JP2008527145A - Polymer materials that form surface microdomains - Google Patents

Abstract

A polymeric material having a surface containing raised microdomains can be prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate.

Description

Government Rights Statement The US Government has a paid authorization in the present invention and, in limited circumstances, grant number N00014-03-1 awarded by the Office of Naval Research. You have the right to require the patent owner to grant authorization to others for items provided by -0702 and N00014-04-1-0597.

Background Block copolymers (PDMS) comprising poly (dimethylsiloxane) are well known. Typically, these are linear copolymers made from a long chain of PDMS covalently bonded to another polymer. For example, PDMS diblock, triblock, and segment / multiblock copolymers with various polymers have been prepared.

  Block copolymers of PDMS and other polymers typically phase separate as a result of the mixing of the two different blocks. However, due to the covalent bonds between the blocks, phase separation is limited and only micro or nanoscale phase separation occurs. In many PDMS block copolymer systems, PDMS has a significantly lower surface energy than the second block and thus tends to be more abundant at the surface of the copolymer.

  Similarly, block copolymers of PDMS and polyurethane are also known. In many cases, these can function as slightly adhesive surfaces. However, over time, more hydrophilic polyurethane components can migrate to the surface, thereby losing low surface energy. This is particularly problematic when the copolymer is exposed to an aqueous environment (eg, when used as a coating at sea).

  Accordingly, it would be desirable to provide improved polymeric materials, particularly polymeric materials that can form stable surface microdomains when exposed to water. It would be equally desirable to provide improved polymeric materials with well-defined topography.

SUMMARY Described herein are cross-linked polymeric materials that include a polyorganosiloxane and a polyurethane component and that can form topographic surface structures that can be stable in an aqueous environment. The polymeric material may include raised microdomains, such as raised microdomains made primarily from a polysiloxane component surrounded by a polyurethane matrix. The microdomain may be a regular microdomain.

  In one embodiment, the polymeric material may be prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. The polymeric material may have a surface that includes raised microdomains. Microdomains may also be stable when exposed to water for longer than 14 days. The polyorganosiloxane may include a hydroxy-functional polyorganosiloxane, such as a hydroxy-functional polydimethylsiloxane (eg, a hydroxyalkyl-functional polydimethylsiloxane). Polyols may include polyester polyols, polyether polyols, polycarbonate polyols, and acrylic polyols. In one embodiment, the polyol may include a polyol having at least three hydroxy groups. The polyisocyanate may include a polyisocyanate having at least three isocyanate groups.

  In another embodiment, the polymeric material may be prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. Polyols typically have at least three hydroxy groups and / or polyisocyanates have at least three isocyanate groups. By using at least trifunctional polyols and / or isocyanates, the polymeric materials can cross-link with each other to form a more stable surface structure.

  In another embodiment, the crosslinked polymeric material is prepared by reacting a composition comprising up to 15% by weight polyhydroxy functional polyorganosiloxane, together with polyol and polyisocyanate, based on the total solids content of the polymeric material. May be.

  In another embodiment, the crosslinked polymeric material is more hydrophobic than the surrounding polymer matrix by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. It may be prepared by forming a polymeric material that includes surface microdomains. The surface microdomain may include a siloxane polymer, and the surrounding matrix may include polyurethane. The surface domain may have a hydrophobicity that does not appreciably change when exposed to water for 14 days.

  A coating composition that may be used to coat a support layer, such as metal, wood, glass, etc., may be prepared such that when polymerized, the coating composition forms the previously described polymeric material. . In one embodiment, the coating composition comprises up to 15% by weight of polyols, polyisocyanates, polyisocyanates having functional groups capable of reacting with the polyisocyanates based on the total solids in the coating composition after the coating composition is polymerized. Organosiloxane and solvent components may be included. The solvent component may include alkyl alkoxypropionates, dialkyl ketones, and / or alkyl acetates. The coating composition may also include pot life extenders such as alkane-2,4-diones, N, N-dialkylacetoacetamide, alkyl acetoacetates. Isocyanate reaction catalysts such as organotin compounds or tertiary amines may be used to catalyze the reaction of the components in the composition.

  In another embodiment, a method for preparing and using a coating composition comprises adding an isocyanate reaction catalyst to a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. Forming a coating composition, and applying the coating composition to the support layer. The coating composition polymerizes in the support layer to form a polymeric material having raised microdomains.

  The polymeric materials described herein are useful for creating slightly adherent surfaces that may be useful as release papers for adhesive labels, anti-cracking coatings, and antifouling coatings for marine vessels. May be used in many different situations.

DETAILED DESCRIPTION Cross-linked polymeric materials are described herein. In certain embodiments, the polymeric material may be able to form a topographic surface structure that is stable in an aqueous environment. Such surface structures can be stable in an aqueous environment, and polymeric materials are more useful in applications such as marine coatings, medical device or device coatings, etc., and their properties are more stable.

  In general, the polymeric material may be prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. In order to crosslink the polymeric material, at least one of the polyol, polyisocyanate, or polyorganosiloxane includes at least three functional groups that can react with other components in the composition. For example, in one embodiment, the polyol may contain three or more hydroxy groups, or the polyisocyanate may contain three or more isocyanate groups. In some embodiments where more cross-linking is desirable, the composition may include a polyol having at least three hydroxy groups and a polycyanate having at least three isocyanate groups.

  In one embodiment, the polymeric material has a surface that includes regularly raised microdomains of a siloxane polymer surrounded by a polyurethane matrix. Since siloxane polymers are more hydrophobic than polyurethane, polysiloxane-rich microdomains are more hydrophobic than the surrounding polyurethane-rich matrix. In some embodiments, the surface morphology may be fixed in situ so that microdomains do not appreciably change their size and shape when exposed to water for more than 14 days. In other embodiments, the microdomains may be exposed to water or remain, but may be subject to varying degrees of change or change of direction.

  The microdomain may be any number of sizes. The average diameter of the microdomains may range from about 0.1 microns to 10 microns, desirably from about 0.5 microns to 5 microns, or suitably from about 1 micron to 3 microns. The average height of the microdomains may range from about 0.01 microns to 0.2 microns, desirably from about 0.025 microns to 0.15 microns, or suitably from about 0.03 microns to 0.1 microns. In one embodiment, the microdomains may be spatially separated at regular intervals and may be substantially uniform in size. For example, the microdomains may have an average spacing of about 0.5 microns to 10 microns, or desirably about 1 micron to 5 microns.

