JP7579644B2 - Fluorine-containing diene compound, polymer, method for producing polymer, and surface treatment agent - Google Patents

Description

The present invention relates to a fluorine-containing diene compound, a polymer, a method for producing a polymer, and a surface treatment agent.

2. Description of the Related Art Ring-structure-containing copolymers that can be used in paints and the like and have structural units that contain a ring structure derived from a 1,6-diene-2-carboxylate monomer or the like are known (for example, Patent Document 1).
The repeating units derived from 1,6-diene-2-carboxylate monomers or the like contained in the ring structure-containing copolymer generally have an ester bonded in the form of a side chain to a 5- or 6-membered ring structure contained in the main skeleton of the repeating unit.

JP 2010-37549 A

Under these circumstances, the present inventors, referring to Patent Document 1, prepared a composition containing a ring structure-containing copolymer and evaluated it as a surface treatment agent, and found that such a surface treatment agent may have poor sliding properties.
Therefore, an object of the present invention is to provide a surface treatment agent having excellent slip-off properties.
Another object of the present invention is to provide a polymer having excellent slip-off properties, a method for producing said polymer, and a fluorine-containing diene compound capable of forming said polymer.

As a result of intensive research aimed at solving the above problems, the present inventors have found that when a fluorinated diene compound has a fluoroalkyl group or a fluoroether group, the fluoroalkyl group or the like is introduced into a polymer, thereby obtaining the desired effects, and have arrived at the present invention.
The present invention is based on the above findings and has the following specific configuration to solve the above problems.

[1] A fluorinated diene compound represented by the following formula (1):

In formula (1),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.
[2] The above X and Z are each independently a methylene group,
The fluorine-containing diene compound according to [1], wherein Y is an oxygen atom, a sulfur atom or an imino group.
[3] The fluorinated diene compound according to [1] or [2], which is a fluorinated diene compound represented by the following formula (2):

In formula (2),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
[4] The fluorine-containing diene compound according to any one of [1] to [3], wherein each Rf is independently a perfluoroalkyl group.
[5] The fluorine-containing diene compound according to any one of [1] to [4], wherein the number of carbon atoms in each Rf is independently 6 or less.
[6] A polymer having a structural unit derived from the fluorinated diene compound according to any one of [1] to [5].
[7] The polymer according to [6], wherein the structural unit includes a structural unit represented by the following formula (3) and/or formula (4):

In formula (3),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

In formula (4),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.
[8] The polymer according to [6] or [7], wherein the content of the structural unit in the polymer is 25 mass% or more.
[9] The polymer according to [8], wherein the content of the structural unit in the polymer is 50 mass % or more.
[10] The polymer according to [8] or [9], wherein the content of the structural unit in the polymer is 80 mass % or more.
[11] A method for producing a polymer, comprising polymerizing the fluorinated diene compound according to any one of [1] to [5] in an organic solvent to produce the polymer according to [6].
[12] The method for producing a polymer according to [11], wherein the organic solvent contains a fluorine-containing organic solvent.
[13] A surface treatment agent comprising the fluorinated diene compound according to any one of [1] to [5] or the polymer according to any one of [6] to [10].
[14] The surface treatment agent according to [13], further comprising an organic solvent.

The surface treatment agent of the present invention has excellent sliding properties.
The polymer of the present invention has excellent sliding properties.
According to the method for producing a polymer of the present invention, a polymer having excellent slip-off properties can be provided.
The fluorine-containing diene compound of the present invention can provide the polymer of the present invention.

1 is a GC-MS chart (gas chromatogram) of fluorine-containing diene compound 1. 1 is a GC-MS chart (mass spectrum) of fluorine-containing diene compound 1. 1 is a ¹ H-NMR chart of fluorine-containing diene compound 1. 1 is a ¹ H-NMR chart of specific polymer 1. FIG. 5 is an enlarged view of the ¹ H-NMR chart of Specific Polymer 1 shown in FIG.

The present invention will be described in detail below.
In this specification, (meth)acrylate refers to acrylate or methacrylate, (meth)acryloyl refers to acryloyl or methacryloyl, and (meth)acrylic refers to acrylic or methacrylic.
In addition, in this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In this specification, unless otherwise specified, each component may use the substance corresponding to that component alone or in combination of two or more kinds. When a component contains two or more kinds of substances, the content of the component means the total content of the two or more kinds of substances.
In this specification, unless otherwise specified, the production method of each component is not particularly limited. For example, a conventionally known method may be used. In addition, each component may be a commercially available product.
In this specification, better slippage properties may be referred to as better effects of the present invention.
"wt %" means "mass %" and "vol %" means "volume %".

It is believed that the surface treatment agent of the present invention has the desired effect because it contains the polymer of the present invention having a repeating unit derived from the fluorinated diene compound of the present invention, etc. The reason is not clear, but it is speculated that the reason is as follows when the surface treatment agent of the present invention contains the polymer of the present invention.
As described above, in the ring structure-containing copolymer derived from a 1,6-diene-2-carboxylic acid ester monomer or the like, the repeating unit from the above monomer usually has an ester bonded to a five- or six-membered ring structure.
On the other hand, in the polymer of the present invention derived from the fluorine-containing diene compound of the present invention, the repeating unit due to the fluorine-containing diene compound of the present invention has a 5-membered or 6-membered ring structure, and a fluoroalkyl group or a fluoroether group is bonded to the ring structure via at least an ester bond or an amide bond.
In this way, since the repeating units of the fluorine-containing diene compound of the present invention have the above-mentioned ring structure as the main skeleton in the repeating units, the polymer of the present invention is less likely to move between adjacent repeating units, and therefore the fluoroalkyl groups, etc. bonded to the ring structure in each repeating unit at least via an ester bond, etc., tend to be oriented in a certain direction, which is thought to result in improved sliding properties on the surface of the surface treatment agent of the present invention.
The present invention will be described in detail below.

[Fluorine-containing diene compound]
The fluorine-containing diene compound of the present invention is a fluorine-containing diene compound represented by the following formula (1).

In formula (1),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

<A>
In the present invention, A in formula (1) is O (oxygen atom) or NH (imino group).
The above A is preferably O from the viewpoint of obtaining superior effects of the present invention.

<Q>
In the present invention, Q in formula (1) is an organic group or a single bond having a valence of n+1. Since n in formula (1) is 1 to 2, the n+1 valence is divalent or trivalent.

