TWI737671B - 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

High pressure method for applying and curing organic polymerizable treatments

The invention relates to a method for applying and curing a polymerizable coating on a substrate.

Polymer coatings are used on porous and non-porous substrates to provide these materials with a variety of additional properties.

The 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 evaporation rate of the absorbed water. Sportswear, for example, may have a hydrophilic coating applied thereon to help absorb sweat and help wick the sweat over a large area of the garment to accelerate evaporation and evaporative cooling.

Instead, hydrophobic coatings are applied on different substrates to protect them from moisture. In textile applications, for example, hydrophobic coatings are used to provide waterproof finishes to clothing such as rain gear and outerwear such as coats, hats, and shoes. These coatings are used in a variety of industrial, vehicle and construction 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 would be house "cladding" and roofing materials. Electronic packaging is another area that benefits from hydrophobic coatings.

Apply an oleophobic coating to textiles or other materials to prevent oil-based liquids from staining Dirt or penetrate the substrate. Oleophobic coatings are often oleophobic, lipophobic and hydrophobic.

Highly effective coating materials have been developed. However, the method of application is often inappropriate, especially when very low coating weights are desired, which is often the case. In textile applications, for example, heavy coatings add undesirable weight and may impart a heavy and hard feel to the fabric. This has an adverse effect on the sense of touch and physical properties commonly referred to in the industry as "breathability", "drapability" and "feel". Weight is also an important factor in electronic packaging and other industrial applications. Thin coatings also potentially have cost advantages because less coating materials are required.

The methods used to apply very thin polymer coatings are constrained by high cost, inappropriate coating properties, or both. Inappropriate coating performance is generally due to defects in the coating when applied at low coating weights.

Textiles, for example, are usually porous materials that are often made of intersecting fibers. Ideally, one wants to apply an effective coating without blocking most of the pores, because doing so reduces breathability, drape, and feel. Conventionally, the most common way to apply a hydrophobic coating to textiles is to use the "pad and cure" method, which involves pulling a length of woven or knitted fabric through a water-based 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 ingredients, the use of large amounts of energy to remove water or solvents, and the need to recycle or dispose of Large amounts 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 quickly Precipitate 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 Office The open case 2008/0107822 describes a method: the textile is coated with monomers condensed by the vapor of the nano-level layer plus additional chemicals, followed by a plasma-based curing method to polymerize the coated monomers. The plasma-based curing requires expensive equipment, slow operation, and is a line-of-sight method that does not produce uniform curing.

Non-porous substrates such as electronic devices can have small cracks or gaps between their components that are difficult to seal without applying a heavy coating. These devices are usually sealed by enclosing them in a gasket shell, or by spraying them with a hydrophobic treatment, or by a plasma-based chemical vapor deposition method. The sealed gasket shell contains trapped gas. When under sub-atmospheric pressure, as is often encountered, for example, on airplanes or at high altitudes, the trapped gas expands and may crack the shell. Hydrophobic treatment of spray has difficulty in sealing small cracks and openings. Plasma-enhanced chemical vapor deposition is an expensive, slow, and line-of-sight method that does not easily cover all surfaces of the device.

The present invention is a method for applying an organic polymer to coat a substrate. The method includes the following steps: 1) Under non-polymerization conditions, a curable coating composition that is a liquid or a suspension of one or more solids in the liquid phase at 22°C is applied to at least one surface of the substrate, wherein the curable coating The composition contains i) at least one polymerizable monomer, which polymerizes in the presence of free radicals, has exactly one radical polymerizable group per molecule and has a boiling temperature of at least 100°C under one atmospheric pressure, And 2) at least one thermally activated polymerization initiator, the curable composition containing no more than 10% by weight of an organic compound having a boiling temperature lower than 100°C at one atmospheric pressure based on the total weight of the coating composition And not more than 5% by weight Of water; then 2) Purging molecular oxygen from the inside of the container containing the substrate with the curable coating applied under non-polymerization conditions, 3) During and/or after step 2), the purged container containing the substrate with the applied curable coating is pressurized with an oxygen-depleted gas to an actual gas pressure of at least 120 kPa, and then, the purged container is not The substrate of the applied curable coating is exposed to an atmosphere containing 1 mole percent or more of oxygen, 4) At least partially by heating the substrate with the applied curable coating composition under oxygen-poor conditions to a temperature sufficient to activate the heat-activated polymerization initiator and initiate the 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.

The present invention is also a reaction vessel for curing a substrate coated with a curable coating composition. The reaction vessel includes: an outer wall defining an inner space of the reaction vessel for accommodating the coated substrate; at least one A sealable opening for inserting and removing the coated substrate; a device for sealing the sealable opening; at least one gas port for introducing and removing gas into the internal space; at least one gas port arranged in the interior A mandrel in a space, the mandrel has a longitudinal hole and a plurality of openings, the openings create a fluid path from the longitudinal hole into the inner space of the reaction vessel, the longitudinal hole is also located at the at least one gas port Fluid communication; for delivering gas to at least one of the at least one gas port, through the mandrel, through the opening of the mandrel, and through the internal space and with the internal space A device that the coated substrate contacts and exits from at least one of the at least one gas port, a device for pressurizing the internal space of the reaction vessel, and a heating device for heating the internal space of the reaction vessel.

1: reaction vessel

2: Central mandrel

2A: Lower support

2B: Board

3: heating device

4: The first gas port

5: Internal space

6: Pressure gauge

7: Base

8: The direction of gas flow

9: Second gas port

10: External opening

11: junction

12: Nuts and bolts

13A: Top section

13B: bottom section

Figure 1 is a front view of the equipment used in the method of the present invention.

Figure 2 is a front cross-sectional view of the equipment used in the present invention.

Fig. 3 is a front cross-sectional view of the apparatus used in the present invention, with a wound textile arranged in a reaction vessel and wound around the central mandrel 10 of Fig. 2 by winding the textile around the mandrel.

In step 1) of the method of the present invention, a curable coating composition as described herein is applied to the substrate. Because the curable composition is a liquid or suspension, it can be applied to the substrate by any of many conventional methods, such as rolling, brushing, spraying, immersing the substrate in the composition, and applying Stir a puddle and scrape the composition onto or into the substrate using, for example, an air knife or a spatula, among other methods. When the curable coating composition contains a large amount of liquid carrier, a dipping method can be used. The dipping method is usually followed by a means for removing excess coating composition before curing.

The conditions during step 1) are non-polymerization conditions. The non-polymerization conditions are conditions such that little (not more than 10 mol%, preferably not more than 5 mol%) curing of one or more monomers or no curing occurs during this step. In particular, the temperature during step 1) is selected so 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 thermally activated polymerization initiator. In addition, better The point is that there are no free radicals from other sources during this coating step. For the purpose of the present invention, conditions including a temperature lower than the one-hour half-life temperature of the thermally activated polymerization initiator and excluding free radicals from other sources are regarded as non-polymerization conditions.

The pressure and temperature conditions during step 1) are also selected so that the one or more monomers and the thermally activated polymerization initiator are not significantly volatilized. For example, step 1) can be performed at an atmospheric pressure of about 1 bar, that is, about 50 to 150 kPa or about 90 to 119 kPa.

Preferably, the area-based coating weight from 1 to 150 grams / square meter of coated substrate (g / m ^2), in particular 1.5g / m ² to 70g / m ² or 1.5 to 20g / m ^2. In certain specific examples, 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 , but for heavier substrates (especially porous substrates), the coating The weight can be higher. Higher coating weights can be applied by dipping filling or by using two or more chemical transfer devices in series or by passing the substrate through a chemical transfer device multiple times. The significant advantage of the present invention is that the very low coating weight is easily applied and there is minimal chemical "waste" or evaporation loss.

The molecular oxygen is then purged from the container containing the coated substrate. By "purge", it simply refers to the removal of molecular oxygen from the atmosphere in the container. Preferably, the purging step also removes molecular oxygen that is in contact with the surface of the substrate, as well as any pores or interstitial spaces in the substrate that are connected to the surface of the substrate by the fluid remaining in the substrate and can therefore interact with the applied during the process. Molecular oxygen in contact with curable coatings. For example, before purging, molecular oxygen can occupy all or part of the pores or interstitial spaces. In this case, the molecular oxygen is typically present as a component that traps air. Textiles, for example, are generally highly porous materials with void spaces between the intersecting fibers that make up the material. Some molecular oxygen can be chemically adsorbed or physically adsorbed to one or more surfaces of the substrate. During this purge step, chemically adsorbed or physically adsorbed molecular oxygen is preferably removed, and molecular oxygen is preferably removed from such interstitial spaces. The electronic device may have through holes, or small cracks or openings at the junctions of its constituent parts, and molecular oxygen from the through holes, or small cracks or openings is preferably removed during the purging step 2).

