JP6914711B2 - Composition - Google Patents

Description

The present invention relates to compositions.

In addition to the water- and oil-repellent function, wear resistance of the film is further required for applications of a film having water- and oil-repellent properties, such as window glass of an automobile or a building.

Since the surface free energy of the fluorooxyalkylene group-containing compound is very small, it has water repellency, oil repellency, chemical resistance, mold releasability and the like. Utilizing this property, Patent Document 1 states that (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and / or a partially hydrolyzed condensate thereof, and the average of the (A) component. A fluorine-containing coating agent containing a (B) fluorooxyalkylene group-containing polymer having an average molecular weight equal to or less than the molecular weight is disclosed.

Further, in Patent Document 2, (A) a hydrolyzable group-containing silane modified with a fluoropolyether group-containing polymer and / or a partially hydrolyzed condensate thereof, and (B) a fluoropolyether-polysiloxane copolymer modified. A fluorine-containing coating agent containing the hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof is disclosed.

JP 2015-199915 Japanese Unexamined Patent Publication No. 2015-196716

However, although the above-mentioned Patent Document 1 evaluates the wear resistance, there is still room for improvement, and the wear resistance of Patent Document 2 has not been examined. Further, the film having water and oil repellency may be required to have visibility in addition to abrasion resistance, but the manifestation of these physical properties was not sufficient.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of obtaining a water-repellent oil-repellent film having good wear resistance and visibility.

In the present invention, the number average molecular weight of the compound (A) in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom is 0.05 to 0.15% by mass. Is a polyalkylene glycol having a value of 1000 to 30,000, and the hydrogen atom of the OH group may be substituted with a fluoroalkyl group, and at least a part of the hydrogen atom of the alkylene group is substituted with a fluorine atom. A composition containing 0.02 to 0.15% by mass of B).

The composition of the present invention preferably further contains a fluorine-based solvent (C) having a molecular weight of 1000 or less.

The hydrolyzable group contained in the compound (A) is preferably at least one selected from the group consisting of an alkoxy group, an acetoxy group and a halogen atom.

Further, it is also preferable that the compound (A) is at least one selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2).

［上記式（１）において、
Ｒｆはフッ素原子または１個以上のフッ素原子に置換された炭素数１〜２０のアルキル基を表し、
Ｒｆ²はそれぞれ独立して、フッ素原子または１個以上のフッ素原子に置換された炭素数１〜２０のアルキル基を表し、
Ｒ³はそれぞれ独立して水素原子または炭素数が１〜４のアルキル基を表し、
Ｒ⁴はそれぞれ独立して、炭素数１〜２０のアルキル基を表し、
Ｄはそれぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＮＲ−（Ｒは水素原子、炭素数が１〜４のアルキル基又は炭素数が１〜４の含フッ素アルキル基）を表し、
Ｅはそれぞれ独立して、アルコキシ基、アセトキシ基、又はハロゲン原子を表し、
ａ２、ｂ２、ｃ２、ｄ２、ｅ２はそれぞれ独立して０以上６００以下の整数であって、ａ２、ｂ２、ｃ２、ｄ２、ｅ２の合計値は１３以上であり、
ｎは１以上３以下の整数であり、
ａ２、ｂ２、ｃ２、ｄ２、ｅ２を付して括弧でくくられた各繰り返し単位の順序は、少なくとも一部でパーフルオロポリエーテル構造を形成する順で並ぶ限り、式中において任意である。
上記式（２）において、
Ｒｆはフッ素原子または１個以上のフッ素原子に置換された炭素数１〜２０のアルキル基を表し、
Ｒｆ³はそれぞれ独立して、フッ素原子または１個以上のフッ素原子に置換された炭素数１〜２０のアルキル基を表し、
Ｒ⁵はそれぞれ独立して水素原子または炭素数１〜４のアルキル基を表し、
Ｒ⁶はそれぞれ独立して、炭素数１〜２０のアルキル基を表し、
Ｇはそれぞれ独立して、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＲ−、−ＮＲＣＯ−、−ＣＯＮＲ−（Ｒは水素原子又は炭素数１〜４のアルキル基又は炭素数１〜４の含フッ素アルキル基）を表し、
Ｊはそれぞれ独立して、アルコキシ基、アセトキシ基、又はハロゲン原子を表し、
Ｙはそれぞれ独立して、水素原子または炭素数１〜４のアルキル基を表し、
Ｚはそれぞれ独立して、水素原子またはハロゲン原子を表し、
ａ３、ｂ３、ｃ３、ｄ３、ｅ３はそれぞれ独立して０以上６００以下の整数であり、ａ３、ｂ３、ｃ３、ｄ３、ｅ３の合計値は１３以上であり、
ｈ３は０以上２以下の整数であり、
ｐは１以上３以下の整数であり、
ｑは１以上２０以下の整数であり、
ａ３、ｂ３、ｃ３、ｄ３、ｅ３を付して括弧でくくられた各繰り返し単位の順序は、少なくとも一部でパーフルオロポリエーテル構造を形成する順で並ぶ限り、式中において任意である。］

[In the above formula (1)
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
Rf ² independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms.
D is independently of -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. Represents a fluorine-containing alkyl group of ~ 4)
Each E independently represents an alkoxy group, an acetoxy group, or a halogen atom.
a2, b2, c2, d2, and e2 are independently integers of 0 or more and 600 or less, and the total value of a2, b2, c2, d2, and e2 is 13 or more.
n is an integer of 1 or more and 3 or less,
The order of each repeating unit in parentheses with a2, b2, c2, d2, and e2 is arbitrary in the equation as long as it is arranged in the order of forming a perfluoropolyether structure at least in part.
In the above formula (2)
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
Rf ³ independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Each R ⁶ independently represents an alkyl group having 1 to 20 carbon atoms.
G is independently of -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. Fluorine-containing alkyl group)
Each of J independently represents an alkoxy group, an acetoxy group, or a halogen atom.
Each Y independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z independently represents a hydrogen atom or a halogen atom,
a3, b3, c3, d3, and e3 are independently integers of 0 or more and 600 or less, and the total value of a3, b3, c3, d3, and e3 is 13 or more.
h3 is an integer of 0 or more and 2 or less,
p is an integer of 1 or more and 3 or less,
q is an integer between 1 and 20
The order of each repeating unit in parentheses with a3, b3, c3, d3, e3 is arbitrary in the equation as long as it is arranged in the order of forming a perfluoropolyether structure at least in part. ]

The composition of the present invention preferably further contains a hydrolyzable oligomer (D2), and more preferably the hydrolyzable oligomer (D2) is a compound represented by the following formula (10).

