Method for evaluating weather resistance of coating, method for forming coating, and article having coating

Abstract

This invention provides a method for evaluating the weather resistance of a coating, a method for forming the coating, and an article having the coating. The coating is a polymer comprising a perfluoropolyether group, exhibiting excellent water and oil repellency, weather resistance, and adhesion. The coating also comprises a cured product of the perfluoropolyether group polymer, with a film density of 1.40 g / cm³ as measured by X-ray reflectance. 3 Above and 2.50 g / cm 3 The polymer having a perfluoropolyether group has residues of a divalent perfluoroalkylene oxide polymer and has a perfluoropolyether group, and has at least one hydrolytic group at at least one end in a molecule.

Description

[0001] This application is a divisional application of Chinese patent application No. 202110422474.5, filed on April 20, 2021, entitled “Method for evaluating the weather resistance of a coating and a method for making the coating and an article having the coating”. Technical Field

[0002] This invention relates to a method for evaluating the weather resistance of a coating, a method for forming the coating, and articles having the coating. Specifically, this invention relates to a method for evaluating the weather resistance of a coating comprising a polymer having perfluoropolyether groups, exhibiting excellent water and oil repellency, weather resistance, and adhesion, a method for forming the coating, and articles having the coating. Background Technology

[0003] Generally, compounds with fluorinated polyether groups possess water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties due to their very low surface free energy. Utilizing these properties, these compounds are widely used in industrial production as water and oil repellents and antifouling agents for paper / fibers, lubricants for magnetic recording media, oil repellents for precision machinery, mold release agents, cosmetic materials, and protective films. However, these properties also mean they are non-adhesive and non-adhesive to other substrates. Even if the compound containing fluorinated polyether groups can be coated onto the substrate surface, it is difficult to adhere the film containing the compound to the substrate.

[0004] On the other hand, silane coupling agents are widely known as materials for bonding organic compounds to the surface of substrates such as glass or cloth, and are widely used as coating agents for various substrate surfaces. A silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air to form a coating. This coating becomes a durable coating through chemical / physical bonding between the hydrolyzable silyl group and the surface of glass or metal.

[0005] Therefore, a composition has been disclosed (International Publication No. WO2017 / 038832 (Patent Document 1), Japanese Patent Application Publication No. 2019-131807 (Patent Document 2), and Japanese Patent Application Publication No. 2019-119747 (Patent Document 3)). The composition utilizes a polymer with perfluoropolyether groups in which hydrolyzable silyl groups have been incorporated into a compound having perfluoropolyether groups, thereby facilitating adhesion to the surface of a substrate and enabling the formation of a film on the surface of the substrate that exhibits water and oil repellency, chemical resistance, lubricity, mold release properties, and antifouling properties.

[0006] Cured coatings such as lenses or antireflective films, which are surface-treated with a composition containing a hydrolyzable silyl group introduced into the polymer having a perfluoropolyether group, exhibit excellent slipperiness and water and oil repellency, but their weather resistance has not yet been fully utilized.

[0007] Existing technical documents

[0008] Patent documents

[0009] [Patent Document 1] International Publication No. 2017 / 038832

[0010] [Patent Document 2] Japanese Patent Application Publication No. 2019-131807

[0011] [Patent Document 3] Japanese Patent Application Publication No. 2019-119747 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] Therefore, the object of the present invention is to provide a method for evaluating the weather resistance of a coating, a method for forming the coating, and an article having the coating. The method is used to provide a coating comprising a polymer having a perfluoropolyether group, and exhibiting excellent water and oil repellency, weather resistance, and adhesion.

[0014] Solution to the problem

[0015] Through diligent research in order to achieve the above objectives, the inventors discovered that by properly curing the film after its formation and controlling the film density within a given range, the weather resistance of the film can be improved, thus completing the present invention.

[0016] That is, the present invention provides a method for evaluating the weather resistance of a coating, a method for making the coating, and an article having the coating.

[0017] [1] A method for evaluating the weather resistance of a coating,

[0018] The evaluation method is a method for evaluating the weather resistance of a coating containing a polymer with a perfluoropolyether group.

[0019] The evaluation method involves determining the film density of a polymer coating with perfluoropolyether groups applied to a substrate surface using X-ray reflectance measurement, and determining that the film density is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 The following process, wherein the coating comprises a cured polymer having a perfluoropolyether group.

[0020] [2] The method for evaluating the weather resistance of a coating as described in [1]

[0021] Polymers having a perfluoropolyether group are polymers containing a divalent perfluoroalkylene oxide polymer residue in one molecule and having a perfluoropolyether group. The divalent perfluoroalkylene oxide polymer residue is designated as -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - indicates that the polymer having a perfluoropolyether group has at least one hydrolyzable group at at least one end of a molecule. In the above formula, p, q, r, s, and t are each independently an integer from 0 to 200, and p+q+r+s+t=3 to 500. Each perfluoroalkylene oxide repeating unit shown in parentheses can be randomly bonded, and d is independently an integer from 0 to 8. The unit can be either straight-chain or branched.

[0022] [3] The method for evaluating the weather resistance of a coating as described in [1] or [2],

[0023] The polymer having a perfluoropolyether group is selected from at least one of the fluorinated hydrolyzable organosilicon compounds represented by the following general formulas (1) to (5).