This purging step 2) is carried out under non-polymerization conditions as described with respect to step 1). In addition, the pressure and temperature conditions during the purging step 2) are selected so that the one or more monomers and the thermally activated polymerization initiator are not volatilized.

This purging step can be performed in a variety of ways.

One way to perform this purge step is to place the substrate with the curable coating applied 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 pores. Thus, for example, a substrate with an applied curable coating can be placed in a container and a stream of oxygen-depleted gas can be introduced into the container while removing the gas so that the flow path of the oxygen-depleted gas passes through the substrate and/or through 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, gas pressure is used to explain the replacement of trapped air in tiny openings and small cracks and gaps between circuit components and printed circuit boards. A pressure drop of about 0.1 to 2 MPa across the container and/or through the substrate 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 flow can continue until the molecular oxygen content of the extracted gas drops to less than 1 mol percent and less than 0.1 mol percent, Or some lower value, if desired.

The oxygen-depleted system used for the purpose of the present invention contains a gas containing up to 1 mole percent of molecular oxygen (O ₂ ), preferably not 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 of inert gas such as nitrogen, argon, carbon dioxide, steam, helium, or any A mixture of two or more. In some specific examples, the oxygen-depleted gas may contain one or more gas-phase, polymerizable monomers that have a boiling temperature of 40° C. or less and one or more polymerizable carbons at one atmospheric pressure. -Carbon double bond. Examples of such gas phase monomers include ethylene, propylene, tetrafluoroethylene, hexafluoropropylene, and the like. A preferred oxygen-depleted gas includes at least 98 mole percent of nitrogen and up to 0.1 mole percent of molecular oxygen, and the remainder is trace gas, which is a gas at room temperature and 1 atmosphere. Another preferred oxygen-depleted gas includes at least 50 mol percent nitrogen, up to 1 mol percent or up to 0.1 mol percent molecular oxygen, up to 49.9 mol percent gas-phase monomer, and the remainder (if If any) is a trace gas, which is a gas at room temperature and 1 atmosphere. Another oxygen-depleted gas includes at least 98 mole percent of steam and up to 0.1 mole percent of molecular oxygen, and the remainder is trace gas, which is a gas at room temperature and 1 atmosphere. Yet another preferred oxygen-depleted gas includes steam at least 50 mole percent, molecular oxygen up to 1 mole percent or up to 0.1 mole percent, gas phase monomer up to 49.9 mole percent, and the remainder ( If any) are trace gases, which are gases at room temperature and 1 atmosphere.

The purge step can be performed by mechanically compressing the substrate with the applied curable coating to remove molecular oxygen from pores or other interstitial locations, if the mechanical compression can be accomplished without damaging the substrate. This compression can be performed on the textile, for example, by compressing the coated textile between rollers, one or two of the rollers can be heated, against a drum or other surface (which can be heated again ) Tighten the coated textile, by physically compressing and releasing the folded fabric pile, or in other ways. Mechanical compression can be performed in an oxygen-depleted gas so that molecular oxygen does not re-enter the void space when the compressive force is removed.

Another way to purge molecular oxygen is to place the substrate under reduced atmospheric pressure, as long as the one or more monomers and free radical initiators do not volatilize to less than their initial concentration in the curable coating composition. Less than 30% concentration.

A combination of the above methods for removing air can be used.

During and/or after step 2), the reaction vessel containing the purged substrate with the applied curable coating is pressurized with oxygen-depleted gas to an actual gas pressure of at least 120 kPa. Just like steps 1) and 2), this pressurization step 3) is carried out under non-polymerization conditions.

In the pressurizing 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 for the gas pressure, except for the restrictions on the reaction vessel and related equipment. The actual limit of the gas pressure is about 15 MPa. In some specific examples, the gas pressure 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 specified.

It has been found that the pressure applied in the pressurization step 3) affects the properties of the treated substrate. When the substrate is a fabric, increasing the pressure during the pressurization step 3) tends to produce a treated fabric with higher air permeability than when a lower pressure is used. Therefore, the selection of the pressure applied during the pressurization step 3) can be used as an instruction argument to change the air permeability of the treated fabric. Although the invention is not limited to any theory, it is believed that higher pressure tends to produce a thinner coating, which increases the space between the yarns, thereby increasing air permeability.

It is believed that the pressurization step explains to push the coating into the interior of a porous substrate, such as a textile, and also helps spread the coating against the individual fibers and/or filaments that make up the substrate. This is believed to allow the coating composition to penetrate between individual fibers and/or filaments, even in the case of fabrics woven from spun fibers such as spun staple fibers, it is very difficult to not use a pressing step accomplish.

For electronic device substrates, the pressing step is considered to push the coating into the circuit elements and the minute spaces between the circuit elements and the printed circuit board (for example) and into minute openings such as contact points and metal vias.

In some specific examples, the pressurizing step 3) can be performed as part of the purging step 2). For example, the purging step 2) can be performed by performing one or more pressurization/depressurization cycles, in which the container 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 depressurize to, for example, an actual pressure of 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 parts of this cycle correspond to pressurization step 3); in this case no subsequent pressurization step is needed and can therefore be eliminated as desired, but a final pressurization step can be performed if desired.

When the substrate has low air permeability before being coated, such as 3 standard cubic feet/minute/square feet (0.01524m/sec) or less measured ^{using Textest FX 3300 instrument and 38cm 2 test area according to ASTM D797} At this time, it is particularly beneficial to perform the pressurization/depressurization cycle as just described.

The curable coating composition is then at least partially cured by heating the substrate with the applied curable coating composition under oxygen-poor conditions. "Oxygen-depleted conditions" for the purposes of the present invention means that the polymerization is carried out in an oxygen-depleted atmosphere as previously described, or when the substrate is immersed in a liquid or supercritical fluid. The preferred liquid has a boiling temperature (under 1 atmosphere) of 80°C to 220°C, preferably 80°C to 145°C. After pressurizing with an 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) is performed.

In some specific examples, the polymerization step 4) is performed and the coated substrate from step 3) is under an oxygen-depleted gas. In such specific examples, the polymerization step 4) can be performed in the same vessel where the pressurization step 3) is performed. In such a case, step 4) can be performed under super-atmospheric pressure as described with respect to pressurizing step 3).

In some specific examples, the coated substrate continues to be maintained under such super-atmospheric pressure conditions from step 3) until the polymerization step 4) is performed. The curing of the polymer under superatmospheric pressure is believed to hold the polymer in place so that when the pressurized conditions are released, the polymer remains in place to provide the desired coating characteristics.

In other specific examples, polymerization step 4) is performed in which the coated substrate from step 3) is immersed in a liquid or supercritical fluid such as supercritical carbon dioxide.

In the 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.

When the curing step 4) is performed, the container may be sealed to prevent gas from escaping from the inside of the container. Even if sealed, the container may contain a device such as a safety valve for venting gas from the inside of the reactor if the pressure of the reactor 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 the gas flow through the vessel during step 4) as long as the required pressure is maintained and the atmosphere in the vessel (if any) remains oxygen-depleted.

In the case of immersion in a supercritical fluid, the pressure may be reduced after or during the polymerization step, so that the supercritical fluid is converted into a gas phase. The remainder of the polymerization, if any, can be carried out in such a gas phase, at atmospheric pressure or superatmospheric pressure.

The preferable 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. A lower curing temperature in the above range can be beneficial for processing more heat-sensitive fabrics, such as polyester, nylon, and polypropylene fabrics. At lower curing temperatures, especially at 150°C or lower, less fabric shrinkage is often seen. 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 treating acrylic and aromatic polyamide fabrics, and temperatures up to 150°C are particularly suitable for treating cotton.

The curing under oxygen-poor conditions is continued until at least 50 mole percent, preferably at least 75 mole percent, of the one or more polymerizable monomers in the curable coating composition is converted into a polymer. In some specific examples, curing is carried out under pressurized oxygen-depleted 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 into polymers. The conversion rate during this step can reach 100%.

