JP2014201724A - Surface treatment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface treatment composition that does not comprise a linear perfluoroalkyl group having 8 or more carbons, comprises a perfluoroalkyl group having 6 carbons that has less influence on the living body and the environment and exhibits both water repellent, oil repellent property and slipperiness, to provide various kinds of treatment agents including the surface treatment composition, and to provide a member to which both water repellent, oil repellent property and slipperiness are imparted by the surface treatment composition and the treatment agent.SOLUTION: There is provided a surface treatment composition that does not contain a linear perfluoroalkyl group having 8 or more carbons, and contains a perfluoroalkyl group having 6 carbons and an organopolysiloxane group. A member having a coating comprising various kinds of treatment agents including the surface treatment composition as well as the surface treatment composition or the various kinds of treatment agents are also provided.

Description

  The present invention relates to a surface treatment composition that imparts water / oil repellency and slipperiness to various substrates.

  In the modern living environment, there are many facilities, devices, and machinery that require or require water repellency, and the types are also used for automotive window glass, painted surfaces, kitchen equipment, kitchen utensils, and kitchen equipment. There are a wide variety of exhaust devices, bathing facilities, wash facilities, medical facilities, medical equipment, mirrors, eyeglasses, inkjet printer parts, and the like. Conventionally, when imparting water repellency to these objects, generally, a method of making it difficult to wet, that is, increasing the water contact angle of the object surface has been applied. Typically, surface coating is performed with a so-called hydrophobic material such as a silicone compound or a resin, a fluorine resin, or a polyolefin resin.

In particular, among the fluororesins, polymers containing perfluoroalkyl groups are known as materials that are difficult to wet. Typically, it is a (meth) acrylate polymer, for example, CH ₂ = C (R ¹ ) COO-QR ^f (wherein R ^{1 is a} hydrogen atom or a methyl group, Q is a divalent linking group, R ^f : A polymer of (meth) acrylate represented by C4-14 perfluoroalkyl group) has been proposed as a solder flux creeping-up inhibitor (see Patent Document 1). In such a polymer, it is known that when the carbon number of the perfluoroalkyl group is 8 or more, not only the water repellency but also the oil repellency is particularly strong.

  However, the water / oil repellent coating with a perfluoroalkyl group cannot impart slipperiness. For imparting slipperiness, a silicone compound is superior to a perfluoroalkyl group. However, a film made of a silicone compound does not have oil repellency.

  By achieving both water and oil repellency and slipperiness, excellent performance can be expected for antifouling agents, mold release agents, solid lubricants, and the like.

  In addition, a preliminary risk study report on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, was released in March 2003 by the US Environmental Protection Agency (USEPA). Then, it was pointed out that the perfluoroalkyl group having 8 carbon atoms that might generate PFOA has an impact on the living body and the environment. In January 2006, PFOA and its related substances, and precursors thereof were pointed out. Perfluoroalkyl groups contained in compounds with a carbon number of 6 or less have been short since advocating to fluororesin manufacturers, etc. to participate in reduction plans for the release of substances into the environment and content reduction in products Is desired.

JP-A-10-303536

  The present invention does not include a linear perfluoroalkyl group having 8 or more carbon atoms, includes a perfluoroalkyl group having 6 carbon atoms that has little impact on the living body and the environment, and has slipperiness along with water and oil repellency. It is an object of the present invention to provide a surface treatment composition to be shown, various treatment agents containing the surface treatment composition, and a member imparted with water repellency and oil repellency as well as lubricity by the surface treatment composition and the treatment agent.

  As a result of intensive studies based on the above findings, the present inventor has found that the surface treatment composition does not contain a linear perfluoroalkyl group having 8 or more carbon atoms and has 6 carbon atoms. It has been found that by including a group and an organopolysiloxane group, water repellency, oil repellency and slip performance can be simultaneously maintained. Therefore, the present invention makes it possible to provide a surface treatment composition that imparts the following water / oil repellency and slipperiness.

  The present invention relates to a surface treatment composition characterized by not containing a linear perfluoroalkyl group having 8 or more carbon atoms but containing a perfluoroalkyl group having 6 carbon atoms and an organopolysiloxane group. It is.

