WO2006109468A1

WO2006109468A1 - Oil-repellent composition and oil-repellent film

Info

Publication number: WO2006109468A1
Application number: PCT/JP2006/305717
Authority: WO
Inventors: Fumiko Nonaka; Toyomichi Shimada
Original assignee: Asahi Glass Co., Ltd.
Priority date: 2005-03-30
Filing date: 2006-03-22
Publication date: 2006-10-19
Also published as: JP2006307129A

Abstract

Disclosed is an oil-repellent composition containing a copolymer (A) and a solvent, wherein the copolymer (A) has a polymerization unit derived from a (meth)acrylate (a1) having a polyfluoroalkyl group, a polymerization unit derived from a (meth)acrylate (a2) having a blocked isocyanate group, and a polymerization unit derived from a (meth)acrylate (a3-1) having a hydroxyl group or a (meth)acrylic acid (a3-2). Also disclosed is an oil-repellent film obtained from such an oil-repellent composition. The oil-repellent composition enables to obtain an oil-repellent film which exhibits excellent and durable oil repellency and does not decrease in adhesion to a base material even when it is exposed to high-temperature oil for a long time. The oil-repellent film is excellent in oil repellency and durability.

Description

Specification

Oil repellent composition and oil repellent film

Technical field

The present invention relates to an oil repellent composition and an oil repellent film.

Background art

[0002] Oil repellents containing fluoropolymers are used as oil sealants for preventing oil from seeping out from fluid bearings of motors in electronic devices and the like. For example, in a fluid bearing portion of a cooling fan motor for a microprocessor, an optical disk rotating device, a computer hard disk, or the like, an end face of the bearing or sleeve is used to prevent the oil filled as a lubricant from oozing out. Is provided with an oil repellent film made of an oil repellent containing a fluorine-containing copolymer (see, for example, Patent Document 1). As a fluorine-containing copolymer having oil repellency, a polymer having a fluorine-containing aliphatic ring structure is also known (for example, see Patent Document 2).

However, since the temperature of the oil in the fluid bearing portion rises due to heat generated from the motor portion, the oil repellent film may be exposed to high temperature oil, and the oil may penetrate into the oil repellent film. Therefore, there is a problem that the oil repellency of the oil repellent film is lowered due to swelling of the oil repellent film, the adhesion between the oil repellent film and the bearing or sleeve, and the function of preventing oil oozing out.

[0003] As a fluorine-containing resin composition having excellent adhesion to a substrate, a fluorine-containing resin having a fluorine-containing ring structure and a functional group having polarity and soluble in a fluorine-based solvent is used. A composition containing a compound has been proposed (see Patent Document 3). However, since the fluorine-containing resin having the fluorine-containing ring structure has an ether bond in the ring structure and is amorphous, the surface polarity is not sufficiently exhibited, the oil repellency is insufficient, and the oil is not used. There is a possibility that there is not enough repelling power.

In addition, as an oil repellent, a composition containing a polymer having a polymer unit based on a (meth) acrylate containing a polyfluoroalkyl group is known (for example, Patent Document 4).

). However, although the composition has excellent initial oil repellency as an oil sealant, it retains oil repellency. There is a problem that is inferior in nature.

Furthermore, since ordinary oil sealants are colorless and transparent and it is difficult to visually recognize the film, the application state of the oil sealant cannot be evaluated, and it is difficult to ensure stable quality. To solve this problem, a technique has been proposed in which a dye characterized by vaporization by heating at 90 ° C to 150 ° C is mixed and inspected before calorific heat (see Patent Document 5).

However, in the case of Patent Document 5, the degree of coloration is reduced by vaporization after heating, and the application state of the oil sealant cannot be visually recognized. It is difficult to evaluate the state. There is also a problem that sorting is not possible when parts not coated with oil sealant are mixed.

Patent Document 1: JP 2000-297818

Patent Document 2: Japanese Patent Laid-Open No. 63-238111

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-115622

Patent Document 4: Japanese Unexamined Patent Publication No. 2000-160148

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2004-211851

Disclosure of the invention

Problems to be solved by the invention

[0004] The object of the present invention is to provide an oil repellency that is excellent in oil repellency and that does not deteriorate the adhesion to the substrate even when exposed to high temperature oil for a long time, and that can provide an oil repellency film having excellent oil repellency It is an object of the present invention to provide a composition and an oil-repellent film excellent in oil repellency and durability.

Another object of the present invention is to provide an oil repellent composition capable of obtaining an oil repellent film excellent in visibility, and an oil repellent film excellent in visibility.

Means for solving the problem

[0005] The oil-repellent composition of the present invention is based on a polymer unit based on a (meth) acrylate (al) having a polyfluoroalkyl group, and on a (meth) acrylate (a2) having a blocked isocyanate group. A polymer unit (A) having a hydroxyl group-containing (meth) acrylate (a3_l) or (meth) acrylic acid (a3-2) -based copolymer (A), and a solvent. It is characterized by.

The copolymer (A) is a polymer based on a (meth) acrylate (a4) further having an alkyl group. You may have a unit.