In some specific examples, step 4) is carried out under an oxygen-depleted gas at superatmospheric pressure as described with respect to step 3) until the conversion rate of the polymerizable monomer in the curable coating composition is 50 to 99 Mole percent, preferably 75 to 95 mole percent and more preferably 85 to 95 mole percent, and further curing is carried out at a gas pressure actually lower than 120 kPa, for example, 75 to 119 kPa or 95 to 105 kPa . In other specific examples, step 4) is carried out under oxygen-poor conditions until the conversion rate of the polymerizable monomer in the curable coating composition is 50 to 99 mol percent, preferably 75 to 99 mol. Percentage, and further curing is carried out under air. In this work, "curing" and "polymerization" are used interchangeably.

The time required to perform step 4) is typically relatively short, for example from 0.5 to 60 minutes or from 5 to 20 minutes, although longer or shorter times may 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.

It is generally useful for performing at least steps 2), 3) and 4) in a single reaction vessel. Therefore, the substrate with the curable coating composition applied is arranged in the reaction vessel and the molecular oxygen and the reaction vessel are purged. The reaction vessel is then pressurized with an oxygen-depleted gas and heated to the polymerization temperature to effect curing of the curable coating composition.

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 device adapted for applying thin coatings. It is not necessary to perform steps 2), 3) and 4) immediately after coating step 1).

A suitable reaction vessel is an autoclave or other vessel capable of handling the pressure encountered in steps 3) and 4). Such a reaction vessel preferably includes various gas processing equipment to carry out the introduction and removal of gas from the internal space of the vessel, for pressurizing the vessel and for applying heat. Such devices are well known and no special design of such devices is necessary.

Figures 1-3 depict a suitable device for performing steps 2), 3) and 4) of the present invention.

In FIGS. 1-3, the reaction vessel 1 includes a bottom section 13B and a top section 13A, which together define an internal space 5, in which a substrate 7 (FIG. 3) is arranged for performing steps 2), 3) 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 (Figure 1) use any suitable sealing method along the junction 11 (Figure 1), such as, for example, nuts and bolts 12 (Figure 1), others Mechanical sealing devices such as clamps, clamps or rivets, magnetic sealing devices, adhesives, gaskets, and similar seals. In the specific example shown in Fig. 1, the base (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 holes and has external openings 10 (FIG. 2) that create a fluid path from the longitudinal holes into the internal space 5 of the reaction vessel 1.

The reaction vessel 1 further includes a device for introducing gas into the internal space 5 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 a second gas port 9 as appropriate. As shown, the second gas port 9 is in fluid communication with the central hole of the central mandrel 2. Alternatively, a single gas port can serve as both the inlet and outlet ports.

During the purge step 2), oxygen-depleted gas is introduced into the internal space 5, passes through the opening 10 in the central mandrel 2, and is removed through one of the gas ports 4 and 9. The gas can flow between the gas port 4 and the gas port 9 in either direction. The gas port 4 may be an inlet port through which the oxygen-depleted gas enters the internal space 5 and flows through the substrate 7 therefrom, enters the opening 10, passes through the central hole of the mandrel 2 and exits through the gas port 9. Alternatively, the direction of gas flow may be reversed, flowing into the central hole of the central mandrel 2 through the gas port 9 through the gas port 9 before being extracted from the internal space 5 via the gas port 4, entering the internal space 5 through the opening 10 and passing through the base 7.

The specific example shown in Figures 1-3 is a better design and is particularly well adapted for processing into rolled goods such as rolled textiles. As shown in Fig. 3, a flexible substrate 7, such as a rolled textile, is wound around the central mandrel 2, or on a core, which is then mounted on the 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 therefrom (or in the opposite direction from the gas port 9 to the gas port 4), it therefore travels through The flexible substrate 7. The movement of this gas through the substrate is an effective way to remove molecular oxygen trapped in the pores or other gaps of the substrate 7.

In the specific example shown in FIGS. 1-3, the pressurizing step 3) and the curing step 4) are also performed in the reaction vessel 1.

During the operation, the substrate with the curable coating applied is inserted into the internal space 5 of the reaction vessel 1 (if the coating step 1 is not performed therein)). A flow of oxygen-depleted gas is established that enters, passes through, and then exits the inner 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 mol percent, below 0.1 mol percent, or other predetermined value. Alternatively, the gas flow may continue until a volume of gas equal to a predetermined multiple of the volume of the internal space 5 (for example, from 2 to 50 reaction volumes or 2 to 10 reactor volumes) has been passed through the reaction vessel 1.

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 internal 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 oxygen-depleted gas while maintaining the pressure as previously described. The heating is maintained until at least 50 mole percent of the polymerizable monomer has been converted to 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 device can be, for example, a heating jacket, an electric heater, or a radiant heater. The reaction vessel 1 is placed in an oven or an oil bath heated by natural gas or electric power, or other suitable heating devices. It is also possible to perform necessary heating by heating the oxygen-depleted gas fed into the reaction vessel 1.

In an alternative specific example, the textile substrate coated with the curable coating composition is pleated, and steps 2), 3) and 4) are performed on the pleated textile. In such a specific example, the pleated, coated textile can be contained in a tank having one or more gas ports through which gas can be introduced or removed for blowing Sweeping, pressing and curing steps. The pleated, coated textile can be pleated to form a series of horizontal layers in the bin. In such cases, the gas ports can be arranged at or near the bottom and top of the tank, so that during the purge step 2) gas flow can be established up or down through the pleated, coated Layers of textiles.

In the alternative specific example just described, the bin may be modular to allow loading, pleating, and unloading outside of the larger pressure vessel in which the purging, pressurizing, and curing steps are performed. After loading, introduce one or more of such bins into the pressure vessel, and perform purging, pressurization and polymerization steps 2), 3) while the loaded bin stays in the pressure vessel. And 4). The pressure vessel includes one or more inlet ports and a heating device, the one or more inlet ports are used to introduce and remove gas into the pressure vessel and one or more tanks, and the heating device makes the one or more The contents of the multiple bins reach the required polymerization temperature.

In a specific embodiment, the present invention is a reaction device for curing a substrate coated with a curable coating composition. The reaction device includes A. An external pressure chamber that defines an internal space, and the external pressure chamber can bear Actual internal pressure of 0.5 to 15 MPa; B. A material box that defines an internal volume for the layered substrate contained in the material box, so that the layers of the substrate are arranged horizontally in the material box, Such a tank is adapted to be installed in the internal space of the pressure chamber; C. A gas space located at the bottom of the internal volume of the tank, the gas space has a plurality of gas spaces that allow gas to enter the internal volume during operation An opening in the bin; D. At least one opening located at or near the top of the bin is used to remove gas from the internal volume of the bin; and E. Used to heat the internal volume of the bin Heating device; F. is used to build into the gas space and pass through the gas space when the material box is the internal space of the external pressure chamber, pass through the layered fabric in the material box and pass through the material box A gas circulation device for the at least one opening at or near the top of the gas flow leaving the tank; and G. a device for establishing super-atmospheric pressure in the internal space of the external pressure chamber.

Using such a device, the layered substrate is coated with the curable coating composition and introduced into the bin in a layered manner so that a plurality of horizontally arranged coated substrate layers are present in the bin. The tank is then introduced into the interior of the external pressure chamber, where purging step 2), pressurizing step 3), and polymerization step 4 are performed. During at least the purge step 2), a cleaning gas is introduced into the tank through an opening in the gas space, flows upward through the layers of the substrate, and is drawn at or near the top of the tank. The extracted gas can flow into the internal space of the external pressure chamber. The pressurization step 3) is carried out with the tank in the external pressure chamber by: or by a) introducing gas into the tank through the opening of the gas space (while or preventing the gas from flowing 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 the pressurized gas to pass through one or more connecting internal spaces and The fluid conduit inside the hopper enters the hopper from the internal space of the external pressure chamber.

The heating device F. can be any heating device as described above.

The gas circulation device G. includes a conduit for supplying gas from a gas source to the gas space, and a device for establishing a pressure difference that provides for moving gas through an opening in the gas space, passing through the material The base layer in the box and the power leaving the opening at or near the top of the box. The device for establishing the pressure difference may include, for example, a source of pressurized gas; a fan or blower or pump; a vacuum pump and the like.

It has been found that the sequential steps of coating, purging, and pressing before curing result in a significant and unexpected improvement in the effectiveness of the cured coating, especially when applied to textiles and electronic devices. In particular, coatings applied and cured in this way generally exhibit significantly better water repellency than when the pressing step 3) is omitted. Although the present 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, by This helps the coating composition 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.