Examples of the n+1 valent linking group include a linear or branched n+1 valent alkylene group or alkenylene group, an n+1 valent oxyalkylene group, a 6-membered aromatic group, a 4- to 6-membered saturated aliphatic group, a 4- to 6-membered unsaturated aliphatic group, or a 5- to 6-membered heterocyclic group, or a divalent linking group represented by the following formula (q). These n+1 valent linking groups may be combined, and the ring groups may be condensed.
-Y-Z-(q)
The symbols in the formula have the following meanings.
Y: a linear or branched divalent alkylene group, a 6-membered aromatic group, a 4- to 6-membered saturated or unsaturated aliphatic group, a 5- or 6-membered heterocyclic group, or a condensed ring group thereof.
Z: -O-, -S-, -CO-, -COO-, -COS-, -N(R)-, -SO ₂ -, -PO ₂ -, -N(R)-COO-, -N(R)-CO-, -N(R)-SO ₂ -, -N(R)-PO ₂ -.
R: a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

The n+1-valent linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a cyano group, an alkoxy group (such as a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, or a methoxyethoxy group), an aryloxy group (such as a phenoxy group), an alkylthio group (such as a methylthio group or an ethylthio group), an acyl group (such as an acetyl group, a propionyl group, or a benzoyl group), a sulfonyl group (such as a methanesulfonyl group or a benzenesulfonyl group), an acyloxy group (such as an acetoxy group or a benzoyloxy group), a sulfonyloxy group (such as a methanesulfonyloxy group or a toluenesulfonyloxy group), a phosphonyl group (such as a diethylphosphonyl group), or an amide. groups (acetylamino group, benzoylamino group, etc.), carbamoyl groups (N,N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, etc.), aryl groups (phenyl group, toluoyl group, etc.), heterocyclic groups (pyridyl group, imidazolyl group, furanyl group, etc.), alkenyl groups (vinyl group, 1-propenyl group, etc.), alkoxyacyloxy groups (acetyloxy group, etc.), alkoxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, etc.), and polymerizable groups (vinyl group, acryloyl group, methacryloyl group, silyl group, cinnamic acid residue, etc.).
However, when Q is an (n+1)-valent alkylene group or an (n+1)-valent oxyalkylene group having a structure substituted with a fluorine atom, the structure of Q is also determined based on the definition of the determination of the number of carbon atoms of Rf described later.

The above Q can be appropriately selected as long as it is a single bond or an (n+1)-valent linking group. Among them, a single bond or a linear or branched (n+1)-valent alkylene group is preferable, and a linear (n+1)-valent alkylene group is more preferable.
When Rf described later is a perfluoroalkyl group, the number of carbon atoms in the linear (n+1) valent alkylene group having no fluorine atoms as Q is preferably 1 to 4, and more preferably 1 to 2, from the viewpoint of obtaining superior effects of the present invention.

<Rf>
In the present invention, Rf in formula (1) is each independently a fluoroalkyl group or a fluoroether group. When n in formula (1) is 2, multiple Rf may be the same or different.
In this specification, Rf in formula (1) may be referred to as an "Rf group."

(Fluoroalkyl group)
The fluoroalkyl group means a partially fluoro-substituted or perfluoro-substituted alkyl group in which one or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The fluoroalkyl group may have either a straight-chain structure or a branched structure. In addition, the number of carbon atoms in the fluoroalkyl group includes the number of carbon atoms in the branched structure.
Examples of the linear structure of the alkyl group constituting the fluoroalkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the branched structure of the alkyl group constituting the fluoroalkyl group include an isopropyl group, an s-butyl group, a t-butyl group, a 3-methylbutyl group, an isopentyl group, a neopentyl group, and an isohexyl group. In the examples of the alkyl group constituting the fluoroalkyl group, one or all of the hydrogen atoms of the alkyl group are substituted with a fluorine atom.

The number of carbon atoms in the fluoroalkyl group is determined so as to include all carbon atoms having fluorine atoms bonded thereto and to minimize the number of carbon atoms contained in the group.
For example, in formula (1), when "-Q-Rf" is a group represented by "-C ₂ H ₄ -C ₆ F ₁₃ ", Q is "C ₂ H ₄ " and Rf is "C ₆ F ₁₃ ". Similarly, when "-Q-Rf" is a group represented by "-CH ₂ -CHF-CH ₂ -CF ₂ H", Q is "CH ₂ " and Rf is "CHF-CH ₂ -CF ₂ H".

(fluoroether group)
The fluoroether group means a group in which an ethereal oxygen atom is inserted between one or more carbon-carbon atoms in the above-mentioned fluoroalkyl group. When an ethereal oxygen atom is inserted between two or more carbon-carbon atoms in the above-mentioned fluoroalkyl group, the fluoroether group becomes a fluoropolyether group.

Structure of Rf group, etc. The Rf group may be either a straight-chain structure or a branched structure, but from the viewpoint of increasing the packing of the Rf group, the Rf group preferably has a straight-chain structure. For the same reason, when the Rf group has a branched structure, it is preferable that the branched portion exists at the terminal portion of the Rf group.
Furthermore, since the Rf groups are superior in the effects of the present invention and have excellent surface tension reducing ability, they are each independently preferably a polyfluoroalkyl group (an alkyl group having a plurality of fluorines), and more preferably a perfluoroalkyl group (an alkyl group in which all hydrogen atoms are replaced with fluorines).

The number of carbon atoms in the Rf group is preferably 1 to 6, independently, from the viewpoint of achieving superior effects of the present invention and superior antifouling properties and surface smoothness (leveling properties) of the resulting surface treatment agent.

From the viewpoint of achieving superior effects of the present invention and of providing a cured product having excellent stain resistance and surface smoothness (leveling properties), it is preferred that the Rf groups are each independently a linear perfluoroalkyl group having 1 to 6 carbon atoms.
From the viewpoints of achieving superior effects of the present invention and of providing a cured product having excellent stain resistance and surface smoothness (leveling properties), it is preferred that the Rf groups are each independently -C ₆ F ₁₃ , -C ₅ F ₁₁ , -C ₄ F ₉ , -C ₂ F ₅ or -CF ₃ .

The number of fluorines contained in the Rf groups is preferably 3 or more, and more preferably 3 to 13, from the viewpoint of achieving superior effects of the present invention and of providing a cured product with excellent stain resistance and surface smoothness (leveling properties).

The Rf group is preferably bonded to the terminal of the Q group, and more preferably to the terminal carbon atom of the Q group, since this provides better effects for the present invention and has better surface tension reducing ability.
When there is one Rf group, the Q group is divalent, and when there are two Rf groups, the Q group is trivalent.
Examples of the case where one Rf group is bonded to the terminal carbon atom of the Q group include CF ₃ --CH ₂ -- and C ₆ F ₁₃ --CH ₂ --.
When there are two Rf groups, the effect of the present invention is more excellent and the surface tension reducing ability is excellent, so it is preferable that the two Rf groups are bonded to the terminal of the Q group, and it is more preferable that the two Rf groups (both) are bonded to the terminal carbon atom of the Q group.
An example of a group in which two Rf groups are bonded to the terminal carbon atom of the Q group is (CF ₃ ) ₂ CH--.