In the copolymer (A), the proportion of polymerized units based on (meth) acrylate (al) is preferably 70 to 98% by mass of all polymerized units (100% by mass).

The oil repellent composition preferably further contains one or more pigments.

The dye is preferably a fluorescent dye.

[0006] The oil-repellent film of the present invention is a polymer unit based on a (meth) acrylate (al) having a polyfluoroalkyl group, and a (meth) acrylate (a2) having a blocked isocyanate group. And a copolymer (A) having a polymer unit based on a (meth) atalylate (a3_l) or a (meth) atalinoleic acid (a3-2) having a hydroxyl group. .

The copolymer (A) may further have a polymer unit based on the (meth) acrylate (a4) having an alkyl group.

The oil repellent film preferably further contains one or more pigments.

The dye is preferably a fluorescent dye.

The invention's effect

[0007] According to the oil-repellent composition of the present invention, an oil-repellent film having excellent oil repellency, no deterioration in adhesion to a substrate even when exposed to high-temperature oil for a long time, and excellent oil repellency endurance is obtained. be able to. The oil repellent film of the present invention is excellent in oil repellency and durability, and is excellent in visibility. BEST MODE FOR CARRYING OUT THE INVENTION

[0008] (Copolymer (A))

The copolymer (A) is a polymer unit based on a (meth) acrylate having a polyfluoroalkyl group (hereinafter referred to as al), and a (meth) acrylate having a blocked isocyanate group (hereinafter referred to as al). Polymerized units based on (a2)) and polymerized units based on (meth) acrylate (hereinafter referred to as a3-1) or (meth) acrylic acid (hereinafter referred to as a3-2) having a hydroxyl group Containing. In the present invention, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid.

[0009] As al, a compound represented by the following formula [1] is preferred: Where R ^f is polyfluoroal Kill group, Q represents a divalent organic group, R represents a hydrogen atom or a methyl group.

[0010] [Chemical 1]

[0011] R ^f is preferably an alkyl group in which two or more hydrogen atoms are substituted with fluorine atoms. R¾ The number of carbon atoms is preferably 220, more preferably 4 to 16; R ^f is more preferably a linear structure that may be a linear structure or a branched structure. In the case of a branched structure, a short chain having a branched portion at the terminal portion of R ^f and having about 14 carbon atoms is preferred. R ^f may contain an etheric oxygen atom or a thioetheric sulfur atom. ^Examples of the structure of the terminal portion of R ^f include CF CF (CF) CF—CF H—CFH — and the like, and CF CF is preferred.

[0012] The number of fluorine atoms in R ^f is represented by [(number of fluorine atoms in R ^f ) Z (number of hydrogen atoms contained in an alkyl group having the same number of carbon atoms as R ^f )] X 100 (%) In this case, 60% or more is preferable, and 80% or more is more preferable, and 100% is most preferable. R ^f in the case of 100% is referred to as a perfluoroalkyl group (hereinafter also referred to as R ^F group).

The number of carbon atoms in the R ^F group is preferably 2-20, more preferably 4-16. When the number of carbon atoms in R ^F group is in the range, polymerization of al, the solution stability after polymerization has excellent initial woodwasp oil and oil repellent volatility Yogu oil repellency composition.

[0013] Specific examples of R ^f include the following groups (including structurally isomeric groups).

C F _: F (CF) —, (CF) CFCF one, (CF) C one, CF CF (CF) CF_ etc.

C F-: F (CF) —etc.

CF one: F (CF) (CF) CF (CF) First class. CF-: F (CF) —etc.

8 17 2 8

C F One: F (CF) (CF) CF (CF) First class.

9 19 2 9 3 2 2 6

C F-: F (CF) —etc.

10 21 2 10

C F-: F (CF) —etc.

12 25 2 12

C F-: (CF) CF (CF) —etc.

13 27 3 2 2 8

C F-: F (CF) —etc.

14 29 2 14

C F-: F (CF) —etc.

16 33 2 16

[0014] Specific examples of the case where R ^{f has} an etheric oxygen atom or a thioetheric sulfur atom include the following groups. However, k shows the integer of:! ~ 5.

F (CF) OCF (CF) _,

2k 3

F (CF CF O) CF CF

2 2 k 2 2

F (CF CF CF O) CF CF

2 2 2 k 2 2

F [CF (CF) CF O] CF (CF)

3 2 k 3

F [CF (CF) CF O] CF (CF) CF CF

3 2 k 3 2 2

F (CF) SCF (CF)

2k 3

F (CF CF S) CF CF

2 2 k 2 2

F (CF CF CF S) CF CF

2 2 2 k 2 2

F [CF (CF) CF S] CF CF

3 2 k 2 2

F [CF (CF) CF S] CF (CF) CF CF First class.

3 2 k 3 2 2

[0015] R ^f is more preferably a linear R ^F group, specifically, F (CF)-, F (CF)

2 4 2 5 F (CF) F (CF) F (CF) F (CF) F (CF) F (CF)

2 6 2 7 2 8 2 9 2 10 2

-, F (CF)-are particularly preferred.

