JP6767106B2 - Polyfluoropolyether-containing compound - Google Patents

Description

The present invention generally relates to polyflouropolyether-containing compounds containing non-isomerizable aliphatic unsaturated groups; compositions containing the compounds, silicon-containing polyfluoropolyethers prepared from the compounds, and the like. With respect to surface treatment materials synthesized, formed or derived from compounds, as well as bonded coatings. The present invention also relates to methods of making these compounds, compositions and materials, as well as surface treated articles including surface treated materials or bond coatings.

The functional and / or decorative surfaces of electronic devices / parts and optics / parts, vehicles, and appliances are susceptible to stains and stains, primarily due to contact with the skin, such as fingers. For example, electronic devices including interactive touch screen displays, such as smartphones, are often stained and / or stained by fingerprints, sebum, sweat, cosmetics, etc. when used. Equipment such as stoves, refrigerators and dishwashers, as well as vehicles such as trucks and automobiles, also suffer from such stains and stains. Once these stains and / or stains have adhered to the display of the device or the surface of the appliance or vehicle, these stains and / or stains are not easily removed. In addition, their stains and / or stains reduce the appearance, function and ease of use of these devices, reduce the appearance of these devices and also reduce the appearance and function of these vehicles (eg, resistors). Increase force).

In an attempt to minimize the effect, appearance and spread of such stains and stains, surface treatment materials are applied on the functional and / or decorative surfaces of equipment requiring anti-stain and / or anti-stain treatment. To. Such devices include displays for electronic devices, as well as the outer surfaces of appliances and vehicles. The applied surface treatment material forms a film on such functional and / or decorative surfaces of the equipment, allowing those surfaces to resist stains and stains. These films help maintain the appearance, functionality, and ease of use of the device, including the function and appearance of touch-sensitive displays such as touch screens of electronic devices. If these films are worn out, for example as a result of equipment use, additional surface treatment materials can be reapplied to the functional and / or decorative surfaces to re-form the films.

The present invention comprises a polyfluoropolyether-containing compound containing a non-isomerizable aliphatic unsaturated group (abbreviated herein, a non-isomerizable aliphatic unsaturated polyfluoropolyether, or abbreviated as poly. A surface treatment composition containing a non-isomerizable aliphatic unsaturated polyfluoropolyether and a SiH-functional compound (referred to as a fluoropolyether-containing compound), synthesized from this surface treatment composition (eg, by hydrosilylation). Silicon-containing polyfluoropolyethers, surface-treated materials formed or composed of the silicon-containing polyfluoropolyethers, bond coatings made by curing the surface-treated materials (eg, by condensation or free radical curing), Also provided are various embodiments including related methods and uses. The non-isomerizable aliphatic unsaturated polyfluoropolyether has the following general formula (A). Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Q. In the general formula (A), each X is independently a divalent organic group, − [divalent organic group] −O− or O, Y is F, H or −X−Q, and Z is , Independently-(CF ₂ )-,-(CF (CF ₃ ) CF ₂ O)-,-(CF ₂ CF (CF ₃ ) O)-,-(CF (CF ₃ ) O)-,-( CF (CF ₃ ) CF ₂ )-,-(CF ₂ CF (CF ₃ ))-and-(CF (CF ₃ ))-is selected, where a is an integer from 1 to 200 and b, c, d, e, f and g are integers independently selected from 0 to 200, respectively, and each Q is independently -C≡CH or -Y'-CR = CH ₂ , and each R. Are independently H, CH ₃ or Y'-hydrocarbyl, and each Y'is independently a mobile isomer of a carbon-carbon double bond of O, -N (R)-, S, or Q. It is a hydrocarbylene group that prevents the formation. Non-isomerizable aliphatic unsaturated polyfluoropolyethers may be lacking or absent of silicon atoms.

The present invention also discloses a method for forming the above-mentioned non-isomerizable aliphatic unsaturated polyfluoropolyether.

The present invention also discloses methods for forming silicon-containing polyfluoropolyethers and surface treatment materials. This method comprises a surface composed of a silicon-containing polyfluoropolyether by reacting a non-isomerizable aliphatic unsaturated polyfluoropolyether with a SiH-functional compound in the presence of a hydrosilylation catalyst. It comprises the step of producing a silicon-containing polyfluoropolyether useful as a treatment material, which silicon-containing polyfluoropolyether is not contaminated with by-products containing an isomerized C = C bond.

The present invention further provides surface-treated articles. This surfaced treated article includes an article exhibiting a surface. A layer is deposited on the surface of the article, which is formed from a surface treatment material.

The surface-treated material of the present invention forms a surface-treated article having a large water contact angle (before or after polishing). Thus, those surface-treated articles are soiled and stained, especially when compared to surface-treated materials formed from silicon-containing polyfluoropolyethers contaminated with by-products containing isomerized C = C bonds. The resistance to is increased, and in many cases this resistance is more durable.

The summary and abstract are incorporated herein by reference. The present invention provides various embodiments as described above. The present invention comprises a polyfluoropolyether-containing compound containing a non-isomerizable aliphatic unsaturated group (in the present specification, a non-isomerizable aliphatic unsaturated polyfluoropolyether, or further abbreviated, (Refered to be polyfluoropolyether-containing compounds), and related methods for forming them. The present invention also provides a surface treatment composition comprising a non-isomerizable aliphatic unsaturated polyfluoropolyether and a SiH-functional compound. In some embodiments, the SiH-functional compound further comprises at least one curable group, in another embodiment the SiH-functional compound is free of curable groups. Each curable group may independently be a hydrolyzable group or a free radical reactive group. In some embodiments, the surface treatment composition further comprises a hydrosilylation catalyst.

The present invention also provides a method of forming a silicon-containing polyfluoropolyether from a surface treatment composition containing a non-isomerizable aliphatic unsaturated polyfluoropolyether and a SiH-functional compound. The forming method may include a hydrosilylation reaction between a non-isomerizable aliphatic unsaturated polyfluoropolyether of the surface treatment composition and a SiH-functional compound.

Furthermore, the present invention relates to surface treatment materials containing or composed of these silicon-containing polyfluoropolyethers, related methods for producing the surface treatment materials, and the surface treatment materials. Provide surface-treated articles containing. When the surface treatment material is formed from a surface treatment composition in which the SiH-functional compound further contains at least one curable group, the surface treatment material itself is curable. The surface treatment material is cured via a condensation reaction (when at least one curable group is a hydrolyzable group as described later) or by a free radical reaction (at least one curable group is an acrylate group, etc.). In the case of a free radical reactive group).

The present invention also provides a binding coating formed by curing a surface treatment material, such as by condensation curing or free radical curing, on the surface of equipment requiring anti-staining and / or anti-staining treatment. Curing takes place after the surface treatment material has been deposited on the instrument. The present invention also provides a binding coating formed by curing a surface treatment material synthesized on an instrument. The curing may be condensation curing or free radical curing. The surface treatment material is formed by forming a layer of the surface treatment composition on an instrument, subjecting the layer of the surface treatment composition to a hydrosilylation reaction, and synthesizing the surface treatment material as a layer on the instrument in a fixed position. , Can be synthesized on the device. The in-situ synthesized surface treatment material can then be cured to form a bond coating on the device.

The present invention addresses the problems of non-inventive surface treatment compositions comprising a mixture of SiH-functional components and a non-inventive aliphatic unsaturated polyfluoropolyether. The non-invented composition may be hydrosilylation reactive and is useful for preparing non-invented surface treatment materials by hydrosilylation reaction. We have found that these non-inventive surface treatment materials may have some beneficial effects on antifouling and / or antistain resistance (unconfirmed), but they are the functionality and / or decoration of the device. It has also been found to have a detrimental effect when used as a non-inventive coating on the surface. Non-invented coatings have poor chemical and / or mechanical properties. Also, the non-invented coating has unreacted components such as unreacted conventional aliphatic unsaturated polyfluoropolyether, which leaches and / or scrapes the non-invented coating to people and objects that touch it. Can be This leachate pollutes the environment and also makes non-invented coatings fragile. In addition, non-invented coatings wear down due to insufficient wear resistance on their equipment, or wear more frequently than if they have sufficient or desirable wear resistance. The coating is fragile.

We have sought a technical solution to this problem. Finding a solution was difficult. First, we needed to identify the cause of the poor performance of non-invented coatings, and then find ways to translate this finding into improved coatings. Was the component of the non-invented coating the cause of the problem? Which ingredient is it? After extensive research, we have surprisingly found that a mixture of conventional aliphatic unsaturated polyfluoropolyethers is a hydrosilylation-reactive aliphatic unsaturated polyfluoropolyether component and a hydrosilylated non-reactive fat. It was found to contain both group unsaturated polyfluoropolyether components. The present inventors have determined what is the difference between the hydrosilylated reactive aliphatic unsaturated polyfluoropolyether component and the hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component, and by changing the component. We wondered if the coating properties would be improved.

We found that the hydrosilylated reactive aliphatic unsaturated polyfluoropolyether component contains a terminal aliphatic unsaturated bond, whereas the hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component contains an internal fat. It was found to contain a family unsaturated bond. This difference in the position of the unsaturated bond can explain the difference in the hydrosilylation reactivity of each component of the mixture of conventional aliphatic unsaturated polyfluoropolyethers. Hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component The aliphatic unsaturated bond located inside the molecule has a higher steric disorder, so that the hydrosilylation reaction with the SiH functional component of the surface treatment composition is more important. It is less accessible and therefore less accessible with respect to the formation of covalent bonds to the SiH functional component. In contrast, the aliphatic unsaturated bond located at the end of the hydrosilylation-reactive aliphatic unsaturated polyfluoropolyether component molecule is more accessible for the hydrosilylation reaction with the SiH functional component due to its lower steric hindrance. It is easy and therefore more accessible with respect to the formation of covalent bonds to SiH functional components. During the hydrosilylation reaction of the SiH-functional component with a mixture of conventional aliphatic unsaturated polyfluoropolyethers, the hydrosilylation-reactive aliphatic unsaturated polyfluoropolyether component reacts with the hydrosilylation-reactive fat. It forms macromolecules formed by covalent bonds formed between the group unsaturated polyfluoropolyether component and the SiH functional component. Hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether components do not react or react very slowly. Therefore, we found that the hydrosilylated reactive aliphatic unsaturated polyfluoropolyether component contains a terminal aliphatic unsaturated bond, whereas the hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component. Is considered to contain an internal aliphatic unsaturated bond.

