 Coatings
专利摘要:
The present invention provides an electronic or electrical device or component thereof comprising a cross-linked polymer coating on a surface of the electronic or electrical device or component thereof; wherein the cross-linked polymer coating can be obtained by exposing the electronic or electrical device or component thereof for a period of time long enough to permit the formation of the cross-linked polymer coating on a surface thereof to a plasma comprising a monomer compound and a cross-linking reagent, wherein the monomer compound has the following formula: R 1 R 2 C = CR 3 R 4 wherein R 1, R 2 and R 4 are all independently selected from hydrogen, optionally substituted C 1 -C 6 alkyl or haloalkyl with a branched or straight chain, or aryl optionally substituted by halogen, and R3 is selected from: -COO [CX2] n1CX3 or -OCO [CX2] n1CX3 where each X is independently selected from hydrogen, a branched or straight chain C 1-6 alkyl or haloalkyl, or aryl optionally substituted by halogen; and n1 is an integer from 1 to 27; and wherein the cross-linking reagent comprises two or more unsaturated bonds that are attached by means of one or more connecting moieties and has a boiling point at standard pressure of less than 500 ° C. 公开号:BE1023998B1 申请号:E2016/5424 申请日:2016-06-08 公开日:2017-10-26 发明作者:Stephen Coulson；Delwyn Evans；Angeliki Siokou；Clive Telford 申请人:P2I Ltd； IPC主号:
专利说明:
Coatings FIELD OF THE INVENTION This invention relates to protective coatings. In particular, the present invention relates to protective coatings for electronic or electrical devices and components thereof, and to methods for forming such coatings. The coatings can protect because they are hydrophobic and therefore prevent the entry of water-based liquids into electronic devices, or they can protect because they form a barrier coating and therefore provide an electrical resistance between the electrical parts of the telephone and water-based liquids. BACKGROUND OF THE INVENTION Monounsaturated monomers are used to produce barrier coatings using plasma polymerization processes (see pending patent application). The perfluoroalkyl chain monomers are also used to form hydrophobic surfaces by pulsed plasma deposition processes (see WO 9858117 A1). The ability of the polymerization initiated by the plasma influences the nature of the polymer prepared. The higher average energy supplies from plasmas with a continuous wave lead to more fragmentation of the monomer, and therefore the polymer loses structural properties of the monomer. In the case of 1 H, 1 H, 2 H, 2 H perfluorocyl acrylate (PFAC8), less of the perfluoroalkyl chain is retained and the contact angle of the surface coating is compromised. Higher plasma energies also lead to more cross-linking. For the lower average energy supplies from pulsed plasmas, there is better retention of monomer structure and less cross-linking. The greater retention of the perfluorinated chain under conditions of lower energy with pulsed plasma leads to the best levels of contact angles for the surface coating. If the perfluoroalkyl chains have eight or more fluorinated carbon atoms (long chain), the polymer prepared from the monomer has a crystalline structure. If the perfluoroalkyl chains have fewer than eight fluorinated carbon atoms, the resulting polymer is amorphous and may therefore be unstable in the presence of water (see "Molecular Aggregation Structure and Surface Properties or Poly (fluoroalkyl acrylate) Thin Films, Macromolecules, 2005, vol. 38, pp. 5699-5705). If long chain perfluoroalkyl polymers are produced by high medium power (continuous wave or CW) or low average power (pulsed wave or PW) plasmas, due to the crystalline structure of the long chains, the polymers do not feel sticky and they are stable in the presence of water. However, the feel and water stability of coatings of short-chain polymers is influenced by the plasma powers used. For example, if PFAC6 (1H, 1H, 2H, 2H-perfluorooctyl acrylate) is polymerized under low-power plasma conditions, the resulting polymer coating can have several drawbacks. The coating may, for example, cause water droplets to spread a little (settle), which may be characterized by the presence of a water droplet on its surface, may feel sticky or may be easily spread out (for example on substrates of silicon wafers and ABS plastic). By increasing the capacity of the plasma used for the polymerization, the polymer becomes more cross-linked and becomes more resistant to smearing. However, increasing the power has the simultaneous effect of lowering the contact angle for water through more monomer fragmentation (as described above). Figure 1 shows the effect of increasing the ratio between power and flow rate of the CW plasma monomer in a 125-liter chamber: at a speed of 4 W / pl / min, the contact angle for water is ~ 85-95 degrees and the coating is non-sticky. However, as the speed decreases, the contact angle increases and the appearance of sticky / greasy coatings also increases. Figure 2 shows the same effect for pulsed plasma conditions. These results demonstrate that the workspace for the production of non-sticky and non-greasy coatings has a limited variation in plasma process and that the final coating has a non-optimum contact angle for water. Therefore, it is an object of the invention to solve one or more of the aforementioned problems that occur with prior art coatings. Description of the invention An aspect of the present invention provides an electronic or electrical device or component thereof, comprising a protective cross-linked polymer coating on a surface of the electronic or electrical device or component thereof; wherein the protective crosslinked polymeric coating can be obtained by exposing the electronic or electrical device or component thereof for a period of time long enough to allow formation of the protective crosslinked polymeric coating on a surface thereof to a plasma comprising a monomer compound and a crosslinking reagent, wherein the monomer compound has the following formula: wherein Fb, R2 and R4 are all independently selected from hydrogen, optionally substituted branched or straight chained CVCe alkyl or haloalkyl, or aryl optionally substituted by halogen, and R3 is selected from: wherein each X is independently selected from hydrogen, a halogen, optionally substituted C 1 -C 6 alkyl or haloalkyl with a branched or straight chain, or aryl optionally substituted by halogen; and n 1 is an integer from 1 to 27; and wherein the cross-linking reagent comprises two or more unsaturated bonds that are attached by means of one or more connecting moieties, and has a boiling point at standard pressure of less than 500 ° C. High levels of polymer cross-linking (previously only feasible with high-power continuous wave plasmas) can be achieved by adding a cross-linking molecule to the monomer to obtain a cross-linked copolymer. This has the advantage of increasing the variation in plasma action so that stable coatings can now be produced under conditions with a pulsed low-energy plasma. The high degree of retention of the hydrophobic monomer structures at the low energy pulsed plasma gives coatings of the copolymer a good hydrophobic coating (as proven by contact angles for water) and gives a coating that does not feel sticky or greasy. Thus, these properties make it suitable for the coating of electronic devices to prevent water-based liquids from entering due to accidental damage. Such coatings generally have a thickness of 1 to 100 nm, preferably of 1 to 50 nm. The coating can be described as a liquid-repellent layer, generally a water-repellent layer. The coating can repel water, an aqueous liquid such as rainwater, or oil. Alternatively or additionally, the coating to form a liquid-repellent layer may be a physical barrier layer. The coating can form a physical barrier, i.e. the coating provides a physical barrier for mass and electron transport. The physical barrier layer limits diffusion of water, oxygen and ions. If the coating is a physical barrier, it generally has a thickness of