JP2019094398A - Lubricating surface treatment composition, member having film obtained by drying the lubricating surface treatment composition and facility using the member - Google Patents

Abstract

To provide a lubricating surface treatment composition capable of imparting lubricating property to a surface with simple treatment and to provide a member and a facility having a surface having excellent lubricating property.SOLUTION: There is provided a lubricating surface treatment composition which comprises a copolymer containing a constitutional unit derived from a compound represented by the following formula (a) and a constitutional unit derived from a compound represented by the following formula (b) and a solvent, wherein in the copolymer, the mass percentage of the mass a of the constitutional unit derived from a compound represented by the formula (a) to the total mass a+b of the constitutional unit derived from a compound represented by the formula (a) and the constitutional unit derived from a compound represented by the formula (b) is 20 mass% to 70 mass%. CH=CR-COO-Rf(a) and CH=C(CH)-COO-CHCH(CF)F (b). In the formula (a), Ris a hydrogen atom or a methyl group and Rfis a polyfluoroalkyl group having a main chain having 2 to 3 carbon atoms and an end group of CF.SELECTED DRAWING: None

Description

  The present invention relates to a lubricious surface treatment composition, a member having a coating formed by drying the lubricious surface treatment composition, and equipment using the member.

  When oil or oil smoke adheres to cooking equipment such as range hoods, machine tools such as cutting machines, sewage treatment equipment, air conditioning equipment, and various transport / transfer equipment, the appearance is degraded, the sanitation is degraded, and , The deterioration of the original function may occur. For this reason, although it is necessary to remove the adhered oil, various efforts have been made to facilitate the removal of the oil.

  Until now, many methods for suppressing the adhesion of oil have been put into practical use by coating materials having low surface energy. For example, Patent Document 1 discloses a co-addition polymer of an acrylic and / or methacrylic monomer containing a perfluoroalkyl group having 6 carbon atoms as component (a) and a monomer having a functional group as component (b), Water- and oil-repellent agent composed of a fluorine-based solvent capable of dissolving the polymer as component (c), anti-soiling agent, mold release agent, lubricant, flux creeping inhibitor, moisture-proof coating agent, oil barrier, etc. A fluorine-based surface modifying composition is described (Claim 1).

  Also, in recent years, many non-wettable surfaces based on the Lotus (Lotus lotus) effect have been studied. The Lotus effect is an effect that extremely high liquid repellency can be obtained by subjecting a microfabricated surface to liquid repellent treatment. As a result, the oil that has deposited adheres into a ball shape, and the oil flows down, so it is considered that an antifouling function can be obtained. For example, in Patent Document 2, a smooth surface has primary irregularities formed of fine particles having a particle size of 100 nm or more and secondary irregularities formed of fine particles having a particle size of 7 to 90 nm, and is further coated with an oil repellent agent. A super-oil-repellent coated article is described which is characterized in that it has super-oil repellent properties with a contact angle to a low surface tension liquid of 22.6 mN / m or less at 150 ° or more (Claim 3).

JP, 2009-057530, A JP, 2011-140625, A

  However, in the method of improving the water and oil repellent performance of the surface using the fluorine-based surface modification composition of Patent Document 1, it is possible to suppress the adhesion and adhesion of the adhered oil, and the wiping and cleaning are easy. Effect is obtained, but the adhesion of oil itself can not be suppressed.

  Moreover, in the super-oil-repellent coated article of Patent Document 2, primary irregularities are formed on the surface of the article to be coated with fine particles having a particle size of 100 nm or more, secondary irregularities are formed from fine particles having a particle size of 7 to 90 nm, It needs to be coated, and the surface treatment takes time. Furthermore, if the fine irregularities on the surface deteriorate due to wear and the like, the Lotus effect is lost and super oil repellency can not be obtained.

  By the way, conventionally, the liquid repellency such as water repellency and / or oil repellency has been emphasized as an index of antifouling property, the water repellency is large in the size of the contact angle with water, and the oil repellency is large in the size of the contact angle with n-hexadecane However, each was often evaluated.

  However, when the present inventors examined oil stains, it is necessary to prevent the adhesion of oil even on surfaces with high oil repellency due to a large contact angle with n-hexadecane because the oil that is the source of the stain has a low surface tension. Turned out to be difficult.

  Thus, the inventor has considered that it is practically important that even if the oil that is the source of the dirt adheres to the surface, it flows down with a slight inclination and the oil does not remain on the surface and remains attached. Therefore, it was decided to focus not on oil repellency but on oil repellency.

  Then, an object of this invention is to provide the member and equipment which have a surface with a lubricious oil surface treatment composition which can impart excellent lubricity to a surface by simple processing, and a lubricious oil surface.

  As a result of intensive studies to achieve the above object, the inventor of the present invention has found a structural unit derived from a compound represented by a specific formula (a) and a configuration derived from a compound represented by a specific formula (b) A lubricant surface treatment composition comprising a copolymer comprising units and a solvent, wherein the formula (a) has a mass a of constituent units derived from the compound represented by the formula (a) in the above copolymer. Wherein the percentage by mass is 20% by mass to 70% by mass with respect to the total mass a + b of the constituent unit derived from the compound represented by formula (b) and the constituent unit derived from the compound represented by formula (b) A member having a coating formed by drying the lubricant surface treatment composition on at least a part of the surface, and equipment using the member, which can impart excellent lubricity to the surface by a simple treatment Has a lubricious surface Become known that, has led to the completion of the present invention.

That is, the present invention is the following [1] to [9].
[1] A lubricious surface treatment composition comprising a copolymer comprising a constituent unit derived from a compound represented by the following formula (a) and a constituent unit derived from a compound represented by the following formula (b), and a solvent The object,
In the following copolymer, the structural unit derived from the compound represented by the following formula (a) and the following formula (b) with a mass a of the constituent unit derived from the compound represented by the following formula (a) The oil-soluble surface treatment composition whose mass percentage is 20% by mass to 70% by mass with respect to the total mass a + b of the constituent units derived from the compound.
CH ₂ = CR ^a1 -COO-Rf ¹ (a)
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 (CF 2) 6 F (b)
In formula (a),
R ^{a1 is a} hydrogen atom or a methyl group,
Rf ¹ : a polyfluoroalkyl group in which the number of carbon atoms in the main chain is 2 to 3 and the terminal group is CF ₃ .
[2] The lipophilic surface treatment composition as described in [1] above, wherein the compound represented by the above formula (a) is a compound represented by the following formula (a1).
^{_{CH 2 = C (R a1)}} -COO-CH 2 -CF 3 (a1)
In formula (a1),
R ^{a1 is a} hydrogen atom or a methyl group.
[3] The above copolymer further includes a constitutional unit derived from a compound represented by the following formula (c),
In the copolymer, a structural unit derived from the compound represented by the above formula (a) and a mass unit represented by the above formula (b) with a mass a of the structural unit derived from the compound represented by the above formula (a) Oily surface treatment composition as described in said [1] or [2] whose mass percentage with respect to total mass a + b of the structural unit derived | led-out from the compound is 25 mass%-70 mass%.
CH ₂ = CR ^c1 -Q ¹ -Y (c)
In formula (c),
R ^{c1 is a} hydrogen atom or a methyl group,
Q ^{1 is a} single bond or a divalent linking group,
Y: an organopolysiloxane group having a number average molecular weight (Mn) of 1,000 to 30,000.
[4] In the above copolymer, a structural unit derived from the compound represented by the above formula (a), a structural unit derived from the compound represented by the above formula (b), and a component represented by the above formula (c) The lubricious surface treatment composition as described in the above-mentioned [3], wherein the total mass of the constituent units derived from the compound is 40% by mass or more of the total mass of the copolymer.
[5] In the above copolymer, the total mass of the structural unit derived from the compound represented by the above formula (a) and the structural unit derived from the compound represented by the above formula (b) is the same as that of the above copolymer The lubricious surface treatment composition according to the above [3] or [4], which is 50% by mass or more of the total mass.
[6] The lubricious surface treatment composition according to any one of the above [1] to [5], wherein the copolymer further contains a constitutional unit derived from a compound represented by the following formula (e) .
CH ₂ = CR ^e1 -Q ³ -W (e)
During the ceremony
R ^{e1 is a} hydrogen atom or a methyl group,
Q ^{3 is a} single bond or a divalent linking group,
W: a hydroxyl group, a carboxy group or a C1-C3 alkoxysilyl group.
[7] The lubricious surface treatment composition according to any one of the above [1] to [6], wherein the copolymer further contains a constitutional unit derived from a compound represented by the following formula (d) .
(CH ₂ = CR ^d1 -COO-) _n Q ² (d)
In formula (d),
R ^{d1 is a} hydrogen atom or a methyl group,
n: an integer of 2 or more,
Q ² : n-valent linking group.
[8] A member having a coating formed by drying the oil-soluble surface treatment composition according to any one of the above [1] to [7] on at least a part of the surface.
[9] An installation using the member according to the above [8].

