JP5309622B2 - Surface treatment agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment agent having high chemical stability and coating self-repairing ability, and high fixiability to a base material, and being capable of being subjected to an orientation process of terminal groups in the coating step to the base material by the irradiation of ultraviolet rays. <P>SOLUTION: A surface treatment agent comprising (X-)<SB>x</SB>(W-)<SB>w</SB>(Z-)<SB>z</SB>Y, wherein X, W, and Z each represents formulae (X), (W), and (Z), respectively; Y represents a perfluorinated saturated hydrocarbon group and the like of (x+w+z) value, wherein x is an integer of one or more; each w and z is an integer of 0 or above; and (x+w+z) is an integer of 3 or larger; and U-(CH<SB>2</SB>CH<SB>2</SB>O)<SB>a</SB>-(CH<SB>2</SB>)<SB>b</SB>-CF<SB>2</SB>O(CF<SB>2</SB>CF<SB>2</SB>O)<SB>c</SB>-...(X), R<SP>W</SP>-(CH<SB>2</SB>CH<SB>2</SB>O)<SB>d</SB>-(CH<SB>2</SB>)<SB>e</SB>-CF<SB>2</SB>O(CF<SB>2</SB>CF<SB>2</SB>O)<SB>f</SB>-...(W), R<SP>F</SP>O(CF<SB>2</SB>CF<SB>2</SB>O)<SB>g</SB>-...(Z), wherein, U represents an ultraviolet rays absorbing group; a and b are each an integer from 0 to 100; c is an integer from 1 to 200; R<SP>W</SP>represents HO-, HOC(O)- or the like; d and e are each an integer from 0 to 100; f is an integer from 1 to 200; R<SP>F</SP>represents a perfluoroalkyl group or the like; and g is an integer from 3 to 200. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a surface treatment agent such as a lubricant.

  As the external storage device, an external storage device of a system (CSS system) in which a recording / reproducing element (head) is operated by rotating a hard disk having a recording medium layer at a high speed is generally used. Hard disks include fixed magnetic disks, optical disks, magneto-optical disks, and the most popular hard disks are fixed magnetic disks.

In order to increase the capacity of the external storage device, it is necessary to increase the surface recording density of the recording medium layer. For this purpose, it is necessary to reduce the distance between the head and the hard disk in order to reduce the bit size. Accordingly, it is necessary to increase the smoothness of the hard disk surface. However, increasing the smoothness of the surface of the hard disk makes it easier for the head to stick to the surface of the hard disk.
In addition, in order to obtain high-speed response, it is necessary to increase the rotation speed of the hard disk. However, increasing the rotational speed increases the probability of contact between the hard disk and the head, wear, and the like.

In order to solve this problem, a lubricant, which is a kind of surface treatment agent, is applied to the surface of a hard disk. The following are known as the lubricant.
(1) A polyfluorinated polyether compound having two hydroxyl groups at the terminals (hereinafter, the polyfluorinated polyether compound is referred to as PFPE).

However, since the PFPE (1) has low fixability on the surface of the hard disk, if the rotational speed of the hard disk is further increased, the lubricant moves and disappears from the surface of the hard disk by centrifugal force. In order to solve this problem, a method of increasing the amount of lubricant applied can be considered.
However, when the coating amount increases, the sliding resistance of the surface of the hard disk increases, and the adsorption force of the head to the surface of the hard disk increases, so that the hard disk comes into contact with the head and breaks.

Further, in the step of applying the lubricant to the surface of the hard disk, after the lubricant is applied to the surface of the hard disk, a process of orienting the end groups of the lubricating oil is performed. As the treatment, ultraviolet irradiation treatment or heat treatment is known. The ultraviolet irradiation treatment is more advantageous than the heat treatment in that the time required for the process is short.
However, since the PFPE of (1) does not absorb at wavelengths in the ultraviolet region, when only the PFPE of (1) is applied, the ultraviolet irradiation treatment cannot be adopted.

As the lubricant for solving the problem, the following has been proposed.
(2) PFPE in which a group having an absorption wavelength in the ultraviolet region is bonded to one hydroxyl group of PFPE having two hydroxyl groups at the terminal (Patent Document 1).
However, even PFPE classified as (2) cannot solve the problems of low chemical stability and low coating film self-healing performance after coating.

JP 2002-293787 A

  The surface of the present invention has high chemical stability and coating film self-healing property, and has high fixability to the base material, and can be subjected to end group orientation treatment by ultraviolet irradiation in the coating process to the base material. A treatment agent is provided.