[0024] (A-Rf) α -ZW β (1)

[0025] Rf-(ZW) β )2(2)

[0026] Z'-(Rf-ZW) β ) γ (3)

[0027] In the formula, Rf represents -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d- indicates a divalent perfluoroalkylene oxide polymer residue, p, q, r, s, and t are each an independent integer from 0 to 200, and p+q+r+s+t=3~500. Each perfluoroalkylene oxide repeating unit shown in parentheses can be randomly bonded. d is an independent integer from 0 to 8, and this unit can be either straight-chain or branched. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated with a -CF3 group, a -CF2H group, or a -CH2F group. Z and Z' are independent single bonds or can include nitrogen, oxygen, silicon, phosphorus, or sulfur atoms, and can also be fluorine-substituted 2~8 valent organic groups. W is a monovalent organic group with a hydrolytic group at the end. α and β are each an independent integer from 1 to 7, and α+β=2~8 valent integers. γ is an integer from 2~8.

[0028] A-Rf-Q-(Y) δ -B(4)

[0029] Rf-(Q-(Y)) δ -B)2(5)

[0030] In the formula, Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is an integer from 1 to 10, Y is a divalent organic group with a hydrolytic group, and B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen atom.

[0031] [4] The method for evaluating the weather resistance of a coating as described in [3]

[0032] Wherein, Z is an organic group having a silylidene or cyclic siloxane structure.

[0033] [5] The method for evaluating the weather resistance of a coating as described in [3]

[0034] Wherein, Q is an organic group having a silymine or cyclic siloxane structure.

[0035] [6] A method,

[0036] The method is a method for preparing a coating, wherein the coating is used in any one of [1] to [5] in the method for evaluating the weather resistance of the coating and comprises a cured product of a polymer having a perfluoropolyether group.

[0037] The method for preparing the film includes the following steps.

[0038] The film density, measured by X-ray reflectance method, is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 The following method is used to cure / form a polymer coating with perfluoropolyether groups applied to the surface of a substrate.

[0039] [7] An item,

[0040] It has a coating comprising a cured polymer having a perfluoropolyether group, and the film density, measured by X-ray reflectance method, is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 the following.

[0041] The effects of the invention

[0042] The film of the evaluation object in the evaluation method of the present invention has excellent water and oil repellency and weather resistance because it includes a polymer with a perfluoropolyether group and the film density of the cured polymer is within a given range. Detailed Implementation

[0043] The present invention will now be described in detail.

[0044] The film evaluated in the evaluation method of the present invention is a film (cured product) comprising a polymer having a perfluoropolyether group, and has a film density of 1.40 g / cm³ as measured by X-ray reflectance method. 3 Above and 2.50 g / cm 3 The following membrane.

[0045] In the evaluation method of this invention, the membrane density of the evaluation object is from 1.40 g / cm³. 3 Up to 2.50 g / cm 3 Preferably, it is from 1.45 g / cm³ 3 Up to 2.30 g / cm 3 More preferably, from 1.50 g / cm 3 Up to 2.00 g / cm 3 The membrane density is less than 1.40 g / cm³. 3 The membrane failed to exhibit sufficient water and oil repellency. Furthermore, the membrane density was higher than 2.50 g / cm³. 3 Because the bulk density of the coating material significantly exceeds that of the perfluoropolyether-based polymers used as raw materials, it is difficult to manufacture such a coating.

[0046] The film density of the coating used in the evaluation method of the present invention can be determined by the X-ray reflectance method. For example, the X-ray reflectance of the coating is measured under the conditions shown below, and the film density of the coating can be calculated from the critical angle of total internal reflection obtained therefrom.

[0047] Measurement apparatus: ATX-G X-ray diffractometer (manufactured by Rigaku Corporation, Japan)

[0048] X-ray generating device: Rotating cathode type Cu

[0049] Output: 50kV 300mA

[0050] Measurement range: 0.3-4.0°

[0051] Stride length: 0.001°

[0052] Scanning speed: 0.2° / min

[0053] In this invention, the film density can be specified within the range shown above by appropriately setting curing conditions after preparing a film comprising a polymer having a perfluoropolyether group.

[0054] As a polymer having a perfluoropolyether group, it is preferably exemplified as a compound having a fluoroalkylene oxide (i.e., a monovalent or divalent perfluoropolyether residue) in one molecule. The fluoroalkylene oxide is a compound with a -C group. j F 2j Compounds having a (poly)fluoroalkylene oxide structure (divalent perfluoroalkylene oxide polymer residues) with multiple straight-chain (inline) bonds of repeating units represented by O- (where j is 1 or more, preferably 1 to 6, more preferably an integer from 1 to 4). Examples of polymers having perfluoropolyether groups include, in particular, polymers having 3 to 500 repeating units, preferably 15 to 200 repeating units, more preferably 20 to 100 repeating units, and more preferably 25 to 80 repeating units.

[0055] The above repeating unit-C j F 2j O- itself can be either straight or branched. For example, the following units can be listed, and more than two of these repeating units can be bonded together.