  According to the present invention, it is possible to provide a lubricious surface treatment composition capable of imparting excellent lubricity to the surface by a simple treatment, and a member and equipment having a lubricious surface.

  In the present invention, "surface treatment composition" may be referred to as "surface treatment agent".

  In the present invention, the compound represented by the formula (x) may be referred to as "compound (x)". For example, the compound (a), the compound (b) and the compound (a1) respectively represent a compound represented by the formula (a), a compound represented by the formula (b) and a compound represented by the formula (a1) means.

  In the present invention, a structural unit derived from a compound represented by the formula (x) may be referred to as a structural unit (x). For example, the structural unit (a), the structural unit (b) and the structural unit (a1) are each derived from a structural unit derived from the compound represented by the formula (a) and a compound represented by the formula (b) It means a constitutional unit derived from a constitutional unit and a compound represented by the formula (a1).

  Furthermore, in the present invention, the range represented using “to” means a range including both ends thereof. For example, for the character strings arranged in alphabetical order "A, B, C, D, E, F, G, H", "B to F" are characters from "B" to "F", that is, " B, C, D, E, F ".

  In the present invention, "arene" means monocyclic or polycyclic aromatic hydrocarbon, and "aryl group" is obtained by removing one hydrogen atom of one ring carbon atom from arene. The term "arylene group" means a divalent group produced by removing one hydrogen atom of each of two ring carbon atoms from an arene.

  Further, in the present invention, “heteroarene” is to replace methine (—CH =) and / or vinylene (—CH = CH—) contained in arene with one or more, respectively, divalent or trivalent heteroatoms. Refers to a heterocyclic compound that is formally derived by the following and the property of a continuous π electron system as an aromatic system and the number of out-of-plane π electrons corresponding to the Huckel rule are kept, “heteroaryl group” is A monovalent group formed by removing one hydrogen atom from any one ring atom of heteroarene, and “heteroarylene” is one each from any two ring atoms of heteroarene The bivalent group produced by removing the hydrogen atom of

  In the present invention, the "divalent alicyclic group" is a divalent group formed by removing one hydrogen atom of each of two ring carbon atoms from a saturated or unsaturated alicyclic compound. Say

  Further, in the present invention, "alkylene group" means "alkanediyl group", "alkenylene group" means "alkene diyl group", and "alkynylene group" means "alkyndiyl group". Furthermore, unless otherwise specified, each of the alkylene group, the alkenylene group and the alkynylene group may be either branched or unbranched.

  In the present invention, “(meth) acrylic group” means “acrylic group” and “methacrylic group”, “(meth) acryloyl group” means “acryloyl group” and “methacryloyl group”, “( The meta) acryloyloxy group "means an" acryloyloxy group "and a" (meth) acryloyloxy group ".

[-CO-]
Moreover, in this invention, the bivalent group (carbonyl group) represented by the following chemical formula may be described with "-CO-." However, in the following chemical formulas, " _* " and " ^* " represent bonding points with other atoms or atomic groups.

[-SO _2- ]
Further, in the present invention, the divalent group represented by the following chemical formula (sulfonyl group) _- may be referred to as "-SO 2". However, in the following chemical formulas, " _* " and " ^* " represent bonding points with other atoms or atomic groups.

[-N (R)-]
Moreover, in this invention, the bivalent group (imino group) represented by the following chemical formula may be described with "-N (R)-." However, in the following chemical formulas, " _* " and " ^* " represent bonding points to other atoms or atomic groups, and "R" represents a hydrogen atom or a monovalent group.

[-COO-, -OCO-]
Moreover, in this invention, the bivalent group (carbonyloxy group, oxycarbonyl group) represented by the following chemical formula may be described with "-COO-", "-OCO-", respectively. However, in the following chemical formulas, " _* " and " ^* " represent bonding points with other atoms or atomic groups.

[-COS-, -SCO-]
Moreover, in this invention, the bivalent group represented by the following chemical formula may be described with "-COS-" and "-SCO-", respectively. However, in the following chemical formulas, " _* " and " ^* " represent bonding points with other atoms or atomic groups.

[-PO (OR)-, -P (= O) (OR)-]
Moreover, in this invention, the bivalent group represented by the following chemical formula may be described with "-PO (OR)-" or "-P (= O) (OR)-." However, in the following chemical formulas, " _* " and " ^* " represent bonding points to other atoms or atomic groups, and "R" represents a monovalent group.

[Liquid oil surface treatment composition]
The oil-soluble surface treatment composition of the present invention comprises a copolymer comprising the structural unit (a) and the structural unit (b), and a solvent.

  The lubricious surface treatment composition of the present invention can impart excellent lubricity to the surface by a simple treatment.

<Slippery, slippery, slippery>
In the present invention, the term “slip down” is defined as having the property that when both 10 μL droplets are placed on a slope having a certain degree of inclination or more, the both ends of the drop flow while maintaining a constant distance. There is. The fact that the gap between the two ends of the droplet continues to spread and falls (drops like rain streaks) does not apply to slipping. If the droplet is water, it is defined as slippery, and if the droplet is oil, it is defined as lubricated.
The slippage angle is preferably less than 30 degrees, and the slippage angle is less than 20 degrees, the slippage oil is judged to be good, and the fall angle is judged to be extremely good if it is less than 10 degrees.

<< Dropping angle measurement method >>
The glass plate is immersed in the surface treatment composition at room temperature for 1 minute, taken out, and dried at 120 ° C. for 5 minutes to prepare a surface-treated coated glass plate.
A 10 μL portion of a commercially available salad oil (food seasoning oil, manufactured by Nisshin Oillio Co., Ltd.) is placed on the surface-treated coated glass plate, and the sliding angle is measured using an automatic contact angle meter OCA-20 (manufactured by Data Physics Co., Ltd.). The moving speed of the falling angle at the time of measuring the falling angle is about 1.6 degrees / second, and the angle when the droplet starts moving is the falling angle (degree).

<Copolymer>
The copolymer includes the structural unit (a) and the structural unit (b), and is further selected from the group consisting of the structural unit (c), the structural unit (d), the structural unit (e) and the structural unit (f) It may also include one or more of the following.

<< Constituent Unit (a) and Constituent Unit (b) >>
The structural unit (a) and the structural unit (b) will be described.

・ Constituent unit (a)
The constituent unit (a) contained in the above-mentioned copolymer is a constituent unit derived from a compound [compound (a)] represented by the following formula (a).
CH ₂ = CR ^a1 -COO-Rf ¹ (a)
In formula (a),
R ^{a1 is a} hydrogen atom or a methyl group,
Rf ¹ is a polyfluoroalkyl group in which the number of carbon atoms in the main chain is 2 to 3 and the terminal group is CF ₃ .

  In the copolymer, the structural unit (a) may be a structural unit derived from one type of compound (a), or may be a structural unit derived from two or more types of compounds (a) .

・ R ^a1
In said Formula (a), although said R ^a1 will not be specifically limited if it is a hydrogen atom or a methyl group, Preferably it is a methyl group. When the above R ^a1 is a methyl group, the lubricity of the oil-soluble surface treatment composition of the present invention becomes better.

・ Rf ¹
In the above formula (a), the above Rf ¹ is not particularly limited as long as it is a polyfluoroalkyl group in which the carbon number of the main chain is 2 to 3 and the terminal group is CF ₃ .

- in the main chain carbon number of the Rf ^1, the "main carbon number of chain" and "backbone carbon atoms" are both a carbon atom bonded with Rf ¹ other atomic group of carbon atoms in Rf ¹ It means the number of carbon atoms of the longest carbon atom chain in Rf ^{1 that is} terminal.

-Polyfluoroalkyl group In the above Rf ¹ , "a polyfluoroalkyl group in which the end group is CF ₃ " means that three or more of the hydrogen atoms of the alkyl group are substituted with a fluorine atom, and at least one terminal methyl group (-CH ₃₎ means a partial fluoro substituted or perfluoroalkyl-substituted alkyl group are substituted with trifluoroalkyl group (-CF _3). Here, the alkyl group is a branched or unbranched alkyl group, and the methyl group at the terminal of the alkyl group may be a methyl group at the end of the main chain, or a side chain (a carbon atom of the main chain It may be a methyl group at the end of the carbon chain other than the main chain to be bonded.