Polymeric material may also have a microdomain surface density of about 0.1 to 1.5 microdomains / micron ² or typically about 0.2 to 0.65 microdomains / micron ^2,. It should be appreciated that the polymeric material may have any suitable microdomain surface density.

  The polyol used to prepare the polymeric material may be a number of any polyols. Suitable polyols may include polyester polyols, polyether polyols, polycarbonate polyols, and acrylic polyols. As already mentioned, the polyol may have at least three hydroxy groups to promote crosslinking of the polymeric material. In one embodiment, the polyol may include a polycaprolactone polyol such as polycaprolactone triol. In another embodiment, the polyol may have an average hydroxyl equivalent weight of about 100-300, or desirably 150-200. The polymeric material may include about 10 wt% to 40 wt%, or desirably about 20 wt% to 30 wt% polyol, based on the total solids content of the polymeric material.

  Any number of suitable polyisocyanates may be used to prepare the polymeric material. As already mentioned, the polyisocyanate may have at least three isocyanate groups to promote crosslinking of the polymeric material. In one embodiment, the polyisocyanate may include a polyisocyanate based on isophorone. In another embodiment, the polyisocyanate may have an isocyanate equivalent weight of about 150 to 600, or desirably about 250 to 450. The polymeric material may include about 30% to 85% polyisocyanate, or desirably about 50% to 75% by weight, based on the total solids content of the polymeric material.

  Any number of polyorganosiloxanes may be used as long as they can react with the polyisocyanate. For example, polyorganosiloxanes may include hydroxy or amino functional polyorganosiloxanes, such as hydroxy or amino functional PDMS. In one embodiment, the polyorganosiloxane may include a hydroxy or aminoalkyl functional polyorganosiloxane, such as a hydroxy and / or aminopropyl functional polyorganosiloxane. In another embodiment, the polyorganosiloxane may have an average hydroxyl equivalent weight of about 200-800, or desirably 350-700. One suitable polyorganosiloxane may be α, ω-bis [3- (2′-hydroxyethoxy) propyl] polydimethylsiloxane. In some embodiments, the polymeric material may include from about 1 wt% to 15 wt% polyorganosiloxane based on the total solid content of the polymeric material, while in other embodiments, the polymeric material includes May include less than about 15 wt% or less than about 14 wt% polyorganosiloxane. In other embodiments, the polymeric material may include about 2% to 14%, about 3% to 13%, or suitably 5% to 12% by weight. PDMS may also have any suitable molecular weight. In one embodiment, the molecular weight of PDMS may be about 10,000 g / mole or less, about 7,500 g / mole or less, or suitably about 5,000 g / mole or less. In other embodiments, PDMS may have a molecular weight greater than 10,000 g / mol.

  Coating compositions that can be applied to the support layer may be prepared such that the polymeric materials described herein are formed upon polymerization. The coating composition may include polyols, polyisocyanates, polyorganosiloxanes, and solvent components. Solvent components include alkyl propionates (eg, preferably lower alkyl propionates having preferably 5-10 carbon atoms), alkoxypropionates, alkyl alkoxypropionates (eg, preferably 5-10 carbon atoms). Lower alkyl alkoxy propionate), alkoxy alkyl propionates (eg, alkoxy alkyl propionates having 5 to 10 carbon atoms), dialkyl ketones (eg, dialkyl ketones having 5 to 10 carbon atoms), Alkyl acetates (eg preferably lower alkyl acetates having 5 to 10 carbon atoms), alkylalkoxyacetates (eg preferably lower alkylalkoxyacetates having 5 to 10 carbon atoms), alkoxyalkylacetates (eg carbon atoms) Have 5-10 pieces Alkoxyalkyl acetates) may include toluene and / or xylenes. In one embodiment, the solvent component may include ethyl 3-ethoxypropionate (EEP), methyl n-amyl ketone (MAK), and / or butyl acetate. The coating composition may also include potlife extenders such as alkane-2,4-diones (eg, 2,4-pentadione), N, N-dialkylacetamide, or alkylacetoacetates. The amount of a component in the coating composition may be the amount in the following examples, or an amount that is within 15% above or below the amount of any particular component in any example in the Examples section. May

  In one embodiment, the solvent component may include BuAc, EEP, and MAK. The ratio of MAK: EEP may vary from 45: 5 to 5:45. In general, if the ratio is changed to include a larger amount of EEP, the average diameter of the formed domains can increase. In another embodiment, the solvent component may have a formed vapor pressure that is about 12 mm Hg or less, or desirably about 11 mm Hg or less.

  The coating composition also includes an isocyanate reaction catalyst such as a dialkyltin dicarboxylate, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, dialkyltin dihalide or mixtures thereof used to initiate the reaction. May be included. Suitable examples of isocyanate reaction catalysts include diethyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, or mixtures thereof. In one embodiment, the isocyanate reaction catalyst includes a tin catalyst.

  In general, the coating composition may be prepared by mixing all components except the polyisocyanate and the isocyanate reaction catalyst. After the polyisocyanate and the isocyanate reaction catalyst are added and the composition is allowed to react for a while, it is applied to the support layer. The period of time until the coating is applied to the support layer depends on the level of isocyanate reaction catalyst and / or the level of polyorganosiloxane, polyol and / or polyisocyanate. After the coating composition is applied to the support layer, it is polymerized at room temperature and then forced to dry at 80 ° C.

EXAMPLES The following examples are provided for illustration and are not to be construed as limiting the claims. All percentages are by weight unless otherwise specified. The materials shown in Table 1 were used in the examples and were supplied from the following suppliers.

¹ ヒドロキシ末端、α,ω-ビス[3-(2'-ヒドロキシエトキシ)プロピル]ポリジメチルシロキサン
² 3-アミノプロピル末端PDMS
³ イソホロンジイソシアネートに基づくポリイソシアヌレートタイマー（timer）
⁴ ヘキサンジイソシアネートに基づく。

¹ -hydroxy-terminated, α, ω-bis [3- (2'-hydroxyethoxy) propyl] polydimethylsiloxane
² 3-aminopropyl-terminated PDMS
³ Polyisocyanurate timer based on isophorone diisocyanate
Based on ⁴ hexane diisocyanate.