Ｐｈ−Ｏ− ・・・（Ｕ２１）、
ＣＨ _２ ＝ＣＨ（ＣＨ _２ ） _ｎ ＮＨＣ（Ｏ）− ・・・（Ｕ３１）、
ＨＯ（ＣＨ _２ ） _ｎ ＮＨＣ（Ｏ）− ・・・（Ｕ３２）、
（ＨＯ（ＣＨ _２ ） _ｎ −） _２ ＮＣ（Ｏ）− ・・・（Ｕ３３）、
Ｒ ^ｃ ＯＣ（Ｏ）− ・・・（Ｕ４１）、
ＣＨ _２ ＝ＣＨ（ＣＨ _２ ） _ｑ Ｏ− ・・・（Ｕ５１）。
ただし、Ｒは、水素原子、塩素原子、−ＣＨ _２ ＣＨ _２ ＣＨ _３ 、−ＮＨ _２ 、−ＯＰｈ、−ＯＣＨ _２ （ＣＦ _２ ） _ｐ Ｈまたは−ＯＣＨ _２ ＣＦ _２ ＣＦ _３ で表される基であり、Ｐｈは、置換基を有していてもよいフェニル基であり、ｐは、１〜８の整数であり、Ｒは、それぞれ同一であってもよく、異なっていてもよく、ｎは、１〜３の整数であり、Ｒ ^ｃ は、水素原子、炭素数が１〜４のアルキル基、炭素数が１〜４のハロゲン化アルキル基、アリール基、置換アリール基、アリールオキシ基または置換アリールオキシ基であり、ｑは、１〜３の整数である。 The surface treating agent of the present invention is characterized by containing a compound represented by the following formula (A).
(X−) _x (W−) _w (Z−) _z Y (A).
However, X is group represented by the following Formula (X), W is group represented by the following Formula (W), Z is group represented by the following Formula (Z), Y Is a (x + w + z) -valent perfluorinated saturated hydrocarbon group or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group, x is an integer of 1 or more, and w is 0 or more Z is an integer of 0 or more, and (x + w + z) is an integer of 3 to 5 .
_{U- (CH 2 CH 2 O)} a - (CH 2) b -CF 2 O (CF 2 CF 2 O) c - ··· (X),
^{_{R W - (CH 2 CH 2}} O) d - (CH 2) e -CF 2 O (CF 2 CF 2 O) f - ··· (W),
^{_{R F O (CF 2 CF 2}} O) g - ··· (Z).
However, U is a group represented by the following formula (U1), a group represented by the following formula (U21), a group represented by the following formula (U31), a group represented by the following formula (U32), A group represented by the formula (U33), a group represented by the following formula (U41), a group represented by the following formula (U51) , a is an integer of 0 to 100, and b is is an integer of 0 to 100, c is an integer of 1 to 200, ^{R W} is HO - a and, d is an integer of 0 to 100, e is an integer from 0 to 100 , F is an integer of 1 to 200, and R ^F is a linear perfluoroalkyl group having 1 to 20 carbon atoms or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group. , G is an integer from 3 to 200.

Ph-O- (U21),
_{CH 2 = CH (CH 2)} n NHC (O) - ··· (U31),
HO (CH ₂ ) _n NHC (O) − (U32),
(HO (CH ₂ ) _n −) ₂ NC (O) − (U33),
R ^c OC (O) − (U41),
_{CH 2 = CH (CH 2)} q O- ··· (U51).
Here, R is a hydrogen atom, a chlorine _{atom, -CH 2 CH 2 CH 3,} -NH 2, -OPh, a group represented by -OCH 2 _{(CF 2) p} H or -OCH ₂ CF ₂ CF ₃ , Ph is an optionally substituted phenyl group, p is an integer of 1 to 8, R may be the same or different, and n is 1 And R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an aryl group, a substituted aryl group, an aryloxy group or a substituted aryloxy group. And q is an integer of 1 to 3.

The compound represented by the formula (A) preferably has no —OCF ₂ O— structure.
(X + w + z) is preferably 3 or 4.
Y represents a group represented by the following formula (Y ³ -1) to a group represented by the following formula (Y ³ -4), a group represented by the following formula (Y ⁴ -1) to the following formula (Y ⁴ It is preferably any one of a group represented by -5) and a group represented by the following formula (Y ⁵ -1). However, the formula ^(Y 3 -4) shows a perfluoro-cyclohexane-1,3,5-triyl group.

The group represented by the formula (X) is preferably a group represented by the following formula (X1) or a group represented by the following formula (X2).
U ¹ —CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _c − (X1),
U ² —CF ₂ O (CF ₂ CF ₂ O) _c − (X2).
However, ^{U 1} is a group represented by the formula (U1), a group represented by the group or the formula represented by the formula ^{(U21) (U51), U} 2 is represented by the formula (U31) A group represented by the formula (U32), a group represented by the formula (U33), a group represented by the formula (U41) or a group represented by the formula (U51), and c is 1 to 200 Is an integer.

The group represented by the formula (W) is preferably a group represented by the following formula (W1).
HO—CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _f − (W1 ).
However , f is an integer of 1-200.

The group represented by the formula (Z) is preferably a group represented by the following formula (Z1).
_{CF 3 (CF 2) m -O-} (CF 2 CF 2 O) g - ··· (Z1).
However, m is an integer of 0-19 and g is an integer of 3-200.
The surface treating agent of the present invention preferably contains a solvent.

  The compound of the present invention is a compound represented by the following formula (A3-1).

  However, c1-c3 is an integer of 1-200, respectively.

  The compound of the present invention is a compound represented by the following formula (A4-1).

  However, c1-c3 is an integer of 1-200, respectively.

  The surface treatment agent of the present invention has high chemical stability and coating film self-healing property, and has high fixability to the substrate, and in the coating step to the substrate, the end group is subjected to orientation treatment by ultraviolet irradiation. Is possible.

In this specification, a compound represented by the formula (A) is referred to as a compound (A). The same applies to compounds represented by other formulas.
A group represented by the formula (X) is referred to as a group (X). Groups represented by other formulas are also described in the same manner.

The surface treating agent of the present invention contains a compound (A).
(X−) _x (W−) _w (Z−) _z Y (A).
Compound (A) is a compound in which x X, w W and z Z are bonded to Y. x is an integer of 1 or more, w is an integer of 0 or more, z is an integer of 0 or more, and (x + w + z) is an integer of 3 or more. That is, in the compound (A), one or more Xs are bonded to a trivalent or higher group represented by Y. Z and W are optionally bonded groups.

