Hybrid composition

Abstract

To provide a mixed composition that can form a film having excellent liquid repellency (in particular water repellency) and provide a film of the cured mixed composition and glass having the film.SOLUTION: The present disclosure provides a mixed composition of a compound (A1) represented by formula (a1), an organosilicon compound (B) represented by formula (b1), and an organosilicon compound (C) represented by formula (c1). The mass ratio [A1 / (B+C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.060 or greater.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a mixed composition capable of forming a film having liquid repellency on various substrates, a film obtained by curing the mixed composition, and glass having the film.

Background Art

[0002] In various vehicles, houses, building facilities, etc., problems such as deterioration of visibility due to dirt on the surface of window glass and poor appearance may occur. Therefore, it is required that the surface of a substrate such as glass has good liquid repellency. In particular, it is required not only to prevent droplets from adhering to the substrate surface but also to easily remove the adhered droplets. As a film that can improve liquid repellency by forming on the substrate surface, Patent Document 1 discloses a transparent film containing a polysiloxane skeleton and a trialkylsilyl group-containing molecular chain bonded to some of the silicon atoms forming the polysiloxane skeleton.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a mixed composition capable of forming a film excellent in liquid repellency (particularly water repellency). Another object of the present invention is to provide a film obtained by curing the above mixed composition and glass having the above film.

Means for Solving the Problems

[0005] The present invention is as follows. [1] A mixed composition of a compound (A1) represented by formula (a1), an organosilicon compound (B) represented by formula (b1), and an organosilicon compound (C) represented by formula (c1), wherein the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.060 or more. [Chemical formula] [In formula (a1), A a1 represents a hydroxy group or a hydrolyzable group. When there are a plurality of A a1 , the plurality of A a1 may be different from each other. Z a1 represents a hydrocarbon group, a trialkylsilyl group-containing molecular chain, or a siloxane skeleton-containing group. When there are a plurality of Z a1 , the plurality of Z a1 may be different from each other. r1 represents an integer from 1 to 3. R a1 represents a group represented by formula (a11).] [Chemical formula] [In formula (a11), R s2 each independently represents an alkyl group having 1 to 4 carbon atoms. R a11 represents a hydrocarbon group or a trialkylsilyloxy group. The hydrogen atoms contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with fluorine atoms. When there are a plurality of R a11 , the plurality of R a11 may be different from each other. A a11 represents a hydroxy group or a hydrolyzable group. When there are a plurality of A a11 , the plurality of A a11 may be different from each other. Z s1 represents -O- or a divalent hydrocarbon group. The -CH2- contained in the divalent hydrocarbon group may be replaced with -O-. Y s1 represents a single bond or -Si(R s2 )2-L s1represents - and L s1 represents a divalent hydrocarbon group, and the -CH2- contained in the divalent hydrocarbon group may be replaced by -O-. r2 represents an integer of 0 to 3, r10 represents an integer of 1 or more, and * represents a bond.] Si(R b1 ) b20 (X b1 ) 4-b20 (b1) [In formula (b1), R b1 represents a hydrocarbon group having 1 to 5 carbon atoms, X b1 represents a hydrolyzable group, and b20 is 0 or 1.] R c1 -Si(X c1 )3(c1) [In formula (c1), R c1 represents a hydrocarbon group having 6 to 30 carbon atoms, and X c1 represents a hydrolyzable group.] [2] The mixed composition according to [1], wherein the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.2 or more and 15 or less. [3] The mixed composition according to [1] or [2], wherein the mass ratio (A1 / C) of the compound (A1) to the organosilicon compound (C) is 0.2 or more and 30 or less. [4] The mixed composition according to any one of [1] to [3], wherein water (D) is mixed, and when the total of the mixed composition is 100% by mass, the amount of the water (D) is less than 20% by mass. [5] The mixed composition according to any one of [1] to [4], wherein a solvent (E) is mixed. [6] The mixed composition according to any one of [1] to [5], wherein a weak acid (G) having a pKa of 1 or more and 5 or less is mixed. [7] A film obtained by curing the mixed composition according to any one of [1] to [6]. [8] A film characterized in that when a spraying test for measuring the number of water sprayings A until water droplets slide off is continuously performed three times, the average of the number of sprayings A is less than 4.0 times. [9] The film according to [8], wherein the contact angle of water with respect to the film surface is 100° or more, and the sliding angle of water with respect to the film surface is 20° or less.

[10] Glass having the film according to any one of [7] to [9] on at least one side surface. In the present specification, when the ranges of the amounts, molar ratios, or mass ratios of the respective components are described, the ranges can be adjusted during the preparation of the mixed composition. [Advantages of the Invention]

[0006] By using the mixed composition of the present invention, a film excellent in liquid repellency (particularly water repellency) can be provided. [Embodiments for Carrying Out the Invention]

[0007] The mixed composition of the present invention is a mixed composition of a compound (A1) represented by the formula (a1), an organosilicon compound (B) represented by the formula (b1), and an organosilicon compound (C) represented by the formula (c1), and the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.060 or more. By using the above mixed composition, a film excellent in liquid repellency (particularly water repellency) can be formed. Further, by using the above mixed composition, the slipperiness of droplets with respect to the film is significantly increased, so that even fine droplets can be easily removed, and the droplet removability (particularly water droplet removability) of the film is also improved. Further, by mixing the organosilicon compound (C), the reaction is promoted and the film formation time can be shortened.

[0008] It is important that the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.060 or more. When the mass ratio [A1 / (B + C)] is 0.060 or more, the liquid repellency (particularly water repellency) can be further improved. Further, the droplet removability (particularly water droplet removability) of the film can also be improved. The mass ratio [A1 / (B + C)] is more preferably 0.065 or more, still more preferably 0.07 or more, even more preferably 0.1 or more, particularly preferably 0.2 or more, and most preferably 0.4 or more. The upper limit of the mass ratio [A1 / (B + C)] is, for example, 100 or less, more preferably 50 or less, still more preferably 30 or less, and particularly preferably 15 or less.

[0009] The following describes each component.

[0010] [Compound (A1)] The mixed composition of the present invention is mixed with a compound (A1) represented by the following formula (a1).

[0011] [Chemical formula]

[0012] In formula (a1), A a1 represents a hydroxy group or a hydrolyzable group. When there are a plurality of A a1 , the plurality of A a1 may be different from each other. Z a1 represents a hydrocarbon group, a trialkylsilyl group-containing molecular chain, or a siloxane skeleton-containing group. When there are a plurality of Z a1 , the plurality of Z a1 may be different from each other. r1 represents an integer of 1 to 3, and R a1 represents a group represented by formula (a11).

[0013] [Chemical formula]

[0014] In formula (a11), R s2 each independently represents an alkyl group having 1 to 4 carbon atoms, and R a11 represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with a fluorine atom. When there are a plurality of R a11 , the plurality of R a11 may be different from each other. A a11 represents a hydroxy group or a hydrolyzable group. When there are a plurality of A a11 , the plurality of A a11 may be different from each other. Z s1represents -O- or a divalent hydrocarbon group, and -CH2- contained in the divalent hydrocarbon group may be replaced by -O-, Y s1 is a single bond or -Si(R s2 )2-L s1 - represents, and L s1 represents a divalent hydrocarbon group, and -CH2- contained in the divalent hydrocarbon group may be replaced by -O-. r2 represents an integer from 0 to 3, r10 represents an integer of 1 or more, and * represents a bond.

[0015] When the above compound (A1) is mixed in a mixed composition, the liquid repellency (especially water repellency) is improved. Also, the droplet removability (especially water droplet removability) is improved.

[0016] First, in the group represented by the above formula (a11), the part represented by the following formula (s2) (hereinafter sometimes referred to as the molecular chain (s2)) will be described.

[0017] [Chemical formula]

[0018] In the molecular chain (s2), the number of carbon atoms of the alkyl group represented by R s2 is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2. Examples of the alkyl group represented by R s2 include a methyl group, an ethyl group, a propyl group, a butyl group, etc. A methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

[0019] In the molecular chain (s2), r10 is preferably an integer from 1 to 100, more preferably an integer from 1 to 80, still more preferably an integer from 1 to 60, particularly preferably an integer from 1 to 50, and most preferably an integer from 1 to 30.

[0020] In the molecular chain (s2), Z s1 or L s1The divalent hydrocarbon group represented by preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. The divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched. Further, the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkanediyl group. Examples of the divalent hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.

[0021] Furthermore, some of the -CH2- contained in the divalent hydrocarbon group may be replaced by -O-. In this case, two adjacent -CH2- are not simultaneously replaced by -O-, and the -CH2- adjacent to the Si atom is not replaced by -O-. When two or more -CH2- are replaced by -O-, the number of carbon atoms between -O- and -O- is preferably 2 to 4, and more preferably 2 or 3. Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by -O- include a group having a (poly)ethylene glycol unit, a group having a (poly)propylene glycol unit, and the like.

[0022] In the molecular chain (s2), Z s1 is preferably -O- or a divalent aliphatic hydrocarbon group, and more preferably -O-.

[0023] In the molecular chain (s2), Y s1 is preferably a single bond.

[0024] In the molecular chain (s2), Z s1 is -O-, and Y s1 is a single bond, that is, it is preferable that the molecular chain (s2) consists only of a repetition of a dialkylsilyloxy group.

[0025] Examples of the molecular chain (s2) include a molecular chain represented by the following formula. In the formula, r21 represents an integer of 1 or more, and * represents a bond bonded to a silicon atom. r21 is in the same numerical range as r10 described above, and the preferred range is also the same.