more than 50 nm. The coating is a protective layer, i.e. the coating prevents damage due to contact with water or other liquids. The coating can provide protective functionality by forming a liquid-repellent layer and / or a physical barrier layer. The coating is preferably essentially free of holes so that it can form a physical barrier. Preferably, ΔΖ / d is <0.15, where ΔΖ is the average height variation with an AFM line scan in nm (as shown in Figure 3) and d is the thickness of the coating in nm. The value of ΔΖ / d shows us to what extent defects / open spaces on the surface of the coating extend into the coating, i.e. the depth of the defect as a percentage of the total coating thickness. For example, ΔΖ / d = 0.15 means that the open spaces on the surface only extend downwards to 15% of the coating thickness. A coating with a ΔΖ / d <0.15 is described in this patent as substantially free of holes. If the open spaces are larger than this, it is unlikely that the desired functionality will be achieved. The coating is preferably form-following, which means that it takes on the 3D shape of the electronic or electrical device or component thereof, and substantially covers an entire surface of the device. This has the advantage that it is ensured that the coating has a sufficiently large thickness to provide optimum functionality over a full surface of the device or component. The meaning of the term "essentially covers an entire surface" depends to some extent on the type of surface to be covered. For some components, for example, it may be necessary to completely cover the surface to allow the component to function after immersion in water. However, for other components or housings, minor breaks in the coating can be tolerated. The coating can have a thickness of 50 to 10000 nm, optionally from 50 to 8000 nm, 100 to 5000 nm, preferably from 250 nm to 5000 nm, most preferably from 250 nm to 2000 nm. The coating can be electrically insulating and sufficiently flexible to ensure that electrical connectors can be coupled to an electronic or electrical device or component thereof and an electrical connection is made between the electrical connectors g / l and the electronic or electrical device or component without first having to remove the coating. In that case, the force exerted on the coating by the electrical connector is sufficient to change the structure or even to break through the coating at the location of the electrical connector, which makes it possible to make a connection. Electrical connectors can generally be connected in this way to the electronic or electrical device or component for coating thicknesses below 5000 nm, and for coatings with high performance of less than 2000 nm. The electronic or electrical device or component thereof is generally resistant to immersion in up to 1m of water for more than 30 minutes without any error or corrosion occurring while power is being supplied to the electronic or electrical device or component. The effectiveness of the coating can be determined by measuring its electrical resistance at a fixed voltage if it is immersed in water for a certain period of time; for example, by applying an electrical voltage of 8V over the coating of a device that is immersed in water for 13 minutes. Coatings with a resistance value of 1x107 Ohm or higher are effective barrier coatings in this test, and the coated electronic or electrical device or component thereof will pass an IPX7 test successfully. The IPX7 test is the entry protection test, which classifies and classifies the degree of protection against water that is obtained. In the IPX7 test for telephones, the device is immersed in water under specified conditions of pressure and time for a period of 30 minutes (up to 1 m immersion). The device must be switched on during the test and must continue to function after 24 hours. In one embodiment, the coating is electrically insulating and its thickness is less than 1 micron, a force of 5 to 20 g applied to the coating using a round probe with a diameter of 1 mm makes it possible make an electrical connection to an electronic or electrical device or component thereof in the local area where the force was applied. In another embodiment, the coating is electrically insulating and its thickness is 1-2.5 microns, with a force of 20-100 g applied to the coating by using a round probe with a diameter of 1 mm, makes it possible to make an electrical connection to an electronic or electrical device or component thereof in the local area where the force has been applied. The coating may have a higher density than that of the corresponding monomer from which the coating is formed. The increase in density may, for example, be at least 0.1 g / cm 3. The increase in density is explained by the highly cross-linked coating. The high density of the coating improves the barrier properties of the coating. The coating can form a surface that is fixed by a static water contact angle (WCA) of at least 70 °. A coating with a WCA of at least 90 ° is a liquid-repellent, generally a water-repellent, layer. For fluorinated polymers, the coating can have a static contact angle for water of at least 100 °. The contact angle for a liquid on a solid substrate gives an indication of the surface energy which in turn illustrates the liquid repellency of the substrate. Contact angles were measured on a VCA Optima contact angle analyzer, by using droplets of deionized water of 3 µl at room temperature. Cross-linking agent A basic requirement for the crosslinking reagent is the presence of two or more unsaturated bonds, for example -C = C or alkyl groups. The unsaturated bonds are attached by means of one or more connecting residues. As long as it connects the two or more unsaturated bonds, no special restrictions are imposed on the binding remainder. The crosslinking reagent should have a boiling point at standard pressure of less than 500 ° C, preferably from -10 to 300 ° C, optionally from 180 to 270 ° C, most preferably from 205 to 260 ° C. It is preferred, but not required, that the crosslinking reagent is not excessively hazardous when used with plasma processing, that is, it can be used in a production environment in which low levels of vapor do not present significant problems with the cause health and safety (eg, strong oxidizing, explosive, toxic, or possessing an unpleasant odor (eg, smelly reagent)). The cross-linking reagent preferably has one of the following structures: wherein Y1; Y2, Y3, Y4, Y5, ββ> Y7 and Y8 are all independently selected from hydrogen, optionally substituted cyclic C 1-6 alkyl with a branched or straight chain, or aryl; and wherein L is a connecting moiety. Most preferably, L has the following formula: wherein each Y9 is independently selected from a bond, -O-, -OC (O) -, -C (O) -0-, -YirO-C (O) -, -C (O) -0-Yn-, -OYir and -YnO-, wherein Yn is an optionally substituted cyclic or straight chained C 1 -C 6 alkylene; and Y 10 is selected from optionally substituted cyclic C 1 -C 8 alkylene with a branched or straight chain, and a siloxane-containing group. In a very highly preferred embodiment, Y10 has the following formula: wherein each Y12 and Y13 is independently selected from branched or straight chained H, halogen, optionally substituted cyclic CVC8 alkyl, or -OY14, wherein Y14 is selected from optionally substituted branched or straight chained C1 -C6 alkyl, or alkenyl, and n is an integer from 1 to 10. Optionally, each Y12 is H and each Y13 is H, i.e., Y10 is a linear alkylene chain. In this embodiment, Y9 is preferably a vinyl ester or vinyl ether group. Optionally, each Y12 is fluorine and every Y13 is fluorine, i.e., Y10 is a linear perfluoroalkylene chain. In general, n is 4 to 6. In another embodiment, Y10 has the following formula: wherein each Y15 is independently selected from optionally substituted branched or straight chain C 1 -C 6 alkyl. In one embodiment, each Y15 is methyl and each Y9 is a bond. In another embodiment, Y10 has the following formula: (vi) wherein Y16 to Y19 are both independently selected from H and optionally