The surface treatment composition does not contain a structural unit having a linear perfluoroalkyl group having 8 or more carbon atoms, and includes a structural unit derived from a compound represented by the following formula (a) and the following formula (b It is preferable to include a polymer (1) containing at least one of the structural units derived from the compound represented by
_{^{CH 2 = C (R a1)}} -C (O) X-Q a -C 6 F 13 ··· (a)
Where
R ^a1 : a hydrogen atom or a methyl group,
X: —O— or —NR ^a2 —,
Q ^a : a single bond or a divalent linking group.
However, R ^<a2> : A hydrogen atom or a C1-C3 alkyl group.
_{^{CH 2 = C (R b1)}} -Q b -Y ··· (b)
Where
R ^b1 : a hydrogen atom or a methyl group,
Q ^b : a single bond or a divalent linking group,
Y: An organopolysiloxane group having a number average molecular weight (Mn) of 3000 to 30000.

The polymer (1) preferably further contains a structural unit having a carboxyl group, which is derived from a compound represented by the following formula (c).
_{^{CH 2 = C (R c1)}} -Q c -COOH ··· (c)
Where
R ^c1 : a hydrogen atom or a methyl group,
Q ^c : a single bond or a divalent linking group.

  In the polymer (1), the content of the structural unit derived from the compound represented by the formula (a) is preferably 50% by mass or more.

  The present invention provides a water-repellent agent, an oil-repellent agent, an antifouling agent, a release agent, and a low friction imparting agent containing the surface treatment composition.

  The present invention provides a member provided with water repellency / oil repellency and slipperiness by forming a film comprising the surface treatment composition or various treatment agents on at least a part of the surface.

  The present invention does not include the specific group described above, and includes the specific group described above, thereby imparting water repellency / oil repellency and slipperiness with less influence on the living body and the environment. It was possible to provide a treatment composition.

  The surface treatment composition of the present invention is characterized by not containing a linear perfluoroalkyl group having 8 or more carbon atoms but containing a perfluoroalkyl group having 6 carbon atoms and an organopolysiloxane group. The surface treatment composition uses a compound having no linear perfluoroalkyl group having 8 or more carbon atoms and having both a perfluoroalkyl group having 6 carbon atoms and an organopolysiloxane group as an active ingredient. Alternatively, a compound having a C 6 perfluoroalkyl group and a compound having an organopolysiloxane group may be mixed and used as an active ingredient. The active ingredient may be a non-polymerizable compound or a polymer obtained by copolymerizing a polymerizable compound, or a mixture of both can be used.

  The perfluoroalkyl group means a perfluoro-substituted alkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

  The perfluoroalkyl group may have a linear structure or a branched structure, but a linear structure is preferred.

Examples of the organopolysiloxane group include groups derived from an organopolysiloxane having a repeating unit represented by-(SiO)-and having a hydrogen atom, an alkyl group, or a phenyl group bonded to a silicon atom. . Among these, a polydimethylsiloxane group derived from polydimethylsiloxane having a repeating unit represented by — (Si (CH ₃ ) ₂ O) — is preferable.

The surface treatment composition of the present invention preferably contains a polymer copolymerized with the polymerizable compound (hereinafter also referred to as “polymer of the present invention”). The polymer contains at least one structural unit derived from a compound represented by the following formula (a) and a structural unit derived from a compound represented by the following formula (b).
In the present specification, the compound represented by the formula (a) is also referred to as the compound (a), and the compound represented by the formula (b) is also referred to as the compound (b). The compounds represented by other formulas may be expressed similarly.

_{^{CH 2 = C (R a1)}} -C (O) X-Q a -C 6 F 13 ··· (a)
Where
R ^a1 : a hydrogen atom or a methyl group,
X: —O— or —NR ^a2 —,
Q ^a : a single bond or a divalent linking group.
However, R ^<a2> : A hydrogen atom or a C1-C3 alkyl group.
_{^{CH 2 = C (R b1)}} -Q b -Y ··· (b)
Where
R ^b1 : a hydrogen atom or a methyl group,
Q ^b : a single bond or a divalent linking group,
Y: An organopolysiloxane group having a number average molecular weight (Mn) of 3000 to 30000.