[0026] [Chemical formula]

[0027] [Chemical formula]

[0028] Next, the part other than the molecular chain (s2) in the group represented by the above formula (a11) will be described.

[0029] In formula (a11), R a11 represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atoms contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with fluorine atoms. When the number of carbon atoms is A, the number of substituted fluorine atoms is preferably 1 or more, more preferably 3 or more, and preferably 2×A + 1 or less.

[0030] R a11 When it is a hydrocarbon group, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. When R a11 is a hydrocarbon group, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0031] R a11 When it is a trialkylsilyloxy group, the alkyl group constituting the trialkylsilyloxy group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The three alkyl groups constituting the trialkylsilyloxy group may be the same or different, and are preferably the same. Note that the trialkylsilyloxy group means a group in which an oxygen atom is bonded to the silicon atom of the trialkylsilyl group.

[0032] In formula (a11), A a11represents a hydroxy group or a hydrolyzable group. The hydrolyzable group may be any group that gives a hydroxy group (silanol group) upon hydrolysis, and examples thereof preferably include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group, acetoxy group, chlorine atom, isocyanate group, etc. A a11 is more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms.

[0033] R represented by the above formula (a11) a1 is preferably a group represented by the following formula (a11-1) or formula (a11-2).

[0034]

Chemical formula

[0035] In formula (a11-1), Z s1 , R s2 , Y s1 , and r10 have the same meanings as described above, and R a13 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group may be substituted with a fluorine atom, and * represents a bond to a silicon atom.

[0036]

Chemical formula

[0037] In formula (a11-2), R s2 , and r10 have the same meanings as described above, and A a12 represents a hydroxy group or a hydrolyzable group. When there are a plurality of A a12 , the plurality of A a12 may be different from each other, R a12 represents a hydrocarbon group, and when there are a plurality of R a12 , the plurality of R a12They may be different from each other, and y12 represents an integer from 1 to 3. * represents a bond with a silicon atom.

[0038] First, the group represented by the formula (a11-1) will be described.

[0039] In the formula (a11-1), R a13 Examples of the hydrocarbon group represented by are the same as the hydrocarbon groups described above for R a11 An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms is even more preferable. In particular, when all of R a13 are hydrocarbon groups, R a13 is preferably an alkyl group. The three R a13 may be the same or different, and it is preferable that they are the same. When all of R a13 are hydrocarbon groups, the total number of carbon atoms of the three R a13 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less. It is preferable that at least one of the three R a13 is a methyl group, more preferably at least two are methyl groups, and particularly preferably all three R a13 are methyl groups.

[0040] In the formula (a11-1), examples of the trialkylsilyloxy group represented by R a13 are the same as the trialkylsilyloxy groups described above for R a11 , and the preferable ranges are also the same. In the formula (a11-1), at least one of R a13 may be a trialkylsilyloxy group, and it is also preferable that all of R a13 are trialkylsilyloxy groups.

[0041] The group represented by formula (a11-1) is more preferably a group represented by the following formula (s3-1), and even more preferably a group represented by the following formula (s3-1-1). Also, the group represented by formula (a11-1) is more preferably a group represented by the following formula (s3-2), and even more preferably a group represented by the following formula (s3-2-1).

[0042]

Chemical formula

[0043] In formulas (s3-1) and (s3-1-1), Z s1 , R s2 , Y s1 , r10 have the same meanings as described above. R s3 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond to a silicon atom.

[0044]

Chemical formula

[0045] In formula (s3-2) and formula (s3-2-1), Z s1 , R s2 , Y s1 , R s3 , r10 have the same meanings as described above. * represents a bond to a silicon atom.

[0046] R s3 The alkyl group represented by preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. Also, in formula (s3-1), formula (s3-1-1), formula (s3-2), and formula (s3-2-1), the total number of carbon atoms of R s3 contained in -Si(R s3 )3 is preferably 9 or less, more preferably 6 or less, even more preferably 4 or less. Further, among R s3 contained in -Si(R s3 )3, at least one is preferably a methyl group, more preferably two or more R s3 are methyl groups, and even more preferably all three Rs3 It is particularly preferred that all are methyl groups.

[0047] Examples of the group represented by formula (a11-1) include the group represented by formula (s3-I). In formula (s3-I), Z s10 , R s20 , n10, Y s10 , R s10 are preferably in the combinations shown in the following table.

[0048]

Chemical formula

[0049]

Table 1

[0050]

Table 2

[0051] n10 shown in Table 1 and Table 2 above is preferably an integer of 1 to 30.

[0052] Next, the group represented by formula (a11-2) will be described. In formula (a11-2), A a12 represents a hydroxy group or a hydrolyzable group. Examples of the hydrolyzable group include groups that give a hydroxy group (silanol group) upon hydrolysis, such as alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group, acetoxy group, chlorine atom, isocyanate group, etc. can be preferably mentioned. A a12 is preferably an alkoxy group having 1 to 4 carbon atoms or a hydroxy group, and more preferably an alkoxy group having 1 or 2 carbon atoms or a hydroxy group. When there are a plurality of A a12 , the plurality of A a12 may be the same or different, and are preferably the same.

[0053] In formula (a11-2), R a12Examples of the hydrocarbon group represented by the following formula include the same groups as the hydrocarbon groups described above for R a11 and an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is even more preferable. When there are a plurality of R a12 , the plurality of R a12 may be the same or different, and it is preferable that they are the same.

[0054] y12 is preferably 1 or 3.

[0055] Examples of the group represented by formula (a11-2) include the group represented by formula (s3-II). In formula (s3-II), A a0 , R s22 , n20, y0, R a0 are preferably in the combinations shown in the following table.

[0056]

Chemical formula

[0057]

Table 3

[0058] n20 shown in Table 3 above is preferably an integer of 1 to 30.

[0059] Next, formula (a1) will be described. A a1 in formula (a1) represents a hydroxy group or a hydrolyzable group, and examples of the hydrolyzable group include groups that give a hydroxy group (silanol group) upon hydrolysis, such as alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, and butoxy group, acetoxy group, chlorine atom, isocyanate group, etc. A a1 is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 or 2 carbon atoms. When there are a plurality of A a1 , the plurality of A a1 may be the same or different, and it is preferable that they are the same.

[0060] Z in formula (a1) a1 represents a hydrocarbon group, a molecular chain containing a trialkylsilyl group, or a group containing a siloxane skeleton.

[0061] Z a1 When Z is a hydrocarbon group, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2. Z a1 When Z is a hydrocarbon group, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, etc., a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0062] The molecular chain containing a trialkylsilyl group means a monovalent group having a structure in which a trialkylsilyl-containing group is bonded to the end of the molecular chain. Z a1 When Z is a molecular chain containing a trialkylsilyl group, it is a group represented by the above formula (a11-1), and when R a13 are all hydrocarbon groups, a group in which R a13 is an alkyl group is preferred.

[0063] Also, Z a1 When Z is a group containing a siloxane skeleton, the group containing a siloxane skeleton is a monovalent group containing a siloxane unit (Si-O-), and it is preferably composed of a smaller number of atoms than the number of atoms constituting R a1 . Thereby, the group containing a siloxane skeleton becomes a group having a shorter length or a smaller steric spread (bulkiness) than R a1 . The group containing a siloxane skeleton may contain a divalent hydrocarbon group.

[0064] The group containing a siloxane skeleton is preferably a group represented by the following formula (s4).

[0065]

Chemical formula

[0066] In formula (s4), R s2 has the same meaning as described above and each independently represents an alkyl group having 1 to 4 carbon atoms.

[0067] R s5 represents a hydrocarbon group or a hydroxy group, and -CH2- contained in the hydrocarbon group may be replaced by -O-, and a hydrogen atom contained in the hydrocarbon group may be substituted by a fluorine atom.

[0068] Z s2 represents -O- or a divalent hydrocarbon group, and -CH2- contained in the divalent hydrocarbon group may be replaced by -O-.

[0069] Y s2 represents a single bond or -Si(R s2 )2-L s2 -. L s2 represents a divalent hydrocarbon group, and -CH2- contained in the divalent hydrocarbon group may be replaced by -O-.

[0070] r40 represents an integer from 0 to 5. * represents a bond to a silicon atom.

[0071] In formula (s4), as the hydrocarbon group represented by R s5 , groups similar to the hydrocarbon groups described for R a11 above are exemplified. An aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0072] Z s2 or L s2 As the divalent hydrocarbon group represented by, groups similar to the divalent hydrocarbon group represented by Z s1 above are exemplified. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. Also, Z s2 or L s2The divalent hydrocarbon group represented by [formula] is preferably a divalent aliphatic hydrocarbon group, more preferably a linear or branched alkanediyl group.

[0073] r40 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3.

[0074] The total number of atoms of the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more. Also, R a1 The difference between the number of atoms of [group] and the number of atoms of the siloxane skeleton-containing group is preferably 10 or more, more preferably 20 or more, preferably 1000 or less, more preferably 500 or less, still more preferably 200 or less.

[0075] Specific examples of the siloxane skeleton-containing group include groups represented by the following formula.

[0076]

Chemical formula

[0077] In formula (a1), r1 represents an integer of 1 to 3, preferably 2 or 3, more preferably 3.

[0078] Examples of the compound (A1) represented by formula (a1) include compounds represented by the following formula (a1-1) or the following formula (a1-2).

[0079] Examples of the compound (A1) represented by formula (a1) include the compound represented by the following formula (a1-1), that is, the compound in which R in formula (a1) a1 is a group represented by formula (a11-1) and r1 in formula (a1) is 3.