In the case where the curable coating composition contains small particles, some or all of the small particles can be forced into such openings to form a mechanical seal or used to anchor the particles, thereby providing useful information Both clothing durability and abrasion resistance of particle loss.

The increased pressure in step 4) tends to limit the volatilization of various components of the curable coating composition during curing step 4), especially 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 1 to 67 kPa (about 10 to 500 Torr), especially 6.7 to 53 kPa (about 50 to 400 Torr) at the temperature of the polymerization step 4) This method is quite beneficial for compounds with vapor pressure. Such compounds may be, for example, one or more monomers and/or one or more carrier materials as described below. Examples of the components 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-heptadecafluorodecane) Base) Silane, perfluorohexyl ethyl acrylate, perfluorohexyl ethylene and perfluorooctyl ethylene. The curable coating composition may include, 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 .

The substrate coated in this way is not particularly limited, and any solid material on which a coating can be produced according to the present invention can be used in the substrate. Particular benefits are seen in situations where the substrate is porous and/or has small cracks or interstitial spaces to be sealed by the applied coating.

Useful porous substrates include fibrous textiles. By "fibrous" it is meant that the surface of the textile is composed of or includes at least one type of fiber. The fibers define interstitial void spaces in which air and/or molecular oxygen are trapped during application and during the pressurization step 3) and the applied curable coating composition can penetrate into the spaces. The characterization of such porous fabric may have, prior to coating in accordance with the present invention, such as the Textest FX 3300 instrument using 38cm ² and tested according to the area of at least 0.2 cubic feet / minute / square foot as measured ASTM D737 (0.001016m / 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) feet/minute/square feet (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 foot (1.016 m/s). Some fabrics, such as membrane fabrics based on PTFE or polyurethane, can be more permeable to moisture vapor than they are to air. Such a fabric may have a moisture permeability of at least 1000 g/m²/24 hours, preferably 5000 to 20,000 g/m²/24 hours as measured according to JISL 1099B1.

The fibers of the porous substrate, for example, woven, knitted, entangled, knotted, felted, glued or otherwise formed to have sufficient mechanical integrity to be conveyed through the method of the present invention Fabrics, non-woven fabrics or textiles. Such fabrics include fibers, which can be, for example, natural fibers such as cotton, hemp, wool, flax, silk, tencel, rayon, leather, bamboo, cellulose and the like, or synthetic fibers , Such as nylon, para- or meta-aromatic polyamide, polypropylene, polyester (including PET), polyacetate, polyacrylic acid, polylactic acid, cellulose ester, or other fibers and any two of the above Or more blends. It can be a smooth or raised fabric and it can contain a small amount (up to 50% by weight, preferably up to 10% or up to 3%) of stretchable fibers, such as Elastane, Lycra elastic fiber (Lycra), or spandex (Spandex).

As previously described, the present invention is particularly suitable for processing textile roll materials. When the substrate is in the form of a sheet, it should have a thickness of no more than about 12 mm, and preferably a thickness of no more than 10 mm or no 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 specific examples, the curable composition is applied to textile roll articles, which may have a width of 100 mm or more, such as 1600 mm to 7 meters or more.

The method is not limited to roll material fabrics. Folded or unfolded textile sheets can be used as substrates, such as finished products with textile components. The present invention is useful for applying coatings to clothing such as shirts, pants, sweaters, coats, long-sleeved sweatshirts, gloves, hats, scarves, leg-and-arm-warmers and stockings, as well as shoes and other footwear, curtains , Bedding and other textile materials are useful. The method of the present invention can be used to retreat items of clothing that have been worn or washed off or otherwise removed from previously applied coatings, and it requires reapplication of the coating to restore the desired functional properties.

In other specific examples, including, but not limited to shoes, usually the substrate can be coated with, for example, leather or synthetic leather products, such as vinyl, on one side, or for sports shoes, coated with polyester, poly Acrylic or nylon, including a mixture of synthetic fibers and natural fibers, these fibers have exposed fiber or net-like surfaces on the coated side. The coating, and therefore the cured polymer, can be applied to the top of applied features such as sewn seams, logos, labels, decorative features, Velcro fasteners, buttons, buckles, rivets, and zippers. The substrate can be a non-woven fabric or a cellulose material, such as paper, tissue or cardboard, and the like.

In other specific examples, the substrate is an electronic component. These types of electronic components are not critical. The electronic components may be, for example, discretely packaged basic electronic components, or an array or network of electronic components such as semiconductor integrated circuits, hybrid integrated circuits or thick film devices. It can be a complete unit, such as, for example, mobile phones, MP3 players, fitness electronics, "smart" textiles (ie, wearable electronic devices), and military electronics. Each individual basic electronic component can be, for example, a semiconductor device such as a transistor, vacuum tube or diode, passive components such as resistors, inductors, transformers or capacitors, optoelectronic devices, and optical detectors or transmitters, Power supplies, magnetic induction devices, memory, and RC or LC networks, antennas, piezoelectric devices, crystals, resonators, terminals or connectors, antennas, cables, switches, protection devices such as fuses, circuit breakers, varistors, or inrush current Limiters, or electromechanical components, among others.

Optionally, the oxidation pretreatment step can be performed before the coating step 1). Such an oxidative pretreatment step may include heating the substrate to an elevated temperature of, for example, 100°C to 220°C, preferably 150°C to 190°C under super atmospheric pressure in an oxygen-containing atmosphere. The temperature should be lower than the temperature at which the substrate degrades or deforms permanently. The oxygen-containing atmosphere may contain at least 20 mole percent, at least 50 mole percent, or at least 75 mole percent molecular oxygen, and may contain up to 100 mole percent, up to 99 mole percent, or up to 95 mole percent Of molecular oxygen. The super-atmospheric pressure may be, for example, 125 kPa to 15 MPa, preferably 300 kPa to 5 MPa. The substrate may be maintained under the conditions of the oxidative pretreatment step for a period of time ranging from 1 minute to 1 hour, for example.

It has been found that this oxidative pretreatment step improves the performance of subsequently applied coatings. Specifically, when this oxidative pretreatment step is performed, better water repellent properties and/or better oleophobic properties are obtained. Although the present 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 manufacturing are oxidatively removed during this oxidative pretreatment step, thereby allowing the substrate surface to interact with curable Better contact between coating components.

This oxidative pretreatment provides significant advantages over alternative methods. The removal of lubricant from the fabric (desizing) can be accomplished using a water-based cleaning step. However, it is known that some fabrics such as aromatic polyamides are exposed to water to weaken fiber strength, and in addition, the water cleaning step requires a drying step and often promotes fabric shrinkage. Oxygen-containing atmospheric piezoelectric plasma, a gas mixture containing, for example, 90% argon + 10% oxygen, can also be used in this desizing step. However, it should be noted that the plasma-based cleaning system is more expensive than the high-pressure oxygen cleaning method described above The method and exposure of the fabric to atomic oxygen can weaken the fibers. The high-pressure oxidation pretreatment step avoids the problems that may occur with plasma-based cleaning. Both of these methods can be used to provide anhydrous cleaning or desizing of textiles and nonwovens and/or for adhesion promotion and/or for improved laundry durability for this treatment.

The curable coating composition comprises a) one or more free radical curable monomers, and the free radical curable monomers have exactly one free radical polymerizable group per molecule. The free radical 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 here are given at one atmosphere, unless otherwise specified.

The free-radical curable monomer preferably has at least one hydrocarbyl group, and the hydrocarbyl group has at least six carbon atoms directly or indirectly bonded to the polymerizable group. The hydrocarbyl groups can be partially fluorinated, perfluorinated or non-fluorinated.

Preferably, at least one monomer of component a) has a vapor pressure of not more than 6.7 kPa, more preferably not more than 1 kPa, at the polymerization temperature in step 4) of the method.

The one or more component a) monomers may be liquid or solid at 22°C. If mixtures of monomers are used, they may all be liquids, they may all be solids, or they may include mixtures 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.

The radical polymerizable group may be any one polymerized in radical polymerization, but is preferably an alkenyl group, an acrylate group, a methacrylate group or a chlorosilane group. Acrylate groups and/or methacrylate groups are the most preferred.