X is a group (X).
_{U- (CH 2 CH 2 O)} a - (CH 2) b -CF 2 O (CF 2 CF 2 O) c - ··· (X).

a is an integer of 0 to 100, preferably an integer of 0 to 10, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
b is an integer of 0 to 100, and when U has an oxygen atom at the bond terminal, an integer of 1 to 10 is preferable, 1 or 2 is particularly preferable, and U is a carbonyl group (C═O) at the bond terminal. When it has, 0 is preferable.
c is an integer of 1 to 200, preferably an integer of 3 to 100, and more preferably an integer of 5 to 50.

U is a monovalent group having an absorption wavelength in the ultraviolet region.
U is preferably a group having at least one structure selected from a cyclophosphazene ring, a benzene ring, an amide bond, an ester bond, and a vinyl group, and particularly preferably a group having an amide bond.

  Examples of U when U is a group having a cyclophosphazene ring include group (U1).

Here, R is a hydrogen atom, a chlorine _{atom, -CH 2 CH 2 CH 3,} -NH 2, -OPh, a group represented by -OCH 2 _{(CF 2) p} H or -OCH ₂ CF ₂ CF ₃ , Ph is an optionally substituted phenyl group, and p is an integer of 1-8. R may be the same or different from each other, and preferably all are the same.
As the group (U1), a group (U11) is preferable.

^Rb is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an aryl group, a substituted aryl group, aryloxy Group or a substituted aryloxy group.

Examples of U in the case where U is a group having a benzene ring include group (U21) and group (U22).
Ph-O- (U21).
However, Ph is a phenyl group which may have a substituent.

Examples of U when U is a group having an amide bond include groups (U31) to (U33). The group (U31) can also be included in a group having a vinyl group.
_{CH 2 = CH (CH 2)} n NHC (O) - ··· (U31),
HO (CH ₂ ) _n NHC (O) − (U32),
_{(HO (CH 2) n -} ) 2 NC (O) - ··· (U33).
However, n is an integer of 1-3.

Examples of U in the case where U is a group having an ester bond include group (U41).
R ^c OC (O) − (U41).
However, ^Rc is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 halogenated alkyl group, an aryl group, a substituted aryl group, an aryloxy group, or a substituted aryloxy group.

Examples of U in the case where U is a group having a vinyl group include group (U51).
_{CH 2 = CH (CH 2)} q O- ··· (U51).
However, q is an integer of 1-3.

The group (X) is preferably a group (X1) or a group (X2).
U ¹ —CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _c − (X1),
U ² —CF ₂ O (CF ₂ CF ₂ O) _c − (X2).
U ¹ is a monovalent group having a cyclophosphazene ring, a benzene ring or a vinyl group, and U ² is a monovalent group having an amide bond, an ester bond or a vinyl group.
The group (X) is preferably a group in which U has an amide bond from the viewpoint of easy availability of the compound.

W is a group (W).
^{_{R W - (CH 2 CH 2}} O) d - (CH 2) e -CF 2 O (CF 2 CF 2 O) f - ··· (W).

R ^W is HO—, HOC (O) —, or R ^a OC (O) —.
R ^a is an alkyl group and is preferably a lower alkyl group having 1 to 6 carbon atoms.

d is an integer of 0 to 100, an integer of 0 to 10 is preferable, an integer of 0 to 2 is more preferable, and 0 or 1 is particularly preferable.
e is an integer from 0 to 100, when ^{R W} is -OH, preferably 1 or 2, if ^{R W} is -C (O) OH or -C (O) OR ^a, preferably 0 .
f is an integer of 1 to 200, preferably an integer of 3 to 100, and more preferably an integer of 5 to 50.

The group (W) is preferably a group (W1) to a group (W3).
HO—CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _f − (W1),
HOC (O) —CF ₂ O (CF ₂ CF ₂ O) _f − (W2),
R ^a OC (O) —CF ₂ O (CF ₂ CF ₂ O) _f − (W3).

Z is a group (Z).
^{_{R F O (CF 2 CF 2}} O) g - ··· (Z).

R ^F is a linear perfluoroalkyl group having 1 to 20 carbon atoms or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group.
g is an integer of 3 to 200, preferably an integer of 3 to 100, more preferably an integer of 3 to 70, and particularly preferably an integer of 5 to 50.

The group (Z) is a group having —CF ₃ at the terminal and can contribute to the reduction of the friction coefficient. Group (Z) from the viewpoint of flexibility of the -CF ₃ is high in the molecule preferably has a certain degree of chain length.
As the group (Z), a group (Z1) is preferable, and a group (Z11) to a group (Z13) are more preferable.
CF ₃ (CF ₂ ) _m —O— (CF ₂ CF ₂ O) _g − (Z1),
CF ₃ —O— (CF ₂ CF ₂ O) _g − (Z11),
CF ₃ (CF ₂ ) ₂ —O— (CF ₂ CF ₂ O) _g − (Z12),
_{CF 3 (CF 2) 5 -O-} (CF 2 CF 2 O) g - ··· (Z13).
However, m is an integer of 0-19.

x is an integer greater than or equal to 1, 1- (x + w + z) is preferable and 1-3 are more preferable.
w is an integer greater than or equal to 0, and 0-1 are preferable.
z is an integer greater than or equal to 0, and 0-1 are preferable.
(X + w + z) is preferably 3 or 4. That is, Y is preferably a trivalent or tetravalent group.