[0080]

Chemical formula

[0081] In formula (a1-1), Aa1 , Z s1 , R s2 , Y s1 , R a13 , and r10 have the same meanings as defined above, respectively.

[0082] Among the compounds represented by formula (a1-1), the compounds represented by the following formula (I-1) are preferred, and the compounds represented by formula (I-1-1) are more preferred. Further, the compound represented by formula (a1-1) may be a compound represented by the following formula (I-2), preferably a compound represented by formula (I-2-1).

[0083] [Chemical formula]

[0084] In formula (I-1) and formula (I-1-1), A a1 , Z s1 , R s2 , Y s1 , R s3 , and r10 have the same meanings as defined above, respectively.

[0085] [Chemical formula]

[0086] In formula (I-2) and formula (I-2-1), A a1 , Z s1 , R s2 , Y s1 , R s3 , and r10 have the same meanings as defined above, respectively.

[0087] Specific examples of the compound represented by formula (a1-1) include the compounds represented by the following formula (I-I). In formula (I-I), A a20 , Z s10 , R s20 , n10, Y s10 , R s10 are preferably the combinations shown in the following table.

[0088] [Chemistry]

[0089] [Table 4-1]

[0090] [Table 4-2]

[0091] [Table 5-1]

[0092] [Table 5-2]

[0093] The n10 shown in the above Table 4-1, Table 4-2, Table 5-1, and Table 5-2 is preferably an integer from 1 to 30.

[0094] Among the compounds represented by the above formula (I-I), for example, the above (I-I-26) is represented by the following formula (a1-I).

[0095] [Chemistry]

[0096] In the formula (a1-I), n represents an integer from 1 to 60. n is more preferably an integer of 2 or more, still more preferably an integer of 3 or more, more preferably an integer of 50 or less, still more preferably an integer of 45 or less, particularly preferably an integer of 30 or less, and most preferably an integer of 25 or less.

[0097] Examples of the method for synthesizing the compound represented by the formula (a1-1) include the method described in JP-A-2017-201009.

[0098] Among the compounds (A1) represented by the formula (a1), as the compound represented by the above formula (a1-1), "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. can be used. "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. represented by the following formula has a trimethoxysilyl group only at one end, and the other end has no hydroxy group and hydrolyzable group, and is a compound containing a siloxane bond in the structure. When represented by the formula (a1), r1 is 3, and A a1 represents a methoxy group, and R a1 is a group represented by the formula (a11-1), and the weight average molecular weight is 3400.

[0099]

Chemical formula

[0100] As the compound (A1) represented by the formula (a1), a compound represented by the following formula (a1-2), that is, R in the formula (a1) a1 is a group represented by the formula (a11-2), and Z in the formula (a1) a1 is a hydrocarbon group, and the compound is also included.

[0101]

Chemical formula

[0102] In the formula (a1-2), A a1 , R s2 , A a12 , R a12 , r1, r10, and y12 have the same meanings as above, and Z a12 represents a hydrocarbon group. When there are a plurality of Z a12 , the plurality of Z a12 may be different from each other.

[0103] In the formula (a1-2), A a1 and A a12 may be the same or different, and it is preferably the same.

[0104] Za12 Examples of the hydrocarbon group represented by the above Z a1 include the same groups as those described above for Z. A methyl group or an ethyl group is preferred, and a methyl group is more preferred. Z a12 and R a12 may be the same or different, and are preferably the same.

[0105] Each of r1 and y12 is preferably 1 or 3. r1 and y12 may be the same or different, and are preferably the same.

[0106] Examples of the compound represented by formula (a1-2) include those in which R s2 is a methyl group, r10 represents an integer of 1 to 60, A a1 and A a12 are an alkoxy group or a hydroxy group having 1 to 2 carbon atoms, Z a12 and R a12 are a methyl group or an ethyl group, and r1 and y12 are the same and represent an integer of 1 to 3.

[0107] Specific examples of the compound represented by formula (a1-2) include the compounds represented by the following formula (I-II). In formula (I-II), A a00 , Z a0 , R s22 , n20, y0, A a0 , R a0 preferably have the combinations shown in the following table.

[0108]

Chemical formula

[0109]

Table 6

[0110] n20 shown in Table 6 above is preferably an integer of 1 to 30.

[0111] As the compound represented by the formula (a1-2), compounds (I-II-1) to (I-II-3), (I-II-13) to (I-II-15) are preferable, and more preferably compound (I-II-3), compound (I-II-13) or compound (I-II-14).

[0112] Among the compounds (A1) represented by the formula (a1), as the compound represented by the formula (a1-2), “DMS-S12” manufactured by Gelest or “KR-410” manufactured by Shin-Etsu Chemical Co., Ltd. can also be used. “DMS-S12” manufactured by Gelest is a compound in which n20 is 4 to 7 in the formula (I-II-3) shown in Table 6 above. “KR-410” manufactured by Shin-Etsu Chemical Co., Ltd. is a compound in which n20 is 10 in the formula (I-II-14) shown in Table 6 above.

[0113] The compound (A1) represented by the formula (a1) is preferably a compound represented by the formula (a1-1) or a compound represented by the formula (a1-2), and more preferably a compound represented by the formula (a1-1).

[0114] Only one kind of the compound (A1) may be used, or a plurality of them may be used in combination.

[0115] When the total of the mixed composition is 100% by mass, the amount of the compound (A1) is preferably 0.01 to 30% by mass. When a plurality of the compounds (A1) are used, the amount is the total amount thereof. The amount of the compound (A1) is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, more preferably 25% by mass or less, and still more preferably 10% by mass or less.

[0116] [Organic silicon compound (B)] The mixed composition of the present invention is mixed with an organic silicon compound (B) represented by the following formula (b1). By mixing the organic silicon compound (B), the liquid repellency is improved. Also, by mixing the organic silicon compound (B), the droplet removability is improved. Si(R b1 ) b20 (Xb1 ) 4-b20 (b1)

[0117] In formula (b1), R b1 represents a hydrocarbon group having 1 to 5 carbon atoms, X b1 represents a hydrolyzable group, and b20 is 0 or 1.

[0118] In the above formula (b1), the number of carbon atoms of the hydrocarbon group represented by R b1 is preferably 2 or more, preferably 4 or less, and more preferably 3 or less.

[0119] In the above formula (b1), the hydrocarbon group represented by R b1 is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group. As the alkyl group, a methyl group, an ethyl group, and a propyl group are particularly preferable.

[0120] In the above formula (b1), b20 is preferably 0.

[0121] In the above formula (b1), examples of the hydrolyzable group represented by X b1 include groups that give a hydroxy group (silanol group) upon hydrolysis, preferably an alkoxy group having 1 to 6 carbon atoms, a cyano group, an acetoxy group, a chlorine atom, an isocyanate group, etc. A plurality of X b1 may be the same or different, and are preferably the same. As X b1 , an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms) or an isocyanate group is preferable, an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms) is more preferable, and it is even more preferable that all X b1 are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms).

[0122] As the organosilicon compound (B), b20 is 0 and X b1It is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). Specific examples of the organosilicon compound (B) include tetramethoxysilane, tetraethoxysilane (tetraethyl orthosilicate), tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, etc., and tetramethoxysilane or tetraethoxysilane is preferred. The organosilicon compound (B) may be used alone or in combination of a plurality.

[0123] When the total amount of the mixed composition is 100% by mass, the amount of the organosilicon compound (B) is preferably 0.01 to 25% by mass. When a plurality of organosilicon compounds (B) are used, the amount thereof is the total amount thereof. The amount of the organosilicon compound (B) is more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, more preferably 20% by mass or less, still more preferably 5% by mass or less.

[0124] The molar ratio (B / A1) of the organosilicon compound (B) to the compound (A1) is preferably 0.1 or more and 1000 or less. The molar ratio (B / A1) is more preferably 0.3 or more, still more preferably 0.5 or more, even more preferably 0.8 or more, more preferably 800 or less, still more preferably 250 or less, even more preferably 30 or less, even more preferably 6 or less, and particularly even more preferably 4 or less. By setting the molar ratio (B / A1) within the above range, the storage stability of the composition can be improved.

[0125] The mass ratio (A1 / B) of the compound (A1) to the organosilicon compound (B) is preferably 0.001 or more and 40 or less. The mass ratio (A1 / B) is more preferably 0.01 or more, still more preferably 0.03 or more, more preferably 30 or less, still more preferably 20 or less.

[0126] [Organosilicon Compound (C)] The mixed composition of the present invention is mixed with an organosilicon compound (C) represented by the following formula (c1). By mixing the organosilicon compound (C), the reaction between the above compound (A1) and the above organosilicon compound (B) can be promoted, and the film formation time can be shortened. R c1 -Si(X c1 )3 (c1)

[0127] In formula (c1), R c1 represents a hydrocarbon group having 6 to 30 carbon atoms, and X c1 represents a hydrolyzable group.

[0128] In the above formula (c1), the number of carbon atoms of the hydrocarbon group represented by R c1 is preferably 7 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 12 or less.

[0129] R c1 The hydrocarbon group represented by is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and still more preferably a linear alkyl group. Examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. More preferably, they are an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group, and still more preferably an octyl group, a decyl group, and a dodecyl group.

[0130] In the above formula (c1), examples of the hydrolyzable group represented by X c1 include groups that give a hydroxy group (silanol group) upon hydrolysis, preferably an alkoxy group having 1 to 6 carbon atoms, a cyano group, an acetoxy group, a chlorine atom, an isocyanate group, etc. The three X c1 may be the same or different, and are preferably the same. X c1As the group, an alkoxy group or a cyano group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms) is preferred, an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms) is more preferred, and all X c1 is more preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms).