  PDMS B was synthesized as follows. In a 250 ml three-necked round bottom flask, 2.04 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 10 g of octamethylcyclotetrasiloxane were mixed. The solution was heated with stirring under nitrogen. By the time the temperature reached 80 ° C., 0.1% catalyst (tetramethylammonium 3-aminopropyldimethylsilanolate) was added to the solution. After heating for 1 hour, the viscosity increased slightly and the remaining octamethylcyclotetrasiloxane (90 g) was added to the addition funnel and added dropwise to the solution. The dropwise addition of octamethylcyclotetrasiloxane was performed over 7 to 10 hours. After all the octamethylcyclotetrasiloxane addition was complete, heating was continued for an additional 2-3 hours. The temperature was then increased from 80 ° C. to 150 ° C. and the catalyst was decomposed at that temperature. After decomposition, the solution was cooled to room temperature.

  PDMS C uses 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 1.02 g + first added octamethylcyclotetrasiloxane 5 g, octamethylcyclotetrasiloxane 95 g was added using a dropping funnel and synthesized according to the technique described above for PDMS B.

  Atomic force microscopy (AFM) testing was performed with a Dimension 3100 microscope equipped with a Nanoscope IIIa controller (Digital Instruments, Inc. California). Experiments were performed in tapping mode at ambient conditions or in contact mode in water. A silicon probe with a spring constant of 0.1 to 0.4 N / m and a resonance frequency of 17 to 24 kHz were used. The setpoint ratio for acquiring TMAFM data was 0.9.

  Nanoindentation measurements were performed using a Dimension 3100 microscope equipped with a Berkovich diamond indenter hardness tester probe. The spring constant of the probe was 177.3 N / m. A force deflection curve from a standard sapphire substrate was used to calibrate the deflection voltage and was found to average 220.8 nm / V. An array of indentations to the surface of the coating was obtained using a force threshold of 20 μN.

  For SEM (scanning electron microscope) experiments, samples were encapsulated in aluminum encapsulant and coated with gold by a Technics Hummer II sputter coating apparatus. Images were obtained using a JEOL JSM-6300 scanning electron microscope. X-ray information was obtained by ThermoNoran EDS detector using VANTAGE Digital Acquisition Engine.

  For TEM (Transmission Electron Microscope) experiments, a sample was embedded in Epon-Araldite-DDSA and a 60 nm thick section was prepared using a microtome. Cross-sectional images were obtained using a JEOL JEM-100CX II electron microscope.

Example 1
The polymeric material formulations shown in Samples 1-9 in Table 2 were prepared according to the following technique. 30 wt% PDMS A in EEP, 30 wt% PDMS B in EEP, 30 wt% PDMS C in EEP, 90 wt% PCL triol in MAK, 90 wt% PCL triol in EEP, 1 wt in MAK A stock solution of% DBTDA was prepared. For each sample, 0.075 wt% DBTDA and 10 wt% 2,4-pentanedione were added based on resin solids. For samples 1-4 and 9, the NCO: OH equivalent ratio was kept constant at 1.1: 1.0. Weigh PDMS, PCL triol (90% EEP solution for Example 2, 90% MAK solution for the rest of the sample), and 2,4-pentanedione and mix thoroughly with a magnetic stir bar in a 20 ml vial. Samples 1-9 were prepared by After thorough mixing, DBTDA and polyisocyanate were added and mixed for the specified times shown in Table 2. The coating was applied on an aluminum panel and maintained at ambient conditions for 24 hours, followed by 45 minutes of polymerization in an 80 ° C. dryer. The thickness of the coating film was 50 to 70 μm.

^*触媒の重量％はポリマー材料の総固体重量に関して与えられる。

^* The weight percent of the catalyst is given with respect to the total solid weight of the polymer material.

  The coatings prepared in samples 1-9 are reactive oligomers (eg PDMS, PCL triol, polyisocyanate) in a solvent mixture of the catalyst (DBTDA) and the potlife extender (2,4-pentanedione) already described. As a solution (in the amount shown in Table 2). Since PDMS has a much lower surface energy than polyurethane, PDMS is expected to layer against the coating surface during film formation and crosslinking, thereby providing a smooth, low surface energy PDMS with a durable polyurethane underlayer A polyurethane coating with an outer layer was obtained. Tapping mode AFM testing of 20 and 30% siloxane-urethane coating compositions (Samples 3 and 4) showed a smooth surface completely covered by PDMS. SEM and AFM images for Sample 3 are shown in FIGS. 4 and 5, respectively. The polyurethane control without PDMS (Example 9) also had a surface with no characteristic structure. Similarly, Samples 5-8 had a smooth surface. Only Samples 1 and 2 showed raised microdomains.

  Sample 1 with 10% PDMS A yielded a microstructured surface with discontinuous domains shown in FIG. The domain had an average diameter of about 1.4 μm and a height of about 50 nm. A plan view of the surface of the polymer formulation from Sample 1 is shown in FIG. An SEM image of Sample 1 is shown in FIG. There were also many smaller domains among the larger domains as well. The distribution of large domain sizes is fairly uniform. Although it may be assumed that domains are composed primarily of PDMS, the size of the domains is significantly larger than expected when they are composed of only 1000 g / mol PDMS A blocks. Thus, these domains may contain a mixture of several polyurethane components along with PDMS A.

Nanoindentation measurements were made on the microstructured siloxane-urethane surface from Sample 1 and also on the control polyurethane surface when the same force threshold of 20 μN was applied. The depth of indentation at the maximum load (h _max ) of the microdomain was considerably higher (179.5 ± 3.7 nm) than the surrounding region (83.6 ± 1.8 nm). The h _max value obtained for a pure polyurethane surface was 78.3 ± 10.4 nm, which approximated the value obtained for a microstructured surface matrix. Thus, the higher indentation depth means that the microdomain coefficient is significantly lower than that of the surrounding material, and thus the microdomain is mainly composed of PDMS A. It shows that it consists of polyurethane with little or no inclusion.

  Similarly, the SEM image of the surface of Sample 1 confirmed the microstructural properties of the polymer surface as shown in FIG. 6 (a). Energy dispersive X-ray mapping of silicon showed that the microstructure domains formed on the surface are rich in silicon, as shown in FIG. 6 (b). In contrast, SEM images and Si mapping for a siloxane-urethane coating with no characteristic structure (Sample 3) revealed that the silicon was evenly distributed on the surface.