The hydrocarbon group may be a linear or branched aliphatic group, an alicyclic group, an aromatic group, or a group containing two or more of them. The hydrocarbyl group may contain at least 10 or at least 12 carbon atoms. The hydrocarbon 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 specific examples, the hydrocarbyl group is a straight-chain alkyl or alkenyl group having 8 to 24, 10 to 20, or 12 to 18 carbon atoms. In some specific examples, the hydrocarbyl group is partially or perfluorinated and contains 6 to 24, or preferably 8 to 20 carbon atoms.

The hydrocarbyl group can be directly bonded (that is, by a covalent bond) to the radical polymerizable group, or indirectly bonded to it via a linking group.

Preferably, water is soluble in the one or more component a) monomers to not more than 2 parts by weight per 100 parts by weight of the one or more monomers at 30°C, more preferably not more than 1 part by weight, and More preferably, it is not more than 0.25 parts by weight.

Examples of component a) monomers include, but are not limited to, one or more of the following items: acrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate , N-octyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, stearyl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate , 2-(perfluorohexyl) ethyl acrylate, 2-(perfluorooctyl) ethyl acrylate, 2-(perfluorodecyl) ethyl acrylate, 2-(perfluorohexyl) ethyl methacrylate, methyl methacrylate 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 single system described above is the most preferred.

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 heat-activated or UV-activated free radical initiators. Suitable polymerization initiators include free radical initiators, such as, for example, 1) acyl peroxides, such as acetyl or benzyl peroxides, 2) alkyl peroxides, such as cumyl, two Cumene, lauryl, or tertiary butyl peroxide, 3) hydroperoxide, such as tertiary butyl or cumyl hydroperoxide, 4) perester, such as tertiary butyl Perbenzoate, 5) other organic peroxides, including 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, acylalkylsulfonate Base peroxide, dialkyl peroxy dicarbonate, 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 that 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 1-minute half-life temperature of at least 100°C are particularly preferred. In some specific examples, 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.

The curable coating composition of the present invention may also contain one or more of the following optional components:

c) at least one crosslinking monomer, the at least one crosslinking monomer has at least two 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. Unless otherwise specified, all boiling temperatures in this specification are at one atmosphere. The crosslinking monomer is preferably a liquid at 22°C. The radically curable polymerizable groups may be as described above with respect to component a), with acrylate or methacrylate groups being preferred. The crosslinking monomers may have, for example, 2 to 20, preferably 2 to 8, and more preferably 2 to 6 radical curable groups per molecule. Examples of crosslinking monomers include polyacrylate or polymethacrylate compounds 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-hexanedi Alcohol diacrylate, 1,8-octanediol diacrylate, cyclohexane dimethanol diacrylate, trimethylolpropane triacrylate, glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol hexaacrylate, the corresponding methacrylate, and the like. So-called drying oils like linseed oil, safflower oil and tung oil are also useful crosslinkers.

d) One or more free radical curable monomers not used in components a) and c). Such monomers may have a boiling temperature below 100°C. Such a monomer may have exactly one radical polymerizable group, or may have more than one such group, in which case it will act as a crosslinker. Such monomers can be liquid or solid at 22°C. The component d) monomer (if present) is preferably copolymerizable with the component a) and c) monomers. The 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, vinyl benzene, chlorostyrene, and similar Things.

e) One or more carriers. Useful carriers or carrier mixtures are materials that are liquid at 22°C or 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 radical polymerizable groups. Preferred carriers have water solubility characteristics as described with respect to the monomers of the component a). However, the carrier is preferably soluble or becomes partially entrained in the polymer formed when the coating composition is cured.

Examples of useful carriers are (i) aliphatic monoalcohols or aliphatic monocarboxylic acids having 14 to 30 carbon atoms; (ii) esters of fatty acids and fatty alcohols, the esters having 18 to 48 carbon atoms, preferably Is 20 to 36 carbon atoms; (iii) polyethers with one or more hydroxyl groups; (iv) polysiloxanes, which can be linear, branched or cyclic; v) Polysiloxane-poly(alkylene glycol) copolymer; (vi) Waxes, such as polyethylene wax, beeswax, lanolin, carnauba wax, candelilla wax, coronal wax, sugarcane 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 Wax with a melting temperature of ℃; (vii) fluoropolymer, (viii) solid vegetable and/or animal oil or fat; (viii) another organic oligomer or polymer with a pure phase melting or softening temperature up to 100℃物, or (ix) various plasticizers.

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 fatty alcohols having one or more carbon-carbon unsaturation sites in the fatty alcohol chain. Among the useful esters of fatty acids and fatty alcohols are, for example, hexyl octadecanoic acid, octyl octadecanoic acid, dodecyl octadecanoic acid, and octadecyl octadecanoic acid. Esters (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.

Suitable polyethers are polymers of one or more cyclic ethers (such as propylene oxide, tetramethylene glycol and the like). The molecular weight is high enough to produce a polymer with a melting temperature of up to 100°C. The polyether may contain one or more hydroxyl groups. It can be linear or branched. The polyether may 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, ethylene oxide Alkyl-propylene oxide copolymers and their monoalkyl esters, poly(tetrahydrofuran) and the like.

Useful polysiloxanes include, for example, poly(dimethylsiloxane) (PDMS) and copolymers thereof. The polysiloxane may be linear, branched or cyclic. Useful silicone-poly(alkylene glycol) copolymers include, for example, poly(dimethylsiloxane-poly(ethylene glycol) copolymers, which can have block or graft structures .

唑啉)以及類似物。 Organic polymers having a melting temperature below 100°C that are useful as a component of the carrier or a mixture of carriers include low molecular weight polyamides, low molecular weight polyethers, low molecular weight polystyrenes, low molecular weight acrylate polymers and copolymers. (E.g. poly(ethylene glycol) methyl ether methacrylate (PEGMEA)), polypropylene amide, poly( N -isopropylacrylamide), poly(acrylic acid), low molecular weight thermoplastic cellulose ethers and esters , Poly(2-ethyl acrylic acid), poly(vinylphosphonic acid), poly(4-styrene sulfonate), poly(2-ethyl-2-

Oxazoline) and the like.

Among these plasticizers are phthalate, trimellitate, adipate, maleate, benzoate, terephthalate, various fatty acid esters, Epoxidized vegetable oils, sulfonamides, organophosphates, alkyl citrates, acetylated monoglycerides and the like.

The carrier can provide certain functional properties to the cured composition. In some embodiments, the carrier provides increased hydrophobicity and/or oleophobic properties to the cured composition. It can also perform plasticizing functions.

Particularly preferred carriers include silicone oils, waxes and alcohol carriers. Particularly preferred polysiloxane oils include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and linear or branched polydimethylsiloxane (PDMS) oils (such as hexamethylsiloxane). Disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane), polymethylhydrosiloxane (PMHS) oil, and other liquid cyclic polysiloxanes Methylsiloxane. Paraffin wax or beeswax is a particularly preferred wax carrier. Stearyl alcohol and cetyl alcohol are particularly preferred alcohol carriers and are solid at 22°C.

；百里酚；甘油；山梨醇或其他糖；和二伸苄基山梨醇。 The carrier may also include low molecular weight organic compounds having a boiling temperature lower than 100°C, but if such materials are present, they preferably constitute not more than 2 weight percent of the curable composition in total, and preferably It is not more than 1 weight percent or 0.25 weight percent. 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, icosane, and 20 Dioxane, tricosane, tetracosane, pentadecane, hexadecane, heptadecane, octadecane, nonacosane, triacontan and the like; liquid alcohols, such as normal Propanol, isopropanol, n-butanol, tertiary butanol, methanol and ethanol; fluorinated alkanes, such as perfluorohexane, perfluoroheptane, perfluorodecane-pinane, perfluorodecane-octane , Perfluorododecane and the like; 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 glycerol 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-naphthylene amine; biphenyl; benzophenone; diphenylamine; 1,2 -Diphenylethane; Maleic anhydride; Pyridine

; Thymol; Glycerin; Sorbitol or other sugars; and Dibenzylsorbitol.

