monomers, if present, may be combined together, for example, from 0.5% to 100% by weight of the curable composition. In some embodiments, the components a) and c) together comprise at least 1%, at least 1.5%, at least 2%, at least 5%, at least 10%, at least the weight of the curable coating composition. 25% or at least 40%. The components a) and c) together may constitute up to 90%, up to 80%, up to 70%, up to 60%, up to 50%, up to 40% by weight of the curable coating composition, Up to 25%, up to 10% or up to 5%. In some embodiments, component c) constitutes from 5% to 50%, 10% to 40%, 10% to 30%, or 15% to 25% of the combined weight of components a) and b).

組分d)單體(如果存在的話)可構成該可固化的組成物的重量的最高達50%，其條件係如果該組分d)單體具有小於100℃的沸騰溫度，則它以使得該可固化的組成物含有按重量計不大於2%的具有小於100℃的沸騰溫度的有機化合物的量存在。如果該組分d)單體低於100℃沸騰，較佳的量(如果存在任何一種)係該可固化的塗料組成物的重量的按重量計0.01%至25%、或0.01%至10%。在一些具體實例中，組分d)單體(如果存在的話，全部)構成組分a)、b)和c)的組合重量的最高達5%、最高達2%或最高達1%。 Component d) a monomer, if present, may constitute up to 50% by weight of the curable composition, provided that if the component d) monomer has a boiling temperature of less than 100 ° C, then The curable composition is present in an amount of no more than 2% by weight of an organic compound having a boiling temperature of less than 100 °C. If the component d) monomer is boiled below 100 ° C, the preferred amount, if any, is from 0.01% to 25%, or from 0.01% to 10% by weight of the curable coating composition. . In some embodiments, component d) monomer, if present, constitutes up to 5%, up to 2%, or up to 1% of the combined weight of components a), b), and c).

聚合引發劑如自由基引發劑可以構成該可固化組成物的重量的最高達20%。較佳的量係按重量計0.1%至10%。更較佳的量係該可固化的組成物的按重量計的2%-5%。在一些具體實例中，該一種或多種聚合引發劑以組分a)、c)和d)的組合重量的最高達30%(如其3%至20%或5%至15%)的量存在。 A polymerization initiator such as a radical initiator may constitute up to 20% by weight of the curable composition. A preferred amount is from 0.1% to 10% by weight. A more preferred amount is from 2% to 5% by weight of the curable composition. In some embodiments, the one or more polymerization initiators are present in an amount up to 30% (eg, 3% to 20% or 5% to 15%) of the combined weight of components a), c), and d).

該載體或者載體的混合物(如果存在的話)可以構成，例如，該可固化的組成物的重量的2%至98%。在22℃下是固體的載體較佳的是以 單體(即，組分a)、c)和d))的重量的最高達150%的量存在。在一些具體實例中，此類固體載體係以單體重量的至少10%、至少20%或至少30%、並且在相同的基礎上最高達150%、最高達125%或最高達100%的量存在。特別地蠟(以上載體類型(vi))較佳的是以如在先前的句子中指出的量存在。 The carrier or mixture of carriers, if present, can be constructed, for example, from 2% to 98% by weight of the curable composition. The support which is solid at 22 ° C is preferably present in an amount up to 150% by weight of the monomers (i.e., components a), c) and d)). In some embodiments, such solid support is present in an amount of at least 10%, at least 20%, or at least 30% by weight of the monomer, and up to 150%, up to 125%, or up to 100% on the same basis. presence. In particular, the wax (above carrier type (vi)) is preferably present in an amount as indicated in the previous sentence.

液體(在22℃下和在大氣壓下)載體可行使稀釋作用並且因此在一些具體實例中可構成該可固化的組成物的多達98重量%、或者低至其約2重量%。在具體具體實例中，該可固化的組成物可以含有至少5重量%、至少10重量%、至少25重量%、至少40重量%、至少50重量%或至少70重量%的一種或多種液體載體。在具體具體實例中，它可含有最高達96重量%、最高達90重量%、最高達75重量%、最高達50重量%、最高達35重量%、最高達25重量%或最高達10重量%。 The liquid (at 22 ° C and at atmospheric pressure) can act to dilute and thus, in some embodiments, can constitute up to 98% by weight of the curable composition, or as low as about 2% by weight. In a particular embodiment, the curable composition can contain at least 5% by weight, at least 10% by weight, at least 25% by weight, at least 40% by weight, at least 50% by weight, or at least 70% by weight of one or more liquid carriers. In a specific embodiment, it may contain up to 96% by weight, up to 90% by weight, up to 75% by weight, up to 50% by weight, up to 35% by weight, up to 25% by weight or up to 10% by weight .

最終處理屬性化學品(當存在時)可合計構成該可固化的組成物的重量的從0.01%至70%，較佳的是0.01%至25%並且更較佳的是0.01%至10%。司法鑒定標記物可能甚至是更低的，處於1-1000ppm的水平。 The final treatment attribute chemical (when present) may add from 0.01% to 70%, preferably from 0.01% to 25%, and more preferably from 0.01% to 10% by weight of the curable composition. Judicial identification markers may even be lower, at a level of 1-1000 ppm.

其他材料可合計構成該可固化的組成物的重量的0.01%至70%、較佳的是0.01%至50%、更較佳的是0.01%至25%、並且還更較佳的是0.01%至10%。 The other materials may add up to 0.01% to 70%, preferably 0.01% to 50%, more preferably 0.01% to 25%, and still more preferably 0.01% by weight of the curable composition. Up to 10%.

較佳的可固化的組成物含有4%至85%的組分a)，2%至25%的組分c)，10%至70%、更較佳的是15%至50%的一種或多種載體，以及0至35%、較佳的是1%至25%的一種或多種功能屬性材料。另一種較佳的可固化的組成物含有16%至70%的組分a)，3%至20%的組分c)，25%-50%的 一種或多種載體，以及0至35%、較佳的是1%至25%的一種或多種功能屬性材料。此類較佳的可固化的組成物含有1至10重量百分比的一種或多種自由基引發劑。在此類較佳的可固化的組成物的一些具體實例中，組分a)包括一種或多種丙烯酸酯或甲基丙烯酸酯單體；組分c)包括一種或多種具有2至6個丙烯酸酯或甲基丙烯酸酯基團的單體，組分c)(如果存在的話)包括一種或多種脂肪酸丙烯酸酯化合物，並且組分e)包括蠟和矽酮油中的一種或多種。 Preferred curable compositions contain from 4% to 85% of component a), from 2% to 25% of component c), from 10% to 70%, more preferably from 15% to 50% of one or A plurality of carriers, and from 0 to 35%, preferably from 1% to 25%, of one or more functional property materials. Another preferred curable composition contains from 16% to 70% of component a), from 3% to 20% of component c), from 25% to 50% of one or more carriers, and from 0 to 35%, Preferred is from 1% to 25% of one or more functional property materials. Such preferred curable compositions contain from 1 to 10 weight percent of one or more free radical initiators. In some embodiments of such preferred curable compositions, component a) comprises one or more acrylate or methacrylate monomers; component c) comprises one or more of from 2 to 6 acrylates Or a monomer of a methacrylate group, component c) (if present) comprises one or more fatty acid acrylate compounds, and component e) comprises one or more of a wax and an oxime oil.