  To confirm that the surface domain did not consist of unreacted PDMS on the coating surface, the coating from Sample 1 was treated with toluene that would dissolve unbound PDMS oligomers. AFM testing showed that although the domains swelled, they were not removed and were thus covalently attached to the network.

  To test the stability of the microstructure surface of Sample 1 in water, a tapping mode AFM image was made after 2 weeks immersion in water. For comparison purposes, the AFM image from FIG. 2 is reproduced as FIG. 7 (a), and the AFM image of the coating from sample 1 after 2 weeks immersion in water is shown in FIG. 7 (b). The PDMS domain did not disappear, although the size and size distribution changed. The average diameter of the domain was 1.4 μm before and after soaking in water, and the average diameter of the larger domain in FIG. 7 (b) was 3.82 μm. The fact that several domains can grow in size indicates that there is some motility in the polymer at the coating surface. Water can plasticize the polyurethane matrix and allow the PDMS rich polymer to diffuse between the domains.

  Another sample that formed microdomains was Sample 2, which also contained 10 wt% PDMS A. Figures 8 (a) and (c) are AFM images of the coating surface of Sample 2 obtained in tapping mode in air before soaking in water and contact mode in water before soaking in water, respectively. Indicates. Figures 8 (b) and (d) are respectively obtained in the tapping mode in air after being immersed in water and obtained in the contact mode in water after being immersed in water for 2 weeks. An AFM image of the coating is shown. The microstructure surface domain of the sample 2 coating showed a change of 0.17 μm in average diameter when the coating was immersed in water.

Example 2
In this example, a number of samples were prepared to determine the effect of the solvent on the formation of microdomains in the polymer material. The resin formulation in all samples was 10 wt% PDMS A, 26.67 wt% PCL triol, and 63.33 wt% polyisocyanate D. Solvent testing was performed using a statistical experimental design approach based on the D-optimal special cubic mixture design. Solvents examined in this study were MAK, toluene, EEP, BuAc, and IPA. Since polyisocyanate D supplied in BuAc was used as a cross-linking agent, all solvent compositions had minimal amounts of BuAc. Thus, depending on the experimental design, the amount of BuAc changed from 45% to 100% and the solvent balance changed from 0% to 55%. A summary of the design is shown in Table 3 below.

  Samples were prepared as follows. The 35 solvent compositions used are shown in Table 4 below. Stock solutions of 30 wt% PDMS A, 90 wt% PCL, 1 wt% DBTDA were prepared individually in the five solvents investigated (MAK, toluene, EEP, BuAc, and IPA). For each sample, 0.075 wt% DBTDA and 10 wt% 2,4-pentanedione were added based on the resin solids. Samples were prepared by weighing each stock solution of PDMS A, PCL triol, 2,4-pentanedione, and DBTDA and mixing in a 20 ml vial with a magnetic stir bar. After thorough mixing, polyisocyanate D was added and mixed well for 4 hours. The coating was applied to the aluminum panel and maintained at ambient conditions for 24 hours, and then polymerized in an oven at 80 ° C. for 45 minutes. The thickness of the coating film was 50 to 70 μm. Experiments were performed in random order.

After coating application and polymerization, AFM images (40 μm × 40 μm) of all 35 coatings were taken in tapping mode in air. The formation of microdomains and their surface density were induced by their solvent composition. All 35 AFM images are shown in FIG. A wide range of behavior is observed depending on the solvent composition used. Domains are not present in some coatings, and a series of sized domains are evident when present. In order to develop a quantitative model of behavior, a numerical response was created. Domain formation was considered as one of the reactions. “No domain” on the surface is assigned to “0”, and if there is a domain, “1” is assigned regardless of its size. For surfaces with domains, the number of domains / μm ² was calculated by the image analysis software and the values were taken into account in the reaction. The response was fitted to a statistical model. Equations 1 and 2 are the equations for the goodness model for domain formation and domain density, respectively.
Domain = 0.97 A + 0.99 B + 1.17 C + 1.01 D + 0.34 E−3.17 BD (1)
Sqrt (domain density +0.01) = 0.47 A + 0.66 B + 0.35 C + 0.76 D + 0.18 E−1.85 BD−1.26 DE (2)

  Both of these models have shown that there is an interaction term between solvents. The interaction terms BD for domain formation and the interaction terms BD and DE for domain density were significant factors. Since these interaction terms all had negative coefficients, they would be inconvenient for domain formation. This means that the faster evaporating solvent combination (BuAc, toluene, and IPA) in any solvent composition may be inconvenient for the formation of a structured surface. Since all solvent compositions have some amount of BuAc, the presence of toluene or IPA in the solvent composition will generally be inconvenient for the formation of structural surfaces due to interaction with BuAc.

Further insight into the effect of the solvent composition on domain formation can be gained by specifying target conditions and creating a set of solutions. Two sets of solutions were obtained. The first set is obtained by specifying a domain formation equal to zero (ie, no domain) as shown in Table 5 and the second set is a domain equal to 1 as shown in Table 6. It was obtained by specifying formation (domain formation) as a condition. The proposed solvent composition in Table 5 is the absence or minimal amount of MAK and EEP, and the presence of only a large amount of IPA, or the presence of both toluene and BuAc, has a microstructure domain. It proved inconvenient for surface formation. From Table 6, it was found that the proposed solvent composition would be favorable for the formation of microstructured surface domains in the absence or minimal amount of IPA and in the presence of MAK and EEP. These two sets of solvent compositions can be separated with respect to vapor pressure and solubility parameters. In the case of “no domain”, the vapor pressure of the solvent composition is in the range of 13.95 mm Hg to 24.89 mm Hg, and the solubility parameter is in the range of 8.61 (cal / cm ³ ) ^{0.5 to} 9.84 (cal / cm ³ ) ^0.5 . Met. For domain formation, the vapor pressure of the solvent composition was 5.27 mm Hg to 10.54 mm Hg, and the solubility parameter ranged from 8.56 (cal / cm ³ ) ^{0.5 to} 8.62 (cal / cm ³ ) ^0.5 .