11 2 12

[0016] Examples of Q include the following groups. However, Ra represents ^a hydrogen atom or an alkyl group, p and q each independently represents 0 or an integer of 1 or more, and p + q is an integer of:! -22.

-(CH) ―,

2 P + q

― (CH) CONR ^a (CH)

2 p 2 q

— (CH) OCONR ^a (CH)

2 p 2 q One (CH) SO NR ^a (CH)

2 p 2 2 q

One (CH) NHC〇NH (CH)

2 p 2 q

(CH) CH (OH) (CH)

2 p 2 q

-(CH) CH (OCOR ^a ) (CH) —etc.

2 p 2 q

[0017] Q is:-(CH)--(CH) CONR ^a (CH)-or _ (CH) SO

2 p + q 2 p 2 q 2 p:

NR ^a (CH) _ (p is 0 or an integer of 1 or more, q is an integer of 2 or more, p + q is 2 6

2 q

It is. Ethylene group, propylene group, butylene group, pentamethylene group or hexamethylene group is most preferable.

[0018] As al, the following compounds are preferable. R represents a hydrogen atom or a methyl group.

F (CF) CH OCOCR = CH (1-

2 4 2 2-1),

F (CF) CH OCOCR = CH (1- -2),

2 5 2 2

H (CF) CH OC ○ CR = CH (1 -3),

2 4 2 2

H (CF) CH OC ○ CR = CH (1 -4),

2 6 2 2

H (CF) CH OC ○ CR = CH (1-5),

2 8 2 2

H (CF) CH OCOCR = CH (1 -6),

2 10 2 2

H (CF) CH CH OCOCR = CH

2 8 2 2 2 [1-7],

F (CF) CH CH OC ○ CR = CH (-8),

2 4 2 2 2 1-

F (CF) CH CH OC ○ CR = CH (-9),

2 6 2 2 2 1-

F (CF) CH CH OC ○ CR = CH (-10),

2 8 2 2 2 1-

F (CF) CH CH OC ○ CR = CH 〔

2 9 2 2 2 1- -11),

F (CF) CH CH OCOCR = CH Ci- -12),

2 10 2 2 2

F (CF) CH CH OCOCR = CH Ci- -13),

2 12 2 2 2

F (CF) CH CH OCOCR = CH Ci--14),

2 14 2 2 2

F (CF) CH CH OCOCR = CH Ci- -15),

2 16 2 2 2

F (CF) (CH) OCOCR = CH Ci-16),

2 8 2 3 2

F (CF) (CH) OCOCR = CH Ci-17),

2 8 2 4 2

(CF) CF (CF) CH CH OCOCR = CH (CF CF (CF) CH CH OC ○ CR = CH [1-19]

(CF CF (CF) CH CH OC ○ CR = CH [1-20]

(CF CF (CF) (CH) OC〇CR = CH [1-21],

(CF CF (CF) CH CH (OH) CH OCOCR = CH [1-22] (CF CF (CF) CH CH (OH) CH OCOCR = CH [1-23], (CF ') CF (CF) CH CH (OC〇CH) OCOCR = CH [1-24]

F (CF) SO N (CH) CH CH OCOCR = CH [1-25], F (CF) SO

N (C H) CH CH OCOCR = CH [1-26]

F (CF) SO N (C H) CH CH OCOCR = CH (1-27),

F (CF) CONHCH CH OCOCR = CH [1-28].

[0019] For al, [1_ :! ] To [1-28], [1_3] to [: 1_15] are more preferred, [1-8]

~ [: 1-13] is most preferred.

[0020] a2 is a compound obtained by reacting a (meth) acrylate having an isocyanate group and a blocking agent.

Examples of the (meth) acrylate having an isocyanate group include 2-isocyanate ethyl (meth) acrylate, 1, 3, 3-trimethyl 4-isocyanate cyclohexylmethyl amidoxychetyl (meth) acrylate, etc. Is mentioned.

[0021] Blocky Asymmetric IJ includes 2 butanone oxime, cyclohexanone oxime, ε-force prolatata, acetoacetate ethyl, acetyl acetone, phenol, methanol, jetyl malonate, bisulfite, pyrazole, 3-methylbirazole 3, 5-dimethyl bilazole, indazole and the like. Among these blocking agents, 2-butanone oxime, acetoacetate ethyl, jetyl malonate, pyrazonole, 3 methylpyrazole, and 3,5_dimethylbiazole are more stable because of their excellent stability and reactivity Preferred are 2-butanone oxime, 3-methylvilazole, and 3,5-dimethylpyrazole.

[0022] As a3_l, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate , 2-Ataryllooxychetyl _2-Hydroxyethyl roof Tanolate, 3_Black _2-Hydroxypropyl (meth) acrylate, Polyoxyalkylene No (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxyethylene polyoxypropylene mono (meth) acrylate, and the like.