第三較佳的可固化的組成物含有1%至75%的組合的組分a)和c)，其中組分c)構成組分a)和c)的組合重量的15%至85%；2%至98%的一種或多種載體，以及0至35%、較佳的是1%至25%的一種或多種功能屬性材料。在這種較佳的可固化的組成物中，該載體較佳的是包括至少一種液體載體和至少一種固體(22℃下)載體，並且該固體載體較佳的是以基於單體(組分a)、c)和d))的10至150重量百分比的量存在。第四較佳的可固化的組成物含有1%至60%的組合的組分a)和c)(其中組分c)構成組分a)和c)的組合重量的20%至65%)，基於單體的重量30%至100%的一種或多種固體載體，2-98重量%的一種或多種液體載體，以及0至35%、較佳的是1%至25%的一種或多種功能屬性材料。該等第三和第四較佳的可固化的組成物較佳的是含有基於單體的重量3至20或5至15重量百分比的一種或多種自由基引發劑。在此類第三和第四較佳的可固化的組成物的一些具體實例中，組分a)包括一種或多種丙烯酸酯或甲基丙烯酸酯單體；組分c)包括一種或多種具有2至6個丙烯酸酯或甲基丙烯酸酯基團的單體，組分d)(如果存在的話)包括一種或多種脂肪酸丙烯酸酯化合物，並且組 分e)包括蠟和矽酮油中的一種或多種。 The third preferred curable composition contains from 1% to 75% of the combined components a) and c), wherein component c) constitutes from 15% to 85% of the combined weight of components a) and c); 2% to 98% of one or more carriers, and 0 to 35%, preferably 1% to 25%, of one or more functional property materials. In such a preferred curable composition, the carrier preferably comprises at least one liquid carrier and at least one solid (at 22 ° C) carrier, and the solid carrier is preferably based on a monomer (component) The amounts of 10 to 150 weight percent of a), c) and d)) are present. The fourth preferred curable composition contains from 1% to 60% of the combined components a) and c) (where component c) constitutes from 20% to 65% of the combined weight of components a) and c) 30% to 100% by weight of the monomer, one or more solid carriers, 2 to 98% by weight of one or more liquid carriers, and 0 to 35%, preferably 1% to 25%, of one or more functions Attribute material. Preferably, the third and fourth preferred curable compositions comprise from 3 to 20 or from 5 to 15 weight percent, based on the weight of the monomer, of one or more free radical initiators. In some embodiments of such third and fourth preferred curable compositions, component a) comprises one or more acrylate or methacrylate monomers; component c) comprises one or more of 2 To 6 acrylate or methacrylate group monomers, component d) (if present) comprises one or more fatty acid acrylate compounds, and component e) comprises one or more of wax and fluorenone oil .

尤其較佳的可固化的組成物(包括剛在前述兩個段落中描述的較佳的組成物)包括至少一種固體(22℃下)組分a)單體和至少一種液體(22℃下)組分a)單體。該一種或多種固體組分a)單體可構成所有組分a)單體的總重量的20%-85%或20%至65%。在此類組成物中，該固體組分a)單體可以包括脂肪酸丙烯酸酯(其中該脂肪酸基團含有18或更多個碳原子)，並且該液體組分a)單體可以是脂肪酸丙烯酸酯(其中該脂肪酸基團含有最高達16個碳原子)和/或脂肪酸甲基丙烯酸酯(其中該脂肪酸基團含有最高達18個碳原子)。此類尤其較佳的可固化的組成物可以含有3%-20%的組分c)。在此類組成物中的組分c)材料可以包括以下項中的一種或多種：烷烴二醇二丙烯酸酯、季戊四醇或二季戊四醇聚丙烯酸酯和乾性油(如亞麻籽油、紅花油或桐油)。這種尤其較佳的可固化的組成物可以含有20%-50%的組分e)，其中組分e)較佳的是包括脂肪醇、蠟和矽酮油中的至少一種。這種尤其較佳的可固化的組成物視情況可含有1%-25%的至少一種最終處理屬性化學品，並且可含有最高達2%的組分d)單體(如果有的話，全部)。 Particularly preferred curable compositions (including the preferred compositions just described in the previous two paragraphs) include at least one solid (at 22 ° C) component a) monomer and at least one liquid (at 22 ° C) Component a) Monomer. The one or more solid components a) monomer may constitute from 20% to 85% or from 20% to 65% of the total weight of all components a). In such a composition, the solid component a) monomer may include a fatty acid acrylate (wherein the fatty acid group contains 18 or more carbon atoms), and the liquid component a) monomer may be a fatty acid acrylate (wherein the fatty acid group contains up to 16 carbon atoms) and/or fatty acid methacrylate (wherein the fatty acid group contains up to 18 carbon atoms). Such particularly preferred curable compositions may contain from 3% to 20% of component c). The component c) material in such a composition may include one or more of the following: an alkane diol diacrylate, pentaerythritol or dipentaerythritol polyacrylate, and a drying oil (such as linseed oil, safflower oil or tung oil). . Such particularly preferred curable compositions may contain from 20% to 50% of component e), wherein component e) preferably comprises at least one of a fatty alcohol, a wax and an oxime oil. Such particularly preferred curable compositions may optionally contain from 1% to 25% of at least one final processing attribute chemical and may contain up to 2% of component d) monomers (if any, all) ).

以下的實施例旨在說明本發明而不限制其範圍。除非另外指明，否則所有份數和百分比都是按重量計。 The following examples are intended to illustrate the invention without limiting its scope. All parts and percentages are by weight unless otherwise indicated.

實施例1Example 1

如在防彈保護衣服中使用的疏鬆編織的對-芳族聚醯胺織物被用作在此實施例中的基底。芳族聚醯胺纖維內部的水的存在被認為減弱纖維。 A loosely woven p-aromatic polyamide fabric as used in ballistic protective clothing is used as the substrate in this embodiment. The presence of water inside the aromatic polyamide fibers is believed to weaken the fibers.

將含有按重量計30%丙烯酸十八烷基酯、18%石蠟、9% 1,6-己二醇二丙烯酸酯、8%丙烯酸月桂酯、3%二季戊四醇五-/六丙烯酸酯、5%過氧化月桂醯和27%十甲基環戊矽氧烷的可固化的、基於單體的組成物混合並且然後用聚二甲基矽氧烷(5厘司托克士)1：2稀釋以製造可固化的塗料組成物，該可固化的塗料組成物包含可自由基聚合並且具有高於100℃的沸騰溫度的單體與熱活化的聚合引發劑。兩個相同的8.5英吋x 8.5英吋芳族聚醯胺織物樣本藉由將它們浸入這種塗料組成物中並且然後在兩個加壓輥之間擠出過量液體進行塗覆。 Will contain 30% by weight of octadecyl acrylate, 18% paraffin, 9% 1,6-hexanediol diacrylate, 8% lauryl acrylate, 3% dipentaerythritol penta-/hexaacrylate, 5% The curable, monomer-based composition of ammonium lauryl peroxide and 27% decamethylcyclopentaoxane is mixed and then diluted 1:2 with polydimethyl methoxy alkane (5 centi-six) to make A curable coating composition comprising a monomer that is free-radically polymerizable and has a boiling temperature above 100 ° C and a thermally activated polymerization initiator. Two identical 8.5 inch x 8.5 inch aromatic polyamide fabric samples were coated by dipping them into the coating composition and then extruding excess liquid between the two pressure rolls.

施用到第一樣本(實施例1)的塗層的重量係26.1g/m²。將該塗層如下固化：氮氣氣體在室溫和1大氣壓下流動通过高壓釜以吹掃分子氧直到該高壓釜中的氣體包含小於0.1莫耳百分比的氧氣。然後將該高壓釜密封、用氮氣加壓到1.4MPa，並且然後加熱至121℃持續40分鐘來活化聚合引發劑並固化該組成物。在升高的壓力下固化的樣品的固化後塗層添加劑的重量與固化前的重量相同並且在26.1g/m²下不變。 The weight of the coating applied to the first sample (Example 1) was 26.1 g/m ² . The coating was cured as follows: Nitrogen gas was passed through the autoclave at room temperature and 1 atm to purge molecular oxygen until the gas in the autoclave contained less than 0.1 mole percent oxygen. The autoclave was then sealed, pressurized to 1.4 MPa with nitrogen, and then heated to 121 ° C for 40 minutes to activate the polymerization initiator and cure the composition. The weight of the cured coating additive of the sample cured under elevated pressure was the same as the weight before curing and did not change at 26.1 g/m ² .