Example 3
In this example, after examining the negative interaction terms (toluene-butyl acetate and butyl acetate-IPA) in the model and the solvent composition proposed from Table 6, eight different solvent compositions without toluene and IPA Were selected for further evaluation. Other than the solvent composition, the formulations and methods for preparing the formulations were similar to the formulations prepared in Example 2 (eg, the same amount of PDMS A, PCL triol, and polyisocyanate D). Selected solvent compositions are shown in Table 7. The amount of BuAc was maintained at a minimum level of 45%, and the MAK: EEP ratio was systematically varied from 45:10 to 10:45. Coatings were prepared using an automated formulation application unit, and each of the 8 coatings was prepared 3 times to create a library of 24 samples. Painting was done on primed and bare aluminum panels. Another set of coatings was prepared in the laboratory for bare aluminum panels. AFM images in tapping mode revealed that these eight solvent compositions always produced microstructured surfaces as expected. Thus, the formation of a microstructured surface was favored by eliminating toluene and IPA from the solvent composition, as shown by the model reaction with the use of a minimal amount of BuAc.

  In order to understand the effect of solvent composition on domain size, the average diameter of the domains was plotted against the MAK: EEP ratio as shown in FIG. For coatings prepared using an automatic unit, the average diameter of the domain varies from 0.41 μm to 1.35 μm when applied to a primed aluminum panel and 0.53 μm to 0.97 μm when applied to a bare aluminum panel. Changed. For coatings prepared in the laboratory, changing the MAK: EEP ratio from 45:10 to 10:45 increased the average diameter from 1.2 μm to 1.9 μm. Since these are relatively thick coatings, the support layer is not expected to have a significant effect on the formation of surface domains, which is reflected in coatings prepared on the two support layers using automated equipment. .

  When MAK was replaced with EEP in this series of formulations, two things happened. The overall solubility parameter of the solvent composition increases due to contribution from the hydrogen bonding interaction parameters. Furthermore, the overall evaporation rate is slowed down. This means that a favorable hydrogen bonding interaction between the solvent and the polyurethane occurs for a longer time. Larger amounts of EEP can delay the phase separation process after application, thereby growing the domain size. In order to understand the domain arrangement of the entire coating, a cross-sectional TEM image of the formulation Si-PU 8 is shown in FIG. TEM analysis revealed that the domains are concentrated mainly at the air interface and darker than the surrounding matrix, as expected from the fact that these domains are mainly composed of PDMS. Similar sized domains were also observed in the bulk of the sample.

Example 4
In the samples tested in Examples 2 and 3, the time from mixing the components and applying the coating to the support layer was constant at 4 hours. In this example, to understand the effect of mixing time on domain formation, the same resin composition (ie, the same amount of PDMS A, PCL triol, and polyisocyanate D as in Example 2), the same solvent composition (MAK: EEP: BuAc = 12: 43: 45), and potlife extender (2,4-pentanedione, 10% on resin solids) but two different levels of DBTDA catalyst (0.075%, series A and 0.15%) Two formulations with series B) were used. During the coating preparation, all reagents other than isocyanate were thoroughly mixed. After the isocyanate was added and mixed well, coatings were applied at 30 minute intervals for 30 minutes to 8 hours or 4 hours for Series A and Series B, respectively.

  An AFM image of the polymerized film was made in the tapping mode of that series of coatings. Images of Series A (0.075% DBTDA) and Series B (0.15% DBTDA) are shown in FIG. Series A can be subdivided into three stages: 1) No domain formed within the first 2 hours of mixing (a1-a4) 2) Domains are observed only after mixing for 2.5 hours (a5), It became uniform after mixing for 3 hours (a6). When mixed up to 4.5 hours, the domain size became uniform (a7 to a9). 3) After 5 hours of mixing, the domain size began to decrease (a10), and in the coating prepared after 7 hours of mixing, the domains disappeared completely, producing a smooth and uniform surface (a14). This indicates that the formation of microstructure surface domains is a function of mixing time and can be controlled by kinetics.

  Since the reaction rate between isocyanate and hydroxyl groups increases with increasing catalyst levels, domain formation was expected to appear earlier in formulations with twice the amount of catalyst. In coatings with twice the amount of series B catalyst, a uniform size domain occurred after 1.5 hours of mixing (b3), which was exactly equal to half the time required in series A. Similarly, the domain begins to decrease in size after 2.5 hours of mixing (b5) compared to 5 hours of mixing in series A (a10) and 3.5 hours of mixing compared to 7 hours of series A (a14). After (b7), it disappeared completely. A plot of domain size versus time for 0.075% and 0.15% DBTDA catalysts is shown in FIG. Since there was a broad size distribution in the Series A samples at 2.5 hours, three data points, one for each major domain size observed, were plotted.

  From the results it can be seen that series A and B formulations must be subjected to a minimum mixing time in order to form domains on the surface of the coating. The results further indicate that some reaction has occurred between the oligomeric species during the coating and film formation to form the surface domain. For Series A coatings, there is also an interesting “window” from 3.5 to 5.5 hours where the domain size is relatively constant. Eventually, the domain size decreases and finally the surface domain disappears, indicating that further reaction results in a more uniform system with no surface phase separation. It shows that a similar level of domain formation occurs in a shorter time when using twice the amount of catalyst, and that both domain formation and size can be controlled kinetically.

  Surface SEM imaging was used to further confirm the formation of microstructured polymer surfaces. SEM images of the surface after 0.5, 3.5, and 7.5 hours of mixing (series A, a1, a7, a15 in Figure 12) show no microstructure domains at 0.5 and 7.5 hours, but domains at 3.5 hours (Figures 14a-c). Corresponding silicon energy-dispersive X-ray mapping showed that the domain is rich in silicon, as shown in Figure 14e, but when the mixing time is 0.5 hours, the energy-dispersive X-ray mapping of silicon Revealed that there was a region rich in scattered silicon (FIG. 14d). When the mixing time was 7.5 hours, the silicon was evenly distributed on the surface (FIG. 14f). From this SEM test by X-ray mapping, in the early stages of the cross-linking reaction, PDMS separates into several discrete regions, and as the reaction proceeds, silicon-rich microdomains are generated on the surface, and finally It has been found that silicon forms a surface with no characteristic structure that is uniformly distributed.