Y is a (x + w + z) -valent perfluorinated saturated hydrocarbon group or a group having an etheric oxygen atom inserted between carbon-carbon atoms of the group. Y preferably does not have —CF ₃ . When Y has a -CF _3, -CF ₃ is preferably bonded to a quaternary carbon atom. A quaternary carbon atom means a carbon atom to which no fluorine atom is bonded.
When Y is a group in which an etheric oxygen atom is inserted between carbon-carbon atoms, the number of etheric oxygen atoms is preferably 1 to 3. Since the etheric oxygen atom exists between carbon-carbon atoms, there is no etheric oxygen atom at the end of Y bonded to X, Z, and W.

Examples of Y in the case where Y is a trivalent group include groups (Y ³ -1) to groups (Y ³ -4). However, the group (Y ³ -4) represents a perfluorocyclohexane-1,3,5-triyl group.

Examples of Y in the case where Y is a tetravalent group include groups (Y ⁴ -1) to groups (Y ⁴ -5).

Examples of Y in the case where Y is a pentavalent group include a group (Y ⁵ -1).

As the compound (A) when Y is a trivalent group, the compound (A ³ -1) to the compound (A ³ -4) are preferable, and the compound (A ³ -4) is particularly preferable.

As the compound (A) when Y is a tetravalent group, the compound (A ⁴ -1) to the compound (A ⁴ -4) are preferable, and the compound (A ⁴ -4) is particularly preferable.

The compound (A) preferably has no —OCF ₂ O— structure from the viewpoint of chemical stability. The compound having no —OCF ₂ O— structure means a compound in which the presence of the structure cannot be detected by a normal analysis method ( ¹⁹ F-NMR, etc.).

  As the compound (A), the compound (A3-1) or the compound (A4-1) is preferable.

  However, c1-c3 is an integer of 1-200, respectively.

The number average molecular weight (hereinafter referred to as Mn) of the compound (A) is preferably 500 to 100,000, more preferably 1000 to 20,000.
1.0-1.5 are preferable and, as for molecular weight distribution (henceforth Mw / Mn) of a compound (A), 1.0-1.25 are more preferable.
If Mn and Mw / Mn are in this range, the viscosity is low, the evaporation component is small, and the uniformity when dissolved in the solvent is excellent.
Mn is measured by gel permeation chromatography (hereinafter referred to as GPC). Mw / Mn is determined from Mn and Mw (mass average molecular weight) measured by GPC.

As a method for producing compound (A), compound (A1) or compound (B1) is produced by the method described in WO 2005/068534 pamphlet, and the terminal of the compound is converted by a known method. It is preferable to manufacture by.
^{_{(R d OC (O) -CF}} 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (A1),
_{(HO- (CH 2) b -CF} 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (B1).
However, ^Rd is a lower alkyl group.

  When the compound (A1) and the compound (B1) are produced by a method that undergoes a liquid phase fluorination reaction described in International Publication No. 2005/068534 pamphlet, and the conditions of the liquid phase fluorination reaction are severe, Terminal cleavage reaction is likely to occur. Therefore, in the liquid phase fluorination reaction, the fluorine concentration contained in the gas blown into the liquid phase is preferably 5.0 to 50% by volume, and more preferably 10 to 30% by volume.

For example, the following method can be illustrated as a manufacturing method of a compound (A).
(I) The compound (A4) in which U is a group (U31) can be produced by reacting the compound (A1) with the compound (U31H). However, the symbols in the formula have the same meaning as described above.
_{CH 2 = CH (CH 2)} n NH 2 ··· (U31H),
_{(CH 2 = CH (CH 2} ) n NHC (O) -CF 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (A4).

(Ii) The compound (A3) in which U is a group (U32) can be produced by reacting the compound (A1) with the compound (U32H). However, the symbols in the formula have the same meaning as described above.
HO (CH ₂ ) _n NH ₂ ... (U32H),
_{(HO (CH 2) n NHC} (O) -CF 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (A3).

(Iii) Compound (A5) wherein U is a group (U33) can be produced by reacting compound (A1) with compound (U33H). However, the symbols in the formula have the same meaning as described above.
(HO (CH ₂ ) _n −) ₂ NH (U33H),
_{((HO (CH 2) n} -) 2 NC (O) -CF 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (A5).

(Iv) Compound (A6) wherein U is a group (U51) can be produced by reacting compound (B1) with compound (U51H). However, the symbols in the formula have the same meaning as described above.
CH ₂ = CH (CH ₂ ) _q Br (U51H),
_{(CH 2 = CH (CH 2} ) q O- (CH 2) b -CF 2 O (CF 2 CF 2 O) c -) x (W-) w (Z-) z Y ··· (A6).

The reactions (i) to (iii) can be carried out by applying a method of amidation reaction.
Since the reaction is completed at about room temperature, the target product can be obtained in an extremely high yield.
It is preferable that a compound (A) is refine | purified as needed. Examples of the purification method include a method of removing metal impurities, anion impurities, and the like with an ion-adsorbing polymer, a supercritical extraction method, and a column chromatography method, and a combination of these methods is preferable.

The surface treating agent of the present invention contains a compound (A). The compound (A) may be one kind or a mixture of two or more kinds.
Two or more compounds are two or more compounds having different types of Y, or two or more compounds having different X, W and Z bond numbers (x, w and z) even if Y is the same. Means. A compound in which Y is the same, x, w and z are the same and the numbers of a to g are the same or different is the same compound.

  The compound (A) contained in the surface treatment agent is preferably a single compound. Moreover, this 1 type of compound consists of a compound from which the number of ag normally differs, and the number of ag is represented as a molar average value.