[0131] As the organosilicon compound (C), R c1 is a linear alkyl group having 6 to 18 carbon atoms (more preferably 8 to 18 carbon atoms, still more preferably 8 to 12 carbon atoms), and all X c1It is preferable that they are the same group and are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms, still more preferably 1 or 2 carbon atoms). Specific examples of the organosilicon compound (C) include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and the like. Among these, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane are preferable, and more preferably, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane. The organosilicon compound (C) may be used alone or in combination of two or more.

[0132] When the total amount of the mixed composition is 100% by mass, the amount of the organosilicon compound (C) is preferably 0.001 to 3% by mass. When a plurality of organosilicon compounds (C) are used, the amount thereof is the total amount of them. The amount of the organosilicon compound (C) is more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and more preferably 2% by mass or less, still more preferably 1% by mass or less.

[0133] When the total amount of the compound (A1), the organosilicon compound (B), and the organosilicon compound (C) (A1 + B + C) is 100% by mass of the entire mixed composition, it is preferably 0.1 to 30% by mass. The total amount (A1 + B + C) is more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and more preferably 15% by mass or less, still more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0134] The molar ratio (A1 / C) of the compound (A1) to the organosilicon compound (C) is preferably 0.001 or more and 5 or less. The molar ratio (A1 / C) is more preferably 0.005 or more, still more preferably 0.01 or more, and even more preferably 0.02 or more, and more preferably 4 or less, still more preferably 3 or less, and even more preferably 2.5 or less.

[0135] The mass ratio (A1 / C) of the compound (A1) to the organosilicon compound (C) is preferably 0.01 or more and 35 or less. The mass ratio [A1 / C] is more preferably 0.1 or more, still more preferably 0.2 or more, particularly preferably 0.3 or more, and more preferably 30 or less, still more preferably 28 or less.

[0136] The molar ratio (B / C) of the organosilicon compound (B) to the organosilicon compound (C) is preferably 0.01 or more and 48 or less. The molar ratio (B / C) is more preferably 0.1 or more, still more preferably 0.3 or more, and even more preferably 0.5 or more, and more preferably 40 or less, still more preferably 25 or less, and even more preferably 10 or less.

[0137] The above-described mixed composition may be mixed with water (D).

[0138] When the total amount of the mixed composition is 100% by mass, the amount of water (D) is preferably less than 20% by mass. More preferably, the amount of water (D) is less than 18% by mass, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The amount of water (D) may be, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more.

[0139] The amount of water (D) relative to compound (A1) is preferably 0.1 or more and 150 or less in terms of mass ratio (D / A1). The mass ratio (D / A1) is more preferably 0.12 or more, still more preferably 0.13 or more, more preferably 100 or less, and still more preferably 50 or less.

[0140] The amount of water (D) relative to the total amount of compound (A1), organosilicon compound (B), and organosilicon compound (C) is preferably 0.01 or more and 3 or less in terms of mass ratio [D / (A1 + B + C)]. The mass ratio [D / (A1 + B + C)] is more preferably 0.03 or more, still more preferably 0.05 or more, more preferably 2 or less, and still more preferably 1.5 or less.

[0141] In the mixed composition of the present invention, in addition to the above-described components, it is preferable that at least one of a solvent (E), a catalyst (F), and a weak acid (G) having an acid dissociation constant pKa of 1 or more and 5 or less is mixed.

[0142] [Solvent (E)] As the solvent (E), it is preferable that an organic solvent is mixed. Among organic solvents, hydrophilic organic solvents such as alcohol solvents, ether solvents, ketone solvents, ester solvents, and amide solvents are more preferable. These solvents may be used alone or in combination of two or more. Examples of alcohol solvents include ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, etc. Examples of ether solvents include dimethoxyethane, dioxane, etc. Examples of ketone solvents include methyl isobutyl ketone, etc. Examples of ester solvents include ethyl acetate, butyl acetate, etc. Examples of amide solvents include dimethylformamide, etc. Among these, as the solvent (E), alcohol solvents are preferable, and 2-propanol or ethanol is more preferable.

[0143] The solvent (E) may be adjusted according to the material of the substrate on which the mixed composition is applied to form a film. For example, when using a substrate of an organic material, it is preferable to use a ketone solvent, and when using a substrate of an inorganic material, it is preferable to use an alcohol solvent.

[0144] When the total of the mixed composition is 100% by mass, the amount of the solvent (E) is preferably 60 to 98.5% by mass. When a plurality of solvents (E) are used, the amount is the total of them. The amount of the solvent (E) is more preferably 65% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, more preferably 98.3% by mass or less, and further preferably 98% by mass or less.

[0145] [Catalyst (F)] As the catalyst (F), inorganic acids such as hydrogen chloride (usually used as hydrochloric acid), phosphoric acid, and nitric acid; carboxylic acid compounds (organic acids) such as maleic acid, malonic acid, formic acid, benzoic acid, phenylacetic acid, butanoic acid, 2-methylpropanoic acid, propanoic acid, 2,2-dimethylpropanoic acid, and acetic acid; basic compounds such as ammonia and amines; and organometallic compounds such as aluminum ethyl acetoacetate compounds can be used. As the catalyst (F), it is preferable to use acidic compounds such as inorganic acids and organic acids, more preferably an inorganic acid, and even more preferably hydrogen chloride (hydrochloric acid). The catalyst (F) may be used alone or in combination of a plurality.

[0146] When the total of the mixed composition is 100% by mass, the amount of the catalyst (F) is preferably 0.00001 to 0.015% by mass. When a plurality of the catalysts (F) are used, the amount thereof is the total amount thereof. The amount of the catalyst (F) is more preferably 0.00003% by mass or more, even more preferably 0.00005% by mass or more, more preferably 0.01% by mass or less, and even more preferably 0.009% by mass or less.

[0147] The amount of the catalyst (F) relative to the compound (A1) is preferably 0.000005 or more and 0.03 or less in terms of mass ratio (F / A1). The mass ratio (F / A1) is more preferably 0.00001 or more, even more preferably 0.00005 or more, more preferably 0.02 or less, and even more preferably 0.01 or less.

[0148] The amount of the catalyst (F) relative to the total amount of the compound (A1), the organosilicon compound (B), and the organosilicon compound (C) is preferably 0.000005 or more and 0.003 or less in terms of mass ratio [F / (A1 + B + C)]. The mass ratio [F / (A1 + B + C)] is more preferably 0.00001 or more, even more preferably 0.00005 or more, more preferably 0.002 or less, and even more preferably 0.001 or less.

[0149] [Weak acid (G) with pKa of 1 or more and 5 or less] When a catalyst other than a phosphoric acid or a carboxylic acid compound is used as the catalyst (F), it is preferable that a weak acid (G) having a pKa of 1 or more and 5 or less is mixed in the mixed composition of the present invention. Thereby, it is possible to suppress the gelation of the mixed composition and the impairment of storage stability. The pKa of the weak acid (G) is preferably 4.3 or less, more preferably 4.0 or less, still more preferably 3.5 or less. The pKa of the weak acid (G) is, for example, 1 or more. When the weak acid (G) has a plurality of pKas, it is determined whether or not it belongs to the pKa range based on the smallest pKa.

[0150] The weak acid (G) may be either an inorganic acid or an organic acid, and examples thereof include carboxylic acid compounds, phosphoric acid compounds, and the like. The weak acid (G) may be one kind or a combination of two or more kinds.

[0151] The carboxylic acid compound means a compound having at least one carboxy group, and may be either a monovalent carboxylic acid compound or a polyvalent carboxylic acid compound (a carboxylic acid compound having two or more carboxy groups), but a polyvalent carboxylic acid compound is preferred. Examples of the polyvalent carboxylic acid compound include oxalic acid in which two carboxy groups are directly bonded, or a polyvalent carboxylic acid compound (particularly a dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid) in which carboxy groups are bonded to both ends of a divalent hydrocarbon group and the number of carbon atoms in the main chain (longest straight chain) of the hydrocarbon group is 1 to 15 (more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms). The divalent hydrocarbon group may be linear or branched, may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and hydroxy groups or carboxy groups may be bonded to carbon atoms other than both ends of the hydrocarbon group.

[0152] Examples of the carboxylic acid compound include dicarboxylic acids such as oxalic acid (pKa = 1.27), malonic acid (pKa = 2.60), succinic acid (pKa = 3.99), maleic acid (pKa = 1.84), fumaric acid (pKa = 3.02), glutaric acid (pKa = 4.13), adipic acid (pKa = 4.26), pimelic acid (pKa = 4.71), tartaric acid (pKa = 2.98), malic acid (pKa = 3.23), phthalic acid (pKa = 2.89), itaconic acid (pKa = 3.85), muconic acid (pKa = 3.87), 1,4 - cyclohexanedicarboxylic acid (pKa = 4.51), 1,4 - naphthalenedicarboxylic acid, 2,6 - naphthalenedicarboxylic acid (pKa = 3.69), 2,7 - naphthalenedicarboxylic acid (pKa = 3.72), 4,4’ - biphenyldicarboxylic acid (pKa = 3.77); tricarboxylic acids such as citric acid (pKa = 2.90), aconitic acid (pKa = 2.8), trimellitic acid (pKa = 2.52), trimesic acid, biphenyl - 3,4’,5 - tricarboxylic acid (pKa = 3.36), tricarballylic acid (pKa = 3.49); tetracarboxylic acids such as butanetetracarboxylic acid (pKa = 3.25); and the like. The carboxylic acid compound is more preferably oxalic acid, or a dicarboxylic acid or tricarboxylic acid in which carboxy groups are bonded to both ends of a saturated or unsaturated linear hydrocarbon group having 1 to 3 carbon atoms (particularly 1 or 2 carbon atoms). Specifically, the above - mentioned carboxylic acid compounds are preferably oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, tricarballylic acid, etc., more preferably oxalic acid, malonic acid, succinic acid, maleic acid, tricarballylic acid, and particularly preferably malonic acid, succinic acid, tricarballylic acid.