[In the above formula (10), X independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and g1 is 0 or more and 100 or less. Integer]

The present invention also includes a film formed from any of the above compositions.

According to the composition of the present invention, the compound (A) characterized by a perfluoropolyether structure and the polyalkylene glycol (B) having a number average molecular weight of 1000 to 30000 are contained in predetermined amounts, respectively. The film obtained from this composition has water and oil repellency, and is excellent in abrasion resistance and visibility.

The composition of the present invention contains a compound (A) characterized by a perfluoropolyether structure and a predetermined polyalkylene glycol (B) having a number average molecular weight of 1000 to 30000. The perfluoropolyether structure of the compound (A) can exhibit water and oil repellency, and the polyalkylene glycol (B) satisfying a predetermined requirement can be used to improve the abrasion resistance and visibility of the film.

The compound (A) may be any compound that contains fluorine and can form a film matrix by bonding the compounds (A) with each other or with other monomers through a polymerization reaction (particularly a polycondensation reaction). The compound (A) is preferably a compound containing a fluorine-containing group and a hydrolyzable group. Among them, in the present invention, the compound (A) is a monovalent group having a perfluoropolyether structure and is hydrolyzable. A compound whose group is bonded to a silicon atom is used.

The perfluoropolyether structure is a structure in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether residue are replaced with fluorine atoms, and is a perfluoropolyalkylene ether group or a perfluoropolyalkylene glycol dialkyl. It can also be called an ether residue. The perfluoropolyether structure has water and oil repellency. The number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200.

In compound (A), the monovalent group having the perfluoropolyether structure is bonded to the silicon atom. A suitable linking group may be present on the side where the perfluoropolyether structure is bonded to the silicon atom, or the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group. As the linking group, for example, a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) alkylene glycol group, or a group in which a part of these hydrogen atoms is substituted with F, and these are appropriately linked. Examples include the groups that have been used. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

A plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoroalkyl groups or perfluoropolyether groups may be bonded to one linking group. The number of monovalent groups having the perfluoropolyether structure bonded to the silicon atom may be 1 or more, may be 2 or 3, but is preferably 1 or 2. It is particularly preferable to have it.

Further, in the compound (A), a hydrolyzable group is bonded to the silicon atom, and the hydrolyzable group is a group of the compounds (A) with each other or with the compound (A) through a hydrolysis / dehydration condensation reaction. It has the function of binding to active hydrogen (hydroxyl group, etc.) on the surface of the material. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an acetoxy group, and a halogen atom (particularly a chlorine atom). Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable.

The number of hydrolyzable groups bonded to the silicon atom may be one or more and may be 2 or 3, but is preferably 2 or 3, and particularly preferably 3. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is bonded to the silicon atom. preferable. The total number of fluorine-containing groups (monovalent groups having a perfluoropolyether structure) and hydrolyzable groups bonded to a silicon atom is usually 4, but may be 2 or 3 (particularly 3). .. In the case of 3 or less, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group, or the like can be bonded to the remaining bonding hands.

The monovalent group having a perfluoropolyether structure of compound (A) may be linear or may have a side chain.

Examples of the compound (A) include compounds of the following formula (1).

In the above formula (1),
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms. Rf is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably having 1 to 5 carbon atoms. It is a perfluoroalkyl group.
Rf ² independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms. Rf ² is preferably a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms independently of each other, and more preferably all of them are fluorine atoms.
R ³ independently represents a hydrogen atom or a lower alkyl group. Each of R ³ is independently, preferably a hydrogen atom, or an alkyl group having 1 or 2 carbon atoms, and more preferably all hydrogen atoms.
Each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms. R ⁴ is preferably an alkyl group having 1 to 5 carbon atoms.
D independently represents -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom, a lower alkyl group or a lower fluorine-containing alkyl group). .. D is preferably -COO-, -O-, -OCO- independently of each other, and more preferably all -O-.
Each E independently represents a hydrolyzable group. E is preferably an alkoxy group, an acetoxy group, or a halogen atom having 1 to 4 carbon atoms, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.
a2, b2, c2, d2, and e2 are independently integers of 0 or more and 600 or less, and the total value of a2, b2, c2, d2, and e2 is 13 or more.
The order of each repeating unit in parentheses with a2, b2, c2, d2, e2 is arbitrary in the equation, as long as it is arranged in the order of forming a perfluoropolyether structure at least in part. Preferably, the repeating unit enclosed in parentheses with b2 on the most fixed end side (the side bonded to the silicon atom of the fluorine-containing group) is the repeating unit enclosed in parentheses with a2 on the most free end side. Repeat units located on the free end side, more preferably enclosed in parentheses with b2 or d2 on the most fixed end side, are enclosed in parentheses with a2 or c2 on the most free end side. It is located on the free end side of the repeating unit.
n is an integer of 1 or more and 3 or less. n is preferably 2 or more and 3 or less, and more preferably 3.

In the formula (1), in particular, Rf is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ² is all a fluorine atom, D is all -O-, E is a methoxy group, an ethoxy group, or a chlorine atom (particularly a methoxy group). Alternatively, it is preferable that ethoxy group), a2, c2 and d2 are all 0, n is 3, e2 is 4 or more, and 600 or less.

Examples of the compound (A) represented by the formula (1) include a compound of the following formula (1-1).

In the above formula (1-1), R ¹⁰ is a perfluoroalkyl group ^{having 1 to 5 carbon atoms, R 11} is a perfluoroalkylene group having 1 to 5 carbon atoms, and R ¹² has 1 carbon atom. ~ 3 are perfluoroalkylene groups, R ¹³ is an alkylene group ^{having 1 to 3 carbon atoms, R 14} is an alkyl group having 1 to 3 carbon atoms, and z2 and z3 are both 1 to 3 carbon atoms. It is an integer, and z1 is a value set so that the compound represented by the above formula (1-1) can maintain a liquid under normal pressure.

Further, as the compound (A), in addition to the compound of the above formula (1), the compound of the following formula (2) can be exemplified, and the compound of the following formula (2) is preferable.

