HK1054955B - Antifouling coating composition comprising a fluorinated resin - Google Patents

Description

Antifouling coating composition containing fluorinated resin

The present invention relates to a fluorinated resin and its use in antifouling coating compositions for marine applications.

Man-made structures such as boat hulls, buoys, drilling platforms, oil production equipment and pipes that are submerged in water are prone to fouling by aquatic organisms such as green and brown algae, barnacles, mussels, and the like. These structures are typically made of metal, but may also comprise other structural materials, such as concrete. Such fouling is detrimental on the hull of the vessel because it increases the frictional resistance through the water as the vessel is sailing, thereby reducing the speed and increasing the cost of fuel. Such fouling is also detrimental on static structures such as the columns of drilling platforms and oil production equipment, firstly because the resistance of thick fouling layers to waves and currents can cause unpredictable and potentially dangerous stresses in the structure, and secondly because fouling makes it difficult to inspect the structure for defects such as stress cracking and corrosion. Fouling is detrimental in pipes such as cooling water inlets and outlets because the effective cross-sectional area is reduced by fouling, thereby reducing the flow velocity.

The most commercially successful method of inhibiting fouling involves the use of antifouling coatings containing substances toxic to aquatic organisms such as tributyltin chloride or cuprous oxide. However, such coatings are becoming increasingly popular because of the potentially damaging effects of such toxins upon release into aquatic environments. There is therefore a need for non-fouling coatings that do not contain significantly toxic substances.

It has been known for many years that silicone rubber coatings, such as disclosed in GB 1,307,001 and US 3,702,778, resist fouling by aquatic organisms. Such coatings are believed to present surfaces to which organisms cannot readily attach, and are therefore referred to as non-fouling coatings rather than antifouling coatings. Silicone rubbers and silicone compounds generally have very low toxicity. However, silicone rubber coatings have gained little commercial acceptance. Silicone rubber is difficult to adhere well to the surface of the substrate to be protected and is mechanically rather weak and prone to damage.

The use of fluorinated polymers in antifouling or non-fouling coating compositions to control fouling is well known.

In JP 04-045170, a fluorinated silicone resin obtained by grafting a fluorine-containing acrylate to a silicone resin having an ethylenically unsaturated bond at the terminal is disclosed.

In JP 61-043668 a coating composition with antifouling properties is disclosed, which is prepared by compounding an alkyd resin with a polymer prepared by reacting a fluorine-containing monomer with an acrylate polymer.

In JP 06-322294 there is disclosed an anticorrosive and antifouling paint comprising a film-forming resin and an organopolysiloxane containing an oxyalkylene group and a perfluoroalkyl group.

Other uses of fluorinated polymers are also known.

In JP 06-239876 a fluorinated polymer with excellent wetting properties for adhesives is disclosed. In US 4,900,474, an organopolysiloxane containing perfluoroethyl ether groups is disclosed for use as a silicone defoamer.

Fluorinated polymers known in the art have not found widespread use in antifouling coating compositions because their inadequate antifouling/stain release properties and/or their mechanical properties make these compositions unsuitable for use in a variety of structures that are immersed in water. In particular, if used as a boat hull coating composition, the mechanical properties should be such that the coating composition has sufficient strength and abrasion resistance to have a service life of several years.

It is an object of the present invention to provide a novel antifouling coating composition having very good antifouling/fouling release properties and sufficient mechanical strength, and a method for inhibiting fouling of a substrate in a marine fouling environment using the novel antifouling coating composition. The method comprises forming a coating comprising a curable fluorinated resin of the formula:

W-L-YFC-O-R^f-CFY-L-W (I)

wherein

-L is an organic linker;

y is F or CF₃；

W is of the formula-Si (R)¹)_α(OR²)_3-αA group wherein α is 0, 1 or 2, preferably α is 0; r¹And

R²independent of each otherIs linear or branched C₁-C₆Alkyl, optionally containing one or more ether groups, or

C₇-C₁₂Aryl or alkyl, R¹And R²Preferably C₁-C₄An alkyl group;

-R^fis a group having a number average molecular weight of 350-:

-CFXO-、-CF₂CF₂O-、-CF₂CF₂CF₂O-、-CF₂CF₂CF₂CF₂O-、-CR⁴R⁵CF₂CF₂-、-(CF(CF₃)CF₂O)-、-CF₂CF(CF₃)_O-，

wherein

X is F or CF₃，

-R⁴And R⁵Independently represent H, Cl or C₁-C₄A perfluoroalkyl group.