<n>
In the present invention, n in formula (1) is 1 to 2. In the present invention, n in formula (1) represents the number of Rfs bonded to Q.
When n is 1, the effect of the present invention is superior and the surface tension reducing ability is superior, so that the carbon number of the Rf group is preferably 4 to 6. When n is 1 and the Rf group is a perfluoroalkyl group, the carbon number of the perfluoroalkyl group is preferably 4 to 6 for the same reasons as above.
When n is 2, the effects of the present invention are more excellent and the surface tension reducing ability is excellent, so that the number of carbon atoms in the Rf groups is preferably independently 1 to 3. When n is 2 and the Rf group is a perfluoroalkyl group, the number of carbon atoms in the perfluoroalkyl group is preferably independently 1 to 3 for the same reasons as above.

<R>
In the present invention, R in formula (1) is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.
From the viewpoint of obtaining superior effects of the present invention, R is preferably a hydrogen atom.

<X, Y, Z>
In the present invention, X, Y, and Z in formula (1) are each independently a methylene group, an oxygen atom, a sulfur atom, or an imino group (-NH-). In the present invention, at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

From the viewpoint of obtaining superior effects of the present invention, it is preferable that X and Z each independently represent a methylene group, and Y represents an oxygen atom, a sulfur atom, or an imino group.
It is more preferable that X and Z are each independently a methylene group, and Y is an oxygen atom.

From the viewpoint of achieving superior effects of the present invention, the fluorine-containing diene compound represented by the above formula (1) is preferably a fluorine-containing diene compound represented by the following formula (2), and more preferably a compound represented by the following formula (5).

In formula (2),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

A, Q, Rf, n, and R in formula (2) are the same as A, Q, Rf, n, and R in formula (1), respectively.

The compound represented by formula (5) is as follows.

(5)

(Method for producing fluorine-containing diene compound)
As a method for producing the fluorinated diene compound of the present invention, when A in formula (1) is O, for example, a method in which a raw material represented by (Rf) _n -QA (wherein A is an oxygen atom)-H is reacted with a raw material represented by HO-CO-C(= _CH2 )-X-Y-Z-C(= _CH2 )-R in the presence of an acid catalyst is mentioned.

The Rf, n and Q in the (Rf) _n -Q-A (A is an oxygen atom)-H as the raw material correspond to the Rf, n and Q in formula (1). The H bonded to A represents a hydrogen atom. The (Rf) _n -Q-A (A is an oxygen atom)-H is not particularly limited as long as it is a compound having Rf, n and Q corresponding to Rf, n and Q in formula (1). Examples of the (Rf) _n -Q-A (A is an oxygen atom)-H include 2-(perfluorohexyl)ethanol, 2-(perfluoromethyl)ethanol and 2,2-di(perfluoromethyl)ethanol.

In the other raw material, HO-CO-C(=CH ₂ )-X-Y-Z-C(=CH ₂ )-R, X, Y, Z, and R correspond to X, Y, Z, and R in formula (1). The raw material is not particularly limited as long as it is a compound in which X, Y, Z, and R correspond to X, Y, Z, and R in formula (1). In the raw material, HO-CO- represents a carboxy group. An example of the HO-CO-C(=CH ₂ )-X-Y-Z-C(=CH ₂ )-R is α-allyloxymethylacrylic acid (H-AMA).

Examples of the acid catalyst include organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

The reaction temperature for the above reaction may be 70 to 120°C. It is more preferable that the reaction temperature is 80 to 100°C.

Furthermore, when A in formula (1) is NH, an example of the method for producing the fluorinated diene compound of the present invention is to react a raw material represented by (Rf) _n -QA (wherein A is NH)-H with a raw material represented by a halogen atom -CO-C(= _CH2 )-X-Y-Z-C(= _CH2 )-R. Examples of the halogen atom include chlorine, bromine and iodine.
Examples of the (Rf) _n -QA (A is NH)-H include 2-(perfluorohexyl)ethylamine, 2-(perfluoromethyl)ethylamine, and 2,2-di(perfluoromethyl)ethylamine.
The halogen atom --CO--C( _{.dbd.CH.sub.2} )--X--Y--Z--C( _{.dbd.CH.sub.2} )--R is, for example, .alpha.-allyloxymethylacrylic acid chloride.
The reaction temperature for the above reaction may be from -25 to 100°C, preferably from -10 to 80°C.

The production of the fluorine-containing diene compound can be carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction. For example, a hydrocarbon compound such as cyclohexane, an ether compound, or a ketone can be mentioned.
In the production of the fluorine-containing diene compound, a polymerization inhibitor such as a hydroquinone compound may be added to the reaction system. Examples of the hydroquinone compound include hydroquinone, methylhydroquinone, dimethylhydroquinone, and 4-methoxyphenol.
After the reaction, the reaction product can be purified, for example, by distillation.
The production of the fluorinated diene compound is preferably carried out in an apparatus capable of removing water produced in the reaction from the reaction system.

[Polymer]
The polymer of the present invention is a polymer having structural units derived from the fluorinated diene compound of the present invention.
In this specification, the polymer of the present invention may be referred to as a "specific polymer."
The fluorine-containing diene compound used as a monomer for producing the polymer of the present invention is not particularly limited as long as it contains at least the fluorine-containing diene compound of the present invention.

The above-mentioned structural unit (repeating unit) derived from a fluorinated diene compound constituting the specific polymer preferably contains a structural unit represented by the following formula (3) and/or formula (4), from the viewpoint of achieving superior effects of the present invention.

In formula (3),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

In formula (4),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

A, Q, Rf, n, X, Y, and Z in formula (3) are the same as A, Q, Rf, n, X, Y, and Z in formula (1). The same applies to formula (4).

The content of the structural unit derived from the above-mentioned fluorine-containing diene compound (or the structural unit represented by formula (3) and/or formula (4) as a preferred embodiment; the same applies hereinafter) (when the specific polymer has structural units represented by formula (3) and formula (4), the total amount thereof; the same applies hereinafter) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more and 100% by mass or less in the specific polymer, from the viewpoint of achieving superior effects of the present invention.
When the specific polymer further contains a repeating unit having no ring structure derived from the fluorine-containing diene compound, the upper limit of the content of the repeating unit having a ring structure derived from the fluorine-containing diene compound (e.g., a structural unit represented by formula (3) and/or formula (4)) may be less than 100% by mass. The repeating unit having no ring structure derived from the fluorine-containing diene compound is represented, for example, as a repeating unit having a repeating unit number p in the polymer represented by formula (6) described later.

The content of the structural units derived from the above-mentioned fluorine-containing diene compound (or the structural units represented by formula (3) and/or formula (4) as a preferred embodiment) can be the same whether the polymer of the present invention is a homopolymer of the above-mentioned fluorine-containing diene compound or a copolymer of monomers containing the above-mentioned fluorine-containing diene compound and other monomers. When the polymer of the present invention is the above-mentioned copolymer, the upper limit of the content of the structural units derived from the above-mentioned fluorine-containing diene compound is less than 100% by mass.