The surface treatment agent of the present invention may contain other compounds.
Examples of the other compound include PFPE other than the compound (A) (hereinafter referred to as other PFPE). Other PFPEs can be appropriately selected in consideration of the manufacturing process and use conditions after application.
Examples of other PFPEs that do not have an ultraviolet absorbing group at the terminal include FOMBLIN Z-DiOL and Z-TetraOL manufactured by Solvay, and DEMNUM SA manufactured by Daikin. Moreover, PFPE etc. which are described in the international publication 2005/068534 pamphlet can also be used preferably.
Other PFPEs having UV-absorbing groups at their ends include: FOLMBLIN Z-DIAC, Z-DEAL, AM2001, Z-DISOC manufactured by Solvay, DENMU SH, SP, SY manufactured by Daikin, and Matsumura Sekiyu Moresco A20H.
The amount of the compound (A) when other PFPE is included is preferably 0.01 to 99.9% by mass, and preferably 0.5 to 60% by mass with respect to the total mass of the compound (A) and the other PFPE. Is particularly preferable, and 1 to 25% by mass is particularly preferable.

The surface treating agent of the present invention is preferably used as a liquid composition containing a solvent.
Examples of the solvent include perfluoroamines (perfluorotripropylamine, perfluorotributylamine, etc.), perfluoroalkanes (Bertrel XF (manufactured by DuPont), etc.) or hydrofluoroethers (AE-3000 (manufactured by Asahi Glass Co., Ltd.)). ) Are preferred, and hydrofluoroethers are more preferred. The solvent is preferably selected from solvents having a boiling point suitable for the coating process.

The liquid composition may be any of a solution, a suspension or an emulsion, and a solution is preferable.
The concentration of the compound (A) in the liquid composition is preferably 0.001 to 50% by mass, and more preferably 0.01 to 20% by mass.

The liquid composition may contain components other than the surface treatment agent and the solvent of the present invention (hereinafter referred to as other components).
Examples of other components include radical scavengers (for example, X-1p (manufactured by Dow Chemicals), etc.).

When using a liquid composition as a lubricant, it is preferable that the liquid composition does not contain metal ions, anions, moisture, a low-molecular polar compound, a plasticizer, and the like.
Metal ions (Na, K, Ca, Al, etc.) may combine with an anion to produce a Lewis acid catalyst and promote the decomposition reaction of PFPE.
Anions (F, Cl, NO ₂ , NO ₃ , PO ₄ , SO ₄ , C ₂ O _4, etc.) may corrode the surface of the substrate.
The water content of the liquid composition is preferably 2000 ppm or less.

  The thin film comprising the surface treating agent of the present invention is formed by applying a liquid composition to the surface of a substrate, drying it, and then irradiating with ultraviolet rays or short wavelength ultraviolet rays.

  Examples of the coating method include a roll coating method, a casting method, a dip coating method (dipping method), a spin coating method, a water casting method, a die coating method, a Langmuir-Projet method, a vacuum deposition method, and the like. From the viewpoint of productivity, the dipping method is preferred.

The wavelength of the ultraviolet light is preferably 184 nm, 253 nm, or a mixed wavelength thereof.
The irradiation time is preferably 1 to 120 seconds, more preferably 3 to 60 seconds, and particularly preferably 5 to 30 seconds.
You may wash | clean the base material after ultraviolet irradiation to a fluorine-type solvent for the purpose of the removal of a deposit | attachment, and the removal of an excess surface treating agent.

By performing ultraviolet irradiation, X of the terminal group of the compound (A) can be oriented on the surface of the substrate, and the adsorptivity of the compound (A) to the surface of the substrate can be enhanced.
Moreover, the thin film which consists of a surface treating agent with which the terminal group of the compound (A) orientated has high water repellency and high oil repellency. Therefore, moisture and the like are prevented from entering the inside of the base material from the surface of the base material, so that corrosion and deterioration of the base material are prevented. In addition, the surface on which the thin film is formed has the advantage of low surface energy and a low friction coefficient.
The water contact angle (room temperature) on the surface of the thin film after ultraviolet irradiation is preferably 70 ° or more, more preferably 80 ° or more, and particularly preferably 85 ° or more.

The thin film comprising the surface treating agent of the present invention is transparent, has a low refractive index, and is excellent in heat resistance or chemical resistance. Further, the thin film retains high lubricity and also has a self-repairing property.
The thickness of the thin film is preferably 0.001 to 50 μm.

The surface treatment agent of the present invention is used as a lubricant for imparting lubricity to a diamond-like carbon protective film (DLC film) of a magnetic disk.
Other uses of the surface treatment agent of the present invention include a surface modifier, a surfactant, a wire coating material, an ink repellent agent (ink repellent agent for painting, an ink repellent agent for printing equipment (inkjet, etc., etc.). ), Semiconductor element adhesives (LOC (lead-on-chip) tape adhesives, etc.), semiconductor protective coatings (moisture-proof coating agents, solder scooping prevention agents, etc.), thin films used in the optical field (pellicle films, etc.) )), Surface treatment agents for antireflection films for displays, antireflection films for resists, and the like.
When the surface treatment agent of the present invention is used for such applications, stable performance can be maintained over a long period of time.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples:
Tetramethylsilane to TMS,
CCl ₂ FCClF ₂ as R-113,
Dichloropentafluoropropane as R-225,
CClF ₂ CClFCF ₂ OCF ₂ CClF ₂ the CFE-419,
Hexafluoroisopropyl alcohol HFIP,
Isopropyl alcohol is referred to as IPA.

(NMR analysis)
TMS was used as a reference material for ¹ H-NMR (300.4 MHz).
CFCl ₃ was used as a reference substance for ¹⁹ F-NMR (282.7 MHz).
As a solvent, R-113 was used unless otherwise specified.