L is preferably a divalent linking group, more preferably selected from one or more of the following groups:

a)-(CH₂-(OCH₂CH₂)_n)_m-CO-NR′-(CH₂)_q，

wherein

R' is H, C₁-C₄Alkyl or phenyl;

m is an integer of 0 or 1, preferably 1;

n is an integer from 0 to 8, preferably from 0 to 5;

q is an integer from 1 to 8, preferably from 1 to 3;

b)-CH₂O-CH₂CH₂CH₂-

c)-CH₂O-CH₂-CH(OH)CH₂-S-(CH₂)q。

l may also be a trivalent radical. In this case, -L-W in the following formula (I) becomes-L- (W)₂。

Preferred are compounds wherein L is A) m is 1, n is 0-5 and q is 1-3.

Further preferred is R^fOne selected from the following structures:

1)-(CF₂O)_a′-(C₂F₄O)_b′-, where a '/b' is from 0.2 to 2, a 'and b' are integers up to the abovementioned molecular weights;

2)-(C₃F₆O)_r-(C₂F₄O)_b-(CFXO)_t-, where r/b is 0.5 to 2 and (r + b)/t is 10 to 30, b, r and t being integers up to the above molecular weight;

3)-(C₃F₆O)_r′-(CFXO)_t′-CF₂(R′f)_y-CF₂O-(CFXO)_t’-(C₃F₆O)_r’-, where t 'is greater than 0, R'/t 'is from 10 to 30, R' and t 'are integers up to the abovementioned molecular weights, y is 0 or 1, R' f is C₁-C₄A fluoroalkyl group;

4)-(C₃F₆O)_z-CF₂-(R′f)_y-CF₂O-(C₃F₆O)_z-, where z is an integer up to the stated molecular weight, y is 0 or 1, R' f is C₁-C₄A fluoroalkyl group;

5)-(OCF₂CF₂CR⁴R⁵)_q-OCF₂-(R′f)_y-CF₂O-(CR⁴R⁵CF₂CF₂O)_s-, where q and s are integers up to the above stated molecular weight, R⁴And R⁵Having the meaning given above, y is 0 or 1,

r' f is C₁-C₄A fluoroalkyl group.

In the above structure, - (C)₃F₆O) -may be- (CF)₃)CF₂O) -or- (CF)₂CF(CF₃)O)-。

The product of formula (I) may be prepared by the process disclosed in US 4,746,550.

It was found that coating compositions comprising fluorinated resins of formula (I) obtainable by reacting a silicon compound as defined below with a fluorinated resin containing-OH or-COOR (R stands for H or C) of the general formula₁-C₃) The end-group bifunctional perfluoropolyether is obtained by reaction:

H-(OCH₂CH₂)_n-OCH₂-CF₂-O-R^f-CF₂-CH₂O-(CH₂CH₂O)_nh (II) or

ROOC-CF₂-O-R^f-CF₂-COOR (III)

Wherein R is^fAnd n has the meaning previously described. These compounds are available from Ausimont under the trade name Fomblin^ZDOL, ZDAL, ZDOL-TX. However, difunctional perfluoroethers containing other terminal groups, such as epoxy groups, can also be used.

Examples of suitable silicon compounds which can be reacted with the above difunctional perfluoropolyether precursors are compounds of the general formula (IV),

R³-Si-(R⁴)₃ (IV)

wherein R is³Is a group capable of coupling silicon compounds to fluorinated polyethers, R⁴Independently of one another, are ether or ester groups, preferably groups comprising straight-chain or branched alkyl moieties having from 1 to 4 carbon atoms.

For example, wherein R³The silicon compound being an isocyanate function may be coupled with a fluorinated polyether containing at least two functional groups chosen from hydroxyl, amine or carboxylic acid functionsAnd (4) connecting. Wherein R is³The silicon compound being an amine function may be coupled to a fluorinated polyether containing at least two functional groups selected from carboxylate or epoxy functional groups. Wherein R is³The silicon compound that is a thiol functional group may be coupled to a fluorinated polyether that contains at least two epoxy functional groups.

Examples of preferred silicon compounds are alkoxyalkyl isocyanates, alkoxysilylalkyl isocyanates, alkoxysilyl alkyl esters, alkoxysilanes, alkoxyalkyl silanes and alkoxyalkylsilylmercapto-, amino-and glycidyl-functional compounds, such as 3-methyldimethoxysilylpropyl isocyanate, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.

The fluorinated resins thus obtained are also subject of the present invention.