When the polymer of the present invention has a constituent unit derived from a monomer (other monomer) other than the above-mentioned fluorine-containing diene compound, the above-mentioned other monomer is not particularly limited as long as it is a compound having an ethylenically unsaturated bond. For example, a (meth)acrylate-based compound or a (meth)acrylamide-based compound other than the above-mentioned fluorine-containing diene compound, or (meth)acrylic acid or a styrene-based compound can be mentioned.

From the viewpoint of achieving superior effects of the present invention, the polymer of the present invention is preferably a homopolymer of the above-mentioned fluorine-containing diene compound.

When the polymer of the present invention is a homopolymer of the above-mentioned fluorine-containing diene compound, an example of the homopolymer of the above-mentioned fluorine-containing diene compound is a polymer represented by the following formula (6).

A, Q, Rf, n, X, Y, and Z in formula (6) are the same as A, Q, Rf, n, X, Y, and Z in formula (1), respectively.
In formula (6), l, m, and p represent the number of repeating units of each repeating unit.
l, m and p each independently represent 0 or 1 or more, and l+m represents 1 or more.
The value of l+m can correspond to the content of the structural units derived from the above-mentioned fluorine-containing diene compound (or, as a preferred embodiment, the structural units represented by formula (3) and/or formula (4)).

From the viewpoint of obtaining superior effects of the present invention, the polymer of the present invention preferably contains a polymer represented by the following formula (7).

In formula (7), l, m, and p are the same as l, m, and p in formula (6).

The number average molecular weight (Mn) of the polymer of the present invention is preferably from 5,000 to 100,000, and more preferably from 10,000 to 40,000, from the viewpoint of obtaining superior effects of the present invention.
The weight average molecular weight (Mw) of the polymer of the present invention is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000, and even more preferably from 20,000 to 80,000, from the viewpoint of obtaining superior effects of the present invention.
The molecular weight distribution (weight average molecular weight/number average molecular weight) of the polymer of the present invention is preferably from 1.0 to 20, and more preferably from 1.0 to 3, from the viewpoint of obtaining superior effects of the present invention.

[Production method of the polymer of the present invention]
The method for producing a polymer of the present invention is a method for producing a polymer of the present invention by polymerizing the fluorinated diene compound of the present invention in an organic solvent.

The fluorine-containing diene compound used as a monomer in the process for producing the polymer of the present invention is not particularly limited as long as it is a fluorine-containing diene compound of the present invention.
In the method for producing a polymer of the present invention, the organic solvent can function as a polymerization solvent.
According to the method for producing a polymer of the present invention, the polymer of the present invention (specific polymer) can be produced.

The organic solvent preferably contains a fluorine-containing organic solvent, from the viewpoints that the diene in the fluorine-containing diene compound can be efficiently cyclized, the effects of the present invention are excellent, and when the fluorine-containing diene compound (monomer) is polymerized, cyclopolymerization can be performed at a relatively high molecular weight.

The fluorine-containing organic solvent is not particularly limited as long as it is an organic solvent that contains fluorine and is capable of dispersing or dissolving the fluorine-containing diene compound or specific polymer.
Examples of the fluorine-containing organic solvent include hydrofluoroethers (HFEs), hydrofluorocarbons (HFCs), and perfluoroketones (PFKs).

From the viewpoint of achieving superior effects of the present invention, the fluorine-containing organic solvent preferably contains a hydrofluorocarbon (HFC), and more preferably contains an aromatic hydrocarbon compound having a fluoroalkyl group.

Hydrofluorocarbons (HFCs) generally refer to compounds whose skeletons are composed of carbon, with some or all of the hydrogen atoms bonded to the carbon being replaced with fluorine.
Examples of aromatic hydrocarbon compounds having a fluoroalkyl group include xylene hexafluorides such as m-xylene hexafluoride (hereinafter referred to as m-XHF) and p-xylene hexafluoride.
The aromatic hydrocarbon compound having a fluoroalkyl group is preferably m-XHF, from the viewpoint of obtaining superior effects of the present invention.

As for hydrofluoroethers (HFEs), hydrofluorocarbons (HFCs) other than aromatic hydrocarbon compounds having a fluoroalkyl group, and perfluoroketones (PFKs), the same ones as those described in the organic solvents that can be further contained in the surface treatment agent of the present invention, which will be described later, can be mentioned.

In the method for producing the polymer of the present invention, for example, a polymerization initiator can be used. Examples of the polymerization initiator include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate) and azobisisobutyronitrile, organic peroxides, and persulfates.
In the method for producing a polymer of the present invention, the polymerization temperature can be, for example, 50 to 80°C.
The polymer produced by the method for producing a polymer of the present invention may further contain an unreacted fluorine-containing diene compound and/or an organic solvent as a polymerization medium.

[Surface treatment agent]
The surface treatment agent of the present invention is a surface treatment agent containing the fluorinated diene compound of the present invention or the polymer of the present invention.

The fluorine-containing diene compound contained in the surface treatment agent of the present invention is not particularly limited as long as it is the fluorine-containing diene compound of the present invention.
The polymer contained in the surface treatment agent of the present invention is not particularly limited as long as it is the polymer of the present invention (specific polymer).
From the viewpoint of obtaining superior effects of the present invention, the surface treatment agent of the present invention preferably contains a specific polymer, more preferably contains a polymer represented by formula (6), and further preferably contains a polymer represented by formula (7).

From the viewpoint of obtaining superior effects of the present invention, it is preferred that the surface treatment agent of the present invention further contains an organic solvent.
The organic solvent is not particularly limited as long as it is an organic compound capable of dissolving or dispersing the fluorine-containing diene compound or the specific polymer. The organic solvent is preferably not reactive to the fluorine-containing diene compound or the specific polymer.

Examples of the organic solvent include fluorine-containing organic solvents, hydrocarbon compounds, ether compounds, alcohol compounds, and ketones.
Among the above organic solvents, organic solvents other than the fluorine-containing organic solvents do not contain fluorine.

The organic solvent preferably contains a fluorine-containing organic solvent, from the viewpoint of providing excellent solubility or dispersibility for the fluorine-containing diene compound or the specific polymer and thus providing superior effects of the present invention.
The fluorine-containing organic solvent may be a compound in which at least a part or all of the hydrogen atoms of a hydrocarbon compound are substituted with fluorine atoms. The hydrocarbon compound may further have an ether bond, a carbonyl group, etc. in addition to the fluorine atoms.

Examples of the fluorine-containing organic solvent include hydrofluoroethers (HFEs), hydrofluorocarbons (HFCs), and perfluoroketones (PFKs).