[0023] By using a2 and a3-1 or a3-2 (hereinafter a3 _ l and a3 _2 are collectively referred to as a3), the al (meth) talate and a2 or Copolymerization of a3 (meth) acrylate leads to higher molecular weight of copolymer (A). Further, when forming the oil repellent film, the isocyanate group of a2 reacts with the hydroxyl group of a3-1 or the carboxylic acid group of a3-2 to form a urethane bond, thereby forming a three-dimensional crosslinked product. The oil repellent film using such a high molecular weight copolymer (A) and having become a three-dimensional crosslinked body exhibits good oil repellency without swelling and peeling even when immersed in high temperature oil. .

[0024] The copolymer (A) may further have polymerized units based on (meth) acrylate (hereinafter referred to as a4) having an alkyl group. In the case where the number of carbon atoms in the al ^RF group exceeds 8, it is preferable to have a polymerized unit based on a4.

[0025] As a4, methyl (meth) acrylate, ethyl (meth) acrylate, propynole (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethyl hexyl Sil (meth) acrylate, n-hexyl (meth) acrylate, 3-ethoxyethyl (meth) acrylate, 3-benzoyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ate Rate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, isobronyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, tetrahydrofurfuryl (Meth) Atalylate, Benzyl (Meth) Tartrate, Phenoxetyl (Meth) Tarireto, isobornyl (meth) Atari rate or the like can be mentioned up. Of these a4, ethyl acrylate, propyl acrylate and cyclohexyl acrylate are preferred.

[0026] By using a4 having a molecular weight of 200 or less, al (meth) acrylate and a4 (meth) acrylate are copolymerized to increase the molecular weight of copolymer (A). Further, the alkyl group of the polymer unit based on a4 suppresses the crystallinity of the ^RF group of the polymer unit based on al, and the precipitation of the copolymer (A) in the oil repellent composition is suppressed, and the oil repellent composition The product becomes a uniform solution and storage stability is improved. Furthermore, by having polymerized units based on a4 The film forming property of the oil repellent composition is improved, and a uniform oil repellent film can be obtained. Further, by using a4 having a molecular weight of 200 or more, the crystallinity of the oil-repellent film is improved, the dynamic wettability such as the receding contact angle is improved, the oil is easy to roll, and the oil containment can be strengthened.

[0027] The copolymer (A) may have a polymer unit based on a polymerizable monomer other than al, a2, a3, and a4 (hereinafter referred to as a5). Having a polymerized unit based on a5 is excellent in adhesion to the substrate. As a5, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, (meth) acrylate with polydimethylsiloxane group, triaryl cyanurate, maleic acid dialkyl ester, N-substituted aminoalkyl (meth) acrylate And polyoxyalkylene glycol bis (meth) acrylate.

[0028] In the copolymer (A), the polymer units based on al, the polymer units based on a2, the polymer units based on a3, and the polymer units based on a4 may each be one type or two or more types. When two or more polymerized units based on al are contained, the number of carbon atoms in ^Rf of each al is preferably different. Also, if it contains polymerized units number of carbon atoms of R ^f is based on different al 2 or more carbon atoms al in R ^f is expressed as the mean value.

[0029] The proportion of the polymer units based on al in the copolymer (A) is preferably 70 to 98% by mass, more preferably 80 to 98% by mass of the total polymer units (100% by mass). -98% by weight is most preferred. When the polymerization unit based on al is within this range, the oil repellency of the oil repellent film is excellent.

[0030] The ratio of the polymerized units based on a2 in the copolymer (A) is preferably 0.5 to 10% by mass of the total polymerized units (100% by mass): more preferably 8 to 8% by mass. Preferred:! To 5% by mass is most preferred.

The proportion of polymerized units based on a3 in the copolymer (A) is preferably 0.5 to 10% by mass of all polymerized units (100% by mass): more preferably 8 to 8% by mass. :! To 5% by mass is most preferable.

When the polymer unit based on a2 and the polymer unit based on a3 are within this range, the three-dimensional crosslinked body is sufficiently formed and the adhesiveness is sufficiently expressed while maintaining the oil repellency of the obtained oil repellent film. As a result, the oil repellency is excellent.

[0031] The proportion of the polymer units based on a4 in the copolymer (A) is preferably 20% by mass or less.

However, when the number of carbon atoms in the al group exceeds 8, the group in a4 in the copolymer (A) The proportion of polymerized units is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass of the total polymerized units (100% by mass). preferable. When a4 is within this range, the oil-repellent composition is excellent in storage stability and film-forming property.

The proportion of polymerized units based on a5 in the copolymer (A) is preferably 10% by mass or less of the total polymerized units (100% by mass).

[0032] (Solvent)

Examples of the solvent include halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, and organic acids.

Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers.

Examples of the halogenated hydrocarbon include hide mouth fluorocarbon, hide mouth fluorocarbon, hydrobromocarbon, and fluorine-containing alcohol.

The following compounds can be cited as examples of the hide mouth fluorocarbon.

CH CC1 F,

3 2

CHC1 CF CF,

2 2 3

CHC1FCF CC1F etc.

twenty two

[0033] Examples of the hide-mouthed fluorocarbon include the following compounds.