[0153] The carboxylic acid compound may be a polymer having at least one carboxy group in the molecule. Examples of the polymer include polymers containing a structural unit having a carboxy group in the side chain, and may contain a structural unit having two or more types of carboxy groups in the side chain. Examples of the polymer having at least one carboxy group in the molecule include (meth)acrylic polymers having a carboxy group, polyester polymers having a carboxy group, polyolefin polymers having a carboxy group, and the like.

[0154] The carboxylic acid compound preferably has a molecular weight of 1000 or less, more preferably 500 or less. The molecular weight is preferably 50 or more, more preferably 80 or more, and still more preferably 90 or more.

[0155] The carboxylic acid compound is preferably a compound represented by the following formula (g1).

[0156]

Chemical formula

[0157] In the above formula (g1), R g1 and R g2 each independently represent a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a carboxy group and / or a hydroxy group, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a carboxy group, or a single bond. R g3 and R g4 each independently represent an alkyl group having 1 to 10 carbon atoms which may have a carboxy group, a carboxy group, or a hydrogen atom. g10 is 0 or 1.

[0158] R g1 and R g2 The divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by may be linear, branched, or cyclic, and specifically, examples include alkanediyl groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.

[0159] R g1 and R g2 Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by include a phenylene group.

[0160] R g1 and R g2 The divalent aliphatic hydrocarbon group represented by may have a carboxy group and / or a hydroxy group, and the divalent aromatic hydrocarbon group may have a carboxy group.

[0161] R g1 is preferably a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a carboxy group, and R g1 is more preferably a single bond or a divalent linear aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a carboxy group. R g2 is preferably a single bond.

[0162] R g3 and R g4 The alkyl group having 1 to 10 carbon atoms represented by may be linear, branched or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group and the like.

[0163] R g3 is preferably a hydrogen atom. R g4 is preferably a hydrogen atom.

[0164] The compound represented by the above formula (g1) is more preferably a compound represented by the following formula (g2). In the following formula (g2), g20 is an integer of 0 to 2.

[0165]

Chemical formula

[0166] g20 is preferably 1.

[0167] The carboxylic acid compound may be one kind or a combination of two or more kinds.

[0168] Examples of the phosphoric acid compound include orthophosphoric acid (pKa = 1.83); polyphosphoric acids such as pyrophosphoric acid (pKa = 1.57), tripolyphosphoric acid (pKa = 0.71), tetrapolyphosphoric acid (pKa = 0.33), trimeta - phosphoric acid, phosphorus pentoxide, and metaphosphoric acid. Among these, orthophosphoric acid is preferred. The phosphoric acid compound may be one kind or a combination of two or more kinds.

[0169] When the total of the mixed composition is 100% by mass, the amount of the weak acid (G) is preferably 0.001 to 3% by mass. When a plurality of weak acids (G) are used, the amount of the weak acid (G) is the total amount thereof. The amount of the weak acid (G) is more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more, and more preferably 2% by mass or less, still more preferably 1% by mass or less, even more preferably 0.5% by mass or less.

[0170] The amount of the weak acid (G) relative to the compound (A1) is preferably 0.001 or more and 1.5 or less in terms of mass ratio (G / A1). The mass ratio (G / A1) is more preferably 0.005 or more, still more preferably 0.01 or more, and more preferably 1 or less, still more preferably 0.8 or less.

[0171] The amount of the weak acid (G) relative to the total amount of the compound (A1), the organosilicon compound (B), and the organosilicon compound (C) is preferably 0.001 or more and 2 or less in terms of mass ratio [G / (A1 + B + C)]. The mass ratio [G / (A1 + B + C)] is more preferably 0.01 or more, even more preferably 0.015 or more, and more preferably 1 or less, even more preferably 0.5 or less.

[0172] In the mixed composition of the present invention, other components such as antioxidants, rust preventives, ultraviolet absorbers, light stabilizers, fungicides, antibacterial agents, anti - biofouling agents, deodorants, pigments, flame retardants, antistatic agents, etc., various additives may be mixed as long as the effects of the present invention are not inhibited.

[0173] The mixed composition of the present invention can be used as a mixed composition for forming a film excellent in liquid repellency (especially water repellency). Further, by using the mixed composition of the present invention, a film excellent in droplet removability (especially water droplet removability) can be formed. Further, the mixed composition of the present invention is also excellent in storage stability, and a film excellent in droplet removability (especially water droplet removability) can be provided even when using the mixed composition after long-term storage.

[0174] The mixed composition of the present invention can be produced by mixing the above-described components, for example, at room temperature.

[0175] As a method for imparting liquid repellency (more particularly, droplet removability) to a substrate using the mixed composition of the present invention, a method of forming a film on the surface of the substrate using the mixed composition of the present invention is preferable. As a method of forming a film on the surface of a substrate using the mixed composition of the present invention, a method of bringing the mixed composition of the present invention into contact with the substrate and then allowing it to stand still in air can be adopted.

[0176] As a method of bringing the mixed composition of the present invention into contact with the substrate, there are hand coating (a method of impregnating a cloth or the like with the mixed composition and applying the mixed composition to the substrate. When applying, it is preferable to reciprocate a plurality of times on the substrate), spin coating method, dip coating method, pouring (a method of directly pouring the mixed composition onto the substrate using a dropper or the like), spraying (a method of applying the mixed composition to the substrate using spraying), or a combination of these methods.

[0177] By allowing the mixed composition of the present invention to stand still in air at room temperature in a state where it is in contact with the substrate, the mixed composition cures, and a film (hereinafter sometimes referred to as a cured film) can be formed on the substrate. The film formed on the substrate is preferably a transparent film.

[0178] The standing time is not particularly limited, but for example, 10 minutes to 24 hours is preferable. Since the above organosilicon compound (C) is mixed in the mixed composition of the present invention, the reaction between the compound (A1) and the organosilicon compound (B) is promoted, and film formation can be achieved in a short time. The standing time is preferably 30 minutes or more, preferably 12 hours or less, more preferably 8 hours or less, still more preferably 5 hours or less, and particularly preferably 3 hours or less. It is also preferable to further dry the obtained film, for example, by blowing air.

[0179] The thickness of the film is preferably 1 nm or more, more preferably 1.5 nm or more, and the upper limit is, for example, 50 nm or less, and may be 20 nm or less. Since it is expected that good liquid repellency (particularly water repellency) can be stably exhibited when the film thickness is a certain value or more, it is preferable. Also, it can be expected that the droplet removability (particularly water droplet removability) is stably exhibited.

[0180] The present invention also includes a laminate including a cured film obtained from the above-described mixed composition and a substrate in contact with the cured film.

[0181] The material of the substrate used in the present invention may be an organic material or an inorganic material.

[0182] Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, and urethane resin; and the like.

[0183] Examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; and the like. Among them, glass is preferable.

[0184] The shape of the substrate used in the present invention is not particularly limited, and it may be either a flat surface or a curved surface, or a three-dimensional structure in which a large number of surfaces are combined.

[0185] The base material used in the present invention may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. Further, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, etc. may be performed, or a glass film such as polysilazane may be previously coated on the base material.

[0186] In the laminate of the present invention, the base material and the cured film may be laminated via a layer (X) different from the base material and the cured film.

[0187] The thickness of the layer (X) is, for example, preferably 0.1 nm or more, more preferably 1 nm or more, preferably 100 μm or less, more preferably 60 μm or less, and still more preferably 10 μm or less.

[0188] Examples of the layer (X) include a layer (X1) formed from at least one selected from the group (X1) consisting of an active energy ray-curable resin and a thermosetting resin, or a layer (X2) formed from at least one selected from the group (X2) consisting of titanium oxide (TiO2), zirconium oxide (ZrO2), aluminum oxide (Al2O3), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), lanthanum oxide (La2O3), and silica (SiO2).

[0189] [Layer (X1)] Active energy rays are defined as energy rays that can decompose a compound that generates active species to generate active species. Examples of active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays, and electron beams. Active energy ray-curable resins include, for example, acrylic resins, epoxy resins, oxetane resins, urethane resins, polyamide resins, vinylbenzyl chloride resins, vinyl resins (such as polyethylene and vinyl chloride resins), styrene resins, phenolic resins, vinyl ether resins, or silicone resins, or ultraviolet-curable resins such as mixed resins thereof, and electron beam-curable resins. In particular, ultraviolet-curable resins are preferred. As the group (X1), acrylic resins, epoxy resins, polyamide resins, vinyl resins (particularly vinyl chloride resins), styrene resins, phenolic resins, and silicone resins are particularly preferred.

[0190] When the layer (X) is formed from at least one selected from the group (X1), the layer (X) functions as a hard coat layer (hc) having surface hardness and can impart scratch resistance to the substrate. The hardness of the hard coat layer (hc) is usually B or more in terms of pencil hardness, preferably HB or more, more preferably H or more, and still more preferably 2H or more.