(Hydrofluoroethers (HFEs))
Examples of hydrofluoroethers (HFEs) include 1,1,2,2,3,3,3-heptafluoropropyl methyl ether (CF ₃ CF ₂ CF ₂ OCH ₃ ), 1,1-difluoroethyl-2,2,2-trifluoroethyl ether (CF ₃ CH ₂ OCF ₂ CH ₃ ), perfluoro-1-ethylbutyl methyl ether (CF ₃ CF ₂ CF ₂ CF(CF ₂ CF ₃ )OCH ₃ ), 2,2-difluoroethyl-2,2,2-trifluoroethyl ether (CF ₃ -CH ₂ -OCH ₂ -CF ₂ -H), methyl nonafluorobutyl ether (C ₄ F ₉ OCH ₃ ), and ethyl nonafluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ). However, the hydrofluoroethers (HFEs) that can be used in the present invention are not limited to these.
The above hydrofluoroethers (HFEs) can be used alone or in combination of two or more.

The above-mentioned HFE is preferably at least one type selected from the group consisting of CF ₃ -CH ₂ -OCH ₂ -CF ₂ -H, methyl nonafluorobutyl ether (C ₄ F ₉ OCH ₃ ) and ethyl nonafluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ) because it can reduce the surface tension of the surface treatment agent, has excellent effects of the present invention, and has a low global warming potential (GWP).In addition to the above, from the viewpoint of excellent drying properties and workability, CF ₃ -CH ₂ -OCH ₂ -CF ₂ -H and/or ethyl nonafluorobutyl ether are more preferable, and ethyl nonafluorobutyl ether is even more preferable.

The nonafluorobutyl groups (i.e., perfluorobutyl groups) of the methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether may each be linear or branched.

The above methyl nonafluorobutyl ether and the above ethyl nonafluorobutyl ether may each be a pure substance consisting of one type of compound having the same structure of the nonafluorobutyl group, or a mixture consisting of two or more types of isomers having different structures of the nonafluorobutyl group.

As the ethyl nonafluorobutyl ether, for example, at least one compound selected from the group consisting of the compound represented by the following formula (A-1-a), the compound represented by the following formula (A-1-b), and the compound represented by the following formula (A-1-c) can be used alone or as a mixture of two or more compounds, and a combination of the compound represented by the following formula (A-1-a) and the compound represented by the following formula (A-1-b) is one preferred embodiment.

(Hydrofluorocarbons (HFCs))
Hydrofluorocarbons (HFCs) generally refer to compounds whose skeletons are composed of carbon, with some or all of the hydrogen atoms bonded to the carbon being replaced with fluorine.
As an example of a preferred embodiment of the HFC that can be further contained in the surface treatment agent of the present invention, an aliphatic HFC in which part or all of the hydrogen atoms in an aliphatic hydrocarbon are substituted with fluorine can be mentioned. The main chain of the aliphatic HFC may be linear, branched, or cyclic, or a combination thereof.
Additionally, the aliphatic HFC may be one that does not have an aromatic hydrocarbon group such as a benzene ring.

Examples of hydrofluorocarbons (HFCs) include:
1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₃ ), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (CF ₃ CHFCHFCF ₂ CF ₃ ), heptafluorocyclopentane (c-C ₅ F ₇ H ₃ ), tridecafluorohexane (C ₆ HF ₁₃ ), 1,1,1,2,2,3,3,4,4-nonafluorohexane (CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₃ ), and 1,1,1,3,3-pentafluoro-n-butane (CF ₃ CH ₂ CF ₂ CH _{3 ).} ), aliphatic HFCs;
Examples of the HFC that can be used in the present invention include aromatic HFCs having an aromatic hydrocarbon group, such as m-XHF. However, the hydrofluorocarbons (HFCs) that can be used in the present invention are not limited to these.
The above hydrofluorocarbons (HFCs) can be used alone or in combination of two or more.

(Perfluoroketone (PFK))
Examples of perfluoroketones (PFKs) include dodecafluoro-2-methylpentan-3-one ((CF ₃ ) ₂ CFC(═O)CF ₂ CF ₃ ), tetradecafluoro-2-methylhexane-3-one (CF ₃ CF ₂ CF ₂ C(═O)CF(CF ₃ ) ₂ ), and tetradecafluoro-2,4-dimethylpentan-3-one ((CF ₃ ) ₂ CFC(═O)CF(CF ₃ ) ₂ ). However, the perfluoroketones (PFKs) that can be used in the present invention are not limited to these.
The perfluoroketones (PFKs) may be used alone or in combination of two or more.
When two types of perfluoroketones (PFK) are combined, for example, a mixture of tetradecafluoro-2-methylhexan-3-one ((CF ₃ ) ₂ CFC(═O)CF ₃ CF ₂ CF ₂ ) and tetradecafluoro-2,4-dimethylpentan-3-one ((CF ₃ ) ₂ CFC(═O)CF(CF ₃ ) ₂ ) can be used.

From the viewpoint of obtaining superior effects of the present invention, the fluorine-containing organic solvent is preferably a hydrofluoroether (HFE) and/or a hydrofluorocarbon (HFC),
A combination of a hydrofluoroether (HFE) and a hydrofluorocarbon (HFC) is more preferred,
More preferred is a combination of at least one selected from the group consisting of CF3 _{- CH2} - _{OCH2 - CF2 - H} , methyl nonafluorobutyl ether ( _C4F9OCH3 ) and ethyl _{nonafluorobutyl} ether ( _C4F9OC2H5 ) with an aromatic HFC having an aromatic hydrocarbon group, and even more preferred is a combination of _{ethyl nonafluorobutyl ether} ( _C4F9OC2H5 ) and _XHF .
The surface treatment agent of the present invention may contain, as an organic solvent, for example, a polymerization solvent, derived from the production of the specific polymer.

When the surface treatment agent of the present invention contains the specific polymer, the content of the specific polymer is preferably 0.1 to 50 mass%, and more preferably 0.5 to 10 mass%, of the total amount of the surface treatment agent, from the viewpoint of achieving better effects of the present invention.
The content of the fluorinated diene compound when the surface treatment agent of the present invention contains the fluorinated diene compound, or the total content of the fluorinated diene compound and the specific polymer when the surface treatment agent of the present invention contains the fluorinated diene compound and the specific polymer, is similar to the above.

The surface treatment agent of the present invention may further contain additives in addition to the above-mentioned essential components.
Examples of the additives include various polymerization initiators that can be used to polymerize the fluorinated diene compound, curing agents, curing catalysts, fillers, pigments, dyes, polymerization inhibitors, release agents, thickeners, viscosity reducers, defoamers, foaming agents, separation inhibitors, leveling agents, plasticizers, emulsifiers, desiccants, reinforcing fibers such as glass fibers and carbon fibers, surfactants, low shrinkage agents, and colorants.

The method for producing the surface treatment agent of the present invention is not particularly limited.
When the surface treatment agent of the present invention contains only the specific polymer, the specific polymer may be used as it is.
The specific polymer may be in a state of a mixture with the organic solvent or the like used as a polymerization solvent in producing the specific polymer.
When the surface treatment agent of the present invention further contains, in addition to the specific polymer, the organic solvent described above in the surface treatment agent of the present invention and the additives that can be used as necessary, the surface treatment agent of the present invention can be produced by mixing the specific polymer with the organic solvent and/or the additives.
The total amount of organic solvents that can be contained in the surface treatment agent of the present invention (including the organic solvent used as the polymerization solvent when the specific polymer is used in a mixed state with the above-mentioned organic solvent used as the polymerization solvent in producing the specific polymer) is preferably 50 to 99.9 mass % and more preferably 90 to 99.5 mass % of the total amount of the surface treatment agent, from the viewpoint of obtaining superior effects of the present invention.