In the hydrosilylation reaction with the SiH-functional component, the present inventors hydrosilylation-reactivity of a mixture of conventional aliphatic unsaturated polyfluoropolyethers with respect to the hydrosilylation non-reactive aliphatic unsaturated polyfluoropolyether component. It was determined that increasing the proportion of the aliphatic unsaturated polyfluoropolyether component would increase the formation of covalent bonds between the hydrosilylation-reactive aliphatic unsaturated polyfluoropolyether component and the SiH functional component. We have made this modification to a comparative surface treatment material made compared to the properties of the surface treatment composition before hydrosilylation and with a low percentage of reactivity / non-reactivity, and a control surface treatment material. The chemical and / or mechanical properties of the resulting surface treatment material (hydrosilylation reaction composition) are improved as compared to the control surface treatment material thus formed with less covalent bonds. I thought it would be. The more covalent bonds formed per unit surface treatment material, the higher the molecular weight of the surface treatment material, thus further improving the chemical and / or mechanical properties of the surface treatment material.

A further problem with non-invented surface treatment materials has been found in unique situations where the SiH functional component further contains curable groups such as hydrolyzable groups or free radical reactive groups. A weakly bound or unbound coating is prepared from a mixture of conventional aliphatic unsaturated polyfluoropolyether components. When placed on a substrate such as the surface of an instrument, the weakly bonded coating has little covalent bond to the surface of the instrument. The unbonded coating is a layer that is not covalently bonded to the device surface. Non-bonded coatings are not cured because no curing conditions have been applied to the layers, or because the layers are formed from SiH functional components that lack or do not contain curable groups. We have found that if a weakly bound or unbound coating is used, the coating needs to be reapplied on a regular basis. Therefore, conventional surface treatment materials formed from a mixture of SiH functional components having other types of curable groups (eg, condensation curable groups) and non-invented aliphatic unsaturated polyfluoropolyethers It has the functionality of the device and / or some ability to form a weakly bonded coating on the decorative surface. However, the aliphatic unsaturated bond located inside the hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component molecule of the mixture of conventional aliphatic unsaturated polyfluoropolyether forms a covalent bond with the Si functional component. The inability to form means that fewer silicon-containing polyfluoropolyether molecules are produced or crosslinked. The resulting coating is fragile. The function of the silicon-containing polyfluoropolyether and the instrument after curing due to less covalent bonds formed by hydrosilylation between the components and fewer silicon-containing polyfluoropolyether molecules formed in the surface treatment material. There are fewer molecules with other types of curable groups so that less covalent bonds are formed with the sex and / or decorative surface. Furthermore, if the proportion of hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component molecules in a mixture of conventional aliphatic unsaturated polyfluoropolyethers is too high, the SiH functionality itself is bound to the surface of the instrument. A coating contaminated with the ingredients can be formed instead.

Therefore, a non-reactive aliphatic unsaturated polyfluoropoly to a reactive aliphatic unsaturated polyfluoropolyether component in the mixture as compared to the proportions found in the mixture of conventional aliphatic unsaturated polyfluoropolyethers described above. Reducing the proportion of ether components would be desirable in view of our findings. However, achieving this technical solution is unexpectedly difficult. The present inventors have obtained a surface treatment composition using a high-purity lot of a conventional aliphatic unsaturated polyfluoropolyether component having an unsaturated bond located only at the terminal position as a starting material, even when the surface is obtained. After hydrosilylation to react the treatment composition, the resulting surface treatment material was found to unnecessarily contain a non-reactive aliphatic unsaturated polyfluoropolyether component with an unsaturated bond located at an internal position. It was. This was as if we were using a mixture of conventional aliphatic unsaturated polyfluoropolyethers as a starting material. We present a reaction by-product in which a hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component is formed in situ from a hydrosilylated non-reactive aliphatic unsaturated polyfluoropolyether component. I made a hypothesis that there is. Furthermore, we have found that they are internally unsaturated as found in non-reactive components via the mobile isomerization of the terminal unsaturated bonds of the reactive aliphatic unsaturated polyfluoropolyether component. Suspected of forming a bond. That is, in conventional mixtures of aliphatic unsaturated polyfluoropolyethers, the terminal aliphatic unsaturated bonds can be isomerized before they all participate in the hydrosilylation reaction. An alternative way to express such mobile isomerization is to say that the vicinal hydrogen atom moves. In contrast, perhaps internal aliphatic unsaturated bonds, once formed, cannot be reisomerized or are much slower to reisomerize compared to the hydrosilylation kinetics. (Otherwise, they will be attracted to terminal unsaturated in equilibrium isomerization until all of the terminal isomers have reacted).

The present invention solves at least one of the problems described above. To achieve a technical solution, we sought to discover a new aliphatic unsaturated polyfluoropolyether component that has a terminal unsaturated bond and has a combination of the following two contraindicated features: .. (A) The terminal unsaturated bond must be sufficiently hydrosilylation reactive to form the covalent bond described above with other components of the surface treatment composition, such as SiH-functional silane or SiH-functional siloxane. There are, and (b1) end unsaturated bonds (or vicinal hydrogen atoms) are not migratory and isomerizable, or need to be sufficiently unlikely to migrate and isomerize, or (b2) rapidly. Reversibly migrating and isomerizable, i.e., the resulting internally unsaturated bond relocates and isomerizes at a rate faster than the rate of the hydrosilylation reaction, resulting in a terminal unsaturated bond. Must be possible, either. To achieve this technical solution, we, for example, by changing the acidity and / or scissionability of a vicinal hydrogen atom (s), and / or neighbors. Decreased accessibility to vicinal hydrogen atoms (s) by increasing or decreasing the size of the group and increasing or decreasing the steric hindrance around the vicinal hydrogen atoms (s). Or, by increasing the amount, it was considered whether or not the vicinal hydrogen atom (s) could be less susceptible to or more susceptible to migration.

The present invention is a novel aliphatic unsaturated polyfluoropolyether having a terminal unsaturated bond having both the characteristics (a) and (b1), that is, a polyfluoropolyether containing a non-isomerizable aliphatic unsaturated group. The technical problem is solved by providing the contained compound. The present invention also provides related surface treatment compositions, including such aliphatic unsaturated polyfluoropolyethers, and surface treatment materials formed by the hydrosilylation reaction of such surface treatment compositions. In some embodiments, the silicon-containing polyfluoropolyethers and surface treatment materials of the present invention are non-curable or non-curable. In another embodiment, the silicon-containing polyfluoropolyethers and surface treatment materials of the present invention are curable as described below. The present invention also provides a binding coating formed by curing a surface treatment material, such as condensation curing or free radical curing, as well as methods and use of the binding coating.

We are between the non-isomerizable aliphatic unsaturated polyfluoropolyether of the present invention and a SiH functional component containing yet another type of curable group (eg, condensation curable group). It has been found that the covalent bonds formed are advantageous for introducing these other types of curable groups into the silicon-containing polyfluoropolyethers of the present invention for the surface treatment materials of the present invention. The result is an embodiment of a curable surface treatment material, namely a SiH-functional component containing at least one other type of curable group and a non-isomerizable aliphatic unsaturated polyfluoropolyether component. It is a curable surface treatment material of the present invention formed by the hydrosilylation reaction of the surface treatment composition of the present invention containing. The binding coating of the present invention may be formed by curing a curable surface treatment material by condensation curing or free radical curing on the functional and / or decorative surface of the device. The result of such curing is the surface-treated equipment of the present invention, which comprises the functional and / or covalently bonded coating on the decorative surface of the equipment. Upon curing, some of the other types of curable groups in the curable surface treatment material react with functional groups on the functional and / or decorative surface to cure the curable surface treatment material and cure the surface treatment. The coating is covalently bonded to the device by forming a covalent bond between the material and the functional and / or decorative surface of the device (hence the term "bonding coating"). In addition, curing of the surface treatment material increases the crosslink density in the bond coating as compared to the crosslink density of coatings formed with conventional mixtures of aliphatic unsaturated polyfluoropolyethers. Therefore, the covalent bond between the bond coating of the present invention and the functional and / or decorative surface and the increase in the internal crosslink density preferably increase the wear resistance and water contact angle of the bond coating on their equipment. I can let you. Increased wear resistance means that the bonded coatings of the present invention do not wear out or wear out less frequently than the weakly bonded or unbonded coatings of the comparative controls. We have found that the need to reapply the binding coatings of the invention is relatively low. The present invention provides the binding coating of the present invention and a curable surface treatment material useful for making the binding coating. As later shown in the Examples, the binding coating formed from the new surface treatment composition is from a non-invention surface treatment composition having a mixture of conventional aliphatic unsaturated polyfluoropolyethers susceptible to mobile isomerization. It has improved water contact angles and improved mechanical and / or chemical properties compared to the unbonded or weakly bonded coatings formed. The non-isomerizable aliphatic unsaturated polyfluoropolyether embodiment of the present invention lacks (does not include) an internal aliphatic unsaturated bond (eg, C = C or C≡C). The non-isomerizable aliphatic unsaturated polyfluoropolyether embodiment of the present invention lacks (does not contain) a vicinal hydrogen atom, and nevertheless, surprisingly, the terminal unsaturated bond is SiH-functional. It is sufficiently reactive to form the covalent bonds described above with other components of the surface treatment composition, such as sex compounds. Embodiments of silicon-containing polyfluoropolyethers lack (do not include) aliphatic unsaturated bonds.