・ Rf ¹ (non-branching)
Among the above R f ^{1, as} a non-branched one, 1,1,1-trifluoroethane-2-yl group (main chain carbon number: 2), 1,1,1-trifluoropropan-3-yl group Examples thereof include (main chain carbon number: 3) and groups in which one or more hydrogen atoms of these groups are substituted with a fluorine atom.

・ Rf ¹ (branch)
Further, among the above R f ¹ , as branched ones, 1-trifluoromethylethane-1-yl group (main chain carbon number: 2), 1,1-dimethyl-2,2,2-trifluoroethane- 1-yl group (main chain carbon number: 2), 2-trifluoromethylpropan-1-yl group (main chain carbon number: 3), 1-trifluoromethylpropan-1-yl group (main chain carbon number: 3), 1-methyl-3,3,3-trifluoropropan-1-yl group (main chain carbon number: 3), 2,2-dimethyl-3,3,3-trifluoropropan-1-yl group (Main chain carbon number: 3), 1,1-dimethyl-3,3,3-trifluoropropan-1-yl group (main chain carbon number: 3), 1-methyl-1-trifluoromethylpropane-1 -Fluoryl group (one carbon atom in the main chain: 3) and one or more hydrogen atoms of these groups The group which the child substituted is mentioned.

Specific Examples of Compound (a) Specific examples of the compound (a) are shown in the following table, but the compound (a) is not limited to these.

・ Compound (a1)
The compound (a) is preferably a compound represented by the following formula (a1) [compound (a1)].
CH ₂ = CR ^a1 -COO-CH ₂ -CF ₃ (a1)
In formula (a1),
R ^{a1 is a} hydrogen atom or a methyl group.

・ Constituent unit (b)
The structural unit (b) contained in the copolymer is a structural unit derived from a compound represented by the following formula (b) [compound (b)].
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 (CF 2) 6 F (b)

・ A / (a + b)
% By mass relative to the total mass a + b of the structural unit (a) and the structural unit (b) in the copolymer of the total mass a of the structural unit (a) [P _{{a / (a + b)}} ≡ {a / (A + b)} × 100 mass%] is not particularly limited as long as it is in the range of 20 to 70 mass%, but is preferably 20 to 65 mass%, more preferably 20 to 60 mass%, and further Preferably it is 20-55 mass%, More preferably, it is 30-55 mass%.
When the copolymer includes the structural unit (b) in addition to the structural unit (a) and the structural unit (c), the present invention is that the P _{{a / (a + b)}} is within this range. The lubricity of the lubricious surface treatment composition is better.

・ Constituent unit (a) + constitutional unit (b)
The total mass of a + b, the co mass percentage to the total mass _{w COPOLYMER} the polymer _{[P (a + b) / w} ≡ of the structural units of said copolymer (a) and the structural units (b) {(a + b ) / w _COPOLYMER } × 100% by mass] is not particularly limited, but is preferably 20% by mass or more (less than 100% by mass), more preferably 30% by mass or more (less than 100% by mass), further preferably 40 More than 50% by mass (less than 100% by mass), more preferably more than 80% by mass (less than 100% by mass).

  In the present invention, the mass ratio of each constituent unit in the above-mentioned copolymer [mass percentage of the total mass of a specific constituent unit to the total mass of the other constituent units in the copolymer] is a raw material used for polymerization Are all values considered to constitute the constitutional unit. Therefore, for example, the mass ratio of the structural unit (a) is substantially the mass percentage of the total mass of the structural units (a) in the copolymer to the total mass of the other structural units. It is determined as a mass percentage of the total mass of (a) with respect to the total mass of other polymerization starting compounds. The mass ratio of the other constituent unit in the above-mentioned copolymer can be similarly determined.

・ Constituent unit (c)
The copolymer may contain a structural unit [structural unit (c)] derived from a compound represented by the following formula (c) [compound (c)].
CH ₂ = CR ^c1 -Q ¹ -Y (c)
In formula (c),
R ^{c1 is a} hydrogen atom or a methyl group,
Q ^{1 is a} single bond or a divalent linking group,
Y: an organopolysiloxane group having a number average molecular weight (Mn) of 1,000 to 3,000.

  In the copolymer, the structural unit (c) may be a structural unit derived from one type of compound (c), or may be a structural unit derived from two or more types of compounds (c) .

・ R ^c1
In said Formula (c), although said ^Rc1 will not be specifically limited if it is a hydrogen atom or a methyl group, Preferably it is a methyl group. When the above R ^c1 is a methyl group, the lubricity of the oil-soluble surface treatment composition of the present invention becomes better.

・ Q ¹
In the above formula (c), the above Q ¹ is not particularly limited as long as it is a single bond or a divalent linking group.
As said bivalent coupling group, a C1-C10 alkylene group, a C2-C10 alkenylene group, a C1-C10 oxyalkylene group, a 6-membered arylene group, 4- to 6-membered 2 Ataiaburawamoto rings, 5 or 6-membered heteroarylene ^{group, -X 1 -, - X 1} -X 2 -, - Z 1 -X 1 -, - X 1 -Z 1 -X 2 -, - ^{Z 1 -X 1 -X 2 -,} - Z 1 -X 1 -Z 2 -X 2 -, and include a divalent group formed by combining two or more of these. Here, in a divalent group formed by combining a plurality of ring groups, two single rings may be fused.

The ^{-X 1 -, - X 1 -X} 2 -, - Z 1 -X 1 -, - X 1 -Z 1 -X 2 -, - Z 1 -X 1 -X 2 - and ^-Z 1 -X ¹ -Z ² -X ² - in,
Each of X ¹ and X ² independently represents an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, a 6-membered arylene group, a 4 to 6-membered divalent alicyclic group, 5 or Two or more single rings comprising a combination of two or more of a 6-membered heteroarylene group, a 6-membered arylene group, and a 4 to 6-membered divalent alicyclic group and a 5 or 6-membered heteroarylene group Represents a divalent group selected from the group consisting of divalent groups which may be fused,
Z ¹ and ^{Z 2:} independently, -O -, - S -, - CO -, - COO -, - OCO -, - COS -, - SCO -, - N (R 1) -, - SO 2 - ^{, -PO (OR 1) -,} - N (R 1) -COO -, - COO-N (R 1) -, - N (R 1) -CO -, - CO-N (R 1) -, - _{^{N (R 1) -SO 2 -}} , - SO 2 -N (R 1) -, - N (R 1) -PO (oR 2) -, and ^{-PO (oR 2) -N (R} 1) - from And R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

The above Q ¹ is preferably a single bond, an alkylene group having 1 to 6 carbon atoms, -COO-, -N (R ¹ )-, -SO _2- , or a divalent linking group obtained by combining these. More preferably -Z ¹ -X ^1- . Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z ¹ represents -COO-, and X ¹ represents an alkylene group having 1 to 6 carbon atoms.

-Substituent of Q ¹ The divalent linking group may have a substituent.
Examples of the substituent include halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I); hydroxy group; cyano group; methoxy group, ethoxy group, butoxy Groups and alkoxy groups such as octyloxy group; aryloxy groups such as phenoxy group; alkylthio groups such as methylthio group and ethylthio group; acyl groups such as acetyl group, propionyl group and benzoyl group; such as methanesulfonyl group and benzenesulfonyl group A sulfonyl group; an acyloxy group such as an acetoxy group and a benzoyloxy group; a sulfonyloxy group such as a methanesulfonyloxy group and a toluene sulfonyloxy group; a phosphonyl group such as a diethylphosphonyl group; an amide group such as an acetylamino group and a benzoylamino group; N, N-dimethyl car Carbamoyl groups such as bamoyl group and N-phenylcarbamoyl group; alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group and butyl group; aryl groups such as phenyl group and tolyl group; pyridyl group, imidazolyl group And heterocyclic groups such as furanyl group; alkenyl groups such as vinyl group and 1-propenyl group; alkoxyacyloxy groups such as methoxyacetyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; and vinyl group, Examples thereof include polymerizable groups such as (meth) acryloyl group, methacryloyl group, silyl group and cinnamic acid residue.

・ Y
In the above formula (c), Y is not particularly limited as long as it is an organopolysiloxane group having a number average molecular weight (Mn) of 1,000 to 30,000.
Examples of the organopolysiloxane group include groups in which a hydrogen atom, an alkyl group, a phenyl group or the like is substituted on the silicon atom of the repeating unit represented by-(SiO) x-, and particularly preferably-(Si It is a polydimethylsiloxane group represented by (CH ₃ ) ₂ O)-.
The end of the organopolysiloxane group is preferably not a polymerizable group, more preferably an alkyl group, an alkoxy group or a polyether group, and still more preferably an alkyl group. Here, the above-mentioned alkyl group, alkoxy group and polyether group may have a substituent.