[0056] -CF2O-

[0057] -CF2CF2O-

[0058] -CF2CF2CF2O-

[0059] -CF(CF3)CF2O-

[0060] -CF2CF2CF2CF2O-

[0061] -CF2CF2CF2CF2CF2O-

[0062] -C(CF3)2O-

[0063] The above-mentioned (poly)fluorinated alkylene oxide structures (divalent perfluorinated alkylene oxide polymer residues), particularly -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - Wherein, p, q, r, s, and t are each independently an integer from 0 to 200; preferably, p is an integer from 5 to 100, q is an integer from 5 to 100, r is an integer from 0 to 100, s is an integer from 0 to 50, and t is an integer from 0 to 100, and p + q + r + s + t = an integer from 3 to 500; preferably, an integer from 10 to 105. It should be noted that in the above formula, except for the two terminal perfluoroalkylene units (CF2)... d In addition, each perfluoroalkylene oxide repeating unit shown in the brackets can also be randomly bonded. d is independently an integer from 0 to 8, preferably an integer from 0 to 5, more preferably an integer from 0 to 2, and the repeating unit can be either straight-chain or branched. In particular, it can be represented by the following structure.

[0064]

[0065] (In the formula, p', q', r', s', and t' are each independent integers from 1 to 200, and the sum of p', q', r', s', and t' is from 3 to 500. In the above formula, except for the two terminal perfluoroalkylene units (CF2)...) d’ In addition, each of the perfluoroalkylene oxide repeating units shown in parentheses can also be randomly bonded. d' is an independent integer from 0 to 5, and the repeating unit can be either straight-chain or branched.

[0066] The polymers having perfluoropolyether groups involved in this invention are more preferably fluorinated hydrolyzed organosilicon compounds represented by any one of the following general formulas (1) to (5). They can be used alone or in combination of two or more.

[0067] (A-Rf) α -ZW β (1)

[0068] Rf-(ZW) β )2(2)

[0069] Z'-(Rf-ZW)β ) γ (3)

[0070] A-Rf-Q-(Y) δ -B (4)

[0071] Rf-(Q-(Y)) δ -B)2(5)

[0072] In equations (1) to (5), Rf is -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - represents a divalent perfluoroalkylene oxide polymer residue. In Rf, p, q, r, s, and t are each independent integers from 0 to 200, and p+q+r+s+t=3~500. In the above formula, except for the two terminal perfluoroalkylene units (CF2) d In addition, each of the perfluoroalkylene oxide repeating units shown in the brackets can also be randomly bonded. d is an integer independently of 0 to 8, and the unit can be either straight-chain or branched.

[0073] A is a monovalent fluorine group containing a fluorine atom, a hydrogen atom, or a terminal -CF3, -CF2H, or -CH2F group. Z and Z' are independently single bonds or can include nitrogen, oxygen, silicon, phosphorus, or sulfur atoms, and can be substituted with fluorine, and are 2-8 valent organic groups, preferably including silane or cyclic siloxane structures. W is a monovalent organic group with a hydrolytic group at the end. α and β are independently integers from 1 to 7, wherein α is preferably an integer from 1 to 3, more preferably an integer of 1, β is an integer from 1 to 3, and α + β = an integer from 2 to 8, preferably an integer from 2 to 4. γ is an integer from 2 to 8, preferably 2 or 3.

[0074] Additionally, Q is a single bond or a divalent organic group, preferably including a silane or a cyclic siloxane structure. δ is an integer from 1 to 10, Y is a divalent organic group with a hydrolyzable group, and B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen atom.

[0075] In the above formulas (1) to (5), Rf is -(CF2) of the above (poly)fluorinated alkylene oxide structure (divalent perfluorinated alkylene oxide polymer residue). d -O-(CF2O) p (CF2CF2O) q(CF2CF2CF2O)r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - and can be exemplified as the same structure as above.

[0076] In formulas (1) and (4) above, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine group terminated with a -CF3 group, a -CF2H group, or a -CH2F group. Examples of monovalent fluorine groups terminated with a -CF3 group, a -CF2H group, or a -CH2F group include -CF3 group, -CF2CF3 group, -CF2CF2CF3 group, -CH2CF(CF3)-OC3F7 group, and -CH2OCF2CFH-OC3F7 group. Preferably, A is a -CF3 group, a -CF2CF3 group, a -CF2CF2CF3 group, or a -CH2OCF2CFH-OC3F7 group.

[0077] In formulas (1) to (3) above, Z and Z' are independently single bonds or can include nitrogen, oxygen, silicon, phosphorus, or sulfur atoms, and can also be 2- to 8-valent organic groups substituted with fluorine. These organic groups can be composed of (L) e -M (e is an integer from 1 to 7, preferably an integer from 1 to 3) represents this.

[0078] Here, L is a single bond or an oxygen atom, a sulfur atom, or a divalent organic group, and in formulas (1) to (3) above, L of Z is a linking group between Rf and M (or W), and L of Z' is a linking group between M (or Rf) and Rf. As a divalent organic group, it is preferably a diorganosilyl group selected from amide bonds, ether bonds, carbonyl bonds, ester bonds, or dimethylmethylenesilyl groups, etc., or -Si[OH][(CH2)] f The group represented by Si(CH3)3]- (f is an integer from 2 to 4) is a divalent organic group with 2 to 12 unsubstituted or substituted carbon atoms, more preferably a divalent hydrocarbon group with 2 to 12 unsubstituted or substituted carbon atoms in the structure.