In general, fluorinated resins have been found to have good results in terms of both antifouling/non-fouling properties and mechanical strength when their Tg is in the range-120 ℃ to 20 ℃ and surface energy is in the range 10-25 mN/m. In general, mechanical properties are improved when the Tg of the resin is increased and fouling release properties are improved when the Tg of the material is decreased. Therefore, for each fluorinated resin, the optimum balance between mechanical properties and stain removal performance must be found by adjusting the Tg of the resin. Such adjustment may be, for example, by changing R^fThe length of the segment or W segment.

The coating composition may be prepared by mixing a fluorinated resin, a curing catalyst such as a condensation catalyst, an optional co-catalyst, an optional resin cross-linking agent, a reactive or non-reactive flow additive, a solvent, a filler, a pigment and/or a thixotropic agent.

Examples of catalysts that may be used include carboxylates of various metals such as tin, zinc, iron, lead, barium and zirconium. Preferred salts are long chain carboxylates such as dibutyltin dilaurate, dibutyltin dioctoate, iron stearate, tin (II) octoate and lead octoate. Other examples of suitable catalysts include organobismuth and organotitanium compounds and organophosphates such as 2-ethylhexyl hydrogen phosphate. Other possible catalysts include chelates, such as dibutyltin acetylacetonate. In addition, the catalyst may comprise a halogenated organic acid containing at least one halogen substituent on a carbon atom alpha to the acid group and/or at least one halogen substituent on a carbon atom beta to the acid group, or a derivative which is hydrolysable under the condensation reaction conditions to such an acid.

The resin cross-linking agent is only necessary to be present when the resin is not curable by condensation. Depending on the functional groups present in the fluorinated resin. In general, the crosslinking agent need not be present when the fluorinated resin contains alkoxy groups. If the fluorinated resin contains alkoxy-silyl groups, it is generally sufficient to have a small amount of condensation catalyst and water present to achieve complete cure of the coating after application. For these compositions, normal atmospheric humidity is sufficient to initiate cure, and it is generally not necessary to heat the coating composition after application.

The optional crosslinker may be a crosslinker comprising a functional silane and/or one or more oxime groups. Examples of such cross-linking agents are listed in WO 99/33927. Mixtures of different crosslinking agents may also be used.

Examples of reactive or non-reactive flow additives that can be used in the coating composition of the present invention are non-or monofunctional fluorinated polyethers. These compounds may be represented by the following structures:

T-O-CFY-O-R^f-CFY-(L)_k-T₁ (V)

wherein

-k is an integer 0 or 1,

-T is selected from-CF₃、-C₂F₅、-C₃F₇、CF₂Cl、C₂F₄Cl、C₃F₆Cl，

-T when k is 0₁is-O-T; t when k is 1₁Is W. And wherein R^fY and L have the meanings indicated above.

Commercial products are available from Ausimont, for example as Fomblin^Y25. Other non-reactive oils may also be used, such as silicone oils (in particular methyl-phenyl silicone oils), petrolatum, polyolefin oils or polyaromatic oils. The proportion of these reactive or non-reactive flow additives may be from 0 to 25% by weight, based on the total weight of the coating composition.

Examples of solvents that may be used in the coating composition of the present invention include polar solvents or mixtures thereof, such as methyl isobutyl ketone or butyl acetate. A non-polar solvent or a mixture thereof, such as xylene, may be used as a co-solvent.

Examples of fillers that can be used in the coating composition of the present invention are barium sulfate, calcium carbonate, silicas or silicates (e.g., talc, feldspar and china clay), aluminum pastes/flakes, bentonite or other clays. Certain fillers can have a thixotropic effect on the coating composition. The proportion of fillers may be from 0 to 25% by weight, based on the total coating composition.

Examples of pigments which can be used in the coating composition of the present invention are black iron oxide and titanium dioxide. The proportion of pigments may be from 0 to 10% by weight, based on the total weight of the coating composition.

The coating compositions of the present invention can be applied by conventional techniques such as brushing, rolling or spraying (airless and conventional). To achieve proper adhesion to the substrate, the antifouling/non-fouling coating composition of the invention is preferably applied to a primed substrate. The primer can be any conventional primer/sealer coating system. Good results, particularly in terms of adhesion, have been found when using primers comprising an acryloxy functional polymer, a solvent, a thixotropic agent, a filler and optionally a moisture scavenger. Such primers are disclosed in WO 99/33927.