施用到第二樣本(比較樣品A)的塗層的重量係33.7g/m²。此塗層以與實施例1相同的方式藉由吹掃分子氧固化，並且然後在121℃下固化，但是在固化步驟期間該壓力係一個大氣壓並且該容器不密封，這樣在該反應器中的氣體可以自由地排到空氣中。在大氣壓下固化的樣品的固化後重量增加顯著地低於僅22.7g/m²，或僅是如所施用的未固化的塗層的重量的約三分之二。 The weight of the coating applied to the second sample (Comparative Sample A) was 33.7 g/m ² . This coating was cured by purging molecular oxygen in the same manner as in Example 1, and then cured at 121 ° C, but during the curing step the pressure was one atmosphere and the container was not sealed, thus in the reactor The gas can be freely discharged into the air. The post-curing weight increase of the sample cured at atmospheric pressure was significantly lower than only 22.7 g/m ² , or only about two-thirds the weight of the uncured coating applied.

這兩個樣本然後根據10分鐘邦迪斯門(Bundesmann)拒水性試驗進行評價。在這個試驗中藉由實施例1增加的水重量係6.95%，並且 穿過該塗覆的樣品的水滲透係16mL。相比之下，比較樣品A的水重量增加係11.97%並且穿過該樣品的水滲透係30mL。藉由在壓力下在密封容器中加壓和固化，水重量增加和水滲透被降低了幾乎一半。 The two samples were then evaluated according to the 10 minute Bundesmann water repellency test. The weight of water added by Example 1 in this test was 6.95%, and the water permeate through the coated sample was 16 mL. In contrast, the water weight increase of Comparative Sample A was 11.97% and the water permeate through the sample was 30 mL. By pressurizing and solidifying in a sealed container under pressure, water weight increase and water penetration are reduced by almost half.

實施例2Example 2

兩種由63%尼龍、25%聚酯和12%萊卡組成的緊密編織的運動服裝織物樣本浸漬塗覆有可固化的塗料組成物並且如在實施例1中所描述的在加壓輥之間擠壓出。將第一樣本(實施例2)在高壓容器中在1.4MPa和在125℃下固化持續40分鐘。它具有14.140g/平方碼的固化的塗層重量。將其他樣本(比較樣品B)塗覆兩次並且然後在相同溫度下在氮氣氣氛中在大氣壓力下在未密封的反應器中固化。比較樣品B具有23.360g/平方碼的固化的塗層重量。儘管比較樣品B的高得多的塗層重量，它在AATCC 22噴霧試驗中僅達到“70”噴霧等級，其中在實施例2中使用的更低的塗層重量達到完全的“100”噴霧等級。 Two tightly woven sportswear fabric samples consisting of 63% nylon, 25% polyester and 12% Lycra were dip coated with a curable coating composition and between the pressure rolls as described in Example 1. Squeeze out. The first sample (Example 2) was cured in a high pressure vessel at 1.4 MPa and at 125 ° C for 40 minutes. It has a cured coating weight of 14.140 g/square yard. The other samples (Comparative Sample B) were coated twice and then cured in an unsealed reactor at atmospheric pressure in a nitrogen atmosphere at atmospheric pressure. Comparative Sample B had a cured coating weight of 23.360 g/square yard. Despite comparing the much higher coating weight of Sample B, it only achieved a "70" spray rating in the AATCC 22 spray test, where the lower coating weight used in Example 2 reached a full "100" spray rating. .

實施例3Example 3

使用在實施例1中相同的混合物塗覆被用作層壓的聚酯/聚胺甲酸酯膜織物的外層的緊密編織的100%聚酯織物。將兩個樣品以相同的方式和相同的劑量塗覆。一個(實施例3)以關於實施例1描述的方式在126℃的固化溫度下固化。另一個(比較樣品C)以相同的方式，但在大氣壓下固化。實施例1達到了在邦迪斯門拒水性試驗中完全的“5”等級並且增加僅2.53%水重量。比較樣品C達到較低的“4”等級並且增加6.32%水。在邦迪斯門試驗中沒有穿過該等緊密編織的樣品中的任一個的可檢測的水滲透。 A tightly woven 100% polyester fabric used as the outer layer of the laminated polyester/polyurethane film fabric was coated using the same mixture as in Example 1. Both samples were coated in the same manner and at the same dose. One (Example 3) was cured at a curing temperature of 126 ° C in the manner described in relation to Example 1. The other (Comparative Sample C) was cured in the same manner but under atmospheric pressure. Example 1 achieved a complete "5" rating in the Bondis Gate water repellency test and increased only 2.53% water weight. Comparative Sample C reached a lower "4" rating and increased 6.32% water. There was no detectable water penetration through any of these closely woven samples in the Bondis Gate test.

實施例4和5Examples 4 and 5

將通常用於戶外傢俱裝飾的緊密編織的腈綸織物的一式兩份的樣品用相等劑量的如實施例1中描述的可固化的塗料組成物塗覆。類似地，將腈綸篷布(acrylic awning)織物的一式兩份的樣品用相同的組成物塗覆。固化的塗層重量如在下表中所指示。固化的塗層重量係藉由比較該樣品在固化後的重量與未塗覆的樣品的重量確定的。 Duplicate samples of tightly woven acrylic fabrics typically used for outdoor furniture upholstery were coated with equal doses of the curable coating composition as described in Example 1. Similarly, duplicate samples of acrylic awning fabric were coated with the same composition. The cured coating weight is as indicated in the table below. The cured coating weight was determined by comparing the weight of the sample after curing to the weight of the uncoated sample.

在每種情況下，樣品(實施例4和5，分別地)之一在125℃下以與關於實施例1描述的相同的方式固化。一式兩份的樣品(比較樣品D和E，分別地)以相同的方式固化，除了在大氣壓力下。然後將該等樣品使用AATCC 22噴霧試驗評價，其中結果如在下表1中指出。 In each case, one of the samples (Examples 4 and 5, respectively) was cured at 125 ° C in the same manner as described for Example 1. Duplicate samples (compare samples D and E, respectively) were cured in the same manner except at atmospheric pressure. The samples were then evaluated using the AATCC 22 spray test, the results of which are indicated in Table 1 below.

如表1所示，在超大氣壓力下固化導致對於這兩種織物的AATCC等級的顯著改進和較少的水增加。出人意料地，固化的樣品的塗層重量相比用比較樣品比在實施例4和5中顯著更高，儘管具有幾乎相同的預固化重量增加。這表明大量的固化組成物在比較樣品的更低壓力下揮發。 As shown in Table 1, curing at superatmospheric pressure resulted in a significant improvement in the AATCC grade for both fabrics and less water increase. Surprisingly, the coating weight of the cured samples was significantly higher than in Comparative Examples 4 and 5, although with almost the same pre-curing weight increase. This indicates that a large amount of the cured composition volatilizes at a lower pressure of the comparative sample.

實施例6Example 6

將如在實施例1中描述的三種對-芳族聚醯胺織物樣品預先清洗以除去有機污染物。對一種樣品用按體積計1：1的在實施例1中描述的塗料組成物和三甲氧基(1H,1H,2H,2H十七氟癸基)矽烷的混合物塗覆。對第二種用1：1的實施例1塗料組成物和全氟己基乙基丙烯酸酯的混合物塗覆。 Three pairs of para-aramid fabric samples as described in Example 1 were pre-cleaned to remove organic contaminants. A sample was coated with a mixture of the coating composition described in Example 1 and trimethoxy (1H, 1H, 2H, 2H heptadecafluoroindenyl) decane by volume 1:1. The second coating was applied with a 1:1 mixture of the coating composition of Example 1 and perfluorohexylethyl acrylate.