CF CF CF CHF

3 2 2 2,

CF CF CF CH F

3 2 2 2,

CF CF CH CF,

3 2 2 3

CHF CF CF CHF

2 2 2 2,

CHF CH CF CF,

2 2 2 3

CF CHFCH CF,

3 2 3

CF CH CF CHF,

3 2 2 2

CHF CHFCF CHF,

2 2 2

CF CHFCF CH,

3 2 3

CHF CHFCHFCHF,

twenty two

CF CH CF CH, CF CF CH CH,

CHF CH CF CH,

CHF CF CF CF CF,

CF CF CF CHFCF,

CHF CF CF CF CHF,

CF CHFCHFCF CF,

CF CHFCF CH CF,

CF CF (CF) CH CHF,

CF CH (CF) CH CF,

CF CH CF CH CF,

CHF CHFCF CHFCHF,

CHF CF CF CHFCH,

CF CH CH CH CF,

CHF CH CF CH CHF,

CF (CF) CHF,

CF CF CF CF CH CF,

CHF CF CF CF CF CHF,

CF CH (CF) CHFCF CF,

CF CF CH CH (CF) CF,

CF CH CF CF CH CF,

CF CF CH CH CF CF,

CF CF CF CF CH CH,

CF CH (CF) CH CH CF,

CHF CF CH CH CF CHF

CF CF CF CH CH CH etc.

Fluorine-containing alcohols include trifluoroethanol, 2, 2, 3, 3, 3_pentafluoro 1_propanol, 2_ (pentafluorobutinole) ethanol, 2_ (perfluoroe Xysyl) ethanol, 2— (penolephnoleohexyl) ethanol, 2— (penolefluorooctyl) ethanol, 2 (perfluorodecyl) ethanol, 2 (perfluoro-3-methylbutyl) ethanol, 1H, 1H, 3H tetrafluoro Raw 1 propanol, 1H, 1H, 5H—octafluoro-1 _heptanol, 1H, 1H, 9H—hexadecafluoro —1—nonanol, 2H—hexafluoro-2--2-propanol, 1H, 1H, 3H—hexafluoro-2-butanol Etc.

[0035] Examples of the hydrocarbane mochabon are the following compounds.

CH Br,

CH BrCH CH,

CH CHBrCH,

CH BrCHBrCH etc.

Examples of the halogenated ether include hydrated fluoroether. Examples of the hyde mouth fluoroether include a separated type hyde mouth fluoroether and a non-separable type hyde mouth fluoroether. The separated type hyde mouth fluoro ether is a compound in which a perfluoroalkyl group or a perfluoroalkylene group and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. The non-separated hydrofluoroether is a hydrocarbyl ether containing a partially fluorinated alkyl group or alkylene group.

[0036] Examples of the separated hide-mouthed fluoroether include the following compounds.

CF CF CF OCH,

(CF) CFOCH,

CF CF CF OCH CH,

CF CF CF CF OCH,

(CF) CFCF OCH,

(CF) COCH,

CF CF CF CF OCH CH,

(CF) CFCF OCH CH,

(CF) COCH CH, CF CF (〇CH) CF (CF),

CF CF (〇CH CH) CF (CF)

C F OCH CH,

CF CF CF CF (OCH CH) CF (CF)

CH 0 (CF) OCH,

CH OCF CF OCH CH

C H OCF (CF) CF OCH

F (CF) OCH (n is 6 to 10), etc.

Examples of non-separating type hyde mouth fluoroether include the following compounds _c

CHF OCF OCHF,

CH FCF OCHF,

CF CF CF 〇CHF,

CF CF OCH CHF,

CHF CF OCH CF,

CHF CF CH OCF,

CF CF CH OCHF,

CHF CF OCH CHF,

CF CH OCF CHF,

CHF CF CF OCH,

CHF CF CH OCH,

CF CF CF OCH CF,

CF CF CH OCF CF,

CF CF CF OCH CHF,

CF CF CH OCF CHF,

CHF CF CH OCF CF,

CHF CF CH OCF CHF

CF CHFCF CH OCF, CF CHFCF CH OCHF,

CF CF CF CH OCH,

(CF) CHCF OCH,

CF CF CF OCH CF CF,

CF CF CF OCH CF CHF,

CF CF CF CF OCF CHF,

CF (CF) OCHF,

CHF OCF CF OCHF,

CHF OCF OCF CF OCHF,

CHF OCF OCF OCF OCHF etc.

[0038] Examples of the hydrocarbon include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

Aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethinolevbutane, 2,3-dimethylenolevbutane, heptane, sucrose, 2, 2,4-trimethylenopentane, 2 2, 2, 3-trimethylenohexane, decane, undecane, dodecane, 2, 2, 4, 6, 6-pentamethylheptane, tridecane, tetradecane, hexadecane and the like.

Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.

Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isoptyl ketone.

[0039] Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.

Examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran and the like.

Nitrogen compounds include pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like. Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.

Examples of the inorganic solvent include liquid carbon dioxide.

Examples of the organic acid include acetic acid, propionic acid, malic acid, and lactic acid.