Method of Measuring Number Average Molecular Weight In the present invention, the number average molecular weight (Mn) of the organopolysiloxane group can be measured by gel permeation chromatography (GPC).
Specific examples of GPC measurement conditions include the following.
(1) The sample is diluted with ASAHIKLIN AK-225 (manufactured by Asahi Glass Co., Ltd.) so that the concentration of the polymer is about 1%, and used as a measurement sample.
(2) It measures on condition of the following measurement using Shodex GPC-104 made from Showa Denko KK.
(GPC measurement conditions)
Separation column: GPC LF-604 × 2 (filler: styrene divinyl benzene copolymer, manufactured by Showa Denko KK)
Default column: KF600RH × 2 (filler: none, Showa Denko KK made)
Clean liquid: Asahi Clean AK-225 (manufactured by Asahi Glass Co., Ltd.)
Flow rate: 0.2 ml / min
Reference material: polymethyl methacrylate

・ Compound (c1)
The above compound (c) is preferably a compound [compound (c1)] represented by the following formula (c1).
CH ₂ = CR ^c1 -COO- (CH ₂ ) _n- (Si (CH ₃ ) ₂ O) _m -Si (CH ₃ ) ₂ -R ^c2 (c1)
In formula (c1),
R ^{c1 is a} hydrogen atom or a methyl group,
n is an integer of 1 to 6,
m: an integer of 10 to 800,
R ^c2 is an alkyl group which may have a substituent,
_{"- (Si (CH 3)} 2 O) m -Si (CH 3) 2 -R c2" number average molecular weight polydimethyl siloxane group represented by (Mn) of a 1,000 to 30,000.

・ R ^c1
In the above formula (c1), the above R ^c1 is not particularly limited as long as it is a hydrogen atom or a methyl group, but is preferably a methyl group.

M
It said m is not particularly limited as long as it is an integer of 10 to _{800, -} the number average polydimethylsiloxane group represented by _{"(Si (CH 3) 2} O) m -Si (CH 3) 2 -R c2" The molecular weight is preferably 5000 to 15000, and more preferably 10000 to 15000.

N
Although said n will not be specifically limited if it is an integer of 1-6, Preferably it is 2-4.

・ R ^c2
R ^c2 is an alkyl group which may have a substituent, preferably an alkyl group in which a hydrogen atom of an alkyl group having 1 to 5 carbon atoms may be substituted, and more preferably a non-alkyl group. It is a substituted C1-C5 alkyl group.

  Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; cyano group; alkoxy group such as methoxy group and ethoxy group; aryloxy group such as phenoxy group; methylthio group And alkylthio groups such as ethylthio group; acyl groups such as acetyl group and benzoyl group; carboxy groups; sulfonyl groups such as methanesulfonyl group and benzenesulfonyl group; acyloxy groups such as acetoxy group and benzoyloxy group; methanesulfonyloxy group and toluene Sulfonyloxy group such as sulfonyloxy group; phosphonyl group such as diethylphosphonyl group; amino group; amide group; alkyl group such as methyl group, ethyl group, propyl group and isopropyl group; aryl group such as phenyl group and tolyl group; Pili Group, a heterocyclic group such as imidazolyl or furanyl group; and the like alkoxy acyl group such as a methoxyacetyl group and the like. However, the said substituent does not contain polymerizable functional groups, such as a vinyl group, a (meth) acryloyl group, an epoxy group, and an isocyanate group.

_-Content of structural unit (c) The mass percentage [ _{Pc / w} (c / w _COPOLYMER ) of the total mass e of the structural unit (c) in the above-mentioned copolymer to the total mass w _COPOLYMER of the above-mentioned copolymer Although it does not specifically limit,) * 100 mass%] Preferably it is 5-40 mass%, More preferably, it is 10-20 mass%.
When the above P _{c / w} is in this range, the sliding property of the oil-soluble surface treatment composition of the present invention becomes better.

-Content of structural unit (a) + structural unit (c) When the copolymer contains the structural unit (c), the total of the structural unit (a) and the structural unit (c) in the copolymer The mass percentage [P _{(a + c) / w} ≡ {(a + c) / w _{COPOLY MER} } x 100 mass%] of the mass a + c with respect to the total mass w _COPOLYMER of the above copolymer is not particularly limited, but preferably 40 mass% or more (Less than 100% by mass), more preferably 60% by mass or more (less than 100% by mass).
When the above P _{(a + c) / w} is in this range, the lubricity of the lubricious surface treatment composition of the present invention becomes better.

・ A / (a + c)
When the copolymer includes the structural unit (c), the total mass a of the structural unit (a) is relative to the total mass a + c of the structural unit (a) and the structural unit (c) in the copolymer. The percentage by mass [P _{a / (a + c)} ≡ {a / (a + c)} × 100 mass%] is not particularly limited, but is preferably 40 mass% or more (less than 100 mass%), more preferably 50 to 90 It is mass%, More preferably, it is 60-80 mass%.

· Structural unit (a) + structural unit (b) + structural unit (c)
When the copolymer contains the structural unit (c), the above-mentioned co-weight of the total mass a + b + c of the structural unit (a), the structural unit (b) and the structural unit (c) in the copolymer The percentage by mass [P _{(a + b + c) / w} ≡ {(a + b + c) / w _COPOLYMER } x 100 mass%] _based on the total mass w _{COPOLYMER of the} combination is not particularly limited, but preferably 40 mass% or more (100 mass% or less) More preferably 50% by mass or more (100% by mass or less), further preferably 60% by mass or more (100% by mass or less), still more preferably 70% by mass or more (100% by mass or less), Still more preferably, it is 80% by mass or more (100% by mass or less), and particularly preferably 90% by mass or more (100% by mass or less).
When the above-mentioned copolymer contains the above-mentioned constituent unit (c), when the above P _{(a + b + c) / w} is within this range, the lubricity of the oil- _soluble surface treatment composition of the present invention becomes better.

・ A / (a + b)
When the copolymer includes the structural unit (c), the total mass of the structural unit (a) and the structural unit (b) in the copolymer in the total mass a of the structural unit (a) The mass percentage [P _{{a / (a + b)}}} {a / (a + b)} × 100 mass%] to a + b is preferably 25 to 70 mass%, more preferably 30 to 70 mass%, and further Preferably it is 35-65 mass%, More preferably, it is 45-65 mass%.

・ Constituent unit (a) + constitutional unit (b)
When the copolymer includes the structural unit (c), the total mass a + b of the structural unit (a) and the structural unit (b) in the copolymer is the total mass w of the copolymer w _COPOLYMER The mass percentage [P _{(a + b) / w} ≡ {(a + b) / w _{COPOLY MER} } x 100 mass%]] is not particularly limited, but is preferably 30 mass% or more (less than 100 mass%), more preferably 40 mass % Or more (less than 100% by mass), more preferably 50% by mass or more (less than 100% by mass), still more preferably 50 to 95% by mass, still more preferably 80 to 90% by mass.

<< Constituent unit (d) >>
The copolymer may contain a structural unit [structural unit (d)] derived from a compound represented by the following formula (d) [compound (d)].
(CH ₂ = CR ^d1 -COO-) _n Q ² (d)
In formula (d),
R ^{d1 is a} hydrogen atom or a methyl group,
n is an integer of 2 or more,
Q ^{2 is an} n-valent linking group.

  In the copolymer, the structural unit (d) may be a structural unit derived from one type of compound (d), or may be a structural unit derived from two or more types of compounds (d) .

・ R ^d1
In Formula (d) above, R ^d1 is not particularly limited as long as it is a hydrogen atom or a methyl group, but is preferably a methyl group. When the above R ^d1 is a methyl group, the lubricity of the oil-soluble surface treatment composition of the present invention is better.

・ Q ²
The above Q ² is not particularly limited as long as it is an n-valent linking group (wherein n is an integer of 2 or more), but is particularly preferably a divalent linking group from the viewpoint of controlling the polymerization reaction.

When the above Q ² is a divalent linking group, examples of the divalent linking group include the same as the above Q ¹ .

Specific Example of Compound (d) Specific examples of the compound (d) are shown in the following table, but the compound (d) is not limited to these.

The symbols in Table 2 have the following meanings.
i, j, k: mutually independently represent the integer of 1-20.
o, p, q: mutually independently, the integer of 0-3 is represented.
r, s: r is 2 or 3 and s is 0 or 1; However, r + s = 3.
R ^{d1 is a} hydrogen atom or a methyl group. When there are a plurality of R ^d1 in the same molecule, each R ^d1 is each independently a hydrogen atom or a methyl group.
R ^d2 is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, -CH ₂ OH and -CH ₂ -OCO-CR ^d4 = CH ₂ . Here, R ^d4 is a hydrogen atom or a methyl group.
R ^d3 is any one selected from divalent groups represented by the following formulas (1) to (3). However, in formula, "*" shows a bonding point with a nitrogen atom.