(GPC analysis)
According to the method described in Japanese Patent Application Laid-Open No. 2001-208736, Mw and Mw were measured by GPC under the following conditions to obtain Mw / Mn.
Mobile phase: R-225 (Asahi Glass Co., Ltd., Asahi Clin AK-225 SEC grade 1) and HFIP mixed solvent (R-255 / HFIP = 99/1 volume ratio),
Analytical column: two PLgel MIXED-E columns (manufactured by Polymer Laboratories) connected in series,
Standard sample for molecular weight measurement: 4 types of perfluoropolyethers having a Mw / Mn of less than 1.1, a molecular weight of 2000 to 10000, and Mw / Mn of 1.1 or more and a molecular weight of 1300 seed,
Mobile phase flow rate: 1.0 mL / min,
Column temperature: 37 ° C
Detector: Evaporative light scattering detector.

[Example 1]
Similar to the method described in Example 1 of the example of International Publication No. 2005/068534, polyoxyethylene glycerol ether (manufactured by NOF Corporation, UNIOX G1200) is added to FC (O) CF (CF ₃ ) OCF _2. CF (CF ₃ ) O (CF ₂ ) ₃ F was reacted to obtain a compound (C1-1) which was liquid at room temperature. As a result of NMR analysis, the average value of (c1 + c2 + c3) of the compound (C1-1) was 20.5, and R ^f was —CF (CF ₃ ) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ F. It was. As a result of GPC analysis, Mn of compound (C1-1) was 2600, and Mw / Mn was 1.15.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 3.4 to 3.8, 4.5.
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −76.0 to −81.0, −81.0 to −82.0, −82.0 to −82.5, −82.5 to -85.0, -128.0 to -129.2, -131.1, -144.7.

[Example 2]
In the method described in Example 2-1 of Examples in the pamphlet of International Publication No. 2005/068534, except that R-113 is changed to CFE-419 and the compound (D3-1) is changed to the compound (C1-1). Similarly, liquid phase fluorination reaction was performed, and 99.9 mol% or more of the hydrogen atoms of the compound (C1-1) were substituted with fluorine atoms. The product was a composition (d1-1) containing the compound (D1-1) as a main component. It was confirmed that the compound (D1-1) did not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 5.9 to 6.4.
¹⁹ F-NMR δ (ppm): −54.0, −77.5 to −86.0, −88.2 to −92.0, −120.0 to −139.0, −142.0 to − 146.0.

[Example 3]
In the method described in Example 3 of the example of the pamphlet of International Publication No. 2005/068534, a thermal decomposition reaction was similarly performed except that the compound (D5-1) was changed to the composition (d1-1), and the compound (D1 99.9 mol% or more of the ester group of -1) was thermally decomposed and derived into an acid fluoride group (-COF). The product was a composition (e1-1) containing the compound (E1-1) as a main component. It was confirmed that the compound (E1-1) did not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 5.9 to 6.4.
¹⁹ F-NMR δ (ppm): 12.7, −54.0, −78.1, −88.2 to −92.0, −135.0 to −139.0.

[Example 4]
In the method described in Example 4-1 of the example of the pamphlet of International Publication No. 2005/068534, the same procedure was performed except that the compound (D5-1) was changed to the composition (e1-1) and methanol was changed to ethanol. Then, 99.9 mol% or more of the acid fluoride group in the compound (E1-1) was derived into an ethyl ester group. The product was a composition (a1-1) containing the compound (A1-1) as a main component. As a result of GPC analysis, Mn of the compound (A1-1) was 2800, and Mw / Mn was 1.14. In addition, it was confirmed that the compound (A1-1) does not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 1.33, 4.27.
¹⁹ F-NMR δ (ppm): −54.0, −78.3, −88.2 to −92.0, −135.0 to −139.0.

[Example 5]
A 200 mL round bottom flask charged with a stirrer chip was thoroughly purged with nitrogen. 20.0 g of the composition (a1-1), 20 g of R-225, and 20 g of methanol were added, and the mixture was heated to 50 ° C. and stirred vigorously. After 1 hour, 0.1 L of 0.2N sodium hydroxide aqueous solution was slowly added dropwise over 0.5 hours from a dropping funnel placed at the top of the round bottom flask. After completion of the dropwise addition, stirring was continued at 50 ° C. for 6 hours and cooled to room temperature.

The crude liquid was quenched into 0.1 L of 0.05N aqueous hydrogen chloride solution and transferred to a separatory funnel. The organic phase was recovered and washed with 0.1 L of 0.05N aqueous hydrogen chloride solution four times, and then the separated organic phase was concentrated with an evaporator to give a composition (a2) that is a colorless liquid at room temperature. 17.5 g of -1) was obtained. 99.9 mol% or more of the ethyl ester group of the compound (A1-1) was saponified to a carboxyl group. The composition (a2-1) was mainly composed of the compound (A2-1). As a result of GPC analysis, Mn of the compound (A2-1) was 2500, and Mw / Mn was 1.19. In addition, it was confirmed that the compound (A2-1) does not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 10.4.
¹⁹ F-NMR δ (ppm): −54.0, −77.4, −88.2 to −92.0, −135.0 to −139.0.

[Example 6]
A 100 mL round bottom flask charged with a stirrer chip is thoroughly purged with nitrogen. 20.0 g of composition (a1-1) and 20 g of R-225 are added and stirred vigorously. After 1 hour, a mixture of 1.5 g of compound (U32H-1) and 20 g of R-225 is slowly added dropwise over 0.5 hour from a dropping funnel placed at the top of the round bottom flask. After completion of dropping, the temperature is raised to 50 ° C., and stirring is continued for 6 hours to cool to room temperature.
HOCH ₂ CH ₂ NH ₂ (U32H-1).