[0079] Examples of divalent hydrocarbon groups with 2 to 12 unsubstituted or substituted carbon atoms include, for example, alkylene groups such as ethylene, propyleneene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, octamethylene, etc., arylene groups such as phenylene, or combinations of two or more of these groups (alkylene, aryl, etc.). Alternatively, these groups may be groups in which some or all of the hydrogen atoms bonded to the carbon atoms are replaced by halogen atoms such as fluorine or iodine. Preferably, the unsubstituted or substituted alkylene or phenylene groups have 2 to 4 carbon atoms.

[0080] As a divalent organic group of L, examples include groups with the structures shown below or groups that have bonded two or more of these organic groups.

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] (In the formula, f is an integer from 2 to 4, b is an integer from 2 to 6, preferably an integer from 2 to 4, u and v are integers from 1 to 4 respectively, g is an integer from 2 to 4, and Me is a methyl group.)

[0088] Additionally, in (L) e In the organic group represented by -M (e is an integer from 1 to 7, preferably an integer from 1 to 3), M is a single bond or a nitrogen atom, silicon atom, carbon atom, phosphorus atom, or a group including these, or an organic group with a valence of 2 to 8 (the above (e+1) valence). Specifically, it is a single bond, selected from those denoted by -R 1 2C- represents a divalent group, and -R represents a divalent group. 3 2Si- represents a divalent group, and -NR 4 - indicates a divalent group, -N= indicates a trivalent group, -P= indicates a trivalent group, -PO= indicates a trivalent group, -R... 1 C= represents a trivalent group, -R 3 The group represented by Si is a trivalent group, a tetravalent group represented by -C≡, a tetravalent group represented by -OC≡, and a tetravalent group represented by -Si≡, or a 2- to 8-valent siloxane residue. In the above formulas (1) to (3), the M of Z is a linking group of L (or Rf) and W, and the M of Z' is a group that is linked by L and Rf (or Rf to each other).

[0089] In the above, R 1 The groups are independently alkyl or hydroxyl groups having 1 to 3 carbon atoms, or may contain repeating units of alkylene oxide having 1 to 3 carbon atoms in a diorganosiloxane structure having 2 to 51 silicon atoms, or groups starting with R. 2 3SiO- represents a silyl ether group. R 2Each of the atoms is a hydrogen atom, preferably an alkyl group or phenyl group with 1 to 3 carbon atoms, or an alkoxy group with 1 to 3 carbon atoms.

[0090] R 3 Independently, they are preferably alkyl groups having 1 to 3 carbon atoms, alkenyl groups having 2 or 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, or chloro groups.

[0091] R 4 It is an alkyl group with 1 to 3 carbon atoms, a phenyl group with 6 to 10 carbon atoms, or an aryl group.

[0092] When M is a siloxane residue, it preferably has a straight-chain, branched, or cyclic organopolysiloxane structure with 2 to 51 silicon atoms, more preferably 2 to 13 silicon atoms, more preferably 2 to 11 silicon atoms, and even more preferably 2 to 5 silicon atoms. This organopolysiloxane may also have unsubstituted or fluorinated alkyl or phenyl groups such as methyl, ethyl, propyl, butyl, and C3F7-C3H6- having 1 to 8 carbon atoms. Additionally, it may include a silane-alkylene structure with two silicon atoms bonded by an alkylene group, i.e., including Si-(CH2). n -Si. In the formula, n is an integer from 2 to 6, preferably an integer from 2 to 4.

[0093] Examples of such groups as M are shown below.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] (In the formula, i is an integer from 1 to 20, c is an integer from 1 to 50, and Me is a methyl group.)

[0102] In the above formulas (1) to (3), W is a monovalent organic group with a hydrolytic group at the end, preferably a group represented by the following formula.

[0103]

[0104] (In the formula, R is an alkyl or phenyl group with 1 to 4 carbon atoms, X is a hydrolyzable group, a is 2 or 3, and m is an integer from 0 to 10.)

[0105] In the above formula, the hydrolysis group of X can be listed as alkoxy groups with 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy; alkoxy groups with 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy; acyloxy groups with 1 to 10 carbon atoms, such as acetoxy; alkenoxy groups with 2 to 10 carbon atoms, such as isopropenoxy; halogen groups such as chloro, bromo, and iodo; and amino groups. Among these, methoxy and ethoxy are preferred.

[0106] In addition, R is an alkyl or phenyl group such as methyl or ethyl, having 1 to 4 carbon atoms. Methyl is preferred.

[0107] a is 2 or 3, but from the viewpoint of reactivity and adhesion to the substrate, a is preferably 3. m is an integer from 0 to 10, preferably an integer from 2 to 8, and more preferably an integer from 2 or 3.

[0108] In equations (1) to (3), -ZW is used as the basis for... β The structure can be represented by the following examples.

[0109]

[0110]

[0111]

[0112] (In the formula, L, R, X, f, c, and a are as described above. m1 is an integer from 0 to 10, preferably an integer from 2 to 8. m2 is an integer from 1 to 10, preferably an integer from 2 to 8, and Me is methyl.)