  To further understand the effect of reaction kinetics on coating morphology, dynamic mechanics analysis (DMA) was performed on selected siloxane-urethane samples along with a control polyurethane without PDMS. Dynamic mechanical testing was performed with a TA Instruments Q-800 DMA analyzer. The sample was tested under tension from −140 ° C. to 200 ° C. with a heating rate of 2 ° C./min and a strain of 0.3%. Typically, siloxane-urethane systems are expected to show a transition around -128 ° C to -90 ° C due to good phase separation PDMS segments. A low molecular weight PDMS (1000 g / mol) was used, but at the initial stage of mixing (0.5 hours), the transition associated with PDMS was about -90, as shown in the loss modulus versus temperature curve in FIG. Observed at ° C. As the reaction proceeds (4.5 hours), the intermediate phase appears to collect around 5 ° C, but still suggests a transition remaining at -90 ° C. While not wishing to be bound by theory, it appears that this intermediate phase consists of both PDMS and polyurethane, thereby resulting in the observed phase separated surface structure. However, at the late stage of mixing, the low temperature and the intermediate phase disappeared and the upper transition zone expanded, indicating that the system became homogeneous. Thus, no domain formation is observed at the late stage.

Example 5
In this example, the effect of PDMS wt% on surface domain formation was determined by introducing 5 wt%, 8 wt%, 12 wt% and 15 wt% PDMS into the formulation based on solid resin. . The polymeric material formulations shown in Samples 10-17 in Table 8 were prepared according to the technique described in Example 1. The effect of solvent composition and mixing time was evaluated by using two different solvent compositions for each weight% PDMS and applying to the coating after 3, 4, and 5 hours of mixing.

^*触媒の重量％は、ポリマー材料の総固体重量に関して与えられる。

^* The weight percent of catalyst is given with respect to the total solids weight of the polymer material.

  The results for Samples 10-17 are shown in Table 8. Formulations with higher amounts of BuAc and lower amounts of EEP formed smaller domains than formulations with higher amounts of EEP and lower amounts of BuAc. For the 12 wt% formulation, sample 14 with a more rapidly evaporating solvent composition began to form a domain after 4 hours of mixing, while sample 15 with a slower evaporating solvent component had a domain after 5 hours of mixing. Began to form. It should be noted that no domain was formed in the 15 wt% PDMS formulation even after mixing for 18 hours before painting.

Example 6
In this example, the effect of polymerization conditions on domain formation was determined. The resin formation in all of the samples prepared in this example was 10 wt% PDMS A, 26.67 wt% PCL triol, and 63.33 wt% polyisocyanate D. Three sets with different polymerization conditions were tested. The three sets of polymerization conditions are: (1) Mix the components for 4 hours, apply the mixture to the Al panel and immediately place the mixture in a dryer set at 80 ° C for 45 minutes, (2) Mix the components for 4 hours Mix and apply the mixture to the Al panel, let stand for 1 hour at room temperature, put the panel in the dryer set at 80 ° C for 45 minutes, and (3) mix the ingredients for 4 hours to make the Al panel Apply the mixture and let it stand at room temperature overnight, then put it in a dryer set at 80 ° C. for 45 minutes. The polymer material polymerized with the first set of polymerization conditions formed microdomains having an average diameter of about 0.927 microns. Polymer materials polymerized under the second and third sets of polymerization conditions formed microdomains having an average diameter of about 1.35 to 1.5 microns.

  As used herein (ie, the claims and specification), articles such as “that”, “one”, and “an” mean singular or plural. Yes. Similarly, as used herein, the term “any” (or other similar language that explicitly indicates that “or” explicitly means exclusive, such as x Or the term "or" when used without the other) is to be construed comprehensively, i.e., when it appears alone, it is meant to mean both "and" and "or" Should. Similarly, as used herein, the term “and / or” should also be interpreted as inclusive in the sense that the term means both “and” and “or”. . In situations where “and / or” or “or” are used together for a group of three or more items, the group may include one item alone, all items together, or any combination or number of items. Should be interpreted as included. Moreover, terms used in the specification and claims, such as having, having, included, and included, are synonymous with the terms include and include. It should be interpreted as being.

Illustrative Aspects In the following, reference is made to a number of aspects that are illustrative of the subject matter described herein. The following aspects describe only some selected aspects that may include various features, characteristics, and advantages of the currently described subject matter. Accordingly, the following aspects should be considered to be inclusive of all possible aspects.

  According to one embodiment, a crosslinked polymeric material having a surface containing raised microdomains is prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. Is done. Microdomains may not appreciably change when exposed to water for longer than 14 days. The polyorganosiloxane may comprise a hydroxy functional polyorganosiloxane. The polyorganosiloxane may comprise a hydroxy functional polydimethylsiloxane. The polyol may have at least three hydroxy groups. The polyol may include a polycaprolactone polyol. The polycaprolactone polyol may have at least three hydroxy groups. The polyisocyanate may have at least three isocyanate groups. The polyisocyanate may comprise a polyisocyanate based on isophorone.

  According to another embodiment, a polymeric material is prepared by reacting a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate, wherein the polycaprolactone polyol contains at least three. Polyols having one hydroxy group are included and / or polyisocyanates include isocyanates having at least three isocyanate groups. The polymeric material may have a surface that includes microdomains. Microdomains may not appreciably change in dimensions after 14 days of exposure to water. The microdomain may have an average diameter of about 0.5 microns to 5 microns. The microdomain may have an average height of about 0.01 microns to 0.2 microns. The microdomains may have an average spacing of about 0.5 microns to 10 microns. The composition may comprise a polycaprolactone polyol having at least three hydroxy groups and a polyisocyanate having at least three isocyanate groups. The polyorganosiloxane may comprise a hydroxy functional polyorganosiloxane. The polyorganosiloxane may have an average hydroxyl equivalent weight of about 200 to 800, desirably about 350 to 700. The polyorganosiloxane may comprise α, ω-bis [3- (2′-hydroxyethoxy) propyl] polydimethylsiloxane. The polyorganosiloxane may comprise a hydroxy functional polydimethylsiloxane. The polyorganosiloxane may comprise a hydroxyalkyl functional polydimethylsiloxane. The polyorganosiloxane may comprise an amino functional polyorganosiloxane. The polyorganosiloxane may comprise an aminoalkyl functional polyorganosiloxane. The polymeric material may comprise about 10 wt% to 40 wt% polycaprolactone polyol. The polymeric material may comprise from about 30% to 85% polyisocyanate. The polyisocyanate may have an average isocyanate equivalent weight of about 150 to 600, desirably about 250 to 450. The polymeric material comprises about 20-30 wt% polycaprolactone polyol containing a polyol having at least three hydroxy groups; about 50-75 wt% polyisocyanate containing an isocyanate having at least three isocyanate groups; and about 3-13 It may contain weight percent hydroxy-functional polydimethylsiloxane. The polycaprolactone polyol may comprise a polycaprolactone triol having an average hydroxyl equivalent weight of from about 150 to 200; the polyisocyanate may comprise a polyisocyanate based on isophorone diisocyanate having an average isocyanate equivalent weight of from about 250 to 450, and hydroxy The functional polydimethylsiloxane may comprise α, ω-bis [3- (2′-hydroxyethoxy) propyl] polydimethylsiloxane having an average hydroxyl equivalent weight of about 350-700. The polymeric material may comprise about 10-40% by weight polycaprolactone polyol, about 30-85% by weight polyisocyanate, and about 2-14% by weight polyorganosiloxane.