Ak ^{1 is} a branched or unbranched alkylene group having 1 to 20 carbon atoms.

・ Compound (d1)
The compound (d) is preferably a compound represented by the following formula (d1) [compound (d1)].
^{_{CH 2 = CR d1 -COO- (C}} 2 H 4 O) n -CO-CR d1 = CH 2 (d1)
In the formula (d1),
R ^{d1 is a} hydrogen atom or a methyl group,
n is an integer of 2 to 20.

  The above n is preferably 1 to 4 and more preferably 1.

_-Content of structural unit (d) When the above-mentioned copolymer contains the above-mentioned structural unit (d), mass percentage d of the structural unit (d) with respect to the total mass w copolymer of the copolymer [P _{d / w} Although (d / w _COPOLYMER ) x 100 mass%] is not particularly limited, it is preferably 10 mass% or less (more than 0 mass%), and more preferably 5 mass% or less (more than 0 mass%).
When the copolymer includes the structural unit (d), when the P _{d / w} is in this range, the durability of the oil-soluble surface treatment composition of the present invention is further improved.

<< Constituent unit (e) >>
The copolymer may contain a structural unit [structural unit (e)] derived from a compound represented by the following formula (e) [compound (e)].
CH ₂ = CR ^e1 -Q ³ -W (e)
In formula (e),
R ^{e1 is a} hydrogen atom or a methyl group,
Q ^{3 is a} single bond or a divalent linking group,
W is a hydroxy group, a carboxy group or a C1-C3 alkoxysilyl group.

  In the copolymer, the structural unit (e) may be a structural unit derived from one type of compound (e), or may be a structural unit derived from two or more types of compounds (e) .

・ R ^e1
In the above formula (e), the above R ^e1 is not particularly limited as long as it is a hydrogen atom or a methyl group, but is preferably a methyl group.

・ Q ³
In the above formula (e), the above Q ³ is not particularly limited as long as it is a single bond or a divalent linking group.
As said bivalent coupling group, the thing similar to said Q ¹ is mentioned, for example.

The above Q ³ is preferably a single bond, an alkylene group having 1 to 6 carbon atoms, -COO-, -N (R ¹ )-, -SO _2- , or a divalent linking group obtained by combining these. More preferably -Z ¹ -X ^1- . Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z ¹ represents -COO-, and X ¹ represents an alkylene group having 1 to 6 carbon atoms.

・ W
In the above formula (e), W hydroxy group (-OH) is not particularly limited as long as it is a carboxyl group (-COOH) or C1~C3 alkoxysilyl group, preferably a carboxy group or "-Si ^(OAk ₃₎ 3 And “Ak ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.” Here, the carboxy group may be in the form of a salt.
Said W is carboxy or C1~C3 alkoxysilyl group; If it is (-Si ^(OAk ₃₎ 3. Wherein Ak ³ is representing a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), lubricating oil of the present invention The adhesion of the surface treatment composition is further improved.

・ Compound (e1)
When W in the above formula (e) is a C1 to C3 alkoxysilyl group, the above compound (e) is preferably a compound [compound (e1)] represented by the following formula (e1).
CH ₂ = CR ^e1 -COO-Q ³¹ -Si (OAk ³¹ ) ₃ (e1)
In the formula (e1),
R ^{e1 is a} hydrogen atom or a methyl group,
Q ^{31 is a} substituted or unsubstituted alkylene group,
Ak ³¹ is an alkyl group having 1 to 3 carbon atoms.

Specific Examples of Compound (e1) Specific examples of the above compound (e1) are shown in the following table, but the compound (e1) is not limited to these.

・ Compound (e2)
When W in the above formula (e) is a hydroxy group (-OH), the above compound (e) is preferably a compound [compound (e2)] represented by the following formula (e2).
_{^{CH 2 = CR e1 -COO-Q}} 32 -OH (e2)
In the formula (e2),
R ^{e1 is a} hydrogen atom or a methyl group,
Q ^{32: -X 31} - or ^-X 32 ^{-X 31} - is.
Here, in the above-mentioned Q ²² , X ³¹ represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a hydroxy group, a phenylene group or a cyclohexylene group, and X ³² represents — (C ₂ H ₄ O) _p-or- (C ₃ H ₆ O) _q -is represented, and p and q are each independently an integer of 1 to 30.

Specific Examples of Compound (e2) Specific examples of the above-mentioned compound (e2) are shown in the following table, but the compound (e2) is not limited to these.

  In Table 4, n is an integer of 1 to 10.

・ Compound (e3)
When W in the above formula (e) is a carboxy group (-COOH), the above compound (e) is preferably a compound [compound (e3)] represented by the following formula (e3).
CH ₂ = CR ^e1 -Q ³³ -COOH (e3)
In the formula (e3),
R ^{e1 is a} hydrogen atom or a methyl group,
Q ³³ : Single bond, C 1-10 alkylene group, phenylene group, phenylene group, cyclohexylene group,-(C ₂ H ₄ O) _r -,-(C ₃ H ₆ O) _s- , -Z ³¹ -X ³³ -, or ^{-Z 32 -X 34 -Z 33 -X 35} - a.
Here, in the above Q ³³ , r and s each independently represent an integer of 1 to 30, Z ³¹ represents -COO-, and X ³³ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, and cyclohexylene. _{group, - (C 2 H 4 O} ) t - or _{- (C 3 H 6 O)} u - represents, t and u are each independently an integer of 1 to ^{30, Z 32} represents -COO-, X ³⁴ represents-(C ₂ H ₄ O) _v-or- (C ₃ H ₆ O) _W- , v and w each independently represent an integer of 1 to 30, and Z ³³ represents -CO- And X ³⁵ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group or a cyclohexylene group.

Specific Examples of Compound (e3) Specific examples of the above-mentioned compound (e3) are shown in the following table, but the compound (e3) is not limited to these.

  In Table 5, m and n are each independently an integer of 1 to 10.

-Content of structural unit (e) When the above-mentioned copolymer contains the above-mentioned structural unit (e), the total mass w of the above-mentioned copolymer of the total mass e of the above-mentioned structural unit (e) in the above-mentioned copolymer mass percentage _{[P e / w ≡ (e /} w COPOLYMER) × 100 wt%] is for _COPOLYMER, but are not limited to, preferably (0 mass percent) 10 wt% or less, more preferably (0 wt% Ultra) 5% by mass or less.
When the above-mentioned copolymer contains the above-mentioned structural unit (e), when the above-mentioned P _{e / w} is in this range, the adhesion of the oil-soluble surface treatment composition of the present invention becomes better.

<< Constituent unit (f) >>
The above copolymer can be copolymerized with the above compound (a) to the above compound (e), and is a constituent unit derived from a compound other than the above compound (a) to the above compound (e) [compound (f)] A unit (f)] may be included.

  In the copolymer, the structural unit (f) may be a structural unit derived from one type of compound (f), or may be a structural unit derived from two or more types of compounds (f) .

・ Compound (f1)
As an example of the said compound (f), the styrene-type compound [compound (f1)] represented by a following formula (f1) can be mentioned.

In the above formula (f1),
^{_{R 3: -H, -CH 3,}} -Cl, -CHO, -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 -}} , a _{-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.

・ Compound (f2)
As another example of the above-mentioned compound (f), the above-mentioned compound (a), the above-mentioned compound (b), the above-mentioned compound (c), the above-mentioned compound (d) and the above-mentioned compound (e) Other acrylic compounds [compound (f2)] can be mentioned.
_{^{CH 2 = CR f -CO-Q}} 4 -R 4 (f2)
In the formula (f2),
R ^{f is a} hydrogen atom, a halogen atom or a methyl group,
Q ^{4 is} -O- or -NH-,
R ^{4 is a} hydrogen atom or a monovalent organic group.
However, among the compounds represented by the above formula (f2), the above compound (a), the above compound (b), the above compound (c), the above compound (d) and the above compound (e) Except for things.

・ Compound (f21)
When the above R ^f is a hydrogen atom or a methyl group, and the above Q ⁴ is —O—, the compound (f 2) is preferably a (meth) acrylate compound represented by the following formula (f 21) f21)].
CH ₂ = CR ^f1 -COO-R ⁴¹ (f21)
In the formula (f21),
R ^f1 : -H or -CH ₃ ,
_{^{R 41: -C i H 2i +}} 1, -CH 2 CH 2 N (CH 3) 2, -CH 2 -C (CH 3) 2 -O-CO-Ph, -CH 2 -Ph, -CH 2 CH 2 - O-Ph, -CH ₂ -N ⁺ (CH ₃ ) ₃ Cl ^- ,-(CH ₂ CH ₂ O) _j -CH ₃ ,-(CH ₂ CH ₂ O) _k -H, -CH ₂ CH ₂ -NCO Or a monovalent organic group represented by any one of the following formulas (1) to (4). Here, i is an integer of 1 to 20, j is an integer of 2 to 20, k is an integer of 1 to 20, and -C _i H _{2i + 1} is a branched or unbranched alkyl group having carbon number i And -Ph represents a phenyl group.