In the above formula (2),
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms. Rf is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably having 1 to 5 carbon atoms. It is a perfluoroalkyl group.
Rf ³ independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms. Rf ³ is preferably a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms independently of each other, and more preferably all fluorine atoms.
R ⁵ independently represents a hydrogen atom or a lower alkyl group. R ⁵ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms independently of each other, and more preferably all hydrogen atoms.
Each R ⁶ independently represents an alkyl group having 1 to 20 carbon atoms. R ⁶ is preferably an alkyl group having 1 to 5 carbon atoms.
G independently represents -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom, a lower alkyl group or a lower fluorine-containing alkyl group). .. G is preferably -COO-, -O-, -OCO- independently of each other, and more preferably all -O-.
Each J independently represents a hydrolyzable group. J is preferably an alkoxy group, an acetoxy group, or a halogen atom, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.
Each Y independently represents a hydrogen atom or a lower alkyl group. Y is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms independently of each other, and more preferably all hydrogen atoms.
Z independently represents a hydrogen atom or a halogen atom. Z is preferably a hydrogen atom.
a3, b3, c3, d3, and e3 are independently integers of 0 or more and 600 or less, and the total value of a3, b3, c3, d3, and e3 is 13 or more. Preferably a3, c3 and d3 are independently less than 1/2 of b3, more preferably less than 1/4, more preferably c3 or d3 being 0, and particularly preferably c3 and d3 being 0. Is.
e3 is preferably 1/5 or more of the total value of a3, b3, c3, and d3, and is less than or equal to the total value of a3, b3, c3, and d3.
b3 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less. e3 is preferably 4 or more and 600 or less, more preferably 4 or more and 200 or less, and further preferably 10 or more and 200 or less. The total value of a3, b3, c3, d3, and e3 is preferably 20 or more and 600 or less, preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less.
h3 is an integer of 0 or more and 2 or less, preferably 0 or more and 1 or less.
q is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less. More preferably, it is 2 or more and 15 or less.
The order of each repeating unit in parentheses with a3, b3, c3, d3, e3 is arbitrary in the equation, as long as it is arranged in the order of forming a perfluoropolyether structure at least in part. Preferably, the repeating unit enclosed in parentheses with b3 on the most fixed end side (the side bonded to the silicon atom of the fluorine-containing group) is the repeating unit enclosed in parentheses with a3 on the most free end side. Repeat units located on the free end side, more preferably enclosed in parentheses with b3 or d3 on the most fixed end side, are enclosed in parentheses with a3 or c3 on the most free end side. It is located on the free end side of the repeating unit.
p is an integer of 1 or more and 3 or less, preferably 2 or more and 3 or less, and more preferably 3.

The lower grade in the above formulas (1) and (2) means that the number of carbon atoms is 1 to 4.

In the formula (2), in particular, Rf is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ³ is all a fluorine atom, G is all -O-, J is a methoxy group, an ethoxy group, or a chlorine atom (particularly a methoxy group or (Ethoxy group), Y and Z are all hydrogen atoms, a3 is 0, b3 is 30 to 150 (more preferably 80 to 140), e3 is 30 to 60, c3 and d3 are 0, and h3 is 0 or more and 1 or less (more preferably). In particular, it is preferable that 0), p is 3, and q is 1-10.

Examples of the compound (A) represented by the above formula (2) include a compound of the following formula (2-1).

In the above formula (2-1), R ²⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ²¹ and R ²² are independently perfluoroalkylene groups having 2 to 6 carbon atoms. ²³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ²⁴ is an alkyl group having 1 to 3 carbon atoms. The carbon numbers of R ²⁰ , R ²¹ , R ²² and R ²³ are preferably 2 to 4 independently, and more preferably 2 to 3 respectively. x1 is 5 to 70, x2 is 1 to 5, and x3 is 1 to 10. x1 is preferably 10 to 60, more preferably 20 to 50, x2 is preferably 1 to 4, more preferably 1 to 3, x3 is preferably 1 to 8, and more preferably 1 to 6.

The content of compound (A) in the composition of the present invention is 0.05 to 0.15% by mass. If the content of the compound (A) is less than 0.05% by mass, good water and oil repellency cannot be obtained. On the other hand, when the content of the compound (A) exceeds 0.15% by mass, HAZE becomes high and visibility is lowered. The lower limit of the content of the compound (A) is preferably 0.06% by mass or more, and more preferably 0.07% by mass or more. On the other hand, the upper limit of the content of the compound (A) is preferably 0.13% by mass or less, and more preferably 0.11% by mass or less.

Next, the polyalkylene glycol (B) having a number average molecular weight of 1000 to 30000 will be described. In the polyalkylene glycol (B) contained in the composition of the present invention, more specifically, the hydrogen atom of the OH group may be substituted with a fluoroalkyl group, and at least a part of the hydrogen atom of the alkylene group is substituted with a fluorine atom. It is a polyalkylene glycol that has been used. When the hydrogen atom of the OH group is substituted, it is preferably substituted with a fluoroalkyl group, more preferably substituted with a perfluoroalkyl group, and further substituted with a trifluoromethyl group. preferable. Further, in the polyalkylene glycol (B), at least a part of hydrogen atoms of the alkylene group is substituted with a fluorine atom, and it is particularly preferable that the polyalkylene glycol (B) contains a perfluorooxyalkylene unit.

In particular, polyalkylene glycol in which the hydrogen atom of the OH group is substituted with a trifluoromethyl group and all the hydrogen atoms of the alkylene group are substituted with a fluorine atom, or the hydrogen atom of the OH group is not substituted. Polyalkylene glycol in which only a part of hydrogen atoms of the alkylene group is replaced with a fluorine atom is preferable.

Examples of the polyalkylene glycol (B) include a compound represented by the following formula (3).

X- (OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d- Y ... (3)

In the formula (3), a, b, c, and d are all symbols representing repeating units, and the range thereof can be appropriately set within a range in which the liquid can be maintained at normal pressure. Further, the repeating units enclosed by a, b, c, and d may be repeated randomly with each other. X is an alkyl group having 1 to 16 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom, and Y is a carbon in which one or more hydrogen atoms may be substituted with a fluorine atom. Represents an alkoxy group or an OH group of the number 1 to 16.

In equation (3),-(OC ₄ F ₈ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF (CF) ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-and-(OCF) It may be any of (CF ₃ ) CF (CF ₃ ))-, preferably − (OCF ₂ CF ₂ CF ₂ CF ₂ ) −. -(OC ₃ F ₆ )-is either-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- It is often, preferably − (OCF ₂ CF ₂ CF ₂ ) −. − (OC ₂ F ₄ ) − may be either − (OCF ₂ CF ₂ ) − or − (OCF (CF ₃ )) −.