The coating composition may also be applied to a substrate containing an aged antifouling coating in the process of the invention. Prior to applying the coating composition of the present invention to such an aged coating, the old coating was cleaned with high pressure water to remove any fouling. The primer disclosed in WO99/33927 can be used as an intermediate layer between the aged coating layer and the coating composition of the present invention.

Generally, low surface energy coatings such as coatings comprising polysiloxanes or fluoropolymers do not provide a solid foundation for the application of the coating composition of the present invention even after the intermediate layer has been applied, because the adhesion between the aged coating and the newly applied coating is generally insufficient.

After the coating is cured, it can be immediately immersed in water and given direct antifouling and fouling release protection.

As mentioned above, the coating composition used in the process of the present invention has very good antifouling and fouling release properties as well as high mechanical strength. This makes these coating compositions very suitable for use as antifouling or non-fouling coatings for marine applications. The coatings can be used for dynamic and static structures such as boat hulls, buoys, drilling platforms, oil production equipment, and submerged pipelines. The coating can be applied to various substrates for these structures, such as metal, concrete, wood or fiber reinforced resins.

The coating composition used in the method of the present invention is preferably applied in a high solids dispensing formulation. These compositions comprise less than 30 wt.%, preferably less than 20 wt.%, more preferably less than 10 wt.% of solvent. These formulations are of the solventless coating grade. Such coatings have the lowest impact on the environment from the standpoint of their low solvent content.

The low (room) temperature cure of the resin combined with the high solids content of the coating composition makes the coating composition of the present invention suitable for application in open air locations.

The invention will be described with reference to the following examples. These examples are intended to illustrate the invention but are not to be construed as limiting its scope in any way.

Examples

Example 1

Preparation of perfluoroethyl ether adducts

200 parts by weight of a bifunctional perfluoropolyether of the formula (II) having n-0 and a number average molecular weight of 1000 are introduced into a top-flanged reaction vessel with a mechanical stirrer, a temperature probe, a water condenser and a feed inlet. After the addition of 0.02 parts by weight of dibutyltin dilaurate (DBTDL), the reaction vessel was heated to 70 ℃. At this temperature, 88 parts by weight of 3- (trimethoxysilylpropyl) isocyanate (TMSPI) were added dropwise over 2 hours. During the addition, the temperature was maintained at 70 ℃ using a temperature control unit. After the addition was completed, the solution was stirred for another 1 hour to complete the reaction. The progress of the reaction can be determined by measuring TMSPI at about 2270cm^-1The decrease in infrared absorption was monitored.

The viscosity of the adduct at 25 ℃ was 4.1 poise (0.41Pa.s) and the Tg was-26 ℃.

Example 2

Preparation of adducts of ethoxylated perfluoroethyl ethers

The same procedure as described in example 1 was used, using a difunctional perfluoropolyether of the formula (II) having n ═ 1.5 and a number average molecular weight of 2000 as perfluoroether starting component in the reaction.

The resulting adduct had a viscosity of 8.1 poise (0.81Pa.s) at 25 ℃ and a Tg of-97 ℃.

Example 3

The method of example 1 is used by a process wherein R is CH₃And the difunctional diester of formula (III) having a number average molecular weight of 2000 is reacted with an equimolar amount of 3-aminopropyltrimethoxysilane at 70 ℃ to give the perfluorinated adduct. During the reaction, methanol was removed by distillation until about 1800cm^-1The IR band of the ester at (b) disappeared completely.

Example 4

A one-component coating composition was prepared by combining the following ingredients:

100g of the adduct of perfluoroethyl ether of example 1

10g of butyl acetate

0.2g of 3-aminopropyltrimethoxysilane

0.1g of dibutyltin dilaurate.

The coating composition was applied to a wood substrate and after curing of the composition, a coating was obtained with a modulus at 20 ℃ of 42.5Mpa (measured according to ASTM D1708) and a pencil hardness of 3H (measured according to ASTM D3363).

Example 5

A one-component coating composition was prepared by combining the following ingredients:

100g of the adduct of perfluoroethyl ether of example 1

20g of butyl acetate

0.2g of 3-aminopropyltrimethoxysilane

0.1g of dibutyltin dilaurate

3g Fomblin Y-25 (a perfluorinated polyether, ex Ausimont).

Example 6

By placing 100g of the adduct of perfluoroethyl ether of example 2 in one package and combining in another package

10g of butyl acetate,

0.2g of 3-aminopropyltrimethoxysilane and

0.1g of dibutyltin dilaurate

A two-component coating composition is prepared.