In said Formula (1)-Formula (4), "*" shows a bonding point with the oxygen atom of "-COO-" in said Formula f (21).

The above R ⁴¹ is preferably a methyl group.

・ Compound (f22)
When the above R ^f is a hydrogen atom or a methyl group, and the above Q ⁴ is —NH—, the compound (f 2) is preferably a (meth) acrylamide compound [compound (f 2)] f22)].
_{^{CH 2 = CR f2 -CONH-R}} 42 (f22)
In the formula (f22),
R ^f2 : -H or -CH ₃ ,
R ^{42 is} —H or —C _h H _{2h + 1} . Here, h is an integer of 1 to 20.

・ Compound (f3)
As still another example of the above compound (f), the above compound (a), the above compound (b), the above compound (c), the above compound (d), and the above compound (e) are represented by the following formula (f3) And vinyl compounds [compound (f3)] other than the above compound (f1) and the above compound (f2).
^{_{CH 2 = CH-R 5 (}} f3)
In the formula (f3),
R ^{5 is a} hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkoxy group, an aryloxy group or an acyloxy group.

The above R ⁵ is preferably a chlorine atom or a cyano group.

The above compound (f3) represents vinyl chloride when the above R ⁵ is a chlorine atom, and represents acrylonitrile when the above R ⁵ is a cyano group.

_-Content of structural unit (f) When the above-mentioned copolymer contains the above-mentioned structural unit (f), mass percentage f of the structural unit (f) with respect to the total mass w copolymer of the copolymer [P _{f / w} The (f / w _COPOLYMER ) x 100% by mass] is not particularly limited, but is preferably (more than 0% by mass) 40% by mass, and more preferably (more than 0% by mass) 20% by mass.

<< The carbon number of perfluoroalkyl group >>
A preliminary risk survey on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wildlife and human blood, released in March 2003 by the United States Environmental Protection Agency (USEPA), The effect on living organisms and the environment is pointed out that the number of carbon atoms of the perfluoroalkyl group that might cause the occurrence of PFOA is 8, and in January 2006, PFOA and its analogues, and their precursors Since we advocated for fluorocarbon resin manufacturers and others to reduce their emissions into the environment and reduce their content in products, it is desirable that the number of carbon atoms in the perfluoroalkyl group contained in the compound be as short as 6 or less It is rare.

  Therefore, in consideration of influences on the living body and the environment, it is desirable that the above-mentioned copolymer contained in the oil-soluble surface treatment composition of the present invention does not contain a linear perfluoroalkyl group having 8 or more carbon atoms. When a perfluoroalkyl group is contained, one having 6 or less carbon atoms should be used.

Molecular weight of copolymer
Although the molecular weight of the said copolymer is not specifically limited, It is a weight average molecular weight (Mw), Preferably it is 1 * 10 < ³ > -1 * 10 < ⁷ >, More preferably, it is 1 * 10 < ⁴ > -1 * 10 < ⁶ >.
While the solubility to the solvent of the said copolymer is favorable in the weight average molecular weight of the said copolymer being this range, the lubricating oil performance of the oil-soluble surface treatment composition of this invention is fully exhibited. Can.

<< Polymerization form of copolymer >>
The above-mentioned copolymer contains the structural unit (a) and the structural unit (c) as an essential structural unit, and can further optionally contain the structural unit (b), the structural unit (d), the structural unit ( It may also include one or more structural units selected from the group consisting of e) and the structural unit (f).
The polymerization form of the above-mentioned copolymer is not particularly limited, and it may be a random copolymer, a block copolymer, a graft copolymer and a combination of two or more of them, preferably a random copolymer. It is union.

<< Method of producing copolymer >>
The method for producing the copolymer is not particularly limited, and various known methods may be employed. For example, it can manufacture by addition polymerization based on the unsaturated group in each compound. In the polymerization, addition polymerization conditions for known unsaturated compounds can be appropriately adopted. For example, as a polymerization initiator, a commonly used polymerization initiator such as an organic peroxide, an azo compound or a persulfate can be used. Moreover, in order to adjust the molecular weight of a copolymer, a molecular weight modifier can also be utilized at the time of a polymerization reaction.

Copolymer concentration
The concentration of the above-mentioned copolymer in the oil-soluble surface treatment composition of the present invention is not particularly limited, but preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.
When the concentration of the above-mentioned copolymer in the oily surface treatment composition of the present invention is within this range, the lubricating oil performance of the oily surface treatment composition of the present invention becomes more excellent.
The concentration of the above-mentioned copolymer in the oil-soluble surface treatment composition of the present invention may be a final concentration, for example, when the oil-soluble surface treatment composition of the present invention is directly prepared as a polymerization composition, It does not matter if the polymer concentration (solid content concentration) of the polymerization composition exceeds 20% by mass. The high concentration polymerization composition can be appropriately diluted so that the concentration finally falls within the above range.

<solvent>
The solvent contained in the oil-soluble surface treatment composition of the present invention is not particularly limited as long as it can dissolve or disperse the above-mentioned copolymer.
As such a solvent, various organic solvents, water, or a mixed medium thereof can be mentioned.
For example, polar solvents other than alcohols or fluorine solvents can be used as the solvent.

  As polar solvents other than the said alcohol, a ketone type (acetone, methyl ethyl ketone etc.), ester type (ethyl acetate etc.), ether type (tetrahydrofuran etc.) are mentioned. Moreover, as said fluorine-type solvent, hydrofluorocarbon (HFC) or hydrofluoroether (HFE) is mentioned. Especially as a solvent used for the oil-soluble surface treatment composition of this invention, a fluorine-type solvent is preferable.

Specific Examples of Solvent Specific examples of the fluorine-based solvent that can be used as a solvent of the lipophilic surface treatment composition of the present invention are shown below, but are not limited thereto.

m-xylene hexafluoride (hereinafter sometimes referred to as "m-XHF")
p-xylene hexafluoride (hereinafter sometimes 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 CFHCFHCF 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 illustration, m and n each represent an integer of 1 to 20.)

Flammability / Flight Point From the viewpoint of safety, it is preferable that the polymer of the present invention is dissolved in a non-flammable solvent and does not have flammability as a lubricant surface treatment agent.
In the present invention, "flammable" is defined as performing a flash point measurement according to the following procedure and having a flash point. Each flash point measurement method shall follow the method defined in JIS-K-2265.

-Measurement procedure of flash point (a) Implementation of flash point measurement by tag sealing method.
(B) In (a), when the flash point can not be measured at a temperature of 80 ° C. or less, the implementation of flash point measurement by the Cleveland open method.

<Other ingredients that may be included>
The oil-soluble surface treatment composition of the present invention does not impair the object of the present invention and does not adversely affect the stability as a composition, lubricating oil performance, appearance and the like, components other than the above-mentioned copolymer and the above-mentioned solvent May be included.

  As components other than the above-mentioned copolymer and the above-mentioned solvent, for example, a pH adjuster for preventing corrosion of the film surface, a rust inhibitor, and a polymer in liquid when the composition is diluted and used And dyes for the purpose of controlling the concentration of the pigments or for distinguishing them from untreated parts, stabilizers for the dyes, flame retardants, antifoaming agents and antistatic agents.

<Production Method of Slippery Surface Treatment Composition>
The oil-soluble surface treatment composition of the present invention is a liquid form containing the above-mentioned copolymer as a film component and containing the copolymer in a solvent.
The method for producing the oil-soluble surface treatment composition of the present invention is not particularly limited.
As one embodiment of the method for producing the oil-soluble surface treatment composition of the present invention, for example, a method for production by dissolving the above-mentioned copolymer in a solvent described later can be mentioned.
Moreover, as another embodiment of the method for producing a lubricious surface treatment composition of the present invention, for example, the compound (a) and the compound (c) are added to a solvent, and the above co-polymerization is carried out by solution polymerization using this solvent as a polymerization medium. The polymer may be synthesized to produce a solution or dispersion containing the copolymer, and the solution may be used as the oil-soluble surface treatment composition of the present invention. In addition, for example, a method of producing a solution or a dispersion containing the above-mentioned copolymer by synthesizing the above-mentioned copolymer by emulsion polymerization, and using this as a slip surface treatment composition of the present invention can also be mentioned. The copolymer thus obtained may be separated and dissolved in another solvent. Moreover, when the compound of the polymerization raw material is gaseous, it may be continuously supplied under pressure using a pressure vessel.