[0113] In formulas (4) and (5) above, Q is a single bond or a divalent organic group, and is a linking group between Rf and Y. The divalent organic group of Q is preferably a diorganosilyl group selected from amide bonds, ether bonds, ester bonds, or dimethylmethylenesilyl groups, or -Si[OH][(CH2)] f The group formed by the group represented by Si(CH3)3]- (f is an integer from 2 to 4) consists of one or more unsubstituted or substituted divalent organic groups with 2 to 12 carbon atoms, more preferably including unsubstituted or substituted divalent hydrocarbon groups with 2 to 12 carbon atoms in the structure.

[0114] As the unsubstituted or substituted divalent hydrocarbon group with 2 to 12 carbon atoms, the same group as the unsubstituted or substituted divalent hydrocarbon group with 2 to 12 carbon atoms illustrated in L above can be exemplified.

[0115] As a divalent organic group of Q, examples include groups represented by the following structures.

[0116]

[0117]

[0118]

[0119]

[0120] (In the formula, f is an integer from 2 to 4, b is an integer from 2 to 6, preferably an integer from 2 to 4, u and v are integers from 1 to 4 respectively, g is an integer from 2 to 4, and Me is methyl.)

[0121] In the above formulas (4) and (5), Y is a divalent organic group with a hydrolyzable group, preferably a group with a structure represented by the following formula.

[0122]

[0123] (In the formula, R, X, and a are as described above. k is an integer from 0 to 10, preferably an integer from 1 to 10, more preferably an integer from 2 to 8. h is an integer from 1 to 6, preferably 1 or 2, and M' is an unsubstituted or substituted hydrocarbon group with a 3 to 8 valence, preferably trivalent or tetravalent, and some or all of the carbon atoms in the hydrocarbon group can be replaced by silicon atoms. In addition, some or all of the hydrogen atoms bonded to the carbon atom can also be replaced by halogen atoms such as fluorine atoms.)

[0124] M' is preferably a group represented by the following structure.

[0125]

[0126] (In the above, M) 1 A diorganosilyl group consisting of a single bond, an unsubstituted or substituted divalent hydrocarbon group or a dimethylmethylenesilyl group, etc., having 1 to 6 carbon atoms. M 2 For -R 1 C= represents a trivalent group or -R 3 Si represents a trivalent group. In M... 2 In the middle, R 1 R 3 Same as above. R 5 (A monovalent hydrocarbon group consisting of methyl, ethyl, propyl, or other alkyl groups having 1 to 6 carbon atoms.)

[0127] As M 1 Examples include single bonds, phenylene, dimethylmethylenesilyl, tetrafluoroethylene, etc. Additionally, as M... 2 Examples of such groups can be found below.

[0128]

[0129] (In the formula, Me is a methyl group.)

[0130] Examples of such a Y group include the following groups.

[0131]

[0132]

[0133] (In the formula, X is the same as above, k1 is an integer from 0 to 10, preferably an integer from 1 to 8, k2 is an integer from 2 to 10, preferably an integer from 2 to 8, and Me is methyl.)

[0134] In equations (4) and (5) above, δ is an integer from 1 to 10, preferably an integer from 1 to 4.

[0135] In addition, B can be a hydrogen atom, an alkyl group such as methyl, ethyl, propyl and butyl with 1 to 4 carbon atoms, or a halogen atom such as fluorine, chlorine, bromine and iodine.

[0136] Examples of polymers (fluorinated hydrolyzed organosilicon compounds) having perfluoropolyether groups, represented by formulas (1) to (5) above, include the following compounds.

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] (In the formula, Me is a methyl group, p1, q1, r1, s1, and t1 are each an independent integer from 1 to 200, and the sum of p1, q1, r1, s1, and t1 is 3 to 500. The repeating units shown in parentheses can also be randomly bonded.)

[0169] It should be noted that the polymers (fluorinated hydrolyzed organosilicon compounds) represented by general formulas (1) to (5) of the present invention may include compounds that hydrolyze part or all of the above-mentioned hydrolyzed groups (X) (compounds in which X is an OH group), or compounds that condense part or all of the OH groups.

[0170] The aforementioned fluorinated hydrolyzable organosilicon compounds are preferably pre-diluted with a solvent. There are no particular limitations on the solvent, as long as it can uniformly dissolve the fluorinated hydrolyzable organosilicon compounds. Examples include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorinated aromatic hydrocarbon solvents (1,3-trifluoromethylbenzene, etc.), fluorinated ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorinated alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum ether, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these solvents, from the viewpoint of solubility and stability, fluorinated solvents are preferred, and particularly preferred are fluorinated ether solvents and fluorinated aromatic hydrocarbon solvents.

[0171] The solvents described above can be used alone or in combination of two or more. Ideally, the solvents should contain 0.01 to 50% by mass, preferably 0.03 to 10% by mass, and more preferably 0.05 to 1% by mass, of the fluorinated hydrolyzed organosilicon compound in the water- and oil-repellent agent (including a solution of the fluorinated hydrolyzed organosilicon compound and the solvent).

[0172] Using known methods such as wet coating (immersion coating, brush coating, spin coating, spray coating, gravure coating, mold coating, rod coating, slot coating), vapor deposition, etc., a water- and oil-repellent agent containing the above-mentioned fluorinated hydrolyzed organosilicon compound can be applied to the substrate.