[0040] As the solvent, from the viewpoint of solubility, Hyde mouth black fluorocarbon, Hyde mouth fluorocarbon, Hyde mouth fluoroether, and perfluorocarbon are preferred. CH CC1

F, CHC1 CF CF, CHC1FCF CC1F, CH FCF OCHF, CF CF CF O

CH F, CF CF OCH CHF, CHF CF OCH CF, CHF CF CH OCF

, CF CF CH OCHF, CHF CF OCH CHF, CF CH OCF CH F, CF

CH OCF CHF, CHF CF CF OCH, CF (CF) CHF, CF (CF) C

H F, CF (CF) OCH force S is more preferable. When the solvent is used, the solubility of the polymer and the storage stability in the form of a solution are excellent.

The solvent may be a single solvent or a mixed solvent of two or more.

[0041] (Oil-repellent composition)

The oil-repellent composition of the present invention is a composition containing a copolymer (A) and a solvent.

The content of the copolymer (A) in the oil-repellent composition is preferably from 0.1 to 20 mass% in the oil-repellent composition (100 mass%), more preferably from 0.1 to 10 mass%. . Within this range, the oil repellency and oil repellency are excellent.

The content of the solvent in the oil repellent composition is preferably from 80 to 99.9% by mass in the oil repellent composition (100% by mass), more preferably from 90 to 99.9% by mass. Within this range, the oil-repellent composition is excellent in storage stability, and an oil-repellent film can be formed by a single coating.

[0042] In the oil-repellent composition of the present invention, in order to improve the adhesion of the oil-repellent film to the substrate, a silane force peeling agent, a primer, etc. are added to the oil-repellent film and the storage stability of the oil-repellent composition. It can be added to the extent that it does not spoil.

In order to increase the oil repellency and oil repellency of the oil-repellent film, the oil-repellent composition of the present invention is added with a fluorine-containing polymer that does not contain a polymer unit based on a (meth) acrylate having a polyfluoroalkyl group. You may be careful. Examples of the fluorine-containing polymer include a polymer having a fluorine-containing aliphatic ring structure in the main chain described in JP-A-63-238111, perfluoropolyether, tetrafluoroethylene monohexafluoropropylene. Polymer, tetrafur Examples include fluoroethylene perfluoroalkyl vinyl ether copolymers.

[0043] (Dye)

It is preferable to add pigments such as dyes and pigments to the oil-repellent composition of the present invention. When pigments are mixed, the presence or absence of the oil-repellent film becomes easy to see and the visibility is excellent.

When adding a dye, it may be added directly to the oil-repellent composition, or after adding the dye to a solvent that is insoluble in the oil-repellent composition, or in a solvent compatible with the oil-repellent composition and the dye. You may do it.

A dye having a high absorbance that develops a color different from that of the substrate is preferred. Even when the substrate is black, a fluorescent dye that emits light by irradiating ultraviolet rays and can visually recognize the oil-repellent film is more preferable. Fluorescent pigments emit more intense light when irradiated with light that is the fluorescent maximum wavelength of the dye, and the oil-repellent film is visually screened. In addition, pigments that can be identified even after heating the oil-repellent composition are preferred. Pigments that tend to retain color even at the heat-curing temperature of the oil-repellent composition are more preferred. The pigment is the most preferred.

Examples of the dye include coumarin, stilbene, thiophene, xanthene, naphthaloid, bilarizone, oxazole, naphthalimide, indico, and atalidine, and stilbene, xanthene, and naphthaloid are preferable because of heat resistance. You can mix two or more dyes.

The amount of the dye added is preferably 0 :! to 30% by mass in the oil-repellent film (100% by mass): more preferably 10 to 10% by mass. 0.1 When the content is 1% by mass or more, the color of the oil-repellent film is excellent. In addition, when the amount is 30% by mass or less, the dye does not precipitate the oil-repellent film and does not separate the layers.

[0044] (oil repellent film)

The oil repellent film of the present invention is a film containing the copolymer (A).

The oil repellent film of the present invention is formed, for example, by applying the oil repellent composition of the present invention to a substrate and completely evaporating the solvent. Examples of the application method include spraying, dipping, brushing, potting and spinning.

Examples of the substrate include resin, metal, fiber and the like. The substrate may be subjected to pretreatment such as corona treatment and UV ozone treatment, primer treatment, and the like. By this treatment, the oil repellent film and the substrate Adhesion with is improved.

[0045] The oil-repellent film of the present invention is a film formed by crosslinking an oil-repellent composition, and adhesion to the substrate is improved by crosslinking. Examples of the method for crosslinking the oil-repellent composition include heat curing, photocuring by UV irradiation, electron beam curing by electromagnetic wave irradiation or electron beam irradiation, and the like. Of these, heat curing is preferred in which no harmful rays are generated with little capital investment. The heating and curing temperature is preferably heated to a temperature that can be tolerated by a substrate where high temperatures are preferred in order to promote curing of functional groups, chemical bonding with the substrate, and anchor bonding. The heating temperature is preferably 100 200 ° C force S, more preferably 100 150 ° C. The heating time is preferably 30 minutes or more. When the temperature and the time range are satisfied, the oil repellent film is cured well and an oil repellent film excellent in oil repellency can be obtained.