f) One or more final treatment attributes chemicals. The "final treatment attribute chemical" is a compound different from the carrier and one or more monomers, and the compound remains together with the substrate after the treatment method of the present invention and imparts some desired characteristics to the substrate. Examples of final disposal properties of chemicals include, for example:

f-1) Hydrophobic treatment, that is, a chemical that imparts water resistance and/or hydrophobicity to the treated substrate;

f-2) Oleophobic and lipophobic treatment agents, that is, substances that cause the treated substrate to not easily absorb fats and oils, or repel fats and oils;

f-3) Superhydrophobic agent; that is, a substance that imparts a very high (>130°) contact angle between water droplets and the surface of the treated substrate. The superhydrophobic agent may include solid particles with a size from 50 nm to 100 microns, such as powdered fluorocarbon polymer powder. Other superhydrophobic reagents include chlorinated or fluorinated silicone compounds, such as heptafluorodecyl trimethoxysilane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, octadecane Dimethylchlorosilane, tris(trimethylsilyloxy)silylethyldimethylchlorosilane, octyldimethylchlorosilane, dimethyldichlorosilane, butyldimethylchlorosilane and Trimethylchlorosilane.

f-4) Functional 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, fumed silica, hydrophobic fumed silica, 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 borates, boron and/or phosphorus compounds, and inorganic hydration Materials, titanium carbide, tungsten carbide, pumice, silicon carbide, zirconia alumina.

f-5) Antimicrobial treatment agents, that is, substances that inhibit the growth of microorganisms and/or kill microorganisms, including Cu, Zn, Ag compounds, and chitosan particles.

f-6) UV absorbers and/or UV reflectors, such as avobenzone, rutile titanium dioxide, silicon dioxide, homosalate, oxybenzone, 4-aminobenzoic acid (PABA), octyl salicylate, octocylene, 2-ethylhexyl 4-dimethylamino benzoate and the like;

f-7) Colorants such as dyes and pigments. These include acid dyes, reactive dyes, and disperse dyes.

f-8) Anti-wrinkle agents, such as melamine-formaldehyde resin and urea-formaldehyde resin;

f-9) Fabric softeners and anti-chafing agents, such as polydimethylsiloxane and polymethylhydrosiloxane;

f-10) Light and/or heat reflective materials, such as light-reflecting metal particles, titanium dioxide or ZnO particles and the like.

f-11) A softening agent that produces, for example, softness, wearing comfort, and/or moisturizing properties.

f-12) Insecticides and/or insect repellents, such as metofluthrin, transfluthrin, dichlorvos, permethrin, thyme oil, rosemary Sesame oil, citronella oil, cinnamon oil, lemon eucalyptus oil, lemongrass oil, and cedar oil.

f-13) Solid or liquid flame retardants, including various organic phosphorus, phosphorus-containing, bromine-containing and boron-containing compounds, including sodium tetraborate and boric acid.

f-14) Trace forensic chemical markers that are added to the formulation to help detect counterfeit goods or counterfeit final treatment agents. Such markers may contain rare earth elements (such as yttrium, scandium, cerium, europium, or erbium), or other elements not normally found in textiles, or compounds that provide detectable fluorescence when exposed to ultraviolet light.

The chemical treatment mixture may also include g) one or more accelerators or activators for polymerization initiators. Metal salts (such as iron salts, titanium salts or vanadium salts) and manganese ions or manganese are examples of such accelerators.

The chemical treatment mixture may further contain h) one or more blowing agents. Suitable blowing agents include physical (endothermic) types that are liquid at 22°C but volatilize under the conditions of the curing step, and physical types that decompose or otherwise react 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 so that the curable composition contains no more than 10% by weight, preferably no more than 5%, more preferably no more than 2% and Still more preferred is not more than 1%, even more preferably not more than 0.25% of organic compounds having a boiling temperature of less than 100°C. Chemical blowing agents preferably generate carbon dioxide or nitrogen; these include so-called azo types, peroxy blowing agents (such as peroxy esters, peroxy carbonates and the like), and certain amino formic acids Esters and citrate compounds.

The selection of the various components of the curable coating composition, their ratios, and the manner of preparing the composition are all carried out such that the coating composition is a liquid at 22°C or one or more at 22°C and standard pressure. A suspension of a variety of solids in the liquid phase, and the coating composition contains, based on the total weight of the coating composition, not more than 10% by weight of organic compounds having a boiling temperature lower than 100°C and no 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 organic compounds having a boiling temperature lower 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% water.

The curable coating composition may contain, for example, at least 1, at least 5, at least 10, or at least 25 weight percent of compounds, which have 1 to 67 kPa, preferably 6.7 to 53 kPa at the temperature of the polymerization step 4). Vapor pressure (under one atmosphere).

The component a) monomers (and the component c) monomers, if present, can be composed together, for example, from 0.5% to 100% by weight of the curable composition. In some specific examples, the monomers of the components a) and c) together constitute at least 1%, at least 1.5%, at least 2%, at least 5%, at least 10%, at least 25% or at least 40%. Components a) and c) together can 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 specific examples, component c) constitutes 5% to 50%, 10% to 40%, 10% to 30%, or 15% to 25% of the combined weight of components a) and b).

Component d) monomer (if present) can 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, it is such that The curable composition contains no more than 2% by weight of organic compounds having a boiling temperature of less than 100°C. If the component d) monomer boils below 100°C, the preferred amount (if any) is 0.01% to 25% by weight, or 0.01% to 10% by weight of the curable coating composition. . In some specific examples, the monomers of component d) (if present, all) constitute up to 5%, up to 2%, or up to 1% of the combined weight of components a), b), and c).

Polymerization initiators such as free radical initiators can constitute up to 20% of the weight of the curable composition. The preferred amount is 0.1% to 10% by weight. A more preferred amount is 2%-5% by weight of the curable composition. In some specific examples, the one or more polymerization initiators are present in an amount of up to 30% (such as 3% to 20% or 5% to 15% thereof) of the combined weight of components a), c), and d).

The carrier or mixture of carriers (if present) may constitute, for example, 2% to 98% of the weight of the curable composition. The carrier that is solid at 22°C is preferably present in an amount of up to 150% of the weight of the monomers (i.e., components a), c), and d)). In some specific examples, such solid support system is based on the monomer weight of at least 10%, at least 20% or at least 30%, and on the same basis up to 150%, up to 125% or up to 100% exist. In particular, wax (carrier type (vi) above) is preferably present in the amount as indicated in the previous sentence.

The liquid (at 22° C. and under atmospheric pressure) carrier can perform a diluting effect and therefore can constitute as much as 98% by weight, or as low as about 2% by weight, of the curable composition in some specific examples. In specific examples, the curable composition may contain at least 5 wt%, at least 10 wt%, at least 25 wt%, at least 40 wt%, at least 50 wt%, or at least 70 wt% of one or more liquid carriers. In specific embodiments, 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. .

The final processing attribute chemicals (when present) can total from 0.01% to 70% of the weight of the curable composition, preferably 0.01% to 25% and more preferably 0.01% to 10%. Forensic markers may be even lower, at levels of 1-1000 ppm.

Other materials can total to constitute 0.01% to 70% of the weight of the curable composition, preferably 0.01% to 50%, more preferably 0.01% to 25%, and still more preferably 0.01% To 10%.

A preferred curable composition contains 4% to 85% of component a), 2% to 25% of component c), 10% to 70%, more preferably 15% to 50% of one or A variety of carriers, and 0 to 35%, preferably 1% to 25% of one or more functional properties materials. Another preferred curable composition contains 16% to 70% of component a), 3% to 20% of component c), 25% to 50% of one or more carriers, and 0 to 35%, Preferably, 1% to 25% of one or more functional property materials. Such preferred curable compositions contain 1 to 10 weight percent of one or more free radical initiators. In some specific examples of such preferred curable compositions, component a) includes one or more acrylate or methacrylate monomers; component c) includes one or more acrylates having 2 to 6 Or methacrylate group monomers, component c) (if present) includes one or more fatty acid acrylate compounds, and component e) includes one or more of wax and silicone oil.

The third preferred curable composition contains 1% to 75% of the combined components a) and c), wherein component c) constitutes 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 properties materials. In this preferred curable composition, the carrier preferably includes at least one liquid carrier and at least one solid (at 22°C) carrier, and the solid carrier is preferably based on monomer (component A), c) and d)) are present in an amount of 10 to 150 weight percent. The fourth preferred curable composition contains 1% to 60% of the combined components a) and c) (wherein component c) constitutes 20% to 65% of the combined weight of components a) and c)) , Based on the weight of the monomer, 30% to 100% of one or more solid carriers, 2-98% by weight of one or more liquid carriers, and 0 to 35%, preferably 1% to 25%, of one or more functions Attribute material. The third and fourth preferred curable compositions preferably contain 3 to 20 or 5 to 15 weight percent of one or more free radical initiators based on the weight of the monomer. In some specific examples of such third and fourth preferred curable compositions, component a) includes one or more acrylate or methacrylate monomers; component c) includes one or more monomers having 2 Up to 6 acrylate or methacrylate group monomers, component d) (if present) includes one or more fatty acid acrylate compounds, and component e) includes one or more of wax and silicone oil .