An example of a method for using the surface treatment agent of the present invention is a method for applying the surface treatment agent of the present invention to a substrate. By applying the surface treatment agent, a layer of the surface treatment agent is formed on the surface of the substrate, and the surface slipperiness of the substrate can be improved.
The method for applying the surface treatment agent of the present invention to a substrate is not particularly limited, and examples thereof include coating.

When the surface treatment agent of the present invention further contains the above-mentioned organic solvent, after the surface treatment agent of the present invention is applied to the substrate, the above-mentioned organic solvent can be dried, for example, under conditions of 10 to 120°C.

Specifically, the surface treatment agent of the present invention can be used as, for example, a paint or a coating agent.
Examples of materials for the substrate include glass, plastic, rubber, metal, and ceramic.
Specific examples of the above-mentioned substrates include wet area molded products such as bathroom components, washbasin components, and kitchen components; daily necessities such as umbrellas, shoes, and bags; exterior-related products for buildings such as bridge piers, roofs, and exterior walls; interior-related products such as floors and interior walls; housing products such as furniture and home appliances; and vehicle bodies (including exterior and interior materials) for ships, airplanes, and automobiles.

The present invention will be specifically explained below with reference to examples. However, the present invention is not limited to these.

<Production of Fluorine-Containing Diene Compound>
Example 1-1: Production of Fluorine-Containing Diene Compound 1 Fluorine-containing diene compound 1 was produced by the following method.
1. First step (synthesis of α-allyloxymethylacrylic acid: H-AMA)
A 500 mL four-neck flask equipped with a thermometer, a stirrer, a Dimroth condenser, and a dropping funnel was used as the reaction vessel. 150.0 g of 10 wt% aqueous sodium hydroxide solution and 55.8 g of Me-AMA (α-allyloxymethylacrylic acid methyl ester, trade name FX-AO-MA, manufactured by Nippon Shokubai Co., Ltd., the same applies below) were charged into the reaction vessel, and the mixture was stirred for one hour while being cooled in a water bath. After confirming the disappearance of Me-AMA by GC analysis, the water bath was changed to an ice bath. 64.2 g of 30 wt% sulfuric acid was charged into the dropping funnel, and dropped while continuing to stir. After the dropping was completed, the mixture was separated using a separating funnel, and washed with 83.5 g of ion-exchanged water (40 wt% relative to the organic layer). To the organic layer after washing with water, 0.2 g (0.1 wt % relative to the organic layer) of hydroquinone was added, and the water contained in the organic layer was distilled off using an evaporator at 2.2 kPa for 1 hour. After distillation, the mixture was filtered using a PTFE membrane filter with a pore size of 1 μm and a suction filter to remove the precipitate (Na ₂ SO ₄ ), yielding 41.8 g of α-allyloxymethylacrylic acid (H-AMA).

Me-AMA H-AMA

2. Second Stage Process (Production of Fluorine-Containing Diene Compound 1)
A 500 mL four-neck flask equipped with a thermometer, a stirrer, a water content receiver, and a flat stopper was used as the reaction vessel. The water content receiver was filled with cyclohexane. 73.7 g of H-AMA obtained in the first step, 80.0 g of cyclohexane, 0.6 g of hydroquinone, 200.0 g of 2-(perfluoro-n-hexyl)ethanol (commercial product), and 5.17 g of p-toluenesulfonic acid were added to the reaction vessel. The reaction was carried out in an oil bath at 90° C. for 9 hours, and the conversion rate was determined by GC analysis (conversion rate 99.7%). 146.1 g of a 10 wt % aqueous sodium hydrogen carbonate solution was added to the solution after the reaction, and the liquids were separated using a separatory funnel. The obtained organic layer was washed with 146.1 g of ion-exchanged water, and 1.45 g of 4-tert-butylpyrocatechol was added to the organic layer. Then, in order to remove cyclohexane, the mixture was distilled at 2.9 kPa for 2 hours to obtain 223.9 g of a product (GC purity 91.2%).
The product was purified by distillation under reduced pressure of about 0.1 kPa, and fractions were collected in the temperature range of 70° C. to 97° C. The fraction collected at about 88° C. was the main fraction (main product). The GC purity of the main product was 97.4%, and the yield was 31.8 g.

H-AMA Fluorine-containing diene compound 1

3. Analysis of the main product The structure of the main product was analyzed by GC-MS and ¹ H-NMR.
(1) GC-MS
As a result of GC-MS analysis of the main product, the parent peak (m/z=489) of the main product obtained in the analysis matched the molecular weight of the target compound (m/z=488).

The measurement conditions for GC-MS are shown below.
Apparatus: GC-2010 and GCMS-QP2010 (manufactured by Shimadzu Corporation)
Column: DB-1301 (manufactured by Agilent Technologies, Inc.) (inner diameter 0.25 mm, length 30 m, film thickness 1.00 μm)
Inlet temperature: 200℃
Injection method: split Split ratio: 20
Flow rate: 11mL/min
Column temperature program: hold at 50° C. for 5 minutes, increase temperature to 250° C. at 10° C./min, hold at 250° C. for 10 minutes. Temperature program ion source temperature: 230° C.
Interface temperature: 230°C
Ionization method: EI

(2) ^1H -NMR
As a result of ¹ H-NMR analysis of the above main product, protons derived from the target compound having the following structure were observed, and the integral value and the number of protons were consistent.

< ^1H -NMR measurement> is described below.
The substance to be measured (the main product or the polymer described below) was dissolved in a deuterated solvent, acetone-d6, so that the concentration of the substance to be measured was adjusted to about 0.2 wt %. The solution thus prepared was transferred to ^{a 1} H-NMR measurement tube.
The measurement conditions are as follows.
Device: 400MHz ear hold magnet 400JJYH (manufactured by JEOL Ltd.)
Nucleus: Proton Accumulation number: 32

From the results of the above GC-MS and ¹ H-NMR analyses, it was concluded that the structure of the main product was as shown above.
In this specification, the main product produced as described above may be referred to as fluorine-containing diene compound 1.
The fluorine-containing diene compound 1 produced as above was used as a monomer in the production of a polymer described below.
Figure 1 shows a GC-MS chart (gas chromatogram) of fluorinated diene compound 1, Figure 2 shows a GC-MS chart (mass spectrum) of fluorinated diene compound 1, and Figure 3 shows a ^1H -NMR chart of fluorinated diene compound 1. In the ^1H -NMR chart shown in Figure 3, X is a peak due to water in the deuterated solvent acetone-d6 used for the ^1H -NMR measurement.