[0046] In the oil-repellent film of the present invention, it is considered that the isocyanate group of the copolymer (A) reacts with a hydroxyl group or a carboxylic acid group, so that the copolymer (A) has a high molecular weight. In addition, it is considered that the oil-repellent film has low oil solubility due to the presence of a urethane bond (crosslinked structure) between an isocyanate group and a hydroxyl group or a carboxylic acid group. Furthermore, because of the large amount of R ^f groups present, it has excellent oil repellency, so even when exposed to oil at 100 ° C or higher for a long time, it does not decompose or dissolve, and has excellent adhesion to the base material. It can last for a long time without significantly impairing oil repellency.

Example

[0047] The present invention will be described with reference to specific examples (Examples: Examples:! To 7, Comparative Examples: Examples 8 to 10), but the present invention is not limited thereto.

The oil repellency was evaluated by the following method.

(Initial oil repellency)

About n_hexadecane was dropped on the test plate, and the contact angle was measured. The oil seal performance was evaluated by the contact angle of n_hexadecane. A contact angle of 50 ° or more was judged to be oil-sealable, and less than 50 ° was judged to be oil-sealable.

(Oil repellent durability)

The test plate was immersed in n-hexadecane at 120 ° C. for 40 hours, pulled up and dried using an air gun, and the contact angle of n-xadecane was measured in the same manner as described above. (Contact angle)

The contact angle was measured by the droplet method at 25 ° C using Kyowa Interface Science CA-A. [0048] [Example 1]

In a 50 mL glass flask, perfluorinated hexyl acetyl acrylate [F (CF)

CH CH OCOCH = CH] (hereinafter referred to as C6FA) 0.12g of 1,4-cyclohexanedimethanol monometatalylate [CH

= CH (CH) COO CH CH CH OH] (hereinafter referred to as CM) 0.09g, 2, 2'_azobis (2-methylbutyronitrile) (hereinafter referred to as AB1) 0 .09g and HCF CF

13.5 g of OCH CF (hereinafter referred to as solvent Y) was added.

After replacing the gas inside the flask with nitrogen gas, the flask was sealed and kept in a 60 ° C. water bath for 15 hours while stirring in the flask to obtain a transparent solution containing the copolymer. Solid impurities were filtered off from the resulting solution using 1 μ filter paper, and the obtained filtrate was diluted with a solvent to give an oil repellent solution having a copolymer concentration of 2 mass%.

Apply the obtained oil repellent solution to the washed SUS plate by spin coating method for 20 seconds under the condition of 500i "pm, and heat-treat at 120 ° C for 60 minutes to obtain a test plate having an oil repellent film. The test plate was evaluated for initial oil repellency and oil repellency, and the results are shown in Table 1.

[0049] [Example 2]

C6FA 5.77g, IS 0.15g, AB1 0.07g, Solvent Y 14g for CM, CM 0.0

2-Hydroxyethyl metatalylate instead of 9g [CH = C (CH) CO ○ CH CH ○

H] (hereinafter referred to as 2HEMA) was used in the same manner as in Example 1 except that 0.008 g was used. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0050] [Example 3]

A test plate was obtained in the same manner as in Example 2 except that 5.92 g of perfluorinated hexylmethacrylate (hereinafter referred to as C6FM A) was used instead of 5.7 g of C6FA. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1. [0051] [Example 4]

In a 50 mL glass flask, perfluoroalkylethyl acrylate (F (CF)

2 n

CH CHOCOCH = CH] (n is a mixture of 6 to 16: n8 or more is 80 mass% or more

2 2 2

And the average value of n is 9. Hereinafter referred to as CmFA. 5.9 g of IS, 0.09 g of IS, 0.05 g of 2HE MA, 0 of ethyl acrylate [CH = CHCOOC H] (hereinafter referred to as EA).

2 2 5

29 g, 0.12 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as AB2), and 13.6 g of solvent Y were added.

After replacing the gas inside the flask with nitrogen gas, the flask was sealed and kept in a 60 ° C hot water bath for 15 hours with stirring in the flask to obtain a transparent solution containing the copolymer. A test plate was obtained in the same manner as in 1. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0052] [Example 5]

5.6 g of CmFA, 0.09 g of IS, 0.05 g of 2HEMA, 13.6 g of solvent Y, and cyclohexyl acrylate (hereinafter referred to as CHA) instead of 0.29 g of EA. A test plate was obtained in the same manner as in Example 4 except that 0 · 12 g was used. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0053] [Example 6]

5.6g of CmFA, 0.09g of IS, 0.05g of 2HEMA, 0.29g of EA, 0.99g of AB1 instead of AB2, and CF (CF) CHF instead of solvent Y For 13 · 6g

3 2 4 2

A test plate was obtained in the same manner as in Example 4 except that a 70 ° C hot water bath was used instead of the 60 ° C hot water bath. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0054] [Example 7]

0.25 g of stilbene dye was added to 99.75 g of methyl ethyl ketone and stirred until a uniform solution was obtained to obtain Solution D. 0.5 g of xanthene dye was added to 99.5 g of trifluoroethanol, and stirred until a uniform solution was obtained.