substituted C 1-8 alkyl or alkenyl with a branched or straight chain. A preferred alkenyl group is vinyl. Optionally, Y18 is H or vinyl, and Y16, Y17, and Y- 9 are all H. In one embodiment, each of the groups Y16 to Y19 is H. In another embodiment, Y18 is vinyl, and Y16, Y17, and Y19 are all H . In preferred embodiments for compound (i), L has one of the following structures: In another embodiment of compound (i), L has one of the following structures: For L according to structure (vii), Y10 is preferably an alkylene chain or a cycloalkylene, such as those represented by structures iv) and vi) above. The alkylene chain can be a straight alkylene chain. If Y10 is a cycloalkylene, cyclohexylene is preferred, with 1,4-cyclohexylene being most preferred. For L according to structure (viii), Y10 is preferably structure (iv), i.e. an alkylene or fluoroalkylene chain. For L according to structure (ix), Y10 is preferably cycloalkylene, such as the cyclohexylene according to structure (vi). For L according to structure (x), Y10 is preferably structure (iv), wherein each Y12 and Y13 is F, i.e., a perfluoroalkylene chain. For L according to structure (xi) or structure (xii), Y10 is preferably alkylene or cycloalkylene. Optionally, the alkylene or cycloalkylene may be substituted with one or more vinyl groups or alkenyl ether groups, preferably one or more vinyl ether groups. If each Y9 is a bond, each Y10 can be one of the structures (iv), (v) and (vi). Preferably, Y10 is a straight chain alkylene such that the cross-linking reagent is a diene such as a heptadiene, octadiene or nonadiene, most preferably 1,7-octadiene. If each Y 9 is O, each Y 10 is preferably a branched or straight chain C 6 -C 6 alkylene, preferably straight chain alkylene, most preferably a straight chain C 4 alkylene, ie the crosslinking reagent 1,4-butanediol divinyl ether. It will be appreciated that any group Y9 can be combined with any other group Y9 and with group Y10 to form the cross-linking reagent. A person skilled in the art will be aware of the possible substituents of each of the above-mentioned cyclic CrC8 alkylene groups with a branched or straight chain. The alkylene groups may be substituted at one or more locations by a suitable chemical group. Halogen substituents are preferred, with fluorine substituents being most preferred. Each C 8 -C 8 alkylene group can be a C 1 -C 8, C 2 -C 8, or C 5 -C 8 alkylene group. Particularly preferred embodiments of the crosslinking agent have alkyl chains for Y10 and vinyl ester or vinyl ether groups on either side. A particularly preferred cross-linking reagent is divinyl adipate (a divinyl ester). Another preferred cross-linking reagent is 1,4-butanediol divinyl ether (a divinyl ether). For the most preferred embodiments, the cross-linking reagent is selected from divinyl adipate (DVA), 1,4-butane diol divinyl ether (BDVE), 1,4-cyclohexane dimethanol divinyl ether (CDDE), 1,7-octadiene (170D), 1,2 , 4-trivinylcyclohexane (TVCH), 1,3-divinyltetramethyldisiloxane (DVTMDS), diallyl-1,4-cyclohexanedicarboxylate (DCHD), 1,6-divinyl perfluorhexane (DVPFH), 1H, 1H, 6H, 6H-perfluorhexanedioldiodioldDADADA (FD) glyoxal bis (diallyl acetal) (GBDA). For the alkyn crosslinking reagents of compound (ii), L is preferably selected from a branched or straight chain C 1 -C 8 alkylene or an ether group. L can be a C3, C4, C5 or C6 alkylene, preferably a straight chain alkylene. Particularly preferred chemical structures for the cross-linking reagents are shown in Table 1 below: Table 1 Monomer compound The monomer compound has the following formula: wherein R 1, R 2 and R 4 are each independently selected from hydrogen, optionally substituted branched or straight chain C 1 -C 6 alkyl or haloalkyl, or aryl optionally substituted by halogen, and R 3 is selected from: wherein each X is independently selected from hydrogen, a halogen, optionally substituted CV, C6 alkyl or haloalkyl with a branched or straight chain, or aryl optionally substituted by halogen; and ^ is an integer from 1 to 27. Preferably, n is 1 to 12. Optionally, ni is 4 to 12, optionally 6 to 8. In a preferred embodiment, R 3 is selected from: wherein m is an integer from 0 to 13 and each X is independently selected from hydrogen, a halogen, optionally substituted CVCV alkyl or branched or straight chain haloalkyl, or aryl optionally substituted by halogen; and m2 is an integer from 2 to 14; In a particularly preferred embodiment, the monomer is a compound of formula 1 (a): 1 (a) wherein each Fh, R2, R4, and R5 to R10 is independently selected from hydrogen or an optionally substituted branched or straight chain CVC8 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1; or the monomer is a compound of formula 1 (b): 1 (b) wherein each R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or an optionally substituted branched or straight chain C 1 -C 6 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1. The halogen can be chlorine or bromine, but in order to comply with the RoHS (Restriction of Hazardous Substances) regulations, it is preferably fluorine. a is 0 to 10, preferably 0 to 6, optionally 2 to 4, most preferably 0 or 1. b is 2 to 14, optionally 2 to 10, preferably 3 to 7. Each R 1, R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or a branched or straight chain C 1 -C 6 alkyl group. The alkyl group can be substituted or unsubstituted, saturated or unsaturated. If the alkyl group is substituted, provided that the polymer obtained provides a suitable liquid-repellent layer and / or barrier layer, no particular restrictions are placed on the location of the substituent or the type of substituent. The person skilled in the art is aware of which Substituents are suitable. When the alkyl group is substituted, a preferred substituent is halogen, i.e., one of the R 1 groups; R 2, R 4, and R 5 to R 10 may be haloalkyl, preferably fluoroalkyl. Other possible substituents may be hydroxyl or amine groups. If the alkyl group is unsaturated, it may comprise one or more olefin or alkyl group. Each Rt, R2, R4 and R5 to R10 can be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, n-hexyl , isohexyl and 3-methyl pentyl. In a preferred embodiment, each R 1, R 2, R 4 and R 5 to R 10 is independently selected from hydrogen or methyl. In a preferred embodiment, a and c are each independently 0 or 1; and b is 3 to 7. In one preferred embodiment, each X is H. In another preferred embodiment, each X is F. Optionally, R 1 and R 2 are both hydrogen. Optionally, R 4 is hydrogen or methyl. Preferably, Fh and R2 are both hydrogen and R4 is hydrogen or methyl. Optionally, R9 is hydrogen and R10 is a branched or straight chain C 1 -C 6 alkyl group. In a preferred embodiment, R10 is methyl. In one embodiment, each R5 to R8 is hydrogen. In one embodiment, each R 1, R 2, R 4, and R 5 to R 10 is hydrogen, each X is H, a = 0 and c = 0. In a particularly preferred embodiment, the monomer compound has the following formula: wherein n is 2 to 10. In another preferred embodiment, the monomer compound has the following formula: wherein n is 2 to 10. The monomer compound can be selected from 1H, 1H, 2H, 2H-perfluorohexyl acrylate (PFAC4), 1H, 1H, 2H, 2H-perfluorooctyl acrylate (PFAC6), 1H, 1H, 2H, 2H-perfluorocyl acrylate (PFAC8) and 1H, 1H, 2H 1 H perfluorododecyl acrylate (PFAC10). The monomer compound can be selected from 1H, 1H, 2H, 2H-pefluorohexyl methacrylate (PFMAC4), 1H, 1H, 2H, 2H-perfluorooctyl methacrylate (PFMAC6) and 1H, 1H, 2H, 2H-perfluorodecyl methacrylate (PFMAC8). The monomer compound of formula I (a) can have the following formula: wherein a and c are both independently 0 or 1, b = 3-7 and n is 4 to 10, where n = a + b + c + 1. The monomer compound of formula I (a) can have the following formula: wherein n is 2 to 12. The monomer compound can be selected from ethyl hexyl acrylate, hexyl acrylate, decyl acrylate, lauryl dodecyl acrylate and isodecyl acrylate. The monomer can have the following formula: wherein n is 4 to 14. The monomer can have the following formula: wherein n is 4 to 14. In an additional aspect, the present