The coating composition was applied to a wood substrate and after curing of the composition, a coating was obtained with a modulus at 20 ℃ of 3.1Mpa (measured according to ASTM D1708) and a pencil hardness of 4B (measured according to ASTM D3363).

Example 7

A one-component coating composition was prepared by combining the following ingredients:

100g of the adduct of perfluoroethyl ether of example 1

10g of butyl acetate

0.2g of 3-aminopropyltrimethoxysilane

0.1g of dibutyltin dilaurate

30g of talc

6g of iron oxide black

25g of aluminum flakes.

Example 8

A one-component coating composition was prepared by combining the following ingredients:

100g of the adduct of perfluoroethyl ether of example 2

20g of butyl acetate

1g of 2-ethylhexyl hydrogen phosphate

3g Fomblin Y-25 (a perfluorinated polyether, ex Ausimont).

The coating compositions of examples 4-8 were applied to a wood substrate coated with an anticorrosion primer and a coating primer as disclosed in WO 99/33927. The coating formulation was applied with a brush and roller to give an average dry film thickness of 25-75 μm.

For static antifouling evaluation, the applied substrates were immersed in a bay known for weeds, slime, crusts and mollusk fouling. After one quarter (February-October), the accumulated offset was significantly less than a control substrate maintained under the same conditions for the same time without the composition applied. Any soiling on substrates coated with the compositions of examples 4 to 8 can be easily removed by gentle wiping or low-pressure water jets. Accumulated stain on the control substrate immersed for the same time period could not be removed in the same manner.

For these coating compositions, the following quantitative fouling properties were found:

examples	Micro fouling%	Mollusk%	Hard animal content	Total amount of fouling%	Push-off (Push-off) (PSI)*
						4	25	1.7	56.7	83.4	20.55
5	23.8	3.5	41.3	68.6	11.04
						6	28.8	2.2	50	81	13.34
7	19.7	2.2	6.8	28.7	6.24
						8	51.4	4.2	22.4	78	9.11

^*) The barnacle type, as determined according to ASTM Standard D-5618: semi balanus Balanoides

Example 9

A coating composition was prepared by combining the following ingredients:

100g of the adduct of example 3 Perfluoroethylene ether

20g of butyl acetate

1g of 2-ethylhexyl hydrogen phosphate

3g Fomblin Y-04 (a perfluorinated polyether, ex Ausimont).

Example 10

A coating composition was prepared by combining the following ingredients:

100g of the adduct of perfluoroethyl ether of example 2

20g of butyl acetate

15g of titanium dioxide

1g of 2-ethylhexyl hydrogen phosphate

6g Fomblin Y-25 (a perfluorinated polyether, ex Ausimont).

The coating compositions of examples 9 and 10 were applied to a wood substrate coated with an anticorrosion primer and the coating primer disclosed in WO 99/33927. The coating formulation was applied with a brush and roller to give an average dry film thickness of 25-75 μm.

For static antifouling evaluation, the applied substrates were immersed in a bay known for weeds, slime, crusts and mollusk fouling.

Claims (8)

1. A method of inhibiting fouling of a substrate in a marine fouling environment, comprising forming on the substrate, prior to exposure of the substrate to said marine fouling environment, a coating comprising a curable fluorinated resin of the general formula:

W-L-YFC-O-R^f-CFY-L-W

wherein

L is an organic linking group;

y is F or CF₃；

W is of the formula-Si (R)¹)_α(OR²)_3-αGroup of which alphaIs 0, 1 or 2, R¹And R²Independently represent linear or branched C₁-C₆Alkyl, optionally containing one or more ether groups, or C₇-C₁₂Aryl or alkyl;

R^fis a group having a number average molecular weight of 350-8000 comprising repeating units comprising at least one of the following structures randomly distributed along the chain length:

-CFXO-、-CF₂CF₂O-、-CF₂CF₂CF₂O-、-CF₂CF₂CF₂CF₂O-、-CR⁴R⁵CF₂CF₂O-、-(CF(CF₃)CF₂O)-、-CF₂CF(CF₃) O-in which

X is F or CF₃，

R⁴And R⁵Independently represent H, Cl or C₁-C₄A perfluoroalkyl group.

2. The process according to claim 1, characterized in that the organic linking group L is selected from one or more of the following groups:

a)-(CH₂-(OCH₂CH₂)_n)_m-CO-NR′-(CH₂)_q

b)-CH₂O-CH₂CH₂CH₂-

c)-CH₂O-CH₂-CH(OH)CH₂-S-(CH₂)_qwherein

R' is H, C₁-C₄Alkyl or phenyl;

m is an integer of 0 or 1;

n is an integer of 0 to 8;

q is an integer of 1 to 8.