  According to another embodiment, the crosslinked polymeric material is prepared by reacting a precursor comprising: a polyhydroxy functional polyorganosiloxane of less than 15% by weight based on the total solids content of the polymeric material; a polyol; And polyisocyanates.

  According to another embodiment, a crosslinked polymeric material is prepared by reacting a composition comprising a polyol; a polyisocyanate; and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate, wherein the polymeric material includes Contains surface microdomains that are more hydrophobic than the matrix. The microdomain may have a hydrophobicity that does not change appreciably when exposed to water for 14 days. The microdomain may have a form that does not change recognizable when exposed to water for 14 days.

  According to another embodiment, the coating composition comprises less than 15% by weight of a hydroxy-functional polyorganosiloxane based on total solids in the coating composition after polymerization of the coating composition; a polycaprolactone polyol; a polyisocyanate; and a solvent component. Including. The solvent component may include alkyl alkoxypropionates, dialkyl ketones and / or alkyl acetates. The solvent component may include a lower alkyl alkoxy propionate; a dialkyl ketone having 4 to 10 carbon atoms; and / or a lower alkyl acetate. The solvent component may include at least one of ethyl 3-ethoxypropionate, methyl n-amyl ketone, and butyl acetate. The coating composition may include a pot life extending agent. The pot life extending agent may include at least one of alkane-2,4-dione, N, N-dialkylacetoacetamide, or alkylacetoacetate. The pot life extending agent may include 2,4-pentanedione. The coating composition may include an isocyanate reaction catalyst. The isocyanate reaction catalyst may comprise a dialkyltin dicarboxylate, a trialkyltin hydroxide, a dialkyltin oxide, a dialkyltin dialkoxide, a dialkyltin dihalide, or a mixture thereof. The isocyanate reaction catalyst may comprise diethyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, or mixtures thereof. The isocyanate reaction catalyst may include a tin catalyst.

  According to another embodiment, the support layer may include a surface coated with a polymeric material from any embodiment described herein.

According to another embodiment, a method of preparing and using a coating composition includes: an isocyanate reaction catalyst in a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate. Adding a coating composition to the surface of the support layer. The coating composition may be polymerized to form a polymer coating having raised microdomains on the support layer surface. The solvent component may have a vapor pressure of about 12 mm Hg or less. The solvent component may have a vapor pressure of about 11 mm Hg or less. The solvent component may have a vapor pressure of about 3 mm Hg to 12 mm Hg. The solvent component may have a solubility parameter of about 8 (cal / cm ³ ) ^{0.5 to} 8.62 (cal / cm ³ ) ^0.5 . The ratio of alkyl alkoxypropionate to dialkyl ketone may be about 45: 5 to 5:45.

  According to another embodiment, the cross-linked polymeric material includes a polyol; a polyisocyanate; a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate; and an alkyl alkoxypropionate, dialkyl ketone, and / or alkyl acetate. It may be prepared by reacting a composition that includes a solvent component; the polymeric material has a surface that includes raised microdomains.

  As used herein, spatial or directional terms such as “left”, “right”, “front”, “rear”, etc. relate to the target substance as shown in the drawings. However, it should be understood that the subject matter described herein may assume a variety of alternative orientations, and therefore such terms should not be considered limiting. Further, as used herein (ie, the claims and specification), articles such as “its”, “one”, and “an” are singular or plural. Can mean. Similarly, as used herein, the term “any” (or other similar language that explicitly indicates that “or” explicitly means exclusive, such as x Or the term "or" when used without the other) is to be construed comprehensively, i.e., when it appears alone, it is meant to mean both "and" and "or" Should. Similarly, as used herein, the term “and / or” should also be interpreted as inclusive in the sense that the term means both “and” and “or”. . In situations where “and / or” or “or” are used together for a group of three or more items, the group may include one item alone, all items together, or any combination or number of items. Should be interpreted as included. Moreover, terms used in the specification and claims, such as having, having, included, and included, are synonymous with the terms include and include. It should be interpreted as being.

  Unless expressly indicated otherwise, all numerical values or formulas used to express dimensions, physical characteristics, etc., as used herein are modified in all cases by the term “about”. Understood. It is very unlikely to limit the doctrine of equivalents to the claims, and each such reference in the specification or claims modified by the term “about” rather than such an attempt. The numerical parameters should be interpreted at least in light of the number of significant digits quoted and by applying conventional rounding techniques. Moreover, all ranges disclosed herein are understood to include any and all subranges submitted therein. For example, a range of 1 to 10 includes all subranges between and including a minimum value of 1 to a maximum value of 10, i.e., starting with a minimum value of 1 or higher and a maximum value of 10 or higher All subranges ending with smaller values (eg 5.5-10) should be considered included.