In the compound (a), Q ^a is a single bond or a divalent linking group. Examples of the divalent linking group include a linear or branched divalent alkylene group or alkenylene group, a divalent oxyalkylene group, a 6-membered aromatic group, and a saturated or unsaturated 4- to 6-membered ring. Examples thereof include an aliphatic group, a 5- to 6-membered heterocyclic group, and a divalent linking group represented by the following formula (q). These divalent linking groups may be combined, and the ring group may be condensed.
-W-Z- (q)
The symbols in the formula have the following meanings.
W: Linear or branched divalent alkylene group, 6-membered aromatic group, 4- to 6-membered saturated or unsaturated aliphatic group, 5- to 6-membered heterocyclic group, or these A fused ring group.
Z: —O—, —S—, —CO—, —COO—, —COS—, —N (R) —, —SO ₂ —, —PO ₂ —, —N (R) —COO—, —N (R) -CO -, - N (R) -SO 2 -, or -N (R) _-PO 2 -.
However, R: A hydrogen atom or a C1-C3 alkyl group.

  The divalent linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a cyano group, an alkoxy group (methoxy, ethoxy, butoxy, octyloxy). , Methoxyethoxy, etc.), aryloxy groups (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), acyl groups (acetyl, propionyl, benzoyl, etc.), sulfonyl groups (methanesulfonyl, benzenesulfonyl, etc.), acyloxy groups (acetoxy, benzoyl, etc.) Oxy), sulfonyloxy groups (methanesulfonyloxy, toluenesulfonyloxy, etc.), phosphonyl groups (diethylphosphonyl, etc.), amide groups (acetylamino, benzoylamino, etc.), carbamoyl groups (N, N-dimethylcarbamoyl, N- Phenylcarbamo Etc.), alkyl groups (methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl etc.), aryl groups (phenyl, toluyl etc.), heterocyclic groups (pyridyl, imidazolyl, furanyl etc.), alkenyl groups (vinyl, 1- Propenyl, etc.), alkoxyacyloxy groups (acetyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), and polymerizable groups (vinyl groups, acryloyl groups, methacryloyl groups, silyl groups, cinnamic acid residues, etc.) Can be mentioned.

Q ^a can be appropriately selected as long as it is a single bond or a divalent linking group. Among them, a single bond or a linear or branched alkylene group is preferable, and a linear alkylene group is particularly preferable.

In the compound (a), X is —O— or —NR ^a2 —. X is preferably —O— or —NH—.

  Specific examples of the compound (a) are shown in Table 1, but the compound (a) is not limited thereto.

  The structural unit derived from the compound (a) as described above (hereinafter sometimes referred to as “structural unit (A)”) can be expressed as follows.

Here, ^{R a} and ^{Q a} are each the same meanings as ^{R a} and ^{Q a} in the formula (a).

  The polymer of the present invention may be a homopolymer composed of one of the above structural units (A) or a copolymer composed of two or more of the structural units (A). Moreover, the copolymer containing 1 type, or 2 or more types of structural units other than a structural unit (A) may be sufficient. In this case, the content of the structural unit (A) in the polymer of the present invention is preferably 50% by mass or more, and more preferably 70% by mass or more. It is because the water- and oil-repellent performance of the surface treatment composition of the present invention is better when the mass ratio of the structural unit (A) in the polymer of the present invention is within the above range. In the present invention, the mass ratio of each structural unit in the polymer is a value that is considered that all the raw materials used for the polymerization constitute the structural unit. Thus, for example, the mass ratio of the structural unit (A) (percentage of the mass of the structural unit (A) contained therein relative to the total structural unit mass) is substantially the polymerization raw material of the mass of the compound (a) used in the polymerization. It is calculated | required as a ratio with respect to the total mass of a compound. The mass ratio of other structural units in the polymer can be obtained in the same manner.

  As the polymerizable compound having an organopolysiloxane group, the compound (b) is preferable.

In the compound (b), ^Qb is a single bond or a divalent linking group. Examples of the divalent linking group include a linear or branched alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an oxyalkylene group, a 6-membered aromatic group, and 4 to 6 A saturated or unsaturated aliphatic group, a 5- or 6-membered heterocyclic group, or a formula —X ¹ —, —X ¹ —X ² —, —Z ¹ —X ¹ —, —X ¹ —Z ^{1 -X 2 -, - Z 1} -X 1 -X 2 - or ^{-Z 1 -X 1 -Z 2 -X 2} - in the divalent linking group are exemplified represented, these divalent linking group They may be combined and a plurality of ring groups may be condensed.
Symbols X ¹ , X ² , Z ¹ and Z ² in the above have the following meanings, respectively.
X ¹ and X ² : each independently a linear or branched alkylene group having 1 to 10 carbon atoms, an oxyalkylene group, a 6-membered aromatic group, a saturated or unsaturated 4- to 6-membered ring An aliphatic group, a 5- or 6-membered heterocyclic group or a condensed ring group thereof;
Z ¹ and Z ² are each independently —O—, —S—, —CO—, —COO—, —COS—, —N (R ^b ) —, —CON (R ^b ) —, —SO _2. —, —PO (OR ^b ) —, —N (R ^b ) —COO—, —N (R ^b ) —CO—, —N (R ^b ) —SO ₂ — or —N (R ^b ) —PO ( OR ^b ) −. However, the directions of these groups may be reversed. ^Rb here is a hydrogen atom or a C1-C3 alkyl group.

