WO2010113646A1 - Surface treatment agent - Google Patents

Abstract

Disclosed is a surface treatment agent which uses a polymer that is obtained from a compound which contains a liner perfluoroalkyl group having 6 carbon atoms and has less influence on the living body and the environment, said surface treatment agent exhibiting excellent water repellency, oil repellency, IPA repellency and water sliding properties. Specifically, the surface treatment agent contains a solvent and a polymer that contains an acrylic polymerization unit (A) derived from a compound represented by formula (a) described below and a methacrylic polymerization unit (B) derived from the compound represented by formula (b) described below. formula (a): CH₂=CH-COO-(CH₂)_n1-(CF₂)₆F (In formula (a), n¹ represents an integer of 0-4.) formula (b): CH₂=C(CH₃)-COO-(CH₂)_n2-(CF₂)₆F (In formula (b), n² represents an integer of 0-4.)

Description

Surface treatment agent

The present invention relates to a surface treatment agent that imparts water repellency, oil repellency, IPA repellency and water slidability to various substrates.

Conventionally, a polymer of (meth) acrylic acid ester having a linear or terminally branched perfluoroalkyl group having a carbon chain length of 8 or more has been used as a fluorine-based surface treatment agent. This is because the crystallinity of the side chain (CF ₂ ) ₈ F group is high water repellency, oil repellency, and the ability to repel 2-propanol (also referred to as IPA) used as a solvent such as flux. This was to show IPA performance.

The US Environmental Protection Agency (USEPA) published a preliminary risk study report on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, in March 2003. In the report, it was pointed out that the perfluoroalkyl group that has the possibility of generating PFOA has 8 carbon atoms and has an impact on the living body and the environment. In January 2006, PFOA, its related substances, and their precursor substances were proposed to fluororesin manufacturers and others to participate in a reduction plan in the environment and a content reduction plan in products.
Examples of the structure to be used here include compounds having a linear perfluoroalkyl group having 8 carbon atoms shown below (see Patent Document 1).
CH ₂ ═CH—COO— (CH ₂ ) ₂ — (CF ₂ ) ₈ F
CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ — (CF ₂ ) ₈ F

JP-A-10-303536

In such a situation, in order to reduce the possibility of the occurrence of PFOA, the carbon number of the perfluoroalkyl group is shortened to 6 or less, specifically, (CF ₂ ) ₈ F in the above formula is changed to (CF It is conceivable to use a compound substituted with ₂ ) ₆ F or (CF ₂ ) ₄ F as an alternative. However, in the study by the present inventors, when the straight-chain perfluoroalkyl group having 8 carbon atoms is simply reduced to 6 or less as it is, there is a decrease in performance due to the perfluoroalkyl group in the polymer. It was confirmed.

Specifically, a polymer of an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms has unique tackiness that causes various adverse effects although it exhibits oil repellency and IPA performance. I found out. On the other hand, it was found that the polymer of methacrylic acid ester having a linear perfluoroalkyl group having 6 carbon atoms is not tacky, but the oil repellency and IPA performance are lowered.

The present invention uses a polymer obtained from a compound having a straight-chain perfluoroalkyl group having 6 carbon atoms and has little influence on the living body and the environment, and has water repellency, oil repellency, IPA performance, and It aims at providing the surface treating agent excellent in the sliding property of water.
Furthermore, it aims at reducing the adhesiveness of a film, maintaining these performances.

As a result of intensive studies to solve the above problems, the present inventor has obtained an acrylic ester having a linear perfluoroalkyl group having 6 carbon atoms and a linear perfluoroalkyl group having 6 carbon atoms. It has been found that the copolymer with the methacrylic acid ester has no adverse tackiness, has high water repellency performance, oil repellency performance and IPA repellency performance, and also has water slidability.

That is, the present invention provides the following surface treatment agent.
The surface treating agent of the present invention contains an acrylic polymer unit (A) derived from a compound represented by the following formula (a) and a methacryl polymer unit (B) derived from a compound represented by the following formula (b). A polymer is included in the solvent.
CH ₂ = CH-COO- (CH ₂ ) _n1- (CF ₂ ) ₆ F Formula (a)
In the formula (a), n ¹ is an integer of 0-4.
CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) _n2 — (CF ₂ ) ₆ F Formula (b)
In the formula (b), n ² is an integer of 0-4.