第三種樣品像其他兩種清洗，但然後用TiCl₃異丙醇的1：5稀釋物噴霧並使其乾燥。這提供了存在於該樣品上的齊格勒-納塔催化劑。該樣品然後用按體積計1：1的實施例1組成物和全氟辛基乙烯的混合物塗覆。 The third sample was washed like the other two, but then sprayed with a 1:5 dilution of TiCl ₃ isopropanol and allowed to dry. This provides a Ziegler-Natta catalyst present on the sample. The sample was then coated with a 1:1 mixture of the composition of Example 1 and perfluorooctylethylene.

該塗覆的樣品然後如實施例1所述的，在125℃的固化溫度下固化。根據AATCC 118烴排斥性試驗測試固化的樣品的疏油性。所有三種表現出最高(“8”)等級，指示對水和正庚烷二者的排斥性。 The coated sample was then cured as described in Example 1 at a curing temperature of 125 °C. The oleophobicity of the cured samples was tested according to the AATCC 118 Hydrocarbon Rejection Test. All three exhibited the highest ("8") rating indicating repellency to both water and n-heptane.

當所有三種類型的一式兩份的樣品在大氣壓下固化時，它們證實很少或沒有疏油性並且是僅防水的。 When all three types of duplicate samples were cured at atmospheric pressure, they demonstrated little or no oleophobicity and were only water resistant.

實施例7Example 7

計算機電路週邊用由36%丙烯酸十八烷基酯、11% 1,6-己二醇二丙烯酸酯、9%丙烯酸月桂酯、5%二季戊四醇五-/六丙烯酸酯、4%過氧化月桂醯和35%十甲基環戊矽氧烷組成的烴單體混合物塗覆，然後將其用5cSt聚二甲基矽氧烷1：2稀釋。然後將塗漆的基底放置在容器中，該容器藉由使氮氣流過該容器吹掃氧氣並且將該塗層在貧氧氮氣環境中在1.4MPa並且在126℃的溫度下固化。當從壓力容器中移除時，可以看出該塗層已經 硬化並且已經在電子元件之間和下被推動並且甚至進入金屬接觸通孔，從而有效地密封該裝置。該塗層係防水的並且經受得住置於該裝置上的幾個水滴的添加。用於顯示水的存在的水分敏感標記按鈕保持未被觸發，即使當水滴被直接放置到在其上方的塗層上。 The computer circuit is surrounded by 36% octadecyl acrylate, 11% 1,6-hexanediol diacrylate, 9% lauryl acrylate, 5% dipentaerythritol penta-/hexaacrylate, 4% peroxide laurel A mixture of hydrocarbon monomers consisting of 35% decamethylcyclopentaoxane was applied and then diluted 1:2 with 5 cSt polydimethyloxane. The painted substrate was then placed in a container which was purged with oxygen by flowing nitrogen through the container and the coating was cured at 1.4 MPa and at a temperature of 126 ° C in an oxygen-lean nitrogen atmosphere. When removed from the pressure vessel, it can be seen that the coating has hardened and has been pushed between and under the electronic components and even into the metal contact vias, effectively sealing the device. The coating is water resistant and survives the addition of several water droplets placed on the device. The moisture sensitive marker button used to indicate the presence of water remains untriggered even when the water droplets are placed directly onto the coating above it.

實施例8和9Examples 8 and 9

使用產生親水處理的單體塗層處理四個不包含芯吸劑的100%聚酯羊毛產品的樣本。第五個樣本不進行處理作為對照。 Four samples of the 100% polyester wool product containing no wicking agent were treated with a monomer coating that produced a hydrophilic treatment. The fifth sample was not processed as a control.

將該等樣本中的兩個在光滑面側上用按體積計5：4：1的丙烯酸、十甲基環戊矽氧烷以及1,1-雙(三級丁基過氧基)-3,3,5-三甲基環己烷的混合物輥塗。在該等中，將一個(實施例8)置於高壓釜中，用氮氣吹掃並且然後在氮氣下在1.48MPa和125℃下在該密封的高壓釜中固化。另一個(比較樣品F在大氣壓氮氣在相同的溫度下固化。實施例8和比較實施例F各自具有大致相等的“濕”塗層重量，但是在固化之後實施例8的塗層重量係6.35g/m²而比較實施例F的塗層重量係僅1.9g/m²。 Two of the samples were on the smooth side with 5:4:1 by volume of acrylic acid, decamethylcyclopentanoxane and 1,1-bis(tertiary butylperoxy)-3. , a mixture of 3,5-trimethylcyclohexane was roll coated. In these, one (Example 8) was placed in an autoclave, purged with nitrogen and then solidified in the sealed autoclave at 1.48 MPa and 125 °C under nitrogen. The other (Comparative Sample F was cured at atmospheric pressure at atmospheric pressure. Example 8 and Comparative Example F each had approximately equal "wet" coating weight, but the coating weight of Example 8 after curing was 6.35 g. /m ² and the coating weight of Comparative Example F was only 1.9 g/m ² .

藉由在面側上輥塗按體積計5：4：1：1的丙烯酸、十甲基環戊矽氧烷、1,1-雙(三級丁基過氧基)-3,3,5三甲基環己烷和乙二醇二甲基丙烯酸酯的混合物製備另兩個樣品。將該等中的一個(實施例9)置於高壓釜中，用氮氣吹掃，並且然後在氮氣下在1.48MPa和125℃下在該密封的高壓釜中固化。另一個(比較樣品G)在大氣壓氮氣在125℃下固化，其中該高壓釜未密封。實施例9和比較實施例G各自具有大致相等的“濕”塗層重量，但是在固化之後實施例9的塗層重量係10.6g/m²而比較實施例G的塗層重量係僅2.1g/m²。 5:4:1:1 by volume of acrylic acid, decamethylcyclopentanoxane, 1,1-bis(tertiary butylperoxy)-3,3,5 by roll coating on the face side Two other samples were prepared from a mixture of trimethylcyclohexane and ethylene glycol dimethacrylate. One of these (Example 9) was placed in an autoclave, purged with nitrogen, and then solidified in the sealed autoclave at 1.48 MPa and 125 ° C under nitrogen. The other (Comparative Sample G) was solidified at atmospheric pressure nitrogen at 125 ° C, wherein the autoclave was not sealed. Example 9 and Comparative Example G each had approximately equal "wet" coating weight, but the coating weight of Example 9 after curing was 10.6 g/m ² and the coating weight of Comparative Example G was only 2.1 g. /m ² .

對照樣品和比較樣品F和G不呈現出親水性：施加到該織物上的水滴甚至在超過1分鐘後不被吸收。實施例8和9呈現出直接親水性，允許施加的液滴在小於2秒內被吸收。 The control sample and the comparative samples F and G did not exhibit hydrophilicity: the water droplets applied to the fabric were not absorbed even after more than 1 minute. Examples 8 and 9 exhibited direct hydrophilicity, allowing the applied droplets to be absorbed in less than 2 seconds.