The linking group may have a substituent, and examples of the substituent include the same as Q ^{a of the} compound (a).

In the formula (b), Q ^b can be appropriately selected as long as it is a single bond or a divalent linking group, but a single bond, an alkylene group having 1 to 6 carbon atoms, —COO—, —N (R ^b ) —, -SO 2 _-, or is preferably a divalent linking group obtained by combining these. Among them, the formula ^-Z 1 -X ¹ - is and is ^{Z 1} is -COO-, what ^{X 1} is an alkylene group having 1 to 6 carbon atoms are preferred.

In the formula (b), Y is an organopolysiloxane group having a number average molecular weight (Mn) of 3000 to 30000. Examples of the organopolysiloxane group include groups in which a silicon atom of a repeating unit represented by-(SiO) x- is substituted with a hydrogen atom, an alkyl group, or a phenyl group. Among these, a polydimethylsiloxane group represented by — (Si (CH ₃ ) ₂ O) — is preferable.
Moreover, it is preferable that the terminal of the organopolysiloxane group does not have a polymerizable group. In particular, an alkyl group, an alkoxy group, and a polyether group are preferable, and an alkyl group is more preferable. In addition, the alkyl group, the alkoxy group, and the polyether group may have a substituent.

Among the compounds represented by the formula (b), it is particularly preferable to use a compound represented by the following formula (b1). Among them, a compound having a structure in which the polydimethylsiloxane group has a number average molecular weight of 5000 to 15000 is particularly suitable.
^{_{CH 2 = C (R b11)}} -COO- (CH 2) n- (Si (CH 3) 2 O) m-Si (CH 3) 2 -R b12 (b1)
In formula (b1),
R ^b11 : a hydrogen atom or a methyl group,
R ^b12 : an alkyl group having 1 to 10 carbon atoms,
m: 10 to 800,
n: An integer from 1 to 6.

In the formula (b1), R ^b12 is an alkyl group. The group may have a substituent, but does not contain a polymerizable functional group in the group.
In the formula (b1), the substituent for R ^b12 includes a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an acyl group, a carboxyl group, a sulfonyl group, an acyloxy group, a sulfonyloxy group, and a phosphonyl group. Group, amino group, amide group, alkyl group, aryl group, heterocyclic group, alkoxyacyloxy group and the like. In the formula (b1), ^examples of the polymerizable functional group excluded from the substituent of R ^b12 include polymerizable unsaturated groups such as a vinyl group, an acryloyl group, and a methacryloyl group, an epoxy group, and an isocyanate group. R ^b12 is preferably an alkyl group having 1 to 5 carbon atoms.

  The content of the structural unit (B) is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the mass ratio of the polymer units (B) in the polymer of the present invention is within the above range, the water-sliding property of the water-sliding treatment agent of the present invention is better.

The polymer of the present invention is derived from a compound represented by the following formula (c) (hereinafter also referred to as “compound (c)”) in addition to the structural unit (A) and the structural unit (B) as described above. The structural unit (C) to be burned may be contained.
_{^{CH 2 = C (R c1)}} -Q c -COOH ··· (c)
Where
R ^c1 : a hydrogen atom or a methyl group,
Q ^c : a single bond or a divalent linking group.

Q ^c is a single bond or a divalent linking group. Q ^c can be appropriately selected as long as it is a single bond or a divalent linking group. ^Examples of the divalent linking group for Q ^c include the same as those for Q ^b .

  Specific examples of the preferred compound (c) are shown in Table 2, but the compound (c) is not limited thereto.

  When the polymer of the present invention contains the other structural unit (C) as described above, the mass in the total amount of these other structural units in the polymer (1) is 10% by mass or less, although it varies depending on the type. It is preferable that it is 5 mass% or less.