invention provides a method for treating an electronic device or component thereof comprising: for a period of time sufficient to form a protective cross-linked polymer coating on a surface of the electronic or electrical device or component make it possible to expose the electronic or electrical device or component thereof to a plasma comprising a monomer compound and a cross-linking reagent; wherein the monomer compound has the following formula: wherein R1; R 2 and R 4 are each independently selected from hydrogen, optionally substituted alkyl or haloalkyl with a branched or straight chain, or aryl optionally substituted by halogen, and R 3 is selected from: wherein each X is independently selected from hydrogen, optionally substituted branched or straight chain C 1 -C 6 alkyl or haloalkyl, or aryl optionally substituted by halogen; and isί is an integer from 1 to 27; and wherein the cross-linking reagent comprises two or more unsaturated bonds, and has a boiling point at standard pressure of less than 500 ° C. The monomer compound and the crosslinking reagent used in the process are described in more detail above. In general, the electronic or electrical device or component thereof is placed in a plasma deposition chamber, a glow discharge is ignited in this chamber and an electrical voltage is applied in the form of a pulsed field. Preferably, the applied electrical voltage is a voltage at a power of 30 to 800 W. Optionally, the voltage is pulsed in a sequence in which the ratio of the on period / off period is in the range of 0.001 to 1, optionally in the range of 0.002 to 0.5. The on period can be, for example, 10-500 ps, preferably 35-45 ps or 30-40 ps, such as about 36 ps, and the off period can be 0.1 to 30 ms, preferably 0.1 to 20 ms ms, optionally 5 to 15 ms, for example 6 ms. The on period can be 35 ps, 40 ps, 45 ps. The off period can be 0.1, 1.2, 3, 6, 8, 10, 15, 20, 25 or 30 ms. The term pulsed may mean that the plasma moves back and forth between a state of no (or essentially no) plasma emission (off state) and a state where a certain amount of plasma is emitted (on state). Alternatively, pulsed means that there is a continuous plasma emission, but that the amount of plasma moves back and forth between an upper limit (on-state) and a lower limit (off-state). In another embodiment, the invention relies on a method of forming a coating on an electronic or electrical device or component thereof as further described above, which method comprises: for a period of time long enough to prevent the formation of a protective polymer coating. enabling the substrate, in a chamber, to expose the substrate to a plasma, preferably a continuous plasma, comprising a monomer compound, wherein during the exposure of the substrate the continuous plasma has a power density of at least 2W / liter, preferably 20W / liter. Optionally, the electrical voltage is applied for a period of time from 30 seconds to 90 minutes in the form of a pulsed field. Optionally the electrical voltage is applied for 5 to 60 minutes in the form of a pulsed field. Optionally, in a preliminary step, a plasma with continuous power is applied over the electronic or electrical device or component thereof. The preliminary step can be carried out in the presence of an inert gas. Before the cross-linking agent and / or the monomer compound enter the deposition chamber, they can both be in the form of a gas, a liquid or a solid (e.g. a powder) at room temperature. However, it is preferred that the crosslinking reagent and the monomer compound are both liquid at room temperature, and it is most preferred that the monomer and crosslinking agent liquids are miscible. The monomer compound and / or the crosslinking agent are suitably in a gas state in the plasma. The plasma can simply comprise a vapor of the monomer compound and the cross-linking agent. Such a vapor can be formed in situ, the compounds being introduced into the chamber in liquid form. The monomer can also be combined with a carrier gas, in particular with an inert gas such as helium or argon. In preferred embodiments, the monomer and / or cross-linking agent may be introduced into the chamber by means of an aerosol device such as a nebulizer or the like, such as, for example, described in detail in WO2003 / 097245 and WO03 / 101621, the contents of which are by reference. is included in this patent. With such an arrangement, it may happen that a carrier gas is not required, which is advantageously helpful in achieving high gas speeds. In one embodiment, the monomer compound and / or the crosslinking reagent are in the gas form and, depending on the chamber volume, while the pulsed electrical voltage is applied, are introduced into the plasma at a rate of 10-5000 mg / minute. Optionally, the plasma is created with an average power of 0.001 to 40 W / liter. The cross-linking agent can be miscible with the monomer and therefore be introduced into the plasma chamber together or separately. Or, the cross-linking agent may be immiscible with the monomer and passed into the plasma chamber separately. In this context, the term "miscible" means that the cross-linking agent is soluble in the monomer, and that a solution with a uniform composition is formed upon mixing. The term "immiscible" is used to indicate that the cross-linking agent is only partially soluble or insoluble in the monomer, and therefore forms an emulsion or disintegrates into two layers. Depending on the specific crosslinking agent, the crosslinking reagent is preferably present in an amount of 10 to 60 (vol./vol.)%, optionally 20 to 40 (vol./vol.)%, optionally 25 to 30 (vol. /vol.)%, possibly 30 to 50 (vol./vol.)%, of the total volume of monomer compound and crosslinking reagent. It will be apparent to those skilled in the art that the amount varies to some extent depending on whether the coating is required to be fluid-repellent or that the coating forms a barrier to the transport of mass and electrons. It will be apparent to those skilled in the art that the (vol./vol.) percentages are those that give a stable cross-linked polymer coating and the highest contact angle for water. Electronic or electrical device or component thereof Although the invention is useful in conjunction with a wide variety of substrates, the substrate can be advantageously an electronic substrate in all aspects of the invention. In a number of embodiments of the invention, the electronic substrate may comprise an electronic or electrical device, i.e., any part of electrical or electronic equipment. Non-limiting examples of electrical and electronic devices include means of communication such as mobile telephones, smartphones and beeps, radios, and sound and audio systems such as speakers, microphones, ringtones or buzzers, hearing aids, personal audio equipment such as personal CD, cassette or MP3 players, televisions, DVD players including portable DVD players, video recorders, digital and other tuning units such as a Sky box, computers and related components such as laptop, notebook, tablet, telephone or handheld computers, personal digital assistants (PDAs), keyboards or instruments, game computers, in particular portable play stations and the like, data storage devices, outdoor lighting or outdoor antenna systems, and other forms of communication equipment. In preferred embodiments of the invention, the substrate may comprise or consist of an electronic component, e.g. a printed circuit board (PCB), a series of printed circuit boards (PCBA), a transistor, resistor or semiconductor chip. The electronic component can thus be an internal component of an electronic device, e.g. be a cell phone. The coatings of the invention are particularly valuable in preventing electrochemical migration into such components. In all aspects of the invention, the precise conditions under which the protective polymeric coating is effectively formed depend on factors such as, but not limited to, the nature of the monomer compound, the crosslinking reagent, the substrate, and also the desired properties of the coating. These conditions can be