In the polymer, the mass ratio (A) / (B) of the polymerization unit (A) and the polymerization unit (B) is preferably 55/45 to 5/95.

In the polymer, the total content of the polymerization unit (A) and the polymerization unit (B) is preferably 80% by mass or more.

Moreover, it is preferable that the polymer further contains a polymer unit (C) derived from a compound represented by the following formula (c).
CH ₂ = C (R) -COO-QY (c)
Symbols in the formula (c) have the following meanings.
R: a hydrogen atom or a methyl group.
Q: a divalent linking group.
Y: a monovalent functional group.

Y in the formula (c) is preferably a hydroxyl group, a carboxy group or an alkoxysilyl group.

The ratio of the polymerization unit (C) in the polymer is preferably 10% by mass or less.

The weight average molecular weight (in terms of polymethyl methacrylate) of the polymer is preferably 100,000 or more.

The surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant oozing-out preventive agent, a waterproof / moisture-proof coating agent, and an electronic component resin adhesion preventive agent.

The present invention also provides a substrate coated with the surface treating agent of the present invention.

The surface treatment agent of the present invention comprises polymer units derived from each of the acrylic compound and the methacrylic compound specified by the above formulas (a) and (b) while suppressing the carbon number of the perfluoroalkyl group to 6 or less. By using the polymer containing, it was possible to have high water repellency performance, oil repellency performance, IPA repellency performance, and water slidability. In addition to the water repellency, oil repellency and IPA performance, by adjusting the mass ratio of the polymerization unit (A) and the polymerization unit (B), the tackiness of the coating can be reduced, and the water slides down. The characteristics are further improved.

In the present specification, the compound represented by the formula (a) is also referred to as a compound (a). The compounds represented by other formulas may be expressed similarly.
In addition, in this specification, (meth) acrylate represents both or one of acrylic ester and methacrylic ester.

The polymer which is an essential component of the surface treating agent of the present invention (hereinafter also referred to as “the polymer of the present invention”) is derived from the polymerization unit (A) derived from the following compound (a) and the following compound (b). Contains polymerized units (B) to be removed.
CH ₂ = CH-COO- (CH ₂ ) _n1- (CF ₂ ) ₆ F Formula (a)
In the formula (a), n ¹ is an integer of 0-4.
CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) _n2 — (CF ₂ ) ₆ F Formula (b)
In the formula (b), n ² is an integer of 0-4.

In the compounds (a) and (b), n ¹ and n ² are both preferably 0 to 3, more preferably 1 or 2.

The polymer of the present invention has both the polymer unit (A) and the polymer unit (B), thereby maintaining the same high water repellency, oil repellency and IPA repellency as the polymer unit (A) alone. In addition, the polymer unit (A) alone is excellent in insufficient water slipping property, and the polymer unit (B) alone is also excellent in IPA performance at a low concentration which is insufficient.
In addition, the sliding property of water is more excellent as the receding contact angle of water is larger, and the receding contact angle of water is preferably 30 ° or more, and particularly preferably 50 ° or more. If it is less than 30 degrees, it is difficult to slide down the water.

The compound (a) and the compound (b) may be one kind or plural kinds respectively. In the present invention, the mass ratio of each polymer unit in the polymer is a value that is considered that all the raw materials used for the polymerization constitute a polymer unit. Thus, for example, the mass ratio of polymerized units (A) (percentage of the mass of polymerized units (A) contained therein relative to the total mass of polymerized units) is substantially equal to 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 raw material compound. In the polymer, the mass ratio of other polymerized units is also determined in the same manner.

The mass ratio (A) / (B) of the polymerized units (A) and polymerized units (B) is 100, where the sum of the mass ratio of the polymerized units (A) and the mass ratio of the polymerized units (B) is 100. Mean values of (A) and (B). The mass ratio (A) / (B) of the polymerization unit (A) and the polymerization unit (B) is preferably in the range of 55/45 to 5/95, and more preferably in the range of 20/80 to 5/95. If it is in said range, while being able to reduce the adhesiveness of a polymer and having a favorable film characteristic, it can make water-repellent performance, oil-repellent performance, and IPA-repellent performance compatible. Moreover, the sliding property of water is also favorable. Hereinafter, the water repellency, oil repellency and IPA performance are collectively referred to as water repellency, oil repellency and IPA performance.