The polymer of the present invention may contain other structural unit (D).
The other structural unit (D) is not particularly limited as long as it is a structural unit derived from the compound (d) that can be copolymerized with the compounds (a), (b), and (c). Specific examples of the compound (d) include a polyfunctional compound (d1) having a plurality of reactive unsaturated bonds, a styrene compound (d2), a (meth) acrylate compound (d3), and other polymerizations. Compound (d4). Specific examples of such compound (d) are shown below, but are not limited thereto.

  Specific examples of preferable compounds as the polyfunctional compound (d1) are shown below, but the compound (d1) is not limited thereto.

  R in the above formula is a (meth) acryloyloxy group.

  Examples of the styrene compound (d2) include styrene compounds represented by the following formula.

In the formula, R ² : —H, CH ₃ , —Cl, —CHO, —COOH, —CH ₂ Cl, —CH ₂ NH ₂ , —CH ₂ N (CH ₃ ) ₂ , —CH ₂ N ⁺ (CH _{3 ^{) 3 Cl -, -CH 2 N}} + H 3 Cl -, -CH 2 CN, -CH 2 COOH, -CH 2 N (CH 2 COOH) 2, -CH 2 SH, -CH 2 SO 3 Na or CH ₂ OCOCH _3.

Examples of the compound (d3) include α-chloroacrylic acid and (meth) acrylate represented by the following formula.
^{_{CH 2 = C (R 1)}} -COO-R 3
In the formula, R ¹ : H or CH ₃ , R ³ : —CH ₃ , —CH ₂ CH ₂ N (CH ₃ ) ₂ , — (CH ₂ ) _m H (m is an integer of 2 to 20), — (CH _{2) m (CF) n F} (m = 2~20 integer, n = 1 to 6 _{integer), - CH 2 CH (CH} 3) 2, -CH 2 -C (CH 3) 2 -OCO-Ph ( "Ph" and so on means a phenyl _{group..), - CH 2 Ph} , -CH 2 CH 2 OPh, -CH 2 N + (CH 3) 3 Cl -, - (CH 2 CH 2 O ) integer _{m CH 3 (m = 2~20)} , - a _(CH 2) 2 -NCO or the following groups.

Examples of the compound (d3) include (meth) acrylamide represented by the following formula.
^{_{CH 2 = C (R 1)}} -CONH-R 4
In the formula, R ^{1 is} H or CH ₃ , R ^{4 is} —C _m H _{2m + 1} (m is an integer of 2 to 20) or H.

Examples of the other polymerizable compound (d4) include vinyl compounds other than the above (d1), (d2) and (d3), such as vinyl chloride (CH ₂ ═CHCl), acrylonitrile (CH ₂ ═CHCN) and the like.

  When the polymer of the present invention contains other structural units (D) as described above, the mass of the total amount of these other structural units in the polymer (1) is 10% by mass or less, although it varies depending on the type. It is preferable that it is 5 mass% or less.

Although the molecular weight of the polymer of this invention is not specifically limited, It is preferable that it is 1 * 10 < ³ > -1 * 10 < ⁷ > by weight average molecular weight (Mw), and it is preferable that it is 1 * 10 < ⁴ > -1 * 10 < ⁶ >. This is because if the molecular weight is within such a range, the water sliding performance can be sufficiently exhibited. On the other hand, if the molecular weight is too large, the solubility of the polymer of the present invention in a solvent tends to be poor.

  The polymer of the present invention is a polymerized form, etc. except that it may contain the structural unit (A) and the structural unit (B) as described above, and optionally the structural unit (C) and / or the structural unit (D). There is no particular limitation. The form of polymerization in the case of a copolymer is not particularly limited and may be any of random, block, graft and the like, but is preferably a random polymer.

  The method for producing the polymer is not particularly limited, and various known methods can be adopted. For example, addition polymerization can be performed based on an unsaturated group in each compound. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source. In order to adjust the molecular weight, a molecular weight modifier can be used during the polymerization reaction.

The surface treatment composition of the present invention preferably contains a polymer as described above as a coating component, and is in a liquid form containing the polymer in a solvent.
The method for producing the surface treatment composition of the present invention is not limited. For example, it can be obtained by dissolving the polymer of the present invention in a known solvent. Further, for example, the compound (a) is added to a solvent, and the polymer of the present invention is produced by solution polymerization using the solvent as a polymerization medium to obtain the solvent containing the polymer of the present invention. It can also be set as a surface treatment composition. A solution containing the polymer of the present invention can be obtained by emulsion polymerization, and this can be used as the water-sliding treatment agent of the present invention. The polymer of the present invention obtained here may be separated and dissolved in another solvent. Further, when the polymerization raw material compound is in a gaseous state, it may be continuously supplied under pressure using a pressure vessel.