[0191] When the layer (X) contains a hard coat layer (hc), that is, when the layer (X) has the function of a hard coat layer, the structure of the hard coat layer (hc) is not particularly limited and may be a single-layer structure or a multilayer structure. The hard coat layer (hc) preferably contains, for example, the above-described ultraviolet-curable resin, particularly preferably contains an acrylic resin or a silicone resin, and preferably contains an acrylic resin in order to exhibit high hardness. In addition, since the adhesion between the substrate and the cured film tends to be good, it is also preferable to contain an epoxy resin.

[0192] When layer (X) includes a hard coat layer (hc), the hard coat layer (hc) may contain an additive. The additive is not limited and examples thereof include inorganic fine particles, organic fine particles, or a mixture thereof. Examples of the additive include, for example, an ultraviolet absorber; metal oxides such as silica and alumina; inorganic fillers such as polyorganosiloxane; By particularly containing an inorganic filler, the adhesion between the base material and the cured film can be improved.

[0193] The thickness of the hard coat layer (hc) is preferably, for example, 1 μm or more, more preferably 2 μm or more, and preferably 100 μm or less. When the thickness of the hard coat layer (hc) is 1 μm or more, sufficient scratch resistance can be ensured, and when it is 100 μm or less, flexural resistance can be ensured, and as a result, curling due to curing shrinkage can be suppressed.

[0194] [Layer (X2)] Layer (X2) is preferably a layer formed of silica (SiO2) among the group (X2).

[0195] When layer (X) is formed from at least one selected from the group (X2), layer (X) functions as an antireflection layer (ar) that prevents reflection of incident light. When layer (X) includes an antireflection layer (ar), the antireflection layer (ar) preferably has a reflection characteristic in which the reflectance is reduced to about 5.0% or less in the visible light region of 380 to 780 nm.

[0196] The structure of the antireflection layer (ar) is not particularly limited and may be a single-layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which a low refractive index layer and a high refractive index layer are alternately laminated is preferable, and the total number of laminations is preferably 2 to 20. Examples of the material constituting the low refractive index layer include silica (SiO2), and examples of the material constituting the high refractive index layer include metal oxides other than silica such as titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, tantalum oxide, or lanthanum oxide. Specific examples of the antireflection layer having a multilayer structure include a layer having a structure in which the material constituting the low refractive index layer is SiO2, the material constituting the high refractive index layer is ZrO2, SiO2 and ZrO2 are alternately laminated, and the outermost layer on the side opposite to the substrate is SiO2, and a layer having a structure in which the material constituting the low refractive index layer is SiO2, the material constituting the high refractive index layer is Nb2O5, SiO2 and Nb2O5 are alternately laminated, and the outermost layer on the side opposite to the substrate is SiO2.

[0197] The antireflection layer (ar) can be formed, for example, by a vapor deposition method.

[0198] The thickness of the antireflection layer (ar) is preferably, for example, 0.1 nm or more and preferably 5 μm or less.

[0199] The layer (X) may contain both the hard coat layer (hc) and the antireflection layer (ar). In this case, it is preferable that the laminate of the present invention is laminated in the order of the substrate, the hard coat layer (hc), the antireflection layer (ar), and the cured film from the substrate side. When the layer (X) is formed from at least one selected from the group (X1), the layer (X) can be formed by applying, for example, a mixed composition constituting the layer (X) to the substrate and curing it with heat or active energy rays such as ultraviolet rays. Further, when the layer (X) is formed from at least one selected from the group (X2), the layer (X) can be formed on the substrate by, for example, a vapor deposition method.

[0200] The film obtained using the mixed composition of the present invention is excellent in liquid repellency (especially water repellency). The water repellency of the film can be evaluated based on the contact angle and sliding angle of water with respect to the film surface. The contact angle of water with respect to the film surface is preferably 100° or more. The contact angle of water with respect to the film surface is more preferably 103° or more, still more preferably 105° or more. The upper limit is not particularly limited, but for example, it is 120° or less. The sliding angle of water with respect to the film surface is preferably 20° or less. The sliding angle of water with respect to the film surface is more preferably 18° or less, still more preferably 17° or less, and particularly preferably 16° or less. The lower limit is not particularly limited, but for example, it is 2° or more. In the present invention, when the contact angle of water with respect to the film surface is 100° or more and the sliding angle of water with respect to the film surface is 20° or less, it is evaluated as excellent in water repellency. The measurement method of the contact angle and sliding angle of water with respect to the film surface will be described in the examples.

[0201] Also, the above film is excellent in droplet removability (especially water droplet removability). The water droplet removability of the film can be evaluated based on the results of the following spray test. In the present invention, when the average of the number of sprays A in the spray test is less than 4.0 times, it is evaluated as excellent in water droplet removability, and when the average of the number of sprays A is less than 2.0 times, it is evaluated as particularly excellent in water droplet removability.

[0202] [Spray Test] Under the conditions of a temperature of 20 ± 15°C, a relative humidity of 65 ± 20%, and no wind, 0.6 mL of water is horizontally sprayed over a length of 40 cm from a position 10 cm away toward the surface of the film with an elevation angle fixed at 85°, and the operation of standing still for 1 minute is repeated 10 times. Observe whether water droplets move downward during the 1-minute standing still in each of the above operations. When the downward movement of water droplets is observed, it is considered that the water droplets have slipped, and the number of sprays when the water droplets first slip is defined as A.

[0203] When the film is curved, for example, the angle formed by the straight line formed by the ground contact surface and the straight line connecting the proximal end of the film in contact with the ground contact surface and the distal end opposite to the proximal end may be used as the elevation angle.

[0204] For water spraying, for example, sprays such as AS ONE Spray "4-5002-01", hand-held spray "GS-55, manufactured by TRUSCO", spray gun head "TSG-500-HD, manufactured by TRUSCO", Canion Spray H-500 "C356-000X-MB, manufactured by Yamazaki Industries (CONDOR)", Compact Trigger "7010020001, manufactured by Takemoto Container Co., Ltd.", TS-800-2-28-400 Spray "7030030029, manufactured by Takemoto Container Co., Ltd." can be used. Among them, it is preferable to use AS ONE Spray "4-5002-01". When using a spray with a water injection volume other than 0.6 mL per time, the length of horizontal movement can be adjusted so that the amount of water on the surface of the membrane becomes 0.15 mL per 100 cm 2 of the membrane surface area. Specifically, when the water injection volume is 0.6 mL per time, it is sprayed horizontally over a length of 40 cm from a position 10 cm away from the surface of the membrane. When the water injection volume is 0.3 mL per time, it may be sprayed horizontally over a length of 20 cm from a position 10 cm away from the surface of the membrane. If the spray nozzle can change the water injection shape, it may be made into a fine mist.

[0205] By using the mixed composition of the present invention, a film excellent in liquid repellency (especially water repellency) can be provided. Further, by using the mixed composition of the present invention, a film excellent in droplet removability (especially water droplet removability) can also be provided.

[0206] The film obtained by using the mixed composition of the present invention is useful, for example, in building materials, automotive parts, factory equipment, etc.

[0207] By applying the hybrid composition of the present invention to glass to form a film, the liquid repellency (especially water repellency) of the glass, and further the droplet removability (especially water droplet removability) can be improved. The present invention also includes glass having a film on at least one side surface. Specifically, by applying the hybrid composition of the present invention to various vehicle glasses and window glasses of buildings, the liquid repellency (especially water repellency), and further the droplet removability (especially water droplet removability) can be improved, and it is only necessary to have a film obtained from the hybrid composition of the present invention on at least one side surface of the glass. In particular, by forming a film on the surface of various vehicle glasses using the hybrid composition of the present invention, droplets are less likely to adhere to the glass surface, so antifouling properties can be imparted and the visibility becomes good.

Examples

[0208] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and it is also possible to make modifications within the scope that can conform to the above and below gists and implement them, and all of them are included in the technical scope of the present invention.

[0209] (Example 1) As compound (A1), 0.076 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.479 ml of isopropyl alcohol (2-propanol), together with 0.146 ml of tetraethyl orthosilicate (tetraethoxysilane) as the organosilicon compound (B) and 0.024 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and stirred at room temperature for 10 minutes. 0.194 ml of 0.01 M hydrochloric acid was added dropwise to the obtained solution, and stirred at room temperature for 1 hour. To the obtained solution, 0.081 ml of a malonic acid solution diluted 10 times by mass ratio with isopropyl alcohol was added dropwise and stirred for 2 hours to prepare sample solution 1. The obtained sample solution 1 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare coating solution 1.

[0210] (Example 2) As the compound (A1), 0.147 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.391 ml of isopropyl alcohol, together with 0.075 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.006 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.107 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.274 ml of a malonic acid solution diluted 10-fold by mass ratio with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 2. The obtained Sample Solution 2 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 2.

[0211] (Example 3) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.425 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.007 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.070 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.276 ml of a malonic acid solution diluted 10-fold by mass ratio with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 3. The obtained Sample Solution 3 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 3.

[0212] (Example 4) As the compound (A1), 0.208 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.462 ml of isopropyl alcohol, together with 0.013 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.009 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.030 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.278 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 4. The obtained Sample Solution 4 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 4.

[0213] (Example 5) As the compound (A1), 0.046 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.437 ml of isopropyl alcohol, together with 0.176 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.029 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.231 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.081 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 5. The obtained Sample Solution 5 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 5.

[0214] (Example 6) As the compound (A1), 0.030 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.415 ml of isopropyl alcohol, together with 0.192 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.032 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.251 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.080 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 6. The obtained Sample Solution 6 (1.000 ml) was mixed with 14 ml of isopropyl alcohol to prepare Coating Solution 6.