實施例10Example 10

具有常規施用的芯吸處理的充分處理的、100%聚酯運動襯衫(即，施加於襯衫織物的水滴立即被芯吸到該織物中)藉由將其放置在服裝模型上並且在該襯衫上用高容量低壓力噴漆器噴霧36mL的實施例1的可固化的單體塗層進行處理用於疏水性。襯衫的所有側面僅在外部噴塗，包括縫製的接縫、衣領和半袖。將該噴塗的襯衫鬆散地放置到含有2.5升的蒸餾水的18L蒸汽高壓釜中。首先將該高壓釜使用乾燥氮氣流吹掃氧氣並且然後使用電浸沒式加熱器開始蒸汽發電。該高壓釜具有當壓力超過150kPa表壓時允許蒸汽逸出的泄壓閥。蒸汽的平衡溫度在這個壓力下是126℃。在產物固化期間不存在氮氣，因為蒸汽代替在該體積中的任何殘餘氮氣(或空氣)。 A fully treated, 100% polyester sports shirt with conventionally applied wicking treatment (ie, water droplets applied to the shirt fabric are immediately wicked into the fabric) by placing it on the garment model and on the shirt 36 mL of the curable monomer coating of Example 1 was sprayed with a high volume, low pressure paint sprayer for hydrophobicity. All sides of the shirt are only sprayed on the outside, including sewn seams, collars and half sleeves. The sprayed shirt was loosely placed in an 18 L steam autoclave containing 2.5 liters of distilled water. The autoclave was first purged with a stream of dry nitrogen and then steamed to start using an electric immersion heater. The autoclave has a pressure relief valve that allows steam to escape when the pressure exceeds 150 kPa gauge. The equilibrium temperature of the steam is 126 ° C at this pressure. No nitrogen is present during the curing of the product because the steam replaces any residual nitrogen (or air) in the volume.

將處理過的襯衫在0.15MPa和126℃下加熱20分鐘，然後關閉電源並且允許該單元冷卻並返回到大氣壓力。在固化之後，該襯衫係完全疏水的，指示最初存在的芯吸劑已經藉由聚合物處理克服。固化的聚合物劑量估計係36g/m²。衣物耐久性試驗與AATCC 22噴霧試驗結合指示在80家庭衣物洗滌/乾燥循環後維持完全的拒水性(在AATCC 22噴霧試驗中100的噴霧等級)。 The treated shirt was heated at 0.15 MPa and 126 °C for 20 minutes, then the power was turned off and the unit allowed to cool and return to atmospheric pressure. After curing, the shirt is completely hydrophobic, indicating that the initially present wicking agent has been overcome by polymer treatment. The cured polymer dose was estimated to be 36 g/m ² . The combination of the laundry durability test and the AATCC 22 spray test indicated complete water repellency (spray rating of 100 in the AATCC 22 spray test) after 80 home laundry/dry cycles.

實施例11Example 11

製備三個被設計用於外衣雨水防護的緊密編織的100%聚酯 樣本用於處理並且在邦迪斯門拒水性測試器中測試。一個樣品係未處理的並且功能係作為對照(比較樣品H)。其他樣品使用藉由以1：2的體積比用5cSt PDMS稀釋在實施例1中描述的組成物製成的塗料組成物塗覆。該塗覆係藉由將樣品浸入液體配製物中並且然後在兩個金屬輥之間擠壓出過量的液體完成的。將塗覆的樣品之一(實施例11)放入壓力容器中，該壓力容器用氮氣吹掃並且然後隨後用氮氣加壓至1.48MPa並且然後加熱至125℃以固化塗層。其他塗覆的樣品(比較樣品I)在大氣壓氮氣下在125℃下固化。所有三個樣品在邦迪斯門測試器中被評價10分鐘，其中結果如表2所示。視覺等級係從1至5(其中5最好)視覺評分。%水重量增加係在測試期間藉由樣品增加的水重量的量。水滲透係穿過該樣品的水的量，其中最小檢出量係<1mL。 Three tightly woven 100% polyester samples designed for rain protection of the outer garment were prepared for processing and tested in a Bondis Door Water Repellent Tester. One sample was untreated and the function was used as a control (Comparative Sample H). Other samples were coated with a coating composition made by diluting the composition described in Example 1 with 5 cSt PDMS in a volume ratio of 1:2. The coating is accomplished by dipping the sample into a liquid formulation and then extruding excess liquid between the two metal rolls. One of the coated samples (Example 11) was placed in a pressure vessel which was purged with nitrogen and then pressurized with nitrogen to 1.48 MPa and then heated to 125 ° C to cure the coating. The other coated samples (Comparative Sample I) were cured at 125 ° C under atmospheric nitrogen. All three samples were evaluated for 10 minutes in a Bondis Gate tester, the results of which are shown in Table 2. The visual rating is visually scored from 1 to 5 (5 of which is best). The % water weight increase is the amount of water weight added by the sample during the test. Water infiltration is the amount of water that passes through the sample, with a minimum detectable amount <1 mL.

如從表3中的結果可見，未處理的對照物完全潤濕。實施例11和比較樣品I二者都基本上防止任何水滲透該樣品，但實施例11(其中在高壓下進行固化)比比較樣品I(其在大氣壓下固化)吸收少約50%的水。 As can be seen from the results in Table 3, the untreated control was completely wetted. Both Example 11 and Comparative Sample I substantially prevented any water from penetrating the sample, but Example 11 (where curing was carried out under high pressure) absorbed about 50% less water than Comparative Sample I (which solidified at atmospheric pressure).

實施例12Example 12

膜織物包括薄的、水蒸汽可透過的膜，如聚胺甲酸酯或PTFE。該膜係水分可透過的因為它非常薄並且在微觀水平上是略微多孔的。因為膜如此薄，它必須藉由將其夾在兩個其他織物層之間受到保護。典型地，存在保護該膜免受被皮膚或其他衣服摩擦的柔軟底部織物，和用於保護該膜免受任何外部磨損和用於衣服的裝飾外觀的面織物。頂部、面織物必須用防水面層處理，使得雨水快速從服裝流下以避免“濕透”。如果這樣的面織物的水飽和發生，然後來自人體的濕蒸汽不能通過該膜逸出，因為它被該潤濕的織物擴散阻擋。因此，希望的是面織物盡可能防水，甚至在強烈陣雨中。 Membrane fabrics include thin, water vapor permeable membranes such as polyurethane or PTFE. The film is moisture permeable because it is very thin and slightly porous at the microscopic level. Because the film is so thin, it must be protected by sandwiching it between two other fabric layers. Typically, there is a soft bottom fabric that protects the film from rubbing by skin or other clothing, and a facial fabric that protects the film from any external wear and decorative appearance for the garment. The top and top fabrics must be treated with a waterproof finish to allow rainwater to quickly flow down the garment to avoid "wetting." If water saturation of such a face fabric occurs, then wet steam from the body cannot escape through the film because it is blocked by the wetted fabric. Therefore, it is desirable that the face fabric be as waterproof as possible, even in strong showers.

多個具有中心PTFE膜的3層膜織物的樣品在頂部、面織物被塗覆並且使用在實施例1中描述的通用程式固化。在塗覆和吹掃之後該等織物在貧氧氣氛下被加壓至或者250psig(1.7MPa)或450psig(3.1MPa)壓力並且在該壓力下在90℃下固化持續15分鐘。該塗覆的織物根據ISO 9865測試方案，持續10分鐘在邦迪斯門拒水性測試器中評估拒水性。在1.7MPa壓力下固化的樣品實現了4.7拒水等級。它增加了15.4%的水重量，並且沒有水滲透該樣品。在3.1MPa壓力下固化的樣品實現了完全的5拒水等級並且增加僅5.7%的水重量。也沒有水穿過該樣品。在該等實驗中，在固化期間的較高壓力明顯地改進了該等結果。 A sample of a plurality of 3-layer film fabrics with a central PTFE film was coated on top, face fabric and cured using the general procedure described in Example 1. The fabrics were pressurized under an oxygen-poor atmosphere to either 250 psig (1.7 MPa) or 450 psig (3.1 MPa) pressure and cured at 90 ° C for 15 minutes after coating and purging. The coated fabric was evaluated for water repellency in a Bondis Gate water repellency tester for 10 minutes according to the ISO 9865 test protocol. The sample cured at 1.7 MPa pressure achieved a water repellent rating of 4.7. It increased the water weight by 15.4% and no water penetrated the sample. The sample cured at a pressure of 3.1 MPa achieved a full 5 water repellency rating and increased water weight by only 5.7%. There is also no water passing through the sample. In these experiments, higher pressures during curing significantly improved the results.