The surface-treated article of the present invention has a large water contact angle. Those surface-treated articles often contain, in particular, comparative silicon-containing polyfluoropolyethers and are contaminated with by-products containing mobile isomerized C = C or C = C = C bonds. Vicinal terminal C = C bond to CH ₂ or CH groups before the control silicon-containing polyfluoropolyether undergoes mobile isomerization when compared to the control's surface-treated material. Alternatively, it has a higher durability of stain / stain resistance and increased resistance to stain and stain adhesion, depending on whether or not it contained a terminal C≡C bond. In general, in the control method for forming a control silicon-containing polyfluoropolyether, a by-product containing a mobile isomerization C = C bond or a C = C = C bond is formed. I found it unfavorable. The comparative method is a non-invention polyfluoropolyether having a vicinal terminal C = C bond or terminal C≡C bond to _two CH groups or CH groups instead of the present polyfluoropolyether-containing compound. It is carried out in the same manner as this method for forming the silicon-containing polyfluoropolyethers of the present invention, except that the containing compound is used. The polyfluoropolyether-containing compounds of non-invention having terminal C = C bond or terminal C≡C bond vicinal respect CH ₂ group or a CH group, vicinal respect CH ₂ group or a CH group The terminal C = C bond is a propene-3-yl-containing group (-CH ₂ CH = CH ₂ ) or 3-methyl-propen-3-yl-containing group (-CH (CH ₃ ) CH = CH ₂ ), respectively. shown, terminal C≡C bond vicinal respect CH ₂ group or a CH group, respectively, propyn-3-yl-containing group _(-CH 2 C≡CH), or 3-methyl - propyne-3-yl It is represented by an containing group (-CH (CH ₃ ) C≡CH). In the non-invented polyfluoropolyether-containing compounds, the present inventors have an internal position (that is, -CH = CH-CH ₃ or -C, respectively) in the pi-bond of the terminal C = C bond or the terminal C≡C bond. by moving _(CH 3) = _CH-CH nonterminal positions such as in ₃ or each -CH = C = CH), or _-C (CH 3) = non-terminal positions, such as in the C = CH), moving It has been found that by-products containing a target isomerized C = C bond or C = C = C bond are formed. The by-product is a non-reactive structural isomer of a non-invented polyfluoropolyether-containing compound having a vicinal terminal C = C bond or terminal C≡C bond to _two CH or CH groups. This transfer of C = C bond or pi- bond is carried out by a non-invented polyfluoropolyether-containing compound having a bicinal terminal C = C bond or terminal C≡C bond to _two CH groups or CH groups. Vicinal terminal C = C or terminal C≡C bond to CH ₂ or CH groups before being able to react with SiH-functional compounds (ie, Si—H-containing compounds) in a comparative method. It can occur in non-invented polyfluoropolyether-containing compounds having. The formation of this by-product containing the isomerized C = C bond results in the formation of a comparatively controll silicon-containing polyfluoropolyether molecule with less desired surface reactivity during synthesis, which is undesirable. Therefore, less surface-reactive comparative silicon-containing polyfluoropolyether molecules are found in the comparative surface-treated materials. Fewer desired surface-reactive molecules in the control surface-treated material is not preferred due to the small water contact angle on the exposed outer surface (before and after polishing) of the control surface-treated material, and therefore outside. It means that the wettability of the surface to water or other contaminants such as fingerprints or sebum is increased, which is not preferable. In comparative articles treated with comparative surface-treated materials, the presence of water on the outer surface or other contaminants as described above results in a negative optical property of the comparative surface-treated article. It is thought to have an impact.

However, embodiments of the non-isomerizable aliphatic unsaturated polyfluoropolyether of the present invention are structurally configured such that their terminal C = C or terminal C≡C bonds are prevented from migrating or isomerizing. Has been done. Therefore, the surface-treated materials of the present invention form layers on the surface presented by articles such as electronic articles in order to improve the physical and optical properties of the articles, as described in more detail below. Is particularly suitable for. However, the surface treatment materials of the present invention are not limited to their use or articles. For example, this surface treatment material is also suitable for forming layers on other articles and / or substrates such as glass, plastic or metal, such as those used in appliances or vehicles.

In various embodiments, the non-isomerizable aliphatic unsaturated polyfluoropolyether of the present invention has the following general formula (A): Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Q. The groups modified by the subscripts b-g, i.e., the groups in square brackets of formula (A), include the general formula (A) above and the different order as represented throughout this specification. It may be present in any order within the non-isomerizable aliphatic unsaturated polyfluoropolyether. In addition, these groups can exist in randomized or non-randomized forms, including block forms. In addition, the group modified by the subscript b is typically linear, i.e. or _{(O-CF 2 -CF 2 -CF} 2) may be described as _b.

In the above general formula (A), Z is independently − (CF ₂ ) −, − (CF (CF ₃ ) CF ₂ O) −, − (CF ₂ CF (CF ₃ ) O) −, − ( _{CF (CF 3) O) -} , - (CF (CF 3) -CF 2) -, - (CF 2 -CF (CF 3)) - and _{- (CF (CF 3))} - it is selected from. Z is typically selected such that the non-isomerizable aliphatic unsaturated polyfluoropolyether does not contain an oxygen-oxygen (OO) bond in the backbone chain. In addition, in this general formula, a is an integer from 1 to 200, and b, c, d, e, f and g are integers independently selected from 0 or 1 to 200, respectively. Each Q is independently -C≡CH or -Y'-CR = CH ₂ , each R is independently H, CH ₃ or Y'-hydrocarbyl, and each Y'is independently. A hydrocarbylene group that prevents the mobile isomerization of the carbon-carbon double bond of O, -N (R)-, S, or Q. In some embodiments, Z is − (CF ₂ ) − and the subscript a is Z _a CF ₂ , CF ₂ CF ₂ , CF ₂ CF ₂ CF ₂ , CF ₂ CF ₂ CF _{2, respectively.} CF ₂ or CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ is 1-5.

In certain embodiments, each Y'is a hydrocarbylene group that independently prevents the mobile isomerization of the C = C bond within the Vicinal-CR = CH ₂ groups of O or Q, and is a transfer. The hydrocarbylene groups that prevent target isomerization are phenylene, -alkylene-phenylene, -C (R ¹ R ² )-or -LC (R ⁵ R ⁶ )-, where R ¹ and R ² are respectively. are independently _(C 1 _{~C 10)} hydrocarbyl group or halogen, ^{R 5} and L may combine to form a cycloalkylene each other, ^{R 6} is a hydrocarbyl group or F. O prevents the mobile isomerization of the C = C bond within the Vicinal-CR = CH ₂ group of Q.

In certain embodiments, each X is independently a divalent organic group,-[divalent organic group] -O- or -O-. O or O in the "-[divalent organic group] -O-" group prevents the mobile isomerization of the C≡C bond within the vicinal-C≡CH group of Q.

As used herein, the term "non-isomerizable aliphatic unsaturated" is used during a hydrosilylation reaction with a SiH-functional compound in the presence of a platinum hydrosilylation catalyst (C = C bond or). It means that it is not subject to mobile isomerization (of the pi-bond of the C≡C bond). The term "surface treatment composition" means a mixture of at least two components that can react with each other by hydrosilylation. The term "surface treatment material" means a substance synthesized by a hydrosilylation reaction.

As used herein, the term "group" means a set of deterministically linked (covalently bonded) atoms or a single atom, or a set of deterministically linked atoms in a molecule. The term "group" may be used interchangeably herein with the term "substituent" or "substituent group".

The term "SiH-functionality" is meant to include a Si-H group capable of undergoing a hydrosilylation reaction with a non-isomerizable aliphatic unsaturated group.

The term "monovalent" means having one free valence. The term "univalent" may be used interchangeably herein with the term "monovalent".

The term "divalent" means having two free valences. The term "bivalent" may be used interchangeably herein with the term "divalent".

The term "monovalent organic group" means organol or organoheteryl. The term "univalent organic group" may be used interchangeably herein with the term "monovalent organic group".

The term "organyl" means a monovalent organic substituent having its free valence at a carbon atom, regardless of functional type (eg, -CH ₃ , -CH (CH ₃ ) ₂ , -C (= O). ) CH ₃ , -C ≡ CH or -C ₆ F ₅ ).

The term "organoheteryl" means a monovalent group that is organic because it contains carbon, but has its free valence in an atom other than carbon (eg, CH ₃ CH ₂ NH-, -OC (= O) CF ₃ ). Or -SC ₆ H ₅ ).

The term "divalent organic group" means organoylene or organoheterylene. Organylene groups have two free valences, each of which is present on the same (eg, -CH _2- or = CH _2- ) or different (eg, -CH ₂ CH _2- ) carbon atoms. Organylene is formally derived by removing hydrogen or halogen atoms, if any, from the carbon atoms of the organol group. The organoheterylene group has two free valences, with at least one free valence, or both free valences, present in atoms other than carbon. For example, CH ₃ CH ₂ N =, OCF ₂ CF ₂ CH ₂ , OCH ₂ CH ₂ CH ₂ O or SC ₆ H ₄ . Organoheterylene is formally derived by removing hydrogen or halogen atoms, if present, from the carbon or heteroatoms of the organoheteryl group. The term "bivalent organic group" may be used interchangeably herein with the term "divalent organic group".

In the present invention, the divalent group X forms one covalent bond with Q of the general formula (A), and − (OC ₃ F ₆ ), − (OCF (CF ₃ ) CF ₂ ), − (OCF ₂ ). It forms another covalent bond with a carbon atom from one of CF (CF ₃ ),-(OC ₂ F ₄ ) or-(CF (CF ₃ )) f- (OCF ₂ ).

In certain embodiments, the divalent organic group of X is − (CH ₂ ) h− and the subscript h is an integer of 1-20. Therefore, for example, when the subscript h is 1, X is a methylene crosslink represented by the formula − (CH ₂ ) −. Similarly, when the subscript h is 2, X is an ethylene crosslink represented by the formula − (CH _2- CH ₂ ) −, and when the subscript h is 3, X is the equation − (CH ₂ −CH ₂ ) −. ₂ CH ₂ CH ₂ )-is a propylene crosslinked represented by −, and so on.

In certain embodiments, Y'is -C (R ¹ R ² )-(in the formula, R ¹ and R ² are independently hydrocarbyl groups or F). In another embodiment, Y 'is _-C 6 _{H 4} or _-Alk-C 6 _{H 4} - (wherein, Alk is an alkylene group). In a further embodiment, Y'is -LC (R ³ R ⁴ )-(in the formula, R ³ and L are bonded to each other to form a cycloalkylene, and R ⁴ is a hydrocarbyl group or F. There is).

In a further embodiment, when Q is -Y'-C (Y'-hydrocarbyl) = CH ₂ , at least one Y'is a hydro that prevents the mobile isomerization of carbon-carbon double bonds in Q. It is a carbylene group.

In a more specific embodiment, the non-isomerizable aliphatic unsaturated polyfluoropolyether of formula [A] is the non-isomerizable aliphatic unsaturated polyfluoropolyether of formula [B]. Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Y'-CH = CH 2.