determined by routine methods or, preferably, by using the techniques and preferred features of the invention described in this patent which operate in particular synergy with the invention. The present invention will now be further described with reference to the following non-limiting examples and the accompanying illustrative drawings, wherein: Figure 1 illustrates the effect of increasing the ratio between power and flow rate of the CW plasma monomer in a 3-liter chamber in a prior art method. Figure 2 shows the same effect for conditions of a pulsed plasma. Figure 3 shows an image of a manner of touching over a 10x10 pm2 field of view of an example specimen (thickness d = 1230 nm) made according to example 1 (left side), and shows a graph with contour lines showing the data used for calculating RMS roughness (right side). The ΔΖ value indicated on the graph is taken over an area of the graph that represents most of the coating. Peaks above the ΔΖ area indicate large particles and troughs that fall below the ΔΖ area show open spaces or holes in the coating. The width of the peaks also gives an indication of the particle size. Figure 4 illustrates the effect of adding the cross-linking agent divinyl adipate to perfluorooctyl acrylate on the contact angle for water in a process in a 125-liter chamber. Figure 5 shows the effect of adding cross-linking agents according to the invention on the electrical resistance per nm of the coatings. Figure 6 shows an image of a manner of touching a 90 nm thick coating made as described in Example 3, over a field of view of 2x2 pm2 (top left), a representative contour line showing the variation in height (z- axis) of the coating (top right), and shows a phase image that indicates a complete substrate coating (bottom left); RMS roughness of the coating is 1.65 nm and Δz / d = 0.05. Figure 7 shows an FTIR / ATR spectrum of a coating formed according to Example 5. Example 1 Example of plasma polymerization of PFAC6 without cross-linking agent in a 3 liter chamber Polymerization was carried out in a 3 liter glass chamber of PFAC6 using a continuous plasma process. In the experimental model form, the continuous plasma was produced by using RF power levels of 50, 100 and 200 watts. The process pressure was set at 30, 60 and 90 mTorr and the flow rate of the monomer was set at 50, 100 and 200 microliters of liquid per minute. The duration of the process was 10 or 40 minutes. The coated substrate was a silicon wafer, and whether the coating was sticky or not was determined by wiping the substrate with a finger and visually determining whether the coating had released greasiness. The results in Figure 1 indicate that for lower CW powers the coating could easily become greasy (ie sticky), but that by increasing the ratio between power and flow rate, the coating became resistant to the release of greasy (ie non-sticky) ), which was to be expected due to the additional cross-linking caused by more monomer fragmentation. It was also observed that the contact angle for water decreased with increasing the ratio between power and flow rate, and this also indicates that more power increases the level of monomer fragmentation. The same 3 liter chamber was used to also look at the effect of the power-to-flow ratios with pulsed plasma polymerization. In these experiments, the peak power was 250 or 500 W. The RF power supply was pulsed with an on period of 35 microseconds and off periods of 5.5 and 1 millisecond. The process pressure was 20, 35, 60 or 80 mTorr. The flow rate of the monomer was 50 or 200 microliters of liquid per minute. Figure 2 shows that low power conditions relative to flow rate can generate coatings that can become greasy (sticky), and that greasiness could be reduced only by increasing the power. This also meant a simultaneous decrease in the contact angle for water. The results of Figures 1 and 2 show that plasma processing of PFAC6 alone leads to non-greasy coatings if the powers are high enough to reduce the other desirable property of the water contact angle. This illustrates the need to add a cross-linking agent to prevent the coating from becoming greasy, and to maintain the contact angle for water. Example 2 Examples of the copolymerization of perfluoroalkyl acrylate with crosslinking agent to show improvements in electrical resistance Perfluorooctyl acrylate monomer was mixed with a single cross-linking agent from the following list: VINYLESTERS: divinyl adipate (DVA) VINYLETHERS: 1,4-butanediol diol vinyl ether (BDVE); 1,4-cyclohexanedimethanol divinyl ether (CDDE) D1 or TRIVINYLEN: 1,7-octadiene (1,7-OD); 1,2,4-trivinylcyclohexane (TVCH); DIVINYL with alkyl fluorine group: 1,6-divinyl perfluorohexane (DVPFH) DIVINYL with silicon group: 1,3-divinyltetramethyldisiloxane (DVTMDS) DIVINYL with cyclic ring and carboxylate groups: diallyl-1,4-cyclohexanedicarboxylate (DCHC, 1 HAT, HAT, 1 HAT, HAT, 1 HAT, HAT, 1 HAT, HAT, 1HAT, 1 HAT, HAT, 1 H , 6H-perfluorohexanediol diacrylate (PFHDA) The cross-linking agent was mixed with the PFAC6 as a volume percentage, in the following percentages: 20, 40.60, 80 and 100%. Plasma-initiated polymerization reactions were conducted in a 3-liter glass plasma chamber. The substrates were printed circuit boards to be tested. The PFAC6 / cross-linking agent mixture was introduced at a rate of 0.04 - 0.06 μΙ / min and the process pressure was 40 mTorr. The process plasma consisted of a 1-minute continuous plasma (CW) step of 50W, followed by a 10-20-minute step of pulsed plasma (PW) of 50W and an RF power supplied by a sequence of pulses with a duty cycle of 6.9%. The coated printed circuit boards were immersed in tap water and an electrical voltage of 8V was applied for 13 minutes. The final amperage readings were used together with the coating thickness measurements to calculate the electrical resistance per nm coating. Figure 5 below shows the effect of adding a variety of cross-linking agents on the electrical resistance per nm of the barrier coatings. Figure 5 clearly shows the improvement of the resistance that can be obtained by adding the cross-linking agent to the PFAC6 monomer. In addition, all tested cross-linking agents with concentration levels of 20% and above gave non-greasy / non-sticky coatings, except DVTMDS, DCHD, PFHDA and DVPFH that were non-greasy at levels of 40% and above. Example 3 Example of the concentration of the crosslinking agent on a water-repellent coating Water-repellent coatings were prepared in a room with a volume of 125 liters by using PFAC6 with different levels of divinyl adipate (DVA), and using helium as carrier gas. The deposition process consisted of a 3-minute CW step with a power of 300 W and a pulsed step with a power of 150 W and a duty cycle of the RF pulse of 0.018%. Silicon wafers were used as test substrates and the contact angle of the coated wafer was determined by applying a drop of 3µΙ deionized water to the coated wafer and measuring the contact angle using a VCA Optima (AST Products) with image analysis software. The variation of contact angle with (vol./vol.)% DVA crosslinking agent is shown in Figure 4. It was also noted that for the DVA concentration of 10 (vol./vol.)% The water droplet where its perimeter was located left a mark on the coated slab. This indicated that a higher level of cross-linking agent was needed to give a more stable coating. These observations, in combination with the results of Figure 4, suggest an optimum range of 20-40 (vol./vol.)% DVA cross-linking agent, although this can probably vary, generally within the range of 10-60 (vol.) ./vol.)