實施例13和14Examples 13 and 14

根據在實施例1中描述的通用程式塗覆具有表面潤滑劑的芳族聚醯胺織物的一式兩份的樣品，除了固化係在135℃和1.7MPa表壓下進行。 Duplicate samples of the aromatic polyamide fabric with surface lubricant were applied according to the general procedure described in Example 1, except that the curing was carried out at 135 ° C and a gauge pressure of 1.7 MPa.

一個樣品沒有預處理被塗覆。在ISO 9865試驗中，該塗覆的樣品增加20%-25%水重量。 One sample was coated without pretreatment. In the ISO 9865 test, the coated sample was increased by 20%-25% water by weight.

使第二個樣品(實施例13)經受藉由將其在50psi(345kPa)純氧下加熱至150℃持續15分鐘的氧化預處理。在塗覆後，該樣品增加僅2.9%水重量。該結果係與其中該潤滑劑藉由水洗滌(增加3.5%水重量)和電漿處理(增加2.5%水重量)被除去的另外的比較樣品可比較的。 The second sample (Example 13) was subjected to an oxidation pretreatment by heating it to 150 ° C under 50 psi (345 kPa) of pure oxygen for 15 minutes. After coating, the sample increased by only 2.9% water by weight. The results were comparable to additional comparative samples in which the lubricant was removed by water washing (3.5% water weight increase) and plasma treatment (2.5% water weight increase).

使第三個樣品(實施例14)經受藉由將其在50psi(345kPa)純氧下加熱至190℃持續15分鐘的氧化預處理。在塗覆後，該樣品增加僅0.9%水重量，這與對照的任一種相比得以顯著改善。 The third sample (Example 14) was subjected to an oxidative pretreatment by heating it to 190 ° C under 50 psi (345 kPa) of pure oxygen for 15 minutes. After coating, the sample increased by only 0.9% water by weight, which was significantly improved compared to either of the controls.

Claims (32)