[0215] (Example 7) As the compound (A1), 0.016 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.396 ml of isopropyl alcohol, together with 0.206 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.034 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.268 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.080 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 7. The obtained Sample Solution 7 (1.000 ml) was mixed with 14 ml of isopropyl alcohol to prepare Coating Solution 7.

[0216] (Example 8) As the compound (A1), 0.207 ml of the compound (hereinafter sometimes referred to as "Compound 1") in which the average of n10 is 24 in (I-I-26) shown in Table 4-2 above, 0.015 ml of tetraethyl orthosilicate as the organosilicon compound (B), and 0.010 ml of n-decyltrimethoxysilane as the organosilicon compound (C) were dissolved in 0.150 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.033 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 3 hours. To the resulting solution, 0.251 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol and 0.334 ml of isopropyl alcohol were added dropwise to prepare Sample Solution 8. The obtained Sample Solution 8 (1.000 ml) and 14 ml of acetone were mixed to prepare Coating Solution 8.

[0217] (Example 9) As the compound (A1), 0.088 ml of "DMS-S12" manufactured by Gelest, 0.134 ml of tetraethyl orthosilicate as the organosilicon compound (B), and 0.022 ml of n-decyltrimethoxysilane as the organosilicon compound (C) were dissolved in 0.297 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.192 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.268 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 9. The obtained Sample Solution 9 (1.001 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 9.

[0218] (Example 10) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.429 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.006 ml of hexyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare sample solution 10. The obtained sample solution 10 (1.001 ml) and 14 ml of isopropyl alcohol were mixed to prepare coating solution 10.

[0219] (Example 11) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.428 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.007 ml of n-octyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare sample solution 11. The obtained sample solution 11 (1.001 ml) and 14 ml of isopropyl alcohol were mixed to prepare coating solution 11.

[0220] (Example 12) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.426 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.008 ml of dodecyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 12. The obtained Sample Solution 12 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 12.

[0221] (Example 13) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.425 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.010 ml of hexadecyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 13. The obtained Sample Solution 13 (1.001 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 13.

[0222] (Example 14) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd., as the organosilicon compound (B), 0.045 ml of tetraethyl orthosilicate, and as the organosilicon compound (C), 0.011 ml of octadecyltrimethoxysilane were dissolved in 0.424 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 14. The obtained Sample Solution 14 (1.001 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 14.

[0223] (Example 15) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd., as the organosilicon compound (B), 0.045 ml of tetraethyl orthosilicate, and as the organosilicon compound (C), 0.007 ml of n-decyltrimethoxysilane were dissolved in 0.429 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.274 ml of an oxalic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 15. The obtained Sample Solution 15 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 15.

[0224] (Example 16) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.427 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.007 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.276 ml of a maleic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 16. The obtained Sample Solution 16 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 16.

[0225] (Example 17) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.136 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.007 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.567 ml of a succinic acid solution diluted 5-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare Sample Solution 17. The obtained Sample Solution 17 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 17.

[0226] (Example 18) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd., as the organosilicon compound (B), 0.045 ml of tetraethyl orthosilicate, and as the organosilicon compound (C), 0.007 ml of n-decyltrimethoxysilane were dissolved in 0.425 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution and stirred at room temperature for 1 hour. To the resulting solution, 0.278 ml of a tricarballylic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise and stirred for 2 hours to prepare Sample Solution 18. The obtained Sample Solution 18 (1.000 ml) and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution 18.

[0227] (Example 19) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd., as the organosilicon compound (B), 0.045 ml of tetraethyl orthosilicate, and as the organosilicon compound (C), 0.007 ml of n-decyltrimethoxysilane were dissolved in 0.427 ml of isopropyl alcohol and stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution and stirred at room temperature for 1 hour. To the resulting solution, 0.276 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise and stirred for 2 hours to prepare Sample Solution 19. The obtained Sample Solution 19 (1.000 ml), 13.250 ml of isopropyl alcohol and 0.750 ml of water (D) were mixed to prepare Coating Solution 19.

[0228] (Example 20) As the compound (A1), 0.177 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.427 ml of isopropyl alcohol, together with 0.045 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.007 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. 0.068 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.276 ml of a malonic acid solution diluted 10 times by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution 20. 1.000 ml of the obtained Sample Solution 20, 11.750 ml of isopropyl alcohol, and 2.250 ml of water (D) were mixed to prepare Coating Solution 20.

[0229] (Comparative Example 1) As the compound (A1), 0.076 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.503 ml of isopropyl alcohol, together with 0.146 ml of tetraethyl orthosilicate as the organosilicon compound (B), and the mixture was stirred at room temperature for 10 minutes. 0.194 ml of 0.01 M hydrochloric acid was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. 0.081 ml of a malonic acid solution diluted 10 times by mass with isopropyl alcohol was added dropwise to the resulting solution, and the mixture was stirred for 2 hours to prepare Sample Solution A. 1.000 ml of the obtained Sample Solution A and 14 ml of isopropyl alcohol were mixed to prepare Coating Solution A.

[0230] (Comparative Example 2) As the compound (A1), 0.013 ml of "X-24-9011" manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 0.397 ml of isopropyl alcohol, together with 0.209 ml of tetraethyl orthosilicate as the organosilicon compound (B) and 0.034 ml of n-decyltrimethoxysilane as the organosilicon compound (C), and the mixture was stirred at room temperature for 10 minutes. To the resulting solution, 0.267 ml of 0.01 M hydrochloric acid was added dropwise, and the mixture was stirred at room temperature for 1 hour. To the resulting solution, 0.080 ml of a malonic acid solution diluted 10-fold by mass with isopropyl alcohol was added dropwise, and the mixture was stirred for 2 hours to prepare a sample solution B. The obtained sample solution B (1.000 ml) was mixed with 14 ml of isopropyl alcohol to prepare a coating solution B.

[0231] The component compositions (mass %) of each coating solution are shown in Tables 7-1 to 7-3. The amounts of each component represent the values when the total coating solution is 100 mass %. Note that the amount of water (D) shown in Tables 7-1 to 7-3 includes the water in the catalyst (F). Also, Tables 7-1 to 7-3 below show the molar ratios and mass ratios of the components calculated based on the amounts of each component.

[0232] [Table 7-1]

[0233] [Table 7-2]

[0234] [Table 7-3]

[0235] (Examples 1 to 20, Comparative Examples 1, 2) Using a glass substrate (soda-lime glass, top surface) with a size of 10 cm × 40 cm whose surface was activated by atmospheric pressure plasma treatment as the base material, the coating solutions 1 to 20 obtained in Examples 1 to 20, or the coating solutions A and B obtained in Comparative Examples 1 and 2 were applied by hand using a non-woven fabric. The amount of the applied coating solution was 0.5 ml. After application, the excess was wiped off with a cotton towel and left to cure at normal temperature and normal humidity for 90 minutes to form a cured film on the glass substrate, and a laminate in which the base material and the cured film were laminated was obtained. For the film on the glass substrate obtained with a curing time of 90 minutes, the contact angle and the sliding angle were measured by the following method. Also, for the film on the glass substrate obtained with a curing time of 90 minutes, a mist spraying test was performed by the following method to evaluate the water droplet removability of the film.

[0236] (Reference Example 1) Regarding the glass substrate whose surface was activated by atmospheric pressure plasma treatment, the contact angle and the sliding angle were measured by the following method without forming a cured film. Also, regarding the glass substrate whose surface was activated by atmospheric pressure plasma treatment, a mist spraying test was performed by the following method without forming a cured film to evaluate the water droplet removability of the glass substrate.

[0237] (Example 21) As the base material, glass with a thickness of 0.7 mm was used. On the base material, SiO2 and metal oxides other than SiO2 were alternately laminated by vacuum evaporation to form a layer (X) (antireflection layer) whose surface on the side opposite to the base material was SiO2. SiO2 constitutes a low refractive index layer, and metal oxides other than SiO2 constitute a high refractive index layer. The film formation surface of the layer (X) was subjected to an activation treatment using an atmospheric pressure plasma device (manufactured by Fuji Machinery Co., Ltd.). Next, the coating solution 3 obtained in Example 3 was applied by hand using a non-woven fabric on the activated antireflection layer. The amount of the applied coating solution was 0.5 ml. After application, the excess was wiped off with a cotton towel and left to cure at normal temperature and normal humidity for 90 minutes to form a cured film on the antireflection layer, and a laminate in which the base material, the antireflection layer, and the cured film were laminated in this order was obtained. For the film on the antireflection layer obtained with a curing time of 90 minutes, a mist spraying test was performed by the following method to evaluate the water droplet removability of the film.

[0238] [Measurement of Contact Angle] Using a DM700 manufactured by Kyowa Interface Science Co., Ltd. as a contact angle measuring device, the contact angle of water with respect to the film surface was measured by the droplet method. The analysis method of the droplet method was the θ / 2 method, and the water droplet volume was 3.0 μL.

[0239] [Measurement of Sliding Angle] Using a DM700 manufactured by Kyowa Interface Science Co., Ltd. as a contact angle measuring device, the sliding angle of water with respect to the film surface was measured by the sliding method to evaluate the dynamic water repellency of the film surface. The analysis method of the sliding method was the tangent method, and the water droplet volume was 10 μL. The tilting method was intermittent tilting, and the sliding detection was after sliding. The movement determination was the advancing angle, the sliding determination time was 10000 ms, and the sliding determination distance was 5 dots. A dot means a pixel at the resolution when photographed with the camera attached to the DM700. Note that 5 dots is 0.13 mm.

[0240] Based on the measurement results of the contact angle and the sliding angle, the water repellency was evaluated according to the following criteria.