<<Production of Polymer>>
<Example 2-1: Production of specific polymer 1 (ring + F)>
A polymerization solution was prepared by adding 11.0 g of the fluorine-containing diene compound 1 produced as described above as a monomer to a 100 mL medium bottle, 44.0 g of m-xylene hexafluoride (m-XHF, commercially available product) as an organic solvent (polymerization solvent), and 0.11 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. In order to remove dissolved oxygen in the solution, nitrogen was bubbled for 1 minute. Thereafter, the medium bottle was placed in a shaking thermostatic bath and polymerized under conditions of 70°C, 18 hours, and a shaking rate of 120 to 130 min ^-1 to produce a specific polymer 1, which is a homopolymer of the fluorine-containing diene compound 1. The specific polymer 1 has a constitutional unit (repeating unit) derived from the fluorine-containing diene compound 1. Among the repeating units contained in the specific polymer 1, some of the repeating units have a (CF ₂ ) ₆ F group and a ring structure formed by a diene.
The mixture containing the specific polymer 1 and the organic solvent obtained after the polymerization was in a homogeneous state.

(Comparative Example 2-1: Preparation of Comparative Polymer 1 (Non-cyclic + F))
Polymerization was carried out in the same manner as in the above <Production of Specific Polymer 1>, except that the fluorine-containing diene compound 1 was changed to a fluorine-containing non-diene compound (commercially available product) having the following structure, to produce Comparative Polymer 1, which is a homopolymer of the above compound. The repeating unit in Comparative Polymer 1 has a ( _CF2 ) _6F group but does not have a ring structure.
After the polymerization, the mixture containing Comparative Polymer 1 and the organic solvent was in a homogeneous state.

(Comparative Example 2-2: Preparation of Comparative Polymer 2 (Ring+C))
Except for changing the fluorine-containing diene compound 1 to a non-fluorine diene compound, Me-AMA (same as above, structure below), polymerization was carried out in the same manner as in <Production of Specific Polymer 1> above to produce Comparative Polymer 2, which is a homopolymer of Me-AMA. The repeating unit of Comparative Polymer 2 has a ring structure due to a diene, but does not have a fluorine atom.
After the polymerization, a white solid was precipitated in the solution obtained.

(Comparative Example 2-3: Preparation of Comparative Polymer 3 (Ring+C))
Except for changing the fluorine-containing diene compound 1 to Me-AMA (same as above), which is a non-fluorine diene compound, and changing m-XHF as the organic solvent (polymerization solvent) to methyl ethyl ketone (MEK), polymerization was carried out in the same manner as in <Production of Specific Polymer 1> above, to produce Comparative Polymer 3, which is a homopolymer of Me-AMA. The repeating unit of Comparative Polymer 3 has a ring structure due to a diene, but does not have a fluorine atom.
After the polymerization, the mixture containing Comparative Polymer 3 and the organic solvent was in a homogeneous state.

(Comparative Example 2-4: Preparation of Comparative Polymer 4 (Non-cyclic + C))
Except for changing the fluorine-containing diene compound 1 to a non-fluorine non-diene compound, methyl methacrylate (MMA, structure shown below, commercially available product), polymerization was carried out in the same manner as in the above <Production of specific polymer 1> to produce comparative polymer 4, which is a homopolymer of methyl methacrylate. The repeating unit of comparative polymer 4 does not have a fluorine atom or a ring structure.
After the polymerization, the mixture containing Comparative Polymer 4 and the organic solvent had a higher viscosity than the mixture obtained in Example 2-1.

(Comparative Example 2-5: Preparation of Comparative Polymer 5 (Non-cyclic + C))
Except for changing the fluorine-containing diene compound 1 to methyl methacrylate, a non-fluorine non-diene compound, and changing m-XHF as the organic solvent (polymerization solvent) to methyl ethyl ketone (MEK), polymerization was carried out in the same manner as in the above <Production of Specific Polymer 1> to produce Comparative Polymer 5, a homopolymer of methyl methacrylate. The repeating unit of Comparative Polymer 5 does not have a fluorine atom or a ring structure.
After the polymerization, the mixture containing Comparative Polymer 5 and the organic solvent was in a homogeneous state.

<Analysis of Specific Polymer 1: Cyclization Ratio>
In order to confirm that the specific polymer 1 produced as described above has a ring structure due to a diene, ¹ H-NMR measurement was carried out as follows. The results are shown in Figure 4. Figure 5 is an enlarged view of the ¹ H-NMR chart of the specific polymer 1 shown in Figure 4. Note that X in the ¹ H-NMR chart shown in Figure 4 is a peak due to water in the deuterated solvent acetone-d6 used for the ¹ H-NMR measurement. The same is true for Figure 5.
The cyclization rate was calculated from the integral value of each proton. The calculation procedure for the cyclization rate is described below.
The ¹ H-NMR measurement of the polymer is the same as that described above in < ¹ H-NMR Measurement>.

First, the protons of the monomer (fluorine-containing diene compound 1) and the polymerizable polymer were labeled with a to i as follows.

Amount of Unreacted Monomer in Specific Polymer 1 Since g labeled to the monomer is not found in the polymer, the amount (mol) of the unreacted monomer in Specific Polymer 1 was calculated to be 0.0309 mol from the peak integral value of g in the result of ^1H -NMR of Specific Polymer 1 using the formula described below.

Amount of repeating units of uncyclized diene in specific polymer 1 The amount of repeating units of uncyclized diene in the polymer was determined from the total peak integral value of a and b. However, since the monomer also has a and b, the amount of unreacted monomer in specific polymer 1 obtained as above was subtracted based on the total integral value of a and b in ^{the 1H} -NMR result of specific polymer 1 using the calculation formula described below, and the amount of repeating units of uncyclized diene (uncyclized portion) in specific polymer 1 was calculated to be 0.00365 mol.

Amount of repeating units in which diene is cyclized in specific polymer 1 The amount of repeating units in which diene is cyclized in the polymer was determined from the peak integral value of h. However, since there are also repeating units in which the monomer and diene are not cyclized, the amount of repeating units in which diene is cyclized (cyclized portion) in specific polymer 1 was calculated to be 0.96545 mol based on the integral value of h in the ^1H -NMR results of specific polymer 1, by subtracting the amounts of unreacted monomers and uncyclized repeating units in specific polymer 1 obtained as described above, using the calculation formula described below.

From the above results, the cyclization rate of Fluorine-containing Diene Compound 1 in Specific Polymer 1 was 99.6%. The results are shown in the "Cyclization rate of polymer" column in Table 1.

The cyclization rates of the comparative polymers 2 and 3 were also analyzed in the same manner as for the specific polymer 1.
Since Comparative Polymer 2 was not dissolved in the deuterated solvent used in measuring ¹ H-NMR, it was not possible to measure the cyclization rate in Comparative Polymer 2. The above result is shown in Table 1 as "measurable."
The cyclization rate of the non-fluorinated diene compound in Comparative Polymer 3 was 99.5%.