In formula [B], each X is independently a divalent organic group, [divalent organic group] -O- or O, and Y is F, H or -X-Y'-CH = CH ₂ . Yes, Z is independently-(CF ₂ )-,-(CF (CF ₃ ) CF ₂ O)-,-(CF ₂ CF (CF ₃ ) O)-,-(CF (CF ₃ ) O) Selected from −, − (CF (CF ₃ ) CF ₂ ) −, − (CF ₂ CF (CF ₃ )) − and − (CF (CF ₃ )) −, where a is an integer from 1 to 200. b, c, d, e, f and g are integers independently selected from 0 to 200, and each Y'is independently O, -N (R)-, S, or Q. It is a hydrocarbylene group that prevents the mobile isomerization of carbon-carbon double bonds.

In another more specific embodiment, the non-isomerizable aliphatic unsaturated polyfluoropolyether of formula [A] is the non-isomerizable aliphatic unsaturated polyfluoropolyether of formula [D]. Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Q.

In formula [D], each X is independently a divalent organic group,-[divalent organic group] -O- or O, Y is F, H or -X-Q, and Z is. Independently-(CF ₂ )-,-(CF (CF ₃ ) CF ₂ O)-,-(CF ₂ CF (CF ₃ ) O)-,-(CF (CF ₃ ) O)-,-(CF) (CF ₃ ) CF ₂ )-,-(CF ₂ CF (CF ₃ ))-and-(CF (CF ₃ ))-, where a is an integer from 1 to 200, b, c, d , E, f and g are integers independently selected from 0 to 200, each Q is independently -C≡CH or -Y'-C≡CH, and each Y'is Independently O, -N (R)-, S or hydrocarbylene groups.

In particular, in the above specific formula, which is an exemplary non-isomerizable aliphatic unsaturated polyfluoropolyether, one or more fluorine atoms are subject to at least two fluorine atoms remaining in the molecule. , May be replaced with another atom. For example, other halogen atoms (eg, Cl) may be present in the non-isomerizable aliphatic unsaturated polyfluoropolyether, or the non-isomerizable aliphatic unsaturated polyfluoropolyether is fluorine. The degree of isomerization may be relatively low. A relatively low degree of fluorination means that one or more of the fluorine atoms of any of the above general formulas can be replaced by hydrogen atoms, provided that at least two fluorine atoms remain in the molecule. To do.

The present invention also provides methods for preparing non-isomerizable aliphatic unsaturated polyfluoropolyethers.

Generally speaking, the method is used to form non-isomerizable aliphatic unsaturated polyfluoropolyethers of the general formula [A] (where Q is -Y'-CR = CH ₂ ). Includes the step of reacting a polyfluoropolyether alcohol with 4-vinylbenzyl chloride and tetraethylammonium bromide.

Thus, for example, in order to form a more specific general formula [B] Isomerization impossible aliphatic unsaturated polyfluoropolyether of polyfluoropolyether alcohol used, wherein _[A] Y-Z _a − [(OC ₃ F ₆ ) _b − (OCF (CF ₃ ) CF ₂ ) _c − (OCF ₂ CF (CF ₃ )) _d − (OC ₂ F ₄ ) _e − (CF (CF ₃ )) _f − ( OCF ₂ ) _g ] -XY'-OH (in the formula, Z, X, Y'and the subscripts a to g are as described above in relation to the general formula [A]).

In another embodiment, the polyfluoropolyether alcohol according to the general formula [a] is CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OH (in the formula, subscript). The non-isomerizable aliphatic unsaturated polyfluoropolyether obtained according to the general formula [B], which comprises (the letter n is 5 to 75) and is formed by the above process, is CF ₃ CF _2. CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ is included.

In two more specific embodiments, the polyfluoropolyether alcohol according to the general formula [a] is CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OH (in the formula). , The subscript n is 10 or 17), and the non-isomerizable aliphatic unsaturated polyfluoropolyether obtained by the general formula [B] formed by the above process is CF. ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ (where n is 10 or 17 in the formula) is included. ..

In certain of these embodiments, the divalent organic group X of the polyfluoropolyether alcohol of formula [a] is − (CH ₂ ) h− (where h is an integer of 1 to 20). Is.

Generally speaking, in order to form a non-isomerizable aliphatic unsaturated polyfluoropolyether of the general formula [A] (where Q is -C≡CH), the method is Br-. It comprises the steps of mixing and reacting CH ₂ C≡CH and tetraethylammonium bromide with a polyfluoropolyether alcohol.

Thus, for example, in order to form a more specific non-isomerizable aliphatic unsaturated polyfluoropolyether of the general formula [D], the polyfluoropolyether alcohol follows the general formula [b]. Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Y'-OH ( wherein, X, Y, Y 'and subscript a~g is in connection with the general formula [D] are as described above is there).

In a further embodiment, the polyfluoropolyether alcohol according to the general formula [b] comprises CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OH, as described above. The non-isomerizable aliphatic unsaturated polyfluoropolyether according to the general formula [D] formed by the process is CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ). Includes CH ₂ OCH ₂ C ≡ CH.

In certain of these embodiments, the divalent organic group X of formula [b] is − (CH ₂ ) h− (where h is an integer of 1 to 20).

The present invention also relates to silicon-containing polyfluoropolyethers derived from non-isomerizable aliphatic unsaturated polyfluoroethers according to any of the formulas described above and the associations for forming these silicon-containing polyfluoropolyethers. And provide the method. Furthermore, the present invention provides surface-treated materials containing or composed of these silicon-containing polyfluoropolyethers and related methods for forming these surface-treated materials. provide.

Methods for preparing silicon-containing polyfluoropolyethers can be readily based on methods generally known in the art. For example, the silicon-containing polyfluoropolyether of the present invention, such as polyfluoropolyethersilane, is typically a silane compound having a non-isomerizable alkenyl-terminated polyfluoropolyether compound and a silicon-bonded hydrogen atom ( That is, it may be prepared by a hydrosilylation reaction with a SiH-functional silane compound, that is, a Si—H-containing silane compound). SiH-functional silane compounds typically have a silicon-bonded halogen atom, a silicon-bonded carboxy group (eg, Si-acetoxy group), and a silicon-bonded alkoxy group (eg, Si-methoxy or Si-). It contains at least one hydrolyzable group such as an ethoxy group) or a silicon-bonded dialkylamino group (eg, Si-dimethylamino group). The silicon-bonded halogen atom can react and be converted to other hydrolyzable groups. For example, the silicon-bonded halogen atom may react with an alcohol such that the resulting polyfluoropolyethersilane compound contains a Si-alkoxy functional group, where the alkoxy is due to the alcohol. If the hydrogen atom is chlorine, the by-product of such a reaction is hydrogen chloride. This conversion may be carried out after the hydrosilylation reaction of the SiH-functional silane compound with a non-isomerizable aliphatic unsaturated polyfluoropolyether. Those skilled in the art will understand how to modify the starting components to obtain the desired structure of the silicon-containing polyfluoropolyether. Specific examples of general methods for preparing material polyfluoropolyether silanes are disclosed in US Patent Application Publication No. 2009/0208728, which is incorporated herein by reference in its entirety.

In certain other embodiments of the invention, the silicon-containing polyfluoropolyether is a non-isomerizable aliphatic unsaturated polyfluoropolyether according to the general formula [A] in the presence of a hydrosilylation catalyst, SiH-. It can be formed by reacting with a functional silane compound. The SiH-functional silane compound may be trimethoxysilane, pentaethoxydisilane, trichlorosilane or 1,1,2,2-tetrachlorodisilane. In these embodiments, the silicon-containing polyfluoropolyethers formed are not contaminated with by-products containing isomerized C = C bonds.

In another embodiment of the invention, the silicon-containing polyfluoropolyether hydrosilylates the non-isomerizable aliphatic unsaturated polyfluoropolyether according to the general formula [B] formed in the particular embodiment described above. It can be formed by reacting with a SiH-functional siloxane compound (ie, a Si—H-containing siloxane compound) in the presence of a catalyst. In certain of these embodiments, the SiH-functional siloxane compound is a cyclic SiH-functional siloxane compound, and in yet another embodiment, the SiH-functional siloxane compound is a non-cyclic SiH-functional. It is a siloxane compound. The acyclic SiH-functional siloxane compound may be pentamethyldisiloxane, and the cyclic SiH-functional siloxane compound may be heptaethylcyclotetrasiloxane or nonamethylcyclopentasiloxane.

In certain other embodiments, the silicon-containing polyfluoropolyether is a hydrosilylation catalyst of the non-isomerizable aliphatic unsaturated polyfluoropolyether according to the general formula [D] formed in the particular embodiment described above. Can be formed by reacting with a SiH-functional compound in the presence of.

The SiH-functional compound may be a SiH-functional silane compound, a SiH-functional siloxane compound, or a mixture of any two or more of these. In some embodiments, the SiH-functional compound is further free of silicon-bound hydrolyzable groups. In another embodiment, the SiH-functional compound further comprises a hydrolyzable group to which at least one silicon is attached. Examples of suitable silicon-bonded hydrolyzable groups include silicon-bonded dialkylamino groups (eg, Si-N (methyl) 2), silicon-bonded carboxy groups (eg, Si-acetoxy groups), and silicon. It is a bonded alkoxy group (Si-methoxy, Si-ethoxy group or Si-butoxy) or a halogen atom to which silicon is bonded (for example, Si-chloro). In some embodiments, the SiH-functional compound further comprises a Si-alkoxy or Si-halogen group.

In some embodiments, the silicon-containing polyfluoropolyether (prepared from a non-isomerizable aliphatic unsaturated polyfluoropolyether and a SiH-functional compound by a hydrosilylation reaction) is a silicon-bound hydrolyzate. It does not further contain degradable groups. In another embodiment, the silicon-containing polyfluoropolyether further comprises a hydrolyzable group to which at least one silicon is attached. In some embodiments, the silicon-bound hydrolyzable group of the silicon-containing polyfluoropolyether is the silicon-bound hydrolysis of the appropriate (ad rem) embodiment of the SiH-functional compound from which it was prepared. It is the same as the sex group. In some embodiments, the silicon-bonded hydrolyzable group of at least one silicon-containing polyfluoropolyether is different from the silicon-bonded hydrolyzable group of the appropriate embodiment of the SiH-functional compound. The silicon-containing polyfluoropolyether was formed from this SiH-functional compound.

In yet another embodiment, the silicon-containing polyfluoropolyether compound of the general formula [C] is of the formula CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ non-isomerizable aliphatic unsaturated polyfluoropolyether was reacted with cyclic SiH-functional siloxane in the presence of a hydrosilylation catalyst to form an intermediate product. It can later be formed by reacting this intermediate product with an unsaturated methacrylate-containing compound. In these embodiments, the subscript n is in the range of 5 to 75, or 9 to 60, or 10 or 11. The silicon-containing polyfluoropolyether of the formula [C] obtained is as follows.
(In the formula, n is 5 to 75.)