[0173] It should be noted that before applying a water- and oil-repellent agent containing fluorinated hydrolyzed organosilicon compounds, the surface of the primer layer on the substrate can be cleaned by plasma treatment, UV treatment, ozone treatment, or subjected to surface activation treatment.

[0174] The thickness of the fluorine layer (water-repellent and oil-repellent layer) of the water-repellent and oil-repellent component formed by the coating in the evaluation method of the present invention is preferably 0.5 to 30 nm, and particularly preferably 1 to 20 nm.

[0175] Depending on the requirements, a hydrolysis-condensation catalyst may also be added to the membrane of the present invention, for example, an organotin compound (dimethoxydibutyltin, dibutyltin dilaurate, etc.), an organotitanium compound (tetrabutyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorinated carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetrabutyl titanate, dibutyltin dilaurate, and fluorinated carboxylic acid are particularly preferred.

[0176] The amount of hydrolysis condensation catalyst added is the catalyst amount, which is typically 0.01 to 5 parts by mass, particularly preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the polymer having fluorinated polyether groups and / or its partial (hydrolyzed) polymer.

[0177] The substrate treated with the coating of the present invention is not particularly limited and can be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The coating of the present invention imparts water and oil repellency to the substrate. The coating of the present invention is particularly suitable for use as a surface treatment material for glass or films treated with SiO2.

[0178] Articles treated with the coating of the present invention include, but are not limited to, medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital camcorders, PDAs, portable audio players, car stereos, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastroscopes; photocopiers; PCs; liquid crystal displays; organic EL displays; plasma displays; touch panel displays; protective films; and anti-reflective films. The coating of the present invention, because it can prevent fingerprints and sebum from adhering to said articles and can further impart scratch resistance, is particularly useful as a water- and oil-repellent layer for touch panel displays, anti-reflective films, etc.

[0179] The coating of the present invention is useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins; an anti-fouling coating for glass windows or tempered glass, headlight covers, etc. of automobiles, trains, airplanes, etc.; a water- and oil-repellent coating for exterior building materials; an oil-resistant coating for kitchen building materials; an anti-fouling and anti-posting / anti-graffiti coating for telephone booths; an anti-fingerprint coating for artworks, etc.; an anti-fingerprint coating for optical discs, DVDs, etc.; a mold release agent or coating additive for molds; a resin modifier, a flow modifier or dispersant modifier for inorganic fillers; and a lubricity improver for tapes, films, etc.

[0180] Method for manufacturing film

[0181] In the weather resistance evaluation method of this invention, the film of the evaluation object is only required to have a film density of 1.40 g / cm³ obtained by X-ray reflectance method. 3 Above and 2.50 g / cm 3The following is acceptable. There are no particular limitations on the application method (coating method) or curing method for the substrate surface of the polymer with perfluoropolyether groups used to manufacture this film; conventional methods can be used. However, depending on the type (molecular structure) of the polymer with perfluoropolyether groups applied, a film density of 1.40 g / cm³, measured by X-ray reflectance method, can also be used. 3 Above and 2.50 g / cm 3 The following application method (coating method) applies a polymer with perfluoropolyether groups to the surface of a substrate, and the film density, measured by X-ray reflectance method, is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 The following curing method (under conditions of temperature, humidity, time, etc.) is used to cure and form a film, thereby creating a coating layer that can be used in the evaluation method of the present invention. It should be noted that the method for determining the film density of the coating by X-ray reflectance is as described above.

[0182] [Example]

[0183] Film formation and curing

[0184] [Coating Method]

[0185] (A) Vacuum evaporation

[0186] First, the surface of the tempered glass (Gorilla3 manufactured by Corning Incorporated) was subjected to plasma treatment cleaning under the following conditions.

[0187] Next, each surface treatment agent was prepared by dissolving the polymers with perfluoropolyether groups obtained in Examples 1-6, 9-11, 13, 14, and Comparative Examples 1-3, 5 in Novec 7200 (ethyl perfluorobutyl ether manufactured by 3M) at a concentration of 20% by mass. Then, 4 μL of each of the prepared surface treatment agents was coated onto each tempered glass substrate with a film thickness of approximately 10 nm, thereby obtaining each film (processing conditions: pressure: 2.0 × 10⁻⁶). -2 Pa, heating temperature: 700℃; vacuum evaporation equipment: model: VTR-350M / ERH, manufactured by Albak Kiko.

[0188] [Conditions for plasma treatment]

[0189] Equipment: PDC210 plasma drying and cleaning system

[0190] Gases: 80cc oxygen, 10cc argon

[0191] Output: 250W

[0192] Time: 30 seconds

[0193] (B) Spraying

[0194] First, under the same conditions as described above, the surface of the tempered glass (Gorilla3 manufactured by Corning Incorporated) was subjected to plasma treatment cleaning.

[0195] Next, at a concentration of 0.1% by mass, the polymers with perfluoropolyether groups obtained in Examples 7, 8, 12, 15, and Comparative Examples 4 and 6 were dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to prepare various surface treatment agents. Using a spray coating apparatus (manufactured by T&K Inc. NST-51), the surface treatment agents obtained above were coated onto each tempered glass with a film thickness of approximately 10 nm to obtain various films.