In the polymer of the present invention, the total content of the above polymerized units (A) and polymerized units (B) is preferably 80% by mass or more, and more preferably 90% by mass or more. This is because when the total content of the polymer units (A) and polymer units (B) in the polymer of the present invention is within the above range, the water and oil repellency and IPA performance of the surface treatment agent of the present invention is better. .

The polymer of the present invention preferably contains a polymer unit (C) derived from a compound represented by the following formula (c). The content of the polymerization unit (C) is usually 10% by mass or less. Among these, 0.1 to 10% by mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 2% by mass is particularly preferable. When the polymerization unit (C) is contained, the adhesion to the substrate is improved. However, when the content is too large, the water / oil / oil repellency / IPA performance is lowered.
CH ₂ = C (R) -COO-QY (c)
Symbols in the formula (c) have the following meanings.
R: a hydrogen atom or a methyl group.
Q: a divalent linking group.
Y: a monovalent functional group.

R is preferably a methyl group because it does not increase the adhesion of the film and does not decrease the hardness of the film.

Y can be appropriately selected as long as it is a monovalent functional group. Among these, a hydroxyl group, a carboxy group, or an alkoxysilyl group is preferable because it improves adhesion to the substrate.

Q in the formula is a divalent linking group. Q can be appropriately selected as long as it is a divalent linking group.

Examples of the divalent linking group include linear or branched alkylene groups or alkenylene groups, oxyalkylene groups, 6-membered aromatic groups, 4- to 6-membered saturated or unsaturated aliphatic groups, and 5-6. And a divalent linking group represented by the formula -X ¹ -ZX ^2- . These divalent linking groups may be combined, and a plurality of cyclic groups may be condensed. You may do it.
The symbols in the above formula have the following meanings.
X ¹ and X ² are each independently a linear or branched alkylene group, oxyalkylene group, 6-membered aromatic group, 4- to 6-membered saturated or unsaturated aliphatic group, 5 to 6 A membered heterocyclic group or a condensed ring group thereof;
Z: —O—, —S—, —CO—, —COO—, —COS—, —N (R ¹ ) —, —SO ₂ —, —PO (OR ¹ ) —, —N (R ¹ ) — COO—, —N (R ¹ ) —CO—, —N (R ¹ ) —SO ₂ — or —N (R ¹ ) —PO (OR ¹ ) —.
R ¹ : a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

The above linking group may have a substituent. Examples of the substituent include a halogen atom (F, Cl, Br, I), a hydroxyl group, a cyano group, an alkoxy group (methoxy, ethoxy, butoxy, octyl). Oxy, 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, etc.) , Benzoyloxy etc.), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy etc.), phosphonyl group (diethylphosphonyl etc.), amide group (acetylamino, benzoylamino etc.), carbamoyl group (N, N-dimethylcarbamoyl, N-Fe Rucarbamoyl 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 group, acryloyl group, methacryloyl group, silyl group, cinnamic acid residue etc.) etc. It is done.

The compound (c) is preferably a compound represented by the following formula when Y is a hydroxyl group.
CH ₂ ═C (R) —COO—Q ¹ —OH Formula (c1)
In the formula (c1), R has the same meaning as described above. Q ¹ is a linear or branched alkylene group, — (C ₂ H ₄ O) _n —, — (C ₃ H ₆ O) _n —, or a combination thereof (where n is 1 to 30). Is an integer). These groups may have a substituent.