Particularly preferred curable compositions (including the preferred compositions just described in the preceding 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 component a) monomers can constitute 20%-85% or 20% to 65% of the total weight of all component a) monomers. In such a composition, the solid component a) monomer may include fatty acid acrylate (wherein the fatty acid group contains 18 or more carbon atoms), and the liquid component a) monomer may be 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 3%-20% of component c). The component c) material in this type of composition may include one or more of the following: alkanediol diacrylate, pentaerythritol or dipentaerythritol polyacrylate and drying oil (such as linseed oil, safflower oil or tung oil) . This particularly preferred curable composition may contain 20%-50% of component e), wherein component e) preferably includes at least one of fatty alcohol, wax and silicone oil. This particularly preferred curable composition may optionally contain 1%-25% of at least one final processing chemical, and may contain up to 2% of component d) monomers (if any, all ).

The following examples are intended to illustrate the invention without limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.

Example 1

The loosely woven para-aromatic polyamide fabric as used in ballistic protective clothing is used as the substrate in this embodiment. The presence of water inside the aramid fibers is believed to weaken the fibers.

Will contain by weight 30% octadecyl acrylate, 18% paraffin, 9% 1,6-hexanediol diacrylate, 8% lauryl acrylate, 3% dipentaerythritol penta/hexaacrylate, 5% A curable, monomer-based composition of laurel peroxide and 27% decamethylcyclopentasiloxane is mixed and then diluted 1:2 with polydimethylsiloxane (5 centistokes) to manufacture A curable coating composition comprising a monomer that can be polymerized by radicals and has a boiling temperature higher than 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 this coating composition and then squeezing excess liquid between two pressure rollers.

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 flowed through the autoclave at room temperature and 1 atmosphere to purge molecular oxygen until the gas in the autoclave contained less than 0.1 mole percent oxygen. The autoclave was then sealed, pressurized with nitrogen to 1.4 MPa, and then heated to 121°C for 40 minutes to activate the polymerization initiator and cure the composition. The weight of the coating additive after curing of the sample cured under elevated pressure was the same as the weight before curing and was unchanged ^{at 26.1 g/m 2.}

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 an atmospheric pressure and the container was not sealed, so that the pressure in the reactor The gas can be discharged into the air freely. The post-cured weight gain of samples cured at atmospheric pressure is significantly less than only 22.7 g/m ² , or only about two-thirds of the weight of the uncured coating as applied.

These two samples were then evaluated according to the 10-minute Bundesmann water repellency test. In this test, the weight of water increased by Example 1 was 6.95%, and the water penetration through the coated sample was 16 mL. In contrast, the water weight increase of Comparative Sample A was 11.97% and the water permeation system through this 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.

Example 2

Two samples of tightly woven sportswear fabrics composed of 63% nylon, 25% polyester, and 12% Lycra were dipped and coated with a curable coating composition and placed between the pressure rollers 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 sample (comparative sample B) was coated twice and then cured in an unsealed reactor under atmospheric pressure in a nitrogen atmosphere at the same temperature. Comparative Sample B has a cured coating weight of 23.360 g/square yard. Despite the much higher coating weight of Comparative Sample B, it only reached the "70" spray rating in the AATCC 22 spray test, where the lower coating weight used in Example 2 reached the full "100" spray rating .

Example 3

The tightly woven 100% polyester fabric used as the outer layer of the laminated polyester/urethane film fabric was coated with the same mixture as in Example 1. The two samples were coated in the same way and at the same dosage. One (Example 3) was cured in the manner described with respect to Example 1 at a curing temperature of 126°C. The other (comparative sample C) was cured in the same way but under atmospheric pressure. Example 1 reached a complete "5" rating in the Bondis door water repellency test and increased only 2.53% water weight. Comparative Sample C reached the lower "4" rating and added 6.32% water. There was no detectable water penetration through any of these tightly woven samples in the Bundesgate test.

Examples 4 and 5

Duplicate samples of tightly woven acrylic fabrics commonly used for outdoor furniture decoration were coated with an equal dose 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 is determined by comparing the cured weight of the sample with the weight of the uncoated sample.

In each case, one of the samples (Examples 4 and 5, respectively) was cured at 125°C in the same manner as described with respect to Example 1. The duplicate samples (compare samples D and E, respectively) were cured in the same way, except under atmospheric pressure. These samples were then evaluated using the AATCC 22 spray test, with the results as indicated in Table 1 below.

As shown in Table 1, curing at super-atmospheric pressure resulted in a significant improvement in the AATCC rating of these two fabrics and less water increase. Unexpectedly, the coating weight of the cured sample was significantly higher than in Examples 4 and 5 with the comparative sample, despite having almost the same pre-cured weight increase. This indicates that a large amount of the cured composition volatilized under the lower pressure of the comparative sample.

Example 6

The three para-aromatic polyamide fabric samples as described in Example 1 were pre-washed to remove organic contaminants. One sample was coated with a 1:1 by volume mixture of the coating composition described in Example 1 and trimethoxy (1H, 1H, 2H, 2H heptafluorodecyl) silane. The second one was coated with a 1:1 mixture of the coating composition of Example 1 and perfluorohexyl ethyl acrylate.

The third sample was cleaned like the other two, but then sprayed with a 1:5 dilution of _{TiCl 3 isopropanol and allowed to dry.} This provides the Ziegler-Natta catalyst present on the sample. The sample was then coated with a 1:1 by volume mixture of the composition of Example 1 and perfluorooctylethylene.

The coated sample was then cured as described in Example 1 at a curing temperature of 125°C. The cured samples were tested for oleophobicity according to the AATCC 118 Hydrocarbon Repellency Test. All three showed the highest ("8") rating, indicating repellency to both water and n-heptane.

When all three types of duplicate samples were cured at atmospheric pressure, they demonstrated little or no oleophobicity and were only waterproof.

Example 7

Computer circuit peripherals are composed of 36% octadecyl acrylate, 11% 1,6-hexanediol diacrylate, 9% lauryl acrylate, 5% dipentaerythritol penta/hexaacrylate, 4% lauryl peroxide It is coated with a hydrocarbon monomer mixture composed of 35% decamethylcyclopentasiloxane, and then diluted 1:2 with 5cSt polydimethylsiloxane. The painted substrate was then placed in a container, which was purged of oxygen by flowing nitrogen through the container and the coating was cured in an oxygen-depleted nitrogen environment at 1.4 MPa and at a temperature of 126°C. 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 entered the metal contact through holes, thereby effectively sealing the device. The coating is waterproof and can withstand the addition of several water droplets placed on the device. The moisture sensitive marking button used to indicate the presence of water remains untriggered, even when water droplets are placed directly on the coating above it.

Examples 8 and 9

Four samples of 100% polyester wool products containing no wicking agent were treated with a monomer coating that produced a hydrophilic treatment. The fifth sample was not processed as a control.

Use 5:4:1 acrylic acid, decamethylcyclopentasiloxane, and 1,1-bis(tertiarybutylperoxy)-3 by volume on the smooth side of two of these samples. ,3,5-Trimethylcyclohexane mixture roll coating. Of these, one (Example 8) was placed in an autoclave, purged with nitrogen and then cured in the sealed autoclave at 1.48 MPa and 125°C under nitrogen. Another (Comparative sample F is cured under atmospheric nitrogen at the same temperature. Example 8 and Comparative Example F each have approximately equal "wet" coating weights, but the coating weight of Example 8 after curing is 6.35g /m ² and the coating weight of Comparative Example F is only 1.9 g/m ² .

By roll-coating 5:4:1:1 acrylic acid, decamethylcyclopentasiloxane, 1,1-bis(tertiary butylperoxy)-3,3,5 by volume on the surface side Two other samples were prepared with a mixture of trimethylcyclohexane and ethylene glycol dimethacrylate. One of these (Example 9) was placed in an autoclave, purged with nitrogen, and then cured in the sealed autoclave at 1.48 MPa and 125°C under nitrogen. The other (comparative sample G) was cured under atmospheric pressure nitrogen at 125°C, where the autoclave was not sealed. Example 9 and Comparative Example G each have approximately the same "wet" coating weight, but after curing, the coating weight of Example 9 is 10.6 g/m ² while the coating weight of Comparative Example G is only 2.1 g /m ² .