[A member having a coating formed by drying a lubricious surface treatment composition]
A member having a coating formed by drying the oil-soluble surface treatment composition of the present invention applies the surface treatment composition of the present invention to the surface of the member, is dried to remove the solvent, and It is produced by forming a film of a polymer. A member having a coating formed by drying the oily surface treatment composition of the present invention produced in this manner is provided with excellent lubricating oil performance on its surface.

  The material of the member to be treated is not particularly limited, and examples thereof include stone, wood, glass, plastic, metal, ceramic and the like. Examples of the plastic member include polyvinyl chloride, polyester, polystyrene, ABS resin, polypropylene, polyacetal, nylon, fluorine resin, polycarbonate, acrylic resin, polyethylene terephthalate, polybutylene terephthalate and the like. Examples of metal members include general steel plates (SPCC, SS400, etc.), stainless alloys (SUS304, SUS316L), copper plates, aluminum, titanium and the like. It is more preferable that it is a metal material from the viewpoint of the adhesion of the film and the like.

  When the oil-soluble surface treatment composition of the present invention is applied, it can be used after being diluted to any concentration.

  Moreover, the method of apply | coating the oil-soluble surface treatment composition of this invention is not specifically limited, A general application method can be used. Examples of such a coating method include dip coating, spray coating, coating by a roller and the like.

After the surface treatment composition of the present invention is applied to the surface of a member and then dried to remove the solvent, it is preferable to carry out drying at a temperature equal to or higher than the boiling point of the solvent.
The drying temperature is not particularly limited, but when the heating and drying are difficult due to the material of the member to be treated, etc., the heating can be avoided to dry. The conditions of the heat treatment may be appropriately selected according to the composition of the oil-soluble surface treatment composition to be applied, the application area, and the like.

[Facilities using a member having a coating formed by drying a lubricious surface treatment composition]
As equipment using a member having a film obtained by drying the oil-soluble surface treatment composition of the present invention, for example, a microwave oven using a member having a film obtained by drying the oil-soluble surface treatment composition of the present invention Examples include cooking equipment such as food, machine tools such as cutting machines, sewage treatment equipment, air conditioning equipment, and various transport / transfer equipment.

  The present invention will be specifically described below, but the present invention is not limited to the following examples. In addition, unless otherwise indicated, what is displayed only by "%" in description of the following Example shall represent "mass%."

[Preparation of surface treatment composition]
<Synthesis of (co) polymer>
Synthetic raw materials
The compounds used to synthesize the (co) polymers of Examples and Comparative Examples are shown in Table 6. All of these compounds are compounds which can be obtained as reagents from the market or compounds which can be easily synthesized by known synthetic methods.

<< Compounding method >>
The raw material compounds are charged in a closed vessel at a charging ratio (parts by mass) at which the composition ratio (polymerization composition) of the constituent units of the (co) polymer becomes the ratio shown in Tables 7 to 10, and the reaction is performed at 70 ° C. for 18 hours or more The (co) polymers used in Examples and Comparative Examples were synthesized. The compound concentration at the time of synthesizing the (co) polymer was 20% by mass, and the initiator concentration was 0.2% by mass.
The synthesized (co) polymer corresponds to Examples 1 to 20 and Comparative Examples 1 to 15, and may be referred to as Copolymers 1 to 20 and Comparative (co) polymers 1 to 15, respectively.

Preparation of Lubricant Surface Treatment Composition and Comparative Surface Treatment Composition
The concentration of the active ingredient of the synthesized (co) polymer is 5% by mass, 15% by mass of Asahi Clean AE-3000 (manufactured by AGC Asahi Glass Co., Ltd.), and m-xylene hexafluoride (hereinafter referred to as "m-XHF"). The mixture was mixed so as to be 80% by mass, and a comparative surface treatment composition used in the examples and comparative examples was prepared.
The prepared lubricant surface treatment composition and the comparative surface treatment composition correspond to Examples 1 to 20 and Comparative Examples 1 to 15, respectively, and the lubricant surface treatment composition 1 to 20 and the comparison surface treatment composition, respectively. It may be called 1-15.

  In Table 6, a, b, c, d, e and f respectively represent the compound (a), the compound (b), the compound (c), the compound (d), the compound (e) and the compound (f) , A. 1, b. 1 and c. 1 and the like represent a compound (a.1), a compound (b.1) and a compound (c.1) and the like. The same applies to Tables 7 to 10 below.

In Table 6, m is an integer of 10 to 800 for the compound (c. 1), R ^c2 is a hydrogen atom or a methyl group, and a polydimethylsiloxane group “— (Si (CH ₃ ) ₂ O) The number average molecular weight (Mn) of _m -Si (CH ₃ ) ₂ -R ^c2 "is about 12000, and for the compound (f.9), n is an integer of 1 to 20, and the average value of n is 4 .5.

[Performance evaluation of surface treatment composition]
<Overview>
The performance of the prepared surface treatment composition is as follows: contact angle to water, n-hexadecane (HD) or salad oil (food rape oil, Nisshin Oillio Co., Ltd.), and fall angle to salad oil (food rape oil, Nisshin Oilio Co., Ltd.) Was measured and evaluated. The larger the contact angle with water, the higher the water repellency, and the larger the contact angle with HD or salad oil, the higher the oil repellency. In addition, the smaller the sliding angle of salad oil, the higher the lubricating oil performance.

<Method of measuring contact angle and sliding angle>
<< Preparation of a coated glass plate >>
For each of the examples and comparative examples, a glass plate is dipped in the prepared surface treatment composition, taken out after 1 minute, dried at 120 ° C. for 5 minutes, and coated with a lubricious surface treatment composition or a comparative surface treatment composition. A glass plate (coated glass plate) was produced.

<< Measurement of contact angle to water or HD >>
10 μL of water was deposited on the surface of each of the produced coated glass plates, and the contact angle was measured using an automatic contact angle meter OCA-20 (manufactured by Data Physics Co., Ltd.).
Similarly, the contact angle to HD was also measured.

Measurement of contact angle to salad oil and sliding angle of salad oil
For each of the produced coated glass plates, 10 μL of a commercially available salad oil (food seasoning oil, manufactured by Nisshin Oillio Co., Ltd.) is dropped on the surface, and the contact angle [Analytical contact angle meter OCA-20 (manufactured by Data Physics Co., Ltd.)] Degrees were measured.
Next, the sliding angle [degree] of the coated glass plate after the contact angle was measured was measured using an automatic contact angle meter OCA-20 (manufactured by DATA PHYSICS CO., LTD.). The moving speed of the falling angle at the time of measuring the falling angle was about 1.6 degrees / second. The angle at which the droplet started to move was taken as the falling angle [degree].

<Measurement result of contact angle and sliding angle>
The measurement results of the contact angle and the falling angle of Examples 1 to 20 using the lubricious surface treatment composition 1 to 20 and the comparative examples 1 to 15 using the comparative surface treatment composition 1 to 15 are shown in Tables 7 to 10 It shows in the column of "contact angle [degree]" and the column of "falling angle [degree]".

  In Tables 7 to 10, “100 × a / (a + b)” is the total of the structural unit (a) and the structural unit (b) of the total mass of the structural unit (a) in the (co) polymer “100 × (a + b) / total” represents the mass percentage of the total mass of the structural unit (a) and the structural unit (b) to the total mass of the (co) polymer [mass%] [100% (a + b + c) / total] represents the mass percentage of the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) with respect to the total mass of the (co) polymer [Mass%] is expressed.

Regarding the falling angle of salad oil in Table 7 and Table 8, "ND ¹ " means that the droplets flow like streaks without slipping and the droplets remain on the glass plate, or in the middle of slipping Droplets were broken, meaning that the droplets remained on the glass plate, "ND ² " means that the droplets did not move even if the tilt angle was changed to 90 degrees, and the fall angle could not be measured It means that

In the following description, lubricating oil performance was evaluated as follows.
(1) The falling angle of salad oil is less than 19 degrees ... excellent oil performance (2) the falling angle of salad oil is less than 15 degrees ... more superior oil performance (3) the falling angle of salad oil is less than 11 degrees ... More excellent oil performance (4) Fall angle of salad oil is 9 degrees or less ... More excellent oil performance

  Example 1 in which the mass percentage [mass%] of the total mass of the structural units (a) in the copolymer relative to the total mass of the structural units (a) and the structural units (b) is in the range of 20 to 70 mass% As for -20, the sliding angle of salad oil is 19 degrees or less (5 degrees-19 degrees), and showed excellent lubricating oil performance.