The compound (c) is preferably a compound represented by the following formula when Y is a carboxy group.
CH ₂ ═C (R) —COO—Q ² —COOH Formula (c2)
In the formula (c2), R has the same meaning as described above. Q ² represents a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C ₂ H ₄ O) _n —, — (C ₃ H ₆ O) _n —, or the above formula —X ¹ —Z—. A divalent linking group represented by X ² — (where n is an integer of 1 to 30). These groups may have a substituent.
Among the above formulas -X ¹ -ZX ^2- , preferably
X ¹ and X ² : each independently a linear or branched alkylene group, phenylene group, cyclohexylene group, — (C ₂ H ₄ O) _n — or — (C ₃ H ₆ O) _n — Yes,
Z: —O—, —S—, —CO—, —COO—, —N (R ¹ ) —, —N (R ¹ ) —COO—, —N (R ¹ ) —CO— (R ¹ Is the same as above).

The compound (c) is preferably a compound represented by the following formula when Y is an alkoxysilyl group.
CH ₂ = C (R) —C (O) OQ ³ —Si (OAk) ₃ formula (c3)
In the formula (c3), R has the same meaning as described above. Q ³ is a linear or branched alkylene group, and the alkylene group may have a substituent. Ak is a linear or branched alkyl group having 1 to 3 carbon atoms.

Specific examples of the compound (c) are shown in Tables 1 to 3, but are not limited thereto.
In Tables 1 and 2, m and n each independently represent an integer of 1 to 10.

The polymer according to the present invention may contain other polymer units (D) in addition to the polymer units (A), polymer units (B) and polymer units (C) as described above. The other polymer unit (D) is not particularly limited as long as it is a polymer unit derived from a compound that can be copolymerized with the compound that forms the above-mentioned (A), polymer unit (B), and polymer unit (C). As this compound, the compound (d) which has a polymeric group is mentioned normally, Specifically, about a styrene-type compound (d1), the said polymerization unit (A), a polymerization unit (B), and a polymerization unit (C). Examples thereof include a compound (d) having an unsaturated group such as a (meth) acrylic acid compound (d2) other than the exemplified compounds and a compound (d3) which is another polymerizable compound. Specific examples of such compound (d) are shown below, but are not limited thereto.

Compound (d) is not particularly limited as long as it is another compound capable of forming a polymer with (meth) acrylate. Specific examples include styrene compounds (d1), (meth) acrylic acid compounds (d2) other than the above compounds (a), (b) and (c), and other polymerizable compounds (d3). . Specific examples of such compound (d) are shown below, but are not limited thereto.

As said (d1), the styrene-type compound represented by a following formula is mentioned.

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 it is a ₂ OCOCH _3.

Examples of the compound (d2) include acrylic acid, methacrylic acid, 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 = 2 to 20), —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) _m CH ₃ (m is an integer of 2 to 20), — (CH ₂ ) ₂ —NCO, or the following group.

Examples of the compound (d2) 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 compound (d2) further include (meth) acrylic acid diesters, and (meth) acrylic acid polyesters such as compounds represented by the following formulas.

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

Further, as the compound (d3), vinyl compounds other than the above (d1) and (d2), for example, vinyl chloride (CH ₂ ═CHCl), acrylonitrile (CH ₂ ═CHCN), or a compound having the following epoxy group: Can be mentioned.

In addition to the above, the compound (d) may be a compound having a plurality of polymerizable functional groups. Although the specific example which has 3 or more of vinyl groups or an epoxy group is shown below, it is not limited to these.

When the polymer of the present invention contains other polymer units (D) as described above, the polymer has a mass in the total amount of these other polymer units of 20% by mass or less, although it varies depending on the type. It is preferably 10% by mass or less. When the polymerization unit (D) is excessively contained, the water / oil repellency / IPA performance is lowered.

The molecular weight of the polymer of the present invention is not particularly limited, but is preferably 1 × 10 ³ to 1 × 10 ⁷ in terms of weight average molecular weight (Mw), more preferably 1 × 10 ⁴ to 1 × 10 ^6. More preferably, it is 1 × 10 ⁵ to 5 × 10 ⁵ . When the molecular weight is within such a range, high water / oil repellency / IPA performance can be exhibited even at a low concentration. 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 not particularly limited in the form of polymerization. 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.