3. The process according to claim 2, characterized in that the organic linker L has the general formula

-CH₂-(OCH₂CH₂)_n-CO-NR′-(CH₂)_qWherein n is an integer from 0 to 5 and q is 1 to 3An integer number.

4. Process according to any one of the preceding claims, characterized in that Rf is one or more groups selected from:

1)-(CF₂O _a′-(C₂F₄O)_b-, where a '/b' is 0.2 to 2, and a 'and b' are integers such that the molecular weight is in the range of 350-8000;

2)-(C₃F₆O)_r-(C₂F₄O)_b-(CFXO)_t-, where r/b is 0.5-2 and (r + b)/t is 10-30, b, r and t are integers such that the molecular weight is in the range 350-8000;

3)-(C₃F₆O)_r′-(CFXO)_t′-CF₂(R′f)_y-CF₂O-(CFXO)_t′-(C₃F₆O)_r′-, where t 'is greater than 0, R'/t 'is from 10 to 30, R' and t 'are integers such that the molecular weight is in the range from 350-8000, y is 0 or 1, R' f is C₁-C₄A fluoroalkyl group;

4)-(C₃F₆O)_z-CF₂-(R′f)_y-CF₂O-(C₃F₆O)_zwherein z is an integer such that the molecular weight is in the range of 350-8000, y is 0 or 1, R' f is C₁-C₄A fluoroalkyl group;

5)-(OCF₂CF₂CR⁴R⁵)_q-OCF₂-(R′f)_y-CF₂O-(CR⁴R⁵CF₂CF₂O)_s-, where q and s are integers such that the molecular weight is in the range 350-8000, and R⁴And R⁵Having the meaning given above, y is 0 or 1, R' f is C₁-C₄A fluoroalkyl group,

wherein in the above structure, - (C)₃F₆O) -may be- (CF)₃)CF₂O) -or- (CF)₂CF(CF₃)O)-。

5. The method according to any of the preceding claims, characterized in that the fluorinated resin has a Tg of-120 ℃ to 20 ℃ and a surface energy of 10-25 mN/m.

6. Process according to any one of the preceding claims, characterized in that it further comprises a non-functional or monofunctional resin of the general formula:

T-O-CFY-O-R^f-CFY-(L)_k-T₁wherein

k is an integer of 0 or 1;

t is selected from-CF₃、-C₂F₅、-C₃F₇、CF₂Cl、C₂F₄Cl、C₃F₆Cl；

T when k is 0₁is-O-T; t when k is 1₁Is W;

l is an organic linking group;

y is F or CF₃(ii) a And

R^fis a group having a number average molecular weight of 350-8000 comprising repeating units comprising at least one of the following structures randomly distributed along the chain length:

-CFXO-、-CF₂CF₂O-、-CF₂CF₂CF₂O-、-CF₂CF₂CF₂CF₂O-、-CR⁴R⁵CF₂

CF₂O-、-(CF(CF₃)CF₂O)-、-CF₂CF(CF₃)O-，

wherein

X is F or CF₃，

R⁴And R⁵Independently represent H, Cl or C₁-C₄A perfluoroalkyl group.

7. Use of a curable fluorinated resin of the general formula:

W-L-YFC-O-R^f-CFY-L-W

wherein

L is an organic linking group;

y is F orCF₃；

W is of the formula-Si (R)¹)_α(OR²)_3-αGroup, in which alpha is 0, 1 or 2, R¹And R³Independently represent linear or branched C₁-C₆Alkyl, optionally containing one or more ether groups, or C₇-C₁₂Aryl or alkyl;

R^fis a group having a number average molecular weight of 350-8000 comprising repeating units comprising at least one of the following structures randomly distributed along the chain length:

-CFXO-、-CF₂CF₂O-、-CF₂CF₂CF₂O-、-CF₂CF₂CF₂CF₂O-、-CR⁴R⁵CF₂CF₂O-、-(CF(CF₃)CF₂O)-、-CF₂CF(CF3)O-，

wherein

X is F or CF₃，

R⁴And R⁵Independently represent H, Cl or C₁-C₄A perfluoroalkyl group.

8. Use according to claim 7, characterized in that the fluorinated resin has a Tg of-120 ℃ to 20 ℃ and a surface energy of 10-25 mN/m.