  The solvent for forming the surface treatment composition of the present invention is not particularly limited as long as it can dissolve or disperse the polymer of the present invention, and examples thereof include various organic solvents, water, or a mixed medium thereof. For example, polar solvents other than alcohol and fluorine-based solvents can be used. Examples of polar solvents other than alcohol include ketone systems (such as acetone and methyl ethyl ketone), ester systems (such as ethyl acetate), and ether systems (such as tetrahydrofuran). Examples of the fluorine-based solvent include hydrofluorocarbon (HFC) or hydrofluoroether (HFE). Of these, a fluorinated solvent is preferred. Specific examples of usable fluorine-based solvents are shown below, but are not limited thereto.

m-xylene hexafluoride (hereinafter referred to as m-XHF)
p-Xylene hexafluoride (hereinafter referred to as p-XHF)
CF ₃ CH ₂ CF ₂ CH ₃
CF ₃ CH ₂ CF ₂ H
C ₆ F ₁₃ OCH ₃
C ₆ F ₁₃ OC ₂ H ₅
C ₃ F ₇ OCH ₃
C ₃ F ₇ OC ₂ H ₅
C ₆ F ₁₃ H
C ₆ F ₁₃ CH ₂ CH ₃
CF ₂ HCF ₂ CH ₂ OCF ₂ CF ₂ H
CF ₃ CFHCHFHCF ₂ CH ₃
CF ₃ (OCF ₂ CF ₂ ) _n (OCF ₂ ) _m OCF ₂ H
C ₈ F ₁₇ OCH ₃
C ₇ F ₁₅ OCH ₃
C ₄ F ₉ OCH ₃
C ₄ F ₉ OC ₂ H ₅
C ₄ F ₉ CH ₂ CH ₃
CF ₃ CH ₂ OCF ₂ CF ₂ CF ₂ H
(In the above examples, m and n each represent an integer of 1 to 20.)

The surface treatment composition of the present invention preferably contains 0.1 to 20% by mass of the polymer of the present invention, more preferably 1 to 10% by mass. When the concentration of the polymer of the present invention in the surface treatment composition of the present invention is within this range, the water sliding performance can be sufficiently exhibited.
The concentration of the polymer of the present invention in the surface treatment composition of the present invention may be a final concentration. For example, when the surface treatment composition of the present invention is directly prepared as a polymerization composition, the polymerization composition immediately after polymerization is used. Even if the polymer concentration (solid content concentration) exceeds 20 mass%, there is no problem. The high-concentration polymerization composition can be appropriately diluted so that the final desired concentration is obtained.

  The surface treatment composition of the present invention may contain other components other than those described above as long as they do not adversely affect the stability, water / oil repellency, slipperiness or appearance of the composition. . Such other components include, for example, pH control agents, rust preventives for preventing corrosion of the coating surface, and the purpose of controlling the concentration of the polymer in the liquid when the composition is used diluted. Examples thereof include dyes for distinguishing them from treated parts, dye stabilizers, flame retardants, antifoaming agents, and antistatic agents.

  The surface treatment composition of the present invention can be diluted to an arbitrary concentration and treated on the surface according to the purpose and use, thereby coating the polymer and imparting performance. As a coating method, a general coating method can be adopted. For example, there are methods such as dip coating, spray coating or coating with a roller.

  After application of the surface treatment composition of the present invention, it is more preferable to perform drying at a temperature equal to or higher than the boiling point of the solvent. Of course, when it is difficult to heat and dry due to the material of the part to be processed, it should be dried while avoiding heating. In addition, what is necessary is just to select the conditions of heat processing according to the composition of the composition to apply | coat, an application area, etc.

  Fields of application of the present invention include water / oil repellent, lubrication, antifouling, mold release, friction reduction, etc., and water repellent, oil repellent, lubricant, antifouling agent comprising the surface treatment composition of the present invention. It can be used as a mold release agent, a friction reducing agent, and the like.