X is preferably an alkyl group having 1 to 3 carbon atoms (particularly a trifluoromethyl group) in which one or more hydrogen atoms may be substituted with a fluorine atom, and Y is preferably one or more hydrogen atoms. Is an alkoxy group (particularly a trifluoromethoxy group) or an OH group having 1 to 3 carbon atoms which may be substituted with a fluorine atom.

In the formula (3), it is particularly preferable that a = b = 0, where X is a trifluoromethyl group and Y is a trifluoromethoxy group.

Further, as the polyalkylene glycol (B), a compound represented by the following formula (4) can also be exemplified.

In the above formula (4), p, q, m, and n are all symbols representing repeating units, and the range thereof can be appropriately set within a range in which the liquid can be maintained at normal pressure. Further, the repeating unit enclosed by p and the repeating unit enclosed by q may be repeated at random with each other.

In the composition of the present invention, the polyalkylene glycol (B) has a number average molecular weight of 1000 to 30000. If the number average molecular weight is less than 10,000, the wear resistance of the obtained film deteriorates. On the other hand, when the number average molecular weight exceeds 30,000, HAZE becomes high and visibility is lowered. The lower limit of the number average molecular weight of the polyalkylene glycol (B) is preferably 11000 or more, more preferably 12000 or more. The upper limit of the number average molecular weight is preferably 25,000 or less, more preferably 20,000 or less.

Among the above formulas (3), those represented by the following formula (5) can be preferably used, and as a compound having such a structure, Fomblin M60 (registered trademark, manufactured by Solvay, Inc., number average) can be used. Molecular weight 12500).

The content of polyalkylene glycol (B) in the composition of the present invention is 0.02 to 0.15% by mass. If the content of the polyalkylene glycol (B) is less than 0.02% by mass, the abrasion resistance of the obtained film deteriorates. On the other hand, if the content of the polyalkylene glycol (B) exceeds 0.15% by mass, the visibility of the obtained film deteriorates. The lower limit of the content of the polyalkylene glycol (B) is preferably 0.03% by mass or more, and more preferably 0.04% by mass or more. The upper limit of the content of the polyalkylene glycol (B) is preferably 0.13% by mass or less, and more preferably 0.10% by mass or less.

The composition of the present invention preferably further contains a fluorine-based solvent (C) having a molecular weight of 1000 or less, in addition to the above-mentioned compound (A) and polyoxyalkylene glycol (B).

As the fluorine-based solvent (C), for example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated aromatic solvent and the like can be used, and the boiling point is particularly preferably 100 ° C. or higher. As the fluorinated ether-based solvent, a hydrofluoro ether such as a fluoroalkyl (particularly a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly a methyl group or an ethyl group) ether is preferable, and for example, the following formula (6-1) Alternatively, ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether represented by (6-2) can be mentioned. Examples of the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M, molecular weight of about 264, boiling point 76 ° C.). The fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a third in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group). Primary amines are preferable, and specific examples thereof include tris (heptafluoropropyl) amines represented by the following formula (7), and Florinate (registered trademark) FC-3283 (molecular weight: about 521, boiling point: 128 ° C.) corresponds to this. .. Examples of the fluorinated aromatic solvent include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.) represented by the following formula (8).

As the fluorine-based solvent (C), in addition to the above, hydrochlorofluorocarbons such as Asahiclean AK225 (manufactured by Asahi Glass Co., Ltd.), hydrofluorocarbons such as Asahiclean AC2000 (manufactured by Asahi Glass Co., Ltd.), and the like can be used.

The molecular weight of the fluorine-based solvent (C) is preferably 900 or less, more preferably 800 or less, and the lower limit is not particularly limited, but is, for example, about 300.

The content of the fluorine-based solvent (C) in the composition of the present invention is, for example, 90% by mass or more, more preferably 93% by mass or more, and further preferably 95% by mass or more.

Furthermore, the composition of the present invention may contain at least one of fluoroalkylsilane (D1) and hydrolyzable silane oligomer (D2). By including these, the wear resistance of the obtained film can be further improved. (D1) and (D2) may be high boiling point compounds exhibiting a predetermined vapor pressure. That is, (D1) and (D2) are preferably high boiling point compounds having a vapor pressure of 1 atm or less at a temperature of 100 ° C. The high boiling point compound does not have to have a boiling point, but when it has a boiling point, the compound having a boiling point of 100 ° C. or higher corresponds to the above compound. In the preferred compound, the temperature at which the vapor pressure becomes 1 atm or more is 110 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 130 ° C. or higher. The upper limit of the temperature at which the vapor pressure becomes 1 atm or more is not particularly limited, and the compound may be a compound whose decomposition starts before the vapor pressure becomes 1 atm or more.

The fluoroalkylsilane (D1) is preferably a compound in which a hydrolyzable group is bonded to a silicon atom of the fluoroalkylsilane. The fluoroalkyl group of the fluoroalkylsilane is preferably a group having a fluoroalkyl group at the end, and particularly preferably a group having a perfluoroalkyl group at the end such as a trifluoromethyl group. Examples of the fluoroalkyl group include a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, a fluorohexyl group, a fluoroheptyl group, a fluorooctyl group, a fluorononyl group, a fluorodecyl group and a fluoro. Examples thereof include fluoroalkyl groups having 1 to 12 carbon atoms such as undecyl groups and fluorododecyl groups.

When a hydrolyzable group is bonded to the silicon atom of the fluoroalkylsilane of (D1), examples of the hydrolyzable group include the same hydrolyzable groups as those exemplified in compound (A). Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable. When a plurality of hydrolyzable groups are present, they may be the same or different, but they are preferably the same.

The total number of fluoroalkyl groups and hydrolyzable groups bonded to the silicon atom is preferably 4, in which case the number of fluoroalkyl groups is 3, the number of hydrolyzable groups is 1, and the number of fluoroalkyl groups and hydrolytic groups is 1. The number of hydrolyzable groups may be 2, the number of fluoroalkyl groups may be 1, and the number of hydrolyzable groups may be 3, but the number of fluoroalkyl groups is 1 and the number of hydrolyzable groups is 1. It is preferably 3. The total number of fluoroalkyl groups and hydrolyzable groups bonded to the silicon atom may be 2 or 3 (particularly 3), and if it is 3 or less, the remaining bonding hands may be, for example, an alkyl group (particularly). Alkyl groups having 1 to 4 carbon atoms), hydrogen atoms, cyano groups, etc. can be bonded.