%, for different monomers and cross-linking agents and different room sizes. Pulsed plasma polymerization of perfluoroalkyl acrylate was carried out in a 125 liter chamber in the presence of divinyl adipate (DVA). Figure 4 shows the effects of adding different percentages of liquid volume DVA cross-linking agent to perfluorooctyl acrylate on the contact angle for water on silicon wafer substrate. Example 4 Example of an AFM measurement of a monomer / crosslinker and copolymer coating In a room with a volume of 22 liters, a barrier-like coating was prepared using PFAC6 with 10% DVA. The deposition process consisted of a 1 minute CW step with a ratio of CW power to flow rate of 3.9 (W / microliter / min), and a pulsed step with a PW power / flow rate ratio of the monomer of 0, 28 (W / microliter / min). Figure 6 shows the representative topographic and phase contrast images that were obtained from all samples. Images with a high spatial resolution mainly show the structures of areas between the raised features. The RMS roughness of the coating is 1.65 nm and the Δζ / d = 0.05. If the Δζ / d value is <0.15, this indicates that the physical layer is essentially free of holes. Example 5 Example of an FTIR / ATR determination of a monomer / cross-linking agent and copolymer coating In a chamber with a volume of 22 liters, two barrier-like coatings were prepared using only PFAC6 and PFAC6 with 10% DVA as described in Example 4. The deposition process consisted of a 1 minute CW step with a CW ratio. flow rate of 3.9 (W / microliter / min), and a pulsed step with a PW power / flow rate ratio of the monomer of 0.28 (W / microliter / min). Figure 7 shows the representative FTIR / ATR spectrum obtained from both samples. The FTIR / ATR intensity ratios of peaks attributed to the stretch mode of CF3 and C = 0 groups, CF3 / C = 0, of the coating indicate sufficient crosslinking in the coating to form a physical barrier. CF3 refers to the end groups in the side chain of PFAC6. It is believed that the formation of the barrier coatings is caused by a mixture of cross-linking and controlled fragmentation of the monomers during the polymerization. It is believed that cross-linking occurs predominantly via the CF2-CF3 chain, while fragmentation is believed to occur predominantly by losing the C = O group during the polymerization, and to a lesser extent by shortening the CF2- chain. Cross-linking affects the rate of occurrence of -CF3 groups in the coating, and the controlled fragmentation controls the amount of C = 0 groups in the coating. The ratio of these two functional groups is an indication that sufficient cross-linking and fragmentation has taken place, and the ratio can be determined from the ratio of the intensities of the corresponding FTIR / ATR peaks. Coatings with reduced ratios CF3 / C = 0 have been shown to give higher resistance values in the electrical test, as described in Example 2, where improved coating performance with increased crosslinking (for CF3) and fragmentation (for C = 0) is observed . If the FTIR / ATR intensity ratio of the peaks attributed to the stretching of -CF3 and the stretching of C = 0, CF3 / C = 0, is less than 0.6 "" n '(where n = 6 for PFAC6), the resistance of the coating in the electrical test is expected to be higher than 8 MOhm. The intensity ratio of the peak CF3 / C = 0, the coating thickness and the final current readings during the electrical test are shown in Table 2: Table 2
权利要求:
Claims (91) [1] Conclusions An electronic or electrical device or component thereof comprising a protective cross-linked polymeric coating on a surface of the electronic or electrical device or component thereof; wherein the protective crosslinked polymeric coating can be obtained by exposing the electronic or electrical device or component thereof for a period of time long enough to allow formation of the protective crosslinked polymeric coating on a surface thereof to a plasma comprising a monomer compound and a cross-linking reagent, wherein the monomer compound has the following formula: wherein F 1, R 2 and R 4 are each independently selected from hydrogen, optionally substituted branched or straight chain C 1 -C 6 alkyl or haloalkyl, or aryl optionally substituted by halogen, and R 3 is selected from: wherein each X is independently selected from hydrogen, a halogen, optionally substituted C 1 -C 6 alkyl or haloalkyl with a branched or straight chain, or aryl optionally substituted by halogen; and n 1 is an integer from 1 to 27; and wherein the cross-linking reagent comprises two or more unsaturated bonds that are attached by means of one or more connecting moieties, and has a boiling point at standard pressure of less than 500 ° C. [2] The electronic or electrical device or component thereof according to claim 1, wherein the protective crosslinked polymeric coating forms a physical barrier to mass and electron transport. [3] The electronic or electrical device or component thereof according to claim 1 or claim 2, wherein the protective cross-linked polymeric coating forms a liquid-repellent surface with a static water contact angle (WCA) of at least 90 °. [4] The electronic or electrical device or component thereof according to any of the preceding claims, wherein the cross-linking reagent has one of the following structures: wherein Y1; Y2, Y3, Y4, Y5, Y6, Y7 and Y8 are all independently selected from hydrogen, optionally substituted cyclic branched or straight chained C 1-6 alkyl, or aryl; and wherein L is a connecting moiety. [5] The electronic or electrical device or component thereof according to claim 4, wherein for compound (i) L has the following formula: wherein each Y9 is independently selected from, a bond, -O-, -OC (O) -, -C (O) -0-, -Y ^ -OC ^ O) -, -CiOj-O-Yn-, - O yir, and -Yn O-, wherein Y 4 is an optionally substituted cyclic or straight chained C 3 -C 8 alkylene; and Y10 is selected from optionally substituted cyclic C1 -C8 alkylene with a branched or straight chain, and a siloxane-containing group. [6] The electronic or electrical device or component thereof according to claim 5, wherein for connection (i) L has one of the following structures: [7] The electronic or electrical device or component thereof according to claim 5, wherein for connection (i) L has one of the following structures: [8] The electronic or electrical device or component thereof according to any of claims 5 to 7, wherein Y10 has the following formula: wherein each Y 12 and Y 13 is independently selected from H, halogen, optionally substituted cyclic C 1 -C 8 alkyl with a branched or straight chain, or -OY 14, wherein Y 14 is selected from optionally substituted CVCV alkyl or alkenyl with a branched or straight chain, and n is an integer from 1 to 10. [9] The electronic or electrical device or component thereof according to claim 8, wherein each Y12 is H and each Y13 is H. [10] The electronic or electrical device or component thereof according to claim 8, wherein each Y12 is fluorine and each Y13 is fluorine. [11] The electronic or electrical device or component thereof according to any of claims 8 to 10, wherein n is 4 to 6. [12] The electronic or electrical device or component thereof according to any of claims 5 to 7, wherein Y10 has the following formula: wherein each Y15 is independently selected from optionally substituted branched or straight chain C 1 -C 6 alkyl. [13] The electronic or electrical device or component thereof according to claim 12, wherein each Y15 is methyl and each Y9 is a bond. [14] The electronic or electrical device or component thereof according to any of claims 5 to 7, wherein Y10 has the following formula: wherein Y 16 to Y 19 are both independently selected from H and optionally substituted C 1-6 alkyl or alkenyl with a branched or straight chain. [15] The electronic or electrical device or component thereof according to claim 14, wherein Y18 is H or vinylene, and Y16, Y17 and Y19 are all H. [16] The electronic or electrical device or component thereof according to any one of the preceding claims, wherein the crosslinking reagent is selected from divinyl adipate (DVA), 1,4-butanediol divinyl ether (BDVE), 1,4-cyclohexanedimethanediol divinyl ether (CDDE), 1,7- octadiene (170D), 1,2,4-trivinylcyclohexane (TVCH), 1,3-divinyltetramethyldisiloxane (DVTMDS), diallyl-1,4-cyclohexanedicarboxylate (DCHD), 1,6-divinyl perfluorohexane (DVPFH), 1 H, 1 H , 6H, 6H-perfluorohexanediol diacrylate (PFHDA) and glyoxal bis (diallylacetal) (GBDA). | j Γ / 1) 1 h / w 4 [17] The electronic or electrical device or component thereof according to claim 4, wherein