As described above, the present invention also provides surface treatment materials and compositions, including the silicon-containing polyfluoropolyether compounds described and formed above, as well as methods for forming surface treatment materials.

In some embodiments, the surface treatment composition comprises a polyfluoropolyether-containing compound and a SiH-functional compound such as SiH-functional silane, SiH-functional siloxane, or a combination thereof. Typically, the surface treatment composition further comprises a hydrosilylation catalyst. The surface treatment material is provided by subjecting the surface treatment composition to hydrosilylation reaction conditions.

In certain other embodiments, the surface treatment material is a polyfluoropolyether-containing compound according to the general formula [A] and a SiH-functional silane (ie, a silane compound having a hydrogen atom bonded to silicon) or a SiH-functional compound. It is the product of a hydrosilylation reaction with a sex siloxane, and the product of this hydrosilylation reaction is not contaminated with by-products containing isomerized C = C bonds.

In certain other embodiments, the surface treatment material is the product of a hydrosilylation reaction between a polyfluoropolyether-containing compound according to general formula [B] and a SiH-functional siloxane compound such as a cyclic SiH-functional siloxane compound. Is.

In certain other embodiments, the surface treatment material is the product of a hydrosilylation reaction between a polyfluoropolyether-containing compound according to the general formula [D] and a SiH-functional compound.

As shown above, the present invention further provides a surface-treated article, described in more detail below, and a method for preparing the surface-treated article.

This surface-treated article includes an article exhibiting a surface. Any surface can be treated, but typically the surface requires anti-staining and / or anti-staining treatment. A layer is deposited on the surface of the article. The layer is composed of a surface treatment material. The layer may be formed indirectly from the surface treatment composition, which is then subjected to a hydrosilylation reaction to become a layer of the surface treatment material. Alternatively, this layer may be formed directly from the surface treatment material. The latter (direct formation) aspect is more convenient than the former (indirect formation) aspect. In the direct forming aspect, the surface treatment composition is subjected to hydrosilylation reaction conditions in a container such as a reactor to become a surface treatment material as a bulk material. The bulk surface treatment material is then deposited or formed as a layer of bulk surface treatment material on the surface of the article. Typically, the bulk surface treatment material is removed from the container before being deposited as a layer of bulk surface treatment material on the surface of the article. If desired, a layer of surface treatment material placed on the article may be cured (eg, condensation curing or free radical curing as the case may be) to form a bond coating on the article. Bond coatings are characterized as having a covalent bond between the bond coating and the surface of the article. The article treated with the surface treatment material can be any article, but due to the excellent physical properties obtained from the surface treatment compositions and surface treatment materials of the present invention, this article is typically. It is any one of electronic articles, optical articles, consumer equipment and parts, automobile bodies and parts, and the like. Most typically, this article is one in which it is desirable to reduce the stains and / or stains caused by fingerprints or sebum.

Examples of electronic articles typically include those having an electronic display, such as a liquid crystal display (LCD), a light emitting diode (LED) display, an organic light emitting diode (OLED) display, a plasma display, and the like. These electronic displays are often used in various electronic devices such as computer displays, televisions, smartphones, Global Positioning System (GPS) devices, music players, remote controls, handheld game consoles, portable readers and the like. Exemplary electronic articles include interactive touch screen displays or those with other components that often come into contact with the skin and often exhibit stains and / or stains.

As introduced above, the article may also be a metal article such as consumer equipment and parts. Typical articles are dishwashers, stoves, microwave ovens, refrigerators, freezers and the like, typically those having a glossy metallic appearance such as stainless steel, matte nickel and the like.

Alternatively, the article may be a vehicle body or part such as an automobile body or a part. For example, this surface treatment material is a layer that gives a glossy appearance to an automobile body, and is used to form a layer that is aesthetically pleasing and prevents stains such as dust and stains from fingerprints. It may be applied directly on the top coat.

Examples of suitable optical articles include inorganic materials such as glass plates, inorganic layers, and glass plates containing ceramics and the like. Further examples of suitable optical articles include organic materials such as transparent plastic materials and transparent plastic materials containing an inorganic layer. Specific examples of optical articles include antireflection films, optical filters, optical lenses, spectacle lenses, beam splitters, prisms, mirrors and the like.

Among organic materials, examples of transparent plastic materials include materials containing various organic polymers. In terms of optical properties such as transparency, refractive index, dispersibility and the like, as well as various other properties such as impact resistance, heat resistance and durability, materials used as optical members are usually used. Polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, ethylene vinyl alcohol, acrylic, cellulose (triacetyl) Polyethylene, diacetylcellulose, cellophane, etc.) or copolymers of such organic polymers. These materials can be used in ophthalmic devices. Non-limiting examples of ophthalmic elements include corrected or uncorrected lenses, including single vision or multivision lenses (which may or may not be segmented), such as bifocal, trifocal and multifocal lenses. Examples include, but are not limited to, other elements used for visual correction, protection or improvement, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses and protective lenses or visors. .. Preferred materials for ophthalmic devices are polycarbonate, polyamide, polyimide, polysulfone, polyethylene terephthalate, and polycarbonate copolymers, polyolefins (particularly polynorbornene, diethylene glycol-bis (allyl carbonate) polymers known as CR39, and copolymers), (meth. ) Acrylic polymers and copolymers (particularly (meth) acrylic polymers and copolymers derived from bisphenol A), thio (meth) acrylic polymers and copolymers, urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, and episulfide polymers and copolymers. Includes one or more polymers selected from.

In addition to the articles mentioned above, the surface treatment materials of the present invention can be applied to form layers on other articles such as window members for automobiles or airplanes, thereby providing improved functionality. .. In order to further improve the surface hardness, it is also possible to perform surface modification by a so-called sol-gel process using this surface treatment material in combination with TEOS (tetraethoxysilane).

One specific subject substrate surface treatment material may be applied to form a layer, Corning, Gorilla any generation, which is commercially available from Corning Incorporated of New York (registered _trademark) is a G lass. Another particular substrate of interest is Dragontrail® glass commercially available from the Asahi Glass Company of Tokyo, Japan.

There can be various methods of applying a surface-treated material onto the surface of an article to prepare a surface-treated article.

For example, in certain embodiments, the step of applying a surface treatment material onto the surface of an article to form a wet layer uses a wet coating application method. Specific examples of wet coating application methods suitable for this method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof.

In another embodiment, the step of applying the surface treatment material onto the surface of the article may include the step of forming a layer on the surface of the article using a depositor. For example, when a depositor is utilized, the depositor typically comprises a physical vapor deposition apparatus. In these embodiments, the deposition equipment is typically selected from sputtering equipment, atomic layer deposition equipment, vacuum equipment and direct current (DC) magnetron sputtering equipment. The optimum control parameters for each of these physical vapor deposition devices are based on the surface treatment material used, the article on which the layer will be formed, and the like. In certain embodiments, the depositor comprises a vacuum device.

For example, if the layer is formed using physical vapor deposition (PVD), this method involves combining surface treatment materials and pellets to form impregnated pellets. Pellets typically include metals, alloys or other tough materials such as iron, stainless steel, aluminum, carbon, copper and ceramics. Typically, the pellets have a very high surface area to volume ratio due to contact with the silicon-containing polyfluoropolyether of the surface treatment material. The surface area to volume ratio of the pellets can be due to the porosity of the pellets, i.e. the pellets can be porous. Alternatively, the pellet may contain randomized fibers such as woven fabrics, non-woven fabrics, and / or nanofibers to provide the desired surface area to volume ratio. The pellets may contain, for example, a material selected from SiO ₂ , TiO ₂ , ZrO ₂ , MgO, Al ₂ O ₃ , CaSO ₄ , Cu, Fe, Al, stainless steel, carbon, or a combination thereof. This material may be a plug in a casing, including metals, alloys, or other robust materials. The surface treatment material may be introduced into or to the pellet in any manner as long as the material of the pellet and the silicon-containing polyfluoropolyether are combined or otherwise contacted. For example, the pellets may be immersed in the surface treatment material, or the surface treatment material may be placed in the casing such that the porous material is impregnated with the surface treatment material. In these embodiments, the method further comprises the step of removing the fluorinated vehicle, if present, from the impregnated pellet to form a raw pellet prior to deposition. For example, the fluorinated vehicle, if present, can be swiftly flushed from the pellet by heating. Alternatively, the fluorinated vehicle, if present, can be removed from the pellet by drying at room temperature or slightly higher temperature, optionally in the presence of vacuum or compressed air.

Raw pellets can be stored until they are used in a depositor. In various embodiments, the raw pellets are stored in a vacuum sealed aluminum bag.

One particular example of a vacuum device suitable for forming a layer from a surface treatment material is Hanil Vacuum Machine Co., Ltd. , Ltd. (Incheon, South Korea) is a commercially available HVC-900DA vacuum apparatus. Another example of a depositor is the Edwards AUTO 306 commercially available from Edwalds, Sanborn, NY.

The raw pellets are generally placed on a substrate in the chamber of the depositor with the article to be coated, and the silicon-containing polyfluoropolyether is evaporated using resistance heating evaporation, thereby on the surface of the article. Form a layer.

Independent of the method of forming the layer, once the layer is formed from the surface treatment material on the surface of the article, the layer is further subjected to heating, humidification, catalytic post-treatment, light irradiation, electron beam irradiation and the like. You may. For example, when a surface treatment material is applied by a depositor, the layer formed from the surface treatment material is generally heated at a high temperature, eg 80-150 ° C., for a period of time, eg 45-75 minutes. Alternatively, the layer formed from the surface treatment material can be allowed to stand for a period of time, eg, 24 hours, at room temperature and ambient conditions.

Typically, the thickness of the layer formed from the surface treatment material is 1 to 1,000, or 1 to 200, or 1 to 100, or 5 to 75, or 10 to 50 nanometers (nm). ..

As mentioned above, a layer formed from a surface treatment material can have a large water contact angle and excellent (ie, high) durability. This is true regardless of whether the surface treatment material is applied using wet coating methods or depositors. The durability of a layer formed from a surface treatment material is generally determined by the water contact angle of the layer before and after the layer is subjected to an abrasion test. For example, the less durable the layer, the lower the water contact angle after wear, which usually indicates that the layer has deteriorated at least partially.