The combination of the fluoroalkyl group and the hydrolyzable group is not particularly limited and may include or do not include the formula (9) described later, but a combination of the fluoroalkyl group and the alkoxy group is preferable. Examples thereof include (fluoroalkylalkoxysilanes and the like, particularly fluoroalkyltrialkoxysilanes and the like), combinations of fluoroalkyl groups and halogen atoms (fluoroalkylhalosilanes and the like, especially fluoroalkyltrihalosilanes).

The fluoroalkylsilane of (D1) is more preferably a compound represented by the following formula (9) because of its ease of synthesis.

In the above formula (9),
Rf ¹ represents an alkyl group having 1 to 20 carbon atoms independently substituted with a fluorine atom or one or more fluorine atoms.
Each R ¹ independently represents a hydrogen atom or a lower alkyl group.
R ² independently represents an alkyl group having 1 to 20 carbon atoms.
A independently has -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom or a lower alkyl group, or a lower fluorine-containing alkyl group. Represents)
B each independently represents a hydrolyzable group
a1, b1, c1, d1, and e1 are independently integers of 0 or more and 100 or less, respectively.
The order of each repeating unit in parentheses with a1, b1, c1, d1, e1 is arbitrary in the formula, as long as it is arranged in the order of forming at least a part of the fluoroalkylsilyl group.
The total value of a1, b1, c1, d1, and e1 is 100 or less.
m is an integer of 1 or more and 3 or less.
In the above formula (9), low grade means that the number of carbon atoms is 1 to 4.

Rf ¹ is preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms). R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² is preferably an alkyl group having 1 to 5 carbon atoms. A is preferably —O—, −COO−, −OCO−. B is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and more preferably a methoxy group, an ethoxy group or a chlorine atom. a1 is preferably 1 to 30, more preferably 1 to 25, further preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2. b1 is preferably 0 to 15, more preferably 0 to 10. c1 is preferably 0 to 5, more preferably 0 to 2. d1 is preferably 0 to 4, more preferably 0 to 2. e1 is preferably 0 to 4, more preferably 0 to 2. m is preferably 2 to 3, and more preferably 3. The total value of a1, b1, c1, d1, and e1 is preferably 3 or more, more preferably 5 or more, more preferably 80 or less, more preferably 50 or less, and further preferably 20 or less.

In particular, Rf ¹ is a fluorine atom or a perfluoroalkyl having 1 to 6 carbon atoms, R ¹ is a hydrogen atom, B is a methoxy group or an ethoxy group, and c1, d1 and e1 are all 0. , M is 3, a1 is preferably 1 to 5, and b1 is preferably 0 to 6.

Examples of the fluoroalkylsilane (D1) include CF _3- Si- (OCH ₃ ) ₃ , C _j F _{2j + 1-} Si- (OC ₂ H ₅ ) ₃ (j is an integer of 1 to 12). Among them, especially C ₄ F _9- Si- (OC ₂ H ₅ ) ₃ , C ₆ F _13- Si- (OC ₂ H ₅ ) ₃ , C ₇ F _15- Si- (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ −Si− (OC ₂ H ₅ ) ₃ is preferred. In addition, CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH 2) ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ (K is 5 to 20, preferably 8 to 15). In addition, CF ₃ (CF ₂ ) _m − (CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m − (CH ₂ ) _n Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m − (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ can also be mentioned (m is 1 to 10 and preferably 3 to 7, and n is 1 to 5 and preferably 2 to 4). ). Furthermore, CF ₃ (CF ₂ ) _p − (CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p − (CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p − ( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ can be mentioned (p is 2 to 10 and preferably 3 to 7, and q is 1 to 5 and preferably 2 to 4). Is).

The hydrolyzable silane oligomer (D2) has a silane compound having two or more hydrolyzable groups, preferably two or more (particularly 3) hydrolyzable groups and a fluorine-containing group (particularly lower fluorine-containing alkyl groups). A silane compound is an oligomer produced by hydrolysis and condensation. The number of silicon atoms (condensation number) contained in the oligomer is, for example, 3 or more, preferably 5 or more, and more preferably 7 or more. The number of condensations is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.

Examples of the hydrolyzable group contained in the oligomer include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and a methoxy group and an ethoxy group are preferable. The oligomer can have one or more of these hydrolyzable groups, preferably one.

Examples of the hydrolyzable silane oligomer (D2) include compounds represented by the following formula (10).

In the above formula (10),
Each of X independently represents a hydrolyzable group, a lower alkyl group, or a lower fluorine-containing alkyl group.
g1 is an integer of 0 or more and 100 or less.
In the formula (10), the lower grade means that the number of carbon atoms is 1 to 4.

Examples of the hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. At least one of X is a hydrolyzable group (particularly an ethoxy group and a methoxy group), and g1 is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less. It is also preferable that at least one of X is a lower fluorine-containing alkyl group.

Examples of the hydrolyzable silane oligomer include (H ₅ C ₂ O) _3- Si- (OSI (OC ₂ H ₅ ) ₂ ) ₄ OC ₂ H ₅ , (H ₃ CO) ₂ Si (CH ₂ CH ₂ CF). ₃ ) − (OSiO _{CH 3} (CH ₂ CH ₂ CF ₃ )) _{4 − OCH 3 and the} like can be mentioned.

The content of (D1) and (D2) in the composition of the present invention (in the case of one type, the content of a single type, and in the case of containing two or more types, the total content) is 0.01 to 0.5% by mass. It is preferable to have.

The composition of the present invention may further contain a silanol condensation catalyst. Examples of the silanol condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, metal complexes such as titanium complexes (for example, Organix TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd.) and tin complexes, and metal alkoxides. The amount of the silanol condensation catalyst is, for example, 0.00001 to 0.1% by mass, preferably 0.00002 to 0.01% by mass, and more preferably 0.0005 to 0.001% by mass.

The composition of the present invention is an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, a biological adhesion inhibitor, a deodorant, and a pigment as long as the effects of the present invention are not impaired. , Flame retardant, antistatic agent and the like may be contained.

Examples of the antioxidant include the following phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and hindered amine-based antioxidants.

For example, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2,2-thio-diethylene-bis. -[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], 3,9-Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetra Oxaspiro [5.5] undecane, tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid} pentaerythrityl ester, 2-t-butyl-6- (3-t) -Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t - pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris (3,5-di -t- butyl-4-hydroxybenzyl) benzene, tris (3,5-di -t- butyl - 4-Hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H) , 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 4,4' -Pharmonic antioxidants such as thiobis (6-t-butyl-3-methylphenol).