The surface treating agent of the present invention is a liquid form containing the above specific polymer as a film component and containing the polymer in a solvent.
The method for producing the surface treatment agent 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) and the compound (b) are added to a solvent, the polymer of the present invention is produced by solution polymerization using the solvent as a polymerization medium, and the solvent containing the polymer of the present invention is obtained. This can also be used as the surface treatment agent of the present invention. A solution containing the polymer of the present invention can be obtained by emulsion polymerization, and this can be used as the surface 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 a gas such as vinyl chloride, it may be continuously supplied under pressure using a pressure vessel.

The solvent for forming the surface treating agent 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. As the organic solvent, a fluorine-based solvent is preferable. Examples of the fluorine-based solvent include hydrofluorocarbon (HFC) or hydrofluoroether (HFE). Specific examples of usable fluorinated solvents are shown below, but are not limited thereto.

m-Xylene hexafluoride (hereinafter referred to as m-XHF)
p-xylene hexafluoride 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 ₆ F ₁₃ CH ₂ CH ₃
C ₃ F ₇ OCH ₃
C ₃ F ₇ OC ₂ H ₅
C ₆ F ₁₃ H
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, the subscripts m and n each independently represent an integer of 1 to 20.)
And mixtures of these.
For example, a hydrofluoroether mixture of CF ₃ (CF ₂ ) ₃ OC ₂ H ₅ and (CF ₃ ) ₂ CFCF ₂ OC ₂ H ₅ is available under the trade name Novec HFE 7200 (manufactured by 3M).

It is preferable that the concentration of the surface treatment agent of the present invention is properly used depending on the application. In the waterproof / moisture-proof coating agent, the concentration of the polymer of the present invention is preferably 1 to 20% by mass. In the lubricant preventing agent for lubricating oil and the resin adhesion preventing agent for electronic parts, the concentration of the polymer of the present invention is preferably 1 to 5% by mass. In the solder flux creep-up preventing agent, the concentration of the polymer of the present invention is preferably 0.01 to 1% by mass.
The concentration of the polymer of the present invention in the surface treatment agent of the present invention may be a final concentration. For example, in the case of directly preparing the solder flux creep-up preventing agent of the present invention, a solution containing the polymer immediately after polymerization. Even if the polymer concentration (solid content concentration) exceeds 1% by mass, there is no problem. A solution containing a high-concentration polymer can be appropriately diluted so that the final desired concentration is obtained. The diluted solution can be used as a surface treatment agent as it is.

The surface treatment agent of the present invention may contain components other than those described above as long as the stability, performance, appearance, etc. are not adversely affected. Such other components include, for example, the purpose of controlling the concentration of the polymer in the liquid when diluting a pH adjuster, a rust inhibitor, and a surface treatment agent to prevent corrosion of the coating surface. Examples thereof include dyes for distinguishing from untreated parts, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.

The surface treatment agent of the present invention can be used by forming a film by coating it on a portion where water / oil / oil repellency / IPA performance is desired. The coating film is formed by removing the solvent from the surface treatment agent of the present invention, and is mainly composed of the polymer of the present invention. Here, “mainly” means that the coating film may be formed only from the polymer of the present invention and may contain other components as long as it does not adversely affect as described above. As a coating method, a general coating method can be adopted. For example, there are methods such as dip coating, spray coating, and roller coating.

After applying the surface treatment agent of the present invention, it is preferable to perform drying at a temperature not lower 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 surface treating agent to apply | coat, an application area, etc.

The surface treatment agent of the present invention can be applied to the treatment of various materials, and in particular, for the treatment of precision equipment parts, sliding parts (motors, watches, HDDs), and electrical parts (electronic circuits, substrates, electronic parts, etc.). It is preferable to use it. Among these, the surface treatment agent of the present invention is preferably used as a solder flux creeping-up inhibitor, a lubricant oozing-out preventing agent, a waterproof coating agent, a moisture-proof coating agent and an electronic component resin adhesion preventing agent. In particular, since it has a high IPA repellency even at a low concentration, it is preferably used as a solder flux creep-up preventing agent.

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 as a reagent from the market or can be easily synthesized by a known synthesis method.

[Polymers 1-8 and Comparative Polymers 1-4]
Each compound, polymerization solvent (m-XHF) and initiator (V-601) were charged in a sealed container so that the charging ratio (parts by mass) and concentration shown in Table 5 were obtained, and the reaction was carried out at 70 ° C. for 18 hours or more. The polymers 1 to 8 and comparative polymers 1 to 4 were obtained.
The results of measuring the weight average molecular weight (Mw) of the polymers 1 to 8 and the comparative polymers 1 to 4 are shown in Table 5.