The crude liquid is concentrated with an evaporator, and the residue is washed twice with 0.1 L of n-hexane to obtain 18.5 g of a composition (a3-1) that is a colorless liquid at room temperature. Compound (A1-1) -C (O) over 99 mol% of _OCH 2 CH ₃ in is derivatized to _{-C (O) NHCH 2 CH 2} OH. The main component of the composition (a3-1) is the compound (A3-1). Mn of the compound (A3-1) is 3000, and Mw / Mn is 1.17. In addition, it is confirmed that the compound (A3-1) does not have a —OCF ₂ O— structure.

[Example 7]
A 100 mL round bottom flask charged with a stirrer chip was thoroughly purged with nitrogen. 20.0 g of the composition (a1-1) and 20 g of R-225 were added and vigorously stirred. After 1 hour, a mixture of 1.5 g of the compound (U31H-1) and 20 g of R-225 was slowly added dropwise over 0.5 hours from a dropping funnel placed at the top of the round bottom flask. After completion of the dropping, the temperature was raised to 50 ° C. and stirring was continued for 6 hours to cool to room temperature.
_{CH 2 = CHCH 2 NH 2 ···} (U31H-1).

The crude liquid was concentrated with an evaporator, and the residue was washed twice with 0.1 L of n-hexane to obtain 18.8 g of a composition (a4-1) which was a colorless liquid at room temperature. Compound (A1-1) -C (O) or 99.9 mol% of _OCH 2 CH ₃ of was induced to _{-C (O) NHCH 2 CH =} CH 2. The composition (a4-1) was mainly composed of the compound (A4-1). As a result of GPC analysis, Mn of the compound (A4-1) was 2900, and Mw / Mn was 1.14. In addition, it was confirmed that the compound (A4-1) does not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 7.09, 5.92, 5.38-5.20, 3.72.
¹⁹ F-NMR δ (ppm): −54.0, −77.6, −88.2 to −92.0, −135.0 to −139.0.

[Example 8]
In the method described in Example 5 of the examples of WO 2005/068534 pamphlet, except that the compound (D7-1) is changed to the composition (a1-1), the composition (b1-1) Got. 99.9 mol% or more of the ethyl ester group of the compound (A1-1) was reduced. The composition (b1-1) was mainly composed of the compound (B1-1). As a result of GPC analysis, Mn of the compound (B1-1) was 2900, and Mw / Mn was 1.13. In addition, it was confirmed that the compound (B1-1) does not have a —OCF ₂ O— structure.

¹ H-NMR δ (ppm): 3.94.
¹⁹ F-NMR δ (ppm): −54.0, −80.1, −88.2 to −90.5, −135.0 to −139.0.

[Example 9]
The compositions obtained in Examples 4-8 contain a low polarity component resulting from cleavage of the C—C bond. Therefore, the compositions obtained in Examples 4 to 8 were purified by the following column chromatography method.
A silica gel packed phase having a diameter of 100 mm and a length of 500 mm was packed into a column having a diameter of 150 mm and a length of 500 mm by diluting granular silica gel (manufactured by S-Itech, MS-Gel D75-120A) with R-225.
After putting the composition obtained in Examples 4 to 8 into the silica gel packed phase, only R-225 is passed as an extraction solvent to elute low polar components in the composition. Next, using an extraction solvent (mixed solvent of R-225 and HFIP or IPA), the target product is gradually increased to 10 to 100% depending on the polarity of the terminal group, while the concentration of HFIP or IPA in the extraction solvent is gradually increased. Elute.

[Example 10]
[Example 10-1]
Each of the composition (a1-1) to the composition (a4-1) after purification and the composition (b1-1) after purification are 1/1 mass ratio in terms of the quantitative ratio of the main component compound. It mixes and dilutes to 0.01 mass% with a solvent (the product made from Dupont, Vertrel-XF), and prepares 4 types of liquid compositions.

[Example 10-2]
The purified composition (a1-1) to the composition (a4-1) and the purified composition (b1-1) are mixed at a 1/100 mass ratio in terms of the quantitative ratio of the main component compound. Except that, four liquid compositions were prepared in the same manner as in Example 10-1.

[Example 11]
Using carbon as a target, DLC was vapor-deposited on glass blanks for magnetic disks (2.5 "blanks manufactured by Asahi Glass Co., Ltd.) by high-frequency magnetron sputtering in an Ar atmosphere to form a DLC film, and a simulated disk was produced. The gas pressure of Ar is 0.003 Torr, the input power density during sputtering is 3 W / cm ² per target area, the thickness of the DLC film is 30 nm, and the water contact angle on the surface of the DLC film is It was 40 degrees.

[Example 11-1]
The simulated disk is immersed in the liquid composition obtained in Example 10-1 for 30 seconds and pulled up at a constant speed of 6 mm / second. Using a UV irradiation device (UV Crosslinker CX-2000, manufactured by UVP), the simulated disk coated with the liquid composition is irradiated with UV to form a thin film. The wavelength of ultraviolet rays is a mixed wavelength of 184 nm and 253 nm, and the irradiation time is 15 seconds.

The disk obtained by the ultraviolet irradiation treatment is immersed in a solvent (Vertrel-XF) for 30 seconds and washed. The thickness of the thin film is measured with an ellipsometer before and after cleaning. The fixability is expressed as a percentage of the thickness after cleaning with respect to the thickness before cleaning. Fixability is 70% or more.
The water contact angle and hexadecane contact angle on the surface of the thin film of the disk obtained by the ultraviolet irradiation treatment are 80 ° or more.
The friction coefficient of the surface of the disk thin film obtained by the ultraviolet irradiation treatment is smaller than that before the thin film formation.