For example, 3,3'-thiodipropionic acid di-n-dodecyl ester, 3,3'-thiodipropionic acid di-n-tetradecyl ester, 3,3'-thiodipropionic acid di-n-octadecyl ester, Sulfur-based antioxidants such as tetrakis (3-dodecylthiopropionic acid) pentaerythrityl ester.

For example, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4). -Methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite bis - [2,4-di -t- butyl - (6-methyl) phenyl] ethyl phosphite phosphorus-based antioxidant such as phosphite.

For example, bissebacate (2,2,6,6-tetramethyl-4-piperidyl) ester (melting point 81-86 ° C), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (melting point 58 ° C). , Poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4) -Piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and other hindered amine antioxidants.

As the rust inhibitor, for example, alkanolamines, quaternary ammonium salts, alkane thiols, imidazoline, sodium metavanadate, bismuth citrate, phenol derivatives, polyalkenyl amines, alkyl imidazolines derivatives, shea anode alkylamines, carboxylic acid amides , alkylenediamines, pyrimidine and these carboxylic acids, naphthenic acids, sulphonic acid complex, calcium nitrite, alkyl amines and esters, polyalcohols, polyphenols, sodium mode Ribuden acid, sodium tungstate, sodium nitrite, sodium phosphonate, Sodium chromate, sodium silicate, gelatin, carboxylic acid polymers, aliphatic and aromatic amines or diamines, ethoxylated amines, imidazoles, benzimidazoles, nitro compounds, formaldehyde, acetylene alcohols, aliphatic and aromatic thiols or sulfides, Sulfoxide, thiourea, acetylene alcohol, 2-mercaptobenzimidazole, amine or tetraammonium salt + halogen ion, acetylenethiol and sulfide, dibenzylsulfoxide, alkylamine + potassium iodide, dicyclohexylamine nitrite, cyclohexylamine benzoate, Examples of rust preventives such as benzotriazole, tannin + sodium phosphate, triethanolamine + laurylsarcosine + benzotriazole, alkylamine + benzotriazole + sodium nitrite + sodium phosphate can be exemplified.

Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]-. 2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, methyl -3- [3-t-Butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- UV absorbers such as (4,6-diphenyl-1,3,5-triazine-2-yl) -5 [(hexyl) oxy] -phenol, 2-ethoxy-2'-ethyl-oxalic acid bisanilide / photostable Agents can be mentioned.

Examples of antifungal / antibacterial agents include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3one, sodium (2-pyridylthio-1-oxide), dehydroacetic acid, 2-. Methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazole carbamate, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, mono or dibromo Antifungal / antibacterial agents such as benzimidazoles, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane May be contained.

Examples of the bioadhesion inhibitor include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamic acid) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and dichloro-N-(((). Dimethylamino) sulfonyl) fluoro-N- (P-tolyl) methanesulfenamide, pyridin-triphenylborane, N, N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio) sulfamide, first thiosocyanate Copper (1), cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zincethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) pyridine, N- (2,4,6-trichlorophenyl) maleimide, bis (2-pyridinethiol-1-oxide) zinc salt, bis (2-pyridinethiol-1-oxide) copper salt, 2- Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, grammine compounds, Examples thereof include bioadhesion inhibitors such as isonitrile compounds.

Examples of the deodorant include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acid, alken-1,2-dicarboxylic acid, and cycloalcan-. Organic acids such as 1,2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, naphthalene sulfonic acid; fatty acid metals such as zinc undecylate, zinc 2-ethylhexanoate, zinc ricinolate; iron oxide, iron sulfate , Zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) sodium chlorophyllin, metal (iron, copper, cobalt, etc.) phthalocyanine, metal (iron, copper, cobalt, etc.) phthalocyanate tetrasulfonate , Titanium dioxide, metal compounds such as visible light responsive titanium dioxide (nitrogen-doped type, etc.); Kind: Acrylic acid-based polymers such as porous methacrylic acid polymer and porous acrylic acid polymer, porous divinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer, aromatic polymer such as porous divinylbenzene-vinylpyridine polymer, and both of them. Examples thereof include polymers and deodorants such as polymers such as chitin, chitosan, activated charcoal, silica gel, active alumina, zeolite, and ceramics.

Examples of pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene or perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, and disazo condensation pigments. And pigments such as benzimidazolone pigments.

As the flame retardant, for example, a flame retardant such as decabromobiphenyl, antimony trioxide, a phosphorus-based flame retardant, and aluminum hydroxide can be contained.

Examples of the antistatic agent include a quaternary ammonium salt type cationic surfactant, a betaine type amphoteric surfactant, an alkyl phosphate type anionic surfactant, a primary amine salt, a secondary amine salt, and a second. Cationic surfactants such as tertiary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfated ester salts, fatty alcohol sulfate ester salts, alkyl Sulfate ester salts, fatty acid ethyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, anionic surfactants such as amber ester sulfonates and phosphoric acid ester salts, partial fatty acid esters of polyhydric alcohols, fatty alcohols Nonionic surfactants such as ethylene oxide adducts, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and polyethylene glycol. Examples thereof include activators, antistatic agents such as amphoteric surfactants such as carboxylic acid derivatives and imidazoline derivatives.

When the composition of the present invention contains various additives, the content of the various additives is, for example, 0.01 to 70% by mass, preferably 0.% by mass, based on the total weight of the composition of the present invention. It is 05 to 50% by mass, more preferably 0.1 to 30% by mass, and even more preferably 0.5 to 5% by mass.

Lubricants, fillers, plasticizers, nucleating agents, antiblocking agents, foaming agents, emulsifiers, brighteners, binders and the like may also be contained in the compositions of the present invention.

By applying the composition of the present invention to a substrate and allowing it to stand in the air or drying it by heating (for example, at 120 to 180 ° C. for 10 to 60 minutes), the water in the air is taken in and the hydrolyzable group is hydrolyzed. And a siloxane bond is formed. The obtained film may be further heated and dried.

As a method of applying the composition to the substrate, a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method and the like can be adopted. The film thickness of the obtained film is, for example, about 4 to 10 nm.

The transparent film obtained by the composition of the present invention has water and oil repellency, and is excellent in abrasion resistance and visibility. For example, in the transparent film of the present invention, the contact angle measured by the θ / 2 method with a water droplet volume of 3.0 μl is usually 100 ° or more, preferably 110 ° or more, and the upper limit is not limited, but is 120 ° or less, for example. .. The transmittance (HAZE) measured with a haze meter according to JIS K 7136 can be 0.2% or less, preferably 0.15% or less, and more preferably 0.10% or less. The lower limit of HAZE is, for example, 0.03%.