for compound (ii) L is selected from a C 1 -C 5 alkylene with a branched or straight chain, or an ether group. [18] An electronic or electrical device or component thereof according to any one of the preceding claims, wherein the monomer is a compound of formula I (a): Ka) wherein each Fh, R2, R4, and R5 to R10 is independently selected from hydrogen or an optionally substituted branched or straight chain C 1 -C 6 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1; or wherein the monomer is a compound of formula 1 (b): 1 (b) wherein each R 1, R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or an optionally substituted branched or straight chain C 1 -C 8 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1; [19] The electronic or electrical device or component thereof according to claim 18, wherein the halogen is fluorine. [20] The electronic or electrical device or component thereof according to claim 18 or claim 19, wherein each R1; R 2, R 4, and R 5 to R 10 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, n-hexyl, isohexyl, and * 3-methylpentyl. [21] The electronic or electrical device or component thereof according to claim 20, wherein each R 1, R 2, R 4 1 and R 5 to R 10 is independently selected from hydrogen or methyl. [22] The electronic or electrical device or component thereof according to any of claims 18 to 20, wherein a and c are both independently 0 or 1; and b is 3 to 7. [23] The electronic or electrical device or component thereof according to any of the preceding claims, wherein each X is H. [24] The electronic or electrical device or component thereof according to any of claims 1 to 22, wherein each X is F. [25] The electronic or electrical device or component thereof according to any of claims 18 to 24, wherein and R2 are both hydrogen. [26] The electronic or electrical device or component thereof according to any of claims 18 to 25, wherein R 4 is hydrogen or methyl. [27] The electronic or electrical device or component thereof according to any of claims 18 to 26, wherein R 9 is hydrogen and R 10 is a (branched or straight chain VCe alkyl group). [28] The electronic or electrical device or component thereof according to claim 27, wherein R 10 is methyl. [29] The electronic or electrical device or component thereof according to any of claims 18 to 28, wherein each R 5 to R 8 is hydrogen. [30] The electronic or electrical device or component thereof according to any of claims 18 to 29, wherein each of R 1, R 2, R 4, and R 5 to R 10 is hydrogen, each X is H, a = 0 and c = 0. [31] The electronic or electrical device or component thereof according to any of claims 24 to 30, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 10. [32] The electronic or electrical device or component thereof according to any of claims 24 to 30, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 10. [33] The electronic or electrical device or component thereof according to claim 31, wherein the compound of formula 1 (a) is selected from 1H, 1H, 2H, 2H-perfluorohexyl acrylate (PFAC4), 1H, 1H, 2H, 2H-perfluorooctyl acrylate (PFAC6) 1, 1 H, 1 H, 2 H, 2 H-perfluorocyl acrylate (PFAC8) and 1 H, 1 H, 2H, 2 H-perfluorododecyl acrylate (PFAC10). [34] The electronic or electrical device or component thereof according to claim 32, wherein the compound of formula 1 (a) is selected from 1 H, 1 H, 2PI, 2PI-pefluorohexyl methacrylate (PFMAC4), 1H, 1PI, 2PI, 2PI-perfluorooctyl methacrylate ( PFMAC6) and 1 H, 1 H, 2FI, 2FI perfluorodecyl methacrylate (PFMAC8). [35] The electronic or electrical device or component thereof according to any of claims 18 to 23, wherein the compound of formula I (a) has the following formula: wherein a and c are both independently 0 or 1, b = 3-7 and n is 4 to 10, where n = a + b + c + 1. [36] The electronic or electrical device or component thereof according to any of claims 18 to 23, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 12. [37] The electronic or electrical device or component thereof according to claim 35 or claim 36, wherein the compound of formula I (a) is selected from ethylhexyl acrylate, heyl acrylate, decyl acrylate, lauryl dodecyl acrylate and isodecyl acrylate. [38] An electronic or electrical device or component thereof according to any of claims 18 to 23, wherein the monomer is a compound of formula 1 (b) and has the following formula: wherein n is 4 to 14, optionally wherein R1; R2 and R3 are all H. [39] An electronic or electrical device or component thereof according to any of the preceding claims, wherein the electronic or electrical device or component thereof is selected from mobile telephones, smartphones and beeps, radios, and sound and audio systems such as loudspeakers, microphones, ring tones and / or or buzzers, hearing aids, personal audio equipment such as personal CD, cassette or MP3 players, television sets, DVD players including portable DVD players, video recorders, digital and other tuners, computers and related components such as laptop, notebook, tablet, telephone tablet or handheld computers, personal digital assistants (PDAs), keyboards or instruments, game computers, data storage devices, outdoor lighting systems, radio antennas and other forms of communication equipment and printed circuit boards. [40] A method of treating an electronic or electrical device or component thereof comprising: exposing it for a period of time long enough to allow formation of the protective cross-linked polymer coating on a surface of the electronic or electrical device or component thereof of the electronic or electrical device or component thereof to a plasma comprising a monomer compound and a cross-linking reagent; wherein the monomer compound has the following formula: wherein R 2 and R 4 are each independently selected from hydrogen, optionally substituted branched or straight chain C 1 -C 6 alkyl or haloalkyl, or aryl optionally substituted by halogen, and R 3 is selected from: wherein each X is independently selected from hydrogen, optionally substituted branched or straight chain C 1 -C 6 alkyl or haloalkyl, or aryl optionally substituted by halogen; and n-ι is an integer from 1 to 27; and wherein the cross-linking reagent comprises two or more unsaturated bonds that are attached by means of one or more connecting moieties, and has a boiling point at standard pressure of less than 500 ° C. [41] The method of claim 40, wherein the cross-linking reagent has one of the following structures: wherein Y 2, Y 3, Y 4, Y 5, Y 6, Y 7 and Y 8 are all independently selected from hydrogen, optionally substituted cyclic (branched or straight chain VC 3 alkyl, or aryl; and wherein L is a linking moiety. [42] The method of claim 41, wherein for compound (i) L has the following formula: wherein each Y9 is independently selected from a bond, -O-, -OC (O) -, -C (O) -0-, -Y ^ -OC ^ O) -, -0 (Ο) -Ο-Υ1Γ, -OYn-, and -YnO-, wherein Yn is an optionally substituted cyclic or straight chained C 1 -C 6 alkylene; and Y10 is selected from optionally substituted cyclic CrC8 alkylene with a branched or straight chain, and a siloxane-containing group. [43] The method of claim 42, wherein for compound (i) L has one of the following structures: [44] The method of claim 42, wherein for compound (i) L has one of the following structures: [45] The method of any one of claims 42 to 44, wherein Y10 has the following formula: wherein each Y12 and Y13 is independently selected from H, halogen, optionally substituted cyclic alkyl with a branched or straight chain, or -OY14, wherein Y14 is selected from optionally substituted C1-6 alkyl or alkenyl with a branched or straight chain, and n is an integer from 1 to 10. [46] The method of claim 45, wherein each Y 12 is H and each Y 13 is H. [47] The method of claim 45, wherein each Y 12 is fluorine and each Y 13 is fluorine. [48] The method of any one of claims 45 to 47, wherein n is 4 to 6. [49] The method of any one of claims 42 to 44, wherein Y 10 has the following formula: wherein each Y 15 is independently selected from optionally substituted C 1 -C 6 alkyl with a branched or straight chain. [50] The method