In certain embodiments, the layer formed from the surface treatment material has a water contact angle (WCA) of 75-150, or 80-125, or 90-110 degrees (°) before and after the layer is subjected to an abrasion test. Have. In many cases, the water contact angles of both pre-wear and, more generally, post-wear surface treatment materials contain silicon contaminated with by-products containing isomerized C = C or C = C = C bonds. Greater than the water contact angle for surface treatment materials made of polyfluoropolyether (when applied in the same manner to the same substrate with the same layer thickness). Therefore, such surface-treated materials for surface-treated articles are also compared to the physical properties of conventional layers formed from conventional surface-treated materials, and are also isomerized C = C bond or C = C = C. It is believed to provide articles with high durability and outstanding physical and chemical properties compared to surface treatment materials formed with silicon-containing polyfluoropolyethers contaminated with bond-containing by-products.

The following examples are intended to illustrate the invention and are by no means viewed as limiting the scope of the invention.

Proton Nuclear Magnetic Resonance ( ¹ H NMR) Spectrum: Unless otherwise indicated, all ¹ H NMR spectra are obtained at 400 Megahertz (MHz) Agilent 400 MR in a 5 mm “300 MHz” glass tube with a coaxial insert containing acetone-d _6. It was. The chemical shift (δ) is expressed in PPM based on the acetone reference point. The attribution of peaks is underlined. Peak splits are shown as singlet (s), doublet (d), triplet (t), multiplet (m) and the like. The peak integral is within typical measurement error. The integral value can be compared by setting the integral value for the internal methylene hydrogen atom in −CF (CF ₃ ) CH ₂ OCH ₂ − to be equal to 2.00 H or one molecule. This should account for the sum of all polyfluoropolyether-type molecules (raw material PFPE, reacted PFPE and isomerized PFPE) as they should all have -CF (CF ₃ ) CH ₂ O- segments. Is. For example, in the example below, if the value is set to 2.00 H, or equal to one molecule, the associated peak that may correspond to the unfavorable isomerized allyl ether ((-CH ₂ OCH = CHCH ₃ )). The integral value of was 0.18 molecules, thus 0.18 / (1 + 0.18) = 15 mol% of undesired isomerized isomers and 85 mol% of desired non-isomerized isomers. An integrated value of 0.24 molecules of no isomers corresponds to 0.24 / (1 + 0.24) = 19 mol% of unwanted isomerized isomers and 81 mol% of desired non-isomerized isomers.

Synthesis Example 1-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ synthesis. 31.0 g (g) (15.5 mmol (mmol)) of CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OH 30.0 g (140. To a solution of 2 mmol) of 1,3-bis (trifluoromethyl) benzene was added 2.24 g (40 mmol) of potassium hydroxide. This was mixed at 65 ° C. for 3 hours, then 2.25 g (14.8 mmol) of 4-vinylbenzyl chloride and 0.5 g (1.6 mmol) of tetraethylammonium bromide were added, and the mixture was mixed for 16 hours. The material was neutralized with 3N hydrochloric acid and rinsed 3 times with a 1: 1 mixture of 3N hydrochloric acid and acetone. The collected product layer was then filtered through Celatom FW-80 filtration aids, 5.0 and 0.45 μm filters and then stripped at 100 ° C. and in vacuum to produce raw CF ₃ CF ₂ CF ₂ O. (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ was obtained.

Synthesis Example 2-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ C ≡ CH synthesis. 31.0 g (15.5 mmol) of CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OH of 30.0 g (140.2 mmol) of 1,3-bis 2.24 g (56 mmol) of sodium hydroxide was added to the (trifluoromethyl) benzene solution. This was mixed at 65 ° C. for 3 hours, then 5.0 g (42.4 mmol) of Br-CH ₂ C≡CH and 0.5 g (1.6 mmol) of tetraethylammonium bromide were added, and the mixture was further mixed for 3 hours. The material was neutralized with 3N hydrochloric acid and rinsed 3 times with a 1: 1 (weight / weight) mixture of 3N hydrochloric acid and acetone. The collected product layer was then filtered through Celatom FW-80 filtration aids, 5.0 and 0.45 um filters and then stripped at 100 ° C. and in vacuum to produce raw CF ₃ CF ₂ CF ₂ O. (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ C ≡ CH was obtained.

Synthesis Example 3-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ synthesis .. 10.00 g (4.7 mmol) of CF ₃ CF ₂ CF ₂ O (CF (CF)) prepared in Example 1 in a 50 mL three-necked flask equipped with a magnetic stir bar, a dry ice Dewar type cooler and a dry nitrogen purge. CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ , 7.14 g (33.4 mmol) of 1,3-bis (trifluoromethyl) benzene, 6 .60 g (48.7 mmol) of trichlorosilane and 0.01 g (0.04 mmol) of the silylated carboxylic acid isomer inhibitor compound were added. The reaction is stirred at 53 ° C. and 3.0 milligrams (mg) of a complex of platinum and 1,2-diethenyl-1,1,3,3-tetramethyldisiloxane (25 weight percent (% by weight) Pt). Was added gradually over 3 hours. Excess trichlorosilane and 1,3-bis (trifluoromethyl) benzene were then removed under vacuum. The mixture was then added to 5.69 g (26.6 mmol) of 1,3-bis (trifluoromethyl) benzene, 5.63 g (53.1 mmol) of trimethyl orthoformate and 0.08 g (2.5 mmol) of anhydrous. Methanol was added. After mixing this at room temperature for 66 hours, the excess solvent and reactants were stripped off under vacuum to give 8.38 g of a turbid yellow liquid. By using the final cloudy yellow liquid with 1,3-bis (trifluoromethyl) benzene was diluted to 50 wt%, 5 mm "300MHz" glass tube having a coaxial insert comprising acetone -d _6, NMR Samples were prepared. ^{1 1} H NMR analysis showed no residual vinyl groups (-CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ , δ 5.48-5.34, m, 1H; -CH ₂ OCH ₂ (-CH ₂ OCH ₂ ) C ₆ H ₄ ) CH = CH ₂ , δ 4.52-4.42, m, 1H and 4.01-3.91, m, 1H). No peaks were observed indicating the movement of the vinyl double bond (ie, mobile isomerization), and NMR showed that the final material was the desired product: CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O). ) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (-CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ , Δ 3.45-3.33, s, 2.00H; -CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) 3, δ -0.13- -0.33, t , 2.10H) was confirmed.

Synthesis Example 4-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ Substitute Synthesis. 10.00 g (4.7 mmol) of CF ₃ CF ₂ CF ₂ O (CF (CF)) prepared in Example 1 in a 50 mL three-necked flask equipped with a magnetic stir bar, a dry ice Dewar type cooler and a dry nitrogen purge. CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ , 7.24 g (33.8 mmol) of 1,3-bis (trifluoromethyl) benzene and 5 .64 g (41.6 mmol) of trichlorosilane was added. The reaction is stirred at 60 ° C. and 5.2 mg of a complex of platinum and 1,1,3,3-tetramethyldisiloxane (25 wt% Pt) is added over 3.5 hours. Gradually added. Excess trichlorosilane and 1,3-bis (trifluoromethyl) benzene were then removed under vacuum. The mixture was then added to 5.34 g (25.0 mmol) of 1,3-bis (trifluoromethyl) benzene, 5.75 g (54.2 mmol) of trimethyl orthoformate and 0.08 g (2.5 mmol) of anhydrous. Methanol was added. After mixing this at room temperature for 66 hours, the excess solvent and reactants were stripped off under vacuum to give 7.96 g of a turbid yellow liquid. The final cloudy yellow liquid was diluted to 50% by weight of 1,3-bis (trifluoromethyl) benzene, by using a 5mm glass tube having a coaxial insert comprising acetone -d ^_6, 1 H NMR spectrum Got 1H NMR analysis showed no residual vinyl groups (-CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ , δ 5.48-5.34, m, 1H; -CH ₂ OCH ₂ (C) ₆ H ₄ ) CH = CH ₂ , δ 4.52-4.42, m, 1H and 4.01-3.91, m, 1H). No peaks were observed indicating the movement of the vinyl double bond (ie, mobile isomerization), and NMR showed that the final material was the desired product: CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O). ) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (-CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ , Δ 3.46-3.34, s, 2.00H; -CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (OCH ₃ ) ₃ , δ -0.17 to -0.27, t , 2.07H).

Synthesis Example 5-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ CH = CHSi (OCH ₃ ) ₃ synthesis. 10.00 g (4.9 mmol) of CF ₃ CF ₂ CF ₂ O (CF (CF)) prepared in Example 2 in a 50 mL three-necked flask equipped with a magnetic stir bar, a dry ice Dewar type cooler and a dry nitrogen purge. CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ C≡CH, 7.13 g (33.3 mmol) of 1,3-bis (trifluoromethyl) benzene and 6.21 g (45.8 mmol) Trichlorosilane was added. The reaction is stirred at 60 ° C. and 5.2 mg of a complex of platinum and 1,1,3,3-tetramethyldisiloxane (25 wt% Pt) is gradual over 4 hours. In addition to. Excess trichlorosilane and 1,3-bis (trifluoromethyl) benzene were then removed under vacuum. The mixture was then added to 8.38 g (39.2 mmol) of 1,3-bis (trifluoromethyl) benzene, 7.95 g (74.9 mmol) of trimethyl orthoformate and 0.09 g (2.8 mmol) of anhydrous. Methanol was added. After mixing this at room temperature for 39 hours, the excess solvent and reactants were stripped off under vacuum to give 10.59 g of a turbid yellow liquid. The final cloudy yellow liquid was diluted to 50% by weight of 1,3-bis (trifluoromethyl) benzene, by using a 5mm glass tube having a coaxial insert comprising acetone -d ^_6, 1 H NMR spectrum Got ^{1 1 1} H NMR analysis showed no residual triple bond (-CH ₂ OCH ₂ C ≡ CH, δ 1.30-1.02, t, 1H). This material includes the desired CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF (CF ₃ ) CH ₂ OCH ₂ CH = CHSi (OCH ₃ ) ₃ and the associated −Si (OCH _3). ) ₃ variations (-CH ₂ OCH ₂ CH = CHSi (OCH ₃ ) ₃ , δ 2.95-2.86, m, 2.00H; -CH ₂ OCH ₂ CH = CHSi (OCH ₃ ) ₃ , δ 2.40-2.42, s, 9.92H) was found.