The substrate on which the composition of the present invention is applied is not particularly limited, and may be either an organic material or an inorganic material, and the shape may be either a flat surface or a curved surface, and is three-dimensional in which a large number of surfaces are combined. Structure may be used. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin and polyvinyl alcohol; phenol resin, urea resin, melamine resin and epoxy. Examples thereof include heat-curable resins such as resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of the inorganic material include metals such as iron, silicon, copper, zinc and aluminum, alloys containing these metals, ceramics and glass.

The substrate may be easily bonded 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, a tetraalkoxysilane, or the like may be used.

As the primer layer, a layer formed by using a composition for forming an underlayer containing a compound represented by the following formula (11) and / or a component (E) composed of a partially hydrolyzed condensate thereof is preferable.

Si (X ² ) ₄ ... (11)
(However, in formula (11), X ² independently represents a halogen atom, an alkoxy group or an isocyanate group.)

In the above formula (11), X ² is preferably a chlorine atom, an alkoxy group or an isocyanate group having 1 to 4 carbon atoms, and more preferably four X ^2s are the same.

_{Specifically, Si (NCO) 4} , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4, and the} like are preferably used as the compound represented by the formula (11). As the component (E), one type may be used alone, or two or more types may be used in combination.

The component (E) contained in the primer layer forming composition may be a partially hydrolyzed condensate of the compound represented by the above formula (11). The partial hydrolysis condensation product of the compound represented by the above formula (11) can be obtained by applying a general hydrolysis condensation method using an acid or a base catalyst. However, the degree of condensation (degree of polymerization) of the partially hydrolyzed condensate needs to be such that the product dissolves in the solvent. The component (E) may be a compound represented by the above formula (11) or a partially hydrolyzed condensate of the compound represented by the above formula (11). It may be a mixture of the compound represented by the compound and a partially hydrolyzed condensate thereof, for example, a partially hydrolyzed condensate of the compound containing an unreacted compound represented by the above formula (11). As the compound represented by the above formula (11) and its partially hydrolyzed condensate, there are commercially available products, and such commercially available products can be used in the present invention.

Further, the composition for forming an underlayer is composed of the above component (E), a compound represented by the following formula (12) (sometimes referred to as compound (12)) and / or a partially hydrolyzed condensate thereof (F). A composition containing a component, or a partially hydrolyzed condensate of the component (E) and the component (F) (however, the component (E) and / or the compound (12) may be contained). There may be.

(X ³ ) ₃ Si- (CH ₂ ) _p- Si (X ³ ) ₃ ... (12)
(However, in formula (12), X ³ independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8.)

The compound represented by the formula (12) is a compound having a hydrolyzable silyl group or silanol group at both ends with a divalent organic group interposed therebetween.

In the formula (12), examples of the hydrolyzable group represented by ^{X 3} include the same groups or atoms as in ^{X 2.} From the viewpoint of the balance between the stability of the compound represented by the above formula (12) and the ease of hydrolysis, the X ³ is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. These are appropriately selected and used according to the manufacturing purpose, application, and the like. Equation (12) may be the plurality X ³ present in even different groups in the same group in, it is preferable in terms of ease availability of the same group.

Specifically, as the compound represented by the formula (12), (CH ₃ O) ₃ SCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SCH ₂ CH ₂ Si (NCO) ₃ , Cl ₃ SCH ₂ CH ₂ SiCl ₃ , (C ₂ H ₅ O) ₃ SCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CH ₃ O) ₃ SCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ etc. can be mentioned. As the component (F), one type may be used alone, or two or more types may be used in combination.

The component contained in the primer layer forming composition may be a partially hydrolyzed condensate of the compound represented by the formula (12). The partially hydrolyzed condensate of the compound represented by the formula (12) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of the compound represented by the formula (11). The degree of condensation (degree of polymerization) of the partially hydrolyzed condensate needs to be such that the product dissolves in the solvent. The component (F) may be a compound represented by the formula (12) or a partially hydrolyzed condensate of the compound represented by the formula (12), and may be represented by the formula (12). It may be a mixture of a compound and a partially hydrolyzed condensate thereof, for example, a partially hydrolyzed condensate of the compound containing an unreacted compound represented by the formula (12). As the compound represented by the above formula (12) and its partially hydrolyzed condensate, there are commercially available products, and such commercially available products can be used in the present invention.

Further, as the base layer, various polysilazanes that can obtain an oxide film containing silicon as a main component similar to the above formula (11) may be used.

The composition for forming a primer layer usually contains an organic solvent in consideration of economy, workability, ease of controlling the thickness of the obtained primer layer, and the like, in addition to the solid content as a layer constituent component. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the primer layer forming composition. Examples of the organic solvent include compounds similar to the solvent used in the composition of the present invention. The organic solvent is not limited to one type, and two or more types of solvents having different polarities, evaporation rates, etc. may be mixed and used. When the composition for forming a primer layer contains a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, the solvent used for producing these may be contained.

Further, in the composition for forming a primer layer, even if it does not contain a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, in order to promote the hydrolyzed cocondensation reaction, in the reaction of the partial hydrolyzed condensation. It is also preferable to blend a catalyst such as an acid catalyst similar to that generally used. Even when a partially hydrolyzed condensate or a partially hydrolyzed copolymer is contained, it is preferable to add a catalyst when the catalyst used for their production does not remain in the composition. The composition for forming an underlayer may contain water for the above-mentioned components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction.

As a method for forming the base layer using the primer layer forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the composition for forming a base layer is applied to the surface of a substrate by a method such as brush coating, sink coating, rotary coating, dip coating, squeegee coating, spray coating, hand coating, etc., and is required in the air or nitrogen atmosphere. An underlayer can be formed by drying and then curing according to the above. The curing conditions are appropriately controlled depending on the type and concentration of the composition used. The primer layer forming composition may be cured at the same time as the water repellent film forming composition is cured.

The thickness of the primer layer is not particularly limited as long as it can impart moisture resistance to the transparent film formed on the primer layer, impart adhesion to the substrate, and can barrier alkali and the like from the substrate.

The transparent film obtained by the composition of the present invention includes display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, windowpanes of automobiles and buildings, metal products such as cooking utensils, tableware, etc. It is industrially useful because it can form a film suitable for ceramic products, plastic automobile parts, and the like. It can also be used for fishing nets, insect nets, aquariums and the like. Furthermore, it can be used for kitchens, bathrooms, wash basins, mirrors, articles for each member around the toilet, ceramics such as chandeliers and tiles, artificial marble, and various indoor equipment such as air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes, etc. in factories. It is also suitable for goggles, eyeglasses, helmets, pachinko, textiles, umbrellas, playsets, soccer balls, and the like. Further, it can also be used as an adhesion preventive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples, and it is of course possible to carry out the invention with appropriate modifications within the range that can be adapted to the above-mentioned purpose, and all of them are technical of the present invention. Included in the range.