[Measurement of weight average molecular weight]
After the polymerization, the sample was diluted with Asahi Clin AK-225SEC1 (manufactured by Asahi Glass Co., Ltd.) so that the concentration of the polymer in the solution containing each polymer was about 1%, and used as a measurement sample. Using a Shodex GPC-104 manufactured by Showa Denko KK, GPC was measured under the following conditions.
<GPC measurement conditions>
Analysis column: LF-604 (filler: styrene divinylbenzene copolymer, manufactured by Showa Denko KK) x 2
Reference column: KF600RH (filler: none, Showa Denko KK) x 2
Moving layer: AK-225SEC1
Flow rate: 0.3ml / min
Column temperature: 40 ° C
Reference material: Polymethylmethacrylate

[Surface treatment agents 1 to 8 and comparative surface treatment agents 1 to 4]
Polymer 1 was diluted with m-XHF or HFE-7200 (3M company) to obtain surface treating agent 1 having each polymer concentration (15%, 1%, 0.1%) shown in Table 6. .
The treatment agent with a concentration of 15% was diluted with m-XHF which is the same as the polymerization solvent, and the treatment agents with a concentration of 1% and 0.1% were diluted with HFE-7200. Similarly, surface treating agents 2 to 8 were obtained from polymers 2 to 8, and comparative surface treating agents 1 to 4 were obtained from comparative polymers 1 to 4, respectively.

The following performance was evaluated for the surface treatment agents 1 to 8 and comparative surface treatment agents 1 to 4 obtained above. The evaluation results are shown in Table 6.

[Evaluation of film adhesion]
About 2 g each of high-concentration solutions (15% by mass) of the surface treatment agents 1 to 8 and the comparative surface treatment agents 1 to 4 were collected in aluminum cups (φ45 mm) and dried at room temperature. After drying, the medicine-wrapping paper was placed on the film, and 100 g of weight (φ24 mm) was placed thereon. After 1 minute, the weight was removed and the sticking of the medicine wrapping paper was confirmed.
When the medicine wrapper was peeled off, the film attached to the film and peeled off was evaluated as x. The film slightly stuck, but only the medicine paper was easily peeled out was marked as Δ, and the drug paper was not adhered at all.

[Measurement of contact angle]
A glass plate was immersed in each of the surface treatment agents 1 to 8 and the comparative surface treatment agents 1 to 4 having the polymer concentration adjusted to 1% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained.
Next, water, n-hexadecane (HD), or IPA was dropped on the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
CA-S150 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement of water and HD contact angles. For the measurement of the contact angle of IPA, an automatic contact angle meter OCA-20 (manufactured by Data Physics) was used.
A glass plate was immersed in each of the surface treatment agents 1 to 8 and the comparative surface treatment agents 1 to 4 having the polymer concentration adjusted to 0.1% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained. Next, IPA was dropped on the coating of each glass plate on which each type of coating was formed, and the contact angle was measured. For the measurement of the contact angle, an automatic contact angle meter OCA-20 [manufactured by Data Physics] was used.

[Measurement of receding contact angle of water]
A glass plate was immersed in each of the surface treatment agents 1 to 8 and the comparative treatment agents 1 to 4 having the polymer concentration adjusted to 1% by mass at room temperature. And it took out after 1 minute and was made to dry at room temperature, and each glass plate which has a film of each processing agent was obtained.
Next, after dropping water droplets on the glass plate coatings on which each type of coating was formed, the water in the droplets was sucked up at a speed of 1 μL / s, and the receding contact angle was measured. For the measurement of the receding contact angle, an automatic contact angle meter OCA-20 (manufactured by Data Physics) was used.
In Table 6, the receding contact angle of water (shown as “water (retreating)”) “impossible to measure” indicates that the receding angle could not be confirmed.