[0241] [Evaluation Criteria for Water Repellency] Excellent water repellency: The contact angle is 100° or more and the sliding angle is 20° or less (indicated by ○ in Tables 8-1 to 8-3 below). Insufficient water repellency: The contact angle is 100° or more, but the sliding angle exceeds 20° (indicated by △ in Tables 8-1 to 8-3 below). Poor water repellency: The contact angle is less than 100°, or the contact angle is less than 100° and the sliding angle exceeds 20° (indicated by × in Tables 8-1 to 8-3 below).

[0242] [Spray Test] Under the conditions of normal temperature (temperature 20 ± 15°C), normal humidity (relative humidity 65 ± 20%), and no wind, 0.6 mL of water was sprayed horizontally (laterally) over a length of 40 cm from a position 10 cm away towards the surface of the film with the elevation angle fixed at 85°, and the operation of standing still for 1 minute was repeated 10 times. Observe whether the water droplets move downward during the 1-minute standing still in each of the above operations. For the water spraying, AS ONE spray "4-5002-01" (capacity 500 ml) was used as a spray gun. When the downward movement of the water droplets was observed, it was considered that the water droplets slipped, and the number of spraying times A when the water droplets first slipped was set. That is, after spraying the water, the behavior of the water droplets adhering to the film was observed for up to 1 minute. If the water droplets fell for the first time within 1 minute or even moved slowly, it was determined that "the water droplets slipped", and the number of spraying times A at that time was measured. On the other hand, if the water droplets did not move even 1 minute after spraying the water, the water was sprayed again in the same manner. The smaller the number of spraying times A, the more the minute water droplets slipped from the film surface, and it was evaluated that the water droplet removal property was good. In addition, when the water droplets stopped halfway, it was not determined that "the water droplets slipped", and the water was sprayed again in the same manner until the water droplets fell. The number of test times was 3 times. After measuring the number of spraying times A when the water droplets first fell in each test, the spraying of water was repeated, and the water was sprayed 10 times on the film. After 10 sprays, the water droplets adhering to the film surface were blown off using an air gun, and then the next test was continued. That is, by repeating the 3 tests, the durability of the film was also evaluated together.

[0243] Based on the measurement results of the spraying test, the water droplet removal property was evaluated according to the following criteria.

[0244] [Evaluation Criteria for Water Droplet Removal Property] The average of the number of spraying times A in 3 tests is less than 2.0 times: The water droplet removal property is particularly excellent (indicated by ◎ in Table 8-1 to Table 8-3 below). The average of the number of spraying times A in 3 tests is 2.0 times or more and less than 4.0 times: The water droplet removal property is excellent (indicated by ○ in Table 8-1 to Table 8-3 below). The average of the number of spraying times A in 3 tests is 4.0 times or more: The water droplet removal property is poor (indicated by × in Table 8-1 to Table 8-3 below).

[0245] The measurement results of the contact angle, sliding angle, and number of spraying times are shown in Tables 8-1 to 8-3 below. The evaluation results of water repellency and water droplet removability are also shown together.

[0246]

Table 8-1

[0247]

Table 8-2

[0248]

Table 8-3

[0249] The following considerations can be made from Tables 8-1 to 8-3. As shown in Examples 1 to 20, the films obtained using the coating solutions 1 to 20, which are mixed compositions satisfying the requirements defined in the present invention, had a large contact angle of 100° or more, a small sliding angle of 20° or less, and good water repellency. Also, since the average number of ejection times until the water droplets slid off was less than 4.0 times, it was found that even if the water droplets were tiny, they slid off, indicating excellent water droplet removability. In Example 4, "X-24-9011" was used as the compound (A1), and in Example 8, "Compound 1" was used as the compound (A1). In any of the examples, the water repellency and water droplet removability were good. Comparing Example 3 using "X-24-9011" as the compound (A1) with Example 9 using "DMS-S12" as the compound (A1), the water repellency was good in any of the examples, but Example 3 had better water droplet removability. Examples 3, 10 to 14 are examples in which the type of the organosilicon compound (C) was changed, and in any of the examples, the water repellency and water droplet removability were good. Examples 3, 15 to 18 are examples in which the type of the weak acid (G) was changed. Comparing these, it can be seen that the water droplet removability becomes even better by using malonic acid, succinic acid, or tricarballylic acid. Examples 3, 19, and 20 are examples in which the water content in the coating solution was changed, and it can be seen that the lower the water content, the better the water droplet removability. Example 21 is an example in which a cured film was formed on the antireflection layer using the coating solution 3, which is a mixed composition satisfying the requirements defined in the present invention. It was found that even when a cured film was formed on the antireflection layer, the cured film had excellent water droplet removability.

[0250] On the one hand, as shown in Comparative Example 1, the film obtained using the coating solution A, which is a mixed composition that does not satisfy the requirements defined in the present invention, had a small contact angle of less than 100°, and water droplets did not slide off, indicating poor water repellency. Also, the average number of spraying times was 4.0 times or more, and the water droplet removability was also poor. As shown in Comparative Example 2, the film obtained using the coating solution B, which is a mixed composition that does not satisfy the requirements defined in the present invention, had a large contact angle of 100° or more, but the sliding angle exceeded 20° and was large, indicating insufficient water repellency. Also, the average number of spraying times A was 4.0 times or more, and the water droplet removability was also poor. In Reference Example 1, since no cured film was formed on the glass substrate, the contact angle of water droplets on the glass substrate was 8.2°, and the sliding angle of water on the glass substrate surface could not be measured. Also, even when the spraying test was performed, water droplets adhered to the glass substrate surface, and the water droplet removability could not be evaluated.

[0251] Next, as Reference Examples 2 to 4, the storage stability of the coating solutions 2 to 4 was evaluated. The storage stability was evaluated by holding the obtained coating solutions 2 to 4 at room temperature for 14 days, then forming a film on a glass substrate by the above method, and performing a spraying test on the film on the obtained glass substrate by the above method to evaluate the water droplet removability of the film. The evaluation results of the spraying times and slipperiness in the spraying test after holding are shown in Table 9 below. Reference Example 2 shows the results using coating solution 2, Reference Example 3 shows the results using coating solution 3, and Reference Example 4 shows the results using coating solution 4, respectively.

[0252]

Table 9

[0253] As shown in Reference Examples 2 to 4 of Table 9, it can be seen that the coating solutions that satisfy the requirements defined in the present invention are excellent in storage stability.

Claims

1. A mixed composition of a compound (A1) represented by formula (a1), an organosilicon compound (B) represented by formula (b1), and an organosilicon compound (C) represented by formula (c1), wherein the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.060 or more. 【Chemical 1】 [In formula (a1), A a1 represents a hydroxy group or a hydrolyzable group, and when there are a plurality of A a1 , the plurality of A a1 may be different from each other, Z a1 represents a hydrocarbon group, a molecular chain containing a trialkylsilyl group, or a group containing a siloxane skeleton. When there are a plurality of Z a1 , the plurality of Z a1 may be different from each other. r1 represents an integer from 1 to 3, R a1 represents a group represented by formula (a11). 【Chemical Formula 2】 [In formula (a11), R s2 each independently represents an alkyl group having 1 to 4 carbon atoms, R a11 represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrocarbon group or The hydrogen atom contained in the trialkylsilyloxy group may be substituted with a fluorine atom, and R a11 When there are a plurality of them, the plurality of R a11 may be different from each other, A a11 represents a hydroxy group or a hydrolyzable group, and when there are a plurality of A a11 s, the plurality of A a11 s may be different from each other, Z s1 represents -O- or a divalent hydrocarbon group, and -CH 2 - in the divalent hydrocarbon group may be replaced by -O- Y s1 represents a single bond or -Si(R s2 ) 2 -L s1 -, and L s1 represents a divalent hydrocarbon group and the -CH contained in the divalent hydrocarbon group 2 - may be replaced by -O-, r2 represents an integer from 0 to  3, r10 represents an integer of 1 or more, * represents a bond. ] Si(R b1 )( b20 (X b1 )) 4-b20 (b1) [In formula (b1), R b1 represents a hydrocarbon group having 1 to 5 carbon atoms, X b1 represents a hydrolyzable group, b20 is 0 or 1. ] R c1 -Si(X c1 ) 3 (c1) [In formula (c1), R c1 represents a hydrocarbon group having 6 to 30 carbon atoms, X c1 represents a hydrolyzable group.]

2. The mixed composition according to claim 1, wherein the mass ratio [A1 / (B + C)] of the compound (A1) to the total of the organosilicon compound (B) and the organosilicon compound (C) is 0.2 or more and 15 or less.

3. The mixed composition according to claim 1 or 2, wherein the mass ratio (A1 / C) of the compound (A1) to the organosilicon compound (C) is 0.2 or more and 30 or less.

4. Water (D) is mixed, and when the total of the mixed composition is 100% by mass, the amount of the water (D) is less than 20% by mass. The mixed composition according to any one of claims 1 to 3.

5. The mixed composition according to any one of claims 1 to 4, wherein a solvent (E) is mixed.

6. The mixed composition according to any one of claims 1 to 5, wherein a weak acid (G) having a pKa of 1 or more and 5 or less is mixed.

7. A film obtained by curing the mixed composition according to any one of claims 1 to 6.

8. The film according to claim 7, wherein when a spraying test for measuring the number of water sprayings A until water droplets slide off is continuously carried out three times, the average of the number of sprayings A is less than 4.0 times.

9. The film according to claim 8, wherein the contact angle of water with respect to the film surface is 100° or more, and the sliding angle of water with respect to the film surface is 20° or less.

10. Glass having the film according to any one of claims 7 to 9 on at least one side surface.

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