[Example 11-2]
Example 11 on the four liquid compositions obtained in Example 10-2 and the liquid composition (b1-1) obtained by diluting the composition (b1-1) (Comparative Example) to 0.01% by mass with Vertrel-XF A disk was prepared in the same manner as in -1, and the fixing rate and the hexadecane contact angle before ultraviolet treatment and after ultraviolet irradiation were measured. The results are shown in Table 1.
Furthermore, after another disk treated with the liquid composition (b1-1) was heat-treated at 100 ° C. for 1 hour in a constant temperature furnace, the same evaluation was performed. As a result, the fixing rate was 75%, and hexadecane contact The angle was 72 degrees.

  The surface treating agent of the present invention is useful as a lubricant for imparting lubricity to the surface of a recording medium (hard disk, metal vapor-deposited tape for 8 mm video tape recorder, metal vapor-deposited tape for digital video cassette, etc.).

Claims (10)

A surface treatment agent comprising a compound represented by the following formula (A).
(X−) _x (W−) _w (Z−) _z Y (A).
However, X is group represented by the following Formula (X),
W is a group represented by the following formula (W),
Z is a group represented by the following formula (Z):
Y is a (x + w + z) -valent perfluorinated saturated hydrocarbon group or a group having an etheric oxygen atom inserted between carbon-carbon atoms of the group,
x is an integer of 1 or more,
w is an integer of 0 or more,
z is an integer of 0 or more,
(X + w + z) is an integer of 3 to 5 .
_{U- (CH 2 CH 2 O)} a - (CH 2) b -CF 2 O (CF 2 CF 2 O) c - ··· (X),
^{_{R W - (CH 2 CH 2}} O) d - (CH 2) e -CF 2 O (CF 2 CF 2 O) f - ··· (W),
^{_{R F O (CF 2 CF 2}} O) g - ··· (Z).
However, U is a group represented by the following formula (U1), a group represented by the following formula (U21), a group represented by the following formula (U31), a group represented by the following formula (U32), A group represented by the formula (U33), a group represented by the following formula (U41), a group represented by the following formula (U51) , a is an integer of 0 to 100, and b is , An integer from 0 to 100, c is an integer from 1 to 200,
R ^W is HO - a and, d is an integer of 0 to 100, e is an integer from 0 to 100, f is an integer of 1 to 200,
R ^F is a linear perfluoroalkyl group having 1 to 20 carbon atoms or a group having an etheric oxygen atom inserted between carbon-carbon atoms of the group, and g is an integer of 3 to 200.

Ph-O- (U21),
_{CH 2 = CH (CH 2)} n NHC (O) - ··· (U31),
HO (CH ₂ ) _n NHC (O) − (U32),
(HO (CH ₂ ) _n −) ₂ NC (O) − (U33),
R ^c OC (O) − (U41),
_{CH 2 = CH (CH 2)} q O- ··· (U51).
Here, R is a hydrogen atom, a chlorine _{atom, -CH 2 CH 2 CH 3,} -NH 2, -OPh, a group represented by -OCH 2 _{(CF 2) p} H or -OCH ₂ CF ₂ CF ₃ , Ph is an optionally substituted phenyl group, p is an integer of 1 to 8, and R may be the same or different,
n is an integer of 1 to 3,
R ^c is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an aryl group, a substituted aryl group, an aryloxy group or a substituted aryloxy group,
q is an integer of 1 to 3. Compound represented by the formula (A) is no -OCF ₂ O-structure, surface treatment agent according to claim 1.   The surface treating agent according to claim 1 or 2, wherein (x + w + z) is 3 or 4. Y is a group represented by the following formula (Y ³ -1) to a group represented by the following formula (Y ³ -4), a group represented by the following formula (Y ⁴ -1) to the following formula (Y ⁴ groups represented by -5), any one of groups represented by the following formula (Y 5 ^-1), the surface treatment agent according to claim 1 or 2. However, Formula (Y3-4) represents a perfluorocyclohexane-1,3,5-triyl group.

The surface treatment according to any one of claims 1 to 4, wherein the group represented by the formula (X) is a group represented by the following formula (X1) or a group represented by the following formula (X2). Agent.
U ¹ —CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _c − (X1),
U ² —CF ₂ O (CF ₂ CF ₂ O) _c − (X2).
However, ^{U 1} is a group represented by the formula (U1), a group represented by the group or the formula represented by the formula ^{(U21) (U51), U} 2 is represented by the formula (U31) A group represented by the formula (U32), a group represented by the formula (U33), a group represented by the formula (U41) or a group represented by the formula (U51), and c is 1 to 200 Is an integer. The surface treating agent according to any one of claims 1 to 5 , wherein the group represented by the formula (W) is a group represented by the following formula (W1).
HO—CH ₂ —CF ₂ O (CF ₂ CF ₂ O) _f − (W1 ).
However , f is an integer of 1-200. The surface treatment agent according to any one of claims 1 to 6 , wherein the group represented by the formula (Z) is a group represented by the following formula (Z1).
_{CF 3 (CF 2) m -O-} (CF 2 CF 2 O) g - ··· (Z1).
However, m is an integer of 0-19 and g is an integer of 3-200. The surface treating agent according to any one of claims 1 to 7 , comprising a solvent. A compound represented by the following formula (A3-1).

However, c1-c3 is an integer of 1-200, respectively. A compound represented by the following formula (A4-1).

However, c1-c3 is an integer of 1-200, respectively.