一種用於將有機聚合物塗層施用和固化在基底上之方法，該方法包括以下步驟：1)在非聚合條件下，將在22℃下和在大氣壓下為液體或一種或多種固體在液相中的懸浮液的可固化的塗料組成物施用到該基底的至少一個表面上，其中該可固化的塗料組成物含有i)至少一種可聚合單體，該可聚合單體在自由基的存在下聚合，每分子恰好具有一個可自由基聚合的基團並且具有在一個大氣壓下至少100℃的沸騰溫度，和2)至少一種熱活化的聚合引發劑，該可固化的組成物基於該塗料組成物的總重量含有按重量計不超過10%的具有在一個大氣壓下低於100℃的沸騰溫度的有機化合物和按重量計不超過5%的水；然後2)在非聚合條件下，從含有具有該施用的可固化塗層的該基底的容器的內部吹掃分子氧，然後3)在步驟2)期間和/或之後，用貧氧氣體將含有具有該施用的可固化塗層的該基底的該吹掃的容器加壓至實際至少120kPa的氣體壓力，並且然後，不將該具有施用的可固化塗層的基底暴露於含有1莫耳百分數或更多氧的氣氛下，4)藉由在貧氧條件下將具有該施用的可固化的塗料組成物的該基底加熱至足以活化該熱活化的聚合引發劑並且引發該至少一種可聚合單體的聚合的溫度來至少部分地固化該可固化的塗料組成物，以在該基底上形成至少部分固化的有機聚合物塗層。  A method for applying and curing an organic polymer coating on a substrate, the method comprising the steps of: 1) under non-polymerization conditions, at 22 ° C and at atmospheric pressure, liquid or one or more solids in liquid A curable coating composition of the suspension in the phase is applied to at least one surface of the substrate, wherein the curable coating composition comprises i) at least one polymerizable monomer in the presence of free radicals Polymerization, having exactly one radical polymerizable group per molecule and having a boiling temperature of at least 100 ° C at one atmosphere, and 2) at least one heat activated polymerization initiator based on the composition of the coating The total weight of the material contains no more than 10% by weight of the organic compound having a boiling temperature of less than 100 ° C at one atmosphere and not more than 5% by weight of water; and then 2) under non-polymerization conditions, from The interior of the container of the substrate having the applied curable coating is purged of molecular oxygen, and then 3) during and/or after step 2), the oxygen-depleted gas will contain curable with the application The purged container of the substrate of the layer is pressurized to a gas pressure of at least 120 kPa, and then the substrate having the applied curable coating is not exposed to an atmosphere containing 1 mole percent or more of oxygen, 4) at least partially heating the substrate having the applied curable coating composition under oxygen-depleted conditions to a temperature sufficient to activate the thermally activated polymerization initiator and initiate polymerization of the at least one polymerizable monomer The curable coating composition is cured to form an at least partially cured organic polymer coating on the substrate.   一種用於將有機聚合物塗層施用和固化在具有一個或多個孔、裂縫或 其他開口的基底上之方法，該方法包括以下步驟：1)在非聚合條件下，將在22℃下為液體或一種或多種固體在液相中的懸浮液的可固化的塗料組成物施用到該基底的至少一個表面上，其中該可固化的塗料組成物含有i)至少一種可聚合單體，該可聚合單體在自由基的存在下聚合，每分子恰好具有一個可自由基聚合的基團，具有至少一個具有至少六個直接地或間接地結合到該可自由基聚合的基團上的碳原子的烴基並且具有在一個大氣壓下至少100℃的沸騰溫度，和2)至少一種熱活化的聚合引發劑，該可固化的組成物基於該塗料組成物的總重量含有按重量計不超過10%的具有在一個大氣壓下低於100℃的沸騰溫度的有機化合物和按重量計不超過5%的水；然後2)在非聚合條件下，從含有具有該施用的可固化塗層的該基底的容器的內部吹掃分子氧，3)在步驟2)期間和/或之後，在貧氧氣體中在所施加的超大氣壓的力下迫使該施用的、液體可固化的塗料進入該基底中的至少一個孔、裂縫或其他開口中，並且然後，不將該具有施用的可固化塗層的基底暴露於含有1莫耳百分數或更多氧的氣氛下，4)藉由在貧氧條件下將具有該施用的可固化的塗料組成物的該基底加熱至足以活化該熱活化的聚合引發劑並且引發該至少一種可聚合單體的聚合的溫度來固化至少部分地固化該可固化的塗料組成物，以在該基底上形成至少部分固化的有機聚合物塗層。  A method for applying and curing an organic polymer coating on a substrate having one or more holes, cracks or other openings, the method comprising the steps of: 1) under non-polymerization conditions, at 22 ° C Applying a curable coating composition of a liquid or a suspension of one or more solids in a liquid phase to at least one surface of the substrate, wherein the curable coating composition comprises i) at least one polymerizable monomer, The polymerized monomer is polymerized in the presence of a radical, each molecule having exactly one radical polymerizable group having at least one carbon atom having at least six groups bonded directly or indirectly to the radical polymerizable group a hydrocarbon group and having a boiling temperature of at least 100 ° C at one atmosphere, and 2) at least one heat activated polymerization initiator containing no more than 10% by weight based on the total weight of the coating composition An organic compound having a boiling temperature of less than 100 ° C at one atmosphere and not more than 5% by weight of water; and then 2) under non-polymerization conditions, from containing the application The interior of the container of the substrate of the curable coating is purged of molecular oxygen, 3) during and/or after step 2), forcing the applied, liquid curable under an applied superatmospheric force in an oxygen-depleted gas The coating enters at least one of the holes, cracks or other openings in the substrate, and then, the substrate having the applied curable coating is not exposed to an atmosphere containing 1 mole percent or more of oxygen, 4) Heating the substrate having the curable coating composition of the application under oxygen-depleted conditions to a temperature sufficient to activate the thermally activated polymerization initiator and initiate polymerization of the at least one polymerizable monomer to cure at least partially cured The curable coating composition forms an at least partially cured organic polymer coating on the substrate.   如申請專利範圍第1或2項所述之方法，其中在步驟4)中該等貧氧條件包括具有實際至少120kPa的壓力的貧氧氣氛。  The method of claim 1 or 2, wherein in the step 4) the oxygen-lean conditions comprise an oxygen-lean atmosphere having a pressure of at least 120 kPa.   如申請專利範圍第1或2項所述之方法，其中在步驟4)中該等貧氧條件包括將具有該施用的塗料組成物的該基底浸入在液體或超臨界流體中。  The method of claim 1 or 2, wherein the oxygen-poor conditions in step 4) comprise immersing the substrate having the applied coating composition in a liquid or supercritical fluid.   如以上申請專利範圍中任一項所述之方法，其中該聚合引發劑具有在100℃下至少5分鐘的半衰期。  The method of any of the above claims, wherein the polymerization initiator has a half life of at least 5 minutes at 100 °C.   如以上申請專利範圍中任一項所述之方法，其中進行步驟4)直到該一種或多種單體的轉化率係至少85莫耳百分比。  The method of any of the preceding claims, wherein step 4) is performed until the conversion of the one or more monomers is at least 85 mole percent.   如以上申請專利範圍中任一項所述之方法，其中步驟2)包括將貧氧氣體流動到與該基底接觸的步驟。  A method as claimed in any one of the preceding claims, wherein the step 2) comprises the step of flowing an oxygen-depleted gas into contact with the substrate.   如以上申請專利範圍中任一項所述之方法，其中步驟2)包括將貧氧氣體通过一個或多個孔、裂縫或其他開口流動到該基底中的步驟。  A method as claimed in any one of the preceding claims, wherein step 2) comprises the step of flowing an oxygen-depleted gas through the one or more pores, cracks or other openings into the substrate.   如以上申請專利範圍中任一項所述之方法，其中步驟2)包括執行至少一個加壓/減壓循環的步驟，其中在每個循環中將包含該塗覆的基底的該容器的內部用貧氧氣體加壓至實際至少120kPa的超大氣壓並且然後減壓。  The method of any of the preceding claims, wherein the step 2) comprises the step of performing at least one pressurization/depressurization cycle, wherein the interior of the container containing the coated substrate is used in each cycle The oxygen-depleted gas is pressurized to a superatmospheric pressure of at least 120 kPa and then depressurized.   如以上申請專利範圍中任一項所述之方法，其中該基底係具有在交叉纖維之間的孔隙空間的纖維紡織品或非織造物。  A method as claimed in any one of the preceding claims, wherein the substrate has a fibrous textile or nonwoven having a void space between the intersecting fibers.   如申請專利範圍第10項所述之方法，其中該紡織品或非織造物包括針織的、編織的、簇絨的、打結的、糾纏的和/或纏繞的纖維，並且該紡織品在塗覆之前具有如根據ASTM D737測量的至少0.2英呎/分鐘/平方英呎(0.001016m/s)的空氣滲透率。  The method of claim 10, wherein the textile or nonwoven comprises knitted, woven, tufted, knotted, entangled and/or entangled fibers, and the textile is coated prior to coating It has an air permeability of at least 0.2 inches per minute per square inch (0.001016 m/s) as measured according to ASTM D737.   如申請專利範圍第10或11項所述之方法，其中步驟3)中該可固化組 分在氣體壓力的力下滲透入該紡織品中。  The method of claim 10, wherein the curable component penetrates into the textile under the force of gas pressure in step 3).   如申請專利範圍第10、11或12項所述之方法，其中在步驟3)中該可固化的塗料組成物在氣體壓力的力下流動進入所述間隙空間的一個或多個中。  The method of claim 10, 11 or 12, wherein in step 3) the curable coating composition flows under pressure of gas pressure into one or more of the interstitial spaces.   如以上申請專利範圍中任一項所述之方法，其中該基底係良好安裝在心軸上的輥，該心軸具有縱向孔並且沿著該心軸的長度具有一個或多個開口，並且在步驟2)中該貧氧氣體流過該安裝的基底，沿著該心軸的長度通過至少一個開口並且通過該縱向孔。  The method of any of the preceding claims, wherein the substrate is a roller that is well mounted on a mandrel, the mandrel having a longitudinal bore and having one or more openings along the length of the mandrel, and in steps 2) The oxygen-depleted gas flows through the mounted substrate, passing through at least one opening along the length of the mandrel and through the longitudinal bore.   