Synthesis Example 6-Synthesis of compound [C]
(In the formula, the subscript n is 11.) 9.6 g (3 mmol) of F (CF (CF ₃ ) CF ₂ O) prepared in Example 1 ₁₁ CF (CF ₃ ) CH ₂ OCH ₂ ( of _{C 6 H 4) CH = CH} 2, ( 1,3-bis (trifluoromethyl) benzene solution of 93 mmol), 0.72 g of (3 mmol) _{(SiH (CH} 3) 20 g and _{O 2/2) 4} 1 mg of platinum and a complex of 1,2-diethenyl-1,1,3,3-tetramethyldisiloxane (25 wt% Pt) were added. This was mixed at 70 ° C. and cooled. To this intermediate product are 1.36 g (11 mmol) of allyl methacrylate, 25 g (117 mmol) of 1,3-bis (trifluoromethyl) benzene, 0.01 g (0.05 mmol) of butylated hydroxytoluene and 0.01 g. (0.04 mmol) of a silylated carboxylic acid isomer inhibitor was added. This is mixed at 60 ° C. and cooled to produce the desired product F (CF (CF ₃ ) CF ₂ O) ₁₁ CF (CF ₃ ) CH ₂ OCH ₂ (C ₆ H ₄ ) CH ₂ CH ₂ Si (CH _3). ) O (Si (CH ₃ ) (CH ₂ CH ₂ CH ₂ OCOC (CH ₂ ) CH ₃ ) O) ₃ was obtained. ^{1 1} H NMR analysis showed no residual vinyl groups (-CH ₂ OCH ₂ (C ₆ H ₄ ) CH = CH ₂ , δ 5.48-5.34, m, 1H; -CH ₂ OCH ₂ (C) ₆ H ₄ ) CH = CH ₂ , δ 4.52-4.42, m, 1H and 4.01-3.91, m, 1H), and movement of vinyl double bonds (ie, mobile isomerization) No peak was observed.

Comparative Example 1-CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₇ CF (CF ₃ ) CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ synthesis. 20.72 g (6.5 mmol) of CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) in a 50 mL three-necked flask equipped with a magnetic stir bar, dry ice Dewar type cooler and dry nitrogen purge. ₁₇ CF (CF ₃ ) CH ₂ OCH ₂ CH = CH ₂ , 14.31 g (66.8 mmol) of 1,3-bis (trifluoromethyl) benzene, 7.54 g (55.7 mmol) of trichlorosilane and 0. 021 g (0.1 mmol) of silylated carboxylic acid isomer inhibitor was added. The reaction is stirred at 60 ° C. and 8.9 mg of a complex of platinum and 1,1,3,3-tetramethyldisiloxane (25 wt% Pt) is gradually added over 4.5 hours. Added to. Excess trichlorosilane and 1,3-bis (trifluoromethyl) benzene were then removed under vacuum. The mixture was then added to 4.45 g (20.8 mmol) of 1,3-bis (trifluoromethyl) benzene, 9.70 g (91.4 mmol) of trimethyl orthoformate and 0.118 g (3.7 mmol) of anhydrous. Methanol was added. After mixing this at room temperature for 18 hours, the excess solvent and reactants were stripped off under vacuum to give 20.94 g of a turbid yellow liquid. The final cloudy yellow liquid was diluted to 50% by weight of 1,3-bis (trifluoromethyl) benzene, by using a 5mm glass tube having a coaxial insert comprising acetone -d ^_6, 1 H NMR spectrum Got ^{1 1 1 1} H NMR analysis showed no residual allyl ether (-CH ₂ OCH ₂ CH = CH ₂ , δ 4.81-4.69, m, 1H and δ 4.22-4.02, m, 1H ). The ratio of the isomerized starting material to the desired product is the total amount of PFPE-molecules (-CF (CF ₃ ) CH ₂ OCH _2- , δ 2.90-2.76, d, 2.00H), isomerized. Calculated by comparison with allyl ether (-CH ₂ OCH = CHCH ₃ , δ 3.71-3.64 and 3.38-3.28, m, 0.18H), in this case about 15% isomerization. Allyl ether CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₇ CF (CF ₃ ) CH ₂ OCH = CHCH ₃ , and about 85% of the desired CF ₃ CF ₂ CF ₂ O (CF (CF) CF ₃ ) CF ₂ O) ₁₇ CF (CF ₃ ) CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and related -Si (OCH ₃ ) ₃ variations.

Comparative Example 2-Synthesis of compound [C]'
(In the formula, the subscript n is 18.) 32 g (10 mmol) of F (CF (CF ₃ ) CF ₂ O) ₁₈ CF (CF ₃ ) CH ₂ OCH ₂ CH = CH ₂ of 55 g (257 mmol). A solution was prepared by adding to 1,3-bis (trifluoromethyl) benzene. To this solution, 2.4 g of _{(10mmol) (SiH (CH 3} ) O 2/2) ₄ and 1 mg, platinum and 1,2-diethenyl-1,1,3,3-tetramethyldisiloxane complex ( 25 wt% Pt) was added. This was mixed at 70 ° C. and cooled. To this intermediate product are 4.5 g (36 mmol) of allyl methacrylate, 100 g (467 mmol) of 1,3-bis (trifluoromethyl) benzene, 0.05 g (0.2 mmol) of butylated hydroxytoluene and 0.05 g. (0.2 mmol) of silylated carboxylic acid isomer inhibitor compound was added. This was mixed at 60 ° C. and cooled to give the desired product. ^{1 1 1 1} H NMR analysis showed no residual allyl ether (-CH ₂ OCH ₂ CH = CH ₂ , δ 4.81-4.69, m, 1H and δ 4.22-4.02, m, 1H ). The ratio of the desired product to the isomerized starting material is the total amount of PFPE-molecules (-CF (CF ₃ ) CH ₂ OCH _2- , δ 2.90-2.76, d, 2.00H), isomerized. Calculated by comparison with allyl ethers (-CH ₂ OCH = CHCH ₃ , δ 5.11-4.98 and 4.84-4.64, m, 0.24H), which is about 19% isomers. Allyl Ether F (CF (CF ₃ ) CF ₂ O) ₁₈ CF (CF ₃ ) CH ₂ OCH = CHCH ₃ and about 81% of the desired F (CF (CF ₃ ) CF ₂ O) ₁₈ CF (CF ₃ ) ) CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) O (Si (CH ₃ ) (CH ₂ CH ₂ CH ₂ OCOC (CH ₂ ) CH ₃ ) O) 3 and related variations. Table 1: ¹ Outline of isomerization level by ¹ H NMR

As the results shown in Table 1 show, the non-isomerizable aliphatic unsaturated polyfluoropolyether (PFPE) structure of the starting material used in Synthesis Examples 3-6 has a terminal-CH = CH ₂ migration. Prevented or resulted in undetectable levels of mobile isomerization. On the other hand, the structure of the comparative example was not preferable because the mobile isomerization of terminal-CH = CH ₂ occurred to a measurable level.
Coating example

As a comparison of coating performance, the materials prepared in Comparative Example 1 and Synthesis Example 4 were diluted to 0.2% by weight in 3M Novec 7200 solvent and washed 2 "x 3" (5.08 cm (cm)). It was spray-coated on a microscope slide glass (× 7.62 cm). According to its manufacturer, the 3M Novec 7200 solvent has the empirical formula C ₄ H ₉ OC ₂ H ₅ , and probably "two inseparable species with essentially the same properties" as a 50/50 mixture. Isomers: Consists of (CF ₃ ) ₂ CFCF ₂ OC ₂ H ₅ (CAS No. 163702-06-5) and CF ₃ CF ₂ CF ₂ CF ₂ OC ₂ H ₅ (CAS No. 163702-05-4). The slide glass was washed with detergent, rinsed and treated with atmospheric plasma prior to coating. After coating, the slide glass is condensed and cured for 1 hour in a furnace containing an evaporating dish of deionized water at 125 ° C. to achieve high bond density / bond coating (prepared using Synthesis Example 4) or low bond density / weak bond. The coating (prepared using Comparative Example 1) was obtained. The cured coating / slide glass (ie, the slide glass with a binding coating or a weakly bound coating) was then rinsed with 3M Novec 7200 solvent to remove any excess uncured material. The performance was then evaluated by measuring the static water contact angle. This was done on a glass slide as coated and on a glass slide polished in various ways to assess coating durability (including degree of cross-linking and degree of coating bonding).

In the present specification, according to the modified ASTM 5946-04, 2 microliters (μL) of deionized water was used in accordance with ASTM Products, Inc. Static water contact angles were measured using a VCA Optima XE goniometer manufactured by Billerica, MA. The data reported was the average WCA of 6 measurements at multiple locations on the coating using multiple samples. WCA was measured both before and after the polishing cycle. In general, the larger the WCA after polishing, the higher the durability of the layer.

The wear resistance test used a reciprocating grinder Model 5900 manufactured by Taber Industries of North Tonawanda, New York. This grinder has a stroke length of 1 inch (2.54 cm). One back and forth movement is called a cycle. The test was performed using a plurality of polishing media. In the first case, polishing was performed using 0000 # steel wool over a surface area of 20 mm (mm) x 20 mm at a rate of 60 cycles / minute with a load of 10 Newtons. In the second case, the polishing is silicon carbide or aluminum oxide embedded in a Taber CS-10 polishing medium (elastic or pottery (clay) binder" made by Taber, having a diameter of 0.25 inches (0.635 cm). Abrasive particles) were used and 25 cycles were performed at a rate of 25 cycles / minute with a load of 7.5 Newtons. In the third case, the polishing was carried out using a friction test eraser (Mumbangsawoo Co., Ltd.) having a diameter of 6.0 mm and 1500 cycles at a rate of 40 cycles / minute with a load of 5 Newtons. The results are reported in Table 2 below.

As the results shown in Table 2 show, higher crosslink densities / bonding coatings prepared using materials prepared according to embodiments of the present invention (Example 4) have lower crosslink densities prepared from Comparative Example 1. / Corresponds to superior results for the binding coatings of the invention using embodiments of the materials of the invention that provide superior polishing WCA performance compared to weakly bound coatings and lack detectable mobile isomers. Was. Without being bound by theory, the desired non-isomerized material of the invention having a terminal aliphatic unsaturated bond reacts during the hydrosilylation reaction to form a bond to the SiH functional compound, resulting in a bond. The resulting surface treatment material has a higher bond density / higher molecular weight and then further reacts with the surface of the substrate by condensation curing to form a bond coating with covalent bonds to the substrate and on the substrate. The mobile isomerized material of the comparative example having an internal aliphatic unsaturated bond forms such a bond density or such high molecular weight material, while allowing the formation of a bond coating of. It is believed that this is not possible or that it is not possible to form a sufficient number of covalent bonds between the weakly bonded coating of the comparative example and the surface of the substrate.