From the above results, the surface treatment agent of the present invention is equivalent to or higher in water repellency than the comparative surface treatment agent containing a polymer having only one of the polymerization unit (A) or the polymerization unit (B), It was found to have oil repellency and IPA repellency. In particular, it has been found that it has both good water sliding properties and IPA repellency at a low concentration. Furthermore, in the polymer of the present invention, by adjusting the mass ratio of the polymer units (A) and (B), in addition to the water repellency performance, oil repellency performance and IPA repellency performance, the tackiness of the film can also be reduced. At the same time, it was found that the water sliding property was further improved.

Next, as the polymerization unit (C), a surface treatment agent and a comparison surface treatment agent using a polymerization unit different from the polymer and the comparison polymer were prepared.
The compounds used in the following examples are shown in Table 7. Compound a1 and compound b1 are the same as described above. Compound c3 and compound c4 can be obtained from the market as reagents and can be easily synthesized by known synthesis methods.

Polymers 9 and 10 and comparative polymers 5 to 8 were obtained in the same manner as the polymers 1 to 8 and comparative polymers 1 to 4. The results of measuring the Mw of the obtained polymers in the same manner as in the polymers 1 to 8 and the comparative polymers 1 to 4 are shown in Table 8.

Surface treatment agents 9 and 10 and comparative surface treatment agents 5 to 8 were obtained in the same manner as the surface treatment agents 1 to 8 and comparative surface treatment agents 1 to 4. About these, the result of having evaluated the contact angle and the adhesiveness of the film was described in Table 9. Here, the measurement of the contact angle and the evaluation of the adhesiveness of the coating were performed in the same manner as in the surface treatment agents 1 to 8 and the comparative surface treatment agents 1 to 4.
In Table 9, the receding contact angle of water (indicated as “water (retreating)”) “impossible to measure” indicates that the receding angle could not be confirmed.

Even when the structure of the polymerization unit (C) is changed, the surface treatment agent has superior performance as compared with a comparative surface treatment agent containing a polymer having only one of the polymerization unit (A) or the polymerization unit (B). I found out that

Claims (12)

1. The surface which contains the polymer containing the acryl polymerization unit (A) derived from the compound represented by the following formula (a) and the methacryl polymerization unit (B) derived from the compound represented by the following formula (b) in a solvent Processing agent.
   CH ₂ = CH-COO- (CH ₂ ) _n1- (CF ₂ ) ₆ F Formula (a)
   In the formula (a), n ¹ is an integer of 0-4.
   CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) _n2 — (CF ₂ ) ₆ F Formula (b)
   In the formula (b), n ² is an integer of 0-4.
2. The surface treating agent according to claim 1, wherein in the polymer, a mass ratio (A) / (B) of the polymerized unit (A) and the polymerized unit (B) is 55/45 to 5/95.
3. The surface treatment agent according to claim 1 or 2, wherein in the polymer, the total content of the polymerization unit (A) and the polymerization unit (B) is 80% by mass or more.
4. The surface treating agent according to any one of claims 1 to 3, wherein the polymer further contains a polymer unit (C) derived from a compound represented by the following formula (c).
   CH ₂ = C (R) -COO-QY (c)
   Symbols in the formula (c) have the following meanings.
   R: a hydrogen atom or a methyl group.
   Q: a divalent linking group.
   Y: a monovalent functional group.
5. The surface treating agent according to claim 4, wherein Y in the formula (c) is a hydroxyl group, a carboxy group or an alkoxysilyl group.
6. The surface treating agent according to any one of claims 1 to 5, wherein a ratio of the polymerized units (C) in the polymer is 10% by mass or less.
7. The surface treating agent according to any one of claims 1 to 6, wherein the polymer has a weight average molecular weight (in terms of polymethyl methacrylate) of 100,000 or more.
8. A solder flux creep-up preventing agent using the surface treating agent according to any one of claims 1 to 7.
9. An anti-leaking agent for lubricating oil using the surface treating agent according to any one of claims 1 to 7.
10. A waterproof / moisture-proof coating agent using the surface treatment agent according to any one of claims 1 to 7.
11. A resin adhesion preventive agent for electronic parts using the surface treating agent according to any one of claims 1 to 7.
12. A base material coated with the surface treatment agent according to any one of claims 1 to 7.