3 is an atomic force microscope image of the polymer material surface from Sample 1 in Table 2. FIG. 3 is an atomic force microscope image of the polymer material surface from Sample 1 in Table 2. FIG. 3 is a scanning electron microscope image of the polymer material surface from Sample 1 in Table 2. FIG. 3 is a scanning electron microscope image of the polymer material surface from Sample 3 in Table 2. FIG. 3 is an atomic force microscope image of the polymer material surface from Sample 3 in Table 2. FIG. (A) Scanning electron microscope image and (b) X-ray mapping of silicon on the polymer material surface from Sample 1 in Table 2. Comparison of atomic force microscope images of the polymer material from Sample 1 in Table 2 before (a) soaking in water and (b) after soaking in water for 2 weeks. Of atomic force microscopy images of the polymer material from Sample 2 in Table 2 before soaking in water (8 (a) and (c)) and after soaking in water for 2 weeks (8 (b) and (d)) A comparison is shown. 5 shows atomic force microscope images of 35 polymeric materials prepared using the solvent compositions shown in Table 4. Figure 3 shows a plot of the average diameter of microdomains formed in various polymer materials against the ratio of MAK: EEP used in the solvent to prepare the polymer material. 8 is a transmission electron microscope image of the polymer material from Si-PU 8 shown in Table 7. Figure 2 shows a number of atomic force microscope images taken to show the kinetic effects on the formation of microdomains in one embodiment of a polymeric material. FIG. 13 is a plot of domain size versus time for polymer materials formed in series A and series B from FIG. FIG. 13 shows scanning electron microscope images and corresponding silicon mapping images at (a) 0.5 hour, (b) 3.5 hours, and (c) 7.5 hours for the polymer material from series A in FIG. FIG. 13 is a plot of loss modulus versus temperature as a function of mixing time for a polymeric material from series A in FIG.

Claims (31)

Polyols;
A cross-linked polymeric material prepared by reacting a composition comprising a polyisocyanate; and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate, the polymer having a surface comprising raised microdomains material.   2. The polymeric material of claim 1, wherein the microdomain does not change appreciably when exposed to water for more than 14 days.   The polymeric material of claim 1, wherein the polyorganosiloxane comprises a hydroxy-functional polyorganosiloxane.   4. The polymeric material of claim 3, wherein the polyorganosiloxane has an average hydroxyl equivalent weight of about 200 to 800, and desirably about 350 to 700.   The polymeric material of claim 1, wherein the polyol comprises a polyol having at least three hydroxy groups.   2. The polymeric material of claim 1, wherein the polyol comprises a polycaprolactone polyol.   The polymeric material of claim 1, wherein the polyisocyanate comprises a polyisocyanate having at least three isocyanate groups.   2. The polymeric material of claim 1, wherein the microdomain has an average diameter of about 0.1 microns to 5 microns.   The polymeric material of claim 1, wherein the microdomains have an average height of about 0.01 microns to 0.2 microns.   The polymeric material of claim 1, wherein the microdomains have an average spacing of about 0.5 microns to 10 microns.   The polymeric material of claim 1, wherein the polyorganosiloxane comprises an amino-functional polyorganosiloxane.   The polymeric material of claim 1, wherein the composition further comprises a solvent component.   13. The polymeric material of claim 12, wherein the solvent component comprises alkyl acetate, alkyl propionate, alkyl alkoxy acetate, alkoxy propionate, alkoxy alkyl acetate, alkoxy alkyl propionate, toluene, xylene, and / or dialkyl ketone. . Surface has a microdomain density of about 0.1 to 1.5 microdomains / micron ^2, the polymeric material of claim 1, wherein. Polycaprolactone polyol;
A polymeric material prepared by reacting a composition comprising a polyisocyanate; and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate, wherein the polycaprolactone polyol comprises a polyol having at least three hydroxy groups. A polymeric material comprising and / or polyisocyanate comprising an isocyanate having at least three isocyanate groups.   16. The polymeric material of claim 15, comprising about 10% to 40% by weight polycaprolactone polyol.   16. The polymeric material of claim 15, comprising from about 30% to 85% polyisocyanate.   16. The polymeric material of claim 15, wherein the polyisocyanate has an average isocyanate equivalent weight of about 150-600, and desirably about 250-450. 16. The polymeric material of claim 15, comprising:
About 20-30% by weight of polycaprolactone polyol comprising a polyol having at least three hydroxy groups;
About 50-75% by weight polyisocyanate comprising an isocyanate having at least three isocyanate groups; and about 3-13% by weight hydroxy-functional polydimethylsiloxane. The polycaprolactone polyol comprises a polycaprolactone triol having an average hydroxyl equivalent weight of about 150-200;
The polyisocyanate comprises a polyisocyanate based on isophorone diisocyanate having an average isocyanate equivalent weight of about 250 to 450; and the hydroxy-functional polydimethylsiloxane has an average hydroxyl equivalent weight of about 350 to 700 α, ω-bis [3 20. The polymeric material of claim 19, comprising-(2'-hydroxyethoxy) propyl] polydimethylsiloxane. 16. The polymeric material of claim 15, comprising:
About 10-40% by weight polycaprolactone polyol;
About 30 to 85% by weight polyisocyanate; and about 2 to 14% by weight polyorganosiloxane. Crosslinked polymeric material prepared by reacting a precursor comprising:
Polyols;
About 14% by weight or less of a polyhydroxy functional polyorganosiloxane based on the total solids content of the polymeric material. Polyols;
A cross-linked polymeric material prepared by reacting a composition comprising a polyisocyanate; and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate, wherein the surface microdomain is more hydrophobic than the surrounding matrix A cross-linked polymeric material included.   24. The polymeric material of claim 23, wherein the microdomain has a hydrophobicity that does not appreciably change when exposed to water for 14 days.   24. The polymeric material of claim 23, wherein the microdomain has a form that does not change recognizable when exposed to water for 14 days. A coating composition comprising:
No more than about 14% by weight of hydroxy-functional polyorganosiloxane based on the total solids in the coating composition after the coating composition has polymerized;
Polycaprolactone polyol;
A polyisocyanate; and a solvent component.   27. The coating composition of claim 26, further comprising a pot life extending agent.   27. A support layer comprising a surface coated with the polymeric material of claim 1 or 12 or the coating composition of claim 26. Adding an isocyanate reaction catalyst to a composition comprising a polyol, a polyisocyanate, and a polyorganosiloxane having a functional group capable of reacting with the polyisocyanate to form a coating composition; and the coating composition on the surface of the support layer A method of preparing a coated support layer, comprising: applying a coating composition to polymerize to form a polymer coating having raised microdomains on the surface of the support layer.   30. The coating composition of claim 29, wherein the solvent component has a formed vapor pressure of about 12 mm Hg or less. 30. The coating composition of claim 29, wherein the solvent component has a solubility parameter of about 8 (cal / cm < ³ >) ^{0.5 to} 8.7 (cal / cm < ³ >) ^0.5 .

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