of claim 49, wherein each Y15 is methyl and each Y9 is a bond. [51] The method of any one of claims 42 to 44, wherein Y10 has the following formula: wherein Y 16 to Y 19 are both independently selected from H and optionally substituted C 1 -C 8 alkyl or alkenyl with a branched or straight chain. [52] The method of claim 51, wherein Y18 is vinylene or H, and Y16, Y17 and Y19 are all H. [53] The method of any one of claims 40 to 52, wherein the cross-linking reagent is selected from divinyl adipate (DVA), 1,4-butanediol divinyl ether (BDVE), 1,4-cyclohexanedimethanol divinyl ether (CDDE), 1,7-octadiene (17OD) , 1,2,4-trivinylcyclohexane (TVCH), 1,3-divinyltetramethyldisiloxane (DVTMDS), diallyl-1,4-cyclohexanedicarboxylate (DCHD), 1,6-divinyl perfluorohexane (DVPFH), 1H, 1H, 6H, 6H-perfluoroohexanediacoldiodiacodiaciac (PFHDA) and glyoxal bis (diallylacetal) (GBDA). [54] The method of claim 41, wherein for compound (ii) L is selected from a C 1 -C 8 alkylene with a branched or straight chain, or an ether group. [55] The method of any one of claims 40 to 54, wherein the monomer is a compound of formula I (a): I (a) wherein each R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or an optionally substituted branched or straight chain C 1 -C 6 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1; or wherein the monomer is a compound of formula 1 (b): 1 (b) wherein each R 1, R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or an optionally substituted branched or straight chain CVC 3 alkyl group; each X is independently selected from hydrogen or halogen; a is 0-10; b is 2 to 14; and c is 0 or 1; [56] The method of claim 55, wherein the halogen is fluorine. [57] The method of claim 55 or claim 56, wherein each R1; R 2, R 4, and R 5 to R 10 are independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, n-hexyl, isohexyl, and 3-methyl pentyl. [58] The method of claim 57, wherein each R 1, R 2, R 4, and R 5 to R 10 is independently selected from hydrogen or methyl. [59] The method of any one of claims 55 to 58, wherein a and c are both independently 0 or 1; and b is 3 to 7. [60] The method of any one of the preceding claims, wherein each X is H. [61] The method of any one of claims 41 to 59, wherein each X is F. [62] The method of any one of claims 41 to 61, wherein R 1 and R 2 are both hydrogen. [63] The method of any one of claims 41 to 62, wherein R 4 is hydrogen or methyl. [64] The method of any one of claims 41 to 63, wherein R 9 is hydrogen and R 10 is a branched or straight chain C 1 -C 6 alkyl group. [65] The method of claim 64, wherein R 10 is methyl. [66] The method of any one of claims 41 to 65, wherein each R 5 to R 8 is hydrogen. [67] The method of any one of claims 41 to 66, wherein each of R 1, R 2, R 4, and R 5 to R 10 is hydrogen, each X is H, a = 0 and c = 0. [68] The method of any one of claims 61 to 67, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 10. [69] The method of any one of claims 61 to 67, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 10. [70] The method of claim 68, wherein the compound of formula 1 (a) is selected from 1H, 1H, 2H, 2H-perfluorohexyl acrylate (PFAC4), 1H, 1H, 2H, 2H-perfluorooctyl acrylate (PFAC6), 1H, 1H , 2H, 2H perfluorocyl acrylate (PFAC8) and 1FI, 1FI, 2FI, 2FI perfluorododecyl acrylate (PFAC10). [71] The method of claim 69, wherein the compound of formula 1 (a) is selected from 1 H, 1 H, 2 H, 2 H-pefluorohexyl methacrylate (PFMAC4), 1 H, 1 H, 2 H, 2 H-perfluorooctyl methacrylate (PFMAC6) and 1 H, 1H, 2FI, 2H-perfluorodecyl methacrylate (PFMAC8). [72] The method of any one of claims 41 to 61, wherein the compound of formula I (a) has the following formula: wherein a and c are both independently 0 or 1, b = 3-7 and n is 4 to 10, where n = a + b + c + 1. [73] The method of any one of claims 41 to 61, wherein the compound of formula I (a) has the following formula: wherein n is 2 to 12. [74] The method of claim 72 or claim 73, wherein the compound of formula I (a) is selected from ethylhexyl acrylate, heyl acrylate, decyl acrylate, lauryl dodecyl acrylate and isodecyl acrylate. [75] The method of any one of claims 41 to 60, wherein the monomer is a compound of formula 1 (b), and has the following formula: wherein n is 4 to 14. [76] The method of claim 75, wherein the monomer is a compound of formula 1 (b), and has the following formula: wherein n is 4 to 14. [77] A method according to any of claims 40 to 76, wherein the electronic or electrical device or component thereof is introduced into a plasma deposition chamber, a glow discharge is ignited in this chamber and an electrical voltage is applied in the form of a pulsed pulse field. [78] The method of claim 77, wherein the applied electrical voltage has a power of from 40 to 500 W. [79] A method according to claim 77 or claim 78, wherein the electrical voltage is pulsed in a sequence wherein the on-period: off-period ratio is in the range of 1: 500 to 1: 1500. [80] The method of any one of claims 77 to 79, wherein the electrical voltage is pulsed in a sequence wherein the power is on for 20-50 ps, and off for 1000 ps to 30,000 ps. [81] The method of any one of claims 77 to 80, wherein the electrical voltage is applied in the form of a pulsed field for a period of time from 30 seconds to 90 minutes. [82] The method of claim 81, wherein the electrical voltage is applied in the form of a pulsed field for 5 to 60 minutes. [83] The method of any one of claims 77 to 82, wherein in a preliminary step a plasma with continuous power is applied to the electronic or electrical device or component thereof. [84] The method of claim 83, wherein the preliminary step is conducted in the presence of an inert gas. [85] The method of any one of claims 77 to 84, wherein the monomer compound and / or hBef2 (cross-linking reagent while the pulsed electrical voltage is applied) is introduced into the plasma in gaseous form at a rate of 80-300 mg / minute. [86] The method of any one of claims 77 to 85, wherein the plasma is created with an electrical voltage with an average power of 0.001 to 500 W / m3. [87] The method of any one of claims 40 to 86, wherein the monomer compound is miscible with the crosslinking reagent. [88] The method of any one of claims 40 to 86, wherein the monomer compound is immiscible with the crosslinking reagent. [89] The method of claim 87, wherein the step of exposing the electronic or electrical device or component thereof to a plasma takes place in a plasma chamber; and the monomer compound and the cross-linking reagent before entering the chamber are mixed. [90] A method according to claim 87 or claim 88, wherein the step of exposing the electronic or electrical device or component thereof to a plasma takes place in a plasma chamber; and the monomer compound and the cross-linking reagent are introduced into the chamber separately. [91] The method of any one of claims 40 to 90, wherein the crosslinking reagent is present in an amount of 10 to 60 (volume / volume) of the total volume of the monomer compound and the crosslinking reagent.
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公开号 | 公开日 TW201710411A|2017-03-16| US10421876B2|2019-09-24| US20190375961A1|2019-12-12| CN110804358B|2021-09-17| JP2018517044A|2018-06-28| BE1023998A1|2017-10-25| KR20180018675A|2018-02-21| CN109071966A|2018-12-21| US20210355341A1|2021-11-18| WO2016198857A9|2018-07-05| AU2016275278A1|2018-02-01| EP3307835A1|2018-04-18| GB2556518A|2018-05-30| IL256183D0|2018-02-28| AU2016275278A9|2018-12-06| EP3307835B1|2019-05-08| WO2016198857A1|2016-12-15| BR112017026587A2|2018-08-14| CN110804358A|2020-02-18| US11041087B2|2021-06-22| US20180171171A1|2018-06-21| MX2017015919A|2018-08-21| GB201800279D0|2018-02-21|
引用文献:
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法律状态:
2018-02-05| FG| Patent granted|Effective date: 20171026 | 2020-03-27| MM| Lapsed because of non-payment of the annual fee|Effective date: 20190630 |
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申请号 | 申请日 | 专利标题 EP15386017|2015-06-09| EP15386017.6|2015-06-09| 相关专利
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