The film obtained in the examples of the present invention was measured by the following method.

(1) Measurement of contact angle Using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.), the contact angle of water on the film surface is measured by the sessile drop method (analysis method: θ / 2 method) at a liquid volume of 3 μL. It was measured.

(2) Abrasion resistance evaluation By using a scratch device equipped with an HB pencil with an eraser (manufactured by Mitsubishi Pencil Co., Ltd.) and moving the sample at 40 r / min with a load of 500 g applied while the eraser is in contact with the film surface. A wear test was performed. The contact angle was measured every 1000 times of wear, and the number of times when the contact angle after the wear test decreased by 15 degrees or more for the first time from the initial contact angle was measured.

(3) Transmittance measurement (HAZE measurement)
The transmittance (HAZE) was measured using a haze meter (HZ-2 manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7136. HAZE is calculated by the following formula, and the smaller the value, the better the visibility (higher transparency) of the film.
HAZE (%) = Diffusion Transmittance (%) / [Parallel Light Transmittance (%) + Diffusion Transmittance (%)] x 100

Example 1
Compound a (number average molecular weight of about 8000) represented by the following formula (13) was synthesized by the methods described in Synthesis Examples 1 and 2 of JP-A-2014-15609.

In the above equation (13), n is 43 and m is an integer of 1 to 6.

The compound (A) is the compound a represented by the above formula (13), the polyalkylene glycol (B) is fluorine oil, Fomblin (registered trademark) M60 (manufactured by Solvay, number average molecular weight 12500), and a fluorine-based solvent (C). ), FC-3283 (Fluorinert, manufactured by 3M) was mixed and stirred at room temperature to obtain a composition. In the composition, the ratio of the compound a is 0.08% by mass, and the ratio of the fluorine oil M60 is 0.02% by mass. 200 μl (composition) of the obtained composition was placed on pretreated silica glass (Eagle XG, manufactured by Corning Inc.) at 3000 rpm / min for 20 seconds using a spin coater (MS-A100, manufactured by Corning Inc.). Spin coating was performed under the conditions of (thing). Then, it was dried under the condition of 150 degreeC and 30 min, and a transparent film was obtained on silica glass. As the pretreatment, silica glass is immersed in a 10 mass% sodium hydroxide aqueous solution, ultrasonically cleaned for 20 minutes, rinsed with pure water, and then ultrasonically cleaned with pure water for 10 minutes. The treatment was carried out and dried at 60 ° C. for 1 hour so that no water remained on the surface.

Example 2
A transparent film was prepared on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was changed to 0.05% by mass.

Example 3
A transparent film was prepared on the silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was changed to 0.1% by mass.

Comparative Example 1
As compound (A), 0.05% by mass of compound a represented by the above formula (13), fluorine oil represented by the following formula (14), von Bryn (registered trademark) M03 (manufactured by Solvay, number average molecular weight) Novec (registered trademark) 7200 (manufactured by 3M) was mixed with 0.05% by mass of 4000) as a fluorine-based solvent (C), and the mixture was stirred at room temperature to obtain a composition. Then, a transparent film was formed on the silica glass in the same manner as in Example 1.

Comparative Example 2
A transparent film was prepared on silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was 0.005% by mass and Novec7200 was used as the fluorine-based solvent (C) instead of FC-3283.

Comparative Example 3
A transparent film was prepared on silica glass in the same manner as in Comparative Example 2 except that 0.02% by mass of fluorine oil M03 was used instead of fluorine oil M60.

Comparative Example 4
A transparent film was prepared on the silica glass in the same manner as in Example 1 except that the ratio of the fluorine oil M60 was 0.2% by mass.

The results of Examples and Comparative Examples are shown in Table 1.

From Table 1, it can be seen that according to the composition of the present invention, a water- and oil-repellent film having excellent wear resistance and visibility can be obtained.

Claims (4)

The content of compound (A) in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom is 0.05 to 0.15% by mass.
A polyalkylene glycol having a number average molecular weight of 1000 to 30000, wherein the hydrogen atom of the OH group may be substituted with a fluoroalkyl group, and at least a part of the hydrogen atom of the alkylene group is substituted with a fluorine atom. The alkylene glycol (B) was 0.02 to 0.15% by mass ,
It contains 90% by mass or more of the fluorine-based solvent (C) having a molecular weight of 1000 or less.
A composition in which the compound (A) is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) .

[In the above formula (1)
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
Rf ² independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms.
D is independently of -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. Represents a fluorine-containing alkyl group of ~ 4)
Each E independently represents an alkoxy group, an acetoxy group, or a halogen atom.
a2, b2, c2, d2, and e2 are independently integers of 0 or more and 600 or less, and the total value of a2, b2, c2, d2, and e2 is 13 or more.
n is an integer of 1 or more and 3 or less,
The order of each repeating unit in parentheses with a2, b2, c2, d2, and e2 is arbitrary in the equation as long as it is arranged in the order of forming a perfluoropolyether structure at least in part.
In the above formula (2)
Rf represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
Rf ³ independently represents an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom or one or more fluorine atoms.
R ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Each R ⁶ independently represents an alkyl group having 1 to 20 carbon atoms.
G is independently of -O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms. Fluorine-containing alkyl group)
Each of J independently represents an alkoxy group, an acetoxy group, or a halogen atom.
Each Y independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z independently represents a hydrogen atom or a halogen atom,
a3, b3, c3, d3, and e3 are independently integers of 0 or more and 600 or less, and the total value of a3, b3, c3, d3, and e3 is 13 or more.
h3 is an integer of 0 or more and 2 or less,
p is an integer of 1 or more and 3 or less,
q is an integer between 1 and 20
The order of each repeating unit in parentheses with a3, b3, c3, d3, e3 is arbitrary in the equation as long as it is arranged in the order of forming a perfluoropolyether structure at least in part. ] The composition according to claim 1, further comprising a hydrolyzable oligomer (D2). The composition according to claim 2 , wherein the hydrolyzable oligomer (D2) is a compound represented by the following formula (10).

[In the above formula (10), X independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and g1 is 0 or more and 100 or less. Integer] A film formed from the composition according to any one of claims 1 to 3.