[0196] (C) Impregnation

[0197] First, the surface of the tempered glass (Gorilla3 manufactured by Corning Incorporated) was plasma-treated and cleaned under the same conditions as described above.

[0198] Next, a surface treatment agent was prepared by dissolving the compound obtained in Comparative Example 7 in Novec 7200 (ethyl perfluorobutyl ether manufactured by 3M) at a concentration of 0.1% by mass. After immersing tempered glass in the surface treatment agent for 30 seconds, the tempered glass was lifted out of the surface treatment agent at a speed of 150 mm / min to obtain a coating.

[0199] [Curing Method]

[0200] Choose any one of the curing methods shown below to cure the film.

[0201] (a) Temperature: 40℃, Humidity: 80%, Curing time: 12 hours

[0202] (b) Temperature: 150℃; Curing time: 5 hours

[0203] (c) Temperature: 200℃; Curing time: 1 hour

[0204] (d) Temperature: 25℃; Humidity: 50%; Curing time: 12 hours

[0205] (e) Temperature: 120℃; Curing time: 30 minutes

[0206] (f) Temperature: 200℃; Curing time: 30 minutes

[0207] (g) Temperature: 25℃; Curing time: 1 hour

[0208] Example 1

[0209] Using coating method (A), the compound (I) shown below is applied to the tempered glass, and curing method (a) is selected to cure it, thereby obtaining a film.

[0210]

[0211] Example 2

[0212] Except for changing the curing method to curing method (d), the same method as in Example 1 was used to obtain the film.

[0213] Example 3

[0214] Except for changing the compound to compound (II) shown below, the same method as in Example 2 was used to obtain the film.

[0215]

[0216] Example 4

[0217] Except for changing the curing method to curing method (a), the same method as in Example 3 was used to obtain the film.

[0218] Example 5

[0219] Except for changing the compound to compound (III) shown below, the same method as in Example 1 was used to obtain the film.

[0220]

[0221] Example 6

[0222] Except for changing the compound to the compound (IV) shown below, the same method as in Example 1 was used to obtain the film.

[0223]

[0224] Example 7

[0225] Compound (IV) was applied onto tempered glass using coating method (B), and the resulting film was cured using curing method (b).

[0226] Example 8

[0227] Except for changing the curing method to curing method (e), the same method as in Example 7 was used to obtain the film.

[0228] Example 9

[0229] Except for changing the compound to the compound (V) shown below, the same method as in Example 1 was used to obtain the film.

[0230]

[0231] Example 10

[0232] Except for changing the curing method to curing method (d), the same method as in Example 9 was used to obtain the film.

[0233] Example 11

[0234] Except that the compound was changed to the compound shown below (VI) synthesized according to the method described in International Publication No. 2017 / 038832, the same method as in Example 1 was used to obtain the coating.

[0235] CF3-O-(CF2CF2O-CF2CF2CF2CF2O) X (CF2CF2O)-CF2CF2CF2-CONHCH2CH2CH2-Si(OCH3)3

[0236] (x=13) (VI)

[0237] Example 12

[0238] Except for changing the coating method to coating method (B) and the curing method to curing method (c), the same method as in Example 11 was used to obtain the film.

[0239] Example 13

[0240] Except for changing the compound to compound (VII) disclosed in Japanese Patent Application Publication No. 2019-131807, the same method as in Example 1 was used to obtain the film.

[0241] CF3CF2CF2-O-(CF2CF2CF2O) X -CF2CF2-CONHCH2C[CH2CH2CH2Si(OCH3)3]3

[0242] (x=30)

[0243] (VII)

[0244] Example 14

[0245] Except for changing the curing method to curing method (c), the same method as in Example 13 was used to obtain the film.

[0246] Example 15

[0247] Except for changing the coating method to coating method (B), the same method as in Example 14 was used to obtain the film.

[0248] Comparative Example 1

[0249] Except for changing the curing method to curing method (d), the same method as in Example 6 was used to obtain the film.

[0250] Comparative Example 2

[0251] Except for changing the curing method to curing method (d), the same method as in Example 5 was used to obtain the film.

[0252] Comparative Example 3

[0253] Except for changing the curing method to curing method (d), the same method as in Example 11 was used to obtain the film.

[0254] Comparative Example 4

[0255] Except for changing the curing method to curing method (e), the same method as in Example 12 was used to obtain the film.

[0256] Comparative Example 5

[0257] Except for changing the curing method to curing method (d), the same method as in Example 13 was used to obtain the film.

[0258] Comparative Example 6

[0259] Except for changing the curing method to curing method (f), the same method as in Example 15 was used to obtain the film.

[0260] Comparative Example 7

[0261] Using coating method (C), the compound (VIII) shown below is applied onto the tempered glass and cured using curing method (g) to obtain a coating.

[0262] C6F 12 SiNH 1.5

[0263] (VIII)

[0264] Evaluation of cured film

[0265] [Membrane density measurement]

[0266] The reflectance of X-rays was measured under the conditions described below, and the critical angle for total internal reflection was obtained from the X-ray reflectance measured above. The film density (g / cm³) of each cured film prepared in the Examples and Comparative Examples was then calculated. 3 The results are shown in Table 1.