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 exhibit direct hydrophilicity, allowing the applied droplets to be absorbed in less than 2 seconds.

Example 10

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 treatment for hydrophobicity. All sides of the shirt are sprayed on the outside only, including the 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. First, the autoclave was purged of oxygen with a stream of dry nitrogen and then an electric immersion heater was used to start steam power generation. The autoclave has a pressure relief valve that allows steam to escape when the pressure exceeds 150kPa gauge pressure. The equilibrium temperature of steam at this pressure is 126°C. Nitrogen is not present during the curing of the product because steam replaces any residual nitrogen (or air) in this volume.

The treated shirt was heated at 0.15 MPa and 126°C for 20 minutes, then the power was turned off and the unit was 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 the polymer treatment. The cured polymer dosage is estimated to be 36 g/m ² . The clothing durability test combined with the AATCC 22 spray test indicates that complete water repellency is maintained after 80 household laundry/drying cycles (a spray rating of 100 in the AATCC 22 spray test).

Example 11

Three samples of tightly woven 100% polyester designed for rain protection of outerwear were prepared for processing and tested in a Bundys door water repellency 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 at a volume ratio of 1:2. The coating is done by immersing the sample in a liquid formulation and then squeezing out the excess liquid between two metal rollers. One of the coated samples (Example 11) was placed in a pressure vessel which was purged with nitrogen and then subsequently pressurized with nitrogen to 1.48 MPa and then heated to 125°C to cure the coating. The other coated sample (Comparative Sample I) was cured at 125°C under atmospheric pressure of nitrogen. All three samples were evaluated for 10 minutes in the Bundesgate tester, and the results are shown in Table 2. The visual scale is from 1 to 5 (of which 5 is the best) visual score. The% water weight gain is the amount of water weight added by the sample during the test. Water permeation is the amount of water passing through the sample, where the minimum detectable amount is <1mL.

As can be seen from the results in Table 3, the untreated control was completely wetted. Both Example 11 and Comparative Sample I essentially prevent any water from penetrating the sample, but Example 11 (where curing is performed under high pressure) absorbs about 50% less water than Comparative Sample I (which cures at atmospheric pressure).

Example 12

Membrane fabrics include thin, water vapor permeable membranes such as polyurethane or PTFE. The membrane is water permeable because it is very thin and slightly porous at the microscopic level. Because the membrane 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 against skin or other clothing, and a top fabric that protects the film from any external wear and for the decorative appearance of the clothing. The top and face fabrics must be treated with a waterproof surface layer, so that rainwater can quickly flow down from the garment to avoid "wetting". If water saturation of such a face fabric occurs, then moisture vapor from the human body cannot escape through the membrane because it is diffusely blocked by the wetted fabric. Therefore, it is desirable that the face fabric is as waterproof as possible, even in strong showers.

A number of samples of 3-layer membrane fabric with a central PTFE membrane were coated on the top and top fabric and cured using the general procedure described in Example 1. After coating and purging, the fabrics were pressurized to either 250 psig (1.7 MPa) or 450 psig (3.1 MPa) pressure in an oxygen-depleted atmosphere and cured at 90°C for 15 minutes at this pressure. The coated fabric was evaluated for water repellency in a Bondis door water repellency tester for 10 minutes according to the ISO 9865 test protocol. The sample cured under a pressure of 1.7 MPa achieved a water repellency level of 4.7. It increased the water weight by 15.4%, and no water penetrated the sample. The samples cured under a pressure of 3.1 MPa achieved a complete water repellency rating of 5 and increased water weight by only 5.7%. No water passed through the sample either. In these experiments, the higher pressure during curing significantly improved the results.

Examples 13 and 14

Duplicate samples of the aromatic polyamide fabric with surface lubricant were coated according to the general procedure described in Example 1, except that the curing was carried out at 135°C and 1.7 MPa gauge pressure.

One sample was coated without pretreatment. In the ISO 9865 test, the coated sample increased by 20%-25% water weight.

The second sample (Example 13) was subjected to an oxidative pretreatment by heating it to 150°C under 50 psi (345 kPa) pure oxygen for 15 minutes. After coating, the sample gained only 2.9% water weight. This result is comparable to another comparative sample in which the lubricant is removed by water washing (3.5% water weight increase) and plasma treatment (2.5% water weight increase).

The third sample (Example 14) was subjected to an oxidative pretreatment by heating it to 190°C under 50 psi (345 kPa) pure oxygen for 15 minutes. After coating, the sample gained only 0.9% water weight, which was a significant improvement compared to either of the controls.

1‧‧‧Reaction vessel

2‧‧‧Central Mandrel

3‧‧‧Heating device

4‧‧‧First gas port

5‧‧‧Internal space

6‧‧‧Pressure gauge

8‧‧‧The direction of gas flow

9‧‧‧Second gas port

10‧‧‧External opening

Claims (12)

A method for applying and curing an organic polymer coating on a substrate. The method includes the following steps: 1) Under non-polymerization conditions, it will be liquid or one or more solids in liquid at 22°C and atmospheric pressure. The curable coating composition of the suspension in the phase is applied to at least one surface of the substrate, wherein the curable coating composition contains i) at least one polymerizable monomer in the presence of free radicals Under polymerization, each molecule has exactly one radically polymerizable group and has a boiling temperature of at least 100°C under one atmospheric pressure, and 2) at least one thermally activated polymerization initiator, the curable composition based on the coating composition The total weight of the substance contains no more than 10% by weight of organic compounds having a boiling temperature of less than 100°C at one atmospheric pressure and no more than 5% by weight of water; then 2) under non-polymerization conditions, from containing The interior of the container of the substrate with the applied curable coating is purged of molecular oxygen, and then 3) during and/or after step 2), the substrate with the applied curable coating is replaced with an oxygen-depleted gas The purged container is pressurized to an actual gas pressure of at least 120 kPa, and then, the substrate with the curable coating applied is not exposed to an atmosphere containing 1 mole percent or more oxygen, 4) by The substrate with the applied curable coating composition is heated to a temperature sufficient to activate the heat-activated polymerization initiator and initiate the polymerization of the at least one polymerizable monomer under oxygen-poor conditions to at least partially cure the A cured coating composition to form an at least partially cured organic polymer coating on the substrate. The method described in item 1 of the scope of the patent application, wherein in step 4) the oxygen-depleted condition includes An oxygen-poor atmosphere with an actual pressure of at least 120 kPa. The method described in item 1 or 2 of the scope of patent application, wherein step 2) includes a step of flowing an oxygen-depleted gas to contact with the substrate. The method described in item 1 or 2 of the scope of the patent application, wherein step 2) includes the step of flowing the oxygen-depleted gas into the substrate through one or more holes, cracks or other openings. The method described in item 1 or 2 of the scope of patent application, wherein step 2) includes the step of performing at least one pressurization/decompression cycle, wherein the interior of the container containing the coated substrate is used in each cycle The oxygen-depleted gas is pressurized to an actual super-atmospheric pressure of at least 120 kPa and then depressurized. The method described in item 1 or 2 of the scope of the patent application, wherein the substrate is a fiber textile or non-woven fabric having pore spaces between intersecting fibers. The method described in item 6 of the scope of patent application, wherein in step 3) the curable coating composition flows into one or more of the interstitial spaces under the force of gas pressure. The method described in item 1 or 2 of the scope of the patent application, wherein the substrate is a roller well mounted on a mandrel, the mandrel has a longitudinal hole and has one or more openings along the length of the mandrel, and in the step 2) The oxygen-depleted gas flows through the installed base, passes through at least one opening along the length of the mandrel, and passes through the longitudinal hole. The method described in item 1 or 2 of the scope of the patent application, wherein step 2) includes the step of compressing the coated substrate to remove molecular oxygen from the void space of the substrate. As the method described in item 1 or 2 of the scope of the patent application, the method further comprises, before step 1), subjecting the substrate to an oxidation pretreatment step. The method described in item 10 of the scope of patent application, wherein the oxidation pretreatment step includes The substrate is heated to 100°C to 220°C under super atmospheric pressure in an oxygen-containing atmosphere. The method described in claim 11, wherein the oxidation pretreatment step further comprises exposing the substrate to oxygen-containing atmospheric plasma.

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