  Further, the copolymer includes the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the structural unit (a) and the structure of the total mass of the structural unit (a) in the copolymer Examples 6-20 whose mass percentage [mass%] to the total mass of a unit (b) is in the range of 25-70 mass% are 15 degrees or less (5 degrees-15 degrees) of a falling angle of salad oil, It showed better oil performance.

  The polymer comprises the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the percentage by mass of the total mass of the structural unit (a) and the structural unit (b) with respect to the total mass of the copolymer In Examples 6 to 19 in which [mass%] is 30 mass% or more, the sliding angle of the salad oil is 11 degrees or less (5 degrees to 11 degrees), and further shows excellent lubricating oil performance.

  The polymer comprises the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the percentage by mass of the total mass of the structural unit (a) and the structural unit (b) with respect to the total mass of the copolymer In Examples 6 to 18 in which [mass%] is 40 mass% or more, the sliding angle of the salad oil is 11 degrees or less (5 degrees to 11 degrees), and further shows excellent lubricating oil performance.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a) and the structural unit (b) relative to the total mass of the copolymer Mass percentage [mass%] is 40 mass% or more, and mass percentage [mass with respect to the total mass of structural unit (a) and structural unit (b) of the total mass of structural unit (a) in a copolymer] Examples 7 to 18 in which the%] is in the range of 30 to 70% by mass show that the sliding angle of salad oil is 11 degrees or less (5 to 10 degrees), and further shows excellent lubricating oil performance.

  The polymer comprises the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the percentage by mass of the total mass of the structural unit (a) and the structural unit (b) with respect to the total mass of the copolymer In Examples 6 to 17 in which [mass%] is 50 mass% or more, the sliding angle of the salad oil is 11 degrees or less (5 degrees to 11 degrees), and further shows excellent lubricating oil performance.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a) and the structural unit (b) relative to the total mass of the copolymer Mass percentage [mass%] is 40 mass% or more, and mass percentage [mass with respect to the total mass of structural unit (a) and structural unit (b) of the total mass of structural unit (a) in a copolymer] Examples 7 to 17 in which the percentage] is in the range of 30 to 70% by mass show that the sliding angle of salad oil is 9 degrees or less (5 degrees to 9 degrees) and shows further excellent lubricating oil performance.

  The polymer comprises a structural unit (c) in addition to the structural unit (a) and the structural unit (b), and a copolymer of the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) Examples 6 to 20, in which the mass percentage [mass%] with respect to the total mass of L is 40 mass% or more, show a better lubricating oil performance, with the sliding angle of salad oil being 15 degrees or less (5 degrees to 15 degrees) The

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) is In Examples 6 to 19 in which the mass percentage [mass%] with respect to the total mass of the polymer is 50 mass% or more, the sliding angle of the salad oil is 11 degrees or less (5 degrees to 11 degrees), and further excellent lubricating oil performance showed that.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) is The total of the structural unit (a) and the structural unit (b) of the total mass of the structural unit (a) in the copolymer, which has a mass percentage [mass%] of at least 60 mass% with respect to the total mass of the polymer In Examples 7 to 18 in which the mass percentage [mass%] to the mass is in the range of 30 to 70 mass%, the sliding angle of the salad oil is 11 degrees or less (5 degrees to 10 degrees), and the lubricating oil performance is further excellent showed that.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) is The total of the structural unit (a) and the structural unit (b) of the total mass of the structural unit (a) in the copolymer, which has a mass percentage [mass%] of 70% by mass or more based on the total mass of the polymer In Examples 7 to 17 in which the mass percentage [mass%] with respect to the mass is in the range of 30 to 70 mass%, the sliding angle of the salad oil is 9 degrees or less (5 degrees to 9 degrees), and the lubricating oil performance is further superior. showed that.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) is The total of the structural unit (a) and the structural unit (b) of the total mass of the structural unit (a) in the copolymer, which has a mass percentage [mass%] of at least 80 mass% with respect to the total mass of the polymer In Examples 7 to 16 in which the mass percentage [mass%] to the mass is in the range of 30 to 70 mass%, the sliding angle of the salad oil is 9 degrees or less (5 degrees to 9 degrees), and the lubricating oil performance is further superior. showed that.

  In addition, the polymer contains the structural unit (c) in addition to the structural unit (a) and the structural unit (b), and the total mass of the structural unit (a), the structural unit (b) and the structural unit (c) is The total of the structural unit (a) and the structural unit (b) of the total mass of the structural unit (a) in the copolymer, which has a mass percentage [mass%] of 90% by mass or more based on the total mass of the polymer In Examples 7 and 9 to 14 in which the mass percentage [mass%] to mass is in the range of 35 to 65 mass%, the sliding angle of the salad oil is 9 degrees or less (5 degrees to 8 degrees), and the slip is even better. It showed oil performance.

  The larger the contact angle to water, HD or salad oil, the smaller the sliding angle of the salad oil is not necessarily smaller, and no correlation was found between the contact angle and the sliding angle.

  Heretofore, oil repellency and oil repellency have been considered without distinction, and a surface treatment with high oil repellency has been required as an improvement in antifouling performance. However, according to the present invention, there is no correlation between oil repellency and oil repellency, and just because the contact angle is high does not mean that oil repellency is possessed. In the present invention, it has been found that the use of a specific fluorine-containing polymer can provide a surface treatment agent having high lubricating oil performance.

Claims (9)

It is a lipophilic surface treatment composition comprising a copolymer comprising a constituent unit derived from a compound represented by the following formula (a) and a constituent unit derived from a compound represented by the following formula (b), and a solvent. ,
In the copolymer, a constituent unit derived from the compound represented by the formula (a) and a mass a of the constituent unit derived from the compound represented by the formula (a) are represented by the formula (b) The oil-soluble surface treatment composition whose mass percentage is 20% by mass to 70% by mass with respect to the total mass a + b of the constituent units derived from the compound.
CH ₂ = CR ^a1 -COO-Rf ¹ (a)
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 (CF 2) 6 F (b)
In formula (a),
R ^{a1 is a} hydrogen atom or a methyl group,
Rf ¹ : a polyfluoroalkyl group in which the number of carbon atoms in the main chain is 2 to 3 and the terminal group is CF ₃ . The oil-soluble surface treatment composition according to claim 1, wherein the compound represented by the formula (a) is a compound represented by the following formula (a1).
^{_{CH 2 = C (R a1)}} -COO-CH 2 -CF 3 (a1)
In formula (a1),
R ^{a1 is a} hydrogen atom or a methyl group. The copolymer further includes a constituent unit derived from a compound represented by the following formula (c),
In the copolymer, a constituent unit derived from the compound represented by the formula (a) and a mass a of the constituent unit derived from the compound represented by the formula (a) are represented by the formula (b) The oil-repellent surface treatment composition according to claim 1 or 2, wherein the mass percentage relative to the total mass a + b of the constituent units derived from the compound is 25% by mass to 70% by mass.
CH ₂ = CR ^c1 -Q ¹ -Y (c)
In formula (c),
R ^{c1 is a} hydrogen atom or a methyl group,
Q ^{1 is a} single bond or a divalent linking group,
Y: an organopolysiloxane group having a number average molecular weight (Mn) of 1,000 to 30,000.   In the copolymer, a structural unit derived from the compound represented by the formula (a), a structural unit derived from the compound represented by the formula (b), and a compound represented by the formula (c) The lubricated surface treatment composition according to claim 3, wherein the total mass of the constituent units to be incorporated is 40% by mass or more of the total mass of the copolymer.   In the copolymer, the total mass of the structural unit derived from the compound represented by the formula (a) and the structural unit derived from the compound represented by the formula (b) is the total mass of the total mass of the copolymer The oil-based surface treatment composition according to claim 3 or 4, which is 50% by mass or more. The oil-repellent surface treatment composition according to any one of claims 1 to 5, wherein the copolymer further comprises a constitutional unit derived from a compound represented by the following formula (e).
CH ₂ = CR ^e1 -Q ³ -W (e)
During the ceremony
R ^{e1 is a} hydrogen atom or a methyl group,
Q ^{3 is a} single bond or a divalent linking group,
W: a hydroxyl group, a carboxy group or a C1-C3 alkoxysilyl group. The oil-repellent surface treatment composition according to any one of claims 1 to 6, wherein the copolymer further comprises a constitutional unit derived from a compound represented by the following formula (d).
(CH ₂ = CR ^d1 -COO-) _n Q ² (d)
In formula (d),
R ^{d1 is a} hydrogen atom or a methyl group,
n: an integer of 2 or more,
Q ² : n-valent linking group.   A member having a coating formed by drying the oil-soluble surface treatment composition according to any one of claims 1 to 7 on at least a part of the surface.   The installation in which the member of Claim 8 was used.