10 g of solution D and 20 g of solution E were added to 100 g of the copolymer solution of Example 1 (2% by mass), and the mixture was stirred until uniform. Use this solution as in Example 4 to prepare the test plate. Obtained. In the test plate, the oil repellent film portion was colored pink compared to Example 1, and when the 365 nm light was further irradiated, the oil repellent film portion emitted light, and the oil repellent film was visible.

[0055] [Example 8]

A 50 mL glass flask was charged with 6 g of C6FA, 0.09 g of AB1, and 14 g of solvent Y. After replacing the gas inside the flask with nitrogen gas, the flask was sealed, and the flask was stirred and kept in a 60 ° C hot water bath for 20 hours to obtain a transparent solution containing the copolymer. A test plate was obtained in the same manner as in 1. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0056] [Example 9]

A 50 mL glass flask was charged with 6 g of CmFA, 0.09 g of AB2, and 14 g of solvent Y. After replacing the gas inside the flask with nitrogen gas, the flask was sealed, and the flask was stirred and kept in a 60 ° C hot water bath for 20 hours to obtain a transparent solution containing the copolymer. A test plate was obtained in the same manner as in 1. The test plate was evaluated for initial oil repellency and oil repellency. The results are shown in Table 1.

[0057] [Example 10]

In an autoclave made of glass, 100 g of CF = CFOCF CF CF = CF (hereinafter referred to as CY), 0.5 g of CH OH as a chain transfer agent and ((CH)) as a polymerization initiator

0, 7 g of CHOC (O) O) was added and sealed. The inside of the autoclave was kept at 40 ° C. for 22 hours to conduct a polymerization reaction to obtain a polymer. The intrinsic viscosity of the obtained polymer was 0.2 · dL / g in perfluoro (2-butyltetrahydrofuran) at 30 ° C.

The obtained polymer was heat-treated in a hot-air circulating oven at 300 ° C for 1 hour in an air atmosphere, then immersed in ultrapure water at 110 ° C for 1 week, and then at 100 ° C for 24 hours. The polymer G was obtained by vacuum drying.

As a result of analyzing polymer G by IR spectrum, a peak attributed to a carboxyl group was confirmed. Polymer G had a glass transition point of 108 ° C, was a tough and transparent glass at 25 ° C, and had a light transmittance of 95% or more. The 10% thermal decomposition temperature of Polymer G was 465 ° C. After obtaining a solution in which 2 g of polymer G was dissolved in 99 g of perfluorooctane, a test plate was obtained in the same manner as in Example 1. For the test plate, the initial oil repellency and The oil repellency was evaluated. The results are shown in Table 1.

[0058] [Table 1]

Industrial applicability

[0059] The oil-repellent composition of the present invention can be used for use as an oil sealant. In addition, since the oil-repellent composition of the present invention is excellent in oil repellency and water repellency, it can be used for various protective films such as antifouling films, water and oil repellent films for fibers, antifouling films for inkjet nozzles, and semiconductors. It can be used for waterproof and moisture-proof films, semiconductor wafer protective films, and the like.

[0060] Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. is there.

This application is based on the Japanese patent application filed on March 30, 2005 (Japanese Patent Application 2005-097043) and the Japanese patent application filed on June 2, 2005 (Japanese Patent Application 2005-185577). Incorporated herein by reference.

Claims

The scope of the claims

[1] A polymer unit based on (meth) acrylate (al) having a polyfluoroalkyl group, a polymer unit based on (meth) acrylate (a2) having a blocked isocyanate group, and a hydroxyl group ( A copolymer (A) having polymerized units based on (meth) acrylate (a3 _ 1) or (meth) acrylic acid (a3 _ 2);

With solvent

Oil-repellent composition containing

[2] The oil-repellent composition according to claim 1, wherein the copolymer (A) further has a polymer unit based on the (meth) acrylate (a4) having an alkyl group.

[3] The proportion of polymerized units based on (meth) acrylate (al) in the copolymer (A) is 70 to 98% by mass of all polymerized units (100% by mass). An oil-repellent composition as described in 1.

[4] The oil-repellent composition according to claim 1, 2 or 3, wherein the oil-repellent composition further contains one or more pigments.

[5] The oil-repellent composition according to claim 4, wherein the dye is a fluorescent dye.

[6] Polymerized units based on (meth) acrylate (al) having a polyfluoroalkyl group, polymerized units based on (meth) acrylate (a2) having a blocked isocyanate group, and

An oil repellent film comprising a copolymer (A) having a polymer unit based on (meth) acrylate (a3 — 1) or (meth) acrylic acid (a3 — 2) having a hydroxyl group.

7. The oil repellent film according to claim 6, wherein the copolymer (A) further has a polymer unit based on the (meth) acrylate (a4) having an alkyl group.

[8] The copolymer (A) is 70 to 98% by mass of the total polymerization unit (100% by mass) of the polymer unit based on the (meth) acrylate (al) in the copolymer (A). The oil repellent film according to claim 6 or 7, wherein

[9] The oil repellent film according to claim 6, 7 or 8, wherein the oil repellent film further contains one or more pigments.

10. The oil repellent film according to claim 9, wherein the dye is a fluorescent dye.