<Polymer analysis: molecular weight>
The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the polymer produced as above were measured by GPC. The results are shown in Table 1.

(GPC: Measurement of molecular weight of polymer)
The Mw, Mn and (Mw/Mn) of each of the above polymers were measured using ACQUITY Arc Systems (manufactured by Nihon Waters K.K.) for non-fluorinated polymers, and HLC-8320GPC (manufactured by Tosoh Corporation) for fluorinated polymers (which corresponds to the polymer of the present invention since it contains fluorine). The measurement conditions are shown below.

Measurement conditions for Mw, etc. when the polymer is a non-fluorinated polymer: Apparatus: ACQUITY Arc Systems (manufactured by Nihon Waters K.K.)
Purge solvent: tetrahydrofuran Mobile phase: tetrahydrofuran Injection volume: 20 μL
Flow rate: 0.8mL/min
Column temperature: 40°C
Analysis time: 10min
Detector: ELSD
Columns: ACQUITY APC ^™ XT 45 x 2, ACQUITY APC ^™ XT 200 x 1, ACQUITY APC ^™ XT 450 x 1 (manufactured by Nihon Waters K.K.)

Measurement conditions for Mw, etc. when the polymer is a fluoropolymer: Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation)
Purge solvent: Novec7300 (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ , manufactured by 3M; the same applies below)/hexafluoro-2-propanol=85/15 vol % (volume %)
Mobile phase: Novec7300/hexafluoro-2-propanol=85/15 vol%
Injection volume: 20 μL
Flow rate: 0.3mL/min
Column temperature: 40°C
Analysis time: 40min
Detector: RI
Columns: Shodex GPC LF-604 x 2, Shodex GPC LF-6 x 1, KF-600PH x 1 (Showa Denko K.K.)

<Production of Surface Treatment Agent>
Each surface treatment agent was produced by mixing each polymer and organic solvent used in the surface treatment agent shown under the column "Surface treatment agent" in Table 1 so that the concentration of each polymer was (2.0 wt %).
Each of the polymers produced in the above <<Production of Polymers>> (polymers containing the polymerization solvent) was used for producing a surface treatment agent.

Details of the organic solvents used in the production of the surface treatment agent are as follows:
Novec 7200: a mixture of the following compounds, manufactured by 3M

MEK: Methyl ethyl ketone (commercially available)
In Comparative Example 3-2, Comparative Polymer 2 was not dissolved in MEK, which was the organic solvent used to produce the surface treatment agent, and therefore the surface treatment agent could not be produced. Accordingly, in Table 1, the results of the contact angle and sliding angle of Comparative Example 3-2 are shown as "measurable."

<Evaluation>
The surface treatment agents prepared as described above were used to carry out the following evaluations. The results are shown in Table 1.
1. Preparation of glass plate with surface treatment film A glass plate was immersed in each of the surface treatment agents prepared as described above at room temperature for 1 minute, and the glass plate was removed from the surface treatment agent. The glass plate was then dried at 120° C. for 5 minutes to prepare a glass plate with a surface treatment film having a film of each surface treatment agent (specific polymer or comparative polymer) on the surface of the glass plate.

2. Measurement of Contact Angle Normal hexadecane (3 μL) was dropped onto each of the glass plates with the surface treatment film obtained as described above, and the contact angle (unit: degree) was measured using an automatic contact angle measuring device OCA20 (manufactured by Eiko Instruments Co., Ltd.).

Criteria for evaluating contact angle When the contact angle is 60 degrees or more, the oil repellency is excellent, which is preferable.
The larger the contact angle is, the more excellent the oil repellency is.
When the contact angle was less than 60 degrees, the oil repellency was evaluated as poor.

3. Measurement of sliding angle Normal hexadecane (10 μL) was applied as a drop to each glass plate with the surface treatment film obtained as described above, and the sliding angle was measured using a contact angle meter DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.) The sliding angle movement speed in measuring the sliding angle was about 1.5°/sec, and the angle at which the normal hexadecane droplet started to move was taken as the sliding angle (degrees).

Evaluation Criteria for Sliding Property Based on Sliding Angle In the present invention, the sliding property was evaluated based on the measurement results of the sliding angle when 10 μL of normal hexadecane was used.
In the present invention, when 10 μL of normal hexadecane was used, a sliding angle of 20 degrees or less was evaluated as excellent in sliding property (droplet removal property).
If the above-mentioned sliding angle is smaller than 20 degrees, the sliding property is considered to be superior.
On the other hand, when the above-mentioned falling angle exceeded 20 degrees, the sliding property was evaluated as being somewhat poor.
In addition, when the droplets slid down from the glass plate with the surface treatment film and left a liquid trace of normal hexadecane on the surface of the glass plate with the surface treatment film, this was evaluated as "impossible to measure" regardless of the magnitude of the sliding angle. The above "impossible to measure" was evaluated as very poor sliding property.

As is clear from the results shown in Table 1, since the monomer used in the production of the polymer was a fluorine-containing non-diene compound, Comparative Example 3-1 containing Comparative Polymer 1 having no diene ring structure had a high contact angle but was somewhat poor in sliding properties.
In Comparative Example 3-2, which contained Comparative Polymer 2 that did not have fluorine because the polymerization solvent used in the production of the polymer was m-XHF and the monomer used in the production of the polymer was a non-fluorinated diene compound, Comparative Polymer 2 was not dissolved in MEK, and a surface treatment agent could not be prepared.
Comparative Example 3-3, which contained Comparative Polymer 3 that did not have fluorine because the polymerization solvent used in the production of the polymer was MEK and the monomer used in the production of the polymer was a non-fluorinated diene compound, had very poor slippage properties.
Comparative Examples 3-4 and 5, which contained Comparative Polymers 4 and 5 that did not have a ring structure due to fluorine and diene, had very poor slip properties because the monomers used in the production of the polymers were non-fluorine, non-diene compounds.

In contrast, the surface treatment agent of the present invention had excellent slip resistance. The surface treatment agent of the present invention also had excellent oil repellency.

Claims (2)

A method for producing a polymer, comprising polymerizing a fluorinated diene compound represented by the following formula (1) in an organic solvent containing a fluorinated organic solvent to produce a polymer having structural units derived from the fluorinated diene compound:

In formula (1),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group. A surface treatment agent comprising a fluorine-containing diene compound represented by the following formula (1) or a polymer having a structural unit derived from the fluorine-containing diene compound, and an organic solvent, wherein the organic solvent comprises a fluorine-containing organic solvent:

In formula (1),
A is O or NH;
Q is an (n+1)-valent organic group or a single bond;
Rf's each independently represent a fluoroalkyl group or a fluoroether group;
n is 1 to 2;
R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group;
X, Y, and Z each independently represent a methylene group, an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is an oxygen atom, a sulfur atom, or an imino group, and at least one of X, Y, and Z is a methylene group.

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