[0267] Measurement apparatus: ATX-G X-ray diffractometer (manufactured by Rigaku Corporation)

[0268] X-ray generating device: Rotating cathode type Cu

[0269] Output: 50kV 300mA

[0270] Measurement range: 0.3-4.0°

[0271] Stride length: 0.001°

[0272] Scanning speed: 0.2° / minute

[0273] [Evaluation of water repellency]

[0274] The contact angles (water repellency) of the cured films prepared in the Examples and Comparative Examples were measured using a DropMaster contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., Japan). The results are shown in Table 1.

[0275] [Evaluation of weather resistance (UV test)]

[0276] Under the conditions shown below, each cured film prepared in the Examples and Comparative Examples was irradiated with UV light. Then, the water contact angle (hydrophobicity) of each cured film was measured using the same method as described above. The results are shown in Table 1.

[0277] Device: WEATHER-OMETER Ci4400 (manufactured by ATLAS)

[0278] Light source: metal halide lamp

[0279] Radiation intensity: 770 W / m 2

[0280] Wavelength range: 300-400nm

[0281] Blackboard temperature: 63℃

[0282] Irradiation time: 180 hours

[0283] Table 1

[0284]

[0285] As shown in Table 1, the film density measured by X-ray reflectance method in Examples 1-15 was 1.40 g / cm³. 3 Above and 2.50 g / cm 3 The coating exhibits good weather resistance. Furthermore, the coating also shows good adhesion to the substrate.

Claims

1. A method for evaluating the weather resistance of a coating, The evaluation method is a method for evaluating the weather resistance of a coating containing a polymer with perfluoropolyether groups. The evaluation method involves determining the film density of a polymer coating with perfluoropolyether groups applied to a substrate surface via vacuum evaporation, spray coating, or dip coating using X-ray reflectance measurement, and determining that the film density is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 The following process, wherein the coating comprises a cured polymer having a perfluoropolyether group.

2. The method for evaluating the weather resistance of a coating as described in claim 1, A polymer having a perfluoropolyether group is a polymer having a divalent perfluoroalkylene oxide polymer residue in one molecule and having a perfluoropolyether group, wherein the divalent perfluoroalkylene oxide polymer residue is in the form of -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - indicates that the polymer having a perfluoropolyether group has at least one hydrolyzable group at at least one end of a molecule. In the above formula, p, q, r, s, and t are each independently an integer from 0 to 200, and p+q+r+s+t=3 to 500. Each perfluoroalkylene oxide repeating unit shown in parentheses can be randomly bonded, and d is independently an integer from 0 to 8. This unit can be either a straight chain or a branched chain.

3. The method for evaluating the weather resistance of a coating as described in claim 1 or claim 2, The polymer having a perfluoropolyether group is selected from at least one of the fluorinated hydrolyzable organosilicon compounds represented by the following general formulas (1) to (5). (A-Rf) α -ZW β (1) Rf-(ZW β )2(2) Z’-(Rf-ZW β ) γ (3) In the formula, Rf represents -(CF2). d -O-(CF2O) p (CF2CF2O) q (CF2CF2CF2O) r (CF2CF2CF2CF2O) s (CF(CF3)CF2O) t -(CF2) d - indicates a divalent perfluoroalkylene oxide polymer residue, p, q, r, s, and t are each an independent integer from 0 to 200, and p+q+r+s+t=3~500. Each perfluoroalkylene oxide repeating unit shown in parentheses can be randomly bonded. d is an independent integer from 0 to 8, and this unit can be either straight-chain or branched. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group terminated with a -CF3 group, a -CF2H group, or a -CH2F group. Z and Z' are independent single bonds or can include nitrogen, oxygen, silicon, phosphorus, or sulfur atoms, and can also be fluorine-substituted 2~8 valent organic groups. W is a monovalent organic group with a hydrolytic group at the end. α and β are each an independent integer from 1 to 7, and α+β=2~8 valent integers. γ is an integer from 2~8. A-Rf-Q-(Y) δ -B(4) Rf-(Q-(Y) δ -B)2(5) In the formula, Rf and A are the same as above, Q is a single bond or a divalent organic group, δ is an integer from 1 to 10, Y is a divalent organic group with a hydrolytic group, and B is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a halogen atom.

4. The method for evaluating the weather resistance of a coating as described in claim 3, in, Z is an organic group having a silylidene or cyclic siloxane structure.

5. The method for evaluating the weather resistance of a coating as described in claim 3, in, Q is an organic group having a silymine or cyclic siloxane structure.

6. One method, The method described is a method for preparing a coating, wherein the coating is used in the method for evaluating the weather resistance of the coating as described in any one of claims 1 to 5 and comprises a cured product of a polymer having a perfluoropolyether group. The method for preparing the film includes the following steps. Polymer coatings with perfluoropolyether groups applied to the surface of a substrate by vacuum evaporation, spray coating, or dip coating are cured / filmed under specified curing conditions. The film density, measured by X-ray reflectance method, is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 the following.

7. An item, It has a coating film, which is prepared by the method of claim 6, comprising a cured polymer having a perfluoropolyether group, and the film density measured by X-ray reflectance method is 1.40 g / cm³. 3 Above and 2.50 g / cm 3 the following.

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