The present invention will be specifically described below, but the present invention is not limited to the following examples. Unless otherwise specified, what is indicated by “%” in the description of the following examples represents “mass%”.
The compounds used in the following examples are shown in Table 4. The compound used can be obtained from the market as a reagent, or can be easily synthesized by a known synthesis method.
The following b1 is “LSF-250” manufactured by Shin-Etsu Chemical Co., Ltd., b2 is “FM-0721” manufactured by JNC, and b3 is “FM-0711” manufactured by JNC.

[Execution polymers 1 to 9]
Each compound, polymerization solvent (m-XHF), and initiator (made by Wako Pure Chemical Industries, Ltd., V-601) are charged in an airtight container so that the charging ratio (parts by mass) and concentration shown in Table 5 are obtained. The reaction was carried out at 70 ° C. for 18 hours or more. The m-XHF solution of the obtained polymer was added to a large amount of methanol to precipitate the polymer. The precipitated polymer was washed several times with methanol, and then dried under reduced pressure at 60 ° C. to obtain execution polymers 1 to 9.

  The obtained execution polymer was dissolved in m-XHF to prepare a 2 mass% concentration solution, and Examples 1 to 9 were prepared.

[Comparative polymers 1 to 4]
By the same operation, synthesis of Comparative Polymers 1 and Comparative Examples 1 to 4 were prepared.

The following performance was evaluated about Examples 1-9 obtained above and Comparative Examples 1-4. The evaluation results are shown in Table 5.
[Measurement of contact angle]
Examples 1-9 and Comparative Examples 1-4 were made into normal temperature, and the glass plate was immersed in each. And it took out after 1 minute, it was made to dry at 120 degreeC for 5 minute (s), and each glass plate which has a film of the surface treatment composition of this invention or a comparative composition was obtained.
Next, ion-exchanged water or normal hexadecane (HD) was dropped onto the coating of each glass plate on which each type of coating was formed, and the contact angle (unit: °) was measured. An automatic contact angle meter OCA-20 [manufactured by dataphysics] was used for the measurement of the contact angle.

  From the above results, it was found that in the present invention, a water / oil repellent treatment composition that achieves both sufficient water / oil repellent performance and sliding performance without using a compound that may cause PFOA was obtained. .

Claims (10)

  A surface treatment composition characterized by not containing a linear perfluoroalkyl group having 8 or more carbon atoms but containing a perfluoroalkyl group having 6 carbon atoms and an organopolysiloxane group. A structural unit derived from a compound represented by the following formula (a) without containing a structural unit having a linear perfluoroalkyl group having 8 or more carbon atoms, and a compound represented by the following formula (b) The surface treatment composition according to claim 1, comprising a polymer (1) containing at least one of each of the structural units derived from
_{^{CH 2 = C (R a1)}} -C (O) X-Q a -C 6 F 13 ··· (a)
[Where:
R ^a1 : a hydrogen atom or a methyl group,
X: —O— or —NR ^a2 —,
Q ^a : a single bond or a divalent linking group.
However, R ^<a2> : A hydrogen atom or a C1-C3 alkyl group. ]
_{^{CH 2 = C (R b1)}} -Q b -Y ··· (b)
[Where:
R ^b1 : a hydrogen atom or a methyl group,
Q ^b : a single bond or a divalent linking group,
Y: An organopolysiloxane group having a number average molecular weight (Mn) of 3000 to 30000. ] The surface treatment composition according to claim 2, wherein the polymer (1) further contains at least one structural unit derived from a compound represented by the following formula (c).
_{^{CH 2 = C (R c1)}} -Q c -COOH ··· (c)
[Where:
R ^c1 : a hydrogen atom or a methyl group,
Q ^c : a single bond or a divalent linking group. ]   The surface in any one of Claim 2 or 3 whose content of the structural unit (A) induced | guided | derived from the compound represented by the said formula (a) in the said polymer (1) is 50 mass% or more. Treatment composition.   A water repellent comprising the surface treatment composition according to claim 1.   An oil repellent comprising the surface treatment composition according to claim 1.   An antifouling agent comprising the surface treatment composition according to claim 1.   A mold release agent comprising the surface treatment composition according to claim 1.   A low friction imparting agent comprising the surface treatment composition according to claim 1.   The surface treatment composition according to any one of claims 1 to 4 or the water repellent according to claim 5, the oil repellent according to claim 6, and the antifouling according to claim 7 on at least a part of the surface. The member which has a film which consists of an agent, the mold release agent of Claim 8, or the low-friction imparting agent of Claim 9.