如以上申請專利範圍中任一項所述之方法，其中步驟2)包括壓縮該塗覆的基底以從該基底的空隙空間中去除分子氧的步驟。  The method of any of the preceding claims, wherein step 2) comprises the step of compressing the coated substrate to remove molecular oxygen from the void space of the substrate.   如申請專利範圍第1-9項中任一項所述之方法，其中該基底係電子裝置。  The method of any of claims 1-9, wherein the substrate is an electronic device.   如申請專利範圍第16項所述之方法，其中在步驟3)中，其中該電子裝置具有在該電子裝置的構成部分之間的一個或多個開口，並且在步驟3)中，該可固化組成物在氣體壓力的力下流動進入這樣的開口的一個或多個中並且在固化時密封這樣的一個或多個開口使得它們係耐水滲透的。  The method of claim 16, wherein in step 3), wherein the electronic device has one or more openings between the constituent parts of the electronic device, and in step 3), the curable The composition flows into one or more of such openings under the force of gas pressure and seals one or more of the openings upon curing such that they are water resistant.   如以上申請專利範圍中任一項所述之方法，其中可固化的塗料組成物進一步包含至少一種交聯單體，該交聯單體具有至少兩個自由基可固化的可聚合的基團和等於或大於100℃的沸騰溫度。  The method of any one of the preceding claims, wherein the curable coating composition further comprises at least one crosslinking monomer having at least two radical curable polymerizable groups and A boiling temperature equal to or greater than 100 °C.   如以上申請專利範圍中任一項所述之方法，其中所述可聚合單體的至少一種具有在步驟4)中的聚合溫度下在1大氣壓下不大於6.7kPa的 蒸氣壓力。  The method according to any one of the preceding claims, wherein at least one of the polymerizable monomers has a vapor pressure of not more than 6.7 kPa at 1 atm. at a polymerization temperature in the step 4).   如以上申請專利範圍中任一項所述之方法，其中所述可固化的塗料組成物包含至少10重量百分比的一種或多種化合物，該一種或多種化合物具有在聚合步驟4)的溫度下在1大氣壓下6.7至53kPa(約50至400托)的蒸氣壓力。  The method of any of the preceding claims, wherein the curable coating composition comprises at least 10 weight percent of one or more compounds having a temperature at the temperature of polymerization step 4) Vapor pressure of 6.7 to 53 kPa (about 50 to 400 Torr) at atmospheric pressure.   如以上申請專利範圍中任一項所述之方法，其中所述可固化組成物包含至少一種聚矽氧烷油。  A method as claimed in any one of the preceding claims, wherein the curable composition comprises at least one polyoxyalkylene oil.   如以上申請專利範圍中任一項所述之方法，其中所述可固化的塗料組成物包含三甲氧基(1H,1H,2H,2H十七氟癸基)矽烷、全氟己基乙基丙烯酸酯、全氟己基乙烯和全氟辛基乙烯中的一種或多種。  The method of any one of the preceding claims, wherein the curable coating composition comprises trimethoxy (1H, 1H, 2H, 2H heptadecafluorodecyl) decane, perfluorohexyl ethyl acrylate One or more of perfluorohexylethylene and perfluorooctylethylene.   如申請專利範圍第3項所述之方法，其中該貧氧氣氛包括至少98莫耳百分比的氮氣和最高達0.1莫耳百分比的分子氧，其餘部分係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。  The method of claim 3, wherein the oxygen-lean atmosphere comprises at least 98 mole percent of nitrogen and up to 0.1 mole percent of molecular oxygen, the balance being traces of gas, the traces of gas being in the chamber Mild at 1 atmosphere is a gas.   如申請專利範圍第3項所述之方法，其中該貧氧氣氛包括至少98莫耳百分比的蒸汽和最高達0.1莫耳百分比的分子氧，其餘部分係痕量氣體，該等痕量氣體在室溫和1大氣壓下是氣體。  The method of claim 3, wherein the oxygen-lean atmosphere comprises at least 98 mole percent of steam and up to 0.1 mole percent of molecular oxygen, the balance being traces of gas, the traces of gas being in the chamber Mild at 1 atmosphere is a gas.   如申請專利範圍第3項所述之方法，其中所述貧氧氣氛包括至少氣相、可聚合的單體，該單體具有在一個大氣壓下40℃或更小的沸騰溫度和一個或多個可聚合的碳-碳雙鍵。  The method of claim 3, wherein the oxygen-lean atmosphere comprises at least a gas phase, a polymerizable monomer having a boiling temperature of 40 ° C or less at one atmosphere and one or more Polymerizable carbon-carbon double bond.   如申請專利範圍第25項所述之方法，其中在步驟4)中該氣相、可聚合的單體均聚或與該可固化的塗料組成物中的至少一種單體共聚。  The method of claim 25, wherein in the step 4) the gas phase, the polymerizable monomer is homopolymerized or copolymerized with at least one monomer in the curable coating composition.   如以上申請專利範圍中任一項所述之方法，該方法進一步包括，在步 驟a)之前，使該基底經受氧化預處理步驟。  The method of any of the preceding claims, further comprising subjecting the substrate to an oxidative pretreatment step prior to step a).   如申請專利範圍第27項所述之方法，其中所述氧化預處理步驟包括在含氧氣氛中在超大氣壓下將該基底加熱至100℃至220℃，較佳的是150℃至190℃。  The method of claim 27, wherein the oxidizing pretreatment step comprises heating the substrate to a temperature of from 100 ° C to 220 ° C, preferably from 150 ° C to 190 ° C under superatmospheric pressure in an oxygen-containing atmosphere.   如申請專利範圍第28項所述之方法，其中所述氧化預處理步驟進一步包括使該基底暴露於含氧大氣電漿。  The method of claim 28, wherein the oxidizing pretreatment step further comprises exposing the substrate to an oxygen-containing atmospheric plasma.   一種用於塗覆基底之方法，該方法包括A)使該基底經受氧化預處理步驟，該氧化預處理步驟包括在含氧氣氛中在超大氣壓下將該基底加熱至100℃至220℃，較佳的是150℃至190℃；然後B)將可固化的塗料組成物施用到該基底的至少一個表面上，並且C)固化該可固化的塗料組成物以在該基底的至少一個表面上形成固化的塗層。  A method for coating a substrate, the method comprising: A) subjecting the substrate to an oxidation pretreatment step comprising heating the substrate to a temperature of from 100 ° C to 220 ° C under superatmospheric pressure in an oxygen-containing atmosphere, Preferably, 150 ° C to 190 ° C; then B) applying a curable coating composition to at least one surface of the substrate, and C) curing the curable coating composition to form on at least one surface of the substrate Cured coating.   一種用於固化塗覆有可固化的塗料組成物的基底之反應容器，該反應容器包括：限定用於容納該塗覆的基底的該反應容器的內部空間之外壁；至少一個用於***和移除該塗覆的基底的可密封的開口；用於密封該可密封的開口之裝置；至少一個用於將氣體引入到該內部空間中和去除的氣體端口；至少一個佈置在該內部空間內的心軸，所述心軸具有縱向孔和多個開口，該等開口產生從該縱向孔進入該反應容器的該內部空間中的流體路徑，該縱向孔還與該至少一個氣體端口處於流體連通； 用於將氣體輸送到所述至少一個氣體端口的至少一個中，穿過該心軸，穿過該心軸的開口並且穿過該內部空間並且與佈置在該內部空間中的塗覆的基底接觸並且從所述至少一個氣體端口的至少一個離開的裝置，用於加壓該反應容器的該內部空間之裝置，以及用於加熱該反應容器的該內部空間之加熱裝置。  A reaction vessel for curing a substrate coated with a curable coating composition, the reaction vessel comprising: an outer space outer wall defining the reaction vessel for containing the coated substrate; at least one for insertion and removal a sealable opening in addition to the coated substrate; means for sealing the sealable opening; at least one gas port for introducing gas into and removed from the interior space; at least one disposed within the interior space a mandrel having a longitudinal bore and a plurality of openings, the openings creating a fluid path from the longitudinal bore into the interior space of the reaction vessel, the longitudinal bore also being in fluid communication with the at least one gas port; Means for delivering gas into at least one of the at least one gas port, through the mandrel, through an opening of the mandrel and through the interior space and in contact with a coated substrate disposed in the interior space And means for withdrawing from the at least one of the at least one gas port, means for pressurizing the internal space of the reaction vessel, and for heating the counter A heating device for the internal space of the container.   一種用於固化塗覆有可固化的塗料組成物的基底之反應裝置，該反應裝置包括：A.限定內部空間的外部壓力腔室，該外部壓力腔室能夠承受實際0.5至15MPa的內部壓力；B.限定內部體積的料箱，該內部體積用於容納在該料箱內的層狀基底，使得該基底的該等層在該料箱內被水平地安排，這樣的料箱被適配為安裝在該壓力腔室的內部空間內；C.位於該料箱的內部體積的底部處之氣體空間，該氣體空間具有多個在操作期間允許氣體進入該內部體積料箱中的開口；D.至少一個位於該料箱的頂部處或頂部附近的開口，用於從該料箱的該內部體積中去除氣體；以及E.用於加熱該料箱的該內部體積之加熱裝置；F.用於建立在該料箱係該外部壓力腔室的內部空間時到該氣體空間中並穿過該氣體空間，穿過該料箱中的層狀織物並且通過位於該料箱的頂部處或頂部附近的所述至少一個開口離開該料箱的氣體流之氣體循環裝置；以及 G.用於在該外部壓力腔室的內部空間內建立超大氣壓之裝置。  A reaction apparatus for curing a substrate coated with a curable coating composition, the reaction apparatus comprising: A. an external pressure chamber defining an internal space, the external pressure chamber being capable of withstanding an internal pressure of 0.5 to 15 MPa; B. a bin defining an internal volume for receiving a layered substrate within the bin such that the layers of the substrate are horizontally arranged within the bin, such bin being adapted to Installed in the interior space of the pressure chamber; C. a gas space at the bottom of the inner volume of the tank, the gas space having a plurality of openings that allow gas to enter the inner volume bin during operation; At least one opening at or near the top of the tank for removing gas from the interior volume of the tank; and E. heating means for heating the internal volume of the tank; Established in the gas space and through the gas space as the bin is inside the outer pressure chamber, through the layered fabric in the bin and through the top or near the top of the bin Place Gas circulation means at least one opening of the tank away from the gas stream; and G. means for establishing superatmospheric pressure within the interior space of the outer pressure chamber.