The materials prepared in Comparative Example 2 and Synthesis Example 6 were blended into an ultraviolet (UV) curable hard coating formulation. Mix 20.4 parts of KAYARAd dipenthaerythiritol hexaacrylate (dPHA), 61.2 parts of Nissan MEK-AC-2140Z, 16.3 parts of propylene glycol monomethyl ether and 2.0 parts of Ciba Irgacare 184. To prepare 100 parts of the hard coating formulation. MEK-AC-2140Z is a surface-treated colloidal silica in methyl ethyl ketone, which silica has a particle size of 10 to 15 nm. Irgacure 184 is a 1-hydroxy-cyclohexyl-phenyl-ketone. A mixture of 20% by weight of Synthesis Example 6 or Comparative Example 2 in 1,3-bis (trifluoromethyl) benzene was then added at 2:98, 1:99, 0.5: 99.5 or 0.2. Added to the hard coating formulation at a ratio of: 99.8. This was done at various levels to assess the effectiveness of the control PFPE-acrylate material and the low isomer PFPE-acrylate material in imparting the characteristics of ease of cleaning. These hard coating formulations were then spin coated onto a polycarbonate substrate and the excess solvent was rapidly vaporized in a furnace at 80 ° C. for 10 minutes to produce 2000 millijoules / square centimeter (mJ / cm ² ) UV light. Free radical curing was obtained with a higher crosslink density / bond coating (prepared using Synthesis Example 6) or a lower crosslink density / weakly bound coating (prepared using Comparative Example 2). The water contact angle was then tested as described above. The results are reported in Table 3 below.

As the results shown in Table 3 show, the coatings made according to the embodiment of the present invention (Synthetic Example 6) were loaded with Comparative Examples 2 at 1.0, 0.5 and 0.2 wt%. It provided superior WCA performance as compared to the prepared coatings and correlated with superior results for coatings using embodiments of the materials of the invention lacking detectable mobile isomers. Without being bound by theory, the desired non-isomerized material of the invention having a terminal aliphatic unsaturated bond reacts during the hydrosilylation reaction to form a crosslink or bond to the SiH functional compound. The resulting surface treatment material has a higher crosslink density and then further reacts with the surface of the substrate during subsequent condensation or free radical curing reactions to form a covalent coating with a covalent bond to the substrate. On the other hand, the migratory isomerized material of the comparative example having an internal aliphatic unsaturated bond is unable to form such a crosslink or is with the weakly bound coating and substrate of the comparative example. It is believed that sufficient formation of such covalent bonds between them is not possible.

The appended claims are not limited to the clear and specific compounds, surface treatment materials, or methods described in the detailed description, and the compounds, compositions, or methods are within the appended claims. It may differ between specific embodiments. With respect to any Markush group relied on herein, different, special and / or contingent results are obtained from each member of each Markush group, independent of all other Markush group members. It shall be. Each element of the Markush group may depend individually and / or in combination with specific embodiments within the appended claims, providing appropriate evidence.

Moreover, any scope and subrange that is relied upon in describing the various embodiments of the invention falls within the scope of the appended claims independently and in general, even if all and in this specification. / Or even if some values are not specified, it is understood to explain and conceive the entire range that includes such values. Counting ranges and subranges fully describe and enable various embodiments of the invention, and such ranges and subranges are further associated with one-half, one-third, one-fourth, and five. Those skilled in the art will readily appreciate that they may be detailed in one-third magnitude. As just one example, the range "0.1 to 0.9" is the lower third, or 0.1, 0.3, and the middle third, or 0.4 to 0. 6 and the upper third, ie 0.7-0.9, can be further detailed, which are individually and collectively within the appended claims. It may be individually and / or collectively dependent on a particular embodiment within the scope and may provide appropriate evidence. Further, with respect to terms that define or modify ranges such as "at least", "greater than", "less than", "less than or equal to", it should be understood that such terms include subranges and / or upper or lower limits. As another example, the "at least 10" range essentially includes at least 10-35 subranges, at least 10-25 subranges, 25-35 subranges, etc., and each subrange is attached. It may depend individually and / or collectively on a particular embodiment within the claims and provides appropriate grounds for this. Ultimately, the individual numbers within the disclosed scope may depend on the particular embodiment within the appended claims, providing a good basis for this. For example, the range "1-9" includes various individual integers, such as 3, and individual numbers including a decimal point (or fraction), such as 4.1, which is within the appended claims. It may depend on a particular embodiment and provides a good basis for this.

The present invention has been described in an exemplary manner and the terms used are intended to have descriptive terminality rather than limitation. Many modifications and modifications of the present invention are possible from the above teachings. The present invention can be carried out by a method other than the method specifically described.

The following claims are incorporated herein by reference as numbered embodiments in which the term "claim" has been replaced by the term "aspect" respectively.

Claims (5)

General formula [A]:
Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Q, [A];
(During the ceremony
Each X is independently a divalent organic group,-[divalent organic group] -O- or O,
Y is F, H or -X-Q,
Z is independently − (CF ₂ ) −, − (CF (CF ₃ ) CF ₂ O) −, − (CF ₂ CF (CF ₃ ) O) −, − (CF (CF ₃ ) O) −, -(CF (CF ₃ ) CF ₂ )-,-(CF ₂ CF (CF ₃ ))-and-(CF (CF ₃ ))-are selected from
The subscript a is an integer from 1 to 200 and
Subscripts b, c, d, e, f and g is Ru integer der selected from 0 to 200 independently, however, the subscript b, c, d, e, f and g are , Must not be 0 at the same time
Each Q is independently -C≡CH or -Y'-CR = CH ₂ .
Each R is independently H, CH ₃ or Y'-hydrogenyl and
Each Y'is independently isomerized by O, -N (R)-, S, or a hydrocarbylene group that prevents the mobile isomerization of the carbon-carbon double bond of Q). Possible aliphatic unsaturated polyfluoropolyether. Isomerization impossible aliphatic unsaturated saturated Kazupo Li fluoropolyether according to claim 1, SiH- functional silane or SiH- silicon containing polyfluoropolyether containing the product of the hydrosilylation reaction with the functional siloxane A silicon-containing polyfluoropolyether, wherein the product of the hydrosilylation reaction is not contaminated with a by-product containing a mobile isomerized C = C bond. General formula [B]:
Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Y'-CH = CH 2, [B];
(During the ceremony
Each X is independently a divalent organic group,-[divalent organic group] -O- or O,
Y is F, H or -X-Y'-CH = CH ₂ .
Z is independently − (CF ₂ ) −, − (CF (CF ₃ ) CF ₂ O) −, − (CF ₂ CF (CF ₃ ) O) −, − (CF (CF ₃ ) O) −, -(CF (CF ₃ ) CF ₂ )-,-(CF ₂ CF (CF ₃ ))-and-(CF (CF ₃ ))-are selected from
The subscript a is an integer from 1 to 200 and
Subscripts b, c, d, e, f and g is Ru integer der selected from 0 to 200 independently, however, the subscript b, c, d, e, f and g are , Must not be 0 at the same time
Each Y 'is, O independently, -N (R) -, S, or due to human Dorokarubiren a group), a in a method for forming the isomerization impossible aliphatic unsaturated polyfluoropolyether hand,
The above method
The polyfluoropolyether alcohol comprises the step of reacting with 4-vinylbenzyl chloride and tetraethylammonium bromide to form the non-isomerizable aliphatic unsaturated polyfluoropolyether according to the general formula [B]. The fluoropolyether alcohol has the formula [a] :.
Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Y'-OH, [a];
(In the formula, Y, Y', Z and the subscripts a to g are as described above). Equation [C]:
A method for producing a surface-treated material containing a silicon-containing polyfluoropolyether compound according to (in the formula, the subscript n is 5 to 75).
The above method
The formula CF ₃ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) nCF (CF ₃ ) CH ₂ OCH ₂ (C) is obtained by reacting a polyfluoropolyether alcohol with 4-vinylbenzyl chloride and tetraethylammonium bromide. ₆ H ₄ ) A step of forming a non-isomerizable aliphatic unsaturated polyfluoropolyether by CH = CH ₂ and
A step of producing an intermediate product by reacting the formed non-isomerizable aliphatic unsaturated polyfluoropolyether with a cyclic SiH-functional siloxane compound in the presence of a hydrosilylation catalyst.
A method comprising the step of reacting the intermediate product with an unsaturated methacrylate-containing compound to form the silicon-containing polyfluoropolyether compound according to the formula [C]. General formula [D]:
Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Q [D];
(During the ceremony
Each X is independently a divalent organic group,-[divalent organic group] -O- or O,
Y is F, H or -X-Q,
Z is independently − (CF ₂ ) −, − (CF (CF ₃ ) CF ₂ O) −, − (CF ₂ CF (CF ₃ ) O) −, − (CF (CF ₃ ) O) −, -(CF (CF ₃ ) CF ₂ )-,-(CF ₂ CF (CF ₃ ))-and-(CF (CF ₃ ))-are selected from
a is an integer from 1 to 200,
b, c, d, e, f and g is Ru integer der selected from 0 to 200 independently, however, the subscript b, c, d, e, f and g are 0 at the same time Must not be
Each Q is independently -C≡CH or -Y'-C≡CH,
Each Y'is a method for forming non-isomerizable aliphatic unsaturated polyfluoropolyethers independently of O, -N (R)-, S or hydrocarbylene groups). ,
The above method
Br-CH ₂ C≡CH and tetraethylammonium bromide were expressed in the formula [b] :.
Y-Z _a -[(OC ₃ F ₆ ) _b- (OCF (CF ₃ ) CF ₂ ) _c- (OCF ₂ CF (CF ₃ )) _d- (OC ₂ F ₄ ) _e- (CF (CF ₃ )) _{) f - (OCF 2) g} ] -X-Y'-OH [b];
A method comprising mixing and reacting with a polyfluoropolyether alcohol according to (in the formula, Y, Y', Z and the subscripts a-g are as described above).